CN111842070B - Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating - Google Patents
Construction method of self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating Download PDFInfo
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- CN111842070B CN111842070B CN202010619388.9A CN202010619388A CN111842070B CN 111842070 B CN111842070 B CN 111842070B CN 202010619388 A CN202010619388 A CN 202010619388A CN 111842070 B CN111842070 B CN 111842070B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/587—No clear coat specified some layers being coated "wet-on-wet", the others not
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
Abstract
The invention discloses a construction method of a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating, which belongs to the technical field of chemical industry, and has the advantages of flexibility, simple process, high efficiency, short period, environmental protection, no pollution and strong coating binding force.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a construction method of a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating.
Background
The daily necessities made of the tinplate are accepted by people for long-term durability. The water spraying kettle, the foreign oil tank, the water bucket, the downpipe and the downpipe which are made of the galvanized iron sheet are relatively smooth articles. The household is added with articles, almost every household has daily articles such as an iron kettle, a bucket, a dustpan, a funnel and the like made of white iron sheets. Once the traditional galvanized iron sheet has the phenomenon of cold bridge condensation, dew can be corroded, and after the iron sheet is corroded and rusted, the room environment can be polluted by the rust powder. A major quality problem in applying coatings to galvanized sheet surfaces, such as roofing, drainage, ventilation, windows and doors, and other galvanized sheet items, is poor adhesion. If the coating is applied according to a general method, the coating film is peeled in about half a year indoors and outdoors. The technical personnel in the field need to develop a construction method of a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating so as to meet the existing use requirement and market requirement.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a construction method of a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating.
The invention is realized by the following technical scheme:
a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating is constructed by soaking a pretreated solid metal sample in a cerous nitrate solution, drying at high temperature after soaking, depositing a sodium polystyrene sulfonate and polyacrylamide hydrochloride layer on the sample by using a layer-by-layer self-assembly technology after drying, then depositing through a urushiol emulsion, and finally depositing through a sodium polystyrene sulfonate and polyacrylamide hydrochloride layer for one time, so that cyclic layer-by-layer alternate deposition is realized.
Further, the solid metal pretreatment is to polish the aluminum alloy sample by using sand paper, remove impurities and an oxide film, and then ultrasonically clean and blow-dry the aluminum alloy sample by using acetone for later use.
Furthermore, the solid metal is one of a galvanized aluminum sheet and a galvanized iron sheet.
Further, the layer-by-layer alternate deposition is to sequentially perform alternate deposition of a sodium polystyrene sulfonate and polyacrylamide hydrochloride layer, urushiol deposition and alternate deposition of a sodium polystyrene sulfonate and polyacrylamide hydrochloride layer again on the metal test piece, and specifically includes: soaking the dried metal test piece into 2-3g/L polyacrylamide hydrochloride solution for 5-15 minutes, placing the metal test piece into 6~8 minutes in distilled water after soaking, then placing the metal test piece into 4-8g/L sodium polystyrene sulfonate solution for 5-10 minutes, then taking out the metal test piece and placing the metal test piece into 6~8 minutes in distilled water, and taking the metal test piece as a cycle; repeating the one-time circulation for multiple times to realize the alternate deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer; placing the prepared metal test piece of the alternative deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer in a urushiol emulsion with the concentration of 0.2-0.5 g/L for 20-30 minutes to realize the urushiol deposition self-assembly film; drying the sample after the urushiol is deposited on the self-assembly film, and placing the dried sample in poly with the concentration of 4-6 g/LSoaking in a sodium styrene sulfonate solution for 5-10 minutes, then placing in distilled water for 6~8 minutes, then soaking in a polyacrylamide hydrochloride solution of 2-3g/L for 5-15 minutes, then taking out and placing in distilled water for 6~8 minutes, using as a cycle, repeating the cycle for multiple times to realize the alternate deposition of a polyacrylamide hydrochloride-polystyrene sodium sulfonate layer, then drying by nitrogen, and performing UV-C ultraviolet 1.8-2.4J/m 2 And (5) irradiating for 10 to 15 minutes to obtain the self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating.
