CN112028531A - Concrete corrosion-proof rust-proof composite additive and preparation method thereof - Google Patents
Concrete corrosion-proof rust-proof composite additive and preparation method thereof Download PDFInfo
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- CN112028531A CN112028531A CN202010855662.2A CN202010855662A CN112028531A CN 112028531 A CN112028531 A CN 112028531A CN 202010855662 A CN202010855662 A CN 202010855662A CN 112028531 A CN112028531 A CN 112028531A
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/023—Fired or melted materials
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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
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract
The invention discloses a concrete corrosion-resistant rust-resistant composite additive, which comprises a rust-resistant component, an anticorrosive component and a dense component; the rust-resisting component comprises zinc-aluminum layered double hydroxide roasted substances, polyvinyl alcohol, thiourea and inorganic molybdate salt; the zinc-aluminum layered double hydroxide roasted substance is prepared by uniformly mixing zinc nitrate and aluminum nitrate, slowly dropping the mixture into a soda solution, and performing water bath and roasting treatment. The additive of the invention utilizes the mutual synergistic effect among the zinc-aluminum layered double hydroxide roasted substance, the polyvinyl alcohol, the thiourea and the inorganic salt of molybdic acid in the rust-resisting component, and has better corrosion-resisting and rust-resisting effects.
Description
Technical Field
The invention belongs to the field of concrete additives, and particularly relates to a composite concrete corrosion-resistant rust-proof additive.
Background
The concrete is used as the largest building material and widely applied to engineering structures such as high-rise buildings, large-span bridges, tunnels, subways and the like. Among these engineering structures, the durability of the concrete structure is particularly important, directly determining the service life of the building. With the continuous deepening of marine construction and western construction in China, the service environment of a concrete structure is severe, and the corrosion of harmful erosion ions to concrete and internal reinforcing steel bars is increasingly severe. At present, sulfate and chloride corrosion are known to be one of the main causes of failure and damage of a reinforced concrete structure, sulfate corrosion is also an environmental water corrosion type with the most complex influence factors and the greatest harmfulness, and the final result of corrosion causes expansion cracking, strength loss, steel bar corrosion and the like of the reinforced concrete structure, seriously influences the durability of a building, reduces the service life of the building, and causes serious engineering accidents and huge economic benefit loss.
At present, the main concrete corrosion prevention measures are 3: a single rust inhibitor or preservative is adopted to be doped into the concrete raw material; coating the surface of the concrete structure with an anticorrosive coating; sulfate resistant cement is used. However, these three corrosion protection measures have their own disadvantages: the first measure has higher construction cost; the second measure is easily influenced by environment and other factors, the construction difficulty is high, and the coating is easy to fall off; the third measure has less sulfate-resistant cement manufacturers and high price. In order to solve the problems, the method which is simple and has better effect at present is to add an anticorrosive rust inhibitor into the coagulation.
In the prior art, the chinese patent application CN109879630A provides a high performance corrosion resistant concrete doped with layered double hydroxide rust inhibitor, wherein ZnNO is disclosed3And Al2(NO3)3Uniformly mixing according to the molar ratio of 3: 1-3: 3, then adding alkali liquor at normal temperature, quickly stirring, and crystallizing for 5-15 hours to obtain Zn2Al-NO3A layered double hydroxide rust inhibitor; the rust inhibitor has the principle that the rust inhibitor can generate strong adsorption effect on concrete acid radical ions to avoid the corrosion of reinforced concrete, and has the function of inhibiting the rustExcellent mechanical property and impermeability and durability. However, this application does not disclose specific data on the rust resistance, mechanical properties and permeation resistance durability of the corrosion-resistant concrete. Chinese patent application CN107935434A provides a green high-efficiency reinforced concrete rust inhibitor, which uses sodium molybdate, thiourea, tetraethylenepentamine and phytic acid as raw materials, and forms a precipitation film after the sodium molybdate and the thiourea are compounded, so that a complete and compact protective film layer is formed on the surface of a steel bar to prevent corrosion from occurring and going on; the sulfur in thiourea molecules is combined with Fe, so that Fe corrosion is inhibited, the covered area of the carbon steel surface is enlarged, and the corrosion inhibition effect is enhanced. Although this application has a certain rust inhibiting effect, the influence on the mechanical properties of concrete is unknown.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a concrete corrosion-resistant rust-resistant composite additive, which is realized by the following technology.
