CN115958191A - Composite anticorrosive layer and preparation method thereof - Google Patents
Composite anticorrosive layer and preparation method thereof Download PDFInfo
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- CN115958191A CN115958191A CN202211621959.8A CN202211621959A CN115958191A CN 115958191 A CN115958191 A CN 115958191A CN 202211621959 A CN202211621959 A CN 202211621959A CN 115958191 A CN115958191 A CN 115958191A
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 98
- 239000010959 steel Substances 0.000 claims abstract description 98
- 238000005507 spraying Methods 0.000 claims abstract description 68
- 239000000758 substrate Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 238000007789 sealing Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000010288 cold spraying Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 239000010935 stainless steel Substances 0.000 claims abstract description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- 239000000565 sealant Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 53
- 239000007921 spray Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003973 paint Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 230000003014 reinforcing effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000005422 blasting Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 238000005488 sandblasting Methods 0.000 claims description 5
- 229910001294 Reinforcing steel Inorganic materials 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010963 304 stainless steel Substances 0.000 claims description 2
- 239000010965 430 stainless steel Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
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- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims 3
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- 230000000052 comparative effect Effects 0.000 description 15
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- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
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- 238000010099 solid forming Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- Coating By Spraying Or Casting (AREA)
Abstract
The invention relates to a metal composition for cold spraying, a cold spraying process, a hole sealing agent; the metal composition is used as a spray coating, and the spray coating on the surface of the steel substrate obtained by the cold spraying process comprises a composite anticorrosive layer of a sealing layer formed by the spray coating and the sealant; the invention also provides a steel bar with the composite anticorrosive layer. The metal composition of the present invention comprises: 1 to 5 percent of nickel powder, 1 to 5 percent of Al45Mg55 alloy powder, 5 to 15 percent of stainless steel powder and the balance of zinc powder. The composite anticorrosive layer disclosed by the invention is extremely low in porosity and excellent in corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of metal surface engineering and corrosion prevention, and particularly relates to a composite corrosion-resistant layer comprising a spray coating layer and a sealing layer and a preparation method thereof.
Background
Reinforced concrete is one of the most important building materials, and the shadow frequency of the reinforced concrete appears in railway bridges and tunnels. Along with the rise and advance of railway construction to plateau and coastal areas, the corrosion of reinforced concrete is a crucial factor influencing the durability and reliability of engineering. Structural corrosion of reinforced concrete includes structural corrosion of concrete and corrosion of steel reinforcement. In order to prevent corrosion of the reinforcing bars, the reinforcing bars must be surface-treated to provide the reinforcing bars with a corrosion-resistant layer. Methods for forming an alloy anticorrosive layer on the surface of reinforcing steel bars by thermal spraying techniques have been developed in the prior art. Compared with the traditional thermal spraying, the cold spraying has the problems of low deposition temperature, high deposition efficiency, low porosity, difficult oxidation, decomposition, phase change, growth of crystal grains of the nano-structure material and the like in the deposition process of powder. More particularly, the rapid development of cold spraying technology and equipment in recent years enables cold spraying to be used as a rapid solid forming technology and applied to the anticorrosion treatment and damage repair of key parts such as metal additive manufacturing, aerospace and the like.
Disclosure of Invention
The invention aims to provide a metal composition for cold spraying on the surface of a steel substrate, in particular the surface of a steel bar, a cold spraying process and an alloy spraying layer formed on the surface of the steel substrate, in particular the surface of the steel bar through the cold spraying process. Based on the alloy spraying coating and the sealing layer, the invention also provides a composite anticorrosive coating on the surface of the steel substrate, in particular the surface of the steel bar. The composite anticorrosive layer has excellent performances of corrosion resistance, isolation, wear resistance, alkali resistance and the like, has no red rust for more than 5000h in neutral salt spray, and has alkali resistance of more than 5000h. Compared with the reinforcing steel bar which is not subjected to anti-corrosion treatment, the bond stress of the reinforcing steel bar with the composite anti-corrosion layer and the concrete is improved to a certain degree.
In order to achieve the purpose, the invention adopts the following technical scheme:
a metal composition for cold spraying comprising, based on the total mass of the metal composition: 1 to 5 percent of nickel powder, 1 to 5 percent of Al45Mg55 alloy powder, 5 to 15 percent of stainless steel powder and the balance of zinc powder.