Further, the recycling frequency of the polyacrylamide hydrochloride-sodium polystyrene sulfonate layer is 5 to 10 times, and the recycling frequency of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer is 5 to 10 times.
The preparation method of the urushiol emulsion comprises the steps of adding 22-33 parts of urushiol, 15-21 parts of formaldehyde solution with mass fraction of 37% and 5363 parts of hexamethylenetetramine 4~6 into a reaction kettle with a stirrer, a thermometer and a condensation pipe, uniformly stirring, reacting for 50-60 minutes at 80-90 ℃, increasing the temperature to 120-130 ℃, reacting for 1-2h at constant temperature, reducing the temperature to 25-30 ℃, adding 0.2-0.3 part of sodium allylsulfonate, uniformly stirring, continuing stirring for 20-30 minutes at the stirring speed of 1000-2000r/min, and adding water for dilution to obtain the urushiol emulsion.
The invention has the beneficial effects that:
the invention discloses a construction method of a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating, which is characterized in that the porosity of a zinc coating is shielded, if the porosity is smaller, the self-assembly coating on the zinc coating is more compact, the consumption of the zinc coating only has the function of forming a micro-battery, and the service life of the self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating mainly depends on the purity of zinc. The passage of electrolyte into the iron sheet matrix is reduced, and the tendency that the zinc layer becomes a cathode-protected anode and is gradually dissolved is slowed down. The consumption of the zinc layer is slowed down, the protection time is prolonged, the inevitable pores of the zinc layer are sealed by using the self-assembly coating, and the urushiol serving as an intermediate component of the assembly layer can well play a role in moisture protection. After drying and film forming, the coating has the functions of improving corrosion resistance, moisture resistance, insulation and oxidation resistance.
Compared with the prior art, the invention has the following advantages:
the construction method disclosed by the invention is flexible, simple in process, high in efficiency, short in period, free of pollution and strong in coating binding force, and based on the electrostatic adsorption effect of polyacrylamide hydrochloride and sodium polystyrene sulfonate electrolyte through electrostatic self-assembly, urushiol is combined in the presence of polyelectrolyte to gradually deposit to generate a urushiol coating, and then two polyelectrolytes are deposited in a layer-by-layer assembly mode to uniformly cover the surface of the urushiol coating, so that the adsorption process is more uniform, the formed film is a more compact layer, the anti-corrosion effect is most durable, efficient and stable, the anti-corrosion effects of galvanized iron sheets, aluminum-galvanized iron sheets and the like are obviously improved, the coating has the advantages of high order, good orientation, compact stacking and accumulation, few defects, stable structure, simple and easy preparation and the like, and the migration and transmission of moisture, oxygen and electrolyte to a substrate are slowed down through the spontaneously formed barrier coating, so that the effect of protection is achieved.
Detailed Description
The invention is illustrated by the following specific examples, which are not intended to be limiting.
