CN101811840A - Anti-corrosion admixture for oceanic concrete - Google Patents
Anti-corrosion admixture for oceanic concrete Download PDFInfo
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- CN101811840A CN101811840A CN201010150353A CN201010150353A CN101811840A CN 101811840 A CN101811840 A CN 101811840A CN 201010150353 A CN201010150353 A CN 201010150353A CN 201010150353 A CN201010150353 A CN 201010150353A CN 101811840 A CN101811840 A CN 101811840A
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- 239000004567 concrete Substances 0.000 title claims abstract description 91
- 238000005260 corrosion Methods 0.000 title claims abstract description 57
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 15
- 239000010440 gypsum Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010881 fly ash Substances 0.000 claims description 25
- 235000019353 potassium silicate Nutrition 0.000 claims description 15
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 11
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 11
- 150000008130 triterpenoid saponins Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 25
- 238000001354 calcination Methods 0.000 abstract description 7
- 239000002893 slag Substances 0.000 abstract description 6
- 229910001294 Reinforcing steel Inorganic materials 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 239000004115 Sodium Silicate Substances 0.000 abstract 2
- 239000010883 coal ash Substances 0.000 abstract 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract 2
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 2
- 239000012190 activator Substances 0.000 abstract 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract 1
- 239000004312 hexamethylene tetramine Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 74
- 239000004568 cement Substances 0.000 description 29
- 239000013535 sea water Substances 0.000 description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- 239000011083 cement mortar Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 230000003014 reinforcing effect Effects 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 241000370738 Chlorion Species 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000010276 construction Methods 0.000 description 7
- 238000013461 design Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
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- 238000012423 maintenance Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002956 ash Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
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- 238000002791 soaking Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
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- 239000002994 raw material Substances 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 aluminate compound Chemical class 0.000 description 2
- 230000002742 anti-folding effect Effects 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- 101100008048 Caenorhabditis elegans cut-4 gene Proteins 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
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Classifications
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
-
- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/24—Sea water resistance
-
- 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
Landscapes
- 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 invention relates to an anti-corrosion admixture for oceanic concrete, which can enhance the anti-corrosion capability of the oceanic concrete by using a plurality of anti-corrosion mechanisms. The anti-corrosion admixture for the oceanic concrete comprises the following components by weight percent: 20-30% of calcium nitrite, 15-20% of calcined gypsum, 5-10 % of laminated soluble sodium silicate, 3-5% of hexamethylenetetramine, 1-3% of sodium tripolyphosphate, 0- 20% of water reducing agent, 0-0.4% of air entraining agent and the balance of coal ash. In a preferred scheme of the invention, the the calcined gypsum is obtained by calcining at 600-800 DEG C, and the modulus of the laminated soluble sodium silicate is from 2.1 to 2.3. In the invention, the novel anti-corrosion admixture for the oceanic concrete is formed by combining a corrosion resisting agent of reinforcing steel bars with activators of concrete admixtures (coal ash and grounded furnace slag), thereby the anti-corrosion capability of the oceanic concrete is greatly enhanced.
Description
Technical field
The present invention relates to a kind of concrete admixture, is a kind of anti-corrosion admixture for oceanic concrete specifically.
Background technology
21 century is ocean century.China is an ocean big country, be in rapid economic development period, many costly important buildings, as bridge spanning the sea, subbottom tunnel, offshore production platform, harbour, offshore engineering etc. or under construction, these weather resistance that are in concrete structure under the ocean environment condition become the focus that civil engineering field is paid close attention to naturally.Be to guarantee the weather resistance of prevention of marine concrete structures such as bridge spanning the sea and subbottom tunnel, some ultra-large type engineering even adopted 100 years design reference periods at home, it is the Synthesis durability technical scheme of core that concrete works is taked with the technology of high performance concrete.
