CN103937300A - Anticorrosion treatment method for cooling tower metal parts and coating used in anticorrosion treatment method - Google Patents
Anticorrosion treatment method for cooling tower metal parts and coating used in anticorrosion treatment method Download PDFInfo
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Abstract
The invention discloses a preparation method of an organic-inorganic hybrid anticorrosion coating. The preparation method is characterized by comprising the following steps: 1) adding a silane coupling agent I to an ethanol/water mixed solution, adjusting the pH to 3-6 and then reacting at 25-50 DEG C for 3-12 hours to obtain silica sol; 2) adding a silane coupling agent II to boehmite sol, reacting at 50-100 DEG C for 0.5-2 hours, and drying solid particles to obtain silane coupling agent modified boehmite solid particles; 3) adding the silane coupling agent modified boehmite solid particles to the silica sol, and mixing evenly to form the transparent organic-inorganic hybrid anticorrosion coating. The invention also discloses an anticorrosion treatment method for cooling tower metal parts; the anticorrosion treatment method comprises the steps of coating a metal part with the organic-inorganic hybrid anticorrosion coating, and curing for 0.5-1 hour at 100-150 DEG C so as to form an anticorrosion layer on the surface of the metal part.
Description
Technical field
The invention belongs to cooling tower hardware anti-corrosive treatment field; Be specifically related to the preparation method of anti-corrosive treatment method and the inorganic-organic hybridization nano anticorrosive coating used of cooling tower hardware.
Background technology
Cooling tower is the common equipment in industrial circulating water, is usually used in the fields such as Steel Plant, printing and dyeing mill, Medicine Factory, nuclear power plant, air-conditioning, freezer and chemical fibre, oil.In cooling tower structure, have a lot of hardwares, as steel structure framework, water inlet pillar, motor, blower fan, motor sub-frame, broadcast head, broadcast water pipe, screw, bolt etc.But owing to often containing acidity, alkalescence or salt component material in the water of cooling tower processing, their can corroding metal member, shorten cooling tower work-ing life, cause the raising of the wasting of resources and use cost.Based on this, people improve the novel method of hardware Corrosion Protection in cooling tower in active research.
In patent 202928388, related to a kind of novel anticorrosion cooling tower, in its tower, steel structure framework designs in glass reinforced plastic outside, thereby avoids the direct contact of acidic substance to steel construction, and steel structure surface has also applied polymer fluorocarbon coating simultaneously.This method can extend the work-ing life of steel construction, but it does not relate to the rotproofing to other hardware in cooling tower, and polymer fluorocarbon coating is expensive simultaneously, can increase the price of cooling tower.
In patent 203487820, related to the method for anticorrosion treatment of steel construction in a kind of cooling tower, but its corrosion protection coating do not inform yet, in this section of patent, do not relate to cooling tower simultaneously yet in the rotproofing of other hardware.
In patent 201865970, relate to a kind of blower fan of cooling tower, for improving the resistance to fog corrosive nature of blower fan, applied one deck galvanized anticorrosive layer at fan blade, hub surface.This method can improve the antifog gas corrosion performance of blower fan to a certain extent, if but contain acid, alkali or salt component in fog, the Corrosion Protection of zinc coating or inadequate.
At present, the method of preparing one deck hybrid inorganic-organic erosion shield by sol-gel technique in metallic surface more and more attracts people's attention, its preparation process is simple, nontoxic, pollution-free, applied widely, cost is low, is better than traditional technique such as phosphatization, chromaking at the preservative effect of metallic surface.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of anti-corrosive treatment method and inorganic-organic hybridization nano anticorrosive coating used of cooling tower hardware.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of inorganic-organic hybridization nano anticorrosive coating, comprise the steps:
1), in ethanol/water mixing solutions, add silane coupling agent I, after regulating pH to be 3～6, in 25～50 DEG C of reaction 3～12h, formation silicon sol;
The weight ratio of described ethanol/water mixing solutions and silane coupling agent I is 100:20～50 (being preferably 100:30～40);
In described ethanol/water mixing solutions, the weight ratio of ethanol and water is 100:2～5;
Remarks explanation: the regulative mode of above-mentioned pH belongs to routine techniques, for example can adopt mass concentration is that 10% HCl solution carries out the adjusting of pH;
2), in boehmite sol, add silane coupling agent II, in 50～100 DEG C (being preferably 50～70 DEG C) reaction 0.5～2 hour, filter, collect solid particulate, and under room temperature vacuum-drying to constant weight; Obtain silane coupler modified boehmite solid particulate;
Described boehmite sol is that particle diameter is that 10～50nm (being preferably 20～50nm), solid content are the boehmite sol (for water nano particle colloidal sols) of 20～40% (% by weight); The weight ratio of described silane coupling agent II and boehmite sol is 1～0.2:1;
3), by step 2) the silane coupler modified boehmite solid particulate of gained joins step 1) in the silicon sol of gained, mix, thereby form transparent inorganic-organic hybridization nano protective system;
The weight ratio of described silane coupler modified boehmite solid particulate and silicon sol is 0.01～0.2:1 (being preferably 0.05～0.2:1).
