CN114888440A - Method for converting heat-absorbing coating in situ - Google Patents
Method for converting heat-absorbing coating in situ Download PDFInfo
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- CN114888440A CN114888440A CN202210708897.8A CN202210708897A CN114888440A CN 114888440 A CN114888440 A CN 114888440A CN 202210708897 A CN202210708897 A CN 202210708897A CN 114888440 A CN114888440 A CN 114888440A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
- B23K26/3568—Modifying rugosity
- B23K26/3584—Increasing rugosity, e.g. roughening
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/60—Preliminary treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/70—Auxiliary operations or equipment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
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Abstract
The invention discloses a method for converting a heat absorption coating in situ, which comprises the following steps: (1) cleaning and drying a substrate, and then tightly fixing a protective material on the surface of the substrate; (2) and setting parameters of laser direct writing, and scanning and irradiating the fixed protective material and the substrate to obtain the heat-absorbing coating. The cleaning comprises the following steps: the substrate was sequentially immersed in acetone, ethanol, DI water, ultrasonically cleaned for 5 minutes, respectively, and then rinsed with DI water. The substrate material is selected from copper, titanium, iron, cobalt, nickel, molybdenum, tungsten, tantalum, zirconium, chromium or alloys of the above metals. The protective material is an organic material which can transmit light. According to the invention, the metal sheet coated with the transparent organic matter protective layer is directly written by laser, so that organic matters on the surface are carbonized while the metal sheet is roughened, and the heat-absorbing coating with the functions of corrosion resistance and photo-thermal absorption is obtained.
Description
Technical Field
The invention relates to the technical field of heat absorption coatings, in particular to a method for converting a heat absorption coating in situ.
Background
With the worldwide shortage of energy and environmental crisis, new energy technologies are receiving more and more attention. Solar energy is regarded as the most important new energy in the 21 st century as inexhaustible pure energy. The solar water heater is the most common one in solar energy utilization, and the heat absorption coating in the solar water heater is a core device of the solar water heater.
The preparation method of the heat absorption coating of the solar water heater mainly comprises three methods: an anodic oxidation method, an electroplating black chromium method and a magnetron sputtering method, wherein the anodic oxidation method belongs to a chemical plating method. The chemical plating and electroplating methods have complex process, more manual operations and difficult process control. More troublesome, the generated waste liquid is easy to cause serious environmental pollution; the method for preparing the heat absorption coating of the solar water heater by magnetron sputtering is researched more in recent years, has the advantages of no pollution, suitability for batch production and the like, but the magnetron sputtering method also has many problems, such as the need of adopting magnetron sputtering equipment, higher equipment requirement and environmental requirement and the like, and in addition, the coating prepared by magnetron sputtering has low bonding force with a substrate, so that the phenomenon of coating peeling can occur after a long time. Therefore, a simple and convenient method is needed for preparing the heat-absorbing coating of the solar water heater, and the heat-absorbing coating has the functions of corrosion resistance and photo-thermal absorption and is not easy to fall off.
Disclosure of Invention
In view of the above prior art, it is an object of the present invention to provide a method for converting a heat absorbing coating in situ. According to the invention, the metal sheet coated with the transparent organic matter protective layer is directly written by laser, so that organic matters on the surface are carbonized while the metal sheet is roughened, and a heat-absorbing coating with the functions of corrosion resistance and photo-thermal absorption is obtained; the substrate containing the coating is directly prepared through in-situ conversion, and the coating is not easy to fall off.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, there is provided a method of converting an endothermic coating in situ, comprising the steps of:
(1) cleaning and drying a substrate, and then tightly fixing a protective material on the surface of the substrate;
(2) and setting parameters of laser direct writing, and scanning and irradiating the fixed protective material and the substrate to obtain the heat-absorbing coating.
Laser beams penetrate through the protective material and are focused on the surface of the substrate to coarsen the surface of the substrate, and the protective material is carbonized by heat generated during coarsening, so that the heat-absorbing coating with the corrosion-resistant function is obtained.
