CN113787196B - High-performance aluminum alloy treatment method - Google Patents

High-performance aluminum alloy treatment method Download PDF

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CN113787196B
CN113787196B CN202110977489.8A CN202110977489A CN113787196B CN 113787196 B CN113787196 B CN 113787196B CN 202110977489 A CN202110977489 A CN 202110977489A CN 113787196 B CN113787196 B CN 113787196B
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nickel
arc oxidation
aluminum alloy
polishing
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CN113787196A (en
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喻馨
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Foshan Hongjinyuan Precision Manufacturing Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/024—Anodisation under pulsed or modulated current or potential
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention provides a high-performance aluminum alloy treatment method, which is characterized in that nickel metal with a lower melting point is filled in a micro-arc oxidation film pore canal, then the nickel metal is selectively melted by a laser melting technology, and then the compactness of the micro-arc oxidation film on the surface of the aluminum alloy can be effectively improved by using a nickel hole sealing agent for treatment, so that the corrosion resistance of the micro-arc oxidation film is remarkably improved.

Description

High-performance aluminum alloy treatment method
Technical Field
The invention belongs to the technical field of surface treatment of aluminum alloy materials, and relates to a preparation method of a high-performance and high-corrosion-resistance aluminum alloy material.
Technical Field
The micro-arc oxidation technology is a technology with a complex mechanism and a simple manufacturing process, and can prepare a film structure with excellent performance on the surface of metal in situ, so that the original performance of the metal is enhanced or the metal has new characteristics, namely MAO or PEO for short. The technology mainly comprises the steps of inducing a high-density micro-arc plasma group at a contact interface between a metal matrix and electrolyte by utilizing short-pulse high-intensity electric energy in an environment-friendly alkaline electrolyte, and generating a high-performance micro-arc oxidation ceramic layer by in-situ high-temperature sintering through a series of complex physical and chemical reactions. The cooling rate of molten aluminum oxide gradually decreases from the surface of the aluminum alloy to the direction of the matrix, so that the content of gamma-phase aluminum oxide (gamma-Al 2O 3) gradually decreases and the content of alpha-phase aluminum oxide (alpha-Al 2O 3) gradually increases. The loose layer has coarse grains, uneven surface appearance of the film layer, a plurality of micropores and poor mechanical property; the compact layer is the main body of the micro-arc oxidation ceramic layer, has compact structure, very tight combination with the matrix, microhardness exceeding 2000MPa and excellent wear resistance, corrosion resistance and insulation performance. The loose layer and the dense layer are staggered, and no obvious demarcation exists.
Laser cladding is an important method for laser surface strengthening technology. The method comprises the steps of simultaneously melting a very thin layer on the surface of a substrate and alloy components coated on the surface of the substrate by using a high-energy-density laser beam, forming a rapid solidification process of an alloy layer with completely different components and performances from a substrate on the surface of the substrate, and dividing the laser cladding into a preset method and a synchronous supply method according to different alloy supply modes, wherein the alloy preset method refers to a method of covering an alloy material to be clad on the surface of the substrate in advance by a certain method and then adopting the laser beam to scan on the surface of an alloy precoat layer. The synchronous supply method refers to a method of directly feeding alloy materials into a laser action zone in a laser cladding process by adopting a special feeding system. The alloy material selected by the method can also be powder, wire and plate.
