CN111020663A - Method for producing oxide film, and metal product having oxide film - Google Patents
Method for producing oxide film, and metal product having oxide film Download PDFInfo
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- CN111020663A CN111020663A CN201911257491.7A CN201911257491A CN111020663A CN 111020663 A CN111020663 A CN 111020663A CN 201911257491 A CN201911257491 A CN 201911257491A CN 111020663 A CN111020663 A CN 111020663A
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Abstract
A method for forming an oxide film, comprising: a boosting stage: placing the metal matrix in an electrolyte solution, and slowly increasing the voltage to V1, wherein the voltage increasing speed is in the range of 15-25V/min; and (3) high voltage stage: maintaining a voltage V1, performing a first electrochemical oxidation on the metal substrate, and oxidizing the surface of the metal substrate to generate a porous layer with adsorption pores; a pressure reduction stage: slowly reducing the voltage to V2, wherein the voltage reduction speed is in the range of 8V/min to 11V/min; and (3) low-voltage stage: maintaining the voltage V2, and carrying out secondary electrochemical oxidation on the metal matrix to generate a barrier layer with enhanced pores, namely obtaining the oxide film; wherein the reinforcing hole is formed at the bottom of the adsorption hole. The invention also provides an oxide film and a metal product with the oxide film.
Description
Technical Field
The invention relates to the field of metal materials, in particular to a manufacturing method of an oxide film, the oxide film and a metal product with the oxide film.
Background
The existing aluminum alloy anodic oxidation process is mainly a porous anodic oxidation treatment process, namely, a uniform porous oxide film is generated on the surface of the aluminum alloy by an electrochemical reaction method, and because the film layer has a porous structure, dyes and functional materials can be deposited in pores, so that the product has colorful appearance and is more attractive and durable. However, the oxide film produced by this process is formed by the reaction of aluminum alloy, i.e., it is formed by "growing" and converting from the surface of the aluminum substrate to the outside, and at the corners, edges, etc., the surface area is sharply enlarged, and the oxide film is subjected to tension, so that the cracking condition is easily generated, and the oxide film is easily peeled off; the aluminum alloy substrate is exposed at the cracking position, and when some extreme chemical environment tests (such as artificial sweat tests), the corrosion resistance in partial areas, particularly the cracked areas of the film layer is not enough, so that the conditions of corrosion, heterochromous color and oxide film falling can occur; and the high temperature resistance of the oxide film is poor, and experiments show that the original complete oxide film can crack when the temperature exceeds 90 ℃ in a dry environment.
Disclosure of Invention
In view of the above, it is desirable to provide a method for forming an oxide film, and a metal product having the oxide film.
A method for forming an oxide film, comprising:
a boosting stage: placing the metal matrix in an electrolyte solution, and slowly increasing the voltage to V1, wherein the voltage increasing speed is in the range of 15-25V/min;
and (3) high voltage stage: maintaining a voltage V1, performing a first electrochemical oxidation on the metal substrate, and oxidizing the surface of the metal substrate to generate a porous layer with adsorption pores;
a pressure reduction stage: slowly reducing the voltage to V2, wherein the voltage reduction speed is in the range of 8V/min to 11V/min;
and (3) low-voltage stage: maintaining the voltage V2, and carrying out secondary electrochemical oxidation on the metal matrix to generate a barrier layer with enhanced pores, namely obtaining the oxide film;
wherein the reinforcing hole is formed at the bottom of the adsorption hole.
An oxide film comprising:
a metal substrate;
the barrier layer covers the surface of the metal matrix and is provided with a reinforced hole; and
and the porous layer is arranged on the barrier layer and is provided with adsorption holes corresponding to the enhancement holes.
A metal article comprising:
an oxide film; and
the material layer is formed on the oxide film; wherein the content of the first and second substances,
the oxide film is the oxide film;
the material layer is adsorbed in the adsorption holes and the enhancement holes.
In above-mentioned oxide film and the metal product that has this oxide film, through the barrier layer that forms the higher toughness on metal substrate for the oxide film is in positions such as corner, can not be because of the surface area sharply enlarges the fracture, has guaranteed the integrality of oxide film, has improved the shock resistance of oxide film and the metal product that has this oxide film, and the corrosion resistance of barrier layer and the more pore layer of wearability etc. all have obvious improvement, make the oxide film have corrosion-resistant, wear-resisting, high temperature resistant, the advantage to the tolerance of extreme chemical environment.
