CN101851080B - Acid rain corrosion resisting concrete additive and preparation method thereof - Google Patents
Acid rain corrosion resisting concrete additive and preparation method thereof Download PDFInfo
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- CN101851080B CN101851080B CN2010101283480A CN201010128348A CN101851080B CN 101851080 B CN101851080 B CN 101851080B CN 2010101283480 A CN2010101283480 A CN 2010101283480A CN 201010128348 A CN201010128348 A CN 201010128348A CN 101851080 B CN101851080 B CN 101851080B
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
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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
- 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
- C04B2111/23—Acid resistance, e.g. against acid air or rain
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- 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
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- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention relates to an acid rain corrosion resisting concrete additive and a preparation method thereof. The acid rain corrosion resisting concrete additive is characterized by mainly comprising the following materials in parts by weight: 100 parts of grounded furnace slag, 150-300 parts of high-lime fly ash, 10-50 parts of siliceous dust, a polymer, organic fiber and a function intensifying component, and the addition quantities of the polymer, the organic fiber and the function intensifying component respectively account for 3-5%, 0.5-2.5% and 3-8% of the total mass of the grounded furnace slag, the high-lime fly ash and the siliceous dust, wherein the function intensifying component is a chemical additive prepared by compounding an exciting agent and a dispersing agent in the mass ratio of 1:0.02-0.08. The acid rain corrosion resisting concrete additive is applied to concrete in acid rain environment, can obviously increase the acid rain corrosion resistance of the concrete, can extend the service life of concrete structures, and is low in price.
Description
Technical field
The invention belongs to the material of construction class, be specifically related to acid rain corrosion resisting concrete additive and preparation method thereof.
Background technology
Along with the high speed development of modern industry, topsoil increasingly sharpens, and acid rain has become a kind of general weather phenomena in world many countries and the area, thereby causes serious erosion damage to large-sized concrete structures such as the road under its place environment, bridges.Thereby the height of the antiacid erosion damage ability of concrete that acid rain environment rains is with the concrete structure service life that directly influences under the environment of place.
For the concrete structure under the acid rain environment, the behave that improves its erosion resistance at present is divided into 3 classes: the one, and in cement concrete, singly mix or twoly mix auxiliary glue and imitate gel material (as slag, flyash, silicon ash etc.), optimize grading of aggregate, reduce water cement ratio or use sulphate resisting portland cement to realize.The core of these technique means all is to start with from improving the concrete hole structure and reducing the concrete interface weak area.For example slag micropowder because having secondary hydration effect, micro aggregate effect and filling effect, has significantly improvement effect to concrete degree of compactness and interface weak area, thereby can delay and alleviate acid rain to a certain extent to mixing the erosion damage of slag concrete.But it is the comparatively special chemical erosion of a class that acid rain corrodes, and the attribute of existing general acid attack has the sulphate attack attribute again simultaneously, at Ca (OH)
2, hydrated products such as C-S-H gel and AFt do not get up by " isolation " or " protection " with etching medium; in its military service cycle, will suffer the strong erosion of etching medium gradually, and above-mentioned singly mix or two supplementary cementitious material of mixing only just corrodes object Ca (OH) from improving concrete density and reducing
2The equal size angle is considered, does not obviously reach " isolation " or " protection " effect; The 2nd, in cement concrete, singly mix or two water mixing glass, polymkeric substance (as polyvinyl acetate emulsion) are realized; this technological core mainly is to utilize polymkeric substance or/and " parcel " of water glass and " filling " effect; has the cancellated protective membrane in space inner formation of cement stone; to avoid the hydrated cementitious product directly to contact with etching medium, increase substantially its erosion resistance.But this technical disadvantages also clearly, and for example water glass is or/and polymer loading is big, and concrete strength descends, contraction is big etc., and the concrete structure service life is subjected to obvious influence, and cost is also higher; The 3rd class is to utilize " non-cement " gelling material, and for example water glass and sulphur prepare the acidproof special concrete of non-cement agglutinate.But, this utilization " non-cement " gelling material prepares the technique means of antiacid corrosion concrete, and obvious and raising is widely used in Portland cement concrete (PCC) under the acid rain environment (cement is as agglutinate) the rodent technology of antiacid rain tangible essential distinction.
Thereby, utilize traditional technological line configuration acid rain corrosion resisting concrete, can't reach national departments concerned to the relevant regulations of the antiacid rain erosion performance of actual concrete structure design requirements.
Summary of the invention
The object of the present invention is to provide a kind of acid rain corrosion resisting concrete additive and preparation method thereof, the concrete admixture of this method preparation uses in the concrete under the acid rain environment, can significantly improve its antiacid rain erosion performance, prolong the concrete structure service life, and cheap.