Improvement as the preparation method of inorganic-organic hybridization nano anticorrosive coating of the present invention:
Silane coupling agent I is tetraethoxy, methyltrimethoxy silane, Union carbide A-162, n-propyl triethoxyl silane, dodecyl Trimethoxy silane, APTES, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, two-(trimethoxy-silylpropyl) amine, two-(triethoxysilylpropyltetrasulfide) amine, 1, two (trimethoxy the is silica-based) ethane of 2-, 3, 3, 3-trifluoro propyl triethoxyl silane, at least one in ten difluoro heptyl propyl trimethoxy silicanes,
Silane coupling agent II is methyltrimethoxy silane, Union carbide A-162, n-propyl triethoxyl silane, dodecyl Trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, 1, the one in two (trimethoxy the is silica-based) ethane of 2-.
The present invention also provides the anti-corrosive treatment method that utilizes the cooling tower hardware that above-mentioned inorganic-organic hybridization nano anticorrosive coating carries out simultaneously: inorganic-organic hybridization nano anticorrosive coating is coated on to metal component surface (can adopt the mode such as dip-coating or spraying), and in 100～150 DEG C solidify 0.5～1 hour, thereby metal component surface form corrosion-resistant finishes.
Improvement as the anti-corrosive treatment method of cooling tower hardware of the present invention: controlling coat-thickness is 20～50 microns.
In the present invention, room temperature refers to 15～25 DEG C.
The preparation of inorganic-organic hybridization nano anticorrosive coating of the present invention relates to sol-gel technique and nano-particles filled technology.
In the present invention, hardware refers to the parts such as steel structure framework in cooling tower, water inlet pillar, motor, blower fan, motor sub-frame, drying head, drying pipe, screw, bolt.
Be greater than 5H (by GB/T6739-1996 test) through coating of the present invention hardware hardness after treatment; 30 days coatings unchanged (pressing GB/T10125-1997 test) of resistance to neutral salt spray; At 5% (weight ratio) H
2sO
4in solution, soak 10 days coatings unchanged; In 0.4% (weight ratio) NaOH solution, soak 10 days coatings unchanged.
Given this, the present invention is using inorganic-organic hybridization nano anticorrosive coating as a kind of erosion shield, for cooling tower metal component surface.
The present invention has following beneficial effect:
1, coating takes sol-gel technique and nano-particles filled technology to be prepared from, and its technique is simple, and reaction conditions gentleness is not used human body and the poisonous and hazardous raw material of environment, pollutes little;
2, coating is transparent, does not affect outward appearance and the gloss of protected metal;
3, coating hardness is high, corrosion resistance nature is strong, the service life of energy significant prolongation cooling tower hardware.
Embodiment
The preparation method of embodiment 1, inorganic-organic hybridization nano anticorrosive coating, carries out following steps successively:
1), in water/ethanol (2g/100g) mixing solutions, add 22g tetraethoxy, 5.2g gamma-mercaptopropyltriethoxysilane, 10.4g methyltrimethoxy silane, utilizing concentration is that 10% HCl solution regulates pH=5～6, in 25 DEG C of reactions 12 hours, obtain silicon sol.
2), at 100g boehmite sol (particle diameter 20nm, solid content 20%) in add γ-(methacryloxypropyl) propyl trimethoxy silicane of 50g, in 50 DEG C of reactions 0.5 hour, filter, collect solid particulate, and under room temperature vacuum-drying to constant weight; Obtain the boehmite solid particulate of silane coupling agent surface modification.