Drawings
FIG. 1 is an electron microscopic magnification of a prior art metal article made by an anodic oxidation process.
Fig. 2 is an electron microscopic magnification of 2500 times of the cracking of the oxide film layer at the corner position of the metal product in the prior art.
Fig. 3 is an electron microscopic magnification of 2500 times of another prior art metal article showing oxide film layer cracking at corner locations.
Fig. 4 is a schematic view of an oxide film in one embodiment of the present invention.
Fig. 5 is a flowchart of a method for forming an oxide film according to an embodiment of the present invention.
Fig. 6 is an electron microscopic enlarged view of the oxide film in the embodiment of the present invention.
Fig. 7 is an enlarged view of the oxide film shown in fig. 6 at the interface of the porous layer and the barrier layer under an electron microscope.
Fig. 8 is an electron microscopic enlarged view of an oxide film at a corner position in an embodiment of the present invention.
Fig. 9 is an enlarged view of the oxide film shown in fig. 6 at a corner position by 20000 times under an electron microscope.
Description of the main elements
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1 |
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2 |
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3 |
| Reinforced |
31 |
| Porous layer | 4 |
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41 |
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. When an element is referred to as being "disposed on" another element, it can be directly on the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
FIG. 1 is an electron microscopic magnification of a prior art metal article made by an anodic oxidation process. Fig. 2 and 3 are 2500 times electron microscope enlarged views of the oxide film layer cracking at the corner position of the metal product in the prior art. FIG. 6 is an enlarged view of the oxide film in the present application under an electron microscope. FIG. 7 is an enlarged electron microscope image of the oxide film of FIG. 6 at the interface of the porous layer and the barrier layer. FIG. 8 is an enlarged view of the oxide film at the corner position in the present application under an electron microscope. FIG. 9 is an enlarged view of the oxide film shown in FIG. 8 at a corner position by 20000 times under an electron microscope.
Referring to fig. 5 to 9, a method for fabricating an oxide film according to an embodiment of the present invention is provided. Which comprises the following steps:
in step S1, the metal matrix is placed in an electrolyte solution.
Specifically, the electrolyte solution is a mixed solution containing sulfuric acid and oxalic acid. The concentration of the sulfuric acid is 18 g/L-22 g/L. The concentration of the oxalic acid is 36 g/L-44 g/L.
In one embodiment, the concentration of the sulfuric acid is 20g/L, and the concentration of the oxalic acid is 40 g/L.
Taking a metal matrix as an anode for electrolysis; and putting the cathode body into the electrolyte to be used as a cathode for electrolysis. The cathode body adopts conductive inorganic matter. The conductive inorganic substance may be a metal or a nonmetal. The metal may be gold, silver, copper, aluminum, zinc, tungsten, magnesium, brass, iron, platinum, calcium, molybdenum, cobalt, chromium, nickel, indium, stainless steel, tin, etc., and the nonmetal may be graphite. For one embodiment of the present application, graphite or stainless steel is used for the cathode body.
The material of the metal matrix is at least one selected from magnesium, magnesium alloy, aluminum alloy, titanium alloy, stainless steel, carbon steel and iron.
In one embodiment, the material of the metal substrate is aluminum or aluminum alloy.
In one embodiment, before the metal matrix is placed in the electrolyte solution, the method further comprises the step of pretreating the metal matrix:
degreasing, namely placing the metal matrix in a cleaning agent to remove surface oil stains;
alkali biting, namely washing the metal matrix without oil stain by using strong alkali solution to remove burrs; and
and (4) acid washing, wherein the metal matrix after alkali biting is washed by strong acid solution.
Specifically, a degreasing agent is adopted, reaction is carried out for 3-5 min at the temperature of 52-58 ℃, then washing is carried out for 30s by using distilled water, and the steps are repeated twice; then, putting the mixture into NaOH solution, taking NaOH as an alkali biting agent, reacting for 10-30 s at the temperature of 48-52 ℃, then washing for 30s with distilled water, and repeating twice; and finally, putting the mixture into a phosphoric acid solution, taking phosphoric acid as a pickling agent, reacting for 30-60 s at the temperature of 73-83 ℃, then washing for 30s with distilled water, and repeating twice.