A concrete corrosion-proof rust-proof composite additive comprises a rust-proof component, an anticorrosion component and a dense component; the rust-resisting component comprises zinc-aluminum layered double hydroxide roasted substances, polyvinyl alcohol, thiourea and inorganic molybdate salt;
the preparation method of the zinc-aluminum layered double hydroxide roasted product comprises the following steps:
s1, taking equal amount of Zn (NO) with same concentration3)2Solution and Al (NO)3)3Uniformly mixing the solution;
s2, slowly dripping the mixed solution of the step S1 to 250mL of 1.5mol/L Na2CO3Continuously stirring the solution, and adjusting the pH value of the solution to 10 +/-0.6;
s3, treating the mixed solution obtained in the step S2 by water bath at 55-65 ℃ for 2-3h, filtering, drying to obtain zinc-aluminum layered double hydroxide Zn-Al LDHs, and roasting at 340-360 ℃ for 4h to obtain zinc-aluminum layered double hydroxide roasted Zn-Al CLDHs.
In the composite additive, a zinc-aluminum layered double hydroxide roasted product Zn-Al CLDHs, polyvinyl alcohol, thiourea and sodium/ammonium molybdate are used as rust inhibiting components, and Zn-Al CLDHs enter a concrete system in the presence of chloride ionsThe structural recombination of CLDHs is changed into LDHs, and the LDHs can provide physical barrier for the substrate and absorb corrosive ions such as chloride ions to protect the substrate due to the stable layered structure and the interchangeability of interlayer anions, thereby reducing Cl in the environment-Concentration and simultaneously capable of releasing OH-The pH value of the solution is improved, and the stability of the passivation film on the surface of the steel bar is maintained. Polyvinyl alcohol, thiourea and inorganic molybdate are respectively used as a cathode and an anode rust-resisting component, a layer of protective film is formed by respectively inhibiting the reaction of the cathode and the anode, the corrosion of the steel bar is further prevented or delayed, and the maximum rust-resisting and corrosion-resisting effects can be exerted only by simultaneously using Zn-Al CLDHs, polyvinyl alcohol, thiourea and inorganic molybdate. BaCO3And anhydrite as antiseptic component, the barium salt reacts with sulfate to form precipitate, fill pores and improve the microstructure of slurry, and the anhydrite mainly ensures that the system has sufficient SO4 2-The method can prevent the conversion of ettringite (AFt) to monosulfur calcium sulphoaluminate (AFm), further prevent the formation of secondary ettringite and improve the sulfate erosion resistance of the ettringite. Metakaolin and silica fume are dense components, so that cement hydration is promoted, the compactness of a system is improved, the aperture is optimized, and the strength of concrete is increased. The components mutually promote the permeation of the concrete against harmful ions through the double superposition of physics and chemistry, and have obvious functions of resisting rust and sulfate corrosion.
Preferably, the rust-resisting component comprises, by weight, 40-50 parts of a zinc-aluminum layered double hydroxide roasted product, 12-18 parts of polyvinyl alcohol, 14-20 parts of thiourea and 25-30 parts of inorganic molybdate salt.
More preferably, the rust-resisting component comprises 45 parts by weight of zinc-aluminum layered double hydroxide calcine, 15 parts by weight of polyvinyl alcohol, 16 parts by weight of thiourea and 28 parts by weight of inorganic molybdate.
Preferably, the corrosion inhibitor comprises 10-28 parts of a rust inhibitor component, 10-23 parts of an antiseptic component and 60-78 parts of a dense component in parts by weight;
more preferably, the antirust component 25 parts, the anticorrosion component 20 parts and the compact component 65 parts are included according to the parts by weight.
Preferably, the preservative component is in parts by weightThe method comprises the following steps: BaCO320-25 parts of anhydrite and 75-80 parts of gypsum.
More preferably, the anticorrosive component comprises the following components in parts by weight: BaCO325 parts of anhydrite and 75 parts of gypsum.
Preferably, the dense components comprise the following components in parts by weight: 72-85 parts of metakaolin and 15-28 parts of silica fume.
More preferably, the dense components comprise, in parts by weight: 80 parts of metakaolin and 20 parts of silica fume.
A method for preparing the composite concrete corrosion-and rust-preventing additive of claim 1, which comprises the steps of preparing and weighing the corrosion-and rust-preventing component, the corrosion-preventing component and the compact component, slowly stirring for 5-15min at 35-50r/min, and rapidly stirring for 10-15min at 70-100r/min to obtain a finished product.