In the prior art, micro-arc oxidation is usually carried out on aluminum, then a porous layer obtained by the micro-arc oxidation is subjected to secondary melting through laser melting, so that a smooth surface is obtained, for example, CN201110297310 discloses a ceramic film layer on a metal surface and a preparation method thereof, the surface of light alloy such as aluminum alloy is ceramic, and the ceramic can be thickened through a laser cladding method. And such relatively thick ceramic layers can be used in many applications. In addition, the laser cladding process cannot be popularized in a large scale because the laser cladding process cannot be well combined with metal, and the two points can be well combined by carrying out laser cladding on the micro-arc oxidized ceramic. The metal and the micro-arc oxidation ceramic layer are connected in an atomic level, and the micro-arc oxidation ceramic and the laser cladding ceramic can be connected in an atomic level, so that the metal and the ceramic are laminated into a whole, and the defects of a micro-arc oxidation process and a laser cladding process are overcome. As described in example 1: example 1 taking a mechanical seal ring with aluminum alloy as a substrate as an example, forging and forming the mechanical seal ring by using aluminum alloy 2219, and performing mechanical processing, shaping, grinding and heat treatment to obtain a seal ring blank; then the method is completed after the subsequent treatments of degreasing, cleaning, micro-arc oxidation, cleaning, grinding and the like, wherein the micro-arc oxidation electrolyte takes water glass as a main component, and the pH value is adjusted to be between 11 and 13. The solution flows through the electrolytic cell by a recirculating cooling system. The stainless steel electrolytic tank is connected with a power cathode, and the blank of the aluminum alloy sealing ring is connected with a power anode. And (3) stirring and cooling the electrolyte by using an air pump for 30-50 minutes at the temperature of 20-50 ℃, growing a compact alumina ceramic layer on the surface of the sealing ring in situ, detecting that the thickness is about 60 microns, and after treatment, washing and drying the sample with the film layer by using water, and then directly carrying out laser cladding treatment. The laser remelting adopts an SLCF.X12x25 type C02 laser processing machine, and argon is adopted for protection during remelting. In order to ensure that the remelted ceramic coating maintains a certain nano-structure and simultaneously reduces defects such as remelting layer cracks, the remelting is carried out by adopting relatively low laser power and Chinese alligator density, and the laser remelting process parameters are as follows: the laser power is 900W, the rectangular spot size is 5mm multiplied by 3mm, the laser scanning direction is along the 3mm side of the spot, the scanning speed is 700mm/min, and the lap joint amount is 20%. The ceramic material contains Al2O3-13% TiO2, the aggregate size distribution range is 10-50 microns, and the original nano particles are 30-80 nanometers.
However, it is known by those skilled in the art that cracks and pores are likely to occur in the cladding layer during laser melting, and the laser power employed in the art is 900W, the temperature is extremely high, and the micro-arc oxide film is also melted together with the powder, but at such high temperature, the micro-arc oxide film which has an effective bonding force with the aluminum material is very likely to cause cracks to occur due to thermal stress generated by laser melting, and even the substrate and the oxide film are peeled off.
Disclosure of Invention
Based on the technical problem that the micro-arc oxidation film is cracked or stripped when the micro-arc oxidation film is processed by using a laser melting technology in the prior art, the invention provides a high-performance aluminum alloy processing method, which comprises the following steps:
(1) Surface pretreatment;
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer;
(3) Coating nickel nano dispersion liquid for multiple times;
(4) Selective laser melting treatment;
(5) Inorganic hole sealing;
(6) And (5) polishing treatment.
Further, the surface pretreatment includes:
(1) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(2) Degreasing: 12-15wt.% sulfuric acid, 1.5-2.5wt.% surfactant, at room temperature for 5-7min; washing: distilled water for 15-20s;
(3) Acid washing; 15-25wt.% nitric acid; 10-15wt.% sulfuric acid; room temperature; time: 4-6min; washing: distilled water for 15-20s.
Further, the micro-arc oxidation:
Na 2 SiO 3 5-15g/L, naOH1-2g/L, na2WO41-5g/L; glycerol 4-6ml/L; the positive voltage is 300-500V, the negative voltage is 100-200V, the positive duty ratio is 15-25%, the negative duty ratio is 5-10%, the pulse frequency is 300-400 Hz, and the oxidation time is 20-40 min.
Further, the nickel nano-dispersion liquid has a nickel size of 50-100nm and a nickel content of 15-20wt.%.
Further, the multiple coating is carried out by using a vacuum spin coater, the rotating speed is 2000-2500rpm, the spin coating time is 30-40s, the spin coating times are 5-9 times, and then the spin coating is carried out at 40-50 times o C, vacuum drying for 3-5h.
