CN102101759A - Concrete composite additive and preparation method and use thereof - Google Patents
Concrete composite additive and preparation method and use thereof Download PDFInfo
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- CN102101759A CN102101759A CN 201010613898 CN201010613898A CN102101759A CN 102101759 A CN102101759 A CN 102101759A CN 201010613898 CN201010613898 CN 201010613898 CN 201010613898 A CN201010613898 A CN 201010613898A CN 102101759 A CN102101759 A CN 102101759A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a concrete additive and discloses a concrete composite additive capable of optimizing a hydration heat release process of cement, which is prepared from the following raw materials in percentage by mass: 65 to 75 percent of naphthalene sulfonate-formaldehyde condensation product, 9 to 15 percent of lignosulfonic acid calcium salt, 8 to 10 percent of sodium gluconate and 8 to 10 percent of sucrose. When the additive is used, the hydration heat release of cement has the characteristic of two peaks and equal peak values. When other conditions are the same, the hydration heat half age of the cement mixed with the additive is three times longer than cement mixed with a naphthalene sulfonate water reducer and a concrete thermal-insulation temperature rise at a 7d age is reduced by about 7 DEG C; and the additive allows a cooling measure of introducing water to concrete to play a better cooling role, reduces the temperature rise peak value of the concrete by about 4 DEG C, ensures a remarkable cooling effect and has a great significance for the temperature control and cracking prevention of concrete. In addition, when the product provided by the invention is added, the pressure strength, working performance, durability and the like of concrete are all improved obviously.
Description
Technical field
The present invention relates to concrete field, be specifically related to a kind of composite additive for concrete.
Background technology
Normal silicate moderate heat cement hydration heat caloric value in 1 ~ 2d can reach half of final value under the normal condition, is called hydration heat half value length of time.The mixing of water reducer that water reducer especially has retarding performance can change the hydrated cementitious exotherm, makes the hydration heat half value change the length of time.
At present existing concrete admixture technology is paid attention to be by add admixture with improve concrete intensity, workability and just, final setting time etc., the hydration heat curve of existing admixture is unimodal value basically, the hydration heat curve haves much room for improvement.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of composite additive for concrete of optimizing mass concrete hydration heat process is provided, this admixture has and prolongs hydration heat of cement half value length of time, have and make the hydrated cementitious heat release characteristics that bimodal pattern and peak value equate substantially occur, can make the interior water flowing cooling provision of concrete bring into play advantages such as cooling effect better, significant to the concrete temperature controlled anticracking.
Another object of the present invention is to provide the preparation method of above-mentioned composite additive for concrete.
A further object of the present invention is to provide the application of above-mentioned composite additive for concrete.
The objective of the invention is to be achieved through the following technical solutions:
A kind of composite additive for concrete, by mass percentage, its composition of raw materials is as follows:
Naphthalene sulfonic salt formaldehyde condensation products 65 ~ 75%;
Calcium lignin sulphonate 9 ~ 15%;
Sunmorl N 60S 8 ~ 10%;
Sucrose 8 ~ 10%.
Further, described naphthalene sulfonic salt formaldehyde condensation products is high dense naphthalene water reducer, its NaSO
4Content less than 5wt%.
A kind of preparation method of composite additive for concrete may further comprise the steps:
(1) by mass percentage, 65 ~ 75% naphthalene sulfonic salt formaldehyde condensation products, 9 ~ 15% calcium lignin sulphonates, 8 ~ 10% Sunmorl N 60Ss and 8 ~ 10% sucrose are placed spiral stirring kettle;
(2) stir, churning time was controlled at 10 ~ 15 minutes; Obtain the composite additive for concrete powder product.The packing bag of damp film of setting up defences in this powder product usually adopts is packed.
The application of above-mentioned composite additive for concrete is applied in the concrete, and its volume is 0.5% ~ 0.8% of a glue material weight, is preferably 0.6% ~ 0.7%.Mixture or plain cement that described glue material is cement and flyash.Can directly adopt powder during application, for adopt automatic gauge also solubilized become the certain density aqueous solution, incorporation converts by effective solids content.
