CN113388798A - Corrosion-resistant aluminum alloy coating material - Google Patents
Corrosion-resistant aluminum alloy coating material Download PDFInfo
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- CN113388798A CN113388798A CN202110527441.7A CN202110527441A CN113388798A CN 113388798 A CN113388798 A CN 113388798A CN 202110527441 A CN202110527441 A CN 202110527441A CN 113388798 A CN113388798 A CN 113388798A
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- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 36
- 230000007797 corrosion Effects 0.000 title claims abstract description 35
- 238000005260 corrosion Methods 0.000 title claims abstract description 35
- 238000007750 plasma spraying Methods 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000158 manganese(II) phosphate Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000956 alloy Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 19
- 229910010389 TiMn Inorganic materials 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 238000005488 sandblasting Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000007602 hot air drying Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims 3
- 239000000203 mixture Substances 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001234 light alloy Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- 238000012876 topography Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C4/134—Plasma spraying
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
Abstract
A corrosion-resistant aluminum alloy coating material is characterized in that a plasma-sprayed TiMnN layer and a phosphating film on the surface of the TiMnN layer are sequentially coated on the surface of an aluminum alloy, wherein the thickness of the TiMnN layer is not more than 3.5 microns, and the components in the phosphating film comprise but are not limited to titanium-doped Mn3(PO4)2 .4H2Zn doped with O and titanium3(PO4)2 .4H2O, titanium doped (Mn, Zn)3(PO4)2 .4H2And O, obtaining a coating with high corrosion resistance and high bonding force through plasma spraying and subsequent phosphating treatment, and particularly maintaining higher corrosion resistance when the thickness of the coating is more than 2.5-3.5 microns.
Description
Technical Field
The invention relates to an aluminum alloy material, in particular to a preparation method of a plasma coating and a corrosion-resistant coating obtained by post-treatment phosphating.
Technical Field
Aluminum is a third-period main group element, and the crystal structure belongs to a face-centered cubic lattice without isomorphic transformation. Aluminum and its alloy materials have the excellent characteristics of small density, easy forming, low price, high specific strength and the like, and have become the second largest metal materials second to steel in terms of yield and application. Aluminum alloy is a non-ferrous metal structural material which is most widely applied in industry, has been widely applied in aviation, aerospace, automobile, mechanical manufacturing, ships and chemical industry, and is the most widely applied alloy in light alloy and the most used amount. At present, the application of the aluminum alloy material has the following three aspects: firstly, the component is used as a stress component; secondly, the material is used as the material of doors, windows, pipes, covers, shells and the like; and thirdly, the coating is used as a decoration and heat insulation material. Various ornaments can be made by utilizing the characteristic that the aluminum alloy can be colored after being subjected to anodic oxidation treatment. The surface of the aluminum alloy plate and the section bar can be subjected to secondary processing such as corrosion prevention, embossing, coating, printing and the like to prepare various decorative plates and section bars as decorative materials.
TiN is a coating material with excellent performances of high hardness, wear resistance, corrosion resistance, good non-adhesiveness, good chemical stability, low friction coefficient and the like and wide application, and has become a hot spot for researching hard coatings at home and abroad. In the mechanical industry, TiN is an ideal coating material for low-speed cutting tools, can reduce the adhesion of cutting edge materials, reduce cutting force, increase the feed amount, improve the processing precision, maintain the stability of cutting geometry and improve the surface quality of workpieces. Furthermore, TiN is also an ideal coating for wear parts, especially due to its low sticking tendency, widening the application in many wear systems. Therefore, TiN is widely used for forming technology tool coatings, such as for thin sheet forming tools in the automotive industry.
Many researchers have prepared TiN coatings by reactive thermal spraying, Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD), arc plating, and the like, and studied the deposition process, microstructure, and properties of the coatings. The TiN coating prepared by adopting the CVD, PVD and other technologies has thinner thickness, and the mechanical property of the coating is reduced; the thicker TiN coating can be prepared by utilizing the thermal spraying reaction technology, but the coating contains more pores, has larger brittleness and is not easy to control the coating quality. And the TiN powder is directly sprayed by plasma, so that the thickness of the coating can be ensured, and meanwhile, the Ti oxide phase in the TiN coating can improve the toughness of the coating, so that the TiN coating with better toughness and hardness is obtained.