Further, the laser output power in the selective laser melting treatment is 100-125W; the diameter of the light spot is 2-3mm; the scanning speed of the laser beam is 5-10mm/s, the overlapping rate of the large-area scanning laser is 30% -60%, and inert argon is used for protecting gas.
Furthermore, the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 5-10g/L nickel acetate, 5-7g/L boric acid, 0.3-0.5g/L aminotrimethylene phosphoric acid, 0.1-0.2g/LEDTA-2Na, 0.03-0.05g/L octyl phenol polyoxyethylene ether, pH=5.7+ -0.3, temperature 85-90 ℃ and time 15-20min.
Further, deionized water is used for cleaning after hole sealing, and drying treatment is carried out at 30-40 ℃.
Further, the polishing solution used for polishing mainly comprises alpha-Al 2 O 3 The surface roughness Ra after polishing is less than 0.2 mu m.
Further, the thickness of the micro-arc oxidation film obtained after the micro-arc oxidation treatment is 8-15 mu m, and the thickness of the micro-arc oxidation film removed by polishing is 1-3 mu m.
Before the surface treatment of the workpiece, the invention needs to remove the greasy dirt on the surface, so as to ensure the bonding strength of the micro-arc oxidation film and the matrix metal, ensure the smooth proceeding of the chemical reaction of the conversion film and obtain the conversion film layer with qualified quality. The aluminum alloy is an amphoteric metal which can react with acid or alkali, so that the aluminum alloy can be degreased by an alkaline degreasing method or an acidic degreasing method. Because the dissolution rate of the aluminum alloy in acid is much lower than that in alkali, the surface of a degreased workpiece is not easy to darken.
The aluminum alloy workpiece cannot be subjected to micro-arc oxidation treatment after degreasing, and the surface of the aluminum alloy workpiece generally has the defects of a natural oxide film, processing stripes and the like, and needs to be subjected to corrosion treatment to remove the natural oxide film and activate the surface so that the surface of the aluminum alloy is exposed out of a bright metal matrix, thereby providing a good matrix surface for the next surface treatment.
Washing: any aluminum workpiece treated by the chemical solution should be immediately washed after being removed from the treatment solution, and the faster and better. Because the workpiece is exposed to the air leaving the treatment liquid, the surface is in a non-uniform state, and the chemical agent needs to be immediately washed away by water to terminate the chemical reaction, and at the same time, the chemical agent is prevented from being carried into the next treatment liquid to pollute the next chemical treatment tank. Generally, the workpiece is not allowed to enter the chemical treatment tank in a dry state, and the surface of the workpiece is wetted by water washing and then enters the chemical treatment tank for treatment, so that the partial reaction is prevented from being uneven.
Micro-arc oxidation is embodied as an alkaline electrolyte, which is currently divided into four systems: silicate electrolyte, sodium hydroxide electrolyte, phosphate electrolyte and aluminate electrolyte. In practical application, the composition of the electrolyte is matched with the modified aluminum alloy material, the silicate electrolyte with wider application is adopted, na2SiO3 is a film forming substance, the thickness of the film layer is rapidly increased along with the continuous increase of the content of the film forming substance, and the thickness of a compact layer in the corresponding film layer is also continuously increased. The compact layer is the main layer for improving the comprehensive performance of the film, so that the thickness of the compact layer is improved, and the corrosion resistance of the film is improved.
NaOH is a pH value regulator of the solution, ensures the pH value of the solution to be 10-12, and provides a stable electrolyte environment for preparing the micro-arc oxidation film.
The sodium tungstate additive can act on the compact layer of the film layer without affecting the phase structure of the film layer, and when the content of sodium tungstate is gradually increased, the thickness of the film layer is increased, because the sodium tungstate additive has an effect of promoting the growth of the compact layer, the corrosion resistance of the film layer is also obviously improved.
The glycerol is used as an additive, so that micropores on the surface of the ceramic membrane can be reduced, the surface smoothness is improved, the ceramic membrane is more uniform and compact, and the corrosion resistance is greatly enhanced.