The present invention is directed to present normal concrete admixture and ignore hydration heat of cement half value length of time, ignore shortcoming such as exotherm optimization, adopt a kind of compound additive to overcome above-mentioned shortcoming.Determining optimization of C of the present invention by scientific experimentation, is parent with the dense naphthalene water reducer of height wherein, guarantees the water-reducing effect of admixture.Sunmorl N 60S can effectively prolong the concrete initial set time, sucrose can effectively prolong concrete final setting time, calcium lignin sulphonate not only can prolong concrete just, final setting time, it also have an amount of bleed with and distinctive xylogen macromole can improve concrete workability.
For mass concrete, when if the hydrated cementitious exotherm is optimized for the bimodal pattern (or multimodal type) that peak value equates substantially by general unimodal value, more significant effect is brought into play in the water flowing measure that cools that will help in the concrete, thereby help reducing temperature difference between inside and outside concrete to reduce distress in concrete, the engineering temperature controlled anticracking is had great importance.Composite additive for concrete of the present invention has been optimized the hydrated cementitious exotherm, and hydration heat presents the characteristic of bimodal pattern characteristic and hydration heat half value significant prolongation in the length of time, and this characteristic helps the measure of concrete water flowing cooling technology and plays a greater role.Under the situation that other condition is equal to, concrete external doped product of the present invention with mix the FDN Series Admixtures that generally adopts at present outward and compare, the former has reduced about 4 ℃ than the latter to concrete cooling in the water flowing cooling, reduces the about 0.4MPa of concrete pulling stress, and this is highly beneficial to the concrete temperature controlled anticracking.In addition, concrete external doped product of the present invention is when significantly improving above-mentioned characteristic, and also all having significantly to concrete serviceability, mechanical strength and endurance quality etc., improvement improves effect.
The present invention's advantage and beneficial effect thereof compared with prior art:
(1) with than naphthalene sulfonic salt water reducer compare, the present invention can make the hydration heat of cement half value prolong 3 times the length of time, and 7d age concrete thermal insulation warming reduces about 7 ℃, can significantly reduce the concrete temperature rise value;
(2) the present invention can make the interior water flowing cooling provision of concrete bring into play cooling effect better, helps reducing temperature difference between inside and outside concrete, helps the engineering temperature controlled anticracking;
(3) simple, the low production cost of production technique of the present invention;
(4) the present invention can produce at the large-scale construction project scene, the convenient use.
Description of drawings
Fig. 1 is numbering 1 a plain cement hydration heat duration curve;
Fig. 2 is numbering 2 glue material hydration heat duration curves;
Fig. 3 is numbering 3 glue material hydration heat duration curves;
Fig. 4 is numbering 4 glue material hydration heat duration curves;
Fig. 5 is a concrete thermal insulation warming curve;
Temperature rise curve when Fig. 6 is the concrete water flowing.
Embodiment
Embodiment 1
65kg naphthalene sulfonic salt formaldehyde condensation products (NaSO
4Content less than 5wt%), 15kg calcium lignin sulphonate, 10kg Sunmorl N 60S, 10kg sucrose be placed on earlier in the spiral stirring kettle; Stirred 10 ~ 15 minutes, and made each composition uniform distribution; The strap of damp film of setting up defences in the employing is in time packed; Obtain powder product of the present invention.
Embodiment 2
75kg naphthalene sulfonic salt formaldehyde condensation products (NaSO
4Content less than 5wt%), 9kg calcium lignin sulphonate, 8kg Sunmorl N 60S, 8kg sucrose be placed on earlier in the spiral stirring kettle; Stirred 10 ~ 15 minutes, and made each composition uniform distribution; The strap of damp film of setting up defences in the employing is in time packed; Obtain powder product of the present invention.
