CN115286944A - High-temperature corrosion resistant glass ceramic composite coating and preparation method thereof - Google Patents
High-temperature corrosion resistant glass ceramic composite coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
Abstract
The invention provides a high-temperature corrosion resistant glass ceramic composite coating, which comprises water glass, glass powder, boron oxide, kaolin and quartz. The coating uses water glass as a substrate, so that the coating can be constructed in a simple spraying mode, can form a glass substrate phase through high-temperature conversion, and further obtains a compact coating with the thickness of below 25 mu m, has excellent high-temperature corrosion resistance and good thermal expansion coefficient matching property, has good thermal conductivity, can meet the high-temperature application of heat-resistant steel and other metal parts, and is particularly suitable for being applied to high-parameter power station boiler heat exchange tubes.
Description
Technical Field
The invention relates to a high-temperature-resistant coating, in particular to a high-temperature-corrosion-resistant glass ceramic composite coating, and also relates to a high-temperature-corrosion-resistant glass coating and a preparation method thereof, belonging to the technical field of coating preparation.
Background
The flue gas side of the high parameter utility boiler heat exchange tubes is subject to severe high temperature flue gas/coal ash corrosion. With the improvement of steam parameters of the coal-fired boiler, failure problems caused by high-temperature flue gas/coal ash corrosion problems are not ignored, the supply of domestic electric coal is tightened, high-sulfur coal (the sulfur content is more than 3%) is largely used in domestic coal-fired boiler generator sets, the sulfur content of part of coal mines is up to more than 6%, the sulfur content after washing is still up to 2% -4%, the coal ash and the sulfate and sulfur-containing gas contained in the flue gas formed after the coal is combusted are respectively 1 and 2 percentage points higher than that of low-sulfur coal, and complex and harsh boiler heat exchange tube flue gas side service working conditions are formed: the sulfur-containing flue gas is accompanied by low-melting-point alkali metal sulfate sediment, fly ash particles and the like, so that various solid-gas-liquid chemical and electrochemical reactions occur on the surface of the heat exchange tube, a complex substance migration process is involved, various corrosion products are formed, a protective oxide film is difficult to stably grow, and the heat exchange tube is seriously damaged. In 2019 water wall abrasion-proof and explosion-proof inspection of a certain 660MW coal-fired unit, the large-area reduction of the heat exchange tube wall of the water wall (made of 15 CrMo) at the slope of the cold ash bucket area of the two units is found, the actually measured minimum wall thickness of the water wall tube with the originally designed wall thickness of 7.5mm is 2.15mm, and the proportion of the water wall tube with the tube wall thickness smaller than 4mm reaches 53 percent. Therefore, the problem of high-sulfur smoke/coal ash corrosion of the heat exchange tube of the power station boiler is improved or solved, and the method has important significance in improving the efficiency of a thermal generator set and reducing carbon emission.
The development of a new protective coating is a main approach for solving the problem of high-temperature flue gas/coal ash corrosion of a heat exchange tube, and a typical coating technical idea is to prepare a Cr-rich alloy coating on the surface of the heat exchange tube so as to hopefully generate Cr 2 O 3 A protective oxide film. Typical coatings are: (Ni, fe) -Cr coating, niCrBSi, niCrAlY, niCr-Cr 3 C 2 Ni-Cr-Mo-Si-B, (Ni, fe) -Cr-B, cr-infiltrated coating and the like, wherein the conventional preparation process of the coating comprises supersonic flame spraying, explosion spraying, thermal spraying, laser cladding, powder embedding infiltration and the like. However, inevitable holes, molten drop gaps and the like in the sprayed coating are fatal defects; the embedding infiltration coating and the pipe are mutually diffused to further damage the high-temperature mechanical property of the base material. With the increase of service temperature and the use of high-sulfur and poor-quality coal, the existing coating technology cannot better solve the technical problem.