The ocean is the main source of chlorion, contains the salt about 3% in the seawater usually, wherein mainly is chlorion.With Cl
-Meter, the content in the seawater is about 19000mg/L.According to domestic and international correlation study, be in that wave spatters the sea port dock in district and destroying concrete structure that the reinforcement corrosion of maritime concrete structures causes is quite general and serious.Its reason is except construction quality exists certain problem, and another principal element is that at that time chlorion to be invaded the seriousness understanding that causes steel bar corrosion not enough.Rust of Rebar in Concrete can be brought out by two kinds of factors, and the one, Cl in the seawater
-Corrode, the 2nd, the CO in the atmosphere
2Make the concrete neutralisation.A large amount of both at home and abroad engineering soundings and scientific research result show, causes under the ocean environment that steel bar corrosion destructive principal element is Cl in the concrete structure
-Enter in the concrete, and gather at rebar surface, impel reinforcing bar to produce galvanic corrosion, thereby cause the inside concrete differential expansion, concrete rises and splits behind the stress concentration, and concrete durability worsens.In the investigation of bridge spanning the sea periphery coastal dock, also confirm that carbonization of concrete speed is well below Cl in the ocean environment
-Seepage velocity, the concrete nature carbonization speed average out to 3mm/10 of fair average quality.Therefore, the primary factor that influences bridge spanning the sea structural concrete weather resistance is concrete Cl
-Seepage velocity.
Chlorion is to steel bar corrosion mechanism:
(1) destroys passive film
The high alkalinity of hydrated cementitious makes the concrete reinforcing steel surface produce the passive film of one deck densification.Passive film only is only stable in the high alkalinity environment, when pH＜11.5, just begins instability, and this passive film generates difficulty or the passive film that generated destroys gradually when pH＜9.88.Cl
-Be extremely strong depassivator, Cl
-When entering concrete and arriving rebar surface and be adsorbed in local passive film place, the pH value at this place is reduced rapidly, rebar surface pH value is reduced to below 4, thus the passive film of destruction rebar surface.
(2) form corrosion cell
If have high concentration chloride on large-area rebar surface, then the caused corrosion of muriate may be a uniform corrosion, but in inhomogeneous concrete, commonly local corrosion.Cl
-Destruction to the rebar surface passive film occurs in the part, makes these positions expose the iron-based body, and with still intact passive film zone formation potential difference, the iron-based body is corroded as anode, and big area passive film zone constitutes corrosion cell as negative electrode.The result of corrosion cell effect is that at rebar surface generation pit, because the big corresponding primary anode of negative electrode (passive film district) (passive film breakdown point), the pit development is very rapid.
(3) unpolarizing
Cl
-Not only facilitate the corrosion cell of rebar surface, and quickened the effect of battery.Usually be called the anodic polarization effect anodic process is obstructed, and the accelerating anode polarized action be called unpolarizing, Cl
-Brought into play the anode unpolarizing just.
Related scientific research achievement and long-term engineering practice investigation both at home and abroad shows that the major technique measure of current raising marine steel reinforced concrete project durability has:
(1) adopts high-performance marine concrete
Its technological approaches is that employing quality concrete mineral admixture (mainly being flyash and ground blast furnace slag) and high efficiency water reducing agent are compound, be equipped with the cement and the good coarse-fine aggregate of grating that adapt with it, form low water binder ratio, low defective, high compact, high competent concrete material.High-performance marine concrete is a feature with higher resistance of chloride ion penetration, and the weather resistance that it is excellent and the ratio of performance to price have been subjected to studying in the world the approval with engineering circle.