Example 1
The construction of the self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating of the galvanized iron sheet: taking 29# galvanized iron sheet with the thickness of 0.437mm and a zinc layer with the thickness of 0.02mm, polishing an aluminum alloy sample by using sand paper, removing impurities and an oxide film, ultrasonically cleaning by using acetone, drying, soaking the dried metal test piece into 3g/L polyacrylamide hydrochloride solution for 15 minutes, placing the soaked metal test piece into distilled water for 8 minutes, then placing the metal test piece into 8g/L sodium polystyrene sulfonate solution for 10 minutes, taking out the metal test piece, and placing the metal test piece into the distilled water for 8 minutes, wherein the above steps are used as a cycle; repeating the primary circulation for multiple times to realize the alternate deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer; placing the prepared metal test piece of the alternate deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer in urushiol emulsion with the concentration of 0.5g/L for 30 minutes to realize the deposition of the urushiol self-assembly film; drying the sample after the urushiol deposition self-assembly film, soaking the dried sample in 6g/L sodium polystyrene sulfonate solution for 10 minutes, then placing the soaked sample in distilled water for 8 minutes, and then, placing the solution in the distilled waterSoaking the mixture into 3g/L polyacrylamide hydrochloride solution for 15 minutes, taking the mixture out, placing the mixture into distilled water for 8 minutes to serve as a cycle, repeating the cycle for multiple times to realize alternate deposition of polyacrylamide hydrochloride-polystyrene sodium sulfonate layers, drying the films by nitrogen, and performing UV-C ultraviolet 2.4J/m 2 And irradiating for 15 minutes to obtain the self-assembled environment-friendly long-acting easy-cleaning anticorrosive coating, wherein the repeat cycle of the polyacrylamide hydrochloride-polystyrene sodium sulfonate layer is 10 times, the repeat cycle of the polystyrene sodium sulfonate-polyacrylamide hydrochloride layer is 10 times, and the preparation method of the urushiol emulsion comprises the steps of adding 33 parts of urushiol, 21 parts of formaldehyde solution with the mass fraction of 37% and 6 parts of hexamethylenetetramine into a reaction kettle with a stirrer, a thermometer and a condenser pipe according to parts by weight, uniformly stirring, reacting for 60 minutes at 90 ℃, raising the temperature to 120 ℃, reacting for 1 hour at constant temperature, reducing the temperature to 25 ℃, adding 0.2 part of sodium allylsulfonate, uniformly stirring, continuously stirring for 20 minutes at the stirring speed of 1000 r/minute, and adding water for diluting to obtain the urushiol emulsion. Galvanized iron sheet is purchased from Shandong Anxin white iron sheet wholesale processing Co Ltd
Example 2
The construction of the self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating of the galvanized aluminum sheet: taking a galvanized aluminum iron sheet with the aluminum content of 35% and the thickness of 0.437mm and a zinc layer with the thickness of 0.1mm, polishing an aluminum alloy sample by using sand paper, removing impurities and an oxide film, then ultrasonically cleaning and drying by using acetone, soaking the dried metal test piece into 2g/L polyacrylamide hydrochloride solution for 5 minutes, placing the soaked metal test piece into distilled water for 6 minutes, then placing the metal test piece into 4g/L sodium polystyrene sulfonate solution for 10 minutes, taking out the metal test piece and placing the metal test piece into the distilled water for 2 minutes, and taking the metal test piece out as a primary cycle; repeating the one-time circulation for multiple times to realize the alternate deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer; placing the prepared metal test piece of the alternate deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer in urushiol emulsion with the concentration of 0.2g/L for 20 minutes to realize the deposition of the urushiol self-assembly film; drying the sample deposited with the urushiol self-assembly film, soaking the dried sample in a sodium polystyrene sulfonate solution with the concentration of 4g/L for 10 minutes, and then placing the soaked sample in distilled waterSoaking for 6 minutes, then soaking into 2g/L polyacrylamide hydrochloride solution for 15 minutes, taking out, then placing in distilled water for 6 minutes as a cycle, repeating the cycle for multiple times to realize alternate deposition of polyacrylamide hydrochloride-polystyrene sodium sulfonate layers, then blowing by nitrogen, and performing UV-C ultraviolet 1.8J/m 2 Irradiating for 15 minutes to obtain the self-assembled environment-friendly long-acting easy-to-clean anticorrosive coating.
Further, the number of the repeated cycles of the polyacrylamide hydrochloride-polystyrene sodium sulfonate layer is 10, and the number of the repeated cycles of the polystyrene sodium sulfonate-polypropylene amine hydrochloride layer is 10.