Power mode: the original micro-arc oxidation process adopts a direct current constant current power supply, but the direct current constant current power supply is difficult to control the discharge characteristic of the metal surface, so that the prior micro-arc oxidation process is less used, and pulse voltage generated by a pulse alternating current power supply has the effect of a needle point, so that the local area is greatly reduced, surface micropores are mutually overlapped, and a film layer with small roughness and uniform thickness can be formed.
Pulse frequency: at high pulse frequency, the mass fraction of the compact layer is increased, the surface roughness is reduced, the hardness of the film layer is increased, the wear resistance is enhanced, and the obtained ceramic layer has excellent performance.
Duty cycle: the pulse duty ratio is an important factor affecting the characteristics of the ceramic membrane, the pulse width determines the duration and density of the spark discharge, and the increase of the pulse width is beneficial to increasing the mass fraction of alpha-Al 2O3 and improving the hardness of the ceramic membrane, but too high pulse width can lead the discharge to be more intense, thereby increasing the surface roughness of the ceramic membrane, as shown in the figure 1 (left) and a method diagram thereof, and obvious volcanic micropores can be seen.
Nickel nanodispersion: nickel nanoparticles were prepared by the nano nickel preparation method disclosed in CN101053906a example 1, which is as follows: 18g of nickel chloride, 18g of PVP, 150g of ethanol and 150g of toluene were added to 300g of distilled water and the aqueous mixture was stirred at 40℃to make a reverse microemulsion. 40g of hydrazine hydrate was added to the aqueous reverse microemulsion solution and stirred for 30 minutes to form a nickel-hydrazine complex. 0.04 mol of NaBH4 was added to the inverse microemulsion containing the nickel-hydrazine complex, which was stirred for 1 hour to prepare nickel particles by reduction. The nickel nanoparticles were separated from the inverse microemulsion by centrifugation. After washing the separated nanoparticles 3 times with acetone and distilled water, nickel nanoparticles were obtained by drying at 50 ℃ for 3 hours in a vacuum drying oven. However, by experimental characterization, the size of the nickel nano particles prepared by the method is about 50-100nm, 10-50nm nano nickel obtained by CN101053906A cannot be reasonably obtained, 15-20wt.% of dispersion liquid is prepared from 50-100nm, the dispersion liquid is dripped on the surface of the aluminum alloy subjected to micro-arc oxidation through a dropper, a vacuum spin coater is used, the rotating speed is 2000-2500rpm, the spin coating time is 30-40s, the spin coating times are 5-9 times, and then the time is 40-50 o C, vacuum drying for 3-5h.
The micro-arc surface is provided with a porous layer, an intermediate layer and a compact layer from top to bottom, the porous layer is volcanic micropores, nickel nano particles enter the micropores of the micro-arc oxidation film to be filled in the spin coating process, and then the nickel nano particles are selectively dissolved through subsequent laser melting.
Selective laser melting treatment; the selectivity means that nickel is melted by high-energy laser energy, and micro-arc oxidation is not melted, so that effective hole sealing of nickel is realized, the melting temperature of micro-arc oxidation film alumina is about 2055, the melting point of pure nickel particles is about 1435 ℃, and the temperature of Ni60 alloy is about 1027, which is known in the art o C, the melting temperature of the nickel nano-particles prepared by the invention is about 500 to 600 o C, if selective laser melting is to be realized, only remelting nickel but not melting micro-arc oxide film, controlling output power of laser melting is needed, and according to the test of the invention, when the output power of laser is 75-125W, the local surface temperature is 700-800 o And C, when the laser irradiates the surface of the film layer, the local surface temperature is 1200-1500 ℃, and in addition, the heat can be dissipated to the air and the inside of the film layer to cause the temperature to not reach the melting temperature of nickel, so that the output power of the laser is selected to be 100-125W, and only the dissolution of nickel nano particles occurs under the output power, and the micro-arc oxidation ceramic layer of the aluminum oxide is not influenced at all.
