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CN113818070A - Aluminum alloy surface treatment method - Google Patents

Aluminum alloy surface treatment method Download PDF

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Publication number
CN113818070A
CN113818070A CN202111035203.0A CN202111035203A CN113818070A CN 113818070 A CN113818070 A CN 113818070A CN 202111035203 A CN202111035203 A CN 202111035203A CN 113818070 A CN113818070 A CN 113818070A
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aluminum alloy
cathode
degreasing
anode
treatment
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CN113818070B (en
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白林森
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Chongqing Haste Aluminum Strip Co ltd
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00Electrolytic cleaning, degreasing, pickling or descaling
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F7/00Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The invention provides an aluminum alloy surface treatment method, which can effectively reduce hydrogen embrittlement caused by cathodic electrolysis degreasing through cathodic electrolysis degreasing under proper conditions and anodic oxidation degreasing under high current density, thereby effectively maintaining the physical properties of aluminum alloy, such as compressive strength and elongation at break, while ensuring degreasing efficiency.

Description

Aluminum alloy surface treatment method
Technical Field
The invention belongs to the technical field of aluminum alloy, and particularly relates to an electrochemical low-hydrogen brittle surface oil removal treatment method.
Background
The aluminum alloy has a series of advantages of small density, high strength, good plasticity, corrosion resistance, easy forming, low cost and the like, is widely applied to the industries of transportation, construction, packaging, household appliances and electronics, has obvious influence on the service performance and service life of the aluminum alloy like numerous metals, and can cause damage to the surface and the interior of a material due to various influence factors such as load, temperature, corrosive medium and the like, and simultaneously reduces the corrosion resistance, fatigue resistance and creep damage resistance of the material, thereby reducing the service life of the alloy. Hydrogen is incorporated into the material during fabrication and processing, and hydrogen atoms generally diffuse into the material, thereby reducing the strength and elongation of the material, a phenomenon known as hydrogen embrittlement. When the metal material is prepared and processed in a high-pressure hydrogen environment, the occurrence of hydrogen embrittlement cannot be avoided, and some traditional methods for inhibiting hydrogen embrittlement have relatively high cost, complex process and the like.
Electrochemical degreasing is to put the workpiece to be degreased in a solution with a certain process formula, put on a power supply, use the workpiece as a cathode or an anode (usually, the cathode is first and then the anode is turned), and remove the greasy dirt on the surface of the workpiece through electrolytic treatment. When the process is used for oil removal, the action of hydrogen bubbles and oxygen bubbles separated out from the electrodes can be utilized to promote the strong tearing of an oil film on the surface of a workpiece to change the oil film into discontinuous oil drops, and meanwhile, the solution is stirred, so that the speed of separating oil stains from the surface of the workpiece is accelerated, and the oil removal process is further enhanced, therefore, the electrochemical oil removal has a more thorough and quicker oil removal effect than the chemical oil removal, and the electrochemical oil removal practice usually comprises cathode oil removal and anode oil removal.
In fact, electrochemical degreasing of a single cathode is superior to electrochemical degreasing of an anode. The electrochemical degreasing of the cathode has the characteristics of not corroding a matrix, effectively activating a passive film on the surface of a workpiece and having a good effect on purifying the surface of the workpiece. The electrochemical degreasing of the cathode has the defects that workpieces are easy to seep, hydrogen embrittlement is caused, and even a plating layer foams and peels off.
Electrochemical degreasing with a single anode also has advantages and disadvantages. When the anode is electrochemically degreased, organic matters on the surface of the workpiece matrix can be oxidized and decomposed, residues on the surface of the matrix are removed, and hydrogen embrittlement is avoided. The electrochemical degreasing of the anode has the defects that the degreasing effect is poorer than that of the electrochemical degreasing of the cathode, nonferrous metals are not suitable for adopting the process method, and otherwise, serious corrosion can be generated. The corrosion to steel parts can also occur when the concentration of alkali in the solution is too dilute or when chloride ions exist. Electrochemical degreasing by a single anode is also not suitable.
However, since the disadvantage caused by electrochemical degreasing of the anode cannot be eliminated during electrochemical degreasing of the cathode, this procedure is not desirable, and thus the prior art usually employs combined degreasing of the cathode and the anode, i.e. cathodic electrochemical degreasing is performed in one tank first, and then anodic electrochemical degreasing is performed in another tank.