The coarsened substrate is black and has a good heat absorption effect, and meanwhile, in the laser in-situ conversion process, the protective material is carbonized and then changed into carbon microspheres which are attached to the surface of the coarsened substrate, so that the method has a better heat absorption effect. The roughened substrate is black and has a good heat absorption effect, and meanwhile, in the laser in-situ conversion process, the protective material is carbonized and then changed into carbon microspheres to be attached to the surface of the roughened substrate, so that the method has a better heat absorption effect. The carbon material has sp3 and sp2 and pi electronic structures, photons in light waves are absorbed by the carbon material, transition is generated, and then the carbon material returns to a ground state to emit energy, and heat is generated; meanwhile, the carbon microspheres are black, so that the photo-thermal conversion performance is better; from the perspective of heat radiation, the carbon anticorrosive layer has low heat scattering and low heat loss, so that the coarsened substrate with the carbon microspheres has more excellent photo-thermal conversion effect. The carbon material has stable chemical property and is not easy to react with acid and alkali, and simultaneously, because the method provided by the invention is in-situ conversion, the stainless steel coarsening layer and the carbon microspheres are tightly combined, the carbon material is not easy to fall off and has good corrosion resistance. Therefore, the heat-absorbing coating prepared by in-situ conversion provided by the invention has excellent heat absorption and corrosion resistance.
Preferably, in step (1), the washing is: the substrate was sequentially immersed in acetone, ethanol, DI water, ultrasonically cleaned for 5 minutes, respectively, and then rinsed with DI water.
Preferably, in step (1), the substrate material is selected from copper, titanium, iron, cobalt, nickel, molybdenum, tungsten, tantalum, zirconium, chromium, or an alloy of the above metals.
Preferably, in the step (1), the protective material is an organic material that can transmit light. Such as plastic sheets, adhesive tapes, PDMS sheets, PVP sheets.
Preferably, the thickness of the protective material is 0.2-1 mm.
Preferably, in the step (2), laser direct writing: the samples were processed for 10-40s in a line scan mode with a laser speed of 500-2000mm/s and a laser power of 10-30W.
Influence of setting of parameters of the laser on the degree of carbonization: when the laser power is low, the laser and the substrate have weak action, the coarsening effect on the substrate is weak, and high energy cannot be generated to completely carbonize the protective material. When the laser power is too high, the action of the laser and the substrate material is strong, so that a strong sputtering effect is generated, and the carbon layer on the surface can be erased.
In a second aspect of the invention, a heat absorbing coating prepared by the above method is provided.
In a third aspect of the invention, there is provided the use of a heat-absorbing coating in the manufacture of a solar water heater.
The invention has the beneficial effects that:
(1) the invention adopts the laser direct writing method to convert the heat-absorbing coating in situ, realizes the conversion of the heat-absorbing coating on the surface of the metal substrate in situ by one step, has the characteristics of simple process and environmental protection, and is simple and suitable for mass production.
(2) The invention adopts the laser direct writing method to convert the heat absorption coating in situ, only adopts a laser light source in the aspect of equipment, and has the characteristics of simple equipment and low cost compared with the method for preparing the heat absorption coating by magnetron sputtering.
(3) The laser is adopted to coarsen the metal substrate through the surface of the protective material, the generated heat causes the protective material to be carbonized, and the coarsening of the metal substrate and the carbonization of the protective material are realized in situ.
(4) The invention adopts the laser direct writing method to obtain the heat absorption coating by in-situ conversion, the laser and the metal substrate are separate systems, and the metal sheet substrate and the protective material do not need to be loaded by a fixed cavity or a container, so the invention can be suitable for the in-situ conversion heat absorption coating of the metal substrate with different sizes and different states.
(5) The invention realizes the isolation of the metal substrate and the air by a method of simply covering the metal substrate with the protective layer. The oxidation of the coarsening of the metal substrate is avoided without special operations such as vacuumizing and the like. Meanwhile, the laser penetrates through the organic protective layer to coarsen the metal substrate, the generated heat carbonizes the protective layer on the surface, and the carbonized protective layer plays a role in corrosion prevention.
