CN1403400A - Admixture specially for high-performance marine concrete - Google Patents

Admixture specially for high-performance marine concrete Download PDF

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Publication number
CN1403400A
CN1403400A CN02137419A CN02137419A CN1403400A CN 1403400 A CN1403400 A CN 1403400A CN 02137419 A CN02137419 A CN 02137419A CN 02137419 A CN02137419 A CN 02137419A CN 1403400 A CN1403400 A CN 1403400A
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concrete
performance
flyash
admixture
mix grinding
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CN1207235C (en
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徐强
俞海勇
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Shanghai Building Science Research Institute Co Ltd
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Shanghai Building Science Research Institute Co Ltd
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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
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/74—Underwater applications
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The admixture specially for high-performance marine concrete is produced with mine refuse powder, flyash, silica powder and other industrial active additives in certain proportion and through mixing, grinding and other steps based on the interactive superposing theory of polynary gelatinizing material. It has physical and chemical performance comparative or higher than single admixture mine refuse powder, makes concrete higher in placeability and durability, easy to use and low in production cost and use cost.

Description

Admixture specially for high-performance marine concrete
Technical field
The present invention relates to concrete, specifically is about the admixture specially in the high-performance marine concrete, in order to workability and the weather resistance of improving maritime concrete, thereby improves the weather resistance of concrete structure under ocean environment.
Background technology
Existing about more than 100 years of the applicating history of modern cement-base concrete material in oceanographic engineering can trace back to portland cement concrete in 1849 the earliest and be used for oceanographic engineering.But, because traditional normal concrete self institute inherent characteristics based on portland cement, this type of concrete structure of discovery is subjected to the effect of multiple natural factors such as freezing, stormy waves and water quality and concrete is damaged and shortens its durable years in ocean environment in the application of oceanographic engineering.Particularly the oceanographic engineering of the Large scale construction that begins after World War II finishes of western developed country finds that at late nineteen seventies a large amount of concrete structures wherein destroy, and they are at interval only about 20 years.The survey showed that to 18 Steel Concrete harbours of North China for China 1981, and only using just had 16 harbours to have the serious corrosion of reinforcing bar, the phenomenon of destroying concrete structure in 19 years.
After World War II finishes, the utilisation technologies of industrial active addition material in concrete such as flyash, slag micropowder, silicon ash are developed, their application in maritime concrete, be that industrial active addition materials such as flyash, slag micropowder, silicon ash are mixed or simple polycomponent mixes hybrid mode and is applied in the concrete to substitute part cement with single, in order to improve the endurance quality of concrete under ocean environment, its anti-chlorine ion erosive performance particularly.But, industrial active addition materials such as flyash, slag micropowder, silicon ash are applied to still exist in the concrete problems, for example flyash, the active deficiency of slag micropowder and the concrete coagulating time that causes is long, the decline significantly of early strength, silicon ash concrete causes problems such as shrinkage crack, and the existence of these problems has had a strong impact on its effect that endurance performance of concrete is improved.Therefore, industrial active addition materials such as flyash, slag micropowder, silicon ash single mixed or simple polycomponent mixes hybrid mode, obviously can not satisfy the concrete high-performanceization that in recent years the ocean heavy construction is proposed, the requirement of super durable years (as 100 years or higher).
Needs for the development of satisfying technology of high performance concrete and ocean environment corrosion resistant concrete technology, develop a kind of special-purpose admixture of high-performance marine concrete, it has and improves the especially characteristics of resisting corrosion of chlorine ion performance of concrete workability and endurance quality, is those skilled in the art's important subject.
Summary of the invention
The invention provides a kind of admixture specially for high-performance marine concrete, it also is based on flyash, slag micropowder, industrial active addition materials such as silicon ash, but the theory with the mutual synergistic effect of polynary gelling material is guidance, these one-components are mixed with admixture specially for high-performance marine concrete in advance according to a certain ratio, rational Match by this admixture specially and cement forms high performance composite gelled material system, thereby improve concrete workability and improve especially resisting corrosion of chlorine ion performance of endurance performance of concrete, guarantee that concrete body ties up to the weather resistance under the ocean environment.
The component of admixture specially for high-performance marine concrete of the present invention is active mineral addition material and an auxiliary agent of selecting to improve the concrete material performance, and is formulated through mix grinding technology by certain proportioning.
