CN112522761B - Aluminum alloy electroplated metal treatment method - Google Patents

Aluminum alloy electroplated metal treatment method Download PDF

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CN112522761B
CN112522761B CN202011553437.XA CN202011553437A CN112522761B CN 112522761 B CN112522761 B CN 112522761B CN 202011553437 A CN202011553437 A CN 202011553437A CN 112522761 B CN112522761 B CN 112522761B
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nickel
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anodic oxidation
phosphoric acid
aluminum alloy
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CN112522761A (en
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赵伟
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Hubei Xiexing Environmental Protection Technology Co ltd
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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
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths
    • 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
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • 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
    • C25D11/24—Chemical after-treatment
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Electroplating Methods And Accessories (AREA)

Abstract

The invention discloses a method for electroplating metal on the anode surface of an aluminum alloy, which is characterized in that uniform pore channels with the pore diameter of 150-250nm are obtained through twice anodic oxidation treatment, and a high-hardness and wear-resistant material is obtained through magnetizing and depositing nickel alloy and electroplating nickel-cobalt alloy, wherein a nickel-cobalt coating and a base material can be effectively combined.

Description

Aluminum alloy electroplated metal treatment method
Technical Field
The invention belongs to the technical field of aluminum or aluminum alloy surface treatment, relates to nickel-cobalt alloy electroplating on the surface of aluminum alloy or anodized aluminum alloy, and particularly relates to the field of aluminum alloy of electronic terminals such as mobile phones and the like.
Background
With the continuous development of the field of electronic devices, housing materials for electronic devices are also abundant. For example, the metal plate has more beautiful texture, wear resistance, scratch resistance and other properties, and is applied to electronic equipment such as mobile phones, tablet computers and the like. The aluminum alloy material has been widely used in the manufacture of electronic equipment housings because of its advantages of good processability, light specific gravity, beautiful surface, corrosion resistance, good casting performance, etc.
At present, in the preparation process of the shell, the aluminum alloy material is usually subjected to the processes of anodic oxidation, electroplating or anodic oxidation and nano injection molding, and the invention only researches the processes of anodic oxidation, electroplating, wherein the standard potential of nickel is-0.25V, and the nickel has strong corrosion resistance and is the metal with the maximum use amount, so that the nickel is used as a protective and decorative coating of the aluminum alloy material to be concerned, and becomes a good metal protective coating.
The general electroplating process is electroplating of nickel base alloy, the nickel base alloy is widely applied to various aspects of electroplating industry and used for carrying out surface treatment for corrosion prevention and decoration on metal devices, but as nickel resources belong to non-renewable resources, the supply is seriously insufficient along with the continuous increase of nickel consumption, so that the price is raised suddenly, the nickel base alloy has high nickel plating cost for various electroplating enterprises, the electroplating enterprises search for new nickel-saving and nickel-substituting processes, and the nickel base alloy is the preferred plating species from the aspect of the plating layer.
There are two general types of anodic oxide films of aluminum known in the art, barrier anodic oxide films and porous anodic oxide films. The barrier type anodic oxide film is a compact and nonporous thin anodic oxide film closely attached to the metal surface, and is short for barrier film, the thickness of the barrier type anodic oxide film is generally very thin and not more than 0.1 μm depending on the applied anodic oxidation voltage, and the barrier type anodic oxide film is mainly used for manufacturing electrolytic capacitors. The barrier type anodic oxide film is also called a shielding layer anodic oxide film, and simply, the porous anodic oxide film comprises a shielding layer and a porous layer, which are significantly different in specific structure and composition, wherein the shielding layer is a compact non-porous amorphous oxide, usually gamma-Al 2O3, and the porous layer is composed of amorphous alumina, and the main component of the porous layer is alpha-AlOOH alumina.
Generally, the above-mentioned shielding layer at the bottom of the pore canal of the anodic oxide film has a positive contribution to the corrosion resistance and hardness of the anodic oxide film, for example, the hardness is higher, and the external corrosion can be prevented, i.e. the shielding layer of the aluminum anodic oxide film is usually not required to be concerned in the process of using the shielding layer, and is not required to be subjected to any treatment, but if the electroplating treatment is performed after the anodic oxidation, the electrical conductivity of the shielding layer is poor, and the process of electroplating and the binding force between the plating layer and the anodic oxide film can be obviously lower, which has adverse effects on the subsequent product production.
Regarding the treatment of anodized film barrier layers
CN202010193556a discloses a preparation method of a composite material with high binding force: (1) pretreatment; (2) anodic oxidation; (3) Positioning and marking a protective film, wherein the solution used in the step is mixed solution of gamma-chloropropyl trimethylsilane and anhydrous toluene; (4) Removing the anodic oxide film shielding layer, wherein the solution used in the step is mixed solution of NaOH, naF and ethanol; (5) The nickel metal layer is electroplated, namely gamma-chloropropyl trimethylsilane is adsorbed by positioning to remove the anodic aluminum oxide shielding layer, but gamma-chloropropyl trimethylsilane known in the art easily causes hole sealing phenomenon, the experimental parameters and the process are strictly known, and the technical personnel in the art can hardly ensure that the adsorption quantity of gamma-chloropropyl trimethylsilane in an anodic oxidation pore canal is equal, if the gamma-chloropropyl trimethylsilane is excessive, hole sealing occurs, if the gamma-chloropropyl trimethylsilane is too little, the marking effect is not obvious, and directional corrosion cannot be realized.