Preferably, the fineness of the nickel powder, the Al45Mg55 alloy powder, the stainless steel powder and the zinc powder is less than 5 percent of the mass of 45-micron screen residue.
Preferably, the stainless steel powder is selected from one or more of 304 stainless steel powder, 316L stainless steel powder, 430 stainless steel powder and 310 stainless steel powder.
The invention also provides a preparation method of the metal composition, which comprises the following steps:
preparing the components according to the mass percent, sequentially adding nickel powder, al45Mg55 alloy powder, stainless steel powder and zinc powder into a closed ball mill, uniformly mixing, and then hermetically storing for later use.
In addition, the invention also provides a cold spraying process of the surface of the steel base material, which comprises the following steps:
s-1, performing dust removal and rust removal treatment on the surface of the steel substrate to expose the metal surface of the steel substrate, and enabling the surface roughness of the treated steel substrate to reach Sa2.5 grade or above;
s-2, preheating the steel base material treated in the step S-1 to 350-450 ℃;
s-3, starting cold spraying equipment, spraying by taking one of dry compressed air, helium, nitrogen and argon as accelerating gas, wherein the spraying pressure is 0.5-5 MPa, the temperature of the accelerating gas is 350-450 ℃, the distance from a spray gun nozzle to the surface of the steel substrate is controlled to be 15-30 mm, the spraying speed is 300-900 m/S, the transverse moving speed of a spray gun is 10-25 mm/S, after one side of the steel substrate is sprayed, if necessary, turning the steel substrate by 180 degrees, continuously spraying once, and then naturally cooling to room temperature.
Preferably, in the step S-1, the treatment includes shot blasting the surface of the steel substrate with steel shots having a diameter of 0.1 to 0.3mm, or sand blasting the surface of the steel substrate with quartz sand having a particle size of 0.6 to 1.18 mm.
Preferably, in the step S-3, the spray paint is the metal composition for cold spraying according to the present invention.
Thus, the present invention provides a spray coating on the surface of a steel substrate, which is formed on the surface of the steel substrate by the cold spray process using the metal composition for cold spray according to the present invention as a spray paint.
Preferably, the thickness of the sprayed layer is 30 to 70 μm.
The invention provides a sprayed coating on the surface of a steel bar, which is prepared by taking the metal composition for cold spraying as a spray coating and performing the following process steps:
s-1, performing shot blasting treatment on the surface of the steel bar by using a steel shot with the diameter of 0.1-0.3 mm, or performing sand blasting treatment on the surface of the steel bar by using quartz sand with the particle size of 0.6-1.18 mm to expose the metal surface of the steel bar, wherein the roughness of the surface of the treated steel bar reaches Sa2.5 grade or above;
s-2, preheating the steel bars processed in the step S-1 to 350-450 ℃;
s-3, starting cold spraying equipment, spraying by taking one of dry compressed air, helium, nitrogen and argon as accelerating gas, wherein the spraying pressure is 0.5-5 MPa, the temperature of the accelerating gas is 350-450 ℃, the distance from a spray gun nozzle to the surface of the steel bar is controlled to be 15-30 mm, the spraying speed is 300-900 m/S, the transverse moving speed of a spray gun is 10-25 mm/S, after one surface of the steel bar is sprayed, immediately turning the steel bar for 180 degrees, continuously spraying once, and naturally cooling to room temperature.
Therefore, the invention also provides a steel bar with the spray coating.
In order to reduce the porosity of the sprayed layer, the prior art uses a method of spraying the sprayed material several times, with the result that the bonding force between each layer is poor. The invention adopts a spraying process, thereby avoiding the problem of combination among multiple layers. And meanwhile, the steel bar is preheated during cold spraying, so that the binding force between the sprayed paint and the steel bar after plastic deformation is increased. The fineness of the spray coating adopted by the invention is smaller, so that the spray coating is more compactly stacked after plastic deformation. Therefore, the porosity of the sprayed layer of the present invention can be 0.5% or less.
The invention also provides a hole sealing agent, which takes the total mass of the hole sealing agent as a reference and comprises the following components: 1-5% of water-soluble molybdate, 5-15% of polycarboxylic acid, 1-5% of strong base, 5-15% of silane coupling agent, 5-15% of ethanol and the balance of water.
