CN102337049B - Corrosion-resistant and anti-scaling paint used for aqueous medium heat exchange equipment and preparation method of corrosion-resistant and anti-scaling paint. - Google Patents
Corrosion-resistant and anti-scaling paint used for aqueous medium heat exchange equipment and preparation method of corrosion-resistant and anti-scaling paint. Download PDFInfo
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- CN102337049B CN102337049B CN2010102378609A CN201010237860A CN102337049B CN 102337049 B CN102337049 B CN 102337049B CN 2010102378609 A CN2010102378609 A CN 2010102378609A CN 201010237860 A CN201010237860 A CN 201010237860A CN 102337049 B CN102337049 B CN 102337049B
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Abstract
The invention relates to a corrosion-resistant and anti-scaling nano-titanium paint and a preparation method thereof, in particular to a corrosion-resistant and anti-scaling paint used for aqueous medium heat exchange equipment and a preparation method of the corrosion-resistant and anti-scaling paint. The corrosion-resistant and anti-scaling paint is prepared through three main processing steps of nano-titanium powder pretreatment, epoxy resin modification and paint preparation by adopting nano-titanium powder, a pre-treating agent, epoxide resin, acrylic acid, bisphenol-S epoxy resin or glycidyl ester type epoxy resin or glycidyl amine type epoxy resin, an organic solvent, amino-silicone oil or an organofluorine reagent and distilled water, and has the advantages of corrosion and scaling resistance, capabilities of improving the heat transfer efficiency and prolonging the service life of the heat exchange equipment and the like.
Description
Technical field
The present invention relates to a kind of corrosion-resistant, ant-scaling nano-titanium coating and preparation method thereof, a kind of water medium heat-exchange equipment is with protection against corrosion ant-scaling coating and preparation method thereof specifically.
Background technology
In heating, cooling heat exchanger, plate-type heat-exchange equipment is little owing to having volume, the characteristics such as exchange capability of heat is strong are widely used in mine, metallurgy, oil, chemical industry, machinery, electric power, medicine, food, light textile, papermaking, boats and ships, ocean exploitation and people's daily life.Water often uses as a kind of heat exchange medium as fluid cheap and easy to get, yet owing to can dissolve different kinds of ions in the water, the water quality that is used for heat exchange is usually complicated, be easy to cause heat-exchange equipment corrosion and fouling, thereby reduce the equipment heat exchange efficiency or destroy heat-exchange equipment.Even adopt the stainless steel heat exchanger plates, corrosion and fouling also are that inevitably Corrosion of Stainless Steel mainly is that the chlorion in the solution causes stainless spot corrosion, and the generation of spot corrosion will directly cause the perforation of heat exchanger plates to be lost efficacy.In addition, the stainless steel part, optionally, the corrosion that occurs from the crystal boundary area, the bonding force of intergranule is damaged, also be the very large corrosion failure form of a kind of hazardness.These corrosion cause the stainless steel heat exchanger plates greatly to shorten work-ing life, only have 1-2.Like this, annual replacing heat exchanger plates has also caused the waste of the energy so that cost rises.In order to solve etching problem, enterprise generally adopts pure titanium plate as interchanger sheet material, and the titanium plate has excellent corrosion resisting property, can be provided long work-ing life, but material cost is too high, and can not antiscale, needs routine cleaning or adds Scale inhibitors and increase production cost.Coating and coating technology are a kind of simple and easy to do, effective technological approaches.But the prior art effect is undesirable.Be that ordinary resin and additive in the coating can play protective effect though trace it to its cause in the environment of interchanger harshness, impact is conducted heat, and antiscaling effect is unstable; Although and metal plating conducts heat, its protective effect to matrix in the environment of interchanger harshness is relatively poor, and the antiscale ability is also relatively poor.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming and defect of prior art, a kind of water medium plate-type heat-exchange equipment protection against corrosion ant-scaling coating is provided, this coating is a kind of nano paint, after applying the metal sheet of plate-type heat exchanger, should play protection against corrosion, ant-scaling effect, also not affect the heat transfer efficiency of interchanger.This coating is a kind of two-dimensional nano titanium modified epoxy resin paint, that utilizes the lamella titanium valve stackedly stops the intrusion that suppresses corrosive medium with passivation, utilize the effective overlap joint between the titanium valve that preferably heat-transfer effect is provided, utilize the organic resin of modification to obtain bonding force and the self-cleaning ability good with matrix, realize that coating technology is to the protection of metallic matrix heat exchanger plates, the ant-scaling effect increases the service life effectively.