At this time, the nickel nano particles are filled in the micro holes of the micro-arc oxidation film, and the nickel nano particles are coated in the micro holes of the micro-arc oxidation film in a melt state through laser melting, but after the melt is cooled, a small gap is necessarily formed between the nickel melt and the micro-arc oxidation film, and the corrosion resistance of the micro-arc oxidation film is obviously affected by the existence of the gap, so that the gap between the melt and the pore canal needs to be filled.
In addition, as the thickness of the micro-arc oxidation is 8-15 mu m, the local laser melting nano nickel seal does not generate obvious heat influence on the aluminum material, namely, does not generate heat stress on the base material, so that cracking and peeling phenomena do not occur.
The filling method is an inorganic hole sealing method, and common nickel hole sealing agents in the market are used: 5-10g/L nickel acetate, 5-7g/L boric acid, 0.3-0.5g/L aminotrimethylene phosphoric acid, 0.1-0.2g/LEDTA-2Na, 0.03-0.05g/L octyl phenol polyoxyethylene ether, pH=5.7+/-0.3, the temperature is 85-90 ℃ and the time is 15-20min, the principle adopted in the hole sealing process is that after nickel ions are introduced into gaps, hydrolysis reaction occurs to generate nickel hydroxide precipitate, and the nickel hydroxide precipitate is filled in the holes, thereby achieving the purpose of hole sealing, wherein the reaction formula is that
Ni(CHCOO) 2 +2H 2 O→Ni(OH) 2 +2CH 3 COOH。
In addition, the aminotrimethylene phosphoric acid, EDTA-2Na and octyl phenol polyoxyethylene ether are indispensable additives for improving the hole sealing effect, and it is noted that obvious 'frosting' phenomenon occurs in the hole sealing process, and although the 'frosting' phenomenon can be improved to a certain extent by the additives such as the aminotrimethylene phosphoric acid, the 'frosting' phenomenon is required to be removed because most micro-arc oxidation pore channels are closed by using nickel melt and gaps between the melt and the pore channels are small.
Because of the presence of the bloom and the uneven roughness of the micro-arc oxide film itself, the crater protrusions and the bloom of the micro-arc oxide film need to be treated, and can be effectively removed by polishing, the surface removal amount is 1-3 μm, and the obtained surface roughness is less than 0.2 μm.
As shown in fig. 1 (right), fig. 2, fig. 3, and fig. 4, there is an obvious nickel fusion portion near the volcanic micropores, and in the enlarged view, there is a nickel seal layer introduced with a nickel sealing agent between the nickel fusion portion and the micro-arc oxidation duct.
Beneficial technical effects
1. According to the invention, by controlling the power of laser, the selective laser melting technology selectively melts nickel nano particles without affecting the aluminum oxide micro-arc oxidation layer, so that the cracking problem caused by thermal expansion deformation of the aluminum alloy matrix is effectively avoided.
2. According to the invention, the heat intensity of laser is effectively reduced by selecting the nickel nano dispersion liquid with a low melting point.
3. According to the invention, the nickel hole sealing is introduced between the nickel melting part and the micro-arc oxidation pore canal, so that the porosity of the surface of the micro-arc oxidation film is effectively reduced, the surface density is improved, and the corrosion resistance of the aluminum alloy is further improved.
Drawings
FIG. 1: SEM images of the surface (left) of the micro-arc oxidation film and the micro-arc oxidation film (right) after hole sealing are provided.
Fig. 2: SEM image of the aluminum alloy obtained in example 2 of the present invention.
Fig. 3: SEM image of the aluminum alloy obtained in example 3 of the present invention.
Fig. 4: SEM partial enlarged view of the aluminum alloy obtained in example 2 of the present invention.
Detailed Description
Example 1
A high-performance aluminum alloy treatment method comprises the following steps:
(1) Surface pretreatment:
(a) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(b) Degreasing: 12wt.% sulfuric acid, 1.5wt.% surfactant, room temperature for 5min; washing: distilled water, 15s;
(c) Acid washing; 15wt.% nitric acid; 10wt.% sulfuric acid; room temperature; time: 4min; washing: distilled water, 15s.