The film forming material of the organic high-temperature coating is easy to be subjected to oxidative degradation and thermal degradation in a high-temperature environment, so that the use temperature of the organic high-temperature coating is limited. The aqueous zinc-rich coating contains a large amount of zinc powder, so the service temperature is generally lower than 300 ℃. The nano modified organic silicon-based coating can resist the temperature of 700 ℃, but is only limited to be applied to a small amount of occasions due to higher cost of nano particles, and the mechanical property of the coating is reduced after the organic silicon is decomposed at high temperature, so that the coating is easy to peel off. The inorganic high-temperature protective coating can resist the temperature of 1000 ℃, but is difficult to obtain without detailed research on components and proportion, so the inorganic high-temperature protective coating is usually only used as a temporary protective coating in the alloy hot working process. Such as: in the application of the Chinese patent with the publication number of CN101314808A, the high-temperature anti-oxidation coating material can naturally peel off from the surface of a steel matrix in the cooling process, so the high-temperature anti-oxidation coating material cannot be used as a long-term anti-oxidation coating.
The glass ceramic composite coating has good thermal stability and chemical stability, can resist harsh high-temperature corrosion environment compared with a common metal coating, and can show excellent protective performance in the harsh corrosion environment. However, it is often a concern that the coefficient of thermal expansion of the glass ceramic composite coating matches that of the alloy matrix. In the complicated and harsh high-sulfur flue gas/coal ash corrosion field, the glass ceramic composite coating has good application prospect due to excellent chemical stability, but the heat conduction efficiency is worried about.
One problem of applying the traditional glass ceramic composite coating to the heat-resistant steel is that the high firing temperature in the preparation process of the traditional glass ceramic composite coating may change the microstructure of the heat-resistant steel matrix and further damage the mechanical property of the matrix, so that the applicable temperature and the alloy matrix of the glass ceramic coating prepared by adopting the traditional process are limited to a certain extent. The high-temperature corrosion resistant coating is prepared by taking silicate aqueous solution as a base material and adding a proper amount of metal or ceramic particles, and compared with the traditional smelting-grinding-spraying-enameling preparation process of a glass ceramic coating, the method is simpler.
Therefore, the novel high-temperature-resistant protective coating which is simple in preparation process, is suitable for ferrite plus pearlite or martensite heat-resistant steel, has good thermal expansion coefficient matching performance and long-term high-temperature corrosion resistance is developed, and has important technical value and application prospect for high-temperature application of heat-resistant steel and other metal parts, especially for solving the problem of high-sulfur smoke/coal ash corrosion of a service environment high-parameter power station boiler heat exchange tube.
Disclosure of Invention
In order to solve the problems of poor thermal expansion coefficient matching, pores in the coating, molten drop gaps, poor thermal conductivity, complex preparation process, high firing temperature and the like in the high-temperature corrosion resistant glass coating in the prior art, the first aim of the invention is to provide the high-temperature corrosion resistant glass ceramic composite coating, which contains glass powder and boron oxide, can improve low-temperature formability, and simultaneously can ensure that the formed glass coating has higher compactness and the thickness is below 25 mu m.
The second purpose of the invention is to provide a high-temperature corrosion resistant glass ceramic composite coating, which is formed by curing the glass ceramic composite coating at high temperature. The surface of the glass ceramic composite coating is smooth, no coking is formed, and due to the addition of micron-scale boron oxide and glass powder, the glass powder and boron oxide can be fused into silicate glass formed by converting water glass in the service process of the coating along with the rise of temperature, so that the compactness of the coating is ensured, the diffusion barrier effect of oxygen in the coating is improved, and the diffusion coefficient of oxygen in the coating is reduced; meanwhile, the emissivity of the coating can be reduced by bubbles in the coating, so that the heat transfer efficiency of the heat exchanger is influenced, and the adverse effect of the glass coating on the emissivity of the heat exchanger can be reduced to the greatest extent by the compact coating.
The third purpose of the invention is to provide a preparation method of the high-temperature corrosion resistant glass ceramic composite coating, which is simple and low in cost, does not use organic solvent in the preparation process, and has the characteristics of environmental protection.
In order to achieve the technical purpose, the invention provides a high-temperature corrosion resistant glass ceramic composite coating paint which comprises water glass, glass powder, boron oxide, kaolin and quartz.