To achieve these goals, technical scheme of the present invention is: acid rain corrosion resisting concrete additive, it is characterized in that: it mainly is prepared from by ground slag, high-calcium fly ass, silicon ash, polymkeric substance, organic fibre and function intensified constituent materials, the shared parts by weight of each raw material are: ground slag: 100 parts, high-calcium fly ass: 150-300 part, the silicon ash: 10-50 part, the add-on of polymkeric substance, organic fibre and function intensified component are respectively 3-5%, 0.5-2.5% and the 3-8% of ground slag, high-calcium fly ass and silicon ash total mass.
Described ground slag is: select the commercially available blast furnace water quenching ground slag that meets national standard for use, with its oven dry, the water ratio after the oven dry is less than 2%; Its vitreum content is greater than 80%, most probable particle diameter 20-30 μ m, Blain specific surface 380-400m
2/ kg.
Described high-calcium fly ass is: the levigate high calcium ash of selecting for use coal fired thermal power plant to discharge, and with its oven dry, the water ratio after the oven dry is less than 2%; Its calcium oxide content 10-20%, free calcium oxide content be less than 2.5%, and sulfur trioxide content is less than 1%, most probable particle diameter 15-20 μ m, Blain specific surface 400-450m
2/ kg.
Described silicon ash is: select the active silica fume of city's mid-sales compact substance for use, with its oven dry, the water ratio after the oven dry is less than 1%; Its active SiO
2Content is greater than 90%, and maximum particle diameter is less than 1.0 μ m, median size 0.1 μ m, Blain specific surface 20000-25000m
2/ kg.
Described function intensified component be a kind of by exciting agent and dispersion agent by the composite chemical admixture that forms of mass ratio 1: 0.02-0.08, wherein exciting agent adopts solid solution than 1: the alkali silicate solution of 3-4 and yellow soda ash by mass ratio 1: 0.1-0.5 or employing solid solution than 1: the alkali silicate solution of 1-2.5 and sodium hydroxide are by the composite binary system that forms of mass ratio 1: 0.05-0.1; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, and its solid content is not less than 30%.
Described polymkeric substance by amphoteric ionic polyacrylamide and tributyl phosphate by mass ratio 5-6: 1 composite forming.
The assorted fibre that described organic fibre mixes, forms through modification by mass ratio 2: 1-3 for the polyacrylonitrile fibre grown by the long polypropylene fibre of 2-4mm and 5-8mm.
The preparation method of above-mentioned acid rain corrosion resisting concrete additive is characterized in that it comprises the steps:
1) raw material is chosen: a. chooses ground slag, selects the commercially available blast furnace water quenching ground slag that meets national standard for use, and with its oven dry, the water ratio after the oven dry is less than 2%, and is standby; Described levigate clinker glass body burden is greater than 80%, most probable particle diameter 20-30 μ m, Blain specific surface 380-400m
2/ kg;
B. choose high-calcium fly ass, the levigate high calcium ash of selecting for use coal fired thermal power plant to discharge, with its oven dry, the water ratio after the oven dry is less than 2%, and is standby; Described high-calcium fly ass calcium oxide content 10-20%, free calcium oxide content be less than 2.5%, and sulfur trioxide content is less than 1%, most probable particle diameter 15-20 μ m, Blain specific surface 400-450m
2/ kg;
C. choose the silicon ash, select the active silica fume of city's mid-sales compact substance for use, with its oven dry, the water ratio after the oven dry is less than 1%, and is standby; The active SiO of described silicon ash
2Content is greater than 90%, and maximum particle diameter is less than 1.0 μ m, median size 0.1 μ m, Blain specific surface 20000-25000m
2/ kg;
2) polymer formulation: with amphoteric ionic polyacrylamide and tributyl phosphate by mass ratio 5-6: 1 composite forming, standby;
3) organic fibre preparation: the long polyacrylonitrile fibre of the polypropylene fibre that 2-4mm is long and 5-8mm is by mass ratio 2: 1-3 is mixed into assorted fibre, then with the serial organic solvent of silane with its immersion 30-50 minute, dry, standby;
4) function intensified component preparation: adopt exciting agent and dispersion agent to form by mass ratio 1: 0.02-0.08 is composite, standby, wherein exciting agent adopts solid solution than 1: the alkali silicate solution of 3-4 and yellow soda ash are by mass ratio 1: 0.1-0.5 or adopt solid solution than 1: the alkali silicate solution of 1-2.5 and sodium hydroxide form by mass ratio 1: 0.05-0.1 is composite; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, and its solid content is not less than 30%;
5) by the shared parts by weight of each raw material be: ground slag: 100 parts, high-calcium fly ass: 150-300 part, silicon ash: 10-50 part, take by weighing prefabricated ground slag respectively, high-calcium fly ass and silicon ash, pour in the vibration mill common after mix grinding 20-40 minute, to account for ground slag, the prefabricated polymkeric substance of high-calcium fly ass and silicon ash total mass 3-5% and above-mentioned mix grinding material are poured into to be mixed together in the compound machine and were stirred 3-5 minute, add then and account for ground slag, the prefabricated organic fibre of high-calcium fly ass and silicon ash total mass 0.5-2.5%, continue to stir 6-10 minute, add again and account for ground slag, the prefabricated function intensified component of high-calcium fly ass and silicon ash total mass 3-8%, continue again to stir 5-15 minute, get product.