(2) adopt the reinforcing bar rust inhibitor
The reinforcing bar rust inhibitor is by influencing the electrochemical reaction between reinforcing bar and the dielectric medium; impel the threshold concentration of reinforcement corrosion to stablize the oxide film of rebar surface by improving chlorion; can stop reinforcement corrosion to take place effectively; thereby prolong the work-ing life of Steel Concrete; because the effect of rust inhibitor can spontaneously form passive film on rebar surface; as long as cause blunt environment; even destroying, passive film also can regenerate voluntarily; automatically keep; this not only is better than any artificial coating, and economical, easy.But it is, comparatively suitable as assist measure because its effective level is bigger.Best bet is that electrolytical pH value is brought up to about 12, makes rebar surface have the stable passive film of one deck to make anodic reaction be difficult to carry out, thereby stops the corrosion of reinforcing bar, and can guarantee its steady state for a long time, thereby has stoped the corrosion of reinforcing bar effectively.
(3) adopt the seawater anticorrodent
The seawater anticorrodent is to form with inorganic materials grindings such as slag, anhydrite, natural volcanic ash, activity excitation components.Just a kind of complementary gelling material of its essence.
Physical action: the specific surface area of seawater anticorrodent, its micro mist filling effect has improved the cohesive strength between cement slurry and the orthopaedics, thereby has improved concrete degree of compactness.
Chemical action: 1. the high reactivity micro mist in the seawater anticorrodent, active silica are constantly and the Ca (OH) that comes out of aquation
2Chemical reaction takes place; generate more C-S-H gel; accelerate hydrated cementitious speed; improve the content that the 2. pozzuolanic sulfate resistance of concrete intensity, anti-marine denudation effect are decided by the silicon-dioxide in the volcanic ash; the dioxide-containing silica height can improve concrete weather resistance, the more important thing is the protective membrane that has covered one deck C-S-H gel on the aluminate compound that easily is etched.
Therefore, the general planning that the weather resistance design for scheme of oceanographic engineering, bridge spanning the sea concrete structure is followed is: at first, the concrete structure durability basic measures are to adopt high performance concrete.Simultaneously,, adopt necessary additional anti-corrosion measure, as interior reinforcing bar rust inhibitor, the outer supercoat of concrete etc. mixed according to concrete member structure position of living in and environment for use condition.Under the prerequisite that guarantees construction quality and material quality, the weather resistance of concrete structure can reach design requirements.
But, existing various measures, the mechanism of action is single, and effect is not very good.
Summary of the invention
The invention provides a kind of anti-corrosion admixture for oceanic concrete, use multiple anticorrosive mechanism, can strengthen the resistance to corrosion of ocean concrete greatly.
Described anti-corrosion admixture for oceanic concrete, it consists of: calcium nitrite 20%～30%, calcined gypsum 15%～20%, the instant water glass 5%～10% of stratiform, vulkacit H 3%～5%, tripoly phosphate sodium STPP 1%～3%, water reducer 0～20%, air entrapment agent 0～0.4%, surplus are flyash, and above-mentioned per-cent is mass percent.
As preferred version of the present invention, described calcined gypsum is calcined down at 600～800 ℃ and is obtained.
As preferred version of the present invention, the modulus of layered instant water glass is 2.1～2.3.
As preferred version of the present invention, described air entrapment agent is a triterpenoid saponin.
As preferred version of the present invention, described water reducer is naphthalenesulfonate formaldehyde condensation compound water reducer (hereinafter to be referred as FDN).
As preferred version of the present invention, the mass percent of water reducer, air entrapment agent is respectively 15%～20%, and 0.2%～0.4%.
Anti-corrosion admixture for oceanic concrete of the present invention, reinforcing bar rust inhibitor and concrete admixture (flyash and ground blast furnace slag) exciting agent are combined, form a kind of novel sea concrete anticorrosion additive, it is a kind of anti-corrosion admixture that designs at the ocean high performance concrete specially, can strengthen the resistance to corrosion of ocean concrete greatly.The effect of this admixture is exactly to make concrete itself finer and close as much as possible, and the good concrete of compactness is enough to resist for a long time the intrusion of chlorion in the ocean.Modern marine high performance concrete most important character is exactly the application of a large amount of concrete admixtures (flyash and ground blast furnace slag), the concrete admixture total amount generally accounts for 30～50% of cement based agglutination material consumption, and the instant water glass of calcined gypsum and stratiform all has the effect of good stimulating activity to concrete admixture.Because Additive replaces the consumption of cement in a large number, also can cause the reduction of the inner ionogen basicity of ocean concrete, and the adding of the instant water glass of stratiform, can make concrete basicity have one to keep, the electrolytical pH value of inside concrete is brought up to more than 11, make rebar surface have the stable passive film of one deck to make anodic reaction be difficult to carry out, thereby stop the corrosion of reinforcing bar.Calcium nitrite, vulkacit H, tripoly phosphate sodium STPP all are good reinforcing bar rust inhibitors.Tripoly phosphate sodium STPP still is concrete retardant simultaneously, is convenient to Concrete Construction.