Preferably, the water soluble molybdate is selected from one or more of potassium molybdate, sodium molybdate and magnesium molybdate.
Preferably, the polycarboxylic acid is selected from one or more of a tricarboxylic polycarboxylic acid, a dicarboxylic polycarboxylic acid, and a monocarboxylic polycarboxylic acid.
Preferably, the strong base is selected from one or more of sodium hydroxide, triethanolamine and potassium hydroxide.
Preferably, the silane coupling agent is selected from one or more of aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, an aluminate coupling agent, an aluminum-titanium composite coupling agent, and tetraisopropylbis (dioctylphosphite-oxy) titanate.
The invention also provides a preparation method of the hole sealing agent, which comprises the following steps:
I. preparing the components according to the mixture ratio;
II, dissolving polycarboxylic acid in water, stirring to be in a uniform dispersion state, and adding strong base while stirring until the polycarboxylic acid is completely dissolved to obtain a solution I;
II, mixing a silane coupling agent and ethanol, stirring until the silane coupling agent and the ethanol are completely dissolved, adding the solution I obtained in the step I into the obtained solution, and uniformly stirring to obtain a solution II;
and III, adding water-soluble molybdate into the solution II obtained in the step II, and stirring until the water-soluble molybdate is completely dissolved to obtain the compound.
The invention also provides a composite anticorrosive coating on the surface of the steel substrate, which comprises a spray coating and a sealing layer on the surface of the steel substrate, wherein the sealing layer is formed by the hole sealing agent; the spray coating is disposed between the steel substrate and the seal coat.
Preferably, the thickness of the closing layer is 5 to 10 μm.
Preferably, the spray coating is obtained by taking the metal composition as a spray paint through the cold spraying process; the total thickness of the composite anticorrosive layer is 35-80 mu m.
In addition, the invention also provides a preparation method of the composite anticorrosive layer, which comprises the following steps:
(1) Carrying out surface dust removal and rust removal treatment on the steel base material;
(2) Forming a spray coating on the surface of the treated steel substrate by thermal spraying or cold spraying;
(3) Immersing the steel substrate with the spray coating into the hole sealing agent for 30-60 s, taking out, and naturally airing; or spraying the hole sealing agent on the surface of the spraying layer, and naturally airing; and (5) obtaining the product.
The invention also provides a steel substrate with the composite anticorrosive coating.
As a more preferred embodiment, the present invention provides a steel substrate having the above-mentioned composite anticorrosive coating, wherein the spray coating is obtained by the cold spray process of the present invention using the metal composition of the present invention as a spray paint; the total thickness of the composite anticorrosive layer is 35-80 mu m.
As a further preferred embodiment, the invention provides a steel bar with the above composite corrosion-resistant layer, wherein the sprayed layer is obtained by using the metal composition of the invention as a spray paint through the cold spraying process of the invention; the total thickness of the composite anticorrosive layer is 35-80 mu m.
The invention also provides a preparation method of the steel bar with the composite anticorrosive coating, which comprises the following operations:
immersing the steel bar with the spray coating into the hole sealing agent for 30-60 s, taking out, and naturally airing; or spraying the hole sealing agent on the surface of the spraying layer, and naturally airing; and (5) obtaining the product.
The porosity of the surface of the spray coating layer is below 0.5 percent, after a sealing layer is formed by the sealant, the porosity is basically close to 0 percent, the sealing layer under a microscope is continuous, compact and has certain thickness, and the neutral salt mist resistance, alkali resistance, wear resistance and the like of a steel base material, particularly a steel bar, are greatly improved.
In the present specification, the concentration of the "ethanol" is 100%, unless otherwise specified.
Detailed Description
The invention is illustrated below with reference to specific examples. It will be understood by those skilled in the art that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way.