Admixture specially for high-performance marine concrete of the present invention comprises following component and content:
Component concentration (weight %)
Slag micropowder 60-80
Flyash 15-30
Silicon ash 0-15
Auxiliary agent 1-5
Wherein, slag, flyash and silicon ash all are the waste residues of Steel Plant, power plant and refining Alloy Plant etc., after processing as raw material of the present invention.Slag micropowder should meet GB/T 18046-2000 regulation, and it has the mineral activity, plays effects such as gelling, little filling in adulterant; Flyash should meet GB 1596-1991 regulation, and it has the mineral activity, plays effects such as gelling, little filling, grinding aid, diminishing in adulterant; Silica flour should meet the regulation of JTJ275-2000 appendix A, and it has the mineral activity, plays gelling, effect such as little filling once more in adulterant; Auxiliary agent should meet the JC/T667-1997 regulation, plays a part to excite composition activity, improve processing characteristics in adulterant, mainly includes grinding aid, for example trolamine, diethanolamine, monoethanolamine etc.; Tensio-active agent is arranged, play dissemination, for example naphthalenesulfonate, fatty alcohol polyoxyethylene ether sulfate, alkyl carboxylate etc.; For example calcium oxide of exciting agent is arranged, calcium sulfate etc., auxiliary agent can need be selected wherein one or more for use by the adulterant Recipe.
The production method of admixture specially for high-performance marine concrete of the present invention
By above-mentioned prescription slag micropowder and auxiliary agent were carried out mix grinding 10-60 minute, the mix grinding rotating speed is 15-20 rev/min, adds the flyash mix grinding again, until mix grinding material granularity≤10 μ m, specific surface area 〉=450m 2/ kg meets the requirement of I type finished product adulterant.Also can add silicon ash mix grinding again, until the granularity≤7 μ m of mix grinding material, specific surface area 〉=600m 2/ kg meets the requirement of II type finished product adulterant.In Production Flow Chart, monitor the ratio of flyash and slag micropowder adding, with rapid determination SiO with rapid determination CaO content 2Content is monitored ratio (rapid determination CaO and the rapid determination SiO that the silicon ash adds 2Content method is referring to the GD/T176-1996 Method for chemical analysis of cement).
The admixture specially for high-performance marine concrete that obtains by aforementioned production method is carried out comprehensive physical and chemical performance test, and test result sees Table 1
The performance index contrast of the physical and chemical performance test result of table 1 admixture specially and S75, S95 and S105 level slag micropowder
Project name (1) Slag micropowder (desired value) (2) The admixture specially model
The S75 level The S95 level The S105 level The II type The I type
Density (g/cm 2) ????≥2.8 ????≥2.8 ????≥2.8 ????2.83 ????2.82
Specific surface area (m 2/kg) ????≥350 ????≥350 ????≥350 ????626 ????467
Degree of mobilization is than (%) ????≥95 ????≥90 ????≥85 ????104 ????108
Activity index (%) 7d ????≥55 ????≥75 ????≥95 ????94 ????79
28d ????≥75 ????≥95 ????≥105 ????116 ????109
Chlorion (%) ????≤0.02 ????≤0.02 ????≤0.02 ????0.01 ????0.01
Loss on ignition (%) ????≤8.0 ????≤8.0 ????≤8.0 ????1.7 ????1.8
Granularity (μ m) ????6.5 ????9.2
Sulphur trioxide (%) ????≤4.0 ????≤4.0 ????≤4.0 ????3.4 ????3.5
Water ratio (%) ????≤1.0 ????≤1.0 ????≤1.0 ????0.7 ????0.8
Annotate: the test of (1) projects is to carry out according to a conventional method.
(2) desired value of slag micropowder is selected from " the GBFS GB GB/T 18046-2000 that is used for cement and concrete ".
Can find out the single spike slag micropowder that every physical and chemical performance index of admixture specially for high-performance marine concrete of the present invention all is higher than basically or approaches to use always from the test result of table 1.In addition, by more also finding out, every performance of II type adulterant is said so relatively and is higher than the I type.
