CN104119010B - High-strength underwater concrete additive of a kind of retardation setting type high workability and preparation method thereof - Google Patents
High-strength underwater concrete additive of a kind of retardation setting type high workability and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to building material technical field, be specifically related to the high-strength underwater concrete additive of a kind of retardation setting type high workability.This additive effectively can improve concrete intensity and dispersion resistance energy, and has the advantages such as preparation technology is simple, production cost is low.It is characterized in that: it comprises metakaolin and composite modifier.The mass ratio of metakaolin and composite modifier is 50:1-15:1, wherein said composite modifier is followed successively by 70%-85%, 10%-20% and 5%-15% mixed preparing by polyacrylamide, high efficiency water reducing agent and organic water soluble polysaccharose substance according to mass percent and forms, and the per-cent sum of each component is 100%.This adulterant, as the admixture of underwater concrete, can improve the serviceability of underwater concrete, dispersion resistance energy and delay time of coagulation, significantly improving the intensity in underwater concrete each length of time, especially early strength.Meanwhile, the volume stability of underwater concrete can effectively be improved.
Description
Technical field
The invention belongs to building material technical field, be specifically related to high-strength underwater concrete additive of a kind of retardation setting type high workability and preparation method thereof.
Background technology
Along with human society and civilized development and progression, owing to can become fewer and feweri for the land resources developed, the feeler of the development of human civilization will extend to ocean, and therefore 21 century will be the century of ocean exploitation, and concrete underwater construction will get more and more.And underwater concrete structure is very complicated.Therefore, except requiring concrete intensity, also require that construction technology is simple, economical rationality, good endurance and environmentally safe.One of material of construction that in engineering, concrete remains main and consumption is maximum under water, the performance of underwater concrete will directly affect the quality of underwater engineering.Therefore, non-dispersible underwater concrete becomes the emphasis of numerous scholar and engineering technical personnel's research day by day.And for the performance of anti-dispersant to non-dispersible underwater concrete, there is decisive meaning, the additive development of non-dispersible underwater concrete becomes the main direction of research.
Metakaolin is a kind of Silicon-rich aluminate matter inorganic mineral, dewatered after proper temperature (500-1000 DEG C) is calcined by kaolin and formed, there is very strong pozzolanic activity, now apply in cement concrete, mortar and other cement products as active extra material.Based on the reactive behavior of metakaolin, the concrete material of compact high-strength, weather resistance and excellent anti-corrosion performance can be prepared, now become the focus of material circle research.
But single concrete material system obviously cannot meet above-mentioned requirements.But have in Patents and singly mix cellulose family and polypropylene-base tackify material preparation underwater concrete, but obtain concrete strength lower, and land and water strength ratio only has 65%-70% (7d) and 70%-75% (28d), and concrete slump-loss is large, be not suitable for transport at a distance and construction.Make a general survey of over concrete capable of not dispersing under water investigation and application result on see, the performance of the non-dispersible underwater concrete of preparation has limitation, the strength grade general lower (below C30) of the underwater concrete built, and the frost resistance to non-dispersible underwater concrete, anti-Cl
-the weather resistance such as penetrating quality also lack research.Therefore how to realize the excellent serviceability of underwater concrete, Self-leveling with volume stability strong, good early, need research further, be applied among Practical Project.
Summary of the invention
The object of the present invention is to provide and a kind ofly there is excellent serviceability, slow setting, Self-leveling with the high-strength underwater concrete additive of the retardation setting type high workability of volume stability strong, good early.It more effectively can excite the pozzolanic activity of metakaolin in cement-based material, is especially embodied in early strength aspect, has liquidity value added little simultaneously, also has a better role for concrete weather resistance.
To achieve these goals, technical scheme of the present invention is:
The high-strength underwater concrete additive of a kind of retardation setting type high workability, it is characterized in that, described additive comprises metakaolin and composite modifier, the mass ratio of described metakaolin and composite modifier is 50:1-15:1, described composite modifier is followed successively by 70%-85%, 10%-20% and 5%-15% mixed preparing by polyacrylamide, high efficiency water reducing agent and organic water soluble polysaccharose substance according to mass percent and forms, and the mass percent sum of each component is 100%.
In such scheme, described metakaolin is kaolin behind at 500-1000 DEG C temperature lower calcination 0.5-6.0 hour of grinding cooling is obtained, wherein, and SiO in metakaolin
2with Al
2o
3mass percentage sum>=50wt%, specific surface area>=2300m
2/ kg.