Disclosure of Invention
Based on the above-mentioned findings, although the existing electrochemical degreasing treatment of aluminum alloy surface grease has a remarkable degreasing effect, hydrogen is introduced in the cathode degreasing process to cause a hard-brittle phenomenon, and the strength and tensile rate of the metal substrate are remarkably reduced.
The aluminum alloy surface treatment method is characterized by comprising the following steps:
(1) carrying out surface mechanical treatment on the base material;
(2) carrying out combined oil removal on the cathode and the anode;
(3) washing with water;
(4) vacuum drying;
wherein the cathode-anode joint degreasing process:
(a) the aluminum alloy subjected to surface mechanical treatment is taken as a cathode, an inert metal material is taken as an anode, the electrolysis temperature is 3-7 ℃, and the current density is 2-5A/dm2The electrolyte is composed of Na2CO3 10g/L-15g/L、Na3PO420-25g/L, 0.2-0.3g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water for 3-7 min;
(b) switching the current direction, taking the aluminum alloy subjected to cathode degreasing as an anode, taking an inert metal material as a cathode, and controlling the electrolysis temperature to be 3-7oC; the electrolyte is composed of Na2CO3 10g/L-15g/L、Na3PO420-25g/L, 0.2-0.3g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water;
the current density is 15-20A/dm2The duration is 5-10 ms; the turn-off time is 30-50ms, the turn-off process is continued circularly, and the total time length is not more than 2 min.
Further, the mechanical treatment is sand blasting, the air pressure is 0.05-0.1 Mpa, and the size of the sand blasting is 0.5-0.1 mm.
Further, the electrolyte and the electrolysis temperature used in the steps (a) to (b) are completely consistent.
Further, the hydrogen content growth rate in the aluminum alloy is 4-9%.
Further, the aluminum alloy is a five-series, six-series or seven-series aluminum alloy.
Further, after the aluminum alloy is subjected to vacuum drying treatment, micro-arc oxidation treatment is carried out.
Further, the washing is deionized water, and the washing temperature is 80-90 DEGoAnd C, washing.
Further, the temperature of the aluminum alloy after vacuum drying is 200-220-oC, the vacuum degree is 0.05-0.07 MPa.
In connection with the present invention, blasting is the first, and the main purpose thereof is to reduce the roughness of the surface of a substrate, obtain a flat, smooth surface, remove surface burrs, scratches and other defects, and blasting is a finishing method of blasting an abrasive material onto the surface of a workpiece with compressed air, and removing scale, corrosion and other defects on the surface of the workpiece by utilizing the kinetic energy of a high-speed abrasive material to form a uniform matte surface, and this method is a method of forming a uniform matte surface
The dry sand blasting method has the characteristics of high speed and low cost, dry blasting is adopted, the abrasive for the dry blasting comprises steel grit, alumina, quartz sand, silicon carbide and the like, the quartz sand is used, the blasting effect is related to factors such as the blasting distance, the blasting angle, the pressure, the size and the shape of a nozzle, the size of the abrasive and the like, the abrasive has fine granularity, and a soft, dull and smooth surface can be generated; the air pressure adopted by the invention is 0.05-0.1 Mpa, and the sand blasting size is 0.5-0.1 mm.
Electrochemical oil removal and degreasing: the method is suitable for degreasing workpieces with higher requirements, in the degreasing process, metal is soaked in specific electrolyte, and is electrified with direct current for electrolytic treatment, so as to achieve the purpose of degreasing, the workpiece to be treated can be a cathode or an anode, and the workpiece to be treated respectively corresponds to cathode electrolytic degreasing and anode electrolytic degreasing, compared with chemical degreasing, the electrolytic degreasing efficiency is much higher, and in addition, the method is also suitable for degreasing workpieces with higher requirements, the workpiece to be treated can be a cathode or an anode, and the electrolytic degreasing is greatly higher
Degreasing is thorough.
The cathode deoiling is characterized in that hydrogen is separated out from a workpiece, the hydrogen separation amount is large during deoiling, the dispersibility is good, the bubble size is small, the emulsification effect is strong, the deoiling effect is good, the speed is high, parts are not corroded, and the separated hydrogen can permeate into metal to cause hydrogen embrittlement.