The acid rain etching medium is of a great variety, not only contains the H+ etching medium, also contains NH
4 +, Mg
2+, SO
4 2-Deng etching medium, causing it can not be that simple acid or Sulfates corrodes to concrete erosion damage, and should be the compound erosion damage effect of a class.Acid rain is broadly divided into corrosion initial stage, corrosion mid-term and corrosion 3 stages of later stage to concrete erosion damage process:
(1) at corrosion initial stage, H
+, SO4
2-Deng etching medium at first with the bill of material surface layer in Ca (OH)
2, hydrated product generation series of chemical such as C-S-H, C-A-H:
2H
++Ca(OH)
2＝Ca
2++2H
2O
SO
4 2-+Ca
2+＝CaSO
4
SO
4 2-+Ca
2++2H
2O→CaSO
4·2H
2O
SO
4 2-+C-S-H
+H+→CaSO
2·2H
2O+SiO
2·nH
2O
SO
4 2-+C-A-H+H
+→CaSO
2·2H
2O+Al
2O
3·nH
2O
3CaO·Al
2O
3·3CaSO
4·32H
2O+H
+→CaSO
4·2H
2O+3Al
2O
3·nH
2O
In this stage, the Ca of bill of material surface layer (OH)
2, components such as C-S-H, C-A-H run off gradually because of the acid rain effect, corrosion products such as the gypsum crystal that the generation solid volume obviously increases and the silica gel that has no gelling, aluminium glue, cause material surface tangible pulp and pitting phenomenon to occur, the material surface mechanical property reduces.But these corrosion products do not come off immediately, cover on the contrary on the concrete material surface, acid rain are further corroded have certain delaying and inhibition.
(2) corroding mid-term, along with H
+, SO
4 2-Deng etching medium by concrete pore and interface weak area gradually to its internal migration, above-mentioned chemical reaction begins to take place at material internal, corrosion product generations such as more gypsum crystal have been caused, produce expansion stress at inside concrete, cause concrete to produce microfracture and cracking, concrete strength descends, simultaneously to acid rain further corrosion have and certain delay also therefore to begin part with corrosion products such as the silica gel of inhibition, aluminium glues and come off.
(3) in the corrosion later stage, along with H
+, SO
4 2-From outward appearance to inner essence further move to inside concrete Deng etching medium, cement stone suffers more serious erosion damage by the mode of above-mentioned chemical reaction, cause concrete further loose, softening, pulp and cracking, therefore concrete strength produces decay greatly, and outward appearance shows as concrete surface and large-area disintegration occurs and come off etc.
Under long term like this, the water mudrock structure body in the concrete is decomposed gradually, and finally forming with gypsum, silica gel and aluminium glue etc. is the white sposh shape silt particle mixture of main corrosion product, and concrete strength completely loses.
The present invention has distinguishing feature: acid rain corrosion resisting concrete additive of the present invention is according to acid rain erosion damage process and characteristics thereof, designs and prepares according to the three-dimensional IPN spatial network of organic and inorganic seepage flow theory of ship structures.Particular embodiment is as follows:
(1) adopt silicon ash, ground slag and high-calcium fly ass that different fineness, variable grain grating, pozzolanic activity vary in size as main raw material(s) component of the present invention.On the one hand, according to the maximum tap density theory of particle, they can obviously improve the grain composition of cement, increase the compactness of water mudrock structure, thereby reduce the infiltration capability of acid rain etching medium, improve the antiacid rain aggressiveness of concrete; On the other hand, under the basicity effect that function intensified component of the present invention and hydrated cementitious provide, the pozzolanic activity of these several mineral material all can fully be excited, and can bring into play its effect by the order hydrated theory, thereby guarantee to have in the whole hydration process a large amount of low alkalinity hydrate gels to form continuously and be filled in the cement stone hole, form a comparatively stable inorganic spacial framework with the hydrated cementitious product is common, can obtain long-term antiacid rain erosion effect.