In one embodiment, the degreasing agent is a water-based cleaning agent used in a traditional metal degreasing treatment. The concentration of the NaOH solution is 28 g/L-32 g/L. The specific gravity of the phosphoric acid solution (the specific gravity of the liquid is the ratio of the density of the substance to the density of pure water at 3.98 ℃ under standard atmospheric pressure) is 1.68-1.74.
Step S2, step up stage, slowly increasing the voltage to V1.
Specifically, the voltage of the electrochemical oxidation is gradually increased by the voltage regulator, and the increasing speed is controlled to be in the range of 15V/min to 25V/min. V1 is in the range of 21V to 22V. Generally, the voltage rise time is in the range of 1min to 3min, and the rise time is not too long or too short. Preferably, the rise time is 1min to 1.5 min. If the time is too long, the acid solution used as the electrolyte directly corrodes the surface of the metal matrix, the corrosion reaction is severe, the normal formation of an oxide film on the surface of the metal matrix is influenced, and the electric power is wasted; if the time is too short, the over-high voltage directly contacts the metal substrate, which causes the sparking phenomenon on the surface of the metal substrate, and the metal substrate is easily burnt, so that the surface of the metal substrate is uneven, and the uniformity of the formed oxide film is affected.
In one embodiment, the voltage is raised to 22V by controlling the speed of the voltage rise to 21V/min-22V/min and the time to 1 min.
And step S3, in the high-voltage stage, maintaining the voltage V1, carrying out the first electrochemical oxidation on the metal substrate, and oxidizing the surface of the metal substrate to generate a porous layer with adsorption pores.
Specifically, the metal substrate is electrochemically oxidized by performing an anodic oxidation operation by applying a constant voltage.
In one embodiment, the metal substrate is aluminum or an aluminum alloy. The film forming reaction occurs at the anode: 2Al +3H2O→Al2O3+6H++6e-(ii) a And dissolution reaction: al (Al)2O3+6H+→2Al3++3H2And O. Under the combined action of film forming reaction and dissolving reaction, an oxide layer with holes, namely a porous layer with adsorption holes, is generated on the surface of the metal matrix.
The diameter of the adsorption hole generated on the metal substrate is determined by the voltage of the first electrochemical oxidation reaction, and the value range of the first electrochemical oxidation voltage is 21V-22V. The reaction time determines the thickness of the porous layer to be formed, and the thickness of the porous layer is in the range of 8 to 50 μm. Preferably, the porous layer has a thickness of 8.5 μm to 11.5. mu.m. The reaction time is controlled to be 28 min-42 min.
The adsorption holes have large aperture and strong adsorption effect, and can adsorb functional substances such as dye molecules, magnetic particles and the like, so that the surface of the prepared oxide film product has special performance. The aperture range of the adsorption hole is 15 nm-50 nm. For example, dye molecules are adsorbed by the adsorption pores of the porous layer, and then the pores are sealed, so that a product with a specific color can be obtained.
In one embodiment, the metal matrix is subjected to a first electrochemical oxidation at 25-29 ℃ with a voltage of 22V for 35min to produce a porous layer with a thickness of 10 μm, and the diameter of the adsorption pores is 20-40 nm.
Step S4, step down phase, the voltage is slowly decreased to V2.
Specifically, the voltage of the electrochemical oxidation is gradually reduced through the voltage regulating device, and the reduction speed is controlled to be in the range of 8V/min-11V/min. V2 is in the range of 16.7V to 16.9V. Generally, the voltage drop time is in the range of 30s to 45s, and the drop time is not too long or too short. Preferably, the fall time is 30s to 35 s. If the time is too long, the generated porous layer becomes thick, the performance of the prepared oxide film is influenced, and the power is wasted; if the time is too short, the ignition phenomenon is likely to occur, and the metal substrate is burnt, so that the surface of the porous layer is uneven, and the uniformity of the formed oxide film layer is affected.
In one embodiment, the voltage is controlled to drop to 16.8V at a speed of 9V/min-10V/min for 30 s.