The object of the present invention is achieved like this, and the raw material of this coating forms with the weight proportion of each raw material as follows:
Nano titanium powder: 40～45 parts,
Pretreating agent: 6 parts,
Resins, epoxy: 18～20 parts,
Vinylformic acid: 2～4 parts,
Bisphenol-s epoxy resin or glycidyl ester based epoxy resin or Racemic glycidol amine epoxy resin: 12～15 parts,
Organic solvent: 4 parts,
Amido silicon oil or organic fluorine reagent: 3～5 parts,
Distilled water: 6 parts;
The preparation method is:
The planetary ball mill of packing into after at first nano titanium powder and pretreating agent being mixed carries out pre-treatment to nano titanium powder, obtains the titanium valve slurry, makes the nano titanium powder surface parcel one deck organo-functional group after the processing, can be good at being scattered in the modified epoxy resin paint; Next is to carry out epoxy resin modification, obtains modified resin; With amido silicon oil or organic fluorine reagent modified resin is carried out modification again; Coating preparation at last, with the titanium valve slurry that obtains after the pre-treatment and the Resins, epoxy after the modification according to 1: the 1-1.2 mass ratio mixes, and under strong stirring, adds distilled water again and transfers to and need viscosity, continuation namely made coating of the present invention at ultrasonic auxiliary powerful mechanical stirring 1-3 hour.
It is characterized in that:
A, described nano titanium powder are sheet, diameter＜10 μ m, and thickness is about 100nm;
B, described pretreating agent are a kind of mixtures, and by in Surfactant OP-10, polysorbate60 or the tween 80 one or more, one or more in furfuryl resin or the aminoresin, phthalic acid diisobutyl ester mix, wherein
Promoting agent OP-10, polysorbate60 or tween 80: 2 parts
2 parts in furfuryl resin or aminoresin
2 parts of phthalic acid diisobutyl esters;
C, described Resins, epoxy are any or multiple among E-44, E-42, E-35, E-31, the E-20;
D, described organic solvent are a kind of mixed solvents, by one or both mixtures in toluene, dimethylbenzene, propyl carbinol, n-Octanol, the ethyl acetate;
E, described resol are any in bisphenol-s epoxy resin, the epoxidation lacquer resins, described glycidyl ester based epoxy resin is any among 711#, 731#, the 732#, and described Racemic glycidol amine epoxy resin is any among AG-80, the AFG-90;
F, described organic fluorine reagent are any among WRS series, 3585 series, AG-710,3589, TG-421, TG-527, the EC50.
A kind of water medium heat-exchange equipment is as follows with the concrete steps of protection against corrosion ant-scaling preparation method for coating:
1., nano titanium powder pre-treatment
Adopt physico-chemical process to process nano titanium powder, the nano titanium powder surface parcel one deck organo-functional group after the processing can be good at being scattered in the modified epoxy resin paint, makes coating quality more even.With pretreating agent and nano titanium powder according to mass ratio 1: 5-10 mixes, and compound changes in the planetary ball mill, and stocking volume is 50-85%, passes into protective gas after 10 minutes ball milling 3-5 hour, the titanium valve slurry after both having obtained processing; Described nano titanium powder is sheet, diameter＜10 μ m, and thickness is about 100nm; Described pretreating agent is a kind of mixture, by in Surfactant OP-10, tween 80, the polysorbate60 one or more, a kind of in furfuryl resin, the aminoresin, phthalic acid diisobutyl ester, mix Deng mass ratio, protective gas is nitrogen or argon gas;
2., epoxy resin modification
The sticking power of Resins, epoxy on metallic matrix is low; weakened the protection to metallic matrix; and resistance to elevated temperatures is relatively poor; need to make improvements with applicable heat-exchange equipment application; in addition; Resins, epoxy need to an organic solvent be allocated viscosity, can discharge obnoxious flavour in the construction use procedure human body is damaged, and needs to lack with an organic solvent as far as possible.Therefore, the present invention at first selects in resol, glycidyl ester type of epoxy resin, the glycidyl amine type of epoxy resin one or both that Resins, epoxy is carried out modification, obtains modified resin; With amido silicon oil or organic fluorine reagent the modified resin of upper step is carried out modification again; Concrete grammar is: the Resins, epoxy of getting the 40-55 mass parts, the vinylformic acid of 5-10 mass parts, in