CN115724659A - Multifunctional protective and energy-saving synergistic coating and preparation method thereof - Google Patents
Multifunctional protective and energy-saving synergistic coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 121
- 239000011248 coating agent Substances 0.000 title claims abstract description 117
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 43
- 230000001681 protective effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 23
- 239000011029 spinel Substances 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 20
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 19
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 18
- 239000010431 corundum Substances 0.000 claims abstract description 18
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 17
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000440 bentonite Substances 0.000 claims abstract description 16
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 16
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 16
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013530 defoamer Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
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- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- YQOPHINZLPWDTA-UHFFFAOYSA-H [Al+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Al+3].[Cr+3].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YQOPHINZLPWDTA-UHFFFAOYSA-H 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
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- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001723 curing Methods 0.000 claims description 5
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- 238000000227 grinding Methods 0.000 claims description 4
- 229920002799 BoPET Polymers 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims description 3
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- 238000003837 high-temperature calcination Methods 0.000 claims description 2
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- 239000003245 coal Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000005855 radiation Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
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- 239000000571 coke Substances 0.000 description 5
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- 239000000377 silicon dioxide Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- 238000012546 transfer Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- -1 ethyl silicates Chemical class 0.000 description 1
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention relates to a multifunctional protective and energy-saving synergistic coating, which consists of the following raw materials in percentage by weight: 10 to 30 percent of spinel high-entropy ceramic, 2 to 4 percent of rare earth oxide, 10 to 12 percent of silicon oxide, 8 to 12 percent of aluminum oxide, 8 to 10 percent of aluminum nitride, 6 to 8 percent of cordierite, 3 to 4 percent of brown corundum, 0.5 to 2 percent of bentonite, 30 to 40 percent of composite binder, 0.4 to 0.6 percent of dispersant and 0.4 to 0.6 percent of defoamer. Meanwhile, the invention also discloses a preparation method of the coating. The invention has the characteristics of coking residue prevention and high temperature corrosion resistance.
Description
Technical Field
The invention relates to the technical field of high-temperature protective coatings for radiation heating surfaces of boilers, in particular to a multifunctional protective and energy-saving synergistic coating and a preparation method thereof.
Background
Under the background of 'double carbon' and increasingly strict environmental protection requirements, in order to realize ultralow emission, most domestic coal-fired power plants adopt a low-nitrogen combustion technology. However, the low-nitrogen combustion technology causes severe coking, slagging and high-temperature corrosion of the heating surface (water wall tube, high-temperature superheater, high-temperature reheater and burner nozzle), and further causes the safety and economy of the boiler to be reduced due to coking, slagging and high-temperature corrosion of the heating surface of the coal-fired boiler.
Coking, slagging and high-temperature corrosion of a heating surface of a boiler are complex physical and chemical processes and are closely related to factors such as coal quality characteristics for boiler combustion, boiler design parameters, load conditions, flue gas temperature in the boiler, flue gas atmosphere, heating surface substrate temperature, operation combustion adjustment and the like. In order to avoid risks caused by coking, slagging and high-temperature corrosion and ensure the safe operation of the boiler, a power plant adopts a series of protective measures. Spraying a protective coating on the surface of the heated surface is an important means for solving the problems.
The conventional nickel-based alloy coating such as British ET-4 and the like is generally used at the temperature of 1100 ℃, and the coating can be peeled off when the temperature is over 1100 ℃, so that the application of the coating to an industrial boiler is restricted. The inorganic high temperature resistant, corrosion resistant, anti-coking coatings typically employ silicates, silica sols, ethyl silicates, and phosphates as binders. The long-term service temperature of the four binders is 400-600 ℃, the four binders are commonly used in a water wall area with lower boiler temperature, and the performance of the coating is reduced or the coating fails after the service temperature is exceeded. However, the core temperature of pulverized coal boilers is generally between 1400 ℃ and 1700 ℃, the ambient temperature of the near-wall region is 1200 ℃, and even the wall temperature of the high-temperature reheater and the high-temperature superheater of some boilers exceeds 700 ℃. Therefore, in order to meet the protection requirement of the heating surface of the boiler, a multifunctional protective coating which has higher service temperature, coking and slag prevention and high-temperature corrosion resistance needs to be developed.