Embodiment 3
70kg naphthalene sulfonic salt formaldehyde condensation products (NaSO
4Content less than 5wt%), 12kg calcium lignin sulphonate, 8kg Sunmorl N 60S, 10kg sucrose be placed on earlier in the spiral stirring kettle; Stirred 10 ~ 15 minutes, and made each composition uniform distribution; The strap of damp film of setting up defences in the employing is in time packed; Obtain powder product of the present invention.
Admixture of the present invention and concrete performance test thereof carry out according to national standard and industry standard.The composite additive for concrete powder product of embodiment 3 preparations, naphthalene sulfonic salt water reducer (FDN), P.O 42.5 moderate heat cements, secondary ordinary fly ash, river sand (medium sand), cobble have been adopted in test below.
Cement gel material hydration heat comparative test result:
Table 1The gelling material proportioning
| Numbering | Doping quantity of fly ash/% | Standard consistency/% | The water reducer title | Water reducer volume/% |
| 1 | 0 | 25.4 | -- | ? |
| 2 | 30 | 26.6 | -- | ? |
| 3 | 30 | 20.4 | FDN | 0.7 |
| 4 | 30 | 23.2 | Compound additive of the present invention | 0.7 |
As shown in table 1, the glue material of numbering 1 is a plain cement; The glue material of numbering 2 is a cement 70%+ flyash 30%; In the numbering 3, glue material proportioning is consistent with numbering 2, mixes naphthalene sulfonic salt water reducer (FDN) 0.7% outward; In the numbering 4, glue material proportioning is consistent with numbering 2, mixes compound additive 0.7% of the present invention outward, with the hydration heat test of four kinds of different components cement gel materials, measure gelling material hydration heat curve, study different admixtures and mixing material influence degree the hydration reaction speed of gelling material.Test-results data such as table 2 and Fig. 1 ~ shown in Figure 4.
The different admixtures of table 2 are to the influence (kJ/kg) of gelling material hydration heat
| Numbering | 1d | 2d | 3d | 4d | 5d | 6d | 7d | 28d | Time to peak/h |
| 1 | 138.01 | 173.94 | 204.35 | 226.82 | 242.99 | 254.72 | 264.84 | 285.00 | 14 |
| 2 | 112.47 | 149.70 | 173.26 | 191.94 | 208.37 | 221.77 | 233.73 | - | 21 |
| 3 | 104.97 | 154.62 | 180.27 | 196.81 | 208.63 | 215.96 | 22.50 | - | 24 |
| 4 | 33.3 | 38.63 | 61.53 | 94.35 | 113.39 | 122.03 | 130.74 | - | Bimodal |
The result of above-mentioned test is: as shown in Figure 1, the plain cement hydration heat peak value of numbering 1 is 28.0 ℃; As shown in Figure 2, numbering is mixed 30% flyash in 2 in cement, can delay the time of occurrence of the cement briquette temperature rise peak value that hydration heat causes, but its influence degree is very little, has postponed about 7h approximately, and promotes the temperature rise peak value to some extent; As shown in Figure 3, in the numbering 3, mix 30% flyash and FDN water reducer after, there is further postponement the time that test block temperature rise peak value occurs, but it is little to influence amplitude, and the temperature rise peak value not have to influence substantially; As shown in Figure 4, in the numbering 4, after mixing 30% flyash and compound additive powder product of the present invention, the temperature rise bimodal has appearred in test block, the time that second peak value occurs, than 100% cement briquette thermal spike time of occurrence about 61h that lagged behind, the peak value of temperature rise simultaneously also was greatly reduced greatly about about 75h, the nearly 4 ℃ range of decrease, the peak clipping value reaches 17%.In addition, in table 1, when mixing the FDN water reducer outward, the hydration heat in 7d length of time is 222.50kJ/kg, and hydration heat half-mature length of time is 1.24d, and when mixing product of the present invention outward, the hydration heat in 7d length of time is 130.74kJ/kg, and hydration heat half-mature length of time is 5.39d, has prolonged 4.15d than the former.As seen, product of the present invention has good effect to changing the hydrated cementitious exothermic process, has the dual function of postponing the peak value time of occurrence and reducing peak amplitude.