The anode degreasing is characterized in that oxygen is separated out from a workpiece, and during degreasing, on one hand, the oxygen separation bubbles are few and large, and compared with the cathode electrochemical degreasing, the emulsification capacity is poor, so that the degreasing efficiency is low, and the subsequent electroplating quality is seriously influenced.
In addition, some books believe that the aluminum alloy does not have hydrogen embrittlement phenomenon, so cathodic electrolytic degreasing can be optionally used, and the aluminum alloy is not suitable for anodic electrolytic degreasing due to the problem of anodic oxidation or micro-arc oxidation, namely for the aluminum alloy, the aluminum alloy is suitable for cathodic electrolytic degreasing, but the aluminum alloy does not have the problem of obvious hydrogen embrittlement in the cathodic electrolytic degreasing process, hydrogen evolution reaction can also occur in the cathodic electrolytic degreasing process, H can obviously enter metal, H on the surface layer of the metal is obviously enriched, and the hydrogen embrittlement phenomenon is caused.
In order to reduce the enrichment and diffusion of H, the current direction is changed in time (the cost performance is higher when the tank is not recommended to be changed and only the current direction is changed under the same electrolytic degreasing solution), the aluminum alloy is subjected to anodic electrolytic degreasing by using large current, and the surface H near the electrode is subjected to anodic electrolytic degreasing under the current condition+The metal surface is separated, hydroxyl is further enriched on the surface, the hydroxyl enriched on the surface can be effectively removed under strong current, the H content of the surface layer is reduced, however, the aluminum alloy is valve metal, and the anodic dissolution reaction is very easy to occur, so the reaction time is controlled certainly, and under the large current, the obvious oxidation reaction can occur to form an oxide film, so the turn-off time is set in the anodic electrolytic oil removal process, and the occurrence of anodic oxidation is reduced as much as possible.
In order to avoid the occurrence of anodic oxidation, the alkaline degreasing fluid is used, and the acidic degreasing fluid is forbidden.
The electrochemical degreasing fluid mainly comprises sodium carbonate and sodium phosphate instead of a sodium hydroxide strong electrolyte, the invention is used for avoiding the strong corrosivity of the sodium hydroxide to aluminum materials, on the other hand, the sodium carbonate and the sodium hydroxide are used as electrolyte under the strong current density, and the electric conduction efficiency is not obviously lost, so that the sodium carbonate and sodium phosphate strong base weak acid salt is used as the electrolyte, and simultaneously, the sodium silicate is avoided, the viscosity is too high, the gas release and the separation are not facilitated, and in order to accelerate the separation of bubbles, a small amount of fatty alcohol ethylene oxide propylene oxide copolyether surfactant is added in the electrolysis to improve the surface tension.
In addition, as for the temperature, in theory, the electrolytic degreasing is carried out at a high temperature in the actual electrolytic process, and the higher the temperature is, the better the saponification and emulsification, and the degreasing rate are, but the hydrogen diffusion and enrichment speed is also increased, and the solubility and diffusion rate of hydrogen in metal are increased along with the increase of the temperature. Therefore, the invention is more suitable for using lower temperature and can effectively inhibit the hydrogen embrittlement phenomenon.
The water washing is high-temperature washing, mainly because products obtained after alkaline liquor stabbing, saponifying or emulsifying are left on the surface of the workpiece after electrochemical oil removal, and the substances can be condensed on the surface of the workpiece after meeting cold water and are quickly hardened, so that the subsequent treatment of the aluminum alloy is prevented.
And finally, vacuum drying: the temperature of the aluminum alloy after vacuum drying is 200-220-oAnd C, the vacuum degree is 0.05-0.07MPa, and the vacuum drying can reduce the hydrogen content and the hydrogen embrittlement risk while removing the internal stress of the aluminum material.
The beneficial technical effects are as follows:
according to the invention, through cathodic electrolysis hydrogen evolution oil removal treatment under appropriate conditions and anodic oxygen evolution oil removal treatment under high current density, the hydrogen embrittlement phenomenon caused by cathodic electrolysis oil removal can be effectively reduced, so that the oil removal efficiency is ensured, and the physical properties of the aluminum alloy, such as compressive strength and elongation at break, are effectively maintained.