The traditional solution is to perform thermal spraying on a metal matrix and protect the metal matrix by using supersonic flame spraying, plasma spraying, laser cladding technology and the like. The invention patent CN104264102B discloses a preparation method of a nickel-based alloy coating on a boiler water-cooled wall, wherein a composite coating is arranged on the surface of a tube panel of the boiler water-cooled wall, and the composite coating is formed by firstly spraying a combined bottom layer and then spraying a high-temperature corrosion-resistant and wear-resistant nickel-based alloy coating by adopting supersonic electric arc spraying equipment to form a double-layer structure. The invention patent CN114000088A discloses a coating for on-site protection of a water wall tube of a power station boiler, which is obtained by sequentially carrying out supersonic electric arc spraying and secondary instantaneous online remelting treatment on iron-based amorphous composite powder core wires, and firstly provides a method for on-site protection of a water wall system of the power station boiler by utilizing a remelting iron-based coating local strengthening protection technology, so that the problem of abrasion and corrosion in the operation process of the water wall tube of the boiler is effectively reduced. The invention patent CN107299255A discloses a nickel-based wire material for anticorrosion spraying of a water-cooled wall of a biomass boiler, which comprises metal chromium, metal nickel, metal titanium and rare earth elements, wherein the coating has good high-temperature oxidation resistance and thermal corrosion resistance, and the service life of boiler equipment can be greatly prolonged. The invention patent CN114164391A provides a high-temperature anti-coking electric arc spraying cored wire for an electric coal powder boiler, and the prepared coating has excellent bonding strength and high-temperature anti-coking special electric arc spraying cored wire for the electric coal powder boiler, replaces other anti-coking coatings in the market, and can greatly improve the anti-coking capability of a furnace tube of the coal powder boiler. However, the coatings have single function, narrow application range, large environmental pollution, high cost, complex construction process, poor corrosion resistance and are not suitable for large-scale application.
Therefore, it is necessary to develop an environment-friendly coating technology which is multifunctional, environment-friendly, pollution-free, low in cost, simple in construction process, capable of preventing coking and coke residue, resistant to high-temperature corrosion and suitable for various heating surfaces.
Disclosure of Invention
The invention aims to solve the technical problem of providing a multifunctional protective and energy-saving synergistic coating with coking residue prevention and high-temperature corrosion resistance.
The invention also aims to provide a preparation method of the multifunctional protective and energy-saving synergistic coating.
In order to solve the problems, the multifunctional protective and energy-saving synergistic coating is characterized in that: the coating consists of the following raw materials in percentage by weight: 10 to 30 percent of spinel high-entropy ceramic, 2 to 4 percent of rare earth oxide, 10 to 12 percent of silicon oxide, 8 to 12 percent of aluminum oxide, 8 to 10 percent of aluminum nitride, 6 to 8 percent of cordierite, 3 to 4 percent of brown corundum, 0.5 to 2 percent of bentonite, 30 to 40 percent of composite binder, 0.4 to 0.6 percent of dispersant and 0.4 to 0.6 percent of defoamer.
The spinel high-entropy ceramic is CuO or MnO 2 、Fe 2 O 3 、Cr 2 O 3 、Co 3 O 4 、TiO 2 And any six of ZnO and MgO powder are taken as raw materials, and the high-entropy oxide with the spinel structure and the particle size of 300 to 800nm is prepared by firstly performing ball-milling mixing, drying and grinding, then calcining at high temperature in an air atmosphere, cooling and grinding.
The rare earth oxide is any 1 to 2 of cerium oxide, lanthanum oxide, dysprosium oxide, yttrium oxide and neodymium oxide, and the particle size of the rare earth oxide is 0.5 to 1.0 mu m.
The grain diameters of the silicon oxide and the aluminum oxide are both 1 mu m; the particle size of the aluminum nitride is 200 to 300nm; the particle sizes of the cordierite and the bentonite are both 10 mu m; the particle size of the brown corundum is 1 to 2 mu m.