The test of concrete thermal insulation warming:
Test is as shown in table 3 with mix proportion, and the concrete starting temperature is 20 ℃, and the thermal insulation warming test-results of test block sees Table 4 and Fig. 5.
Table 3 concrete mix (unit: kg/m
3)
| Numbering | Water reducer | Doping quantity of fly ash/% | Water | Cement | Flyash | Sand | Stone | Water reducer |
| A | -- | 30 | 110 | 140 | 60 | 596 | 1549 | -- |
| B | FDN | 30 | 110 | 140 | 60 | 596 | 1549 | 1.4 |
| C | Compound additive of the |
30 | 110 | 140 | 60 | 596 | 1549 | 1.4 |
The different admixtures of table 4 to the influence of concrete thermal insulation warming (℃)
| Numbering | Water reducer | 0.5d | 1d | 3d | 7d | 28d |
| A | — | 27.62 | 31.15 | 37.69 | 40.87 | 42.85 |
| B | FDN | 27.22 | 30.92 | 37.08 | 40.75 | 42.52 |
| C | Compound additive of the present invention | 22.26 | 23.99 | 28.27 | 33.45 | 40.81 |
By table 4 and Fig. 5 as can be known, the concrete seven d thermal insulation warming in the length of time of having mixed compound additive of the present invention outward is 13.45 ℃, mixing FDN water reducer concrete seven d thermal insulation warming in the length of time outward is 20.75 ℃, higher 7.3 ℃ than the former, illustrate that the former has retardance at thermal insulation warming, latter's hydration heat concentrates in early days, and 28d both thermal insulation warmings in the length of time are basic identical.
Combine concrete temperature rise test under the condition with the measure of water flowing refrigeration technique:
Carry out the concrete temperature rise test at the water flowing cooling conditions.The concrete blocks volume is of a size of the cubes of 10m * 10m * 10m, and concrete adopts B, C numbering proportioning configuration in the table 3,20 ℃ of temperature of concrete during construction, 20 ℃ of outside air temperatures, thermal conductivity
a=0.1m
2/ d, the surface heat fraction exchange is got 70kJ/ (m
2H ℃), the water flowing water-cooled tube adopts water conservancy project to manage with PE, buries underground by array pitch between 1m * 1m in concrete, and the water flowing time opening is that 4h rises after the concrete placement, 15 ℃ of water flowing water temperatures, water flowing lasts 21d.The temperature field finite element simulation computation program that adopts the FORTRAN that works out voluntarily to contain water-cooled tube carries out the unstable temperature field of this concrete placement piece and calculates.
The contrast of table 5 different mixture ratio concrete test piece central point temperature (℃)
| The length of time/d | 1 | 3 | 5 | 7 | 9 | 11 | 14 | 21 |
| B | 29.39 | 33.07 | 32.54 | 31.15 | 29.63 | 28.20 | 24.35 | 23.34 |
| C | 23.57 | 27.29 | 28.60 | 28.77 | 28.41 | 27.79 | 26.70 | 26.35 |
Table 5 is B, each feature of C proportioning concrete placement piece central point temperature value comparing result constantly.Fig. 6 is the pairing figure of table 5, by table 5 and Fig. 6 as can be known, owing to the hydration heat half value difference in the length of time, C proportioning concrete top temperature is 28.77 ℃, B proportioning concrete top temperature is 33.07 ℃, differed 4.30 ℃, this explanation product of the present invention more helps the water flowing cooling provision and plays a role, and this temperature controlled anticracking to concrete structure is very favourable.