Because the water glass with certain solid content and good fluidity is adopted as the matrix component, the coating can adopt a simple coating spraying process like the traditional organic coating, the water glass can be converted into a glass matrix phase under the high-temperature condition, the added glass powder can reduce the firing temperature of the coating, the boron oxide can reduce the softening point of the glass and improve the low-temperature formability, the coating formed by the coating has higher compactness under the combined action of the water glass and the glass matrix phase, and meanwhile, the combined components can improve the high-temperature corrosion resistance of the coating.
As a preferable scheme, the paint comprises the following components in percentage by mass: glass powder: 25 to 35 percent; boron oxide: 5 to 15 percent; kaolin: 3 to 7 percent; quartz: 3 to 7 percent; water glass: and (4) the balance.
Under the condition of the distribution ratio of the components, the coating formed by the obtained coating has better comprehensive performance. Through adopting the glass powder with high thermal expansion coefficient, quartz and other particles and accurately adjusting the component proportion, the thermal expansion coefficient of the glass coating formed by the coating can be matched with the substrate, and the problem that the thermal expansion coefficient of the traditional glass ceramic protective coating is not matched with that of the substrate is effectively solved.
As a more preferable scheme, the paint comprises the following components in percentage by mass: glass powder: 30 percent; boron oxide: 10 percent; kaolin: 5 percent; quartz: 5 percent; water glass: and the balance.
As a preferable scheme, the particle size range of the glass powder is 1-10 μm; the particle size range of the boron oxide is 1-10 mu m; the particle size range of the kaolin is 1-10 μm; the particle size range of the quartz is 1-10 mu m.
Preferably, the water glass is sodium silicate water glass and/or potassium silicate water glass, and the modulus of the water glass is 3-3.9. The modulus of the water glass is controlled in a proper range to ensure that the coating has excellent comprehensive performance, and if the modulus of the water glass is too low, the content of alkali metal oxide in the coating is high, so that the chemical stability of the coating is reduced; on the contrary, if the water glass modulus is too high and the content of alkali metal oxide in the coating layer is low, the glass transition point becomes high, which results in deterioration of the firing property of the coating layer at high temperature, and is disadvantageous in molding and densification of the coating layer.
The invention also provides a high-temperature corrosion resistant glass ceramic composite coating which is formed by high-temperature curing of the high-temperature corrosion resistant glass ceramic composite coating.
According to the invention, a proper amount of micron-scale boron oxide and glass powder are added, so that the compactness of the coating is improved, and the glass powder and the boron oxide can be blended into silicate glass converted from water glass along with the rise of temperature in the service process of the coating, so that the compactness of the coating is ensured. On one hand, the dense coating can improve the diffusion barrier effect of oxygen in the coating and reduce the diffusion coefficient of oxygen in the coating; on the other hand, the air bubbles in the coating can reduce the emissivity of the coating, thereby affecting the heat transfer efficiency of the heat exchanger, and the dense coating is beneficial to reducing the adverse effect of the emissivity of the coating to the maximum extent. The formed compact coating has no holes basically, so that the thickness of the compact coating can be reduced to 25 mu m, a thin coating is formed, the emissivity of the coating is further ensured, and the coating is ensured not to influence the heat exchange efficiency of the heat exchanger. Through the thickness and the density of accurate control coating, guarantee that the coating has higher thermal conductivity, and because this coating surface is the glass form, very smooth, surface energy is low, and is stable, has the performance of good suppression deposition slagging scorification, can prevent heat exchange tube surface slagging scorification to increase substantially the heat exchange efficiency of the heat exchange tube of the later stage of being in service. In addition, the glass powder can reduce the firing temperature of the coating, and the boron oxide can reduce the softening point of the glass and improve the low-temperature formability, so that the material production cost can be reduced.
As a preferable scheme, the high-temperature corrosion resistant glass ceramic composite coating is formed by uniformly dispersing glass powder, boron oxide, kaolin and quartz in a glass matrix phase.