The application of admixture specially of the present invention in concrete
(1) mixes concrete physical and mechanical property behind the admixture specially for high-performance marine concrete
To substitute 60% cement respectively with admixture specially for high-performance marine concrete I or II type, the total consumption of gelling material is respectively 350kg/m 3, 450kg/m 3Some mechanical properties of two series concretes make comparisons with common portland cement concrete (normal concrete), and it is 28 days concrete performance data that table 2 and table 3 have been enumerated the length of time:
The comparison of table 2 mechanical performance of concrete
The concrete gel material kind Total consumption (the kg/m of gelling material 3) Ultimate compression strength (MPa) Split tensile strength (MPa) Folding strength (MPa) Axial compressive strength (MPa) Young's modulus (10 4MPa)
?OPC *(100％) ????350 ????43.3 ????4.0 ????7.4 ????29.4 ????3.35
?OPC(40％)+I(60％) ????38.7 ????3.9 ????7.7 ????26.7 ????3.27
?OPC(40％)+II(60％) ????41.0 ????4.1 ????7.6 ????28.9 ????3.55
?OPC(100％) ????450 ????58.5 ????4.0 ????9.0 ????32.2 ????3.69
?OPC(40％)+I(60％) ????52.4 ????3.9 ????8.7 ????31.3 ????3.65
?OPC(40％)+II(60％) ????66.7 ????4.5 ????9.9 ????32.9 ????4.13
Annotate: *OPC is the normal portland cement concrete.
Presentation of results in the table 2, the concrete various mechanical property 28d results of admixture admixture specially for high-performance marine concrete are suitable with the normal portland cement mechanical properties of concrete of gel material content such as grade.
(2) mix durability of concrete behind the admixture specially for high-performance marine concrete
To substitute 60% cement respectively with admixture specially for high-performance marine concrete I or II type, the total consumption of gelling material is respectively 470kg/m 3Durability of concrete and OPC make comparisons, and the result is as follows:
The concrete anti-permeability performance of table 3, anti-freezing property and anti-carbonation properties
The concrete gel material kind Water-cement ratio Gel material content (kg/m 3) Anti-permeability performance Anti-freezing property (100 times) Anti-carbonation properties
Maximum seepage pressure (MPa) Infiltration height (mm) Mass loss (%) Relative dynamic elastic modulus loss (%) Carbonation depth (mm) Concrete strength loss (%) after the carbonization
?OPC(100％) ?0.32 470 ????2.5 ??20.5 ????0.7 ????7.2 ????0.20 ????0.50
?OPC(40％)+I(60％) ????2.5 ??6.6 ????0.5 ????6.8 ????0.17 ????0.38
?OPC(40％)+II(60％) ????2.5 ??5.4 ????0.4 ????6.4 ????0.14 ????0.37
The concrete sulfate resistance performance of table 4, inhibition alkali-aggregate reaction performance and resistance of chloride ion penetration energy
The concrete gel material kind Coefficient against corrosion (vitriol) Rate of expansion (% suppresses the alkali-aggregate reaction performance) Chloride permeability coefficient (E-12 m/s 2) Electric weight (C)
?OPC(100％) ????0.82 ????0.2 ????4.26 ????1345
?OPC(40％)+I(60％) ????1.27 ????0.05 ????1.89 ????466
?OPC(40％)+II(60％) ????1.12 ????0.03 ????1.75 ????309
Table 3 data show, compare with normal concrete, and the concrete that is mixed with I type and II type admixture specially for high-performance marine concrete can effectively improve concrete impervious, freeze proof and anti-carbonation properties.Table 4 data show that the concrete coefficient against corrosion that is mixed with I type and II type admixture specially for high-performance marine concrete greatly increases, rate of expansion, chloride diffusion coefficient and then reduce greatly by electric weight.This has illustrated that with respect to normal concrete, the concrete sulfate resistance performance, inhibition alkali-aggregate reaction performance, the resistance of chloride ion penetration that are mixed with I type and II type admixture specially for high-performance marine concrete can all significantly increase.The remarkable improvement of these performances improves durability of concrete greatly.
