CN114990384B - Corrosion-sensitive coating and spraying method thereof - Google Patents
Corrosion-sensitive coating and spraying method thereof Download PDFInfo
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- C22C18/00—Alloys based on zinc
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- B22—CASTING; POWDER METALLURGY
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- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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- C23C4/06—Metallic material
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- 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
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0836—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with electric or magnetic field or induction
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
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- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0844—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid in controlled atmosphere
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- B22F9/02—Making metallic powder or suspensions thereof using physical processes
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- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
- B22F2009/0896—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid particle transport, separation: process and apparatus
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Abstract
A corrosion-sensitive coating comprises a bottom layer and a surface layer, wherein the bottom layer comprises 12-16 wt.% of Al and WO 3 2 to 5wt percent of ZnO, 5 to 7wt percent of Zn, the balance of Zn, and the surface layer contains 13 to 17wt percent of Al, 1 to 3wt percent of Mg and the balance of Zn. The spraying steps are as follows: proportioning the raw materials according to alloy components, putting the raw materials into a vacuum induction furnace for smelting and melting, crushing and atomizing molten metal into metal liquid drops by high-pressure argon, rapidly cooling and solidifying the metal liquid drops into powder, and sieving the powder to obtain bottom metal powder and surface metal powder, wherein the working gas and the powder carrying gas are N 2 The length of the gun tube is 4 inches, the speed of the Y axis is 30-50 m/min, the powder feeding rate is 40-60 g/min, and the spray distance, the kerosene amount, the oxygen amount 1800-2200, the combustion chamber pressure, the oxygen pressure and the fuel pressure are changed according to the bottom layer and the surface layer.
Description
Technical Field
The invention relates to a corrosion-sensitive coating and a spraying method thereof.
Background
The corrosion problem is spread across various fields of national economy and national defense construction, and a large number of components, equipment and facilities fail due to corrosion, so that huge economic losses are brought to the country. According to statistics, the economic loss caused by corrosion in China is reported to account for about 4% of the total national production value. The data issued by the national statistical bureau shows that the total annual domestic production value in 2021 of China is 1143670 hundred million yuan, so that the economic loss caused by corrosion in 2021 of China is about 40000 hundred million yuan. At present, the corrosion problem relates to various fields of daily life, industry, agriculture, national defense industry and the like, and the corrosion causes the change of the organization structure and chemical components of materials and the reduction of application performance, and can also cause the early repair of equipment parts or the occurrence of accidents. Corrosion not only brings about a huge economic loss, but also causes a waste of a large amount of energy and resources worldwide. In addition to the visible economic loss caused by corrosion, there are also a number of invisible accident losses, and the resulting training is very painful. Safety accidents and environmental pollution caused by breakage and perforation of equipment and steel structures due to local corrosion are difficult to prevent, and the damage caused by the safety accidents and the environmental pollution is huge. For example, chemical plants have equipment loss up to 70% due to local corrosion, aircraft crash due to corrosion of parts, collapse of bridges due to corrosion of steel-structured beam cracks, oil and gas leakage due to corrosion perforation of oil and gas pipes, personal safety problems due to corrosion problems in medical treatment, and accident loss due to corrosion is also a huge loss.
Corrosion can be broadly divided into chemical corrosion and electrochemical corrosion, depending on the type of corrosion mechanism of the material. Moreover, corrosion generally occurs on the surface of a material or from below the surface of the material, so that the most effective method for improving the corrosion resistance of the material is to perform strengthening protection treatment on the surface of a part to prepare a protective coating with a certain thickness and high corrosion resistance on the surface of the part. In order to minimize the loss caused by corrosion, the conventional anti-corrosion methods include a protective coating method, a corrosion inhibitor adding method, a corrosion-resistant coating application method and the like according to corrosion mechanisms. The protective coating method mainly comprises a metal protective coating and a nonmetal protective coating. The corrosion prevention principle is to isolate the protected material from the corrosive medium, thereby achieving the function of corrosion prevention. The main materials used in the nonmetal protective coating method are ceramics, glass, plastics, rubber and the like; the metal protective coating method mainly comprises electroplating, hot dip plating, chemical plating, hot spraying and the like. Although the metal protective coating method achieves a certain effect in the aspect of delaying the corrosion of materials, the two processes of electroplating and hot dip plating have high energy consumption and high pollution, and do not meet the requirements of national green production. The corrosion inhibitor can reduce the speed of electrochemical reaction during material corrosion, and the aim of delaying material corrosion can be achieved by adding some corrosion inhibitors into a corrosion medium. The corrosion inhibitor can be classified into an inorganic corrosion inhibitor and an organic corrosion inhibitor, wherein the principle of the inorganic corrosion inhibitor is that insoluble passivation substances or film layers are generated on the surface of a material so as to achieve the anti-corrosion effect, and the organic corrosion inhibitor is adsorbed on the surface of the material so as to change the surface state of the material and play a role in anti-corrosion. The anti-corrosion paint is easy to cause environmental pollution, has insufficient wear resistance, and is easy to scratch during transportation of workpieces to lose protection.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a corrosion induction coating, which can directly identify the surface corrosion condition through detection technical means such as light, electricity, heat and the like, and can remedy the surface corrosion condition in time, so that larger equipment damage is avoided.