Further, the preparation method of the urushiol emulsion comprises the steps of adding 22 parts of urushiol, 15 parts of formaldehyde solution with the mass fraction of 37% and 4 parts of hexamethylenetetramine into a reaction kettle with a stirrer, a thermometer and a condenser pipe according to the parts by weight, uniformly stirring, reacting for 50 minutes at 80 ℃, raising the temperature to 130 ℃, reacting for 1 hour at a constant temperature, reducing the temperature to 25 ℃, adding 0.2 part of sodium allylsulfonate, uniformly stirring, continuing to stir for 20 minutes at the stirring speed of 1000 r/minute, and adding water to dilute to obtain the urushiol emulsion. Galvanized sheet iron was obtained from Shandong Zheng and Steel plate Co.
Comparative example 1
Compared with example 1, the 29# galvanized iron sheet without coating has a thickness of 0.437mm and a zinc layer with a thickness of 0.02mm.
Comparative example 2
Compared with the example 2, the galvanized aluminum sheet is a galvanized aluminum sheet which is not subjected to coating construction and has the aluminum content of 35 percent, the thickness of 0.437mm and the zinc layer thickness of 0.1 mm.
Comparative example 3
Compared with example 1, the method is characterized in that urushiol emulsion is not used, and only polypropylene amine hydrochloride-polystyrene sodium sulfonate layers are alternately deposited layer by layer in a cycle, and the repeated cycle is 20 times.
The self-assembled environment-friendly long-acting easy-cleaning anticorrosive coatings of the example 1~2 and the comparative example 1~3 are subjected to an application performance test, and the detection results are shown in table 1:
TABLE 1 results of performance tests on metal sheets of example 1~2 and comparative example 1~3
Note: GB/T10125-2012 artificial atmosphere corrosion test salt spray test; GB/T6739-2006 color paint and varnish the pencil method is used for measuring the hardness of the paint film; GB/T232-2010 metal material bending test method; the test method for the adhesion strength of the electrodeposition and chemical deposition layer of the metal covering layer on the GB/T5270-2005 metal substrate is commented; -20 ℃, 72h duration referring to GB/T2423.1-2008 part 2 of environmental test of electrical and electronic products: test methods test a: low temperature; 200 ℃ and the duration of 240h, GB/T2423.2-2008 part 2 of the environmental test of electrical and electronic products: test methods test B: high temperature; GB/T2423.6-1995 Electrical and electronic products environmental test part 2: test methods test Eb and guide rules: collision; GB/T2423.10-2008 electric and electronic product environmental test part 2: test methods test Fc: vibration (sinusoidal).
Claims (3)
1. A construction method of a self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating is characterized in that a pretreated solid metal sample is soaked in a cerous nitrate solution, the soaked solid metal sample is dried at high temperature, a layer-by-layer self-assembly technology is utilized to deposit a sodium polystyrene sulfonate and a polyacrylamide hydrochloride layer on the sample after the drying, then the sodium polystyrene sulfonate and the polyacrylamide hydrochloride layer are deposited through a urushiol emulsion, and finally the sodium polystyrene sulfonate and the polyacrylamide hydrochloride layer are deposited once, so that the cyclic layer-by-layer alternate deposition is realized, namely the self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating is constructed, and the solid metal is one of a galvanized aluminum sheet and a galvanized sheet; the solid metal pretreatment comprises the steps of polishing by using sand paper, removing impurities and an oxidation film, and then ultrasonically cleaning and drying by using acetone for later use; the layer-by-layer alternate deposition is to perform alternate deposition of a sodium polystyrene sulfonate and polyacrylamide hydrochloride layer, urushiol deposition and alternate deposition of a sodium polystyrene sulfonate and polyacrylamide hydrochloride layer again on the metal test piece in sequence, and specifically comprises the following steps: soaking the dried metal test piece into 2-3g/L polyacrylamide hydrochloride solution for 5-15 minutes, placing the metal test piece into 6~8 minutes in distilled water after soaking, then placing the metal test piece into 4-8g/L sodium polystyrene sulfonate solution for 5-10 minutes, then taking out the metal test piece and placing the metal test piece into 6~8 minutes in distilled water, and taking the metal test piece as a cycle; repeating the one-time circulation for multiple times to realize the alternate deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer; placing the prepared metal test piece of the alternative deposition film of the sodium polystyrene sulfonate-polyacrylamide hydrochloride layer in urushiol emulsion with the concentration of 0.2 to 0.5g/L for 20 to 30 minutes to realize urushiol deposition self-assembly film; drying the sample subjected to the urushiol deposition self-assembly film, soaking the sample in a sodium polystyrene sulfonate solution with the concentration of 4-6 g/L for 5-10 minutes, then placing the soaked sample in distilled water for 6~8 minutes, then soaking the sample in a polyallylamine hydrochloride solution with the concentration of 2-3 g/L for 5-15 minutes, then taking the sample out, placing the sample in distilled water for 6~8 minutes, repeating the cycle for many times to realize the alternate deposition film of the polyallylamine hydrochloride and the sodium polystyrene sulfonate layer, then drying the film by nitrogen, and irradiating the film for 10-15 minutes by UV-C ultraviolet 1.8-2.4J/m < 2 >, thus obtaining the self-assembly environment-friendly long-acting easy-cleaning anticorrosive coating.