The experimental procedures in the following examples are conventional unless otherwise specified. The raw materials, reagent materials and the like used in the following examples are all commercially available products unless otherwise specified. Wherein, the purchase conditions of partial reagents and raw materials are as follows:
1. stainless steel powder, zinc powder, aluminum magnesium powder Al45Mg55 and nickel powder: nangong city Xindun alloy welding material spraying limited company
2. AA750 monobasic acid, TAT 736 triply polycarboxylic acid: hangzhou green general chemical engineering science and technology company 3, silane coupling agent: nanjing Quanxi chemical Co., ltd
The metal compositions for cold spraying of the following examples and comparative examples were prepared by the following operations:
preparing the components according to the mass percent, sequentially adding nickel powder, al45Mg55 alloy powder, stainless steel powder and zinc powder into a closed ball mill, uniformly mixing, and then hermetically storing for later use.
The following sealing agents of examples and comparative examples were prepared by the following steps:
I. preparing the components according to the mixture ratio;
II, dissolving polycarboxylic acid in water, stirring to be in a uniform dispersion state, and then adding strong base while stirring until the polycarboxylic acid is completely dissolved to obtain a solution I;
II, mixing a silane coupling agent and ethanol, stirring until the silane coupling agent and the ethanol are completely dissolved, adding the solution I obtained in the step I into the obtained solution, and uniformly stirring to obtain a solution II;
and III, adding water-soluble molybdate into the solution II obtained in the step II, and stirring until the water-soluble molybdate is completely dissolved to obtain the compound.
The steel bar composite corrosion prevention treatment of the following examples and comparative examples comprises the following steps:
s-1, performing shot blasting treatment on the steel bar by using a steel shot with the diameter of 0.1-0.3 mm, or performing sand blasting treatment on the steel bar by using quartz sand with the diameter of 0.6-1.18 mm, and removing dust, impurities, oxide skin and rusty materials attached to the surface of the steel bar to expose the metal surface of the steel bar; the surface roughness of the treated steel bar base material reaches Sa2.5 grade or above;
s-2, preheating the steel bars processed in the step S-1 to 350-450 ℃;
s-3, immediately starting cold spraying equipment, spraying by taking one of dry compressed air, helium gas, nitrogen gas and argon gas as accelerating gas, wherein the spraying pressure is 0.5-5 MPa, the temperature of the accelerating gas is 350-450 ℃, the distance from a spray gun nozzle to the surface of the steel bar is controlled to be 15-30 mm, the speed of spraying material is 300-900 m/S, the transverse moving speed of a spray gun is 10-25 mm/S, after one-pass spraying of one surface of the steel bar is finished, immediately turning the steel bar for 180 degrees, continuing the one-pass spraying, and naturally cooling to room temperature to obtain the steel bar with a sprayed layer;
s-4, immersing the steel bar obtained in the step S-3 into a hole sealing agent for 30-60S, and taking out; or spraying the hole sealing agent on the surface of the steel bar for one time; and naturally drying to obtain the steel bar with the spray coating and the sealing layer.
In the following examples and comparative examples, the performance measurements were based on the following criteria:
the neutral salt spray resistance test is carried out according to GB/T1771; the alkali resistance test is carried out according to GB/T1690, and whether the appearance is unchanged is judged; the hardness of the spray coating is carried out according to GB/T4340.1; the bending resistance of 90v is performed according to GB/T232-2010; the porosity is calculated by a microscope and drawing software; the bond strength test with concrete was performed according to DL/T5150-2001.
Examples 1 to 5 and comparative examples 1 to 3 a metal composition for cold spraying and a sprayed layer formed on a reinforcing bar from the metal composition
The raw material ratios of the metal compositions for cold spray of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1.
The physical and mechanical properties of the sprayed layer formed on the surface of the steel bar by the cold spray process using the metal composition are also shown in table 1.
TABLE 1 Metal composition for Cold spray and Properties of spray coating formed
The spray coatings of examples 1-5 have neutral salt spray resistance of more than 5400h, no red rust, alkali resistance of more than 5000h, porosity of less than 0.5 percent, bending resistance of 90v and no crack. The comparative example 1 does not contain AlMg alloy powder, the comparative example 2 does not contain stainless steel powder, the fineness of the zinc powder, the nickel powder and the aluminum magnesium powder used in the comparative example 3 is 50 meshes, and the obtained spraying layer has high porosity, low hardness, poor neutral salt spray resistance and poor alkali resistance.
Examples 6 to 10 and comparative examples 4 to 6 a sealant and a composite anticorrosive layer including a sealing layer formed of the sealant
The raw material ratios of the hole sealing agents of examples 6 to 10 and comparative examples 4 to 6 are shown in Table 2.