US201113310135a, applicant's universal automotive world technology operation limited company, discloses a method of bonding metal to a substrate, the method comprising:
forming a nanobrush on the substrate surface, the nanobrush comprising a plurality of nanowires extending above the substrate surface;
introducing the metal in a molten state onto the substrate surface, the metal surrounding the plurality of nanowires; and
solidifying the metal surrounding the plurality of nanowires by cooling, wherein during the solidifying at least a mechanical interlock is formed between the metal and the substrate;
wherein the forming of the nanobrush comprises:
forming a plurality of nanopores in a surface of the substrate;
depositing a material into the plurality of nanopores;
growing nanowires from the deposited material in each of the plurality of nanopores; and
a portion of the substrate surface is removed to expose the nanowires grown therein.
With specific reference to fig. 1 and the associated disclosure, it is noted that "in some cases, the oxide structure 18 may be etched to remove portions thereof (including the barrier layer) at the bottom of the nanopore 16, thereby exposing the underlying aluminum substrate 12", i.e., the prior art either directly forgoes processing of the shield layer 19, or directly and implicitly etches it away, without disclosing specific etching methods at all.
In addition to removing the shielding layer to achieve high bonding force between the plating layer and the substrate, the prior art includes forming an intermediate layer by electroless nickel plating or physical deposition to avoid the technical problem of lower conductivity caused by the anodic oxide shielding layer, but simply depositing a conductive layer in the anodic oxide film hole not only has complex process, but also most of the conductive layers easily cause hole closure.
Disclosure of Invention
Based on the problems in the prior art, the invention provides an aluminum alloy anodic oxidation post-treatment method, which obtains anodic oxidation with large aperture through twice anodic oxidation and reaming treatment, and then realizes electrolyte for effective electroplating on the premise of not removing an anodic oxidation inner shielding layer.
The aluminum alloy anodic oxidation post-treatment method is characterized by comprising the following steps of:
(1) Pretreatment: the pretreatment sequentially comprises heat treatment annealing, mechanical polishing, oil and fat removal, alkali washing and neutralization;
(2) Primary anodic oxidation: the anodic oxidation liquid is mixed liquid of oxalic acid and deionized water;
(3) Removing the primary anodic oxide film: the anodic oxidation solution is a mixed solution of phosphoric acid and chromic acid;
(4) Secondary anodic oxidation treatment: the anodic oxidation liquid is a mixed liquid of oxalic acid, phosphoric acid, glycol and deionized water;
(5) Reaming: the reaming solution is phosphoric acid:
(6) Electrochemical treatment: (a) immersing the electrolyte to magnetically deposit nickel particles; (b) turning on a power supply to electrodeposit nickel-cobalt alloy.
Further, the heat treatment anneals: 400-450 o C, ar protection, heat preservation for 1-2h, and natural cooling; mechanical polishing: sequentially polishing with 500-800-1500-2000 mesh sand paper; degreasing: 15-20g/L sodium carbonate and 3-4g/L sodium phosphate deionized water solution at 50-60 o C, soaking for 8-10min; alkali washing: 25-35g/LNaOH, 1-2g/L sodium gluconate aqueous solution at 40-50 o C, soaking for 3-7min; and (3) neutralization: 50-70g/L HNO3 and 4-8g/LNaF for 1-3min.
Further, the primary anodic oxidation is carried out at 30-35V, the oxalic acid content is 3-5wt.%, and the temperature is 30-32 o C, the time is 25-30min.
Further, a phosphoric acid and chromic acid mixed solution: the chromic acid concentration was 1wt% and the phosphoric acid concentration was 6wt%.
Further, the secondary anodic oxidation oxalic acid is 4-5wt.%, phosphoric acid is 10-13wt.%, voltage is 60-80V, and temperature is 15-20 o C, the time is 2-3h.
Further, the magnetic deposited nickel particles are consistent with the solution used for electrodepositing the nickel-iron alloy.
Further, the solution comprises
Nickel salt: 250-300g/L nickel sulfate;
cobalt salt: 20-30g/L of cobalt sulfate;
nickel conductive salt: 30-40g/L of nickel chloride;
buffering agent: boric acid 20-30g/L;
and (2) a surfactant: 1-2g/L of sodium dodecyl sulfonate;
2.5-4wt% high-dispersion nickel nano-dispersion 500-1000ml, ph=4-4.5.
Further, the preparation method of the solution high-dispersion nickel nano-dispersion liquid comprises the following steps:
(1) Dipropylene glycol and glucose are used as reducing agents, and deionized water is sequentially added into the reducing agents at normal temperature;
(2) Sequentially adding a 2-mercaptothiazole complexing agent, P123 and fatty alcohol sodium sulfate AES surfactant and 40-50 into the solution in the step (1) o C, magnetically stirring at 150-200rpm for 10-15min, standing, cooling to normal temperature, adding ammonia water to adjust pH value,
(3) Slowly adding nickel salt into the solution to obtain nickel nano dispersion liquid precursor liquid;
(4) Placing the precursor liquid into a Teflon hydrothermal reaction kettle, sealing the reaction kettle, evacuating nitrogen, and cooling at 30 o Stirring under C for 5-10min, closing nitrogen valve, and increasing to 105-110 o C, continuing stirring, fully reacting for 12-15h, and naturally cooling to room temperature;
(5) Pouring out hydrothermal reaction solution, performing primary centrifugal separation, taking upper solution, discarding lower solution, performing secondary centrifugal separation, taking lower solution, and diluting the lower solution with deionized water to obtain the high-dispersion nickel nano-dispersion liquid.