(2) be mixed into assorted fibre with different scale, polypropylene fibre of different nature and polyacrylonitrile fibre, on the one hand, it can form organic spacial framework in the cement based body, thereby the resistance that can bring into play fiber on different scale, different levels is step by step split and the limit effect, improves concrete strength and impermeability, volume stability and antiacid rain aggressiveness etc.; On the other hand, organic fibre coming off of the corrosion products such as gypsum, silica gel and aluminium glue that generate at the acid rain corrosion initial stage had certain pin down, effect such as constraint, thereby can reduce acid rain to concrete corrosion speed.
(3) described polymkeric substance, on the one hand, formed polymer gel is constantly in seepage flow, the hole that is filled in cement stone spacial framework, the cavity under effects such as Van der Waals force, mechanical force, and aggregate into the one layer of polymeric film, form organic spatial network seepage flow structure, thereby can play effects such as parcel, filling to cement stone, reduce cement stone and the direct touch opportunity of acid rain etching medium, increase substantially its antiacid rain aggressiveness; On the other hand; the free group that the polymkeric substance hydrolysis produces and polar group can be certain with the generations such as fiber that handled through modification on hydrated cementitious product, surface the chemical bonding effect; in order to can make above-described inorganic, organic space network structure IPN; form very stable three-dimensional IPN spatial network seepage flow structure; thereby can form effective provide protection to the hydrated cementitious product, retardance acid rain is to its erosion.
(4) described function intensified component can realize self function, for example seals, wraps up, effect such as filling, can play effects such as alkali-activator, dispersion agent again, accelerates early stage hydration reaction process, and strengthens the performance of the above each material component function.
Said components and proportioning are prepared the acid rain corrosion resisting concrete additive that just can obtain a kind of excellent performance by processing requirement, after it is with 25-50% equivalent substitution cement, can obtain good technical and economical effectiveness, for example: 1, under the acid rain erosion environment, the loss of strength of test specimen is very little, and antiacid rain erosion effect is obvious; 2, endurance qualities such as concrete resistance of chloride ion penetration, volume stability be improved significantly; 3, when reaching above-mentioned technical indicator, concrete physical and mechanical property, for example the workability of fresh concrete, concrete strength are unaffected; 4, can utilize industrial waste in a large number, production technique is simple, low production cost.In a word, acid rain corrosion resisting concrete additive of the present invention can solve present concrete well and be subject to acid rain erosion damage problem, prolong the concrete structure service life, and can reduce industrial waste to the pollution of environment, the significant social economic benefit is arranged, can be applicable in all kinds of cement concrete constructions such as road, bridge in vast acid rain area.
Description of drawings
Fig. 1 (A0) is the concrete appearance figure test specimen A0 of the present invention corrodes the different length of times under acid rain environment after.
Fig. 1 (A1) is the concrete appearance figure test specimen A1 of the present invention corrodes the different length of times under acid rain environment after.
Fig. 1 (A2) is the concrete appearance figure test specimen A2 of the present invention corrodes the different length of times under acid rain environment after.
Fig. 2 be under the acid rain environment of the present invention each concrete flexural strength with the corrosion length of time variation diagram.
Fig. 3 be under the acid rain environment of the present invention each concrete crushing strength with the corrosion length of time variation diagram.
Embodiment
In order to understand the present invention better, further specify content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples, embodiment should not regard limitation of the invention as.
Embodiment 1-2:
1, the preparation method of acid rain corrosion resisting concrete additive, it comprises the steps:
1) chooses starting material and prepare this adulterant by the material mixture ratio shown in the table 1
Raw material ratio in table 1 adulterant
| Embodiment | Ground slag: high-calcium fly ass: silicon ash (weight part) | Polymkeric substance | Organic fibre | Function intensified component |
| 1 | 100∶200∶30 | 3.5％ | 1.2％ | 5％ |
| 2 | 100∶225∶20 | 4％ | 1.8％ | 6％ |
(annotate: ground slag, high-calcium fly ass and silicon ash are chosen and are met the above mineral material of technical indicator separately, and after the drying, water ratio is 0.5%; The add-on of polymkeric substance, organic fibre and function intensified component is the mass percent that accounts for ground slag, high-calcium fly ass and silicon ash quality)
2) polymer formulation: amphoteric ionic polyacrylamide and tributyl phosphate is by 5: 1 composite forming of mass ratio, standby;
3) organic fibre preparation: the long polyacrylonitrile fibre of the polypropylene fibre that 3mm is long and 6mm is mixed into assorted fibre by mass ratio at 2: 1, with silane series organic solvent it is soaked 30 minutes then, dries, and is standby;
4) function intensified component preparation: adopt exciting agent and dispersion agent by 1: 0.05 composite forming of mass ratio, standby, wherein exciting agent employing solid solution than 1: 3.5 alkali silicate solution and yellow soda ash by 1: 0.4 composite forming of mass ratio; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, and its solid content is 35%;
5) ground slag, high-calcium fly ass and silicon ash are taken by weighing, pour in the vibration mill common mix grinding in proportion respectively after 25 minutes, prefabricated polymkeric substance and above-mentioned mix grinding material are poured into be mixed together in the compound machine again and stirred 5 minutes, add prefabricated organic fibre then, continue to stir 9 minutes, add prefabricated function intensified component again, continue again to stir 12 minutes, get product.