In such scheme, described polyacrylamide is anionic, solid content >=95.0%, and molecular weight is 1000-2000 ten thousand, and the scope of effective pH value is 7-14, white solid.
In such scheme, described high efficiency water reducing agent is Powdered polycarboxylate water-reducer.
In such scheme, described organic water soluble polysaccharose substance is sucrose, Sunmorl N 60S or glucose, content >=99.0%, white powder solid.
The preparation method of the high-strength underwater concrete additive of described retardation setting type high workability, it is characterized in that: the metakaolin through drying is put into ball mill, add composite modifier, milling time is 30-120min, obtains the high-strength underwater concrete additive of described retardation setting type high workability.Use time, by obtained additive by massfraction be 3%-15% replace cement, obtain underwater concrete gelling material.
In technical scheme of the present invention, in modification metakaolin modifying process, metakaolin under mechanical action, composite modifier is adsorbed on the surface of metakaolin by physical action and chemical action, enter reunion metakaolin particulate interspaces, it has two significant functions: one is that the metakaolin of agglomerated fully disperses, and two is the modifications to metakaolin particle surface.
The invention has the advantages that:
1) the present invention can significantly improve the early strength of tremie concrete, in ordinary mortar, the volume of modification metakaolin base underwater concrete additive is 3wt%-15wt%, mortar 7d intensity more than 20% can be significantly improved, and 28d strength growth rate still can remain on more than 15%, and 7 days land and water strength ratios remain on 70% ~ 85%, 28 days land and water strength ratios remains on 80 ~ 90%.This be metakaolin as a kind of concrete mineral admixture, due to its pozzolanic activity and micro-packing effect, concrete early strength and later stage weather resistance can be significantly improved.
2) modification metakaolin base underwater concrete additive utilizes the acting in conjunction of metakaolin and polyacrylamide, improves concrete dispersion resistance energy.Metakaolin has high-ratio surface sum fineness, the water retention property of concrete batching system is improved after admixture, concrete cohesion performance is increased, and the current potential of particle surface in the thick components system of mixture can be changed in grout together with polyacrylamide, reduce interparticle repulsive interaction, increase effect attracting between particle, make heterogeneous coarse dispersion agglomerated together, play the effect of thickening.And add watersoluble organic polymer polyacrylamide material, due to structure and the effect of molecule side chain of its polymer molecular chain, network-like structure can be wound, thus more can give full play to reunion cement granules, make concrete generation thickening or throwing out, improve concrete anti-dispersive ability further.Polycarboxylate water-reducer can obviously increase concrete serviceability, can regulate concrete time of coagulation by organic water soluble polysaccharose substance.Polycarboxylate water-reducer and sucrose form diffusion double layer at cement particle surface, change its electro kinetic potential, irreducible water in the space grid structure formed in cement hydration process is discharged, the mobility of cement concrete is increased considerably, the electrostatic row ability of tearing open improving cement tears ability open with three-dimensional row, thus delay, under water regardless of cement hydration process in loose sand slurry, to reduce degree of mobilization gradual loss.After adding modification metakaolin based additive, land and water, concrete seven sky strength ratio is 70% ~ 85%, and within 28 days, land and water strength ratio is 80 ~ 90%.Good fluidity, has better fillibility and self compacting ability.Have the good slump and divergence, quietly stop 1 hour, Slump Time losing of Large is little.
3) the present invention can improve concrete volume stability and weather resistance, after adding metakaolin in normal concrete, due to volcano ash effect and the micro-packing effect of metakaolin, can greatly improve concrete compactness, thus effectively reduce volume of concrete contraction and improve concrete weather resistance.But adding of modification metakaolin, the serviceability improving underwater concrete and the active reaction rate that improve metakaolin, be more conducive to reducing concrete volumetric shrinkage and improving concrete weather resistance.Therefore, modification metakaolin can improve concrete volume stability significantly, improves concrete endurance quality.
Accompanying drawing explanation
Fig. 1 is benchmark sample, metakaolin sample and embodiment 1 mortar specimen drying shrinkage figure.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
The high-strength underwater concrete additive of a kind of retardation setting type high workability, it is obtained at grinding in ball grinder 30min by metakaolin, composite modifier, wherein, the mass ratio of metakaolin and composite modifier is 15:1, and described composite modifier is followed successively by 80%, 15% and 5% mixed preparing by polyacrylamide, polycarboxylate water-reducer and sucrose according to mass percent and forms.