The second technical problem to be solved by the invention is to provide the spraying method of the corrosion induction coating, which has the advantages of simple steps, convenient construction, uniform and continuous coating, no defects of missing coating, air bubbles, flaking, cracks, pits, inclusions and the like, and no obvious local excessive thickness phenomenon.
In order to solve the first technical problem, the present invention provides a corrosion-sensitive coating, which is characterized in that: the floor comprises a floor layer and a surface layer, wherein the floor layer comprises the following components: al content is 12-16 wt.%, WO 3 The content is 2-5 wt%, znO content is 5-7 wt%, and Zn is the rest, wherein the surface layer comprises the following components: 13-17 wt.% of Al, 1-3 wt.% of Mg and the balance of Zn.
The corrosion-sensitive coating provided by the invention adopts zinc aluminum as a basic phase, and is a spray coating material of the current marine corrosion-protective coating, and most of the spray coating materials adopt Zn, al and alloys thereof. The zinc-aluminum alloy coating has better electrochemical protection effect than pure zinc or pure aluminum coating, and has the advantages of both the electrochemical protection effect of the zinc coating and the low corrosion rate of the aluminum coating. The steel members and structures are protected for a long time by adopting the hot spraying zinc, aluminum and alloy coatings thereof, and the hot spraying zinc, aluminum and alloy coatings thereof are applied in the 20 th century and the hot spraying zinc, aluminum and alloy coatings thereof are still commonly adopted as protection measures. Application research of zinc spraying and aluminum spraying is started from the end of the 50 th century in China. The service life of the thermal spraying Zn-Al coating can reach 20-50 years, and the service life of the heavy anti-corrosion coating is only about 15 years. The method for preparing the corrosion induction coating by using the Zn-Al coating as the basic phase has great potential application value. In the invention, the corrosion sensing coating has the bottom Al content of 12-16 wt.% and the surface Al content of 13-17 wt.%.
WO is selected for the corrosion-sensitive coating of the invention 3 And ZnO particles as a coating corrosion-sensitive photochromic component because tungsten oxide (WO 3) is a good photochromic material, irradiated with 253.7nm ultraviolet light from a mercury lamp to WO 3 Crystals, which turn blue. Tungsten trioxide of transition metal oxide (WO 3 ) As a typical multifunctional semiconductor material, the room temperature forbidden band width is 2.6-3.6eV, and the material is an indirect band gap broadband n-type semiconductor. WO (WO) 3 The crystal has a perovskite structure, and is formed by [ WO 6 ]Regular octahedra are arranged in a certain order to form an amorphous WO 3 The octahedral arrangement is a three-dimensional disordered network structure. WO (WO) 3 Has various characteristics in optics and electricity, good electrochemical performance and the like, and is considered as one of the color-changing materials with the most development potential. Furthermore, under the action of electricity, WO 3 The material can also achieve a mutual change in colour and blue, thus, WO 3 The material may be used as a photo-switch or the like. Meanwhile, znO particles are added as a coating corrosion-induced photochromic component, because the ZnO particles can generate photochromism in the visible light range, so that the ZnO particles are added into the coating, and when the mechanical equipment corrosion-protection coating is corroded, the corrosion parts can be found by naked eyes of operators and maintenance staff. In addition, studies have found WO 3 The color-changing efficiency of the ZnO composite system can be improved by more than 200 times compared with that of single-component photochromic particles, thus WO is selected 3 The ZnO composite system can improve the induction sensitivity of the corrosion induction coating. WO in the present invention 3 The content is 2-5 wt.% and the ZnO content is 5-7 wt.%.％。
In order to solve the second technical problem, the invention provides a spraying method of a corrosion induction coating, which comprises the following steps:
(1) The raw materials of the bottom layer and the surface layer are respectively mixed according to proportion and put into a vacuum induction furnace for smelting and melting, and the smelting temperature is 670 ℃ to form bottom layer metal liquid and surface layer metal liquid;