(6) The invention realizes the conversion of the heat absorption coating on the surface of the metal substrate by adopting laser coarsening, and can obtain the light absorption coatings with different coarsening degrees simply by adjusting laser parameters.
Drawings
FIG. 1: example 1 schematic diagram of laser stainless steel surface in-situ conversion heat absorption coating, wherein, 1, stainless steel sheet, 2, transparent adhesive tape, 3, laser beam.
FIG. 2: example 1 optical photograph of in situ conversion of a stainless steel surface to a heat absorbing coating.
FIG. 3: example 1 scanning electron micrograph of in situ conversion endothermic coating on stainless steel surface, (a) scanning electron micrograph with 50 μm scale, and (b) scanning electron micrograph with 1 μm scale.
Fig. 4 is a photo-thermal performance comparison test chart of the stainless steel surface in-situ conversion heat absorption coating in example 1.
FIG. 5 is a graph of the corrosion resistance of the in situ conversion heat absorption coating on the surface of the stainless steel in example 1.
FIG. 6 is an optical photograph of the in-situ conversion heat-absorbing coating on the surface of different metal sheets used in example 2.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background art, in the prior art, a solar heat-absorbing coating needs to be coated on a stainless steel substrate by different methods, and the coating is prepared secondarily and has weak bonding force, so that the substrate and the coating are easy to fall off. Based on the method, the invention provides a method for preparing the heat-absorbing coating by in-situ conversion. According to the invention, the transparent organic material is tightly attached to the surface of the substrate, the substrate can be coarsened by focusing the substrate through laser, and carbon microspheres can be covered on the coarsened layer, so that the carbon material has good corrosion resistance; the stainless steel is coarsened, so that the heat absorption effect is realized, and the problem that the heat absorption coating with weak binding force falls off does not exist; meanwhile, due to in-situ conversion, the stainless steel coarsened layer and the carbon microspheres are tightly combined, and the prepared material has heat absorption and corrosion resistance. The nanosecond laser used in the invention has the advantages of low price, low cost and high universality.
The coarsened substrate is black and has a good heat absorption effect, and meanwhile, in the laser in-situ conversion process, the protective material is carbonized and then changed into carbon microspheres which are attached to the surface of the coarsened substrate, so that the method has a better heat absorption effect. The carbon material has sp3 and sp2 and pi electronic structures, photons in light waves are absorbed by the carbon material, transition is generated, and then the carbon material returns to a ground state to emit energy, and heat is generated; meanwhile, the carbon microspheres are black, so that the photo-thermal conversion performance is better; from the perspective of heat radiation, the carbon anticorrosive layer has low heat scattering and low heat loss, which makes the coarsened substrate with the carbon microspheres show more excellent light conversion effect. The carbon material has stable chemical property and is not easy to react with acid and alkali, and simultaneously, the method provided by the invention has good corrosion resistance because the in-situ conversion is adopted, and the stainless steel coarsened layer and the carbon microspheres are tightly combined. Therefore, the heat-absorbing coating prepared by in-situ conversion provided by the invention has excellent heat absorption and corrosion resistance.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
Description of the drawings: the PDMS solution comprises polydimethylsiloxane prepolymer and curing agent, which are commercially available commercial packages, and the manufacturer is Shanghai Aladdin Biotechnology Ltd.
Example 1:
the embodiment discloses a method for converting a stainless steel surface heat absorption coating in situ by laser, which comprises the following specific implementation steps as shown in fig. 1:
1) the stainless steel sheet was sequentially immersed in acetone, ethanol, DI water for 5 minutes and rinsed with DI water. And drying after cleaning.
2) And (3) tightly attaching the PET transparent adhesive tape with the thickness of 0.2mm to the surface of the stainless steel sheet. Stainless steel sheet below and scotch tape above.