As for concrete crack problem, the applicant finds through secular engineering application practice, most concrete construction incipient fractures all is owing to do not control Concrete Construction rules and do not strictly observe corresponding standard well, human factors such as concrete pouring does not put in place cause, the application does not just consider this factor, and cement expansive material and all kinds of technical fiber be not just among considering.
As for the alkali problem, the applicant has thought the admixture of maritime works's high performance concrete own a large amount of concrete admixtures (flyash and ground blast furnace slag), its ratio accounts for 30～50% of cement based agglutination material total amount, itself can adsorb a large amount of alkali and the activity of digestion gathers materials, in this case, the alkali problem is not to cause the subject matter of maritime works's durability of HPC with high, moreover the generation of alkali, also has under some conditions and just may take place.So the application does not just consider this factor.
Embodiment
Bottom is described further in conjunction with the embodiments.
In following examples, described calcined gypsum is 800 ℃ of calcined gypsums, and water glass is the instant water glass of stratiform (modulus 2.3).In the actual production, because each raw material all is a pulvis, be product after the metering back mixes directly into mixer, precedence is unimportant, no longer carefully states here.
Embodiment 1: a kind of anti-corrosion admixture for oceanic concrete, specifically composed as follows:
Calcium nitrite 30%;
Calcination gypsum 20%;
Water glass 10%;
Vulkacit H 5%;
Tripoly phosphate sodium STPP 3%;
The flyash surplus.
Embodiment 2: a kind of anti-corrosion admixture for oceanic concrete, specifically composed as follows:
Calcium nitrite 20%;
Calcined gypsum 15%;
Water glass 5%;
Vulkacit H 3%;
Tripoly phosphate sodium STPP 2%;
The flyash surplus.
Embodiment 3: a kind of anti-corrosion admixture for oceanic concrete, specifically composed as follows:
Calcium nitrite 25%;
Calcination gypsum 18%;
Water glass 8%;
Vulkacit H 4%;
Tripoly phosphate sodium STPP 1%;
The flyash surplus.
Embodiment 4: a kind of anti-corrosion admixture for oceanic concrete, specifically composed as follows:
Calcium nitrite 30%;
Calcination gypsum 20%;
Water glass 10%;
Vulkacit H 5%;
Tripoly phosphate sodium STPP 3%;
FDN?????????20％；
The flyash surplus.
Embodiment 5: a kind of anti-corrosion admixture for oceanic concrete, specifically composed as follows:
Calcium nitrite 25%;
Calcination gypsum 18%;
Water glass 5%;
Vulkacit H 4%;
Tripoly phosphate sodium STPP 2%;
FDN?????????15％；
The flyash surplus.
Embodiment 6: a kind of anti-corrosion admixture for oceanic concrete, and improve frost resistance and design at the northern area maritime concrete, specifically composed as follows:
Calcium nitrite 25%;
Calcination gypsum 18%;
Water glass 5%;
Vulkacit H 4%;
Tripoly phosphate sodium STPP 2%;
FDN???????15％；
Triterpenoid saponin 0.4%;
The flyash surplus.
