CN109293279B - Marine concrete corrosion-resistant composite additive - Google Patents
Marine concrete corrosion-resistant composite additive Download PDFInfo
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- CN109293279B CN109293279B CN201811495426.3A CN201811495426A CN109293279B CN 109293279 B CN109293279 B CN 109293279B CN 201811495426 A CN201811495426 A CN 201811495426A CN 109293279 B CN109293279 B CN 109293279B
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- concrete
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- reducing agent
- resistant composite
- corrosion
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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
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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
- 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
Abstract
The invention aims to provide a marine concrete corrosion-resistant composite additive. The composition comprises the following components in parts by weight: 5-15 parts of polycarboxylic acid water reducing agent, 1-8 parts of corrosion inhibitor, 1-10 parts of shrinkage reducing agent, 0.01-2 parts of workability regulator, 0.001-1 part of defoaming agent and 64-93 parts of water. The marine concrete corrosion-resistant composite additive can effectively reduce the surface tension of concrete pores, reduce the number of harmful macropores in the concrete, reduce the migration of chloride ions in the pores and improve the durability of the concrete; the concrete shrinkage can be effectively reduced by more than 30%, the shrinkage and cracking of the concrete in a sea wind environment are improved, and the durability of the concrete is improved; the workability and the fluidity of the fresh concrete can be effectively improved, and the compactness of the concrete is high; meanwhile, the concrete admixture is convenient to use and low in admixture amount, and can improve the early strength of the concrete.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a marine concrete corrosion-resistant composite additive.
Background
The 21 st century is the oceanic century, the marine industry in China is developing at a high speed, the blue economy is vigorous, and gradually becomes a new growth point of the economy in China, and in the development and construction process of the blue economy, a large number of ocean engineering infrastructures, such as ports and docks, sea-crossing bridges, ocean oil platforms and the like, are built, and steel and reinforced concrete are two most commonly used materials. However, the composition of seawater is very complex, including water and various salts and gases dissolved in water, the main components of these salts being NaCl, MgCl2Equal chlorine salt, small amount of MgSO4、CaSO4Iso-sulfates and CaCO3Isocarbonate, very small amount of MgBr2The main component of the gas in the sea water is N2、O2And CO2The method is characterized in that the concrete is divided into a plurality of reinforcing steel bar specific surfaces, wherein chloride ions are one of the most main corrosive ions causing the damage of a reinforcing steel bar passive film, chloride ions and carbonate ions in seawater easily permeate into the concrete to perform physical and chemical reactions with related substances in the concrete and separate out, so that the compactness of the concrete is reduced, and in addition, when the chloride ions are accumulated on the specific surfaces of the reinforcing steel bars and reach more than a critical concentration, the reinforcing steel bars are easily subjected to electrochemical corrosion, and the reaction is very rapid. Therefore, in the marine concrete protection, how to improve the durability of concrete has received great attention.
A large number of researches show that the key for improving the durability of the marine concrete is to improve the compactness and impermeability of the concrete, control the shrinkage of the concrete and prevent the migration of chloride ions. At home and abroad, the durability of concrete is improved by adding admixtures, but long-term experiments show that the effect is not obvious, and at present, the outer wall of the concrete is usually coated with a protective layer, but the outer wall is easily damaged and falls off, so that the period for protecting the concrete is short. Therefore, the invention aims at the problems of marine service environment and protection period of concrete from practical application to modify and upgrade the concrete raw material, thereby achieving the purpose of solving the problems.
Disclosure of Invention
The invention aims to provide an anti-corrosion composite additive for marine concrete, which is used for reducing the surface tension of concrete pores, reducing the number of harmful macropores in the concrete, reducing the migration of chloride ions in the pores and improving the durability of the concrete.
In order to achieve the purpose, the technical scheme is as follows:
the marine concrete corrosion-resistant composite additive comprises the following components in parts by weight:
5-15 parts of a polycarboxylic acid water reducing agent, 1-8 parts of a corrosion inhibitor, 1-10 parts of a shrinkage reducing agent, 0.01-2 parts of a workability regulator, 0.001-1 part of a defoaming agent and 64-93 parts of water;
the polycarboxylic acid water reducing agent has the following structural formula:
wherein a, b, c, d and n are integers, wherein a, b and c are from 1 to 30, d is from 1 to 10, and n is from 25 to 80.