And step S5, in a low-voltage stage, maintaining the voltage V2, and performing secondary electrochemical oxidation on the metal matrix to generate a barrier layer with enhanced pores, so as to obtain an oxide film.
Specifically, the metal substrate is electrochemically oxidized by performing an anodic oxidation operation by applying a constant voltage, and the barrier layer having the enhanced pores is oxidized between the metal substrate and the porous layer.
The voltage due to the second electrochemical oxidation determines the toughness, corrosion resistance, high temperature resistance and wear resistance of the barrier layer on the metal substrate, which in turn is determined by the diameter of the resulting enhanced pores. The second time electrochemical oxidation voltage ranges from 16.7V to 16.9V. The reaction time is controlled to be 10 min-14 min.
The barrier layer and the porous layer are both oxide layers of a metal matrix, namely the reinforced holes are generated under the combined action of a film forming reaction and a dissolving reaction, and the reinforced holes are formed at the bottoms of the adsorption holes during electrochemical oxidation. The difference is that the two reaction speeds are different due to the lower voltage of the generated barrier layer, so that the aperture of the reinforced hole in the barrier layer is smaller, the ratio of the aperture of the reinforced hole to the aperture of the adsorption hole is 1: 10-1: 2, and the aperture of the reinforced hole is 5 nm-25 nm. The ratio of the thickness of the porous layer to the thickness of the barrier layer is in the range of 5:2 to 25:1, preferably, the ratio of the thickness of the porous layer to the thickness of the barrier layer is in the range of 17:5 to 23:3, and the thickness of the barrier layer is in the range of 1 μm to 20 μm. Preferably, the thickness of the barrier layer is in the range of 1.5 μm to 2.5 μm. The blocking layer has higher density relative to the porous layer, higher hardness, higher toughness, corrosion resistance and wear resistance, and can ensure that the oxidation film layer covers the metal base material. And because the aperture of the reinforced hole is small, the thickness of the barrier layer is small, the adsorption capacity of the barrier layer is weak, and functional substances such as dye molecules, magnetic particles and the like are not easy to attach to the reinforced hole.
In one embodiment, the metal matrix is subjected to a second electrochemical oxidation at 25-29 ℃ with a voltage of 16.8V for 12min to produce a 2 μm thick barrier layer, and the diameter of the enhanced pores is in the range of 5-10 nm.
In one embodiment, after the step of performing the secondary electrochemical oxidation on the metal substrate, the method further includes a step of performing post-treatment on the obtained oxide film to remove the electrolyte:
cleaning, namely cleaning the obtained oxide film with water; and
and air-drying, and removing the water on the surface of the cleaned oxide film.
Specifically, cleaning with distilled water, reacting at normal temperature for 30-60 s, and repeating twice; and then, putting the mixture into an oven, and drying the mixture at the temperature of 70-80 ℃ for 5-10 min.
The thickness of the porous layer and the barrier layer in the oxide film, the pore diameter of the adsorption pores and the pore diameter of the reinforced pores can be adjusted by controlling the voltage, the operation temperature and the operation time according to the actual requirements, such as whether dyeing is carried out or not, the hardness requirement and the like.
Referring to fig. 4, 6 to 9, the embodiment of the invention further provides an oxide film manufactured by the above method.
The oxide film 1 includes: a metal base 2; the barrier layer 3 covers the surface of the metal matrix 2 and is provided with an enhanced hole 31; and a porous layer 4 provided on the barrier layer 3 and having adsorption holes 41 corresponding to the reinforcement holes 31.
Compared with the prior art, the oxide film 1 of this application, through the barrier layer 3 that forms on metal matrix 2 and have higher toughness, make oxide film 1 in positions such as corner, can not be because of the superficial area sharply enlarges the fracture, guaranteed oxide film 1's is complete, improved oxide film 1's shock resistance, and barrier layer 3's corrosion resistance and wearability etc. all more porose layer 4 have obvious improvement, make oxide film 1 have corrosion-resistant, wear-resisting, high temperature resistant, high hardness, the advantage to the tolerance of extreme chemical environment. The porous layer 4 with the adsorption holes 41 on the surface ensures the adsorption effect of the oxide film 1, so that the oxide film 1 has colorful advantages.