The invention also provides a preparation method of the high-temperature corrosion resistant glass ceramic composite coating, which is obtained by sequentially carrying out spraying, room-temperature curing and baking curing on the high-temperature corrosion resistant glass ceramic composite coating. The spraying adopts carborundum spraying, and the spraying pressure is 0.5MPa.
In the preparation method, water glass is used as a dispersion solution, and the characteristic that the water glass can be converted into a glass matrix phase in the post-firing process is utilized, so that the coating can adopt a simple paint spraying process, compared with the traditional glass ceramic composite coating, the preparation process reduces the glass frit refining and glass glaze grinding processes, greatly simplifies the preparation process, greatly reduces the enameling firing temperature (the enameling firing temperature of the traditional glass ceramic protective coating is usually as high as 800-900 ℃), and is suitable for high-temperature corrosion protection of heat-resistant steel. The firing temperature of the coating is reduced by adding the glass powder, the production energy consumption is reduced, the glass softening temperature is reduced by adding the boron oxide, and the low-temperature formability of the coating is improved. Because the ceramic component content in the coating is very little, the coating after spraying can be molded and used only by baking in the preparation process without high-temperature treatment, the production cost is further reduced, meanwhile, the coating can be fully and compactly spread on an alloy matrix by virtue of the flow characteristic of a potassium silicate aqueous solution without excessively depending on the high-temperature softening property of a glass phase, and the mechanical property of the heat-resistant steel with relatively low service temperature is not damaged. The raw materials in the coating can be mixed by a high-speed stirring dispersion machine to form the coating to be sprayed.
As a preferable scheme, the spraying adopts a normal-temperature atmosphere spraying mode, and the thickness of one-time spraying is not more than 25 mu m. The minimum thickness of the spray is twice the maximum diameter of the quartz particles. In the spraying process, if the spraying thickness is too thick, the heat transfer efficiency of the matrix (heat exchange tube) is affected. However, if the spray thickness is too thin, the uniformity of the coating layer may not be ensured.
As a preferable scheme, the room temperature curing time is 24h.
As a preferred scheme, the baking and curing conditions are as follows: the temperature is 70-300 ℃, and the time is 24-36 h.
As a preferable scheme, the baking and curing adopts a sectional baking mode, baking treatment is carried out for 5-12 h at 70-80 ℃, then baking treatment is carried out for 5-12 h at 110-130 ℃, and then baking treatment is carried out for 5-12 h at 230-260 ℃. The conditions for the baking curing are further preferably: baking at 70 deg.C for 12 hr, baking at 120 deg.C for 12 hr, and baking at 250 deg.C for 12 hr. And the coating can be prevented from generating bubbles by baking at a gradient temperature, so that the reduction of the emissivity is prevented.
Compared with the prior art, the invention has the following beneficial effects:
(1) The coating can form a compact coating, the coating is basically free of holes and thin, can be controlled to be below 25 mu m, does not influence the emissivity of the coating, has smooth surface and good performance of inhibiting dust deposition and slag bonding, does not influence the heat exchange efficiency of a heat exchanger when applied to the heat exchanger, can prevent the surface of the heat exchange tube from being slag bonded, and greatly improves the heat exchange efficiency of the heat exchange tube at the later service stage.
(2) The paint has good matching property with base materials such as ferrite, pearlite, martensite heat-resistant steel, titanium alloy and the like, has good thermal expansion coefficient matching property and high-temperature corrosion resistance, including oxygen corrosion and salt corrosion, has long service life, can meet the high-temperature application of heat-resistant steel and other metal parts, and is particularly suitable for being applied to high-parameter power station boiler heat exchange tubes with service environments below 600 ℃.
(3) The coating preparation method is simple, the process flow is short, the cost is low, the energy consumption is low, no organic solvent is used in the preparation process, and the coating has the characteristics of environmental protection.
(4) By means of the flow characteristic of the potassium silicate aqueous solution, the coating can be fully and compactly spread on the alloy substrate without excessively depending on the high-temperature softening performance of a glass phase, the mechanical property of the heat-resistant steel with relatively low service temperature is not damaged, and the problem that the microstructure and the high-temperature mechanical property of the alloy substrate are influenced by overhigh enameling temperature in the traditional preparation method is solved.