Preferably, said a, b, c are taken from 1 to 18.
According to the scheme, the polycarboxylate superplasticizer is prepared by the following method:
1) mixing ethanolamine and propionic acid in equal molar amount, adding p-toluenesulfonic acid, stirring and heating to 60-65 ℃; adding maleic anhydride for multiple times, controlling the temperature below 90 ℃, carrying out heat preservation reaction until the acid value in the system is not reduced, and cooling to obtain a mixed monomer;
2) dissolving prenyl alcohol polyoxyethylene ether in deionized water, stirring to dissolve, heating to 45 ℃, simultaneously dropwise adding a mixed aqueous solution (mixed material A) of acrylic acid, the mixed monomer and the chain transfer agent, a hydrogen peroxide aqueous solution, an ammonium persulfate aqueous solution (mixed material B) and a sodium bisulfite aqueous solution and a sodium sulfite aqueous solution (mixed material C), and preserving heat for 60min after dropwise adding to obtain the polycarboxylic acid water reducer with the effective content of 50%.
According to the scheme, the molecular formula of the prenol polyoxyethylene ether is as follows:
CH2＝C(CH3)CH2CH2O(CH2CH2O)nH。
according to the scheme, the corrosion inhibitor is a mixture of phytic acid ester and glycerol trimer; wherein the mass ratio of the phytic acid ester to the glycerol trimer is 0.25-1.5.
According to the scheme, the shrinkage reducing agent is a modified polyether type shrinkage reducing agent, and the polyether is an ethylene oxide propylene oxide block polymer with the molecular weight of less than 1000.
According to the scheme, the workability regulator is one or any mixture of xanthan gum, modified xanthan gum and cation modified polyacrylamide.
The preparation method of the marine concrete corrosion-resistant composite additive comprises the following steps: and adding the workability regulator into water, slowly stirring until the viscosity does not change any more, and then sequentially adding the polycarboxylic acid water reducing agent, the shrinkage reducing agent, the corrosion inhibitor and the defoaming agent. The water reducing rate of the obtained marine concrete corrosion-resistant composite additive is 15-25%, and the using amount of the marine concrete corrosion-resistant composite additive is 1.0-1.3% of the mass of the cementing material.
Compared with the prior art, the invention has the beneficial effects that:
(1) the marine concrete corrosion-resistant composite additive can effectively reduce the surface tension of concrete pores, reduce the number of harmful macropores in the concrete, reduce the migration of chloride ions in the pores and improve the durability of the concrete;
(2) the marine concrete corrosion-resistant composite additive can effectively reduce the total shrinkage of concrete by more than 30 percent, improve the shrinkage cracking of the concrete in a sea wind environment and improve the durability of the concrete;
(3) the marine concrete corrosion-resistant composite additive can effectively improve the workability and the fluidity of fresh concrete, and has high concrete density;
(4) the marine concrete corrosion-resistant composite additive is convenient to use and low in mixing amount, and can improve the early strength of concrete.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
The preparation of the polycarboxylic acid water reducing agent comprises the following steps:
firstly, 20mol of ethanolamine is put into a four-mouth bottle, 20mol of propionic acid is added for neutralization, 0.01mol of p-toluenesulfonic acid is added, the mixture is stirred and heated to 60-65 ℃, maleic anhydride (21mol) is added for a plurality of times, the internal temperature is controlled to be less than or equal to 90 ℃ during the feeding period, the reaction is stopped when the reaction is finished at 90 ℃ until the acid value in the system is not reduced any more, and a mixed monomer 1 is obtained after cooling;
adding a certain amount of deionized water into a four-neck round-bottom flask provided with a thermometer, a stirrer, a reflux condenser pipe and a nitrogen purging device, stirring, adding a modified unsaturated polyether macromonomer into the flask in one step under the protection of nitrogen, heating to 45 ℃ after stirring and dissolving, then dropwise adding a mixed aqueous solution (mixed material A) of acrylic acid, the mixed monomer and a chain transfer agent, hydrogen peroxide, an ammonium persulfate aqueous solution (mixed material B) and a sodium bisulfite and sodium sulfite aqueous solution (mixed material C), and preserving heat for 60min after dropwise adding; after the reaction is finished, cooling to normal temperature, and closing nitrogen to obtain the polycarboxylic acid water reducing agent with the effective concentration of 50 wt%.