Further, the parameters of the (a) immersing the electrolyte to perform magnetic deposition of nickel particles are as follows: the power is not turned on, and a magnetic field of 0.3-0.7T, stirring of 200-300rpm and ultrasonic power of 100-200W are applied for 10-30min.
The (b) power supply is turned on to perform electroprecipitationParameters of nickel-cobalt alloy: turning on power supply, removing magnetic field, and making it be 50-60 o C, current density 4-6A/dm 2 。
The preparation method of the invention is as follows:
(1) Annealing by heat treatment, mechanical polishing, degreasing, alkaline washing and neutralization:
and (3) heat treatment annealing: 400-450 o C, ar protection, heat preservation for 1-2h, natural cooling, and effective removal of internal stress of the aluminum alloy through heat treatment, so as to avoid that the binding force between the base material and the coating is not strong due to the stress of the base material in the coating formed by subsequent electroplating.
Mechanical polishing: sequentially polishing by using 500-800-1500-2000-mesh sand paper: polishing to remove natural anodic oxidation on the surface of the anodic aluminum oxide, wherein the existence of the anodic oxidation film can seriously affect the dissolution-deposition process of the anodic oxidation, and in addition, by polishing the aluminum alloy substrate from thick to thin, the uniform aluminum alloy substrate with lower roughness can be obtained, thereby being beneficial to obtaining regular and ordered oxidation pore channels;
degreasing: 15-20g/L sodium carbonate and 3-4g/L sodium phosphate deionized water solution at 50-60 o And C, soaking for 8-10min, wherein the alkalinity of sodium carbonate is weaker than that of sodium hydroxide, the sodium carbonate has certain saponification capacity, the pH value of the solution is buffered, the corrosiveness to metal and the skin irritation are lower than those of sodium hydroxide, the price is low, grease is removed through saponification, if grease exists on the surface of aluminum, the grease is unevenly distributed on the surface of the aluminum, local anodic oxidation phenomenon is avoided, and obvious non-corroded areas are visible after anodic oxidation.
Alkali washing: 25-35g/LNaOH, 1-2g/L sodium gluconate aqueous solution at 40-50 o The purpose of alkaline washing for 3-7min is to completely remove the natural alumina layer, the natural alumina film reacts with sodium hydroxide to form sodium metaaluminate, the corrosion rate of aluminum is in direct proportion to the total content of sodium hydroxide in the solution and rises along with the rise of temperature, wherein sodium gluconate is a complexing agent, so that aluminum ions can be effectively masked, and the generation of aluminum hydroxide precipitation is avoided.
And (3) neutralization: 50-70g/L HNO3 and 4-8g/LNaF for 1-3min, thus obtaining the bright metal surface.
(2) Primary oxidation-removal of oxide film-secondary oxidation: the primary anodic oxidation is carried out at 30-35V, the oxalic acid content is 3-5wt.%, and the temperature is 30-32 o C, the time is 25-30min; the phosphoric acid and chromic acid mixed solution: chromic acid concentration of 1wt% and phosphoric acid concentration of 6wt%; the volume ratio of the oxalic acid to the phosphoric acid is 4-5 wt%, the phosphoric acid is 10-13 wt%, the volume ratio of the ethylene glycol to the deionized water is 2:1, the voltage is 60-80V, and the temperature is 15-20 o C, the time is 2-3h.
The invention adopts secondary anodic oxidation treatment to obtain the large-aperture oxide film expansion, generally like sulfuric acid, under the condition of 15wt.% concentration, the relationship between the pore size and the voltage is 0.8nm/V; such as oxalic acid, at a concentration of 2wt.%, the pore size versus voltage is 0.97nm/V; if phosphoric acid, the pore size and voltage relationship is 1.23nm/V at 15wt.% concentration, i.e. the pore size of the pore canal of the anodic oxide film obtained in the prior art is small at 30-50V, it is not enough to obtain pore canals exceeding 100nm, whereas the highly dispersed nickel particles of the present invention have an average size of 20-40nm, but do not lack particles exceeding 100nm, which, in the presence of such large particles, would significantly block the pore canal of the anodic oxide film, and thus it is necessary to obtain large pore anodic oxide canal.
The invention obtains a large-aperture pore canal by two means: two oxidation treatments and a reaming treatment.
The mechanism of the two anodic oxidation is unclear, and is mainly based on literature references: as 2015101012068: the pretreated aluminum sheet is oxidized once by utilizing a constant-voltage direct current mode, and is put into a chromium phosphate solution, soaked for 24 hours at the temperature of 45 ℃, the anodized aluminum which is generated on the surface is removed, the aluminum sheet from which the anodized aluminum is removed on the surface is oxidized twice in an oxalic acid solution by utilizing the constant-voltage direct current mode, and the technological conditions of the twice oxidation are as follows: the voltage is 40V, the temperature is 3-6 ℃, the concentration of oxalic acid solution is 0.3-0.5 mol/L, and the oxidation time is 5-10 minutes, thus obtaining the ultra-thin anodic aluminum oxide with the thickness of 100-150 nm.