Drawings
FIG. 1 is a schematic diagram of high sulfur flue gas/coal ash corrosion of a heat exchange tube in a coal-fired boiler with a coating (b) obtained in example 1 of the present invention applied thereto and without the coating (a) applied thereto.
FIG. 2 is a microstructure diagram of the 15CrMo alloy sprayed with the composite coating on the surface and obtained in example 1 after being oxidized in air at 550 ℃ for 1h, wherein (a) is the surface microstructure and (b) is the section microstructure.
FIG. 3 is a sectional micro-topography of the 15CrMo alloy sprayed with the composite coating on the surface and obtained in example 1 after being oxidized for 1000h in 550 ℃ air.
FIG. 4 is a comparison graph of the macro morphology of the 15CrMo alloy with the composite coating sprayed on the surface and the 15CrMo alloy without the composite coating on the surface after being oxidized for 1000h in 550 ℃.
FIG. 5 is a comparison graph of the macro morphology of the TiAl alloy sample sprayed with the composite coating and the TiAl alloy sample without the coating in example 2 after being oxidized for 100 hours in a molten salt environment at 900 ℃.
FIG. 6 is a surface coating topography for the alloy sample of comparative example 1.
FIG. 7 is a microstructure of the surface coating of the alloy sample of comparative example 2 after oxidation in air at 550 ℃ for 1 hour.
FIG. 8 is a microstructure of the surface coating of the alloy sample of comparative example 3 after oxidation in air at 550 ℃ for 10 hours.
Detailed Description
Example 1
200g of potassium silicate waterglass with the modulus of 3.9, 120g of glass powder (the particle size is 1-20 mu m), 40g of boron oxide (the particle size is 1-20 mu m), 20g of kaolin (the particle size is 1-20 mu m), 20g of quartz (the particle size is 1-10 mu m) and 10g of distilled water are weighed and stirred in a stirring disperser at the rotating speed of 2000rpm for 20min to obtain the glass coating. And spraying the coating on the surface of the 15CrMo alloy part subjected to sand blasting by adopting a normal-temperature atmospheric spraying mode, wherein the spraying pressure is 0.5MPa, the spraying thickness is 25 mu m, the sprayed coating is cured at room temperature, baked at 70-80 ℃ for 12h, baked at 110-130 ℃ for 10h, baked at 230-260 ℃ for 5h, and taken out for air cooling.
The thickness of the glass ceramic composite coating prepared on the 15CrMo alloy substrate is about 25 mu m, ceramic particles are well dispersed in the coating, the coating is compact in interior, no hole or crack is observed, the surface is smooth, the glass luster is realized, and meanwhile, the coating and the 15CrMo alloy interface are well combined. As shown in figure 1, in the later service period of the alloy sample with the glass ceramic composite coating on the surface, the coating is smooth in surface, low in surface energy and stable in performance, has good performance of inhibiting dust deposition and slag bonding, obviously improves the oxidation resistance, effectively prevents the slag bonding on the surface of the heat exchange tube, and can greatly improve the heat exchange efficiency of the heat exchange tube in the later service period. In contrast, in the service process of the alloy sample without the coating on the surface, the oxide is continuously peeled off, so that the surface roughness is large, the coal ash and the like are easily settled and gradually cause ash deposition, and the heat exchange efficiency of the heat exchange tube is further reduced.
Respectively oxidizing the glass ceramic composite coating prepared on the 15CrMo alloy matrix for 1 hour and 1000 hours in 550 ℃ air, and observing the corrosion condition of the coating. As shown in FIG. 2, after 1h of oxidation, the ceramic particles in the coating are still uniformly dispersed in the coating, and the oxide at the interface of the coating and the alloy is less, so that the composite coating is not corroded basically and shows good corrosion resistance. As shown in FIG. 3, after 1000h of oxidation, the amount of ceramic particles in the coating is slightly reduced, but the oxide increase at the interface of the coating and the alloy is not much, and the coating shows higher corrosion resistance. FIG. 4 shows that after the 15CrMo alloy sample coated with the composite coating is oxidized for 1000 hours at 550 ℃ in air, the surface of the 15CrMo alloy sample is smooth, the coating has certain glass luster, and the peeling of the coating or corrosion products is not seen, however, the TiAl alloy without the coating on the surface is seriously corroded, and the obvious peeling of the corrosion products is generated, which indicates that the coating prepared by the coating has good oxidation corrosion resistance.