Disclosure of Invention
Based on the introduction, the invention provides an aluminum alloy surface treatment method, which comprises the steps of plasma spraying a TiMnN layer, and then carrying out post-treatment phosphorization to obtain the corrosion-resistant coating.
The corrosion-resistant aluminum alloy coating material is characterized in that a plasma-sprayed TiMnN layer and a phosphating film on the surface of the TiMnN layer are sequentially coated on the surface of an aluminum alloy, wherein the thickness of the TiMnN layer is not more than 3.5 microns, and the components in the phosphating film comprise, but are not limited to, titanium-doped Mn3(PO4)2 .4H2Zn doped with O and titanium3(PO4)2 .4H2O, titanium doped (Mn, Zn)3(PO4)2 .4H2O。
Further, the plasma spraying: placing the pretreated aluminum material in an equipment cavity, vacuumizing to a degree lower than 40 pascals in advance, and then preheating the matrix material by using a spray gun, wherein the preheating temperature is 230 ℃ and 250 ℃, and the preheating time is 2-3 minutes; then carrying out reaction spraying of the TiMn powder and nitrogen; and (5) cooling.
Further, the parameters of the plasma spraying are as follows: the reaction powder is TiMn alloy powder, the current is 550-650A, and the powder feeding amount is 15-20 g/min; the flow rate of the ionic argon gas is 30-50L/min, the flow rate of the nitrogen gas is 10-20L/min: the powder feeding gas is nitrogen gas, N2The flow rate is 1.5-3L/min, and the gun distance is 80-140 mm.
Further, the alloy has an atomic ratio of Ti to Mn of 7:1, and the particle size of the TiMn alloy powder is 20-30 μm.
Further, the phosphating solution used for phosphating comprises Zn (H)2PO4)2.6H2O 25-30g/L、Zn(NO3)2 .6H2O 38-41g/L、H3PO 49-12 g/L, HF20-25ml/L with the mass fraction of 45%, free acid 10-11 points, total acid point 55-65 points and temperature 75-80%oC, soaking for 20-25 min.
Further, the pretreatment comprises mechanical polishing, sand blasting, deionized water cleaning, acetone wiping, acid pickling activation and vacuum drying;
further, the mechanical grinding is to sequentially use 240# -1200# silicon carbide sand paper to mechanically grind the sample.
Furthermore, the material for sand blasting is 500-600 μm brown corundum, the sand blasting air pressure is 1MPa, the sand blasting angle is 70 degrees, and the distance between the spray gun and the surface of the die is 0.13 m.
Further, the activating solution is a mixed solution of 30wt% of nitric acid and 2wt% of hydrofluoric acid, and the temperature is 25-30%oC, the time is 1-2 min.
Further, the aluminum alloy is subjected toAfter phosphorization, post-treatment is carried out, wherein the post-treatment comprises hot water washing, cold water washing and hot air blow-drying, and the hot water washing temperature is 80-90 DEG CoC, the time is 1-2min, and the cold water washing temperature is 2-5oC, the time is 3-5min, the hot air temperature is 120-oC, the time is 30-40 min.
Furthermore, the bonding force between the aluminum alloy base material and the surface corrosion-resistant layer is 20-30 Mpa.
The invention obtains a coating with high corrosion resistance and high bonding force by plasma spraying and subsequent phosphating treatment, and the basic principle is as follows:
firstly, TiN coating is prepared mainly by plasma spraying in the prior art, but as known by technicians in the art, phosphating solution is directly used for phosphating TiN, because of the chemical inertness of TiN, a uniform phosphating film cannot be effectively formed, only a few obvious pore passages or incomplete parts of the film form the phosphating film, which causes the coating to be inhomogeneous, and chemical corrosion resistance or other chemical properties to be unstable, based on the problems, Mn is introduced in the plasma spraying process, TiMn alloy is used as powder raw material to react with N to form a TiMnN film, the metal powder raw material known by technicians in the art does not completely react with nitrogen to completely form TiMnN, part of TiMn or simple substance metal exists in the TiMnN, the grain size is obviously increased along with the increase of the thickness of the TiMnN film, the grain interface is obviously separated, which causes the easy occurrence of cracks when the high-thickness TiMnN film is sprayed by plasma, therefore, when the technical problem of how to effectively treat cracks of a coating with high thickness is faced, subsequent phosphating treatment is needed to seal the holes, so that the density of the coating is improved, and the corrosion resistance of the coating is further improved.