(2) Respectively feeding the bottom layer metal liquid and the surface layer metal liquid into an atomization area, atomizing the bottom layer metal liquid and the surface layer metal liquid into metal liquid drops by high-pressure argon, and rapidly cooling and solidifying the metal liquid drops into bottom layer metal powder and surface layer metal powder;
(3) Screening the bottom metal powder and the surface metal powder respectively, wherein the required powder granularity is 50-125 mu m;
(4) Spraying a bottom layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 250-320 mm, the gun barrel length is 4 inches, the Y-axis speed is 30-50 m/min, the kerosene amount is 6-8.5L/h, and the oxygen amount is 1800-2200 m 3 The powder feeding rate is 40-60 g/min, the pressure of a combustion chamber is 6.5-8.5 MPa, the pressure of oxygen is 9.5-12.5 MPa, and the pressure of fuel is 7.5-10.0 MPa;
(5) Spraying a surface layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 300-350 mm, the gun barrel length is 4 inches, the Y-axis speed is 30-50 m/min, the kerosene amount is 5-7L/h, and the oxygen amount is 1500-2000 m 3 And/h, the powder feeding rate is 40-60 g/min, the pressure of a combustion chamber is 6.0-8.0 MPa, the pressure of oxygen is 9.0-12.0 MPa, and the pressure of fuel oil is 7.0-8.5 MPa.
The spray method of the corrosion induction coating provided by the invention adopts vacuum induction melting and gas atomization powder preparation technology to manufacture coating spray powder, and adopts supersonic flame spray technology to prepare the coating. The thickness of the coating is 0.2-1 mm, and the appearance quality of the coating is as follows: the coating should be uniform and continuous, and has no defects such as missing coating, bubbles, flaking, cracks, pits, inclusions and the like, no obvious local excessive thickness phenomenon, the bonding strength of the coating is more than or equal to 10Mpa, and the water resistance is high: after the test, the coating has no bulge caused by falling, the internal tissue of the coating is compact, the porosity is less than or equal to 3 percent, the hardness of the coating is not lower than 9H, the corrosion resistance of the coating is not lower than 120H, the red rust time of the coating is not lower than 120H in the wet heat test, and the corrosion induction sensitivity delta C of the coating is more than 0.01.
Drawings
FIG. 1 is a schematic view of the structure of a corrosion-sensitive coating according to the present invention.
FIG. 2 is a photograph of the topography of the corrosion sensing coating prepared in example three.
Detailed Description
Embodiment one:
a corrosion-sensitive coating comprising a primer layer and a topcoat layer, wherein the primer layer comprises the following components: al content 15wt.%, WO 3 3wt.% ZnO, 6wt.% Zn, balance Zn, wherein the facing layer comprises the following components: the Al content was 13wt.%, the Mg content was 2wt.%, the balance Zn.
A method of spray coating a corrosion-sensitive coating, comprising the steps of:
(1) The raw materials of the bottom layer and the surface layer are respectively mixed according to proportion and put into a vacuum induction furnace for smelting and melting, and the smelting temperature is 670 ℃ to form bottom layer metal liquid and surface layer metal liquid;
(2) Respectively feeding the bottom layer metal liquid and the surface layer metal liquid into an atomization area, atomizing the bottom layer metal liquid and the surface layer metal liquid into metal liquid drops by high-pressure argon, and rapidly cooling and solidifying the metal liquid drops into bottom layer metal powder and surface layer metal powder;
(3) Screening the bottom metal powder and the surface metal powder respectively, wherein the required powder granularity is 50-125 mu m;
(4) Spraying a bottom layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 250-320 mm, the gun barrel length is 4 inches, the Y-axis speed is 50m/min, the kerosene amount is 6L/h, and the oxygen amount is 1800m 3 And/h, the powder feeding rate is 40g/min, the pressure of a combustion chamber is 7.5MPa, the pressure of oxygen is 10.5MPa, and the pressure of fuel oil is 9.0MPa;
(5) Spraying a surface layer: the working gas and the powder-carrying gas are N 2 Gas spraying distance of 330mm, gun barrel length of 4 inches, Y-axis speed of 40m/min, kerosene amount of 7L/h and oxygen amount of 1500m 3 And/h, the powder feeding rate is 50g/min, the pressure of a combustion chamber is 7.0MPa, the pressure of oxygen is 9.0MPa, the pressure of fuel oil is 7.0MPa, and the thickness of a coating is 0.2mm.