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer: na (Na) 2 SiO 3 5g/L, naOH g/L, na WO41 g/L; glycerol 4ml/L; positive voltage 300V, negative voltage 100V, positive duty cycle 15%, negative duty cycle 5%, pulse frequency 300Hz, oxidation time 200min.
(3) Coating nickel nano dispersion liquid for multiple times: the nickel nano-dispersion liquid has the size of nickel of 50-100nm and the content of 15wt.%.
The multiple coating is carried out by using a vacuum spin coater, rotating at 2000rpm, spin coating time being 30s, spin coating times being 5 times, and then at 40 o C, drying in vacuum for 3h.
(4) Selective laser melting treatment: the laser output power in the selective laser melting treatment is 100W; the diameter of the light spot is 2mm; the laser beam scanning speed is 5mm/s, the large-area scanning laser lap joint rate is 30%, and inert argon gas is used for protecting gas.
(5) Inorganic hole sealing: the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 5g/L nickel acetate, 5g/L boric acid, 0.3g/L aminotrimethylene phosphoric acid, 0.1g/LEDTA-2Na, 0.03g/L octyl phenol polyoxyethylene ether, pH=5.7, temperature 85 ℃ and time 15min.
And (3) cleaning the hole sealing by using deionized water, and drying at 30 ℃.
(6) Polishing treatment, wherein the main component of polishing solution used for polishing is alpha-Al 2 O 3 The surface roughness Ra after polishing is less than 0.2 mu m.
Example 2
A high-performance aluminum alloy treatment method comprises the following steps:
(1) Surface pretreatment:
(a) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(b) Degreasing: 14wt.% sulfuric acid, 2wt.% surfactant, room temperature for 6min; washing: distilled water, 17.5s;
(c) Acid washing; 20wt.% nitric acid; 12.5wt.% sulfuric acid; room temperature; time: 5min; washing: distilled water, 17.5s.
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer: na (Na) 2 SiO 3 20g/L, naOH1.5g/L, na2WO 43 g/L; glycerol 5ml/L; positive voltage 400V, negative voltage 150V, positive duty cycle 20%, negative duty cycle 7.5%, pulse frequency 350Hz, oxidation time 30min.
(3) Coating nickel nano dispersion liquid for multiple times: the nickel nano-dispersion had a size of 50-100nm and a content of 17.5wt.%.
The multiple coating is carried out by using a vacuum spin coater, rotating at 2300rpm, spin coating time being 35s, spin coating times being 8 times, and then at 45 o C, drying in vacuum for 4h.
(4) Selective laser melting treatment: the laser output power in the selective laser melting treatment is 120W; the diameter of the light spot is 2.5mm; the scanning speed of the laser beam is 7.5mm/s, the lap joint rate of the laser is 45% in a large-area scanning way, and the inert argon gas is used for protecting gas.
(5) Inorganic hole sealing: the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 7.5g/L nickel acetate, 6g/L boric acid, 0.4g/L aminotrimethylene phosphoric acid, 0.15g/LEDTA-2Na, 0.04g/L octylphenol polyoxyethylene ether, pH=5.7, temperature 87.5 ℃ and time 17.5min.
And (3) cleaning the hole sealing by using deionized water, and drying at 35 ℃.
(6) Polishing treatment, wherein the main component of polishing solution used for polishing is alpha-Al 2 O 3 The surface roughness Ra of polished surface is less than 0.2 mu m。
Example 3
A high-performance aluminum alloy treatment method comprises the following steps:
(1) Surface pretreatment:
(a) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(b) Degreasing: 15wt.% sulfuric acid, 2.5wt.% surfactant, room temperature for 7min; washing: distilled water, 20s;
(c) Acid washing; 25wt.% nitric acid; 15wt.% sulfuric acid; room temperature; time: 6min; washing: distilled water, 20s.
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer: na (Na) 2 SiO 3 15g/L, naOH g/L, na WO 45 g/L; glycerol 6ml/L; the positive voltage is 500V, the negative voltage is 200V, the positive duty ratio is 15-25%, the negative duty ratio is 10%, the pulse frequency is 400Hz, and the oxidation time is 40min.