Embodiments of the invention also provide methods of making metal articles. The method comprises the following steps:
preparing an oxide film;
applying a substance containing a body of material onto a surface of the oxide film;
shaping the mass comprising the body of material to form a metal article.
The oxide film prepared in the above step is an oxide film obtained by the above method for manufacturing an oxide film.
And applying a substance containing a material body onto the surface of the oxide film. Wherein, the material of the material body can be selected from at least one of functional substances such as dye molecules, magnetic particles and the like.
In the step, the step of shaping the material containing the material body to form the metal product is to seal the material body in the hole of the oxide film by adopting a hole sealing technology, and meanwhile, the corrosion resistance, the wear resistance and other properties of the oxide film can be improved by adopting the hole sealing technology.
The above-mentioned hole sealing technique can be set according to the material and the state of the material body.
For example, sealing with boiling water, sealing with high-temperature steam, sealing with cold, electrophoretic coating with organic substances, and sealing with inorganic salts at medium temperature.
In one embodiment, a metal product having a surface with a specific color can be formed by applying a substance containing dye molecules to the surface of the oxide film to adsorb the dye molecules in the adsorption pores and sealing the oxide film.
Embodiments of the invention also provide metal articles made by the above-described methods.
In one embodiment, a metal article is made by the steps of:
pretreating the aluminum alloy:
degreasing, adopting a water-based cleaning agent, reacting for 4min at the temperature of 55 ℃, then cleaning for 30s with distilled water, and repeating twice;
alkali biting, namely putting the mixture into 30g/L NaOH solution, reacting for 20s at 50 ℃ by using NaOH as an alkali biting agent, then washing for 30s by using distilled water, and repeating twice; and
acid washing, placing into phosphoric acid solution with specific gravity of 1.70, reacting at 78 deg.C for 45s with phosphoric acid as acid washing agent, and washing with distilled water for 30s, and repeating twice.
Step S1, the aluminum alloy is placed in the electrolyte solution.
The electrolyte solution contains 20g/L of sulfuric acid and 40g/L of oxalic acid.
Taking aluminum alloy as an anode for electrolysis; graphite is placed in the electrolyte as the cathode for electrolysis.
Step S2, step up, gradually increase the voltage to 21.5V.
The voltage is controlled to rise at 21V/min-22V/min by the voltage regulating device, so that the voltage rises to 21.5V in 1 min.
And step S3, in a high-voltage stage, maintaining the voltage at 21.5V, the temperature at 27 ℃, controlling the reaction time at 34-36 min, carrying out first electrochemical oxidation on the aluminum alloy, oxidizing the surface of the aluminum alloy to generate a porous layer with the thickness of 10 microns, wherein the pore diameter range of the adsorption pores is 20-40 nm.
And step S4, a voltage reduction stage, wherein the voltage is slowly reduced to 16.8V.
The voltage drop speed is controlled to be 9V/min-10V/min by the voltage regulating device. The voltage was dropped to 16.8V at 30 s.
And step S5, in a low-voltage stage, maintaining the voltage at 16.8V, the temperature at 27 ℃, controlling the reaction time at 11-13 min, performing secondary electrochemical oxidation on the aluminum alloy to generate a barrier layer with the thickness of 2 microns on the aluminum alloy, wherein the aperture range of the reinforced holes on the barrier layer is 5-10 nm, and obtaining the oxide film.
Carrying out post-treatment on the obtained oxide film:
cleaning, adopting distilled water, reacting for 30-60 s at normal temperature, and repeating twice; and
and (4) air-drying, putting into an oven, and drying at 70-80 ℃ for 5-10 min.
Dyeing, applying a substance containing an organic dye onto a surface of the oxide film;
and (4) sealing holes, namely filling and sealing holes on the oxide film by using a chromate sealing agent to obtain the metal product.
The aluminium alloy articles produced in the above examples were tested against aluminium alloy articles produced according to the prior art with the following results:
and (3) sealing test: and (3) clicking a dot with the diameter of about 5mm on the metal product test surface by using a black oil pen, wiping the dot by using cleaning cotton dipped with water for 5-10 s, and comparing the form of the test point with a standard grade to judge whether the residual ink trace on the test surface meets the specification or not.