the resol of 30-45 mass parts, glycidyl ester type of epoxy resin, the glycidyl amine type of epoxy resin one or both, be dissolved in the organic solvent of 5-10 mass parts, in the time of 45-80 ℃, Resins, epoxy is carried out modification, then add amido silicon oil or the organic fluorine reagent of 5-15 mass parts, in the time of 60-105 ℃, carry out modification, obtain modified epoxy; Described organic solvent is a kind of mixed solvent, by one or both mixtures in toluene, dimethylbenzene, propyl carbinol, n-Octanol, the ethyl acetate; Described Resins, epoxy is any or multiple among E-44, E-42, E-35, E-31, the E-20; Described resol can be any in bisphenol-s epoxy resin, the epoxidation lacquer resins; Described glycidyl ester based epoxy resin can be any among 711#, 731#, the 732#; Described Racemic glycidol amine epoxy resin can be any among AG-80, the AFG-90; Described organic fluorine reagent can be any among WRS series, 3585 series, AG-710,3589, TG-421, TG-527, the EC 50;
3., coating preparation
With step 1. product and step 2. product according to 1: the 1-1.2 mass ratio mixes, and under strong stirring, adds distilled water again and transfers to and need viscosity, continues at ultrasonic auxiliary powerful mechanical stirring 1-3 hour, namely makes coating of the present invention, barrelling.
The using method of coating of the present invention is: at first, the interchanger metal sheet is carried out derusting by sandblast, dimethylbenzene scouring except the wet goods step process, dry; Then, adopt the mode of spraying or brushing to apply heat exchanger plate with this coating; At last, the heat exchanger plate that applies this coating is placed in the baking oven, 180 ℃ of lower bakings 0.5 hour, naturally be down to room temperature and get final product.
Advantage of the present invention and positively effect:
1, the present invention adopts physico-chemical process to process nano titanium powder, and the nano titanium powder surface parcel one deck organo-functional group after the processing can be good at being scattered in the modified epoxy resin paint, makes coating quality more even.
2, the titanium valve of the sheet of the present invention's employing, diameter＜10 μ m, thickness is 100nm, can be arranged in parallel in coating, forms the protective barrier of multilayer, effectively stops the infiltration of corrosive medium.The good passivation of nano titanium powder also can make the coating formation passivation layer simultaneously, further suppresses the generation of corrosion.Select suitable film-forming resin, can improve by modification the self-cleaning ability of coating, reduce to a certain extent the generation of fouling.The each other overlap joint of sheet titanium valve can form complete thermally conductive pathways, can be as pure organic coating the thermal conductivity of decrease heat exchanger plates.
Like this, in stainless steel plate external coating two-dimensional nano titanium coating, just can improve the performances such as stainless anti-corrosion, ant-scaling; The thin thickness of coating is compared with pure titanium, can significantly reduce cost.
3, heat transfer efficiency is high, coating of the present invention has overcome the low shortcoming of other corrosion resistant coating heat transfer efficiency, coating is tens micron thickness only, the each other overlap joint of sheet titanium valve in coating, can form complete thermally conductive pathways, in addition, the resin after the modification also capacity of heat transmission than Resins, epoxy before the modification is high, so this dope layer can be as pure organic coating the thermal conductivity of decrease heat exchanger plates, can guarantee that efficiency of heat exchanger and metallic matrix approach.
4, corrosion resistance is strong, and the resin after the modification of the present invention and metallic matrix bonding force are strong, the sheet titanium valve of interpolation, diameter＜10 μ m, thickness is 100nm, can be arranged in parallel in coating, form the protective barrier of multilayer with modified resin, effectively stop the infiltration of corrosive medium.The good passivation of nano titanium powder also can make the coating formation passivation layer simultaneously, further suppresses the generation of corrosion.
5, high temperature resistant and the resisting temperature changing capability is strong, the present invention adopts modified resin, under 200 ℃ of temperature, in the time of difference variation 50-100 ℃, also peeling, obscission can not occur.