The concrete performance simultaneous test:
(1) concrete initial set, final setting time comparative test result
Table 6 concrete coagulating time
| Numbering | The water reducer title | Presetting period/h | Final setting time/h |
| A | -- | 6 | 8 |
| B | FDN | 9 | 11.5 |
| C | Compound additive of the present invention | 14.5 | 18.5 |
Mixing of admixture can change concrete time of coagulation, as table 6, mix FDN water reducer concrete initial set time lengthening 3h, final setting time prolongs 3.5h, mix the concrete initial set time lengthening 8.5h of compound additive of the present invention, final setting time prolongs 10.5h, mix product concrete of the present invention just, the final set knot time effectively prolonged.Concrete just, after the final set knot time lengthening, can significantly improve concrete serviceability and pouring quality.
(2) concrete crushing strength comparative test result
The concrete early anti pressured intension decreases after mixing product of the present invention, and as table 7, the concrete 2d ultimate compression strength in the length of time of mixing product of the present invention is 3.6MPa, and compressive strength rate is mixed the low 2.4MPa of intensity of FDN water reducer.The speed that the heat release of cement early hydration has been reacted in the reduction of early age strength of concrete is effectively controlled, and makes the characteristic of its concentrated heat release obtain effective improvement.
Table 7 concrete crushing strength performance (MPa)
| The length of time/d | 1 | 2 | 3 | 7 | 28 | 90 |
| B | 2.5 | 6.0 | 12.7 | 22.5 | 33.5 | 40.2 |
| C | 1.5 | 3.6 | 7.5 | 18.0 | 30.5 | 41.5 |
The concrete early anti pressured intension is not a controlling index for concrete structure, mixing product concrete 2d ultimate compression strength in the length of time of the present invention is 3.6MPa, this intensity has possessed construction joint face cutter hair or has dashed the requirement that hair is handled and removed side form, can satisfy the needs that construction is produced.
(3) endurance performance of concrete comparative test result
Mixing the durability of concrete of product of the present invention is outward effectively improved.As table 8, the test concrete mix is B, a C numbering proportioning in the table 3, and test method is carried out according to " concrete for hydraulic structure tentative specification " (SL352-2006).Concrete external doped product of the present invention is compared with mixing the FDN water reducer outward, and the former anti-permeability performance is than the high grade of the latter, and promptly the impervious grade of the former 180d age concrete is W12, and the concrete impervious grade of the latter is W10; The former improves 7% than the latter freezing and thawing performance, and promptly the former 180d age concrete freeze-thaw-grade is F150, and the latter is F140, and promptly the former endurance performance of concrete is better than the latter.
Table 8 endurance performance of concrete (the 180d length of time)
| The concrete mix numbering | Anti-permeability performance | Freezing and thawing performance |
| B | W10 | F140 |
| C | W12 | F150 |
Claims (5)
1. composite additive for concrete, it is characterized in that: by mass percentage, its composition of raw materials is as follows:
Naphthalene sulfonic salt formaldehyde condensation products 65 ~ 75%;
Calcium lignin sulphonate 9 ~ 15%;
Sunmorl N 60S 8 ~ 10%;
Sucrose 8 ~ 10%.
2. composite additive for concrete according to claim 1 is characterized in that NaSO in the described naphthalene sulfonic salt formaldehyde condensation products
4Content less than 5wt%.
3. the preparation method of a composite additive for concrete is characterized in that may further comprise the steps:
(1) by mass percentage, 65 ~ 75% naphthalene sulfonic salt formaldehyde condensation products, 9 ~ 15% calcium lignin sulphonates, 8 ~ 10% Sunmorl N 60Ss and 8 ~ 10% sucrose are placed spiral stirring kettle;
(2) stir, churning time was controlled at 10 ~ 15 minutes; Obtain the composite additive for concrete powder product.
4. the application of the described composite additive for concrete of claim 1 is characterized in that: be applied in the concrete, its volume is 0.5% ~ 0.8% of a glue material weight.
5. the application of composite additive for concrete according to claim 4 is characterized in that: be applied in the concrete, its volume is 0.6% ~ 0.7% of a glue material weight.