The reinforcing bars having the sprayed coatings obtained in examples 1 to 5 and comparative examples 1 to 3 were formed into a closed layer according to the above-described method. The physical and mechanical properties of the composite anticorrosive coating formed by the spray coating and the sealing layer are also shown in table 2.
TABLE 2 formulary and physico-mechanical properties of examples 6 to 10 and comparative examples 4 to 6
In examples 6 to 10, the porosity of the sealing layer was 0%, and the bond strength with concrete was 9MPa or more. And the sealing layer obtained by 3 comparative examples can reduce the porosity of the anticorrosive layer to a certain extent, but is still larger than the porosity of the composite anticorrosive layers of examples 6-10. In addition, the bond stress between the composite anticorrosive coatings of comparative examples 4 to 6 and concrete was also low.
In summary, the present invention provides a metal composition for cold spray, a spray coating layer formed by cold spray of the metal composition, a sealing agent, and a sealing layer formed by the sealing agent. The invention also provides a composite anticorrosive coating comprising the spray coating and the sealing layer and a steel bar with the composite anticorrosive coating. The composite anticorrosive layer provided by the invention has low porosity and excellent corrosion resistance.
Claims (15)
1. A metal composition for cold spraying comprising, based on the total mass of the metal composition: 1-5% of nickel powder, 1-5% of Al45Mg55 alloy powder, 5-15% of stainless steel powder and the balance of zinc powder;
preferably, the fineness of the nickel powder, the Al45Mg55 alloy powder, the stainless steel powder and the zinc powder is 45 mu m, and the mass of the screen residue is less than 5%;
preferably, the stainless steel powder is selected from one or more of 304 stainless steel powder, 316L stainless steel powder, 430 stainless steel powder and 310 stainless steel powder.
2. A method of making the metal composition of claim 1, comprising:
preparing the components according to the mass percent, sequentially adding nickel powder, al45Mg55 alloy powder, stainless steel powder and zinc powder into a closed ball mill, uniformly mixing, and then hermetically storing for later use.
3. A cold spraying process for the surface of a steel substrate comprises the following steps:
s-1, performing dust removal and rust removal treatment on the surface of the steel substrate to expose the metal surface of the steel substrate, and enabling the surface roughness of the treated steel substrate to reach Sa2.5 grade or above;
s-2, preheating the steel base material treated in the step S-1 to 350-450 ℃;
s-3, starting cold spraying equipment, spraying by taking one of dry compressed air, helium gas, nitrogen gas and argon gas as accelerating gas, wherein the spraying pressure is 0.5-5 MPa, the temperature of the accelerating gas is 350-450 ℃, the distance from a spray gun nozzle to the surface of the steel substrate is controlled to be 15-30 mm, the speed of a spraying material is 300-900 m/S, the transverse moving speed of a spray gun is 10-25 mm/S, after the spraying of one side of the steel substrate is finished, if necessary, the steel substrate is turned over for 180 degrees, the spraying is continued for one time, and then the steel substrate is naturally cooled to the room temperature;
preferably, in the step S-1, the treatment includes shot blasting the surface of the steel substrate with steel shots having a diameter of 0.1 to 0.3mm, or sand blasting the surface of the steel substrate with quartz sand having a particle size of 0.6 to 1.18 mm.
4. The cold spray process according to claim 3, wherein the spray coating material in the step S-3 is the metal composition for cold spray according to claim 1.
5. A spray coating on a surface of a steel substrate, which is formed on the surface of the steel substrate by the cold spray process according to claim 3, using the metal composition for cold spray according to claim 1 as a spray paint;
preferably, the thickness of the sprayed layer is 30 to 70 μm.