2. The method for constructing a self-assembled environment-friendly long-acting easy-cleaning anticorrosive coating according to claim 1, wherein the repeat cycle of the polyacrylamide hydrochloride-polystyrene sodium sulfonate layer is 5 to 10 times, and the repeat cycle of the polystyrene sodium sulfonate-polyacrylamide hydrochloride layer is 5 to 10 times.
3. The construction method of the self-assembled environment-friendly long-acting easy-cleaning anticorrosive coating according to claim 1, characterized in that the preparation method of the urushiol emulsion comprises the steps of adding 22 to 33 parts by weight of urushiol, 15 to 21 parts by weight of 37% by weight of formaldehyde solution and 4~6 parts by weight of hexamethylenetetramine into a reaction kettle provided with a stirrer, a thermometer and a condensation pipe, stirring uniformly, reacting at 80 to 90 ℃ for 50 to 60 minutes, raising the temperature to 120 to 130 ℃, reacting at a constant temperature for 1 to 2h, lowering the temperature to 25 to 30 ℃, adding 0.2 to 0.3 part by weight of sodium allylsulfonate, stirring uniformly, and stirring continuously at a stirring speed of 1000 2000r/min for 20 to 30 minutes, and adding water for dilution to obtain the urushiol emulsion.
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| CN104195535A (en) * | 2014-08-12 | 2014-12-10 | 西南交通大学 | Modification method for improving corrosion resistance and surface functionalization of biomedical magnesium-based metal material |
| CN110643999A (en) * | 2019-09-03 | 2020-01-03 | 中国科学院海洋研究所 | Preparation method of self-assembled hole sealing protective film |
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| CN102716848A (en) * | 2011-03-31 | 2012-10-10 | 北京化工大学 | Method for constructing anticorrosive superhydrophobic nano composite film on non-planar iron surface |
| CN104711571A (en) * | 2015-03-16 | 2015-06-17 | 重庆大学 | Surface modification method of magnesium alloy |
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| CN104195535A (en) * | 2014-08-12 | 2014-12-10 | 西南交通大学 | Modification method for improving corrosion resistance and surface functionalization of biomedical magnesium-based metal material |
| CN110643999A (en) * | 2019-09-03 | 2020-01-03 | 中国科学院海洋研究所 | Preparation method of self-assembled hole sealing protective film |
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Application publication date: 20201030 Assignee: Xuzhou shuangju environmental protection new material Co.,Ltd. Assignor: ANHUI XINDALU SPECIAL PAINT Co.,Ltd. Contract record no.: X2023980035401 Denomination of invention: A Method for Constructing a Self Assembled Environmental Friendly, Long lasting, Easy to Clean, and Anticorrosive Coating Granted publication date: 20221011 License type: Common License Record date: 20230515 |
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