Secondly, in order to improve the phosphating effect, oxidation treatment is required, Mn or Ti or TiMn particles which are not nitrided inside the TiMnN film are exposed by oxidation, oxidized into oxidized particles which consume H ions by reacting with phosphoric acid or hydrofluoric acid in a phosphating solution, and thermal stress between the coating and the substrate can be reduced by heat treatment, thereby improving the bonding force thereof+Reaction with oxidesAnd then the pH value is sharply reduced, so that the dissociation equilibrium of more stages of phosphoric acid is moved rightwards, and finally phosphate radicals are obtained, and Mn is obtained when the phosphate radicals dissociated on the metal surface are reacted with oxide through acidification2+(preferably) or Ti2+When the concentration product is common knowledge, the reaction will occur to form a phosphating film, which contains Mn3(PO4)2Or TixMny (PO)4)2(x + y =3), and the phosphating solution of the invention contains Zn (H2PO4)2.6H2O, the occurrence of hydrolytic equilibrium shift of primary and tertiary phosphates is more sensitive, resulting in the formation of a phosphating film containing, without limitation, titanium doped Mn3(PO4)2 .4H2Zn doped with O and titanium3(PO4)2 .4H2O, titanium doped (Mn, Zn)3(PO4)2 .4H2O。
Advantageous technical effects
(1) The invention obtains the coating with high corrosion resistance and high bonding force by plasma spraying and subsequent phosphating treatment.
(2) High corrosion resistance can be maintained for high thickness coatings, especially for coating thicknesses greater than 2.5-3.5 microns.
Drawings
FIG. 1 is a surface topography of an aluminum alloy.
FIG. 2 is a morphology of a TiMnN layer deposited on the surface of the aluminum alloy of the comparative example 3.
FIG. 3 is a morphology of a TiMnN layer deposited on the surface of the aluminum alloy of the comparative example 4.
FIG. 4 is a morphology chart of a TiMnN layer deposited on the surface of the aluminum alloy of the comparative example 5.
FIG. 5 is a morphology of a 5 μm Ti MnN layer deposited on the surface of an aluminum alloy.
FIG. 6 is a morphology chart of a TiMnN layer deposited on the surface of the aluminum alloy in the embodiment 4.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments thereof. The scope of the invention is not limited to the following examples, but is intended to include the full scope of the claims.
Example 1
The preparation method of the corrosion-resistant aluminum alloy material comprises the following steps:
(1) cleaning the surface of the aluminum alloy: the cleaning treatment comprises mechanical polishing, sand blasting, deionized water cleaning, acetone wiping, acid pickling activation and vacuum drying.
And in the mechanical grinding, 240# -1200# silicon carbide abrasive paper is sequentially adopted to mechanically grind the sample.
The material for sand blasting is 500-600 mu m brown corundum, the sand blasting air pressure is 1MPa, the sand blasting angle is 70 degrees, and the distance between a spray gun and the surface of the die is 0.13 m.
The activating solution is a mixed solution of 30wt% of nitric acid and 2wt% of hydrofluoric acid, and the temperature is 25 DEGoAnd C, the time is 1 min.
(2) Plasma spraying a TiMnN layer on the surface of the aluminum alloy: placing the aluminum material treated in the step (1) in an equipment cavity, vacuumizing and plating the aluminum material to be less than 40 pascals in advance, and then preheating the matrix material by using a spray gun, wherein the preheating temperature is 230 ℃ and the preheating time is 2 minutes; then carrying out reaction spraying of the TiMn powder and nitrogen; and (5) cooling.