6, has good good antiscale property effect, select suitable film-forming resin, can improve by modification the self-cleaning ability of coating, make and be detained the underlayer thickness attenuation, and reduced the chance of scale-forming ion compound in the fouling of plate surface crystallization, reduce to a certain extent the generation of fouling.
7, energy-conserving and environment-protective, the present invention replaces the part organic solvent with water as solvent, reduced the use of organic solvent, when applying and use interchanger, reduced the harm of organic solvent volatilization to environment and workman's health, and, this nano coating of heat exchanger plate application, can improve the corrosion resisting property of plate, prolong the work-ing life of interchanger; Improve interchanger ant-scaling ability, keep interchanger to have for a long time higher heat exchange efficiency, save energy.In addition, behind the common plate application coating of the present invention, can replace the high anti-corrosion plate of pure titanium plate or other prices, significantly reduce the interchanger production cost.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment the present invention is described further, but the scope of protection of present invention not only is confined to the scope that illustrates among the embodiment.
Embodiment 1
The mass fraction of each component of coating is:
Nano titanium powder: 40;
Pretreating agent: 6 (wherein: OP-10,2; Furfuryl resin, 2; The phthalic acid diisobutyl ester, 2);
Epoxy resin E-44: 20;
Vinylformic acid: 4;
Bisphenol-s epoxy resin: 15;
Organic solvent: 4 (wherein: toluene, 2; N-Octanol, 2);
Amido silicon oil: 5;
Distilled water: 6;
The preparation method is: with the planetary ball mill of packing into after titanium valve and the pretreating agent mixing, passed into nitrogen 10 minutes, rear ball milling 3-5 hour of sealing obtains the titanium valve slurry; In the time of 45-80 ℃, carry out modification after epoxy resin E-44, vinylformic acid, bisphenol-s epoxy resin, organic solvent mixed, and then add amido silicon oil and in the time of 60-105 ℃, proceed modification, obtain modified resin; Mechanical stirring under 1500-2500 rev/min of rotating speed is mixed with titanium valve slurry and modified resin, adds distilled water, and ultrasonic wave is auxiliary to be stirred 1-3 hour.Obtain the anticorrosion ant-scaling coating 1 of the present invention.
Embodiment 2
The mass fraction of each component of coating is:
Nano titanium powder: 40;
Pretreating agent: 6 (wherein: tween 80,2; Aminoresin, 2; The phthalic acid diisobutyl ester, 2);
Resins, epoxy E-42:20;
Vinylformic acid: 4;
Glycidyl ester based epoxy resin 711#:15;
Organic solvent: 4 (wherein: dimethylbenzene, 2; Propyl carbinol, 2);
Organic fluorine reagent E C-50:5;
Distilled water: 6;
The preparation method is with example 1.Obtain the anticorrosion ant-scaling coating 2 of the present invention.
Embodiment 3
The mass fraction of each component of coating is:
Nano titanium powder: 45;
Pretreating agent: 6 (wherein: tween 80,2; Aminoresin, 2; The phthalic acid diisobutyl ester, 2);
Resins, epoxy E-35:18;
Vinylformic acid: 2;
Glycidyl ester based epoxy resin 732#:12;
Organic solvent: 4 (wherein: dimethylbenzene, 2; Ethyl acetate, 2);
Organic fluorine reagent A G-710:5;
Distilled water: 8;
The preparation method is with example 1.Obtain the anticorrosion ant-scaling coating 3 of the present invention.
Embodiment 4
The mass fraction of each component of coating is:
Nano titanium powder: 45;
Pretreating agent: 6 (wherein: polysorbate60,2; Furfuryl resin, 2; The phthalic acid diisobutyl ester, 2);
Resins, epoxy E-31:18;
Vinylformic acid: 2;
Glycidyl ester based epoxy resin 711#:15;
Organic solvent: 4 (wherein: dimethylbenzene, 2; Propyl carbinol, 2);
Amido silicon oil: 5;
Distilled water: 5;
The preparation method is with example 1.Obtain the anticorrosion ant-scaling coating 4 of the present invention.