3), by step 2) the boehmite solid particulate (10g) of the silane coupling agent surface modification prepared joins step 1) in the silicon sol (100g) prepared, mix, form transparent inorganic-organic hybridization nano protective system.
Test 1, take spraying method that the inorganic-organic hybridization nano anticorrosive coating of embodiment 1 gained is coated on to cooling tower steel structure framework surface, controlling coat-thickness is 20 microns; And in 120 DEG C solidify 1 hour, thereby form erosion shield.
Detected result is as follows: coating hardness 7H (pressing GB/T6739-1996 test); 30 days coatings unchanged (pressing GB/T10125-1997 test) of resistance to neutral salt spray; At 5% (weight ratio) H
2sO
4in solution, soak 10 days coatings unchanged; In 0.4% (weight ratio) NaOH solution, soak 10 days coatings unchanged.
Comparative example 1-1, cancel the step 2 of embodiment 1), and accordingly by step 3) in " silane coupler modified boehmite solid particulate " make boehmite (particle diameter 20nm) into, weight is constant; All the other contents are with embodiment 1.
Comparative example 1-2, by embodiment 1 step 2) in " in 50 DEG C reaction 0.5 hour " make into " and in 30 DEG C reaction 3 hours "; All the other contents are with embodiment 1.
Comparative example 1-3, by embodiment 1 step 2) in " in 50 DEG C reaction 0.5 hour " make into " and in 120 DEG C reaction 0.5 hour "; All the other contents are with embodiment 1.
Comparative example 1-4, by embodiment 1 step 3) in the consumption of boehmite solid particulate of silane coupling agent surface modification make 0.8g into by 10g; All the other contents are with embodiment 1.
Comparative example 1-5, by embodiment 1 step 3) in the consumption of boehmite solid particulate of silane coupling agent surface modification make 25g into by 10g; All the other contents are with embodiment 1.
Comparative example 1-6, by embodiment 1 step 2) in " adding γ-(methacryloxypropyl) propyl trimethoxy silicane of 50g " make into " adding γ-(methacryloxypropyl) propyl trimethoxy silicane of 15g "; All the other contents are with embodiment 1.
Comparative example 1-7, by embodiment 1 step 2) in " adding 50g γ-(methacryloxypropyl) propyl trimethoxy silicane " make into " adding 110g γ-(methacryloxypropyl) propyl trimethoxy silicane "; All the other contents are with embodiment 1.
The coating of above-mentioned comparative example 1-1～comparative example 1-7 gained is detected according to experiment 1, and acquired results is as shown in table 1.
Table 1
Comparative example 1-8, " 120 DEG C solidify 1 hour " by experiment in 1 are made " 50 DEG C solidify 8 hours " into, and all the other are with experiment 1.
Comparative example 1-9, " 120 DEG C solidify 1 hour " by experiment in 1 are made " 200 DEG C solidify 2 hours " into, and all the other are with experiment 1.
Acquired results is as shown in table 2 below:
Table 2
The preparation method of embodiment 2, inorganic-organic hybridization nano anticorrosive coating, carries out following steps successively:
1), in water/ethanol (5g/100g) mixing solutions, add 22g tetraethoxy, 5.2g1, two (trimethoxy the is silica-based) ethane of 2-, 10.4g methyltrimethoxy silane, utilizing concentration is that 10% HCl solution regulates pH=4～5, in 50 DEG C of reactions 3 hours, obtain silicon sol.
2), in 100g boehmite sol (particle diameter 50nm, solid content 40%), add 100g vinyltrimethoxy silane, in 70 DEG C of reactions 0.5 hour, solid collected by filtration particle, and under room temperature vacuum-drying to constant weight; Obtain the boehmite solid particulate of silane coupling agent surface modification.
3), by step 2) the boehmite solid particulate (20g) of preparing the silane coupling agent surface modification of gained joins step 1) prepare in the silicon sol (100g) of gained, mix, form transparent inorganic-organic hybridization nano protective system.
Test 2, take spraying method that the inorganic-organic hybridization nano anticorrosive coating of embodiment 2 gained is coated on to blower fan of cooling tower blade (aluminium alloy) surface, controlling coat-thickness is 20 microns; And in 100 DEG C solidify 1.0 hours, form erosion shield.