The corrosion-sensitive coating manufactured in the embodiment has the appearance quality: the coating should be uniform and continuous, and has no defects such as missing coating, bubbles, flaking, cracks, pits, inclusions and the like, no obvious local excessive thickness phenomenon, 40MPa of coating bonding strength and water resistance: after the test, the coating has no bulge caused by falling, the internal tissue of the coating is compact, the porosity is 1.0%, the hardness of the coating is 9.2H, the corrosion resistance of the coating is improved, the red rust time of the coating is 180H, the wet heat test is carried out, the red rust time of the coating is 150H, and the corrosion induction sensitivity delta C=0.015.
Embodiment two:
a corrosion-sensitive coating comprising a primer layer and a topcoat layer, wherein the primer layer comprises the following components: al content was 12wt.%, WO 3 The content is 5wt.%, the ZnO content is 5wt.%, the balance Zn, wherein the facing layer comprises the following components: the Al content was 17wt.%, the Mg content was wt.%, the balance Zn.
A method of spray coating a corrosion-sensitive coating, comprising the steps of:
(1) The raw materials of the bottom layer and the surface layer are respectively mixed according to proportion and put into a vacuum induction furnace for smelting and melting, and the smelting temperature is 670 ℃ to form bottom layer metal liquid and surface layer metal liquid;
(2) Respectively feeding the bottom layer metal liquid and the surface layer metal liquid into an atomization area, atomizing the bottom layer metal liquid and the surface layer metal liquid into metal liquid drops by high-pressure argon, and rapidly cooling and solidifying the metal liquid drops into bottom layer metal powder and surface layer metal powder;
(3) Screening the bottom metal powder and the surface metal powder respectively, wherein the required powder granularity is 50-125 mu m;
(4) Spraying a bottom layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 250mm, the gun barrel length is 4 inches, the Y-axis speed is 40m/min, the kerosene amount is 7.5L/h, and the oxygen amount is 2000m 3 And/h, the powder feeding rate is 50g/min, the pressure of a combustion chamber is 6.5MPa, the pressure of oxygen is 9.5MPa, and the pressure of fuel oil is 7.5MPa;
(5) Spraying a surface layer: the working gas and the powder-carrying gas are N 2 Gas spraying distance is 300mm, gun barrel length is 4 inches, Y-axis speed is 30m/min, kerosene amount is 5L/h, and oxygen amount is 1700m 3 And/h, the powder feeding rate is 40g/min, the pressure of a combustion chamber is 6.0MPa, the pressure of oxygen is 10.0MPa, the pressure of fuel oil is 7.5MPa, and the thickness of a coating is 0.5mm.
The corrosion-sensitive coating manufactured in the embodiment has the appearance quality: the coating should be uniform and continuous, and has no defects such as missing coating, bubbles, flaking, cracks, pits, inclusions and the like, no obvious local excessive thickness phenomenon, coating bonding strength of 45MPa and water resistance: after the test, the coating has no bulge caused by falling, the internal tissue of the coating is compact, the porosity is 1.2%, the hardness of the coating is 9.3H, the corrosion resistance of the coating is improved, the red rust time of the coating is 190H, the wet heat test is carried out, the red rust time of the coating is 165H, and the corrosion induction sensitivity delta C=0.018.
Embodiment III:
a corrosion-sensitive coating comprising a primer layer and a topcoat layer, wherein the primer layer comprises the following components: al content was 16wt.%, WO 3 The content was 2wt.%, the ZnO content was 7wt.%, the balance Zn, wherein the facing layer comprises the following components: the Al content was 16wt.%, the Mg content was 3wt.%, the balance Zn.