The composite binder is prepared by mixing chromium aluminum phosphate and ethyl orthosilicate according to the weight ratio of 3:1, stirring and mixing the uniformly mixed compound.
The dispersant is one of Mylar chemical HY-330A + HY-330B, digao Dispers-760W and Kelmett KMT-3021.
The defoaming agent is one of Kelmett KMT-2017, digao Airex-902W and Digao Tego825.
The thickness of the coating is 100 to 200 mu m.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing in proportion;
preparing the coating:
firstly, adding a dispersing agent and a defoaming agent into a composite binder in sequence and fully stirring; then, sequentially adding spinel high-entropy ceramic, rare earth oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and uniformly dispersing at a high speed to obtain a mixture; finally, transferring the mixture into a ball mill, and carrying out ball milling at 300-500rpm for 3-5 hours to obtain the uniform multifunctional protective and energy-saving coating;
thirdly, performing sand blasting treatment on the surface of the base body by adopting quartz or brown corundum with the particle size of 1-5 mu m to ensure that the surface cleanliness of the base material reaches the requirements of grade Sa 2.5-3.0;
preparing a coating:
and (3) spraying for 2 times by using 0.8MPa compressed air under the conditions that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protection and energy-saving synergistic coating.
Compared with the prior art, the invention has the following advantages:
1. the spinel high-entropy ceramic and the rare earth oxide added in the invention can double-synergistically optimize the radiation heat transfer of the boiler, thereby greatly improving the heat exchange efficiency of the boiler.
The spinel high-entropy ceramic has extremely high infrared radiance due to the combined action of doping of various transition metal elements and oxygen vacancies in lattice defects. Because the rare earth oxide element contains unfilled 4f electrons, the rare earth oxide element can absorb or emit light with different wavelengths from ultraviolet, visible and infrared regions, so that the rare earth oxide element has high infrared radiance. In addition, the rare earth oxide has self-diagnosis, self-adjustment and self-repair functions and high-temperature infrared radiation characteristics, is often used as a functional material to optimize the performance of a coating, and is called as industrial vitamin. The spinel high-entropy ceramic and the rare earth oxide are used as main raw materials of the coating, so that the infrared radiance of the coating can be greatly increased under the synergistic effect, and the infrared radiance of the coating is 0.92 to 0.95.
The heat transfer is mainly infrared radiation, the infrared radiance of the surface of an original metal heating surface is about 0.7, heat energy generated by combustion of a hearth is radiated to the heating surface in the form of electromagnetic waves, the metal heating surface absorbs part of the electromagnetic waves and converts the electromagnetic waves into the heat energy, the surface of the heating surface is heated, and the heat is transferred to the internal low-temperature part. At the same time, a large amount of electromagnetic waves are reflected back to the furnace. After the metal heating surface is reformed by using a coating technology, heat energy is radiated to the surface of the coating in the form of electromagnetic waves, and the coating has extremely high infrared radiation rate of 0.92 to 0.95, so that the electromagnetic waves can be more effectively absorbed and converted into heat energy, the temperature of the surface of the coating is rapidly increased, and the heat energy is rapidly transmitted to the metal heating surface and a working medium in a metal pipe through the coating, thereby greatly improving the heat exchange efficiency of the boiler.
2. The surface particle size of the coating is distributed in a stepped manner, so that the risk of coking and slagging of the radiation heating surface can be effectively prevented.
The multifunctional protection and energy-saving synergistic coating is composed of a plurality of micro/nano powder materials, and when the nano powder content is 15 to 35 percent, a micro/nano mastoid secondary structure similar to the lotus leaf surface is formed, so that the surface of the coating has the characteristic of step distribution, namely the characteristic of low surface energy; meanwhile, the composite binder contains the ethyl orthosilicate component and has the characteristic of low surface energy. When the surface energy of the heated surface is lower than the critical free energy of the molten coke particles, the coke particles cannot adhere to the surface of the heated surface.