(3) Coating nickel nano dispersion liquid for multiple times: the nickel nano-dispersion has a size of 50-100nm and a content of 20wt.%.
The multiple coating is carried out by using a vacuum spin coater, rotating at 2500rpm, spin coating time being 40s, spin coating times being 9 times, and then at 50 o C, drying in vacuum for 5h.
(4) Selective laser melting treatment: the laser output power in the selective laser melting treatment is 125W; the diameter of the light spot is 3mm; the laser beam scanning speed is 10mm/s, the large-area scanning laser lap joint rate is 60%, and inert argon gas is used for protecting gas.
(5) Inorganic hole sealing: the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 10g/L nickel acetate, 7g/L boric acid, 0.5g/L aminotrimethylene phosphoric acid, 0.2g/LEDTA-2Na0.03-0.05g/L octyl phenol polyoxyethylene ether, pH=5.7, temperature 90 ℃ and time 20min.
And (3) cleaning the hole sealing by using deionized water, and drying at 40 ℃.
(6) Polishing treatment, wherein the main component of polishing solution used for polishing is alpha-Al 2 O 3 The surface roughness Ra after polishing is less than 0.2 mu m.
Comparative example 1
A high-performance aluminum alloy treatment method comprises the following steps:
(1) Surface pretreatment:
(a) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(b) Degreasing: 14wt.% sulfuric acid, 2wt.% surfactant, room temperature for 6min; washing: distilled water, 17.5s;
(c) Acid washing; 20wt.% nitric acid; 12.5wt.% sulfuric acid; room temperature; time: 5min; washing: distilled water, 17.5s.
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer: na (Na) 2 SiO 3 20g/L, naOH1.5g/L, na2WO 43 g/L; glycerol 5ml/L; positive voltage 400V, negative voltage 150V, positive duty cycle 20%, negative duty cycle 7.5%, pulse frequency 350Hz, oxidation time 30min.
(3) Inorganic hole sealing: the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 7.5g/L nickel acetate, 6g/L boric acid, 0.4g/L aminotrimethylene phosphoric acid, 0.15g/LEDTA-2Na, 0.04g/L octylphenol polyoxyethylene ether, pH=5.7, temperature 87.5 ℃ and time 17.5min.
And (3) cleaning the hole sealing by using deionized water, and drying at 35 ℃.
(4) Polishing treatment, wherein the main component of polishing solution used for polishing is alpha-Al 2 O 3 The surface roughness Ra after polishing is less than 0.2 mu m.
Comparative example 2
A high-performance aluminum alloy treatment method comprises the following steps:
(1) Surface pretreatment:
(a) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(b) Degreasing: 14wt.% sulfuric acid, 2wt.% surfactant, room temperature for 6min; washing: distilled water, 17.5s;
(c) Acid washing; 20wt.% nitric acid; 12.5wt.% sulfuric acid; room temperature; time: 5min; washing: distilled water, 17.5s.
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer: Na 2 SiO 3 20g/L, naOH1.5g/L, na2WO 43 g/L; glycerol 5ml/L; positive voltage 400V, negative voltage 150V, positive duty cycle 20%, negative duty cycle 7.5%, pulse frequency 350Hz, oxidation time 30min.
(3) Coating nickel nano dispersion liquid for multiple times: the nickel nano-dispersion had a size of 50-100nm and a content of 17.5wt.%.
The multiple coating is carried out by using a vacuum spin coater, rotating at 2300rpm, spin coating time being 35s, spin coating times being 8 times, and then at 45 o C, drying in vacuum for 4h.
(4) Inorganic hole sealing: the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 7.5g/L nickel acetate, 6g/L boric acid, 0.4g/L aminotrimethylene phosphoric acid, 0.15g/LEDTA-2Na, 0.04g/L octylphenol polyoxyethylene ether, pH=5.7, temperature 87.5 ℃ and time 17.5min.
And (3) cleaning the hole sealing by using deionized water, and drying at 35 ℃.
(5) Polishing treatment, wherein the main component of polishing solution used for polishing is alpha-Al 2 O 3 The surface roughness Ra after polishing is less than 0.2 mu m.