Compared with the prior art, the invention has the advantages that: by utilizing the mutual synergistic effect among zinc-aluminum layered double hydroxide roasted substances, polyvinyl alcohol, thiourea and inorganic molybdate in the rust resisting component, compared with the layered double hydroxide rust inhibitor which is not subjected to water bath treatment and high-temperature calcination in the prior art, the zinc-aluminum layered double hydroxide disclosed by the invention has good stability and high purity; the concrete system is more compact, so that erosion ions are difficult to permeate into the concrete; by the addition of p-Cl-Curing, OH-The anode and the cathode of the steel bar are prevented from reacting to form a protective film, so that the corrosion of the chloride to the steel bar is reduced; the barium salt reacts with the sulfate to form a precipitate, so that pores can be filled, the microstructure of the slurry is improved, the mechanical property and durability of the cement concrete are improved, the cost is further reduced, and the economic benefit and the social benefit are improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The concrete corrosion and rust preventing composite admixture provided in the following examples and comparative examples was prepared according to the following preparation method unless otherwise specified: firstly preparing and weighing the rust-resisting component, the anticorrosion component and the compact component, slowly stirring for 5-15min at 35-50r/min, and then quickly stirring for 10-15min at 70-100r/min to prepare the additive finished product. The inorganic salt of molybdic acid used in the rust-inhibiting component is sodium molybdate.
The zinc-aluminum layered double hydroxide calcines used in the following examples and comparative examples were prepared according to the following preparation methods unless otherwise specified:
s1, taking equal amount of Zn (NO) with same concentration3)2Solution and Al (NO)3)3Uniformly mixing the solution;
s2, slowly dripping the mixed solution of the step S1 to 250mL of 1.5mol/L Na2CO3Continuously stirring the solution, and adjusting the pH value of the solution to 10 +/-0.6;
s3, treating the mixed solution obtained in the step S2 by water bath at about 60 ℃ for 3h, filtering and drying to obtain zinc-aluminum layered double hydroxide Zn-Al LDHs, and roasting at about 350 ℃ for 4h to obtain zinc-aluminum layered double hydroxide roasted product Zn-Al CLDHs.
Example 1
The concrete corrosion-resistant rust-resistant composite additive provided by the embodiment comprises 25 parts of rust-resistant component, 20 parts of anticorrosive component and 65 parts of dense component; the rust-resisting component comprises 45 parts of zinc-aluminum layered double hydroxide roasted substance, 15 parts of polyvinyl alcohol, 16 parts of thiourea and 28 parts of sodium molybdate; the anticorrosive component comprises BaCO in parts by weight325 parts of anhydrite and 75 parts of gypsum; the dense components comprise 80 parts of metakaolin and 20 parts of silica fume by weight.
Example 2
The composite additive for preventing corrosion and rust of concrete provided by the embodiment is different from the composite additive provided by the embodiment 1 in that the rust-preventing component comprises 50 parts by weight of a zinc-aluminum layered double hydroxide roasted substance, 15 parts by weight of polyvinyl alcohol, 14 parts by weight of thiourea and 28 parts by weight of sodium molybdate.
Example 3
The concrete corrosion and rust prevention composite additive provided by the embodiment is different from the concrete corrosion and rust prevention composite additive provided by the embodiment 1 in that the rust prevention component comprises 40 parts by weight of zinc-aluminum layered double hydroxide roasted substance, 15 parts by weight of polyvinyl alcohol, 20 parts by weight of thiourea and 28 parts by weight of sodium molybdate.
Example 4
The concrete corrosion and rust preventing composite admixture provided by the embodiment is different from the concrete corrosion and rust preventing composite admixture provided by the embodiment 1 in that the concrete corrosion and rust preventing composite admixture comprises 10 parts of a rust preventing component, 23 parts of an anticorrosive component and 60 parts of a dense component in parts by weight.
Example 5
The concrete corrosion and rust preventing composite admixture provided by the embodiment is different from the concrete corrosion and rust preventing composite admixture provided by the embodiment 1 in that the concrete corrosion and rust preventing composite admixture comprises 28 parts of a rust preventing component, 10 parts of an anticorrosive component and 78 parts of a dense component in parts by weight.
Comparative example 1
The concrete corrosion-proof and rust-proof composite additive provided by the comparative example is different from the concrete corrosion-proof and rust-proof composite additive provided by the example 1 in that the zinc-aluminum layered double hydroxide roasted product is replaced by zinc-aluminum layered double hydroxide Zn-Al LDHs, and the preparation method of the zinc-aluminum layered double hydroxide Zn-Al LDHs comprises the following steps:
s1, taking equal amount of Zn (NO) with same concentration3)2Solution and Al (NO)3)3Uniformly mixing the solution;
s2, slowly dripping the mixed solution of the step S1 to 250mL of 1.5mol/L Na2CO3Continuously stirring the solution, and adjusting the pH value of the solution to 10 +/-0.6;
s3, treating the mixed solution obtained in the step S2 in water bath at 60 ℃ for 3h, and performing suction filtration and drying to obtain the zinc-aluminum layered double hydroxide Zn-Al LDHs.