Compared with the surface of the original metal pipe wall, the protective and energy-saving synergistic coating has lower surface energy, so that molten coke particles are difficult to adhere to a heated surface, the contamination of a water-cooled wall is effectively prevented, and the coking is reduced. Even if a small amount of coking exists, the coke blocks exceed the critical value of the adhesive force and fall off automatically when the surface energy of the coating is small, so that large blocks of coking cannot be formed.
In addition, the protective and energy-saving synergistic coating has the function of radiation enhancement, can properly improve the heat absorption capacity of a heated surface, reduces the temperature of a hearth outlet, and can also effectively prevent coking of a reheater and a superheater.
As shown in figure 1, the coating obtained by the invention is prepared on a 12Cr1MoVG pipe and cured for 24 hours at room temperature; then, the mixture was cured at a high temperature of 500 ℃ for 6 hours. Finally, the sample tube was placed in coal slag containing 44.29% alkali metal and kept at 600 ℃ for 72 hours, and then taken out, and the surface of the sample tube was observed, whereby the results showed that: no obvious coking phenomenon, and the coating has good anti-coking performance.
3. The invention adopts the compound of the chromium aluminum phosphate and the ethyl orthosilicate as the coating binder, has extremely high temperature resistance, and ensures that the use temperature of the coating can reach 1700 ℃, thereby further ensuring that the use range of the coating can be expanded to the surfaces of metal heating surfaces with higher temperature, such as a superheater, a reheater and the like.
4. The coating obtained by the invention has the characteristic of high temperature corrosion resistance (the use temperature reaches 1700 ℃).
The conventional silicate system coating is suitable for a water wall area, and the use temperature is lower than 1000 ℃. The binder of the coating is a compound of chromium aluminum phosphate and ethyl orthosilicate, has extremely high temperature resistance, and the using temperature of the coating can reach 1700 ℃, so that the using range of the coating can be expanded to the surfaces of metal heating surfaces with higher temperature, such as a superheater, a reheater and the like. As shown in FIG. 2, the coating obtained by the invention is prepared on a refractory brick and cured for 24 hours at room temperature; then, the mixture was calcined at 1700 ℃ for 48 hours, and the surface of the refractory brick was observed. The result shows that the phenomena of obvious blistering, cracking, shedding and the like do not exist, and the coating has good high-temperature resistance.
In addition, the composite binder of the chromium aluminum phosphate and the ethyl orthosilicate can enable the coating to be tightly combined with the base material. The compact protective and energy-saving synergistic coating effectively isolates the metal matrix from contacting with the outside, isolates the direct chemical reaction with the molten sulfate and the metal substrate, and simultaneously avoids the reductive corrosion gas H 2 S and CO penetrate through the protective layer to corrode the metal pipe wall, so that the high-temperature corrosion resistance of the coating is achieved. As shown in figure 3, the coating sample wafer obtained by the invention is placed in a mixed salt of sodium sulfate and potassium chloride with the ratio of 3.
5. The coating obtained by the invention has high thermal expansion coefficient matching degree with the base material.
The coating is made of spinel high-entropy ceramic, alumina, silica, cordierite and other raw materials with low thermal expansion coefficients, and the percentage of the components of the raw materials can be adjusted to ensure that the coating and the matrix have matched thermal expansion coefficients and improve the thermal shock resistance. As shown in figure 4, the coating prepared by the invention is prepared on a stainless steel sample, the temperature is raised to 1000 ℃, the coating is quenched by cold water, and the coating does not crack or fall off after 40 times, and has good thermal shock resistance.
In addition, the matched thermal expansion coefficient enables the coating to be tightly attached to the surface of the base material, the coating does not fall off or crack, the base material is effectively protected, and the oxidation, abrasion and high-temperature corrosion of the base material are prevented.
6. The coatings obtained according to the invention were subjected to performance tests, the results of which are shown in Table 1.
TABLE 1 Performance index
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows that the multifunctional protective and energy-saving synergistic coating has excellent anti-coking performance. The left graph shows the initial appearance of a 12Cr1MoVG sample tube with a coating placed in coal cinder with 44.29 percent of alkali metal content; the right image is the appearance of the sample tube after being held in the coal cinder at 600 ℃ for 72 hours.