Embodiment 7: a kind of anti-corrosion admixture for oceanic concrete, and improve frost resistance and design at the northern area maritime concrete, specifically composed as follows:
Calcium nitrite 30%;
Calcination gypsum 20%;
Water glass 8%;
Vulkacit H 5%;
Tripoly phosphate sodium STPP 3%;
FDN?????????20％；
Triterpenoid saponin 0.3%;
The flyash surplus.
At above embodiment, the applicant has done following test and has verified.
One, test thinking
Make sand-cement slurry can resist the intrusion of chlorion effectively, will strengthen the compactness of its internal structure by every means.This test proves that at first by the intensity of cement briquette, the comparison of hole structural property embodiment can make compactness significantly strengthen; And then some groups of test blocks of moulding, put into simulated seawater solution and soak, by chlorine ion concentration and the test block depth relationship curve of describing 90d, 180d, 270d and 360d test block, can be verified the resistance of chloride ion penetration of embodiment.
Two, test design
2.1 test raw material
42.5 grades of ordinary Portland cements of conch China factory, standard sand, Avante XD board breeze (S95 level), east wound board flyash (II level), FDN high efficiency water reducing agent (pulvis).Test is with the concentration that simulated seawater adopts (for shortening the test period, quicken the speed of marine denudation test block, under the prerequisite that does not change each salinity ratio, the concentration of salt is the twice in the natural sea-water in the simulated seawater that this test is prepared) as shown in table 1.
Table 1 simulated seawater composition
2.2 test method
2.2.1 the strength trial of cement mortar
This test with the cement mortar test block forming 1d of 40mm * 40mm * 160mm after form removal, take out behind the normal curing 28d, anti-folding/ultimate compression strength of surveying its 28d respectively and in seawater, soaking 60d, 90d, 120d and 180d, thus the influence of embodiment analyzed to glue sand cement intensity of test block.
2.2.2 the microtexture of cement paste test
This paper mainly adopts mercury penetration method to measure the pore structure of concrete base cleaning pulp, to observe the pore structure of slurry, understands the compactness of slurry.Unified water-cement ratio 0.4 is all adopted in test, the test block of preparation 40mm * 40mm * 160mm, moulding form removal after 24 hours, put into the standard curing room maintenance 28 days, a part is directly taken out and is tested, and another part is put into artificial seawater and continued to soak, and takes out after the maintenance to 90 day.Before on-test, with the test block fragmentation, get the fritter of the about 1cm * 1cm of center size, end face and bottom surface keep certain planeness as far as possible, soak test block with raw spirit and make it stop aquation.
2.2.3 chloride permeability test
Actual effect for checking embodiment, with water-cement ratio is that two groups of test blocks of 0.5 are made comparisons, mix embodiment for one group, do not mix for one group, behind test block forming maintenance 28d, paraffin (except that two ends are exposed) is coated on the test block surface, bubble is gone in the seawater of artificial preparation to different number of days, take out test block and remove surperficial paraffin, every 5mm test block is cut into thin piece from outermost end, cut 4 altogether, smash the back to pieces and adopt silver nitrate titration method to measure its chlorine ion concentration respectively, draw the relation of distance (trying fast thickness) and chlorine ion concentration, estimate the resistance of chloride ion penetration energy of two groups of test blocks.
Three, testing data interpretation of result
3.1 cement mortar intensity of test block test
Table 2 cement mortar test recipe table (water-cement ratio 0.50, unit: g)
| Sequence number | Cement | Sand | Flyash | Breeze | Water | Embodiment, volume |
| ??(1) | ??324 | ??1350 | ??108 | ??108 | ??270 | Blank |
| ??(2) | ??324 | ??1350 | ??108 | ??108 | ??270 | Embodiment 1, volume 4% |
| ??(3) | ??324 | ??1350 | ??108 | ??108 | ??270 | Embodiment 2, volume 4% |
| ??(4) | ??324 | ??1350 | ??108 | ??108 | ??270 | Embodiment 3, volume 4% |
The prescription of cement mortar intensity of test block test is as shown in table 2, and wherein the agglutination material total amount is 540g, and flyash and breeze total amount account for 40% of agglutination material consumption.