Embodiment 5
The mass fraction of each component of coating is:
Nano titanium powder: 40;
Pretreating agent: 6 (wherein: tween 80,2; Aminoresin, 2; The phthalic acid diisobutyl ester, 2);
Resins, epoxy E-20:20;
Vinylformic acid: 4;
Racemic glycidol amine epoxy resin AG-80:15;
Organic solvent: 4 (wherein: dimethylbenzene, 2; Ethyl acetate, 2);
Amido silicon oil: 5;
Distilled water: 6;
The preparation method is with example 1.Obtain the anticorrosion ant-scaling coating 5 of the present invention.
Embodiment 6
The mass fraction of each component of coating is:
Nano titanium powder: 44;
Pretreating agent: 6 (wherein: OP-10,2; Furfuryl resin, 2; The phthalic acid diisobutyl ester, 2);
Epoxy resin E-44: 20;
Vinylformic acid: 3;
Racemic glycidol amine epoxy resin AG-80:15;
Organic solvent: 4 (wherein: propyl carbinol, 2; Ethyl acetate, 2);
Amido silicon oil: 3;
Distilled water: 5;
The preparation method is with example 1.Obtain the anticorrosion ant-scaling coating 6 of the present invention.
With the anticorrosion ant-scaling coating of the present invention who obtains, use spraying method application 304# stainless steel plate, application is done the contrast corrosion experiment with the plate of application not in salt fog cabinet.The result is as follows:
Table 1 salt-fog test result
Table 1 as can be known, coating of the present invention has preferably protective effect to matrix, can greatly prolong heat-exchange equipment work-ing life, coating is at the strong adhesion of metal base surface, the phenomenon such as bubbling, peeling do not occur, come off.
The plate of application coating 1 of the present invention and the plate of application not are assembled into respectively interchanger, adopt total exchange coefficient of the heat exchanger assay method test heat exchange heat transfer property, this device is with automatic data acquisition, temperature control pressurization function, be hot-fluid with high density salt solution, simulation test interchanger ant-scaling effect, durability of coating.The result is as follows:
Table 2 local heat transfer result
As shown in Table 2, behind the interchanger application coating of the present invention, heat transfer coefficient is close with the metallic matrix interchanger of not application, does not affect the heat exchanger heat transfer ability.Through continuous trimestral experiment, all have certain thickness dirt on the heat exchanger plate of application and coating process not, but behind the application coating of the present invention, the schmutzband on heat exchanger plate surface is thinner, thickness only be not application plate dirt layer 1/3, and be very easy to wash, show preferably ant-scaling performance; The interchanger of application coating of the present invention through 3 months experiment after, wash that to observe coating behind the schmutzband still intact.
Claims (2)
1. a water medium heat-exchange equipment is with protection against corrosion ant-scaling coating, and it is characterized in that: it is to be made by the raw material of following weight proportioning;
Nano titanium powder: 40～45 parts,
Pretreating agent: 6 parts,
Resins, epoxy: 18～20 parts,
Vinylformic acid: 2～4 parts,
Bisphenol-s epoxy resin or glycidyl ester based epoxy resin or Racemic glycidol amine epoxy resin: 12～15 parts,
Organic solvent: 4 parts,
Amido silicon oil or organic fluorine reagent: 3～5 parts,
Distilled water: 6 parts;
Described pretreating agent is a kind of mixture, and by in Surfactant OP-10, polysorbate60 or the tween 80 one or more, one or more in furfuryl resin or the aminoresin, phthalic acid diisobutyl ester mix, wherein
Promoting agent OP-10, polysorbate60 or tween 80: 2 parts
2 parts in furfuryl resin or aminoresin
2 parts of phthalic acid diisobutyl esters;
Described Resins, epoxy is any or multiple among E-44, E-42, E-35, E-31, the E-20;
The preparation method is:
The planetary ball mill of packing into after at first nano titanium powder and pretreating agent being mixed carries out pre-treatment to nano titanium powder, obtains the titanium valve slurry, makes the nano titanium powder surface parcel one deck organo-functional group after the processing, can be good at being scattered in the modified epoxy resin paint; Next is to carry out epoxy resin modification, obtains modified resin; With amido silicon oil or organic fluorine reagent modified resin is carried out modification again; Coating preparation at last, the titanium valve slurry that obtains after the pre-treatment and the Resins, epoxy after the modification are mixed according to the 1:1-1.2 mass ratio, under strong stirring, add again distilled water and transfer to and need viscosity, continuation namely made coating at ultrasonic auxiliary powerful mechanical stirring 1-3 hour.