2, the performance test of acid rain corrosion resisting concrete additive:
1) concrete correlated performance test
By test proportioning as shown in table 2 (wherein, concrete admixture is in 30.8% ratio equivalent substitution cement), according to " standard for test methods of mechanical properties of ordinary concrete " (GB/T50081-2002), China Civil Engineering Society's standard (CCES 01-2004), U.S.'s ASTM C1202-97 standard and " normal concrete long-term behaviour and durability test method " (GBJ 82-85) moulding concrete sample, test correlated performances such as concrete intensity, chloride-penetration resistance, shrinkage value respectively, the result sees Table 3 respectively, table 4 and table 5.
Table 2 concrete test proportioning
(annotate: cement is the ordinary Portland cement of 42.5 strength grades; River sand is fineness modulus 2.8, II district medium sand; Stone is the quartzite rubble of 5-25cm continuous grading, and acid fastness is greater than 94%; Water reducer is how series high-efficiency water-reducing agent of Hua Wangmai ground 150)
Table 3 concrete strength
Table 4 concrete resistance of chloride ion penetration energy
Table 5 concrete shrinkage value (* 10
-6)
| Sample | 1d | 3d | 7d | 14d | 21d | 28d | 45d | 60d | 90d |
| A0 | 88 | 131 | 185 | 264 | 315 | 368 | 408 | 444 | 465 |
| A1 | 49 | 85 | 140 | 172 | 223 | 242 | 263 | 313 | 387 |
| A2 | 43 | 83 | 129 | 161 | 197 | 212 | 240 | 288 | 344 |
As shown in Table 3, after concrete adopts this product, concrete strength does not reduce, the intensity in opposite each length of time but has raising by a relatively large margin, illustrate: design and this adulterant for preparing according to the three-dimensional IPN spatial network of organic and inorganic seepage flow theory of ship structures, can obviously improve microtexture, the raising concrete density of concrete interface weak area; Also can draw similar conclusion from the test result of concrete resistance of chloride ion penetration and shrinkage: this adulterant is applied in the concrete, can increase substantially the concrete non-deformability, reduce the shrinkage strain cracking, thereby can reduce the infiltration capacity of extraneous etching medium, this undoubtedly to improve the antiacid rain erosional competency of concrete, to prolong the concrete structure service life useful.
2) the antiacid rain erosion performance test of concrete
Adopt acid rain to corrode simulated environment: each concrete sample of normal curing 28d is after acid rain is done wet immersion corrosion 180d, and its appearance change is shown in Fig. 1 (A0), Fig. 1 (A1), Fig. 1 (A2).Wherein, Simulated Acid Rain pH value is 3, and the etching medium composition sees Table 6.
Table 6 Simulated Acid Rain etching medium is formed mol/l
| SO 4 2- | Mg 2+ | NH 4 + | Ca 2+ | H + |
| 0.01 | 0.002 | 0.002 | 0.001 | 0.001 |
By Fig. 1 (A0), Fig. 1 (A1), Fig. 1 (A2) as can be known, at the acid rain corrosion initial stage (30d), though serious erosion damage phenomenons such as ftractureing, coming off does not appear in test specimen A0, but its surface has one deck white cement paste material to generate, show pulp, obviously corrosion phenomenon such as softening, similar breakoff phenomenon has also taken place in test specimen A1, A2, but degree is gently many; Along with the corrosion prolongation in the length of time, the lip-deep cement paste material of test specimen A0 comes off gradually, even more serious breakoff phenomenon has appearred to corroding the later stage, for example test specimen falls limit, arrisdefect and sand grains, stone exposes etc., erosion damage phenomenons such as sand grains, stone expose also appear in test specimen A1, A2, but do not occur not falling serious erosion damage phenomenon such as limit, arrisdefect such as test specimen.From the appearance change of test specimen relatively as can be seen its antiacid rain erosion performance be followed successively by to bad by height: A2＞A1＞A0.