The specific implementation mode is as follows:
example 1
An aluminum alloy surface treatment method comprises the following steps:
(1) carrying out surface mechanical treatment on a base material: the mechanical treatment is sand blasting, the air pressure is 0.05Mpa, and the size of the sand blasting is 0.5 mm.
(2) And (3) carrying out cathode-anode combined oil removal:
(a) the aluminum alloy subjected to surface mechanical treatment is taken as a cathode, an inert metal material is taken as an anode, the electrolysis temperature is 3 ℃, and the current density is 2A/dm2The electrolyte is composed of Na2CO3 10g/L、Na3PO420g/L, 0.2g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water, wherein the time is 3 min;
(b) switching the current direction, taking the aluminum alloy subjected to cathode degreasing as an anode, taking the inert metal material as a cathode, and controlling the electrolysis temperature to be 3oC; the electrolyte is composed of Na2CO3 10g/L、Na3PO420g/L, 0.2g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water;
the current density is 15A/dm2The duration is 5 ms; the turn-off time is 30ms, the turn-off process is cycled continuously, and the total time length is not more than 2 min.
(3) Washing with water: the washing is deionized water, and the washing temperature is 80 DEGoAnd C, washing. .
(4) And (3) vacuum drying: at a temperature of 200 deg.CoC, the vacuum degree is 0.05 MPa.
Example 2
An aluminum alloy surface treatment method comprises the following steps:
(1) carrying out surface mechanical treatment on a base material: the mechanical treatment was sand blasting with an air pressure of 0.075Mpa and a sand blasting size of 0.75 mm.
(2) And (3) carrying out cathode-anode combined oil removal:
(a) the aluminum alloy subjected to surface mechanical treatment is taken as a cathode, an inert metal material is taken as an anode, the electrolysis temperature is 3-7 ℃, and the current density is 3.5A/dm2The electrolyte is composed of Na2CO3 12.5g/L、Na3PO422.5g/L, 0.25g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water, and the time is 5 min;
(b) switching the current direction, taking the aluminum alloy subjected to cathode degreasing as an anode, taking an inert metal material as a cathode, and controlling the electrolysis temperature to be 3-7oC; the electrolyte consists of Na2CO3 12.5g/L、Na3PO422.5g/L, 0.25g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water;
the current density is 17.5A/dm2The duration is 7 ms; the turn-off time is 40ms, the turn-off process is cycled continuously, and the total time length is not more than 2 min.
(3) Washing with water: the water washing is deionized water, and the water washing temperature is 85 DEGoAnd C, washing.
(4) And (3) vacuum drying: at a temperature of 210oC, the vacuum degree is 0.06 MPa.
Example 3
An aluminum alloy surface treatment method comprises the following steps:
(1) carrying out surface mechanical treatment on a base material: the mechanical treatment is sand blasting, the air pressure is 0.1 Mpa, and the size of the sand blasting is 0.1 mm.
(2) And (3) carrying out cathode-anode combined oil removal:
(a) the aluminum alloy subjected to surface mechanical treatment is taken as a cathode, an inert metal material is taken as an anode, the electrolysis temperature is 3-7 ℃, and the current density is 5A/dm2The electrolyte is composed of Na2CO3 15g/L、Na3PO425g/L, 0.3g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water, wherein the time is 7 min;
(b) switching the current direction, taking the aluminum alloy subjected to cathode degreasing as an anode, taking the inert metal material as a cathode, and controlling the electrolysis temperature to be 7oC; the electrolyte is composed of Na2CO3 15g/L、Na3PO45g/L, 0.3g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water;
the current density is 20A/dm2The duration is 10 ms; the turn-off time is 50ms, the continuous turn-off process is circulated, and the total time length is not more than 2 min.
(3) Washing with water: the washing is deionized water, and the washing temperature is 90 DEGoAnd C, washing.
(4) And (3) vacuum drying: at a temperature of 220 deg.CoC, the vacuum degree is 0.07 MPa.
Comparative example 1
An aluminum alloy surface treatment method comprises the following steps:
(1) carrying out surface mechanical treatment on a base material: the mechanical treatment was sand blasting with an air pressure of 0.075Mpa and a sand blasting size of 0.75 mm.