3) The stainless steel sheet covered with the transparent adhesive tape was placed on a laser bench, laser direct writing parameters were set, and the sample was processed for 20s using a laser speed of 1000mm/s and a laser power line sweep pattern of 20W.
Laser beams penetrate through the transparent adhesive tape and are focused on the stainless steel sheet, the surface of the stainless steel sheet is roughened, the transparent adhesive tape is carbonized by heat generated during roughening, and a black sample with the stainless steel substrate surface subjected to micro-nano roughening and the surface covered with a carbon anti-corrosion layer (shown in figure 3) is obtained and is shown in figure 2.
Compared with the heat absorption coating on the stainless steel surface which is only roughened by laser, the laser in-situ conversion heat absorption coating which is formed by coating the protective material on the stainless steel surface has the advantages of good photo-thermal conversion performance and corrosion resistance. In order to verify the influence of stainless steel substrate coarsening and a carbon anticorrosive layer on photo-thermal conversion, a photo-thermal temperature test experiment is carried out by taking a stainless steel sheet (sample 1) and a stainless steel coarsening sample (sample 2) as a comparison sample of a sample (sample 3) in the embodiment; to verify the corrosion protection effect of the carbon corrosion protection layer, we performed a salt spray experiment using stainless steel coarsened sample 2 as a control sample of sample 3 of this example.
The stainless steel substrate coarsening sample 2 is prepared by the following steps:
1) the stainless steel sheet was sequentially immersed in acetone, ethanol, DI water for 5 minutes and rinsed with DI water. And drying after cleaning.
2) The stainless steel sheet is placed on a laboratory table of a laser, the parameters of laser direct writing are set, and the stainless steel sheet is focused on the surface of a sample in a line scanning mode for 20s by adopting the laser speed of 1000mm/s and the laser power of 20W. A coarsened sample of the stainless steel substrate not covered with the carbon anticorrosive layer was obtained (sample 2).
The stainless steel sheet (sample 3) and the comparative samples (samples 1 and 2) prepared in this example were each taken at an area of 1cm 2 The sample is placed under a xenon lamp light source, then the optical density of the light source is measured by a densitometer, the optical density irradiated on the two samples is ensured to be the same, then an infrared temperature measuring instrument is opened to test the photo-thermal temperature, and the final photo-thermal temperature is recorded. As shown in fig. 4, the temperature rise after light absorption of the sample of this example was 164 ℃, and the temperature rise of the comparative sample was 46.5 ℃ (sample 1) and 155 ℃ (sample 2), which indicates that the surface coating of the stainless steel prepared in this example has better photothermal conversion performance. It can also be seen that the improvement in the light-to-heat conversion performance results from the roughening treatment of the substrate material on the one hand and from the presence of the carbon anti-corrosion layer on the other hand.
In the laser in-situ conversion process, the protective material is carbonized and then changed into carbon microspheres attached to the roughened substrate surface, so that the method has a better heat absorption effect. The carbon material has sp3 and sp2 and pi electronic structures, photons in light waves are absorbed by the carbon material, transition is generated, and then the carbon material returns to a ground state to emit energy, and heat is generated; meanwhile, the carbon microspheres are black, so that the photo-thermal conversion performance is better; from the perspective of heat radiation, the carbon anticorrosive layer has low heat scattering and low heat loss, which makes the coarsened substrate with the carbon microspheres show more excellent light conversion effect.
The corrosion resistance of the in-situ conversion heat-absorbing coating of the protective material coated on the surface of the stainless steel of the embodiment is judged by a salt spray exposure test. The stainless steel sheet (sample 3) and the comparative sample (sample 2) prepared in this example were sealed in the untreated places with a hot melt adhesive, each exposed area being 1cm 2 The laser processed area of (a). Two are combinedThe samples were placed in a salt spray apparatus and two-day salt spray experiments were started. And taking out the metal sheet, drying and observing the surface corrosion condition. In this embodiment, the heat absorbing layer in situ conversion has no corrosion, the black surface is maintained, and the surface of the heat absorbing layer has a large area corrosion and the color is changed to brown as shown in fig. 5. The stainless steel surface coating prepared by the embodiment has better corrosion resistance.