FIG. 2 shows the high temperature resistance of the multifunctional protective and energy-saving synergistic coating of the present invention.
FIG. 3 shows the corrosion resistance of the multifunctional protective and energy-saving synergistic coating of the present invention.
FIG. 4 shows the thermal shock resistance of the multifunctional protective and energy-saving synergistic coating of the present invention.
Detailed Description
A multifunctional protective and energy-saving synergistic coating is composed of the following raw materials in percentage by weight (g/g): 10 to 30 percent of spinel high-entropy ceramic, 2 to 4 percent of rare earth oxide, 10 to 12 percent of silicon oxide, 8 to 12 percent of aluminum oxide, 8 to 10 percent of aluminum nitride, 6 to 8 percent of cordierite, 3 to 4 percent of brown corundum, 0.5 to 2 percent of bentonite, 30 to 40 percent of composite binder, 0.4 to 0.6 percent of dispersant and 0.4 to 0.6 percent of defoamer.
Wherein: the spinel high-entropy ceramic is CuO or MnO 2 、Fe 2 O 3 、Cr 2 O 3 、Co 3 O 4 、TiO 2 And any six of ZnO and MgO powders are taken as raw materials, are subjected to ball-milling mixing, drying and grinding, are subjected to high-temperature calcination in an air atmosphere, and are cooled and ground to prepare the high-entropy oxide with the spinel structure and the particle size of 300 to 800nm. The preparation method is 202010919577.8And a method for preparing an oxide having high infrared emissivity and entropy.
The rare earth oxide is any 1 to 2 of cerium oxide, lanthanum oxide, dysprosium oxide, yttrium oxide and neodymium oxide, and the particle size of the rare earth oxide is 0.5 to 1.0 mu m.
The grain diameters of the silicon oxide and the aluminum oxide are both 1 mu m; the grain diameter of the aluminum nitride is 200 to 300nm; the particle sizes of cordierite and bentonite are both 10 mu m; the particle size of the brown corundum is 1 to 2 mu m.
The composite binder is prepared by mixing chromium aluminum phosphate and ethyl orthosilicate according to the weight ratio of 3:1, stirring and mixing the uniformly mixed compound. Chromium aluminium phosphate (Cr) 2 O 3 ·Al 2 O 3 ·2P 2 O 5 ·6H 2 O) is a complex salt consisting of chromium phosphate, aluminum phosphate and phosphoric acid, provided by seiandongsheng new materials technology limited, and is a dark green viscous liquid adhesive.
The dispersant is one of Mylar chemical HY-330A + HY-330B, digao Dispers-760W and Kaimett KMT-3021.
The defoaming agent is one of Kelmett KMT-2017, digao Airex-902W and Digao Tego825.
The thickness of the coating is 100 to 200 mu m.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing in proportion;
preparing the coating:
firstly, adding a dispersing agent and a defoaming agent into a composite binder in sequence and fully stirring; then, sequentially adding spinel high-entropy ceramic, rare earth oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and uniformly dispersing at a high speed to obtain a mixture; finally, transferring the mixture into a ball mill, and carrying out ball milling at 300-500rpm for 3-5 hours to obtain the uniform multifunctional protective and energy-saving coating;
performing sand blasting treatment on the surface of the base by using quartz or brown corundum with the particle size of 1-5 mu m to ensure that the cleanliness of the surface of the base material reaches the Sa 2.5-3.0 grade requirement;
preparing a coating:
and (3) spraying for 2 times by using 0.8MPa compressed air under the conditions that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protection and energy-saving synergistic coating.
Example 1a multifunctional protective and energy saving synergistic coating, which consists of 10% spinel high-entropy ceramic, 4% cerium oxide, 12% silicon oxide, 12% aluminum oxide, 10% aluminum nitride, 6% cordierite, 3% brown alumina, 2% bentonite, 40% composite binder, 0.6% dispersant and 0.4% defoamer.