Each concrete folding strength and ultimate compression strength change respectively as Fig. 2, shown in Figure 3 after acid rain corrodes 180d.
By Fig. 2 and Fig. 3 as can be known, after each, acid rain corroded in the length of time, the intensity of each test specimen all decreased, and especially test specimen A0 reduces the amplitude maximum.The loss of strength rate of three kinds of test specimens is descending to be: A0＞A1＞A2.So the antiacid rain erosional competency of each test specimen is consistent with the conclusion that draws from appearance change.
In summary: after concrete adopted this product, concrete antiacid erosional competency had had and has significantly improved.
Embodiment 3: acid rain corrosion resisting concrete additive, it mainly is prepared from by ground slag, high-calcium fly ass, silicon ash, polymkeric substance, organic fibre and function intensified constituent materials, the shared parts by weight of each raw material are: ground slag: 100 parts, high-calcium fly ass: 250 parts, the silicon ash: 40 parts, the add-on of polymkeric substance, organic fibre and function intensified component is respectively 3%, 1.5% and 6% of ground slag, high-calcium fly ass and silicon ash total mass; Wherein function intensified component by exciting agent and dispersion agent by 1: 0.03 composite forming of mass ratio, exciting agent for adopt solid solution than 1: 2 alkali silicate solution and sodium hydroxide by 1: 0.08 composite binary system that forms of mass ratio; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, its solid content 30%.
Described ground slag is selected the commercially available blast furnace water quenching ground slag that meets national standard for use, with its oven dry, the water ratio 1% after the oven dry, its vitreum content 85%, most probable particle diameter 20-30 μ m, Blain specific surface 390m
2/ kg.The levigate high calcium ash that described high-calcium fly ass selects for use coal fired thermal power plant to discharge is with its oven dry, the water ratio 0.5% after the oven dry, its calcium oxide content 10-20%, free calcium oxide content is less than 2.5%, and sulfur trioxide content is less than 1%, most probable particle diameter 15-20 μ m, Blain specific surface 400-450m
2/ kg.Described silicon ash is selected the active silica fume of city's mid-sales compact substance for use, with its oven dry, the water ratio 0.5% after the oven dry, its active SiO
2Content is greater than 90%, and maximum particle diameter is less than 1.0 μ m, median size 0.1 μ m, Blain specific surface 20000-25000m
2/ kg.Described polymkeric substance by amphoteric ionic polyacrylamide and tributyl phosphate by 6: 1 composite forming of mass ratio.The assorted fibre that described organic fibre mixes, forms through modification by mass ratio for the polyacrylonitrile fibre grown by the long polypropylene fibre of 4mm and 5mm at 2: 3.
The preparation method of above-mentioned acid rain corrosion resisting concrete additive, it comprises the steps:
1) chooses each raw material by each proportioning raw materials;
2) in advance with amphoteric ionic polyacrylamide and the tributyl phosphate composite polymkeric substance that forms in proportion, standby;
3) in advance polypropylene fibre is mixed in proportion into assorted fibre with polyacrylonitrile fibre, with silane series organic solvent it was soaked 35 minutes then, dry, standby;
4) form function intensified component with prefabricated exciting agent and dispersion agent are composite in proportion, standby;
5) will take by weighing prefabricated ground slag, high-calcium fly ass and silicon ash in proportion respectively, pour in the vibration mill common mix grinding into after 35 minutes, prefabricated polymkeric substance and above-mentioned mix grinding material are poured into be mixed together in the compound machine again and stirred 4 minutes, add prefabricated organic fibre then, continue to stir 8 minutes, add prefabricated function intensified component again, continue again to stir 7 minutes, get product.
Embodiment 4: acid rain corrosion resisting concrete additive, it mainly is prepared from by ground slag, high-calcium fly ass, silicon ash, polymkeric substance, organic fibre and function intensified constituent materials, the shared parts by weight of each raw material are: ground slag: 100 parts, high-calcium fly ass: 180 parts, the silicon ash: 15 parts, the add-on of polymkeric substance, organic fibre and function intensified component is respectively 4.5%, 1% and 4.5% of ground slag, high-calcium fly ass and silicon ash total mass; Wherein function intensified component by exciting agent and dispersion agent by 1: 0.07 composite forming of mass ratio, exciting agent for adopt solid solution than 1: 1.5 alkali silicate solution and sodium hydroxide by 1: 0.1 composite binary system that forms of mass ratio; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, and its solid content is not less than 30%.