Illustrate: embodiment 4,5,6,7 main raw materials and mass percent almost are equal to embodiment 1,2,3, formula variation is mainly reflected on water reducer and the air entrapment agent, and an amount of adding of water reducer and air entrapment agent can not cause the reduction of cement-based material cement mortar strength, because the water-reduction of the two can make the cement-based material cement mortar strength improve on the contrary, so needn't do the intensity test.
Anti-folding/ultimate compression strength data results of 28 to 180 days of cement mortar test block is as follows:
Table 3 test block resists folding/pressure resistance kilsyth basalt (unit: MPa)
As seen from the above table:
After the resistance to compression test block is steeped in the seawater, we are as can be seen after the observed data, since 90 days, (1) Zu intensity of test block is slowly reducing, the intensity of (2) (3) (4) group test block is compared with the intensity of benchmark test block and is evident as height simultaneously, illustrate As time goes on, anti-corrosion admixture plays a role step by step, the adding of breeze and flyash excitant has greatly excited the activity of flyash and breeze in the test block, make hydration reaction carry out more fully, thoroughly, the cement mortar slurry becomes finer and close, thereby has improved the resistance to corrosion of test block in seawater.
3.2 the microporous structure of concrete base cleaning pulp test
The concrete base cleaning pulp test block adopts following prescription to carry out microtexture test, mainly clean slurry test block sampling back mark is supported 28 days and mark is supported after 28 days bubble again and gone into simulated seawater, and the sample of maintenance to 90 day compares:
Table 4 concrete base cleaning pulp test block formula table (water-cement ratio 0.4, the g of unit)
| Sequence number | Cement | Flyash | Breeze | The silicon ash | Water | Embodiment | ??FDN |
| ??0 | ??208 | ??80 | ??80 | ??32 | ??160 | ??0 | ??0.8％ |
| ??1 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 1, volume 4% | ??0.8％ |
| ??2 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 2, volume 4% | ??0.8％ |
| ??3 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 3, volume 4% | ??0.8％ |
| ??4 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 4, volume 4% | ??/ |
| ??5 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 5, volume 4% | ??+0.2％ |
| ??6 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 6, volume 4% | ??+0.2％ |
| ??7 | ??208 | ??80 | ??80 | ??32 | ??160 | Embodiment 7, volume 4% | ??/ |
(annotate: agglutination material total amount 400g, wherein flyash 20%, breeze 20%, silicon ash 8%)
Sequence number 0～7 sample is carried out microporous structure press the mercury test, the gained data are as follows:
Table 5 mark is supported and was pressed mercury test void distribution in 28 days
| Sequence number | Overall porosity % | ??＜50nm/％ | ??50～100nm/％ | ??＞100nm/％ |
| ??0 | ??16.81 | ??83.10 | ??3.01 | ??13.89 |
| ??1 | ??14.21 | ??84.68 | ??3.56 | ??11.76 |
| ??2 | ??14.12 | ??83.89 | ??3.87 | ??12.24 |
| ??3 | ??15.15 | ??83.62 | ??4.02 | ??12.36 |
| ??4 | ??14.08 | ??84.29 | ??4.36 | ??11.35 |
| ??5 | ??14.18 | ??84.52 | ??4.23 | ??11.25 |
| Sequence number | Overall porosity % | ??＜50nm/％ | ??50～100nm/％ | ??＞100nm/％ |
| ??6 | ??12.41 | ??87.34 | ??4.18 | ??8.48 |
| ??7 | ??12.38 | ??85.98 | ??4.45 | ??9.57 |
From table 4-6 as can be known: it is little that the overall porosity during 28d is compared difference, and it is more obvious to compare difference to the 90d overall porosity; After in simulated seawater, soaking 90d, blank test block overall porosity is compared during with 28 days raising slightly, the overall porosity of embodiment test block then descends than having comparatively significantly before soaking, the quantity in the harmful hole (aperture is greater than the hole of 100nm) of blank test block has increase slightly, and the shared ratio in the harmful hole of embodiment test block then descends on the contrary to some extent.This is because the activity that flyash in the anti-corrosion admixture and breeze exciting agent have excited mineral admixture has greatly been improved pore structure, makes that the internal structure of test block is finer and close.