The secondary anodic oxidation adopts mixed liquor of oxalic acid and phosphoric acid, the phosphoric acid is used as the main material, the oxalic acid is used as the auxiliary material, the anodic oxidation film is treated by using the phosphoric acid as known in the field, the pore diameter of the obtained pore canal is obviously larger than that of the oxalic acid and sulfuric acid, and the pore diameter range can be further enlarged by using mixed acid of the phosphoric acid and the oxalic acid.
Reaming: phosphoric acid: 4-6wt.%, temperature is 30-40 ℃, time is 60-90min, and the precondition of reaming is to ensure uniformity of the pore canal, and the pore canal array structure cannot be damaged by excessive corrosion.
The pore canal of the obtained anodic oxide film is 150-250nm, the porosity is 62-68%, the thickness is 0.7-1.2 microns, the thickness of the shielding layer is 8-12nm, and the thickness of the pore wall is 30-50nm.
(3) With respect to preparing the highly dispersed nickel nano metal dispersion:
the invention takes dipropylene glycol and glucose as compound reducing agents, in the prior art, the reducing agents usually take the reducing agents with strong reducibility such as hydrazine hydrate and the like for reduction, the stronger the reducibility of the reducing agents is, the faster the metal ions are reduced in solution, and finally the larger the metal particles are caused to be agglomerated or the shape of non-oriented growth is obtained, therefore, the invention adopts dipropylene glycol and glucose as reducing agents, wherein the dipropylene glycol is 50-60ml; 3-5g of glucose, and the reducing agent has weak reducibility and is insufficient for reducing metal salt under normal temperature conditions, so that the invention adopts hydrothermal conditions, pure hydroxyl and aldehyde groups of glucose can show obvious reducibility under the hydrothermal conditions, are slowly and uniformly reduced to form nuclei and aggregate into nano metal, and in addition, the reducing effect of the compound use of dipropylene glycol and glucose is larger than that of the dipropylene glycol which is singly used.
The invention has 50-60ml of dipropylene glycol and 20-30ml of deionized water, namely the main solvent is dipropylene glycol, and the effect of using the pure dipropylene glycol is best in theory, but the subsequent addition of glucose, complexing agent and surfactant can cause the excessive viscosity of the solution, so that the subsequent centrifugal separation has extremely poor centrifugal effect, and a proper amount of water is needed to balance the viscosity of the solution, thereby improving the separation effect.
The pH value is regulated by adding ammonia water, and the pH value is 7.5-7.8.
In the hydrothermal process, the following reaction may occur
CH 2 OH-(CHOH) 4 -CHO+Ni 2+ +2OH - →CH 2 OH-(CHOH) 4 -COOH+Ni↓+H 2 O, if transitional OH-is added, the equilibrium shifts significantly to the right at high pH, accelerating Ni formation, and in addition, ni at high pH 2+ Nickel oxide formation with OH-is not desirable in the present invention.
In the above process, if 2-mercaptothiazole complexing agent (M) is added, the reduction process becomes
CH 2 OH-(CHOH) 4 -CHO+M(Ni) 2+ +2OH - →CH 2 OH-(CHOH) 4 -COOH+M+Ni↓+H 2 O
N atoms and S atoms in the polar amino group in the 2-mercaptothiazole have lone pair electrons, and can form covalent bonds with nickel ions to form nickel complex ions, so that the purported rate of silver particles is effectively controlled.
Hydrothermal temperature 105-110 o C, the hydrothermal temperature is not too high, the reduction carbonization reaction is avoided, in addition, the generated metal atoms are more in number, the hydrothermal reaction temperature is high, the Brownian movement is more severe, the crystal growth is more random, and the method is characterized in that
This does not result in a single shape of metal particles. The specific upper limit of the water heat is not the content of the invention, and is 105-110 o C does not cause any carbonization reaction, and the metal particles are uniform and do not affect the purity of the dispersion, and is a preferable temperature.
And (2) a surfactant: p123 and fatty alcohol sodium sulfate, the person skilled in the art knows that when metal ions are reduced by dipropylene glycol and glucose, metal crystal nucleus is obtained, the crystal nucleus grows slowly, the surface energy of the metal particles just generated is extremely high, the surface energy of the metal particles has extremely strong adsorption performance, adsorption agglomeration can be caused between the same metal ions, the surfactant has relatively strong adsorption capacity, the generated metal particles and the surfactant have mutually competing reaction and preferentially adsorb with the surfactant, and the surfactant P123 of the invention is 0.1-0.15g; if the concentration of the surfactant is too low, the competition reaction is offset, namely when the surfactant is completely coated on the surface of metal ions, the surfactant is too low, so that the metal reasonably does not adsorb the surfactant in a certain direction, and other metal particles with higher surface energy are adsorbed, so that nanowires or nanorods grow, and the linear structure similar to that in CN201810411717 can occur.
If the amount of surfactant used is excessive, the presence of significant bubbles, especially microscopic bubbles, in the solution is detrimental to the uniform reduction of metal ions.
According to the invention, the non-ionic surfactant and the anionic surfactant are compounded, so that the surface tension of the solution is improved, the use amount of the surfactant is reduced, and the formation of bubbles caused by excessive use is avoided.
If the example 2 is followed, the difference is that no surface active agent is added, the nickel metal obtained can be 1-20 microns in size, agglomerated and settled, no suspending ability and low transparency of the solution obtained.
And (3) nitrogen evacuation: sealing the reaction kettle, evacuating nitrogen, and cooling at 30 o C, stirring for 5-10min, closing a nitrogen valve, and introducing air in the solution preparation process, wherein if the air is not removed in time, tiny metal particles and oxygen are inevitably generated, particularly under a hydrothermal condition, oxidation is extremely easy to occur on the surfaces of the metal particles with high surface activity, and the evacuation operation can alleviate the oxidation effect of metal ions to a certain extent.