The aluminum alloy products prepared in the above examples and the aluminum alloy products prepared in the prior art both have qualified test results. And (4) indicating that holes on the surface of the aluminum alloy product are sealed and qualified after hole sealing treatment.
And (3) salt spray testing: cleaning the surface of a metal product, placing the metal product in a test box with the temperature of 35 ℃, the salinity of 5%, the pH value of 6.5-7.2 and the spray amount of 1.0-2.0 ml/h/80cm2, placing at an angle of 75-90 degrees, placing for 24 hours, taking out the metal product, wiping with dust-free cloth dipped with water, wiping with the dust-free cloth dipped with alcohol solution if chemical reagent residues are shown, and observing the surface of the metal product to judge whether corrosion, shedding and heterochrosis exist.
The surfaces of the aluminum alloy products prepared in the above embodiments have no obvious color difference; and the oxidation film is kept complete; in the aluminum alloy product prepared by the prior art, the oxide film is corroded at the corner. It is shown that the aluminium alloy product of the present application has better corrosion resistance.
And (3) wear resistance test: cleaning the surface of a metal product, fixing the metal product on a jig, sticking a 0 x 10mm gasket (Shore hardness is 60+/-10) on the jig by using a 10 x 10mm friction head, fixing white cotton cloth on the gasket, carrying out friction at a speed of 25 circles/minute for 20 minutes, taking out the metal product, dipping water on the metal product by using dust-free cloth for wiping, and observing the surface of the metal product to judge whether corrosion, falling off and abnormal colors exist.
The surfaces of the aluminum alloy products prepared in the above embodiments have no obvious color difference; and the oxidation film is kept complete; however, the aluminum alloy product prepared by the prior art has the phenomenon that the surface has different colors and the oxidation film is worn at one corner. It is shown that the wear resistance of the aluminium alloy product of the present application is better.
And (3) high temperature resistance test: cleaning the surface of a metal product, putting the metal product into a humiture cabinet, storing for 6 hours at the temperature of 75 ℃ and the humidity of 20%, taking out the metal product, wiping the metal product by using dust-free cloth dipped with water, observing the surface of the metal product, and judging whether the metal product is corroded, falls off and has different colors.
The surfaces of the aluminum alloy products prepared in the above embodiments have no obvious color difference; and the oxidation film is kept complete; in the aluminum alloy product prepared by the prior art, an oxidation film cracks on the surface of one corner. It is shown that the aluminium alloy products of the present application are better resistant to high temperatures.
Impact resistance test: cleaning the surface of the metal product, placing the metal product in a roller, running for 23 minutes, taking out the metal product, wiping the metal product by using dust-free cloth dipped with water, observing the surface of the metal product, and judging whether the metal product has shedding and abnormal colors.
The surfaces of the aluminum alloy products prepared in the above embodiments have no obvious color difference; and the oxidation film is kept complete; in the aluminum alloy product prepared by the prior art, the demolding phenomenon of an oxide film occurs on the surface of a corner. It is shown that the aluminium alloy articles of the present application have better impact resistance.
And (3) chemical testing: cleaning the surfaces of metal products, taking a certain chemical through a cotton swab, respectively coating sun cream, detergent, artificial sweat, sebum and oleic acid on the surfaces of a plurality of metal products, uniformly coating for 4 times, rotating the cotton swab for 90 degrees every time, standing for 2 minutes, then putting into a temperature and humidity cabinet, storing for 72 hours at the temperature of 65 ℃ and the humidity of 90 percent, taking out the metal products, firstly wiping by dust-free cloth dipped with alcohol solution, then wiping by the dust-free cloth dipped with water, then observing the surfaces of the metal products, and judging whether corrosion, falling and heterochromatic colors exist.
The surfaces of the aluminum alloy products prepared in the above embodiments have no obvious color difference; and the oxidation films are kept complete; the aluminum alloy product prepared by the prior art has no obvious heterochrosis on the surface which is not at the corner, the oxidation film is kept complete, the oxidation film of the aluminum alloy product coated with the sunscreen cream is kept complete, the oxidation film of the aluminum alloy product coated with the detergent is kept complete, but has heterochrosis, the oxidation film of the aluminum alloy product coated with artificial sweat, sebum and oleic acid has heterochrosis and is corroded, 3, 2 and 2 corrosion points respectively appear, and the situation that the oxidation film falls off appears under the condition of coating the artificial sweat and the sebum. It is shown that the aluminum alloy product of the present application has good resistance to extreme chemical environments.