Parameters of the plasma spraying are as follows: the reaction powder is TiMn alloy powder, the atomic ratio of Ti to Mn of the alloy is 7:1, the particle size of the TiMn alloy powder is 20-30 mu m, the current is 550A, and the powder feeding amount is 15 g/min; the flow rate of the ionic argon gas is 30L/min, the flow rate of the nitrogen gas is 10L/min: the powder feeding gas is nitrogen gas, N2The flow rate is 1.5L/min, and the gun distance is 80 mm;
(3) oxidation treatment: the oxidation treatment parameters are as follows: 200oAnd C, performing air heat treatment for 10 min.
(4) And (3) forming a phosphating film by phosphating: the phosphating solution comprises Zn (H2PO4)2.6H2O 25g/L、Zn(NO3)2.6H2O38 g/L, H3PO 49 g/L, HF20ml/L with the mass fraction of 45 percent and the temperature of 75oAnd C, soaking for 20 min.
(5) And (3) post-treatment: the post-treatment comprises hot water washing, cold water washing and hot air drying.
The hot water washing temperature is 80 DEG CoC, time of dayIs 1min, and the cold water washing temperature is 2oC, the time is 3min, the hot air temperature is 120oC, the time is 30 min.
Example 2
The preparation method of the corrosion-resistant aluminum alloy material comprises the following steps:
(1) cleaning the surface of the aluminum alloy: the cleaning treatment comprises mechanical polishing, sand blasting, deionized water cleaning, acetone wiping, acid pickling activation and vacuum drying.
And in the mechanical grinding, 240# -1200# silicon carbide abrasive paper is sequentially adopted to mechanically grind the sample.
The material for sand blasting is 500-600 mu m brown corundum, the sand blasting air pressure is 1MPa, the sand blasting angle is 70 degrees, and the distance between a spray gun and the surface of the die is 0.13 m.
The activating solution is a mixed solution of 30wt% of nitric acid and 2wt% of hydrofluoric acid, and the temperature is 27.5oC, the time is 1.5 min.
(2) Plasma spraying a TiMnN layer on the surface of the aluminum alloy: placing the aluminum material treated in the step (1) in an equipment cavity, vacuumizing and plating the aluminum material to be less than 40 pascals in advance, and then preheating the base material by using a spray gun, wherein the preheating temperature is 240 ℃ and the preheating time is 2.5 minutes; then carrying out reaction spraying of the TiMn powder and nitrogen; and (5) cooling.
Parameters of the plasma spraying are as follows: the reaction powder is TiMn alloy powder, the atomic ratio of Ti to Mn of the alloy is 7:1, the particle size of the TiMn alloy powder is 20-30 mu m, the current is 600A, and the powder feeding amount is 17.5 g/min; the flow rate of the ionic argon gas is 40L/min, the flow rate of the nitrogen gas is 15L/min: the powder feeding gas is nitrogen gas, N2The flow rate is 2.25L/min, and the gun distance is 110 mm;
(3) oxidation treatment: the oxidation treatment parameters are as follows: 2100oAnd C, performing air heat treatment for 15 min.
(4) And (3) forming a phosphating film by phosphating: the phosphating solution comprises Zn (H2PO4)2.6H2O 27.5g/L、Zn(NO3)2.6H2HF22.5ml/L with O39.5 g/L, H3PO410.5g/L and mass fraction of 45 percent and the temperature of 77.5oC, soaking for 22.5 min.
(5) And (3) post-treatment: the post-treatment comprises hot water washing, cold water washing and hot air drying.
The hot water washing temperature is 85 DEGoC, the time is 1.5min, and the cold water washing temperature is 3.5oC, the time is 4min, the hot air temperature is 130oC, the time is 35 min.
Example 3
The preparation method of the corrosion-resistant aluminum alloy material comprises the following steps:
(1) cleaning the surface of the aluminum alloy: the cleaning treatment comprises mechanical polishing, sand blasting, deionized water cleaning, acetone wiping, acid pickling activation and vacuum drying.