Wherein: the dispersant is prepared from HY-320A: HY-320b =1:1 (g/g). The defoaming agent is HY-1040F.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing in proportion;
preparing the coating:
firstly, adding a dispersing agent and a defoaming agent into a composite binder in sequence and fully stirring; then, sequentially adding spinel high-entropy ceramic, cerium oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and uniformly dispersing at a high speed to obtain a mixture; and finally, transferring the mixture into a ball mill, and carrying out ball milling for 5 hours at 300rpm to obtain the uniform multifunctional protective and energy-saving coating.
And thirdly, performing sand blasting treatment on the surface of the base by adopting quartz or brown fused alumina with the particle size of 1-5 mu m to ensure that the surface cleanliness of the base reaches the requirements of grade Sa 2.5-3.0.
Preparing a coating:
and (3) spraying for 2 times by using 0.8MPa compressed air under the conditions that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after the spraying is finished, and then heating and curing along with a furnace to obtain the multifunctional protection and energy-saving synergistic coating with the thickness of 100 microns.
The resulting coating performance index is shown in table 2.
TABLE 2 Performance index
Embodiment 2 a multifunctional protective and energy-saving synergistic coating, which is composed of 30% of spinel high-entropy ceramic, 1% of yttrium oxide, 2% of dysprosium oxide, 10% of silicon oxide, 8% of aluminum nitride, 6% of cordierite, 3.5% of brown corundum, 0.5% of bentonite, 30% of composite binder, 0.4% of dispersant and 0.6% of defoaming agent.
Wherein: the dispersant is Dispers-706W; the defoaming agent is Airex-902W.
The preparation method of the multifunctional protective and energy-saving synergistic coating comprises the following steps:
weighing in proportion;
preparing the coating:
firstly, adding a dispersing agent and a defoaming agent into a composite binder in sequence and fully stirring; then sequentially adding spinel high-entropy ceramic, yttrium oxide, dysprosium oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and uniformly dispersing at a high speed to obtain a mixture; and finally, transferring the mixture into a ball mill, and performing ball milling for 3 hours at 300rpm to obtain the uniform multifunctional protective and energy-saving coating.
And thirdly, performing sand blasting treatment on the surface of the base by adopting quartz stone or brown corundum with the particle size of 1-5 mu m to ensure that the cleanliness of the surface of the base material reaches the Sa 2.5-3.0 grade requirement.
Preparing a coating:
and (3) spraying for 2 times by using 0.8MPa compressed air under the conditions that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after the spraying is finished, and then heating and curing along with a furnace to obtain the multifunctional protection and energy-saving synergistic coating with the thickness of 200 mu m.
The resulting coating performance indices are shown in table 3.
TABLE 3 Performance index
Embodiment 3 a multifunctional protective and energy-saving synergistic coating, which consists of 18% of spinel high-entropy ceramic, 2% of neodymium oxide, 10% of silicon oxide, 10% of aluminum nitride, 8% of cordierite, 3% of brown corundum, 2% of bentonite, 36% of composite binder, 0.5% of dispersant and 0.5% of defoamer.
Wherein: the dispersant is prepared from HY-320A: HY-320b =1:1 (g/g). The defoaming agent is HY-1040F.
The preparation method of the multifunctional protective and energy-saving synergistic coating is the same as that of example 1, wherein neodymium oxide replaces cerium oxide. The thickness of the obtained multifunctional protective and energy-saving synergistic coating is 150 mu m.
The resulting coating performance index is shown in table 4.
TABLE 4 Performance index
Example 4 a multifunctional protective and energy saving synergistic coating, which consists of spinel high entropy ceramic 24%, yttria 1%, lanthana 2%, silica 10%, alumina 8%, aluminum nitride 8%, cordierite 6%, brown alumina 4%, bentonite 1%, composite binder 35%, dispersant 0.5%, and defoamer 0.5%.
Wherein: the dispersant is KMT-3021; the antifoaming agent was Tego825.