Press mercury test void distribution in table 6 simulated seawater after the maintenance to 90 day
| Sequence number | Overall porosity % | ??＜50nm/％ | ??50～100nm/％ | ??＞100nm/％ |
| ??0 | ??17.70 | ??71.15 | ??9.77 | ??19.08 |
| ??1 | ??12.01 | ??86.12 | ??8.34 | ??5.54 |
| ??2 | ??12.23 | ??85.89 | ??8.41 | ??5.70 |
| ??3 | ??12.12 | ??86.33 | ??8.12 | ??5.55 |
| ??4 | ??11.17 | ??85.00 | ??8.20 | ??6.80 |
| ??5 | ??12.63 | ??85.17 | ??8.17 | ??6.66 |
| ??6 | ??12.03 | ??86.46 | ??8.98 | ??4.56 |
| ??7 | ??12.85 | ??86.13 | ??8.76 | ??5.11 |
Table 7 cement mortar test block formula table (water-cement ratio 0.5, the g of unit)
| Sequence number | Cement | Sand | Flyash | Breeze | Water | Embodiment, volume |
| ??0 | ??324 | ??1350 | ??108 | ??108 | ??270 | Blank |
| ??1 | ??324 | ??1350 | ??108 | ??108 | ??270 | Embodiment 1, volume 4% |
| ??2 | ??324 | ??1350 | ??108 | ??108 | ??270 | Embodiment 2, volume 4% |
| ??3 | ??324 | ??1350 | ??108 | ??108 | ??270 | Embodiment 3, volume 4% |
Table 8 chloride permeability test-results (mol/g of unit, * 10
-5)
3.3 cement mortar test block chloride permeability test
Cement mortar test block prescription is asked for an interview table 7, and water-cement ratio is 0.5, for keeping identical flow of cement mortar, only is embodiment 1,2, and 3 and relatively blank.Be at 0.5 o'clock at water-cement ratio, it is a lot of that embodiment 4～7 can make flow of cement mortar increase, and is not easy to compare with blank.Cement mortar chloride permeability test-results is shown in Table 8.
3.4 chlorion is to the corrosive nature test of Steel Concrete
With reference to U.S. G109-07 " admixture is to the standard test methods of concrete reinforcing steel erosion action in the chloride environment ", consider that can this test objective be improve concrete test block chloride-penetration resistance ability in order to observe maritime works's anti-erosion admixture, for shortening test period, adopt aforementioned simulated seawater, the test block of eight groups of 150mm*150mm*400mm of moulding, to estimate the ability that (water-cement ratio is 0.42) embodiment and common rust inhibitor resisting chloride ion penetration under the identical concrete proportioning corrode reinforcing bar, result's (wherein FA is a flyash) as shown in table 9.
Behind the Steel Concrete test-block standard curing 28 days, move into the electrochemistry experiment chamber.In the pickle making injected plastic box, soak test block after 28 days, begin to read the potential difference between the reinforcing bar up and down with voltmeter, every afterwards 30d writes down once, and wherein every 10d drying and watering cycle is soaked once.When up and down between the reinforcing bar electric current reach 10uA and voltage continuously and be stabilized in 1mv when above, can guarantee to occur reinforcing bar obviously visible corrode, can stop measurement at this moment to test block.The required equipment of this test comprises the high resistance voltage meter that a precision is 0.01mv, and a resistance value is the resistance of 100 ohm (± 5%).Testing data result is as shown in table 10 below.