The coating obtained in example 1 was tested by the laser triangulation method for a coefficient of thermal expansion of 13.4X 10 -6 (K -1 ) And 12CrMoV has a coefficient of thermal expansion of 12.8 to 14.6X 10 -6 (K -1 ) Therefore, the coating prepared by the coating has higher thermal expansion coefficient matching with the matrix.
The thermal conductivity data were measured using a hot constant analyzer from K-analys using the instant flat heat source method (TPS): the experimental environment temperature is 20 ℃, and the thermal conductivity of the 15CrMo alloy sprayed with the glass ceramic composite coating with the thickness of 25 mu m in example 1 is 61.73W (m.K) -1 While the thermal conductivity of the uncoated 15CrMo alloy matrix is 63.55W (m.K) -1 It is shown that the coating produced by the present invention does not affect the heat exchange efficiency of the heat conductive material.
Example 2
200g of potassium silicate sodium water glass with the modulus of 3.9, 120g of glass powder (the particle size is 1-20 microns), 30g of boron oxide (the particle size is 1-20 microns), 25g of kaolin (the particle size is 1-20 microns), 25g of quartz (the particle size is 1-10 microns) and 10g of distilled water are weighed and stirred in a stirring dispersion machine at the rotating speed of 2000rpm for 20min to obtain the glass coating. And spraying the coating on the surface of the 15CrMo alloy part subjected to sand blasting by adopting a normal-temperature atmosphere spraying mode, wherein the spraying pressure is 0.5MPa, the spraying thickness is 25 mu m, the sprayed coating is cured at room temperature, baked at 70-80 ℃ for 12h, baked at 110-130 ℃ for 10h and baked at 230-260 ℃ for 5h, and taken out for air cooling.
The thickness of the glass ceramic composite coating prepared on the TiAl alloy substrate is about 25 mu m. Carrying out a hot corrosion test on the TiAl alloy coated with the composite coating on the surface (hot corrosion is a test under a simulated harsh environment and a high-temperature corrosion environment with molten salt and has certain compatibility with the corrosion of a heat exchange tube), wherein the hot corrosionThe experimental conditions were: sal coating 25NaCl calcium+75Na 2 SO 4 The amount of the coating salt is 1.5-2.5 mg/cm 2 The test temperature is 900 ℃, and the test time is 100h. Meanwhile, the same hot corrosion test is carried out on the TiAl alloy sample without a coating on the surface. The test results are shown in fig. 5, wherein the coating of the TiAl alloy samples of the composite coating produced by surface spraying of the present example has a certain glass gloss, and no flaking of the coating or flaking of corrosion products is macroscopically observed, whereas the hot corrosion of the TiAl alloy without the coating on the surface is very severe, and there is very severe flaking of corrosion products. Therefore, the coating prepared by the coating also has excellent salt corrosion resistance.
Comparative example 1
Coatings and coatings were prepared in the same manner as in example 1, except that: replacing the glass powder with alumina powder (the particle diameter is 1-20 mu m).
As shown in fig. 6, a lot of pores can be observed on the surface of the coating by SEM observation, which indicates that the mobility of the glass is poor during firing of the coating, the glass reacts with the alumina particles more strongly, and the pores in the coating become direct channels for oxygen in the air to reach the substrate through the coating, and further react with the alloy directly, which is not favorable for the high temperature oxidation resistance of the coating. After the sample is oxidized at 550 ℃ for 24 hours, the pores on the surface of the coating still exist, the coating still has a porous structure, and the coating cannot better isolate oxygen in air from the alloy, so that the local oxidation of the alloy is caused.