Described ground slag is selected the commercially available levigate blast furnace slag that meets national standard for use, with its oven dry, the water ratio 1% after the oven dry, its vitreum content 80%, most probable particle diameter 20-30 μ m, Blain specific surface 390m
2/ kg.The levigate high calcium ash that described high-calcium fly ass selects for use coal fired thermal power plant to discharge is with its oven dry, the water ratio 1.5% after the oven dry, its calcium oxide content 15.4%, free calcium oxide content is less than 2.5%, and sulfur trioxide content is less than 1%, most probable particle diameter 15-20 μ m, Blain specific surface 380m
2/ kg.Described silicon ash is selected the active silica fume of city's mid-sales compact substance for use, with its oven dry, the water ratio 0.5% after the oven dry, its active SiO
2Content 91.4%, maximum particle diameter is less than 1.0 μ m, median size 0.1 μ m, Blain specific surface 25000m
2/ kg.Described polymkeric substance by amphoteric ionic polyacrylamide and tributyl phosphate by 5.5: 1 composite forming of mass ratio.The assorted fibre that described organic fibre mixes, forms through modification by mass ratio for the polyacrylonitrile fibre grown by the long polypropylene fibre of 3mm and 6mm at 2: 1.5.
The preparation method of above-mentioned acid rain corrosion resisting concrete additive, it comprises the steps:
1) chooses each raw material by each proportioning raw materials;
2) in advance with amphoteric ionic polyacrylamide and the tributyl phosphate composite polymkeric substance that forms in proportion, standby;
3) in advance polypropylene fibre is mixed in proportion into assorted fibre with polyacrylonitrile fibre, with silane series organic solvent it was soaked 32 minutes then, dry, standby;
4) form function intensified component with prefabricated exciting agent and dispersion agent are composite in proportion, standby;
5) will take by weighing prefabricated ground slag, high-calcium fly ass and silicon ash in proportion respectively and pour in the vibration mill common mix grinding into after 40 minutes, prefabricated polymkeric substance and above-mentioned mix grinding material are poured into be mixed together in the compound machine again and stirred 5 minutes, add prefabricated organic fibre then, continue to stir 6 minutes, add prefabricated function intensified component again, continue again to stir 10 minutes, get product.
Each raw material of the present invention and processing parameter upper lower limit value, interval value can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (4)
1. acid rain corrosion resisting concrete additive, it is characterized in that: it mainly is prepared from by ground slag, high-calcium fly ass, silicon ash, polymkeric substance, organic fibre and function intensified constituent materials, the shared mass fraction of each raw material is: ground slag: 100 parts, high-calcium fly ass: 150-300 part, the silicon ash: 10-50 part, the add-on of polymkeric substance, organic fibre and function intensified component are respectively 3-5%, 0.5-2.5% and the 3-8% of ground slag, high-calcium fly ass and silicon ash total mass;
Described ground slag is: select the commercially available blast furnace water quenching ground slag that meets national standard for use, its vitreum content is greater than 80%, most probable particle diameter 20-30 μ m, Blain specific surface 380-400m
2/ kg; With its oven dry, the water ratio after the oven dry is less than 2%;
Described high-calcium fly ass is: the levigate high calcium ash of selecting for use coal fired thermal power plant to discharge, and with its oven dry, the water ratio after the oven dry is less than 2%; Calcium oxide content 10-20% wherein, free calcium oxide content be less than 2.5%, and sulfur trioxide content is less than 1%, most probable particle diameter 15-20 μ m, Blain specific surface 400-450m
2/ kg;
Described silicon ash is: select the active silica fume of city's mid-sales compact substance for use, with its oven dry, the water ratio after the oven dry is less than 1%; Active SiO wherein
2Content is greater than 90%, and maximum particle diameter is less than 1.0 μ m, median size 0.1 μ m, Blain specific surface 20000-25000m
2/ kg;
Described function intensified component be a kind of by exciting agent and dispersion agent by the composite chemical admixture that forms of mass ratio 1: 0.02-0.08, wherein exciting agent adopts solid solution than 1: the alkali silicate solution of 3-4 and yellow soda ash by mass ratio 1: 0.1-0.5 or employing solid solution than 1: the alkali silicate solution of 1-2.5 and sodium hydroxide are by the composite binary system that forms of mass ratio 1: 0.05-0.1; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, and its solid content is not less than 30%.
2. acid rain corrosion resisting concrete additive according to claim 1 is characterized in that: described polymkeric substance by amphoteric ionic polyacrylamide and tributyl phosphate by mass ratio 5-6: 1 composite forming.
3. acid rain corrosion resisting concrete additive according to claim 1 is characterized in that: the assorted fibre that described organic fibre mixes, forms through modification by mass ratio 2: 1-3 for the polyacrylonitrile fibre grown by the long polypropylene fibre of 2-4mm and 5-8mm.