In the hydrothermal process, as the reaction solution contains partial water and nitrogen is exhausted to remove air in the liquid completely, namely oxidation of metallic nickel is difficult to avoid, metallic oxide is formed, a small amount of black and green sediment is found at the bottom of the hydrothermal reaction kettle after the hydrothermal reaction is finished, and some agglomerated metallic particles are also present except the oxide, and are in a nanowire or a nano rod or an amorphous state, centrifugal separation is needed, one-time centrifugal separation is performed at 2500rpm for 4-5min, the upper solution is taken, the lower solution is discarded, namely one-time centrifugation is performed, and the discarded lower solution mainly contains nickel oxide and agglomerated metallic particles.
And (3) secondary centrifugation: secondary centrifugation parameters: 600 rpm,1-2min; the main purpose is to screen nickel metal with proper particle size, the size of the metal particle size without secondary screening is between 1-40nm, and for some too fine metal particles, the solution stability is not favored, the surface activity energy of the fine nano metal is very high, so that the dispersion liquid without secondary separation has fine and macroscopic sediment at normal temperature and normal pressure for 50-60 days.
(4) Regarding the plating solution: the plating solution mainly comprises nickel salt, cobalt salt, nickel conductive salt, buffering agent, surfactant and 2.5-4wt% of high-dispersion nickel nano dispersion liquid, wherein the anode is nickel-cobalt alloy, and the cobalt content in the nickel-cobalt alloy is 5-7wt%.
In the plating solution, nickel sulfate is used as main salt to provide nickel ions required by electrodeposition. Nickel chloride not only provides nickel ions, but also ensures that the nickel anode is not easy to be passivated due to the addition of chloride ions, thereby improving the conductivity of the plating solution and improving the dispersion capability of the plating solution. Boric acid is a buffering agent, and has the main functions of stabilizing the pH value of the electroplating solution, slowing down the increase of the pH value of the solution in a cathode area, preventing hydroxide from precipitating on a cathode, and improving the polarization of the cathode and the appearance of a plating layer.
Electroplating parameters: pH:4-4.5, temperature 50-55 o C, current density 4-6A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the A magnetic field of 0.3-0.7T, stirring of 200-300rpm, and ultrasonic power of 100-200W is applied.
As described in the background art, because the shielding layer exists in the anodic oxide film, the shielding layer has lower conductivity and is not suitable for directly electroplating on the surface of the aluminum alloy with the anodic oxide film, so that nickel metal particles are introduced into the pore canal of the anodic oxide film by magnetic force before nickel-cobalt alloy electroplating, the conductivity of the anodic oxide film is improved, and then current is applied, thereby facilitating the subsequent electroplating treatment.
In the process of the time magnetic field, the nickel particles in the uniform plating solution are treated by ultrasonic and stirring, so that uniform plating is realized.
Compared with the prior art, the invention has the beneficial effects that:
1. and the anodic oxidation pore canal with large aperture is obtained through twice anodic oxidation and reaming treatment, and the pore canal is obviously larger than the size of nickel metal particles, thereby being beneficial to subsequent magnetic deposition and electrochemical deposition.
2. According to the invention, the Ni salt is reduced to metal ions under the hydrothermal condition by compounding the weak reducing agent, the metal ions are highly dispersed in the solution under the action of the complexing agent and the compound surfactant, and the stability of the nickel metal particle dispersion liquid is excellent.
3. By treating the aluminum alloy, the physical and chemical properties of the aluminum alloy such as hardness, corrosion resistance, wear resistance and the like are effectively improved.
Drawings
FIG. 1 is an optical view of a plated anodized aluminum material obtained by the post-anodizing treatment of the present invention.
FIG. 2 is a schematic illustration of the magnetic deposition and electroplating deposition process of the present invention.
Fig. 3 is an SEM image of an anodized tunnel after two anodic oxidation reaming according to the present invention.
FIG. 4 is a SEM of an anodized layer of the present invention magnetically deposited for 5 minutes.
Fig. 5 is an SEM image of the electroplated nickel-cobalt alloy of the present invention.
Detailed Description
As shown in FIG. 1, the invention obtains the optical diagram of the plating anodized aluminum material obtained by the anodizing post-treatment, and the plating is uniform and glossy.
As shown in figure 2, firstly, an electrode is placed in an electrolytic tank, an aluminum material is used as an anode, inert metal is used as a cathode, the aluminum material is treated by anodic oxidation, so that an anodic oxidation porous film is formed on the surface of the aluminum material, then the electrolytic tank is replaced, the obtained anodic oxidation treated aluminum material is used as the cathode, nickel-cobalt alloy is used as the anode, the electrolytic tank containing nickel-cobalt plating solution is placed in the electrolytic tank, a magnetic field is applied, the magnetic field is parallel to the current direction, a stirring rod and ultrasonic stirring homogenization plating solution are simultaneously applied, nickel in the high-dispersion nickel nano-dispersion solution is deposited in holes of the anodic oxidation film under the induction of the magnetic field, then the magnetic field is stopped being applied, a power supply is turned on, electro-deposition I is carried out to form a plating layer in the holes, the aluminum material is continuously fully covered by electro-deposition II, and the nickel-cobalt plating layer is obtained by polishing, so that a flat surface is obtained.