6. A sprayed coating on the surface of a steel bar, which is prepared by taking the metal composition for cold spraying as claimed in claim 1 as a spray paint through the following process steps:
s-1, performing shot blasting treatment on the surface of the steel bar by using a steel shot with the diameter of 0.1-0.3 mm, or performing sand blasting treatment on the surface of the steel bar by using quartz sand with the particle size of 0.6-1.18 mm to expose the metal surface of the steel bar, wherein the roughness of the surface of the treated steel bar reaches Sa2.5 grade or above;
s-2, preheating the steel bars treated in the step S-1 to 350-450 ℃;
and S-3, starting cold spraying equipment, spraying by taking one of dry compressed air, helium, nitrogen and argon as accelerating gas, wherein the spraying pressure is 0.5-5 MPa, the temperature of the accelerating gas is 350-450 ℃, the distance from a spray gun nozzle to the surface of the steel bar is controlled to be 15-30 mm, the spraying speed is 300-900 m/S, the transverse moving speed of a spray gun is 10-25 mm/S, immediately turning the steel bar for 180 degrees after one side of the steel bar is sprayed, continuously spraying once, and naturally cooling to the room temperature.
7. A steel bar having the sprayed coating according to claim 6.
8. A sealant, based on the total mass of the sealant, comprising: 1-5% of water-soluble molybdate, 5-15% of polycarboxylic acid, 1-5% of strong base, 5-15% of silane coupling agent, 5-15% of ethanol and the balance of water;
preferably, the water-soluble molybdate is selected from one or more of potassium molybdate, sodium molybdate and magnesium molybdate;
preferably, the polycarboxylic acid is selected from one or more of a tricarboxylic polycarboxylic acid, a dicarboxylic polycarboxylic acid, and a monocarboxylic polycarboxylic acid;
preferably, the strong base is selected from one or more of sodium hydroxide, triethanolamine and potassium hydroxide;
preferably, the silane coupling agent is selected from one or more of aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, aluminate coupling agents, aluminum-titanium composite coupling agents, and tetraisopropyl di (dioctyl phosphite acyloxy) titanate.
9. The method of preparing the sealant of claim 8, comprising the steps of:
I. preparing the components according to the mixture ratio;
II, dissolving polycarboxylic acid in water, stirring to be in a uniform dispersion state, and adding strong base while stirring until the polycarboxylic acid is completely dissolved to obtain a solution I;
II, mixing a silane coupling agent and ethanol, stirring until the silane coupling agent and the ethanol are completely dissolved, adding the solution I obtained in the step I into the obtained solution, and uniformly stirring to obtain a solution II;
and III, adding water-soluble molybdate into the solution II obtained in the step II, and stirring until the water-soluble molybdate is completely dissolved to obtain the compound.
10. A composite anticorrosive coating on the surface of a steel substrate, which comprises a spray coating layer and a sealing layer on the surface of the steel substrate, wherein the sealing layer is formed by the sealant according to claim 8; the spraying coating is arranged between the steel base material and the sealing layer;
preferably, the thickness of the closing layer is 5 to 10 μm.
11. The composite corrosion protection layer according to claim 10, wherein said spray coating is obtained by the cold spray process according to claim 3, using the metal composition of claim 1 as a spray paint; the total thickness of the composite anticorrosive layer is 35-80 mu m.
12. A method of producing a composite corrosion protective layer according to claim 10 or 11, comprising:
(1) Carrying out surface dust removal and rust removal treatment on the steel base material;
(2) Forming a spray coating on the surface of the treated steel substrate by thermal spraying or cold spraying;
(3) Soaking the steel substrate with the spray coating into the hole sealing agent of claim 8 for 30-60 s, taking out, and naturally airing; or spraying the hole sealing agent of claim 8 on the surface of the sprayed layer, and naturally airing; and (5) obtaining the product.
13. A steel substrate having the composite corrosion protective layer of claim 12;
preferably, the spray coating is prepared by the cold spraying process of claim 3 by using the metal composition of claim 1 as a spray paint; the total thickness of the composite anticorrosive layer is 35-80 mu m.
14. A reinforcing steel bar having a composite corrosion protective layer according to claim 12, wherein the sprayed layer is obtained by the cold spray process according to claim 3, using the metal composition according to claim 1 as a spray; the total thickness of the composite anticorrosive layer is 35-80 mu m.
15. The method for preparing a reinforcing bar of claim 14, comprising the operations of:
immersing the steel bar of claim 7 in the sealant of claim 8 or the sealant obtained by the preparation method of claim 9 for 30-60 s, taking out, and naturally airing; or spraying the sealant according to claim 8 or the sealant obtained by the preparation method according to claim 9 on the surface of the spray coating, and naturally drying; and (4) obtaining the product.
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