Figure DEST_PATH_IMAGE001
As shown in the table above, the compactness of the micro-arc oxidation film on the surface of the aluminum alloy can be effectively improved by filling nickel metal with a lower melting point in the micro-arc oxidation film pore canal, selectively melting the nickel metal by a laser melting technology, and then treating the micro-arc oxidation film by using a nickel hole sealing agent, so that the corrosion resistance of the micro-arc oxidation film is remarkably improved, and the corrosion current density is 2.6235 x 10 -8 And the hardness of the coating is improved to 1862HV, and in addition, if only nano nickel filling is carried out and laser melting treatment is not carried out, hole sealing cannot be effectively carried out, namely the corrosion resistance and hardness of the aluminum alloy of comparative examples 1-2 are not obviously changed.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by the above embodiments, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.

Claims (5)

1. The high-performance aluminum alloy treatment method is characterized by comprising the following steps of:
(1) Surface pretreatment;
(2) Micro-arc oxidation to obtain a micro-arc oxidation film ceramic layer: the electrolyte used for micro-arc oxidation comprises Na 2 SiO 3 5-15g/L、NaOH1-2g/L、Na 2 WO 4 1-5g/L and 4-6ml/L glycerol; positive voltage of 300-500V, negative voltage of 100-200V, positive duty ratio of 15-25%, negative duty ratio of 5-10%, pulse frequency of 300-400 Hz and oxidation time of 20-40 min;
(3) Coating nickel nano dispersion liquid for multiple times: the size of nickel in the nickel nano dispersion liquid is 50-100nm, the content is 15-20 wt%, the multi-time coating is carried out by using a vacuum spin coater, the rotating speed is 2000-2500rpm, the spin coating time is 30-40s, the spin coating times are 5-9 times, and then the vacuum drying is carried out for 3-5 hours at the temperature of 40-50 ℃;
(4) Selective laser melting treatment: the laser output power in the selective laser melting treatment is 100-125W; the diameter of the light spot is 2-3mm; the scanning speed of the laser beam is 5-10mm/s, the overlapping rate of the large-area scanning laser is 30% -60%, and inert argon is used for protecting gas;
(5) Inorganic hole sealing: the inorganic hole sealing adopts medium-temperature nickel sealing, and the hole sealing liquid comprises the following components: 5-10g/L nickel acetate, 5-7g/L boric acid, 0.3-0.5g/L aminotrimethylene phosphate, 0.1-0.2g/L EDTA-2Na, 0.03-0.05g/L octylphenol polyoxyethylene ether, pH=5.7+ -0.3, temperature 85-90 ℃ and time 15-20min;
(6) And (5) polishing treatment.
2. A method of treating a high performance aluminum alloy as recited in claim 1 wherein said surface pretreatment comprises:
(1) Mechanical polishing: polishing an aluminum alloy sample through 800# abrasive paper and 1200# abrasive paper respectively;
(2) Degreasing: the degreasing fluid is a mixed solution of 12-15wt.% sulfuric acid and 1.5-2.5wt.% surfactant, and the time is 5-7min at room temperature; washing with distilled water for 15-20s after degreasing;
(3) Acid washing; the pickling solution is a mixed solution of 15-25wt.% of nitric acid and 10-15wt.% of sulfuric acid, and the room temperature is kept for 4-6min; washing with distilled water for 15-20s after pickling.
3. The method for treating high-performance aluminum alloy according to claim 1, wherein deionized water is used for cleaning after hole sealing, and drying is carried out at 30-40 ℃.
4. A high performance aluminum alloy processing method as defined in claim 1, wherein said polishing liquid used for polishing comprises the main component of alpha-Al 2 O 3 The surface roughness Ra after polishing is less than 0.2 mu m.
5. The method of claim 1, wherein the micro-arc oxidation film obtained after the micro-arc oxidation treatment in the step (2) has a thickness of 8 to 15 μm, and the polishing treatment in the step (6) has a thickness of 1 to 3 μm.
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