Detected result is as follows:
Coating hardness 6H (pressing GB/T6739-1996 test); 30 days coatings unchanged (pressing GB/T10125-1997 test) of resistance to neutral salt spray; At 5% (weight ratio) H
2sO
4in solution, soak 10 days coatings unchanged; In 0.4% (weight ratio) NaOH solution, soak 10 days coatings unchanged.
The preparation method of embodiment 3, inorganic-organic hybridization nano anticorrosive coating, carries out following steps successively:
1), in water/ethanol (3g/100g) mixing solutions, add 22g tetraethoxy, 1 of 5.2g, two (trimethoxy the is silica-based) ethane of 2-, γ-glycidyl ether oxygen propyl trimethoxy silicane of 10.4g, utilizing concentration is that 10% HCl solution regulates pH=4～5, in 30 DEG C of reactions 10 hours, obtain silicon sol.
2), in 100g boehmite sol (particle diameter 40nm, solid content 35%), add 80g n-propyl triethoxyl silane, in 60 DEG C of reactions 2 hours, filter, collect solid particulate, and vacuum-drying, to constant weight, obtains the boehmite solid particulate of silane coupling agent surface modification under room temperature.
3), by step 2) the boehmite solid particulate (5g) of preparing the silane coupling agent surface modification of gained joins step 1) prepare in the silicon sol (100g) of gained, mix, form transparent inorganic-organic hybridization nano protective system.
Experiment 3,
The inorganic-organic hybridization nano anticorrosive coating of embodiment 3 gained is coated on to fan wheel hub for cooling tower (zinc alloy) surface, control coat-thickness be 35 microns, and in 150 DEG C solidify 0.5 hour, form erosion shield.
Detected result is as follows:
Coating hardness 6H (pressing GB/T6739-1996 test); 30 days coatings unchanged (pressing GB/T10125-1997 test) of resistance to neutral salt spray; At 5% (weight ratio) H
2sO
4in solution, soak 10 days coatings unchanged; In 0.4% (weight ratio) NaOH solution, soak 10 days coatings unchanged.
The preparation method of embodiment 4, inorganic-organic hybridization nano anticorrosive coating, carries out following steps successively:
1), in water/ethanol (2g/100g) mixing solutions, add 18g tetraethoxy, 1 of 5.2g, two (trimethoxy the is silica-based) ethane of 2-, 10.4g dodecyl Trimethoxy silane, 2g Union carbide A-162, utilizing concentration is that 10% HCl solution regulates pH=4～5, in 25 DEG C of reactions 12 hours, obtains silicon sol.
2), in 100g boehmite sol (particle diameter 50nm, solid content 40%), add 1 of 20g, two (trimethoxy the is silica-based) ethane of 2-, in 70 DEG C of reactions 0.5 hour, filter, collect solid particulate, and under room temperature vacuum-drying to constant weight; Obtain the boehmite solid particulate of silane coupling agent surface modification.
3), by step 2) the boehmite solid particulate (5g) of preparing the silane coupling agent surface modification of gained joins step 1) in preparation in silicon sol (100g), mix, form transparent inorganic-organic hybridization nano protective system.
Experiment 4,
Take spraying method that the inorganic-organic hybridization nano anticorrosive coating of embodiment 4 gained is coated on to cooling tower water inlet pillar (pot galvanize) surface, controlling coat-thickness is 50 microns; And in 150 DEG C solidify 0.5 hour, form erosion shield.
Detected result is as follows:
Coating hardness 7H (pressing GB/T6739-1996 test); 30 days coatings unchanged (pressing GB/T10125-1997 test) of resistance to neutral salt spray; At 5% (weight ratio) H
2sO
4in solution, soak 10 days coatings unchanged; In 0.4% (weight ratio) NaOH solution, soak 10 days coatings unchanged.
The preparation method of embodiment 5, inorganic-organic hybridization nano anticorrosive coating, carries out following steps successively:
1), in water/ethanol (2g/100g) mixing solutions, add 18g tetraethoxy, 5.2g1, two (trimethoxy the is silica-based) ethane of 2-, 10.4g dodecyl Trimethoxy silane, γ-(methacryloxypropyl) propyl trimethoxy silicane of 2g, utilizing concentration is that 10% HCl solution regulates pH=3～4, in 25 DEG C of reactions 12 hours, obtains silicon sol.
2), in 100g boehmite sol (particle diameter 50nm, solid content 40%), add 100g Union carbide A-162, in 70 DEG C of reactions 0.5 hour, filter, collect solid particulate, and under room temperature vacuum-drying to constant weight; Obtain the boehmite solid particulate of silane coupling agent surface modification.