Example 1
300g of polycarboxylic acid water reducing agent (mother solution with solid content of 50%), 16g of inositol hexaphosphate, 24g of trimeric glycerol, 60g of modified polyether, 1g of cation modified polyacrylamide, 1g of emulsified silicon paste emulsion and 600g of water are uniformly stirred until the viscosity does not change any more, and the marine concrete corrosion-resistant composite additive HY-1 is obtained.
Example 2
240g of polycarboxylic acid water reducing agent (mother solution with solid content of 50%), 20g of inositol hexaphosphate, 20g of trimeric glycerol, 100g of modified polyether, 2g of cation modified polyacrylamide, 1g of emulsified silicon paste emulsion and 660g of water are uniformly stirred until the viscosity does not change any more, and the marine concrete corrosion-resistant composite additive HY-2 is obtained.
Example 3
280g of polycarboxylic acid water reducing agent (mother solution with solid content of 50%), 40g of inositol hexaphosphate, 30g of trimeric glycerol, 80g of modified polyether, 1.5g of xanthan gum, 0.5g of emulsified silicon paste emulsion and 560g of water are uniformly stirred until the viscosity does not change any more, so that the marine concrete corrosion-resistant composite additive HY-3 is obtained.
Comparative example 1
280g of the polycarboxylate superplasticizer (mother liquor with the solid content of 50%) and 720g of water are uniformly stirred until the viscosity does not change any more, so that the marine concrete corrosion-resistant composite additive HY-4 is obtained.
Comparative example 2
280g of common polycarboxylic acid water reducing agent (mother solution with solid content of 50 percent) (the molecular formula is shown in the following formula), and 720g of water are uniformly stirred until the viscosity does not change any more, so as to obtain the marine concrete corrosion-resistant composite additive HY-5.
Wherein a, c and n are integers, wherein a, c are from 1 to 30 and n is from 25 to 80.
The marine concrete corrosion-resistant composite admixture prepared in the embodiments 1 to 3 of the invention is subjected to a concrete trial experiment, the mix proportion of the concrete for the experiment is shown in table 1, and the experimental result is shown in table 2 below:
TABLE 1 concrete test proportions
Note: the additive mixing amount means that the additive accounts for the percentage of the cementing material (namely the total weight of the cement, the mineral powder and the fly ash) by weight. Wherein the cement is P.O 42.5.5 ordinary portland cement produced by Huangshihua new cement factory; the mineral powder is produced by Wuxin mineral powder factories; the fly ash is Yanghuo II-grade ash; the sand fineness modulus is 2.8; the crushed stone is crushed stone with 5-20mm grain size and continuous gradation.
TABLE 2 results of the experiment
| Serial number | Slump/spread (mm) | 28d compressive strength/MPa | Electric flux/C |
| HY-1 | 255/490 | 42.5 | 560 |
| HY-2 | 250/485 | 43 | 532 |
| HY-3 | 260/490 | 45.6 | 465 |
| HY-4 | 250/480 | 43.6 | 980 |
| HY-5 | 230/460 | 40.5 | 1360 |
As is apparent from the above Table 2, the addition of the special admixture has no significant influence on the working performance and mechanical properties of the concrete, which directly indicates that the shrinkage-reducing agent, the corrosion inhibitor and other components of the invention have good compatibility with the polycarboxylic acid water reducing agent. From the data of electric flux, the improvement effect of the addition of the special additive on the chloride ion permeability resistance of the concrete is obvious. In addition, the comparative examples 1-2 show that the polycarboxylate water reducer adopted in the invention has obvious effect on the aspect of workability adjustment compared with the common polycarboxylate water reducer, and the chloride ion permeation resistance of the polycarboxylate water reducer is better from the aspect of electric flux data. It is apparent that the above embodiments are only examples for clearly illustrating the embodiments, and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (6)
1. The marine concrete corrosion-resistant composite additive is characterized by comprising the following components in parts by weight:
5-15 parts of a polycarboxylic acid water reducing agent, 1-8 parts of a corrosion inhibitor, 1-10 parts of a shrinkage reducing agent, 0.01-2 parts of a workability regulator, 0.001-1 part of a defoaming agent and 64-93 parts of water;
the polycarboxylic acid water reducing agent has the following structural formula:
wherein a, b, c, d and n are integers, wherein a, b and c are from 1 to 30, d is from 1 to 10, and n is from 25 to 80.