As shown in fig. 3, the anodized channels become significantly larger after reaming and the structure of the channels themselves can be maintained.
As shown in fig. 4, by magnetic deposition, the pores of the anodized film are deposited with nano nickel particles, and the nickel particles are deposited only in the pores, not to the surface, which is related to ultrasonic and agitation.
As shown in fig. 5, the bright portions are nickel-cobalt alloy and the black portions are alumina.
The dispersion in all examples of the invention was prepared as follows:
(1) 55ml of dipropylene glycol and 4g of glucose are used as reducing agents, and 25ml of deionized water is sequentially added into the reducing agents at normal temperature.
(2) To the solution in step (1) were added sequentially 1.1g of a 2-mercaptothiazole complexing agent, 0.125g of P123 and 0.075g of sodium fatty alcohol acyl sulfate AES surfactant, and 45 g of o C, magnetically stirring at 200rpm for 12.5min, standing, cooling to normal temperature, and adding ammonia water to adjust the pH value to 7.7.
(3) Slowly adding 0.85g of nickel salt into the solution to obtain a nickel nano dispersion liquid precursor liquid.
(4) Placing the precursor liquid into a Teflon hydrothermal reaction kettle, sealing the reaction kettle, evacuating nitrogen, and cooling at 30 o Stirring for 5-10min under C, closing nitrogen valve, and rising to 108 in 25min o C, continuously stirring and filling
Reacting for 14h, and naturally cooling to room temperature.
(5) Pouring out hydrothermal reaction solution, and performing primary centrifugal separation: 2500rpm,4.5min, taking the upper solution, discarding the lower solution, and performing secondary centrifugation: and 600 rpm,1.2min, taking a solution lower liquid, wherein the lower liquid subjected to secondary centrifugal separation is a high-dispersion nickel nano dispersion liquid.
Example 1
An anodic oxidation post-treatment method for aluminum alloy comprises the following steps:
(1) Pretreatment: the pretreatment comprises the steps of heat treatment annealing, mechanical polishing, oil and fat removal, alkali washing and neutralization in sequence, wherein the heat treatment annealing comprises the steps of: 400 o C, ar protection, heat preservation for 1h and natural cooling; mechanical polishing: sequentially polishing with 500-800-1500-2000 mesh sand paper; degreasing: deionized water solution of 15g/L sodium carbonate and 3g/L sodium phosphate at 50 o C, soaking for 8min; alkali washing: 25g/LNaOH, 1g/L sodium gluconate aqueous solution at a temperature of 40 o C, soaking for 3min; and (3) neutralization: a mixed aqueous solution of 50g/L HNO3 and 4g/LNaF was used for 1min.
(2) Primary anodic oxidation: the anodic oxidation liquid is mixed liquid of oxalic acid and deionized water, the primary anodic oxidation is carried out at 30V, the oxalic acid content is 3 wt%, and the temperature is 30 o C, time 25min.
(3) Removing the primary anodic oxide film: the anodic oxidation liquid is a mixed solution of phosphoric acid and chromic acid, and the mixed solution of phosphoric acid and chromic acid: the chromic acid concentration was 1wt% and the phosphoric acid concentration was 6wt%.
(4) Secondary anodic oxidation treatment: the anodic oxidation liquid is mixed liquid of oxalic acid, phosphoric acid, glycol and deionized water, the volume ratio of the secondary anodic oxidation oxalic acid to the phosphoric acid to the glycol to deionized water is 2:1, the voltage is 60V, and the temperature is 15 o C, time 2h.
(5) Reaming: the reaming solution is phosphoric acid: 4wt.%, temperature 30℃for 60min.
(6) Electrochemical treatment: (a) immersing the electrolyte to magnetically deposit nickel particles; (b) turning on a power supply to electrodeposit nickel-cobalt alloy.
Electrolyte solution:
nickel salt: 250g/L nickel sulfate;
cobalt salt: 20g/L of cobalt sulfate;
nickel conductive salt: 30g/L of nickel chloride;
buffering agent: boric acid 20g/L;
and (2) a surfactant: 1g/L of sodium dodecyl sulfonate;
500ml of high-dispersion nickel nano-dispersion.
(a) The parameters of immersing the electrolyte to carry out magnetic deposition of nickel particles are as follows: the power was not turned on, and a magnetic field of 0.3T, stirring at 200rpm, and ultrasonic power of 100W were applied for 10 minutes.
(b) Parameters of electrodepositing nickel-cobalt alloy by starting a power supply: turning on power supply, removing magnetic field, 50 o C, current density 4A/dm 2 。
Example 2
An anodic oxidation post-treatment method for aluminum alloy comprises the following steps:
(1) Pretreatment: the pretreatment comprises the steps of heat treatment annealing, mechanical polishing, oil and fat removal, alkali washing and neutralization in sequence, wherein the heat treatment annealing comprises the steps of: 430 o C, ar protection, heat preservation for 1.5h and natural cooling; mechanical polishing: sequentially polishing with 500-800-1500-2000 mesh sand paper; degreasing: deionized water solution of 17.5g/L sodium carbonate and 3.5g/L sodium phosphate, temperature 55 o C, soaking for 9min; alkali washing: 30g/LNaOH, 1.5g/L sodium gluconate aqueous solution at a temperature of 45 o C, soaking for 5min; and (3) neutralization: a mixed aqueous solution of 60g/L HNO3 and 6g/LNaF was used for 1-3min.