A method of spray coating a corrosion-sensitive coating, comprising the steps of:
(1) The raw materials of the bottom layer and the surface layer are respectively mixed according to proportion and put into a vacuum induction furnace for smelting and melting, and the smelting temperature is 670 ℃ to form bottom layer metal liquid and surface layer metal liquid;
(2) Respectively feeding the bottom layer metal liquid and the surface layer metal liquid into an atomization area, atomizing the bottom layer metal liquid and the surface layer metal liquid into metal liquid drops by high-pressure argon, and rapidly cooling and solidifying the metal liquid drops into bottom layer metal powder and surface layer metal powder;
(3) Screening the bottom metal powder and the surface metal powder respectively, wherein the required powder granularity is 50-125 mu m;
(4) Spraying a bottom layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 320mm, the gun barrel length is 4 inches, the Y-axis speed is 30m/min, the kerosene amount is 8.5L/h, and the oxygen amount is 2200m 3 The powder feeding rate is 60g/min, the pressure of a combustion chamber is 8.5MPa, the pressure of oxygen is 12.5MPa, and the pressure of fuel oil is 10.0MPa;
(5) Spraying a surface layer: the working gas and the powder-carrying gas are N 2 Gas spraying distance is 350mm, gun barrel length is 4 inches, Y-axis speed is 50m/min, kerosene amount is 6L/h, and oxygen amount is 2000m 3 Per hour, the powder feeding rate is 60g/min, the pressure of a combustion chamber is 8.0MPa, the pressure of oxygen is 12.0MPa, and the pressure of fuel oil is 8.5MPaThe thickness of the coating is 1.0mm.
The corrosion-sensitive coating manufactured in the embodiment has the appearance quality: the coating should be uniform and continuous, and has no defects such as missing coating, bubbles, flaking, cracks, pits, inclusions and the like, no obvious local excessive thickness phenomenon, the bonding strength of the coating is 50MPa, and the water resistance is high: after the test, the coating has no bulge caused by falling, the internal tissue of the coating is compact, the porosity is 0.9%, the hardness of the coating is 9.4H, the corrosion resistance of the coating is realized, the red rust appearing time of the coating is 187H, the wet heat test is carried out, the red rust appearing time of the coating is 145H, and the corrosion sensing sensitivity delta C=0.019.
Claims (2)
1. A corrosion-sensitive coating, characterized by: the floor comprises a floor layer and a surface layer, wherein the floor layer comprises the following components: al content is 12-16 wt.%, WO 3 The content is 2-5 wt%, znO content is 5-7 wt%, and Zn is the rest, wherein the surface layer comprises the following components: 13-17 wt.% of Al, 1-3 wt.% of Mg and the balance of Zn.
2. A method of spraying a corrosion-sensitive coating according to claim 1, comprising the steps of:
(1) The raw materials of the bottom layer and the surface layer are respectively mixed according to proportion and put into a vacuum induction furnace for smelting and melting, and the smelting temperature is 670 ℃ to form bottom layer metal liquid and surface layer metal liquid;
(2) Respectively feeding the bottom layer metal liquid and the surface layer metal liquid into an atomization area, atomizing the bottom layer metal liquid and the surface layer metal liquid into metal liquid drops by high-pressure argon, and rapidly cooling and solidifying the metal liquid drops into bottom layer metal powder and surface layer metal powder;
(3) Screening the bottom metal powder and the surface metal powder respectively, wherein the required powder granularity is 50-125 mu m;
(4) Spraying a bottom layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 250-320 mm, the gun barrel length is 4 inches, the Y-axis speed is 30-50 m/min, the kerosene amount is 6-8.5L/h, and the oxygen amount is 1800-2200 m 3 And/h, the powder feeding rate is 40-60 g/min, the pressure of a combustion chamber is 6.5-8.5 MPa, the pressure of oxygen is 9.5-12.5 MPa, and the pressure of fuel is 7.5-10.0 MPa;
(5) Spraying a surface layer: the working gas and the powder-carrying gas are N 2 The gas spraying distance is 300-350 mm, the gun barrel length is 4 inches, the Y-axis speed is 30-50 m/min, the kerosene amount is 5-7L/h, and the oxygen amount is 1500-2000 m 3 And/h, the powder feeding rate is 40-60 g/min, the pressure of a combustion chamber is 6.0-8.0 MPa, the pressure of oxygen is 9.0-12.0 MPa, and the pressure of fuel oil is 7.0-8.5 MPa.
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