(2) And (3) carrying out cathode-anode combined oil removal:
(a) the aluminum alloy subjected to surface mechanical treatment is taken as a cathode, an inert metal material is taken as an anode, the electrolysis temperature is 3-7 ℃, and the current density is 3.5A/dm2The electrolyte is composed of Na2CO3 12.5g/L、Na3PO422.5g/L, 0.25g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water, and the time is 5 min;
(b) switching the current direction, taking the aluminum alloy subjected to cathode degreasing as an anode, taking an inert metal material as a cathode, and controlling the electrolysis temperature to be 3-7oC; the electrolyte consists of Na2CO3 12.5g/L、Na3PO422.5g/L, 0.25g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water; the current density is 2.5A/dm2For 2 min.
(3) Washing with water: the water washing is deionized water, and the water washing temperature is 85 DEGoAnd C, washing.
(4) And (3) vacuum drying: at a temperature of 210oC, the vacuum degree is 0.06 MPa.
It should be noted here that all the data in the table below are at 30 to highlight the importance of the combined de-oiling in order to reduce the effect of vacuum drying on hydrogen embrittlementoAnd C, drying.
Figure DEST_PATH_IMAGE001
A: after single-cathode oil removal treatment.
B: after the cathode-anode combined oil removal treatment.
As shown in the table above, hydrogen can be obviously introduced into the cathode aluminum alloy through cathode electrolytic degreasing treatment, and the hydrogen content can be obviously reduced through high-current anode degreasing treatment, so that the hydrogen content in the aluminum alloy after electrochemical degreasing treatment is not obviously changed and is only increased by 4-9%, meanwhile, the tensile strength and the elongation at break of the aluminum alloy are effectively maintained, and the hydrogen embrittlement phenomenon is effectively reduced.
Figure 2377DEST_PATH_IMAGE002
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (8)

1. The aluminum alloy surface treatment method is characterized by comprising the following steps:
(1) carrying out surface mechanical treatment on the base material;
(2) carrying out combined oil removal on the cathode and the anode;
(3) washing with water;
(4) vacuum drying;
wherein the cathode-anode joint degreasing process:
(a) the aluminum alloy subjected to surface mechanical treatment is taken as a cathode, an inert metal material is taken as an anode, the electrolysis temperature is 3-7 ℃, and the current density is 2-5A/dm2The electrolyte is composed of Na2CO3 10g/L-15g/L、Na3PO420-25g/L, 0.2-0.3g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water for 3-7 min;
(b) switching the current direction, taking the aluminum alloy subjected to cathode degreasing as an anode, taking an inert metal material as a cathode, and controlling the electrolysis temperature to be 3-7oC; the electrolyte is composed of Na2CO3 10g/L-15g/L、Na3PO420-25g/L, 0.2-0.3g/L fatty alcohol ethylene oxide propylene oxide copolyether and deionized water;
the current density is 15-20A/dm2The duration is 5-10 ms; the turn-off time is 30-50ms, the turn-off process is continued circularly, and the total time length is not more than 2 min.
2. The surface treatment method of an aluminum alloy according to claim 1, wherein the mechanical treatment is sand blasting, the air pressure is 0.05 to 0.1 Mpa, and the size of the sand blasting is 0.5 to 0.1 mm.
3. The method for treating the surface of an aluminum alloy according to claim 1, wherein the electrolytic solution used in the steps (a) to (b) has a substantially uniform electrolytic temperature.
4. The surface treatment method of an aluminum alloy as recited in claim 1, wherein the increase rate of the hydrogen content in the aluminum alloy is 4 to 9%.
5. The method for surface treatment of aluminum alloy according to claim 1, wherein the aluminum alloy is a five-series, six-series or seven-series aluminum alloy.
6. The method for treating the surface of the aluminum alloy as recited in claim 1, wherein the aluminum alloy is subjected to a vacuum baking treatment and then to a micro-arc oxidation treatment.
7. The method of claim 1, wherein the washing is deionized water at a temperature of 80-90 deg.foAnd C, washing.
8. The method as claimed in claim 1, wherein the temperature of vacuum drying of the aluminum alloy is 200-220-oC, the vacuum degree is 0.05-0.07 MPa.
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