(2) Primary anodic oxidation: the anodic oxidation liquid is mixed liquid of oxalic acid and deionized water, the primary anodic oxidation is carried out at 33V, the oxalic acid content is 4wt.%, and the temperature is 31 o C, time 27.5min.
(3) Removing the primary anodic oxide film: the anodic oxidation liquid is a mixed solution of phosphoric acid and chromic acid, and the mixed solution of phosphoric acid and chromic acid: the chromic acid concentration was 1wt% and the phosphoric acid concentration was 6wt%.
(4) Secondary anodic oxidation treatment: the anodic oxidation liquid is mixed liquid of oxalic acid, phosphoric acid, glycol and deionized water, the volume ratio of the secondary anodic oxidation oxalic acid is 4.5wt.%, phosphoric acid is 11.5wt.%, the volume ratio of the glycol to deionized water is 2:1, the voltage is 60-80V, and the temperature is 17.5 o C, time 2.5h.
(5) Reaming: the reaming solution is phosphoric acid: 5wt.%, temperature 35℃and time 75min.
(6) Electrochemical treatment: (a) immersing the electrolyte to magnetically deposit nickel particles; (b) turning on a power supply to electrodeposit nickel-cobalt alloy.
Electrolyte solution:
nickel salt: 275g/L nickel sulfate;
cobalt salt: 25g/L of cobalt sulfate;
nickel conductive salt: 35g/L of nickel chloride;
buffering agent: boric acid 25g/L;
and (2) a surfactant: 1.5g/L sodium dodecyl sulfonate;
750mL of high-dispersion nickel nano-dispersion liquid.
(a) The parameters of immersing the electrolyte to carry out magnetic deposition of nickel particles are as follows: the power was not turned on, and a magnetic field of 0.5T, stirring at 250rpm, ultrasonic power of 150W was applied for 20 minutes.
(b) Parameters of electrodepositing nickel-cobalt alloy by starting a power supply: turning on power supply, removing magnetic field, temperature 55 o C, current density 5A/dm 2 。
Example 3
An anodic oxidation post-treatment method for aluminum alloy comprises the following steps:
(1) Pretreatment: the pretreatment comprises the steps of heat treatment annealing, mechanical polishing, oil and fat removal, alkali washing and neutralization in sequence, wherein the heat treatment annealing comprises the steps of: 450 o C, ar protection, heat preservation for 2h and natural cooling; mechanical polishing: sequentially polishing with 500-800-1500-2000 mesh sand paper; degreasing: deionized water solution of 20g/L sodium carbonate and 4g/L sodium phosphate, temperature 60 o C, soaking for 10min; alkali washing: 35g/LNaOH, 2g/L sodium gluconate aqueous solution at a temperature of 50 o C, soaking for 7min; and (3) neutralization: a mixed aqueous solution of 70g/L HNO3 and 8g/LNaF was used for 3min.
(2) Primary anodic oxidation: the anodic oxidation liquid is mixed liquid of oxalic acid and deionized water, the primary anodic oxidation is carried out at 35V, the oxalic acid content is 5 wt%, and the temperature is 32 o C, time 30min.
(3) Removing the primary anodic oxide film: the anodic oxidation liquid is a mixed solution of phosphoric acid and chromic acid, and the mixed solution of phosphoric acid and chromic acid: the chromic acid concentration was 1wt% and the phosphoric acid concentration was 6wt%.
(4) Secondary anodeAnd (3) oxidation treatment: the anodic oxidation liquid is mixed liquid of oxalic acid, phosphoric acid, glycol and deionized water, the volume ratio of the secondary anodic oxidation oxalic acid to the phosphoric acid to the glycol to deionized water is 2:1, the voltage is 80V, and the temperature is 20 o C, time 3h.
(5) Reaming: the reaming solution is phosphoric acid: 6wt.%, temperature 40 ℃ and time 90min.
(6) Electrochemical treatment: (a) immersing the electrolyte to magnetically deposit nickel particles; (b) turning on a power supply to electrodeposit nickel-cobalt alloy.
Electrolyte solution:
nickel salt: 300g/L nickel sulfate;
cobalt salt: 30g/L of cobalt sulfate;
nickel conductive salt: nickel chloride 40g/L;
buffering agent: boric acid 30g/L;
and (2) a surfactant: 1-2g/L of sodium dodecyl sulfonate;
500-1000mL of high-dispersion nickel nano dispersion liquid.
(a) The parameters of immersing the electrolyte to carry out magnetic deposition of nickel particles are as follows: the power was not turned on, and a magnetic field of 0.7T, stirring at 200-300rpm, ultrasonic power at 200W was applied for 30min.