2. The marine concrete corrosion-resistant composite admixture according to claim 1, wherein the polycarboxylic acid water reducing agent is prepared by the following method:
1) mixing ethanolamine and propionic acid in equal molar amount, adding p-toluenesulfonic acid, stirring and heating to 60-65 ℃; adding maleic anhydride for multiple times, controlling the temperature below 90 ℃, carrying out heat preservation reaction until the acid value in the system is not reduced, and cooling to obtain a mixed monomer;
2) dissolving prenyl alcohol polyoxyethylene ether in deionized water, stirring to dissolve, heating to 45 ℃, simultaneously and respectively dropwise adding a mixed aqueous solution of acrylic acid, the mixed monomer and the chain transfer agent, a mixed aqueous solution of hydrogen peroxide and ammonium persulfate and a mixed aqueous solution of sodium bisulfite and sodium sulfite, and preserving heat for 60min after dropwise adding to obtain the polycarboxylic acid water reducing agent with the effective content of 50%.
3. The marine concrete corrosion-resistant composite additive according to claim 2, wherein the molecular formula of the prenyl polyoxyethylene ether is as follows:
CH2＝C(CH3)CH2CH2O(CH2CH2O)nh; average molecular weight 2400.
4. The marine concrete corrosion-resistant composite admixture according to claim 1, wherein the corrosion inhibitor is a mixture of phytic acid ester and glycerol trimer; wherein the mass ratio of the phytic acid ester to the glycerol trimer is 0.25-1.5.
5. The marine concrete corrosion-resistant composite admixture according to claim 1, wherein the shrinkage-reducing agent is a modified polyether type shrinkage-reducing agent, and the polyether is an ethylene oxide-propylene oxide block polymer having a molecular weight of less than 1000.
6. The marine concrete corrosion-resistant composite admixture according to claim 1, wherein the workability regulator is one or any mixture of xanthan gum, modified xanthan gum and cation modified polyacrylamide.
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| CN201811495426.3A CN109293279B (en) | 2018-12-07 | 2018-12-07 | Marine concrete corrosion-resistant composite additive |
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| CN110396158B (en) * | 2019-08-12 | 2021-09-28 | 德州中科新材料有限公司 | Marine concrete shrinkage-reducing water reducing agent and application method thereof |
| CN110698149A (en) * | 2019-11-14 | 2020-01-17 | 广西云燕特种水泥建材有限公司 | High-corrosion-resistance marine cement cementing material and preparation method thereof |
| CN110668731A (en) * | 2019-11-14 | 2020-01-10 | 广西云燕特种水泥建材有限公司 | Additive for ocean engineering concrete and preparation method thereof |
| CN112745054B (en) * | 2020-12-31 | 2022-02-22 | 临沂海螺新材料科技有限公司 | Salt erosion resistant marine concrete admixture and preparation method thereof |
| CN113831050B (en) * | 2021-09-13 | 2022-07-26 | 中建商品混凝土有限公司 | Green carbon-reducing concrete additive, green carbon-reducing concrete and preparation method |
| CN115231882B (en) * | 2022-08-15 | 2023-04-28 | 广东复特新型材料科技有限公司 | Corrosion inhibitor synergistic water reducer anti-corrosion mortar and preparation method thereof |
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| US7556684B2 (en) * | 2004-02-26 | 2009-07-07 | Construction Research & Technology Gmbh | Amine containing strength improvement admixture |
| CN102491677B (en) * | 2011-11-22 | 2014-06-25 | 浙江五龙新材股份有限公司 | Nuclear power concrete additive and preparation method thereof |
| CN102627744B (en) * | 2012-04-11 | 2013-06-19 | 长沙加美乐素化工有限公司 | Preparation method of ether amphoteric polycarboxylic acid water reducing agent |
| CN103693881B (en) * | 2013-12-26 | 2016-02-10 | 四川石达化学股份有限公司 | A kind of polycarboxylate water-reducer and application thereof and preparation method |
| CN105330193B (en) * | 2015-11-24 | 2017-12-26 | 同济大学 | Nuclear power ultra dense real concrete polycarboxylate water-reducer and preparation method thereof |
| CN106927713B (en) * | 2017-04-06 | 2019-02-19 | 日照市海洋工程研究院 | A kind of maritime concrete anti-crack and anti-seepage additive |
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