Using mortar specimen as investigation object, metakaolin respectively with 6%, 8%, 12% equivalent replace gelling material and add 1% water reducer configuration mortar.Choose the high-strength underwater concrete additive of retardation setting type high workability of river sand (crossing 2.36mm sieve) and embodiment 1 respectively with 6%, 8%, 12% admixture, water cement ratio is 0.45.
According to the degree of mobilization of the mixture of the additive of GB/T2429-2005 " Test method for fluidity of cement mortar " test benchmark sample, metakaolin sample, embodiment 1; According to GB/T17671-1999 " Test method for strength of hydraulic cement mortar ", by 7 days and 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark sample and embodiment 1.Dispersion resistance carries out with reference to China National Petroleum Corporation (CNPC) company standard non-dispersible underwater concrete construction technique normalizing Q/CNPC92-2003.
The performance of table 1 mortar specimen
Table 1 describes: in embodiment 1, the degree of mobilization of mortar specimen compares metakaolin and the benchmark sample of equal volume, is all greatly improved.This illustrates that the high-strength underwater concrete additive of retardation setting type high workability of embodiment 1 is to the serviceability effect of having greatly improved, and can realize mortar Self-leveling.The additive of embodiment 1 and metakaolin are for benchmark sample, due to the viscosifying action of metakaolin with to intensity promoter action, just more than 30MPa can be reached at 7d, and 7d and 28d land and water intensity all shows obvious growth, dispersion resistance can also have further raising, meets the requirement that Q/CNPC92-2003 resists dispersing property.This also illustrates that the present invention has stronger promoter action to early strength, and 28d intensity shows to there is no impact to later strength development simultaneously, also makes test specimen have higher dispersion resistance energy.
The volume selecting the additive of embodiment 1 is 8%, only to starch as investigation object, with reference to the measuring method of cement setting time in GB/T1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", respectively assay standard sample (the new P.O42.5 cement of China), metakaolin sample and embodiment 1 additive (volume is that the quality such as 8% replaces cement) just, final setting time.
The additive of table 2 embodiment 1 is on the impact of time of coagulation
Table 2 describes: the mixing of metakaolin make slurry just, all corresponding shortening of final setting time.But the adding of additive of embodiment 1 has but delayed the time of coagulation of gelling material widely, and wherein the presetting period is for benchmark sample, has delayed about 8h.Illustrate that the present invention has stronger delayed coagulation to concrete, meet the requirement of Q/CNPC92-2003 to time of coagulation.
The volume of additive selecting embodiment 1 is 8%, carries out drying shrinkage experiment with reference to JCJ/T70-2009 standard, and all test specimens are shaping in the die trial of 3 25mm × 25mm × 280mm is placed on that temperature is 20 DEG C, relative humidity is greater than maintenance under the condition of 90%RH.Form removal is placed on that temperature is 20 DEG C, relative humidity is maintenance in the environment of 60%RH, after this surveys its 3d, 5d, 7d, 14d and 28d length respectively, as shown in Figure 1.
Fig. 1 describes: when the volume of the additive in embodiment 1 is 8%, for metakaolin, the additive in embodiment 1 significantly reduces the dry shrinkage of mortar specimen.Illustrate that the present invention is more conducive to the volume stability of mortar.
Embodiment 2
The high-strength underwater concrete additive of a kind of retardation setting type high workability, it by metakaolin, composite modifier at grinding in ball grinder 120min, wherein, the mass ratio of metakaolin and composite modifier is 20:1, and described composite modifier is followed successively by 75%, 20% and 5% mixed preparing by polyacrylamide, polycarboxylate water-reducer and sucrose according to mass percent and forms.
Be investigate object with concrete sample, the additive of embodiment 2 configures concrete, according to the slump and the divergence of GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard " fresh concrete mixture with 10% equivalent replace gelling material; According to GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", by additive 7 days and the 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark sample and embodiment 2; The experiment of agent on crack resistance of concrete dispersiveness is carried out according to Q/CNPC92-2003.Cement number of dropouts is 1.1%, pH is 11.2, and being suspended thing content is 132mg/L.7 days land and water strength ratios are 72%, 28 days land and water strength ratios is 83%; Slump Time losing of Large 9.2% when non-dispersible underwater concrete divergence is 452mm, 1h.
Embodiment 3
The high-strength underwater concrete additive of a kind of retardation setting type high workability, it is obtained at grinding in ball grinder 90min by metakaolin, composite modifier, wherein, the mass ratio of metakaolin and composite modifier is 30:1, and described composite modifier is followed successively by 70%, 25% and 5% mixed preparing by polyacrylamide, polycarboxylate water-reducer and sucrose according to mass percent and forms.