Table 9 Steel Concrete corrosion test proportioning kg/m
3
| Grouping | Water | ??FA | Breeze | Cement | Sand | Rubble | Rust inhibitor, volume | FDN volume % | Slump mm |
| ??A | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Calcium nitrite 30% solution, 4% | ??0.55 | ??180 |
| ??B | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 1,4% | ??0.55 | ??165 |
| Grouping | Water | ??FA | Breeze | Cement | Sand | Rubble | Rust inhibitor, volume | FDN volume % | Slump mm |
| ??C | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 2,4% | ??0.55 | ??165 |
| ??D | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 3,4% | ??0.55 | ??165 |
| ??E | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 4,4% | ??/ | ??190 |
| ??F | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 5,4% | ??/ | ??185 |
| ??G | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 6,4% | ??/ | ??175 |
| ??H | ??180 | ??85 | ??85 | ??255 | ??760 | ??1060 | Embodiment 7,4% | ??/ | ??185 |
Table 10 current potential difference table (unit: mv)
Above data can illustrate: embodiment 1～7 has better resisting chloride ion penetration erosive ability than common calcium nitrite.
Conclusion:
(1) add anti-corrosion admixture after, test block seawater is medium-term and long-term after soaking final strength with benchmark test block compared tangible increase, this admixture can make hydration reaction carry out fully as can be known, can effectively improve the corrosion resistance of test block in seawater again.
(2) adding of breeze and flyash both can reduce the severe degree of early hydration reaction, reduced hydration heat, reduced fissured generation; Again can be by the hydrated product Ca (OH) of secondary hydration reaction consumes cement
2, make Ca (OH) in the slurry
2Concentration reduce, quickened the aquation of cement conversely again, make the gel content that generates increase, improve the internal structure of cement paste; Breeze and flyash are filled closely knit effect makes water mudrock structure and interface structure fine and close more, exciting agent in the anti-corrosion admixture can promote the further hydration reaction of these adulterants greatly, thereby greatly reduce the pore fluid of concrete rate, and the aperture is reduced, make structure become more fine and close.
(3) test by chloride-penetration resistance, the proof anti-corrosion admixture can promote the dense form of cement-based mortar system, thereby reduce the chlorine ion concentration in the test block of glue sand, and well delayed chlorine ion concentration in time prolongation and the trend that increases strengthens the chloride-penetration resistance and the sea-water corrosion ability of structure better.
(4) according to engineering reality, can select embodiment 1～3 (coventional type), 4～5 (pumping types), 6～7 (pumping anti-freezing types) are produced the different concrete corrosion resistant additive for sea construction that require, and satisfy actual demands of engineering.
Claims (6)
1. anti-corrosion admixture for oceanic concrete, it is characterized in that, it consists of: calcium nitrite 20%～30%, calcined gypsum 15%～20%, the instant water glass 5%～10% of stratiform, vulkacit H 3%～5%, tripoly phosphate sodium STPP 1%～3%, water reducer 0～20%, air entrapment agent 0～0.4%, surplus are flyash, and above-mentioned per-cent is mass percent.
2. anti-corrosion admixture for oceanic concrete as claimed in claim 1 is characterized in that, described calcined gypsum is calcined down at 600～800 ℃ and obtained.
3. anti-corrosion admixture for oceanic concrete as claimed in claim 1 is characterized in that, the modulus of layered instant water glass is 2.1～2.3.
4. anti-corrosion admixture for oceanic concrete as claimed in claim 1 is characterized in that, described air entrapment agent is a triterpenoid saponin.
5. anti-corrosion admixture for oceanic concrete as claimed in claim 1 is characterized in that, described water reducer is the naphthalenesulfonate formaldehyde condensation compound water reducer.
6. as each described anti-corrosion admixture for oceanic concrete among the claim 1-5, it is characterized in that the mass percent of water reducer, air entrapment agent is respectively 15%～20%, 0.2%～0.4%.
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