(b) Parameters of electrodepositing nickel-cobalt alloy by starting a power supply: turning on power supply, removing magnetic field, temperature 60 o C, current density 6A/dm 2 。
Finally, it should be noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (7)

1. The aluminum alloy electroplated metal treatment method is characterized by comprising the following steps of:
(1) Pretreatment: sequentially comprises the steps of heat treatment annealing, mechanical polishing, oil removal, degreasing, alkali washing and neutralization;
(2) Primary anodic oxidation: the anodic oxidation liquid is oxalic acid deionized water solution;
(3) Removing the primary anodic oxide film: the solution for removing the primary anodic oxide film is a mixed solution of phosphoric acid and chromic acid;
(4) Secondary anodic oxidation treatment: the anodic oxidation liquid is a mixed liquid of oxalic acid, phosphoric acid, glycol and deionized water;
(5) Reaming: the reaming solution is phosphoric acid solution:
(6) Electrochemical treatment: (a) immersing the magnetically deposited nickel particles; (b) turning on a power supply to electrodeposit nickel-cobalt alloy;
the electrolytic solution used for magnetically depositing nickel particles and electrodepositing nickel-cobalt alloy is consistent;
the electrolyte solution comprises
Nickel salt: 250-300g/L nickel sulfate;
cobalt salt: 20-30g/L of cobalt sulfate;
nickel conductive salt: 30-40g/L of nickel chloride;
buffering agent: boric acid 20-30g/L;
and (2) a surfactant: 1-2g/L of sodium dodecyl sulfonate;
2.5-4wt.% of a highly dispersed nickel nanodispersion 500-1000ml, ph=4-4.5;
the preparation method of the high-dispersion nickel nano dispersion liquid comprises the following steps:
taking dipropylene glycol and glucose as reducing agents, and sequentially adding deionized water into the reducing agents at normal temperature;
(II) sequentially adding a 2-mercaptothiazole complexing agent, P123 and fatty alcohol sodium sulfate AES surfactant into the solution in the step (1), magnetically stirring for 10-15min at 40-50 ℃ at 150-200rpm, standing, cooling to normal temperature, adding ammonia water to adjust the pH value,
(III) slowly adding nickel salt into the solution obtained in the step (II) to obtain nickel nano dispersion liquid precursor liquid;
(IV) placing the nickel nano dispersion liquid precursor liquid into a Teflon hydrothermal reaction kettle, sealing the reaction kettle, evacuating nitrogen, stirring for 5-10min at 30 ℃, closing a nitrogen valve, heating to 105-110 ℃, continuing stirring, fully reacting for 12-15h, and naturally cooling to room temperature;
pouring out the hydrothermal reaction solution, performing primary centrifugal separation, taking the upper solution, discarding the lower solution, performing secondary centrifugal separation, taking the lower solution, and diluting the lower solution with deionized water to obtain the high-dispersion nickel nano-dispersion.
2. A method of aluminum alloy electroplated metal treatment as set forth in claim 1, wherein the heat treatment anneals: protecting by Ar at 400-450 ℃, preserving heat for 1-2h, and naturally cooling; mechanical polishing: sequentially polishing with 500-mesh sand paper, 800-mesh sand paper, 1500-mesh sand paper and 2000-mesh sand paper; degreasing: 15-20g/L of sodium carbonate and 3-4g/L of sodium phosphate, wherein the temperature is 50-60 ℃ and the soaking time is 8-10min; alkali washing: 25-35g/L NaOH and 1-2g/L sodium gluconate aqueous solution, wherein the temperature is 40-50 ℃ and the soaking time is 3-7min; and (3) neutralization: 50-70g/L HNO 3 And 4-8g/L NaF for 1-3min.
3. The method for treating metal plated on an aluminum alloy according to claim 1, wherein the primary anodic oxidation voltage is 30-35V, the oxalic acid content in the oxalic acid deionized water solution is 3-5wt.%, the temperature is 30-32 ℃ and the time is 25-30min.
4. The method for treating an aluminum alloy plated metal according to claim 1, wherein the phosphoric acid and chromic acid mixed solution: chromic acid concentration 1wt.%, phosphoric acid concentration 6wt.%; the concentration of phosphoric acid solution used for reaming is 4-6wt.%, the temperature is 30-40 ℃ and the time is 60-90min.
5. The method for treating metal plated on an aluminum alloy according to claim 1, wherein the secondary anodic oxidation treatment has an oxalic acid concentration of 4-5wt.%, a phosphoric acid concentration of 10-13wt.%, a volume ratio of ethylene glycol to deionized water of 2:1, a voltage of 60-80V, a temperature of 15-20 ℃ and a time of 2-3 hours.
6. The method for electroplating metal according to claim 1, wherein the immersing of the magnetically deposited nickel particles comprises the following parameters: the power is not turned on, a magnetic field of 0.3-0.7T is applied, stirring is performed at 200-300rpm, and ultrasonic power of 100-200W is applied for 10-30min.
7. The method for electroplating metal treatment of aluminum alloy according to claim 1, wherein the parameters of the power-on electrodeposited nickel-cobalt alloy are as follows: turning on power supply, removing magnetic field, and controlling current density at 50-60deg.C and 4-6A/dm 2 。
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CN104233420A (en) * 2013-06-14 2014-12-24 无锡市森信精密机械厂 Method for directly electroplating high-binding-force nickel layer on surface of aluminum or aluminum alloy
CN111172575A (en) * 2020-03-18 2020-05-19 王永芝 Aluminum material subjected to anodic oxidation treatment
CN112095132A (en) * 2020-09-08 2020-12-18 池州市安安新材科技有限公司 Method for anodizing surface of high-corrosion-resistance aluminum profile

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104233420A (en) * 2013-06-14 2014-12-24 无锡市森信精密机械厂 Method for directly electroplating high-binding-force nickel layer on surface of aluminum or aluminum alloy
CN111172575A (en) * 2020-03-18 2020-05-19 王永芝 Aluminum material subjected to anodic oxidation treatment
CN112095132A (en) * 2020-09-08 2020-12-18 池州市安安新材科技有限公司 Method for anodizing surface of high-corrosion-resistance aluminum profile

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