And in the mechanical grinding, 240# -1200# silicon carbide abrasive paper is sequentially adopted to mechanically grind the sample.
The material for sand blasting is 500-600 mu m brown corundum, the sand blasting air pressure is 1MPa, the sand blasting angle is 70 degrees, and the distance between a spray gun and the surface of the die is 0.13 m.
The activating solution is a mixed solution of 30wt% of nitric acid and 2wt% of hydrofluoric acid, and the temperature is 30 DEGoAnd C, the time is 2 min.
(2) Plasma spraying a TiMnN layer on the surface of the aluminum alloy: placing the aluminum material treated in the step (1) in an equipment cavity, vacuumizing and plating the aluminum material to be less than 40 pascals in advance, and then preheating the matrix material by using a spray gun, wherein the preheating temperature is 250 ℃ and the preheating time is 3 minutes; then carrying out reaction spraying of the TiMn powder and nitrogen; and (5) cooling.
Parameters of the plasma spraying are as follows: the reaction powder is TiMn alloy powder, the atomic ratio of Ti to Mn of the alloy is 7:1, the particle size of the TiMn alloy powder is 20-30 mu m, the current is 650A, and the powder feeding amount is 20 g/min; the flow rate of the ionic argon gas is 50L/min, the flow rate of the nitrogen gas is 20L/min: the powder feeding gas is nitrogen gas, N2The flow rate is 3L/min, and the gun distance is 140 mm;
(3) oxidation treatment: the oxidation treatment parameters are as follows: 220oAnd C, performing air heat treatment for 20 min.
(4) And (3) forming a phosphating film by phosphating: the phosphating solution comprises Zn (H2PO4)2.6H2O 30g/L、Zn(NO3)2.6H2O 41g/L、H3PO4 12g/L、HF25ml/L with a mass fraction of 45%, temperature 80oAnd C, soaking for 25 min.
(5) And (3) post-treatment: the post-treatment comprises hot water washing, cold water washing and hot air drying.
The hot water washing temperature is 90 DEG CoC, the time is 2min, and the cold water washing temperature is 5oC, the time is 5min, the hot air temperature is 140oC, the time is 40 min.
Comparative example 1
Comparative example 1 is an aluminum alloy not covered with any coating film, and subjected to only surface cleaning pretreatment.
Comparative example 2
The thickness of the TiMnN layer is about 200nm by controlling plasma spraying parameters, and no phosphating treatment is carried out.
Comparative example 3
The thickness of the TiMnN layer is about 1500nm by controlling plasma spraying parameters, and no phosphating treatment is carried out.
Comparative example 4
The thickness of the TiMnN layer is about 2500nm by controlling plasma spraying parameters, and no phosphating treatment is carried out.
Comparative example 5
The thickness of the TiMnN layer is about 3500nm by controlling plasma spraying parameters, and no phosphating treatment is carried out.
Example 4
By controlling the plasma spraying parameters, the thickness of the TiMnN layer was made approximately 3500nm, and phosphating was performed in the phosphating mode of example 2.
Firstly, as shown in attached figures 1, 2 and 3, with the increase of the thickness of the TiMnN coating, crystal grains obviously grow, when the thickness is 2.5 μm, as shown in attached figure 4, more obvious cracks occur, when the thickness is 5 micrometers, as shown in attached figure 5, the cracks are more obvious, and after the TiMnN is deposited, phosphating is carried out, so that the cracks can be effectively inhibited, less cracks occur, and a phosphating film is formed.
As can be seen from the above table, the aluminum alloys showed more positive corrosion potential and less corrosion current with increasing thickness of the surface TiMnN, i.e., the corrosion resistance increased significantly with the 2500nm thickness TiMnN coating, but with the thickness of the TiMnN coating being 3500nm, Icorr(μA/cm2) 1.12, the corrosion potential is-432 mV, the main reason is that coating cracks occur along with the increase of the thickness and the growth of crystal grains, so that the corrosion is increased, and through subsequent phosphating treatment, as shown in example 4, the corrosion resistance is further reduced, namely, a phosphating film can effectively prevent the cracks from occurring, the density of the coating is improved, and the corrosion resistance of the coating is further improved.