Advantage of the present invention: the present invention is that the theory with the mutual synergistic effect of polynary gelling material is guidance, be mixed with admixture specially for high-performance marine concrete with suitable proportioning first with mixing raw material outside industry such as slag micropowder, flyash, the silicon ash activity, this admixture specially produces synergistic effect, shows the single spike slag micropowder that every physical and chemical performance index of I type and II type admixture specially all is higher than basically or approaches to use always.Engineering example shows that also admixture specially can improve concrete workability greatly, does not have the segregation excreting water phenomenon, and the concrete water amount reduces, and workability is excellent.The application of admixture specially in concrete simultaneously also shown, the concrete various mechanical properties of admixture admixture specially of the present invention can be suitable with the mechanical property of the normal concrete that waits gel material content, and can improve concrete impervious, freeze proof, anti-carbonization, anti-sulphates corrosive effectively, suppress performances such as alkali-aggregate reaction and chloride-penetration resistance, compare with normal concrete, its endurance quality can improve widely, thereby improves the weather resistance of concrete structure under ocean environment.
In addition, from concrete application of engineering project, the composite practical difficulty that exists of multi-component material is carried out at the scene.In the actual concrete production, the metering of multiple gelling material and quality control are a core and important link, also are comparatively complicated processes, if consider that again the optimization of multiple performance index of composite blend is just more complicated.Admixture specially for high-performance marine concrete of the present invention is to be mixed with a product in advance, forms high performance composite gelled material by the rational Match with cement in concrete production.Use the admixture specially of this manufactureization and product seriation, make concrete construction simple, be convenient to measure control and quality control, can reduce production costs to greatest extent and the execute-in-place cost.
The present invention is waste residue, the utilization of waste material of Steel Plant, power plant and refining Alloy Plant with raw material slag micropowder, flyash and the silicon ash of adulterant again, turns waste into wealth, and is therefore with low cost.Just can be mixed with the finished product admixture specially by simple mix grinding, in Production Flow Chart, adopt rapid determination CaO content to monitor the dosage ratio of slag micropowder and flyash, rapid determination SiO again 2Content is monitored the dosage ratio of silicon ash, helps the manufactureization and the product seriation of product, can guarantee constant product quality again.
Preferred forms
Following examples will be further elaborated technical scheme of the present invention, but not limit content of the present invention.
The production of embodiment 1 I type maritime concrete admixture specially
With slag micropowder 15t, sodium naphthalene sulfonate 0.6t and sodium sulfate 0.4t insert and carried out mix grinding in the mixer-mill 15 minutes, the mix grinding rotating speed is 17 rev/mins, adds the about 5t of flyash more gradually, continues mix grinding after 20 minutes, begin sampling in the 10th minute and carry out quick CaO mensuration, and according to measurement result, adjust the flyash amount that adds, blend mill 2 hours, analyze mix grinding material granularity≤10 μ m, specific surface area 〉=450m 2/ kg meets trimmed size, and discharging gets I type admixture specially 21t.Its performance test value is referring to table 1.
The production of embodiment 2 II type maritime concrete admixture speciallies
Slag micropowder 13t and trolamine 0.4t inserted carried out mix grinding in the mixer-mill 15 minutes, the mix grinding rotating speed is 20 rev/mins, add the about 5.4t of flyash more gradually, continue mix grinding after 45 minutes, quick CaO mensuration is carried out in sampling in the 15th minute therebetween, and the proportioning of monitoring slag micropowder and flyash reaches target value, and beginning adds about 1.2t silicon ash gradually, continued mix grinding 1.5 hours, quick SiO is carried out in sampling in per therebetween 20 minutes 2Measure, monitoring silicon ash reaches target value with the proportioning of slag micropowder and flyash, analyzes mix grinding material granularity≤7 μ m, specific surface area 〉=600m 2/ kg meets trimmed size, and discharging gets II type admixture specially 20t.Its performance test value is referring to table 1.
Embodiment 3
This example is an admixture specially for high-performance marine concrete practical engineering application example, and I type and II type admixture specially for high-performance marine concrete that embodiment 1 and 2 is made have carried out harbor work's building with prefabricated and cast-in-place beam in the factory for prefabrication, Shanghai.