Be investigate object with concrete sample, metakaolin based additive, with 12% equivalent replace gelling material configuration concrete, tests the slump and the divergence of fresh concrete according to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard "; According to GB/T50081-2002 " standard for test methods of mechanical properties of ordinary concrete ", by 7 days and 28 days ultimate compression strength of omnipotent pressure testing machine test benchmark sample and example; The experiment of agent on crack resistance of concrete dispersiveness is carried out according to Q/CNPC92-2003.Cement number of dropouts is 1.0%, PH is 10.8, and being suspended thing content is 132mg/L.7 days land and water strength ratios are 82%, 28 days land and water strength ratios is 88%; Slump Time losing of Large 9.4% when non-dispersible underwater concrete divergence is 512mm, 1h.
Claims (5)
1. the high-strength underwater concrete additive of retardation setting type high workability, it is characterized in that, described additive comprises metakaolin and composite modifier, the mass ratio of described metakaolin and composite modifier is 50:1-15:1, described composite modifier is by polyacrylamide, high efficiency water reducing agent and organic water soluble polysaccharose substance are followed successively by 70%-85% according to mass percent, 10%-20% and 5%-15% mixed preparing forms, the mass percent sum of each component is 100%, described metakaolin is kaolin behind at 500-1000 DEG C temperature lower calcination 0.5-6.0 hour of grinding, and cooling is obtained, wherein, SiO in metakaolin
2with Al
2o
3mass percentage sum>=50wt%, specific surface area>=2300m
2/ kg, described polyacrylamide is anionic, solid content>=95.0%, and molecular weight is 1000-2000 ten thousand, and the scope of effective pH value is 7-14.
2. the high-strength underwater concrete additive of retardation setting type high workability according to claim 1, is characterized in that: described high efficiency water reducing agent is Powdered polycarboxylate water-reducer.
3. the high-strength underwater concrete additive of retardation setting type high workability according to claim 1, is characterized in that: described organic water soluble polysaccharose substance is sucrose, Sunmorl N 60S or glucose.
4. the preparation method of the high-strength underwater concrete additive of retardation setting type high workability according to claim 1, it is characterized in that: the metakaolin through drying is put into ball mill, add composite modifier, milling time is 30-120min, obtains the high-strength underwater concrete additive of described retardation setting type high workability.
5. the application of the high-strength underwater concrete additive of retardation setting type high workability in concrete as claimed in claim 1, it is characterized in that, the volume scope of described additive is 8-12%.
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| CN105645833A (en) * | 2016-01-05 | 2016-06-08 | 萧县良宇混凝土有限责任公司 | Concrete additive and preparation method thereof |
| CN106045367A (en) * | 2016-05-26 | 2016-10-26 | 武汉源锦商品混凝土有限公司 | Dispersion-resistant high-strength concrete additive and preparation method thereof |
| CN108178585B (en) * | 2018-02-28 | 2020-10-20 | 兴宁市龙江建材实业有限公司 | Cement for road and bridge |
| CN110304872B (en) * | 2019-08-16 | 2021-09-21 | 陈晓星 | Nano modified cement-based underwater non-dispersible material and preparation method thereof |
| CN111732364B (en) * | 2019-12-12 | 2022-03-11 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | Early strength agent for concrete prefabricated member and preparation method thereof |
| CN111153656B (en) * | 2020-01-18 | 2022-02-08 | 杭州申华混凝土有限公司 | Green slow-setting concrete and production method thereof |
| CN114605120B (en) * | 2022-03-23 | 2023-01-17 | 广东水电二局股份有限公司 | Underwater undispersed concrete and preparation method thereof |
| CN115321878B (en) * | 2022-08-11 | 2023-08-11 | 龙岩学院 | Viscosity regulator for ready-mixed high-strength concrete and use method thereof |
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| CN102153313B (en) * | 2011-04-21 | 2012-12-19 | 江苏锋泰钻石工具制造有限公司 | Concrete complex additive |
| CN102531502B (en) * | 2012-03-02 | 2013-10-30 | 河南省交通科学技术研究院有限公司 | Post-tensioning prestressed concrete porelike grouting agent and preparation method thereof, and grouting material |
| CN102745928A (en) * | 2012-07-24 | 2012-10-24 | 武汉理工大学 | High-activity modified metakaolin-based mineral admixture for concrete and preparation method for mineral admixture |
| 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 |
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