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Cited By (9)
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|---|---|---|---|---|
| CN102863177A (en) * | 2012-10-19 | 2013-01-09 | 南京瑞迪高新技术有限公司 | Special coagulation-delaying high-efficiency slushing agent for dam roller compacted concrete |
| CN103172298A (en) * | 2011-12-21 | 2013-06-26 | 同济大学 | Efficient water reducing agent for recycled aggregate concrete as well as preparation method and application thereof |
| CN104402523A (en) * | 2014-11-20 | 2015-03-11 | 云南建工集团有限公司 | Method for regulating and controlling super-retarding concrete setting time based on sodium gluconate retarder |
| RU2548623C2 (en) * | 2013-07-26 | 2015-04-20 | Общество с ограниченной ответственностью "НПЦ Технопласт" | Plasticising additive for concrete and method of its production |
| CN104610503A (en) * | 2015-02-05 | 2015-05-13 | 江苏苏博特新材料股份有限公司 | Crosslinked hydration heat regulating agent as well as preparation method and application of crosslinked hydration heat regulating agent |
| CZ305271B6 (en) * | 2014-05-27 | 2015-07-08 | Vysoké Učení Technické V Brně | Method of reducing rate of heat liberation in the course of hydration of aluminate cement by the addition of strontium-aluminate cement |
| CN110316993A (en) * | 2019-07-10 | 2019-10-11 | 河南省光大路桥工程有限公司 | A kind of retarder of cement stabilized macadam |
| CN110615633A (en) * | 2018-06-20 | 2019-12-27 | 尧柏特种水泥技术研发有限公司 | Benchmark naphthalene additive and method for evaluating cement performance |
| CN111153627A (en) * | 2020-01-03 | 2020-05-15 | 同济大学 | Anti-mud additive suitable for machine-made sand concrete and compounding method thereof |
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| CN103172298A (en) * | 2011-12-21 | 2013-06-26 | 同济大学 | Efficient water reducing agent for recycled aggregate concrete as well as preparation method and application thereof |
| CN103172298B (en) * | 2011-12-21 | 2014-09-17 | 同济大学 | Efficient water reducing agent for recycled aggregate concrete as well as preparation method and application thereof |
| CN102863177A (en) * | 2012-10-19 | 2013-01-09 | 南京瑞迪高新技术有限公司 | Special coagulation-delaying high-efficiency slushing agent for dam roller compacted concrete |
| RU2548623C2 (en) * | 2013-07-26 | 2015-04-20 | Общество с ограниченной ответственностью "НПЦ Технопласт" | Plasticising additive for concrete and method of its production |
| CZ305271B6 (en) * | 2014-05-27 | 2015-07-08 | Vysoké Učení Technické V Brně | Method of reducing rate of heat liberation in the course of hydration of aluminate cement by the addition of strontium-aluminate cement |
| CN104402523A (en) * | 2014-11-20 | 2015-03-11 | 云南建工集团有限公司 | Method for regulating and controlling super-retarding concrete setting time based on sodium gluconate retarder |
| CN104402523B (en) * | 2014-11-20 | 2016-02-10 | 云南建工集团有限公司 | Based on ultra-retardation concrete regulate and control method time of coagulation of Sunmorl N 60S retardant |
| CN104610503A (en) * | 2015-02-05 | 2015-05-13 | 江苏苏博特新材料股份有限公司 | Crosslinked hydration heat regulating agent as well as preparation method and application of crosslinked hydration heat regulating agent |
| CN110615633A (en) * | 2018-06-20 | 2019-12-27 | 尧柏特种水泥技术研发有限公司 | Benchmark naphthalene additive and method for evaluating cement performance |
| CN110316993A (en) * | 2019-07-10 | 2019-10-11 | 河南省光大路桥工程有限公司 | A kind of retarder of cement stabilized macadam |
| CN111153627A (en) * | 2020-01-03 | 2020-05-15 | 同济大学 | Anti-mud additive suitable for machine-made sand concrete and compounding method thereof |
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