Situ production concrete mix and material properties test data (concrete design strength grade C45) as shown in table 5 below:
Table 5
Numbering Material usage (kg/m in every cube of concrete 3) ???? **The slump (mm) Ultimate compression strength (MPa) The resistance of chloride ion penetration energy
Water Cement Admixture specially Sand Stone The efficient diminishing system of polycarboxylate ??3d ??28d NEL method (1E10-12m 2/s) Coulometry (C)
The I type is prefabricated ????135 ????(0.29) * ??188 ??(40％) ??282 ??(60％) ??663 ??1129 ????24 ??80 ??33.3 ??54.6 ????1.3 ????690
The II type is prefabricated ????140 ????(0.30) * ??188 ??(40％) ??282 ??(60％) ??659 ??1121 ????24 ??70 ??39.1 ??58.9 ????1.0 ????635
The I type is cast-in-place ????146 ????(0.31) * ??188 ??(40％) ??282 ??(60％) ??660 ??1124 ????24 ??160 ??31.0 ??55.7 ????1.5 ????770
The II type is cast-in-place ????150 ????(0.32) * ??188 ??(40％) ??282 ??(60％) ??659 ??1121 ????24 ??150 ??33.5 ??57.9 ????1.2 ????710
Common C45 concrete ????170 ??410 60 (II level flyash) *** ??669 ??1091 ????24 ??160 ??33.9 ??56.4 ????5.2 ????1650
Annotate: *The ratio of water and gelling material.
*In precast concrete, the slump requires 20～40mm usually, and the concrete water amount is 180～200kg/m 3, and after adopting admixture specially, can be under 60～80mm condition in the slump, water consumption is reduced to 135～160kg/m 3In onsite concrete, the slump requires about 160mm usually, and the concrete water amount is 180～200kg/m 3, and after adopting admixture specially, can be under 160～180mm condition in the slump, water consumption is reduced to 140～160kg/m 3
* *In common C45 concrete, the II level flyash of blending 60kg in every cube of concrete.
The test-results explanation, adopt the mechanical property of the concrete material of admixture specially for high-performance marine concrete preparation to meet the demands, and workability is good, there is not the segregation excreting water phenomenon, the concrete water amount reduces, workability is excellent, and resistance of chloride ion penetration can significantly improve again, thereby durability of concrete also improves greatly.

Claims (6)

1, a kind of admixture specially for high-performance marine concrete is characterized in that it comprises following component and content:
Component concentration (weight %)
Slag micropowder 60-80
Flyash 15-30
Silicon ash 0-15
Auxiliary agent 1-5
Described auxiliary agent comprises grinding aid, and tensio-active agent, exciting agent can be from wherein selecting one or more for use.
2, adulterant as claimed in claim 1 is characterized in that described grinding aid is trolamine, diethanolamine or monoethanolamine.
3, adulterant as claimed in claim 1 is characterized in that described tensio-active agent is naphthalenesulfonate, fatty alcohol polyoxyethylene ether sulfate, alkyl carboxylate.
4, adulterant as claimed in claim 1 is characterized in that described exciting agent is calcium oxide, calcium sulfate.
5, the production method of the described admixture specially for high-performance marine concrete of claim 1, it is characterized in that slag micropowder and auxiliary agent were carried out mix grinding 10-60 minute, the mix grinding rotating speed is 15-20 rev/min, adds the flyash mix grinding again, until mix grinding material granularity≤10 μ m, specific surface area 〉=450m 2/ kg also can add silicon ash mix grinding, again until the granularity≤7 μ m of mix grinding material, specific surface area 〉=600m 2/ kg.
6,, it is characterized in that in the Production Flow Chart of described method, monitoring the ratio of slag micropowder and flyash adding, with rapid determination SiO with rapid determination CaO content by the production method of the described adulterant of claim 5 2Content is monitored the ratio that the silicon ash adds.
CNB021374198A 2002-10-14 2002-10-14 Admixture specially for high-performance marine concrete Expired - Fee Related CN1207235C (en)

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CN102648167A (en) * 2009-11-26 2012-08-22 建筑研究和技术有限公司 Inorganic binder system for the production of chemically resistant construction chemistry products
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CN1331797C (en) * 2005-04-30 2007-08-15 南京师范大学 Multifunctional chlorine-free alkali-free compound concrete slag admixture and its preparation process
CN101495420B (en) * 2006-01-20 2013-05-29 考格尼斯知识产权管理有限责任公司 Compounds and methods for treating fly ash
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CN101328050B (en) * 2008-07-31 2013-03-20 中国石油大学(华东) Low temperature low hydration heat cementing cement system
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