4. the preparation method of the described acid rain corrosion resisting concrete additive of claim 1 is characterized in that it comprises the steps:
1) raw material is chosen: a. chooses ground slag, selects the commercially available blast furnace water quenching ground slag that meets national standard for use, and its vitreum content is greater than 80%, most probable particle diameter 20-30 μ m, Blain specific surface 380-400m
2/ kg; With its oven dry, the water ratio after the oven dry is less than 2%, and is standby;
B. choose high-calcium fly ass, the levigate high calcium ash of selecting for use coal fired thermal power plant to discharge, with its oven dry, the water ratio after the oven dry is less than 2%, and is standby; Calcium oxide content 10-20% in the described high-calcium fly ass, free calcium oxide content be less than 2.5%, and sulfur trioxide content is less than 1%, most probable particle diameter 15-20 μ m, Blain specific surface 400-450m
2/ kg;
C. choose the silicon ash, select the active silica fume of city's mid-sales compact substance for use, with its oven dry, the water ratio after the oven dry is less than 1%, and is standby; Active SiO in the described silicon ash
2Content is greater than 90%, and maximum particle diameter is less than 1.0 μ m, median size 0.1 μ m, Blain specific surface 20000-25000m
2/ kg;
2) polymer formulation: with amphoteric ionic polyacrylamide and tributyl phosphate by mass ratio 5-6: 1 composite forming, standby;
3) organic fibre preparation: the long polyacrylonitrile fibre of the polypropylene fibre that 2-4mm is long and 5-8mm is by mass ratio 2: after 1-3 is mixed into assorted fibre,, dries its immersion 30-50 minute with the serial organic solvent of silane, and standby;
4) preparation of function intensified component: adopt exciting agent and dispersion agent to form by mass ratio 1: 0.02-0.08 is composite, standby, wherein exciting agent adopts solid solution than 1: the alkali silicate solution of 3-4 and yellow soda ash are by mass ratio 1: 0.1-0.5 or adopt solid solution than 1: the alkali silicate solution of 1-2.5 and sodium hydroxide are by the composite binary system that forms of mass ratio 1: 0.05-0.1; Dispersion agent is a kind of polycarboxylic acid salt's hyper-dispersant, and its solid content is not less than 30%;
5) by the shared mass fraction of each raw material be: ground slag: 100 parts, high-calcium fly ass: 150-300 part, silicon ash: 10-50 part, take by weighing prefabricated ground slag respectively, high-calcium fly ass and silicon ash, pour in the vibration mill common after mix grinding 20-40 minute, to account for ground slag, the prefabricated polymkeric substance of high-calcium fly ass and silicon ash total mass 3-5% and above-mentioned mix grinding material are poured into to be mixed together in the compound machine and were stirred 3-5 minute, add then and account for ground slag, the prefabricated organic fibre of high-calcium fly ass and silicon ash total mass 0.5-2.5%, continue to stir 6-10 minute, add again and account for ground slag, the prefabricated function intensified component of high-calcium fly ass and silicon ash total mass 3-8%, continue again to stir 5-15 minute, get product.
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| CN104671729B (en) * | 2014-12-29 | 2017-02-01 | 山西四建集团有限公司 | Sulfate-resistant concrete |
| CN106082753B (en) * | 2016-06-12 | 2018-09-18 | 陕西建业环保科技有限公司 | Superfine powder concrete admixture |
| CN106587696B (en) * | 2016-12-20 | 2019-03-22 | 深圳市洪涛装饰股份有限公司 | A kind of building decoration engineering environment-friendly type composite blend and preparation method thereof |
| CN106747126A (en) * | 2017-02-20 | 2017-05-31 | 内蒙古科技大学 | A kind of slag concrete of anti-sulfur dioxide corrosion |
| CN109553314A (en) * | 2018-10-26 | 2019-04-02 | 贾英新 | A kind of cement preparation method of acid rain corrosion resisting |
| CN109851268A (en) * | 2019-01-23 | 2019-06-07 | 江西省水利科学研究院 | A kind of antiacid powder of multifunctional concrete |
| CN111592252A (en) * | 2020-05-30 | 2020-08-28 | 江苏隆昌混凝土有限公司 | High-performance anti-cracking impact-resistant modified concrete and preparation method thereof |
| CN112960918A (en) * | 2021-02-08 | 2021-06-15 | 广东鸿丰水泥有限公司 | Process for improving acid corrosion resistance of set cement by volcanic ash |
| CN114907048B (en) * | 2022-04-15 | 2023-03-31 | 成都建工赛利混凝土有限公司 | Anti-cracking environment-friendly admixture for concrete and preparation method thereof |
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