The carbon material has stable chemical property and is not easy to react with acid and alkali, and simultaneously, the method provided by the invention has good corrosion resistance because the in-situ conversion is adopted, and the stainless steel coarsened layer and the carbon microspheres are tightly combined. Therefore, the heat-absorbing coating prepared by in-situ conversion provided by the invention has excellent heat absorption and corrosion resistance.
Therefore, in the embodiment, the laser beam penetrates through the transparent adhesive tape to coarsen the surface of the stainless steel sheet, the transparent adhesive tape is carbonized by heat generated during coarsening, and the coarsening of the surface of the stainless steel is combined with the carbonization of the transparent adhesive tape to obtain a coarsened surface which is easier to absorb heat, so that better photo-thermal conversion is realized; meanwhile, the carbonized transparent adhesive tape covers the roughened stainless steel surface and plays a role in protecting the stainless steel from corrosion, so that the method for converting the heat-absorbing coating on the stainless steel surface in situ by using laser is simple, and the prepared heat-absorbing coating has the characteristics of heat absorption and corrosion resistance.
Example 2
This example is different from example 1 in that the metal substrate in step (1) is changed into titanium sheet, copper sheet, iron sheet, nickel sheet, aluminum sheet and molybdenum sheet. After the heat absorption coating is converted in situ by laser, samples of heat absorption pictures of in situ conversion on different metal surfaces are obtained, as shown in fig. 6.
Example 3
The difference from the embodiment 1 is that the protective material is PDMS, the PDMS solution is uniformly spin-coated on the stainless steel sheet, the PDMS is dried, the stainless steel sheet covered with the PDMS film is placed on a laser experiment table, the laser direct writing parameters are set, and the sample is processed for 40s by adopting a laser speed of 500mm/s and a laser power line scanning mode of 10W, so as to obtain the heat absorbing coating.
Example 4
The difference from example 1 is that the protective material is a polyethylene film, the polyethylene film is tightly attached to the substrate, the stainless steel sheet covered with the polyethylene film is placed on a laser experiment table, the parameters of laser direct writing are set, and the surface of the sample is processed for 10s in a linear scanning mode by adopting a laser speed of 2000mm/s and a laser power of 30W, so as to obtain the heat-absorbing coating.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (8)
1. A method of converting a heat absorbing coating in situ, comprising the steps of:
(1) cleaning and drying a substrate, and then tightly fixing a protective material on the surface of the substrate;
(2) setting parameters of laser direct writing, scanning and irradiating the fixed protective material and the substrate, focusing laser on the surface of the substrate, roughening the surface of the substrate, and carbonizing the protective material by the generated heat to obtain the heat-absorbing coating with the corrosion-resistant function.
2. The method for converting an endothermic coating in situ according to claim 1, wherein in the step (1), the cleaning is: the substrate was sequentially immersed in acetone, ethanol, DI water, ultrasonically cleaned for 5 minutes, respectively, and then rinsed with DI water.
3. The method for converting an endothermic coating in situ according to claim 1, wherein in the step (1), the base material is selected from copper, titanium, iron, cobalt, nickel, molybdenum, tungsten, tantalum, zirconium, chromium or an alloy of the above metals.
4. The method for converting an endothermic coating in situ according to claim 1, wherein in the step (1), the protective material is an organic material that can transmit light.
5. The method for converting an endothermic coating in situ according to claim 1, wherein the thickness of the protective material is 0.2 to 1 mm.
6. The method for converting an endothermic coating in situ according to claim 1, wherein in the step (2), the coarsening is: the samples were processed for 10-40s in a line scan mode with a laser speed of 500-2000mm/s and a laser power of 10-30W.
7. A heat absorbing coating prepared by the method of any one of claims 1 to 6.
8. Use of the heat absorbing coating according to claim 7 for the production of a solar water heater.
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