Comparative example 2
Coatings and coatings were prepared in the same manner as in example 1, except that: the boron oxide is replaced by quartz powder (the particle size is 1-10 mu m).
FIG. 7 shows the surface morphology of the alloy sample in the comparative example after being fired at 550 ℃ for 1h, the coating presents glass luster under naked eyes, the appearance surface of the coating is smooth under a scanning electron microscope, no holes are observed, EDS analysis shows that the protrusions on the surface of the coating are quartz particles, however, a plurality of cracks can be observed inside the coating, which shows that the coefficient of thermal expansion of the coating is not matched with that of the alloy matrix, the coating risks falling off in the service process, and the coating does not have the long-term high-temperature corrosion resistance.
Comparative example 3
Coatings and coatings were prepared in the same manner as in example 1, except that: the amount of glass frit was changed to 90g and the amount of kaolin was changed to 50g.
As shown in FIG. 8, after the alloy sample coated with the coating layer was oxidized at 550 ℃ for 10 hours, it was found that bubbles were present in the coating layer, a dense coating layer could not be formed, and some cracks were formed.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the present invention, and the high temperature corrosion resistant coating can be used for protecting heat resistant steel parts, and can also be used for protecting other types of materials such as titanium alloy parts. Therefore, various other changes and modifications can be made according to the technical scheme and the technical idea of the invention, and the invention still belongs to the protection scope covered by the invention.
Claims (10)
1. The high-temperature corrosion resistant glass ceramic composite coating is characterized by comprising the following components in parts by weight: including water glass, glass powder, boron oxide, kaolin and quartz.
2. The high temperature corrosion resistant glass ceramic composite coating according to claim 1, characterized in that: comprises the following components in percentage by mass:
glass powder: 25 to 35 percent;
boron oxide: 5 to 15 percent;
kaolin: 3 to 7 percent;
quartz: 3 to 7 percent;
water glass: and (4) the balance.
3. The high temperature corrosion resistant glass ceramic composite coating according to claim 1 or 2, characterized in that:
the particle size range of the glass powder is 1-10 mu m;
the particle size range of the boron oxide is 1-10 mu m;
the particle size range of the kaolin is 1-10 mu m;
the particle size range of the quartz is 1-10 mu m.
4. The high temperature corrosion resistant glass ceramic composite coating according to claim 1 or 2, characterized in that: the water glass is sodium silicate water glass and/or potassium silicate water glass, and the modulus of the water glass is 3-3.9.
5. The high-temperature corrosion resistant glass ceramic composite coating is characterized in that: formed by high-temperature curing of the high-temperature corrosion resistant glass ceramic composite coating according to any one of claims 1 to 5.
6. The high temperature corrosion resistant glass ceramic composite coating according to claim 5, characterized in that: is formed by uniformly dispersing glass powder, boron oxide, kaolin and quartz in a glass matrix phase.
7. A preparation method of a high-temperature corrosion resistant glass ceramic composite coating is characterized by comprising the following steps: the high-temperature corrosion resistant glass ceramic composite coating of any one of claims 1 to 4 is prepared by spraying, room-temperature curing and baking curing in sequence.
8. The method for preparing the high-temperature corrosion resistant glass ceramic composite coating according to claim 7, wherein the method comprises the following steps: the spraying adopts a normal-temperature atmosphere spraying mode, and the thickness of one-time spraying is not more than 25 mu m.
9. The method for preparing the high temperature corrosion resistant glass ceramic composite coating according to claim 7, characterized in that: the baking and curing conditions are as follows: the temperature is 70-300 ℃, and the time is 24-36 h.
10. The method for preparing the high temperature corrosion resistant glass ceramic composite coating according to claim 9, wherein the method comprises the following steps: the baking and curing adopts a sectional baking mode, baking treatment is carried out for 5-12 h at 70-80 ℃, then baking treatment is carried out for 5-12 h at 110-130 ℃, and then baking treatment is carried out for 5-12 h at 230-260 ℃.
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