2. a water medium heat-exchange equipment is characterized in that concrete steps are as follows with the preparation method of protection against corrosion ant-scaling coating:
1., nano titanium powder pre-treatment
Pretreating agent is mixed according to mass ratio 1:5-10 with nano titanium powder, and compound changes in the planetary ball mill, and stocking volume is 50-85%, passes into protective gas after 10 minutes ball milling 3-5 hour, the titanium valve slurry after namely obtaining processing; Described nano titanium powder is sheet, diameter＜10 μ m, and thickness is 100nm; Described pretreating agent is a kind of mixture, by in Surfactant OP-10, tween 80, the polysorbate60 one or more, a kind of in furfuryl resin, the aminoresin, phthalic acid diisobutyl ester, mix Deng mass ratio, protective gas is nitrogen or argon gas;
2., epoxy resin modification
At first select in resol, glycidyl ester type of epoxy resin, the glycidyl amine type of epoxy resin one or both that Resins, epoxy is carried out modification, obtain modified resin; With amido silicon oil or organic fluorine reagent the modified resin of upper step is carried out modification again; Concrete grammar is: the Resins, epoxy of getting the 40-55 mass parts, the vinylformic acid of 5-10 mass parts, in the resol of 30-45 mass parts, glycidyl ester type of epoxy resin, the glycidyl amine type of epoxy resin one or both, be dissolved in the organic solvent of 5-10 mass parts, in the time of 45-80 ℃, Resins, epoxy is carried out modification, then add amido silicon oil or the organic fluorine reagent of 5-15 mass parts, in the time of 60-105 ℃, carry out modification, obtain modified epoxy; Described organic solvent is one or both the mixture in toluene, dimethylbenzene, propyl carbinol, n-Octanol, the ethyl acetate; Described Resins, epoxy is any or multiple among E-44, E-42, E-35, E-31, the E-20; Described resol is the epoxidation lacquer resins; Described glycidyl ester based epoxy resin is any among 711#, 731#, the 732#; Described Racemic glycidol amine epoxy resin is any among AG-80, the AFG-90; Described organic fluorine reagent is any among WRS series, 3585 series, AG-710,3589 series, TG-421, TG-527, the EC50;
3., coating preparation
With step 1. product and step 2. product mix according to the 1:1-1.2 mass ratio, under strong stirring, add again distilled water and transfer to and need viscosity, continue at ultrasonic auxiliary powerful mechanical stirring 1-3 hour, namely make coating, barrelling.
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| CN2010102378609A CN102337049B (en) | 2010-07-20 | 2010-07-20 | Corrosion-resistant and anti-scaling paint used for aqueous medium heat exchange equipment and preparation method of corrosion-resistant and anti-scaling paint. |
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| CN2010102378609A CN102337049B (en) | 2010-07-20 | 2010-07-20 | Corrosion-resistant and anti-scaling paint used for aqueous medium heat exchange equipment and preparation method of corrosion-resistant and anti-scaling paint. |
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| CN104119778A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Modified metal anti-corrosion paint and preparation method thereof |
| CN107057483A (en) * | 2016-12-16 | 2017-08-18 | 安徽苏启化工有限公司 | A kind of chemical industry boiler good antiscale property synergist and preparation method thereof |
| CN108841289B (en) * | 2018-05-25 | 2020-08-14 | 中国人民解放军陆军装甲兵学院 | Long-acting anticorrosion weather-resistant functional coating and preparation method thereof |
| CN113402972A (en) * | 2021-06-01 | 2021-09-17 | 江苏苏杰机械制造有限公司 | Corrosion-resistant, anti-scaling, heat-resistant and anti-oxidation electric heating tube and processing method thereof |
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| CN101012351A (en) * | 2007-01-30 | 2007-08-08 | 华南理工大学 | Weather-resistant rust-proof water paint and preparing method thereof |
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| KR100931618B1 (en) * | 2009-06-16 | 2009-12-14 | 건설화학공업주식회사 | The painting matter and product method of painting matter |
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| CN101012351A (en) * | 2007-01-30 | 2007-08-08 | 华南理工大学 | Weather-resistant rust-proof water paint and preparing method thereof |
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