Comparative example 2
The concrete corrosion-proof and rust-proof composite additive provided by the comparative example is different from the concrete corrosion-proof and rust-proof composite additive provided by the example 1 in that a zinc-aluminum layered double hydroxide roasted product is replaced by a zinc-aluminum layered double hydroxide, and the preparation method of the zinc-aluminum layered double hydroxide of the comparative example comprises the following steps:
s1, taking equal amount of Zn (NO) with same concentration3)2Solution and Al (NO)3)3The solution is mixed uniformlyHomogenizing;
s2, slowly dripping the mixed solution of the step S1 to 250mL of 1.5mol/L Na2CO3Continuously stirring the solution, and adjusting the pH value of the solution to 10 +/-0.6;
and S3, crystallizing the mixed solution obtained in the step S2 at a low temperature for 8 hours, and filtering and drying to obtain the zinc-aluminum layered double hydroxide.
Comparative example 3
The concrete corrosion-proof and rust-proof composite additive provided by the comparative example is different from the concrete corrosion-proof and rust-proof composite additive provided by the example 1 in that the rust-proof component comprises 45 parts by weight of zinc-aluminum layered double hydroxide roasted substance and 15 parts by weight of polyvinyl alcohol, namely the ratio of the zinc-aluminum layered double hydroxide roasted substance to the polyvinyl alcohol is 3:1, and the concrete corrosion-proof and rust-proof composite additive is the same as the concrete corrosion-proof and rust-proof additive provided by the example 1.
Comparative example 4
The composite additive for preventing corrosion and rust of concrete provided by the comparative example is different from that of the concrete provided by the example 1 in that the rust-resisting component comprises 15 parts by weight of polyvinyl alcohol, 16 parts by weight of thiourea and 28 parts by weight of sodium molybdate, namely the dosage proportion of the polyvinyl alcohol, the thiourea and the sodium molybdate is the same as that of the concrete provided by the example 1.
Application example 1: performance test of concrete corrosion and rust preventing composite admixtures prepared in examples 1 to 5 and comparative examples 1 to 4
The concrete corrosion-resistant rust-resistant composite admixture prepared in the above examples 1-5 and comparative examples 1-4 is subjected to performance test according to GB/T31296-2014 concrete corrosion-resistant rust inhibitor, and the corrosion-resistant performance is characterized by adopting two indexes of the salt water immersion resistance performance of the steel bar in JT/T537-2018 reinforced concrete rust inhibitor and the corrosion area percentage of the steel bar in the concrete under the saline water immersion drying environment.
The mixing amount of the concrete corrosion-resistant rust-resistant composite additive is 5%, and the main test indexes are concrete setting time difference, concrete compressive strength ratio, shrinkage ratio, chloride ion migration coefficient ratio, sulfate corrosion coefficient ratio and corrosion electric quantity ratio.
Raw materials used in the test: reference cement; sand in the zone II, the fineness modulus is 2.6-2.9, and the mud content is less than 1%; the tests of the sulfate erosion coefficient ratio and the chloride ion permeability coefficient ratio adopt the macadam with the nominal grain diameter of 5mm-20mm and the secondary composition, which meets the continuous grading requirement; the corrosion electric quantity ratio test adopts I-type crushed stone with nominal grain diameter of 5mm-10 mm; the salt water soaking and drying test adopts crushed stone with nominal grain diameter of 5mm-15mm and meeting the continuous grading requirement. In the test process, the tested concrete and the corresponding reference concrete adopt the same water cement ratio and slump. Controlling the concrete slump to be 80mm +/-10 mm when carrying out sulfate erosion coefficient ratio, chloride ion permeability coefficient ratio and salt water soaking and drying tests; when the corrosion electric quantity ratio test is carried out, the slump of the concrete is controlled to be 50mm +/-10 mm. The reference concrete and the detected concrete are controlled to reach the specified slump by adjusting the water consumption. The concrete corrosion and rust preventing composite admixture of examples 1 to 5 and comparative examples 1 to 4 were tested with the test results of setting time and mechanical properties as shown in Table 1, and the corrosion and rust preventing properties as shown in Table 2.