Compared with the prior art, the metal product of this application, through the barrier layer 3 that forms on metal substrate 2 and have higher toughness for oxidation film 1 can not be because of the surperficial rapid expansion fracture in positions such as corner, guaranteed oxidation film 1's completeness, improved metal product's shock resistance, and barrier layer 3's corrosion resistance and wearability all more porose layer 4 have obvious improvement, make metal product have corrosion-resistant, wear-resisting, high temperature resistant, to the advantage of extreme chemical environment's tolerance.
In addition, other modifications within the spirit of the invention may occur to those skilled in the art, and such modifications are, of course, included within the scope of the invention as claimed.
Claims (10)
1. A method for forming an oxide film, comprising:
a boosting stage: placing the metal matrix in an electrolyte solution, and slowly increasing the voltage to V1, wherein the voltage increasing speed is in the range of 15-25V/min;
and (3) high voltage stage: maintaining a voltage V1, performing a first electrochemical oxidation on the metal substrate, and oxidizing the surface of the metal substrate to generate a porous layer with adsorption pores;
a pressure reduction stage: slowly reducing the voltage to V2, wherein the voltage reduction speed is in the range of 8V/min to 11V/min;
and (3) low-voltage stage: maintaining the voltage V2, and carrying out secondary electrochemical oxidation on the metal matrix to generate a barrier layer with enhanced pores, namely obtaining the oxide film;
wherein the reinforcing hole is formed at the bottom of the adsorption hole.
2. The method for forming an oxide film according to claim 1, wherein,
the ratio of the aperture of the reinforcing hole to the aperture of the adsorption hole is in the range of 1:10 to 1: 2.
3. The method for forming an oxide film according to claim 1, wherein,
the voltage range of the first time electrochemical oxidation time is 21V-22V; the voltage of the second electrochemical oxidation time ranges from 16.7V to 16.9V.
4. The method for forming an oxide film according to claim 1, wherein,
the range of the first time electrochemical oxidation time is 28 min-42 min; the second time of electrochemical oxidation is within the range of 10 min-14 min.
5. The method for forming an oxide film according to claim 1, wherein,
the electrolyte solution comprises sulfuric acid and oxalic acid; the concentration range of the sulfuric acid is 18 g/L-22 g/L; the concentration range of the oxalic acid is 36 g/L-44 g/L.
6. The method for forming an oxide film according to claim 1, wherein,
the material of the metal matrix is at least one selected from magnesium, magnesium alloy, aluminum alloy, titanium alloy, stainless steel, carbon steel and iron.
7. An oxide film comprising:
a metal substrate;
the barrier layer covers the surface of the metal matrix and is provided with a reinforced hole; and
and the porous layer is arranged on the barrier layer and is provided with adsorption holes corresponding to the enhancement holes.
8. The oxide film according to claim 7,
the ratio of the aperture of the reinforcing hole to the aperture of the adsorption hole is in the range of 1:4 to 1: 2.
9. The oxide film according to claim 7,
the material of the metal matrix is at least one selected from magnesium, magnesium alloy, aluminum alloy, titanium alloy, stainless steel, carbon steel and iron.
10. A metal article comprising:
an oxide film; and
the material layer is formed on the oxide film; wherein the content of the first and second substances,
the oxide film is the oxide film according to any one of claims 7 to 9;
the material layer is adsorbed in the adsorption holes and the enhancement holes.
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| CN201911257491.7A CN111020663B (en) | 2019-12-10 | 2019-12-10 | Method for producing aluminum alloy oxide film, and aluminum alloy product |
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| CN201911257491.7A CN111020663B (en) | 2019-12-10 | 2019-12-10 | Method for producing aluminum alloy oxide film, and aluminum alloy product |
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| CN111020663A true CN111020663A (en) | 2020-04-17 |
| CN111020663B CN111020663B (en) | 2021-05-28 |
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