3), by step 2) the boehmite solid particulate (15g) of preparing the silane coupling agent surface modification of gained joins step 1) prepare in the silicon sol (100g) of gained, mix, form transparent inorganic-organic hybridization nano protective system.
Experiment 5,
Take spraying method that the inorganic-organic hybridization nano anticorrosive coating of embodiment 5 gained is coated on to cooling tower drying rotary head (copper alloy) surface, controlling coat-thickness is 40 microns; And in 150 DEG C solidify 0.5 hour, form erosion shield.
Detected result is as follows:
Coating hardness 8H (pressing GB/T6739-1996 test); 30 days coatings unchanged (pressing GB/T10125-1997 test) of resistance to neutral salt spray; At 5% (weight ratio) H
2sO
4in solution, soak 10 days coatings unchanged; In 0.4% (weight ratio) NaOH solution, soak 10 days coatings unchanged.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (4)
1. the preparation method of inorganic-organic hybridization nano anticorrosive coating, is characterized in that comprising the steps:
1), in ethanol/water mixing solutions, add silane coupling agent I, after regulating pH to be 3～6, in 25～50 DEG C of reaction 3～12h, formation silicon sol;
The weight ratio of described ethanol/water mixing solutions and silane coupling agent I is 100:20～50;
In described ethanol/water mixing solutions, the weight ratio of ethanol and water is 100:2～5;
2), in boehmite sol, add silane coupling agent II, in 50～100 DEG C of reactions 0.5～2 hour, filter, collect solid particulate, and under room temperature vacuum-drying to constant weight; Obtain silane coupler modified boehmite solid particulate;
Described boehmite sol is that particle diameter is the boehmite sol that 10～50nm, solid weight content are 20～40%; The weight ratio of described silane coupling agent II and boehmite sol is 1～0.2:1;
3), by step 2) the silane coupler modified boehmite solid particulate of gained joins step 1) in the silicon sol of gained, mix, thereby form transparent inorganic-organic hybridization nano protective system;
The weight ratio of described silane coupler modified boehmite solid particulate and silicon sol is 0.01～0.2:1.
2. the preparation method of inorganic-organic hybridization nano anticorrosive coating according to claim 1, is characterized in that:
Silane coupling agent I is tetraethoxy, methyltrimethoxy silane, Union carbide A-162, n-propyl triethoxyl silane, dodecyl Trimethoxy silane, APTES, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, two-(trimethoxy-silylpropyl) amine, two-(triethoxysilylpropyltetrasulfide) amine, 1, two (trimethoxy the is silica-based) ethane of 2-, 3, 3, 3-trifluoro propyl triethoxyl silane, at least one in ten difluoro heptyl propyl trimethoxy silicanes,
Silane coupling agent II is methyltrimethoxy silane, Union carbide A-162, n-propyl triethoxyl silane, dodecyl Trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, 1, the one in two (trimethoxy the is silica-based) ethane of 2-.
3. utilize the anti-corrosive treatment method of the cooling tower hardware that inorganic-organic hybridization nano anticorrosive coating carries out as claimed in claim 1 or 2, it is characterized in that: inorganic-organic hybridization nano anticorrosive coating is coated on to metal component surface, and in 100～150 DEG C solidify 0.5～1 hour, thereby metal component surface form corrosion-resistant finishes.
4. the anti-corrosive treatment method of cooling tower hardware according to claim 3, is characterized in that: controlling coat-thickness is 20～50 microns.
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| CN109957111A (en) * | 2017-12-25 | 2019-07-02 | 中国科学院上海硅酸盐研究所 | A kind of self-curing anticorrosive metal hydridization silica solution and the preparation method and application thereof |
| CN110563366A (en) * | 2019-10-17 | 2019-12-13 | 上海大学 | biphase organic-inorganic hybrid silica sol, and preparation method and application thereof |
| CN110563366B (en) * | 2019-10-17 | 2021-10-12 | 上海大学 | Biphase organic-inorganic hybrid silica sol, and preparation method and application thereof |
| CN116656230A (en) * | 2022-02-19 | 2023-08-29 | 湖北唯吾新材料科技有限公司 | Preparation method of water-based normal-temperature self-drying organic silicon multi-hybrid resin |
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Application publication date: 20140723 |