TABLE 1 setting time and mechanical Properties results
TABLE 2 results of corrosion and rust resistance
From the above tables 1 and 2, it can be seen that when the usage amounts of the rust-inhibiting component, the anticorrosive component and the dense component of the admixture are changed, or the usage amounts of the zinc-aluminum layered double hydroxide calcined substance, the polyvinyl alcohol, the thiourea and the sodium molybdate in the rust-inhibiting component are changed, or the preparation method of the zinc-aluminum layered double hydroxide calcined substance is changed, the obvious influences on the properties of the final concrete, such as the setting time difference, the compressive strength ratio, the corrosion resistance and the rust resistance, are only successively realized. According to the zinc-aluminum layered double hydroxide roasted material prepared by the preparation method, the prepared admixture is doped into concrete to meet the AB type index in GB/T31296-.
The above description is only an example of the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The concrete corrosion-resistant rust-resistant composite additive is characterized by comprising a rust-resistant component, an anticorrosive component and a dense component; the rust-resisting component comprises zinc-aluminum layered double hydroxide roasted substances, polyvinyl alcohol, thiourea and inorganic molybdate salt;
the preparation method of the zinc-aluminum layered double hydroxide roasted product comprises the following steps:
s1, taking equal amount of Zn (NO) with same concentration3)2Solution and Al (NO)3)3Uniformly mixing the solution;
s2, slowly dripping the mixed solution of the step S1 to 250mL of 1.5mol/L Na2CO3Continuously stirring the solution, and adjusting the pH value of the solution to 10 +/-0.6;
s3, treating the mixed solution obtained in the step S2 by water bath at 55-65 ℃ for 2-3h, filtering, drying to obtain zinc-aluminum layered double hydroxide Zn-Al LDHs, and roasting at 340-360 ℃ for 4h to obtain zinc-aluminum layered double hydroxide roasted Zn-Al CLDHs.
2. The composite concrete corrosion and rust inhibitor additive according to claim 1, wherein the rust inhibitor comprises, by weight, 40-50 parts of a zinc-aluminum layered double hydroxide roasted product, 12-18 parts of polyvinyl alcohol, 14-20 parts of thiourea, and 25-30 parts of an inorganic molybdate salt.
3. The composite concrete corrosion and rust inhibitor additive according to claim 2, wherein the rust inhibitor comprises 45 parts by weight of a zinc-aluminum layered double hydroxide roasted product, 15 parts by weight of polyvinyl alcohol, 16 parts by weight of thiourea and 28 parts by weight of an inorganic molybdate salt.
4. The concrete corrosion-proof rust-proof composite additive according to any one of claims 1 to 3, which is characterized by comprising 10 to 28 parts of rust-proof component, 10 to 23 parts of anticorrosive component and 60 to 78 parts of dense component by weight.
5. The composite concrete corrosion-proof and rust-proof additive according to claim 4, which comprises 25 parts of rust-proof component, 20 parts of anticorrosion component and 65 parts of dense component by weight.
6. The concrete corrosion-proof rust-proof composite additive according to any one of claims 1 to 3, wherein the corrosion-proof components comprise, in parts by weight: BaCO320-25 parts of anhydrite and 75-80 parts of gypsum.
7. The concrete corrosion-resistant rust-resistant composite additive according to claim 6, wherein the corrosion-resistant components comprise, in parts by weight: BaCO325 parts of anhydrite and 75 parts of gypsum.
8. The concrete corrosion-proof rust-proof composite additive according to any one of claims 1-3, wherein the dense components comprise, in parts by weight: 72-85 parts of metakaolin and 15-28 parts of silica fume.
9. The concrete corrosion-resistant rust-resistant composite additive according to claim 8, wherein the dense components comprise, in parts by weight: 80 parts of metakaolin and 20 parts of silica fume.
10. A preparation method of the composite concrete corrosion-proof and rust-proof additive as claimed in claim 1, which is characterized in that the corrosion-proof component, the anticorrosion component and the dense component are prepared and weighed, and then the mixture is slowly stirred for 5-15min at 35-50r/min, and finally the mixture is rapidly stirred for 10-15min at 70-100r/min to prepare a finished product.
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Cited By (3)
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CN114105512A (en) * | 2021-12-22 | 2022-03-01 | 中冶华南建设工程有限公司 | Concrete corrosion and rust inhibitor for cast-in-place pile and application thereof and cast-in-place pile |
CN115893894A (en) * | 2022-11-01 | 2023-04-04 | 桂林理工大学 | Chloride ion curing agent for sea sand concrete and preparation method thereof |
CN115893894B (en) * | 2022-11-01 | 2024-07-09 | 桂林理工大学 | Chloride ion curing agent for sea sand concrete and preparation method thereof |
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