The preparation method of the multifunctional protective and energy-saving synergistic coating is the same as that of the embodiment 2, wherein: lanthanum oxide replaces dysprosium oxide. The thickness of the obtained multifunctional protective and energy-saving synergistic coating is 200 mu m.
The resulting coating performance indices are shown in table 5.
TABLE 5 Performance index
Claims (9)
1. A multifunctional protective and energy-saving synergistic coating is characterized in that: the coating consists of the following raw materials in percentage by weight: 10 to 30 percent of spinel high-entropy ceramic, 2 to 4 percent of rare earth oxide, 10 to 12 percent of silicon oxide, 8 to 12 percent of aluminum oxide, 8 to 10 percent of aluminum nitride, 6 to 8 percent of cordierite, 3 to 4 percent of brown corundum, 0.5 to 2 percent of bentonite, 30 to 40 percent of composite binder, 0.4 to 0.6 percent of dispersant and 0.4 to 0.6 percent of defoamer.
2. As in claimThe multifunctional protective and energy-saving synergistic coating of claim 1 is characterized in that: the spinel high-entropy ceramic is CuO and MnO 2 、Fe 2 O 3 、Cr 2 O 3 、Co 3 O 4 、TiO 2 And any six of ZnO and MgO powders are taken as raw materials, are subjected to ball-milling mixing, drying and grinding, are subjected to high-temperature calcination in an air atmosphere, and are cooled and ground to prepare the high-entropy oxide with the spinel structure and the particle size of 300 to 800nm.
3. The multifunctional protective and energy-saving synergistic coating as claimed in claim 1, wherein: the rare earth oxide is any 1 to 2 of cerium oxide, lanthanum oxide, dysprosium oxide, yttrium oxide and neodymium oxide, and the particle size of the rare earth oxide is 0.5 to 1.0 mu m.
4. The multifunctional protective and energy-saving synergistic coating as claimed in claim 1, wherein: the grain diameters of the silicon oxide and the aluminum oxide are both 1 mu m; the particle size of the aluminum nitride is 200 to 300nm; the particle sizes of the cordierite and the bentonite are both 10 mu m; the particle size of the brown corundum is 1 to 2 mu m.
5. The multifunctional protective and energy-saving synergistic coating as claimed in claim 1, wherein: the composite binder is prepared by mixing chromium aluminum phosphate and ethyl orthosilicate according to the weight ratio of 3:1, stirring and mixing the uniformly mixed compound.
6. The multifunctional protective and energy-saving synergistic coating as claimed in claim 1, wherein: the dispersant is one of Mylar chemical HY-330A + HY-330B, digao Dispers-760W and Kelmett KMT-3021.
7. The multifunctional protective and energy-saving synergistic coating as claimed in claim 1, wherein: the defoaming agent is one of Kelmett KMT-2017, digao Airex-902W and Digao Tego825.
8. The multifunctional protective and energy-saving synergistic coating as claimed in claim 1, wherein: the thickness of the coating is 100 to 200 mu m.
9. The preparation method of the multifunctional protective and energy-saving synergistic coating of claim 1, comprising the following steps:
weighing in proportion;
preparing the coating:
firstly, adding a dispersing agent and a defoaming agent into a composite binder in sequence and fully stirring; then, sequentially adding spinel high-entropy ceramic, rare earth oxide, silicon oxide, aluminum nitride, cordierite, brown corundum and bentonite, and uniformly dispersing at a high speed to obtain a mixture; finally, transferring the mixture into a ball mill, and carrying out ball milling at 300 to 500rpm for 3 to 5 hours to obtain a uniform multifunctional protective and energy-saving coating;
performing sand blasting treatment on the surface of the base by using quartz or brown corundum with the particle size of 1-5 mu m to ensure that the cleanliness of the surface of the base material reaches the Sa 2.5-3.0 grade requirement;
preparing a coating:
and (3) spraying for 2 times by using 0.8MPa compressed air under the conditions that the ambient temperature is 15-30 ℃ and the relative air humidity is lower than 85%, standing for 48 hours after spraying, and heating and curing along with a furnace to obtain the multifunctional protection and energy-saving synergistic coating.
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