As known by the technicians in the field, the bonding strength of the coating is closely related to the thickness of the coating, the bonding strength is obviously reduced along with the increase of the thickness, the bonding strength is the highest in the case of 1500nm in the comparative example 3 and is 32.4MPa, but when the thickness is 3500nm, the bonding strength is obviously reduced, the coating is easy to peel due to cracks, but the direct phosphating treatment after plasma spraying can effectively inhibit the cracks from generating, so that higher bonding strength can be obtained under the condition of high TiMnN coating thickness.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (9)
1. A corrosion-resistant aluminum alloy coating material is characterized in that a TiMnN layer sprayed by plasma and a phosphating film on the surface of the TiMnN layer are sequentially coated on the surface of the aluminum alloy, wherein the thickness of the TiMnN layer is not more than 3.5 microns, and the components in the phosphating film comprise but are not limited to titanium-doped Mn3(PO4)2 .4H2Zn doped with O and titanium3(PO4)2 .4H2O, titanium doped (Mn, Zn)3(PO4)2 .4H2O。
2. A corrosion-resistant aluminum alloy coating material as recited in claim 1, wherein said plasma spraying: placing the pretreated aluminum material in an equipment cavity, vacuumizing to a degree lower than 40 pascals in advance, and then preheating the matrix material by using a spray gun, wherein the preheating temperature is 230 ℃ and 250 ℃, and the preheating time is 2-3 minutes; then carrying out reaction spraying of the TiMn powder and nitrogen; and (5) cooling.
3. A corrosion-resistant aluminum alloy coating material as recited in claim 2, wherein said plasma spraying parameters are: the reaction powder is TiMn alloy powder, the current is 550-650A, and the powder feeding amount is 15-20 g/min; the flow rate of the ionic argon gas is 30-50L/min, the flow rate of the nitrogen gas is 10-20L/min: the powder feeding gas is nitrogen gas, N2The flow rate is 1.5-3L/min, and the gun distance is 80-140 mm.
4. A corrosion-resistant aluminum alloy coating material as recited in claim 3, wherein said alloy has an atomic ratio of Ti and Mn of 7:1, and said TiMn alloy powder has a particle size of 20 to 30 μm.
5. The corrosion-resistant aluminum alloy coating material as recited in claim 2, wherein said phosphating solution for phosphating includes Zn (H)2PO4)2.6H2O 25-30g/L、Zn(NO3)2 .6H2O 38-41g/L、H3PO 49-12 g/L, HF20-25ml/L with the mass fraction of 45%, free acid 10-11 points, total acid point 55-65 points and temperature 75-80%oC, soaking for 20-25 min.
6. The corrosion-resistant aluminum alloy coating material according to claim 2, wherein the pretreatment comprises mechanical polishing, sand blasting, deionized water cleaning, acetone wiping, acid pickling activation, vacuum drying;
the corrosion-resistant aluminum alloy coating material as recited in claim 6, wherein the mechanical polishing is performed by sequentially subjecting the sample to mechanical polishing using No. 240-No. 1200 silicon carbide sandpaper.
7. The corrosion-resistant aluminum alloy coating material as recited in claim 6, wherein the blasting material is 500-600 μm brown corundum, the blasting pressure is 1MPa, the blasting angle is 70 °, and the distance between the lance and the mold surface is 0.13 m.
8. The corrosion-resistant aluminum alloy coating material according to claim 6, wherein the activating solution is a mixture of 30wt% nitric acid and 2wt% hydrofluoric acid at a temperature of 25-30%oC, the time is 1-2 min.
9. The corrosion-resistant aluminum alloy coating material as recited in claim 6, wherein the aluminum alloy is phosphated and then subjected to post-treatment comprising hot water washing at 80-90 ℃, cold water washing, and hot air dryingoC, the time is 1-2min, and the cold water washing temperature is 2-5oC, the time is 3-5min, the hot air temperature is 120-oC, the time is 30-40 min.
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