CN114214717A - Aluminum alloy processing solution and preparation method thereof - Google Patents
Aluminum alloy processing solution and preparation method thereof Download PDFInfo
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title description 6
- 238000005498 polishing Methods 0.000 claims abstract description 98
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 36
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 21
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 21
- 239000011976 maleic acid Substances 0.000 claims abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims abstract description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 46
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 14
- 239000012964 benzotriazole Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- 239000012224 working solution Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000005282 brightening Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 1
- 229960004279 formaldehyde Drugs 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 28
- 229910052751 metal Inorganic materials 0.000 abstract description 26
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- 150000002739 metals Chemical class 0.000 abstract description 2
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- SFUGSFCZHFPQBZ-UHFFFAOYSA-N 4-(3-phenylpropyl)-2h-triazole Chemical compound C=1C=CC=CC=1CCCC=1C=NNN=1 SFUGSFCZHFPQBZ-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007517 polishing process Methods 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
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- 238000007254 oxidation reaction Methods 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
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- 238000003487 electrochemical reaction Methods 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
- C25F3/18—Polishing of light metals
- C25F3/20—Polishing of light metals of aluminium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
Abstract
本发明提供了一种铝合金加工溶液，通过配置含有高氯酸，马来酸，乙二酸的，若丁，磺基水杨酸、丁撑二醇，三乙醇胺，苯丙三氮唑，乙醇和水的电解抛光液，能够有效的降低阳极溶解过程形成的粘膜电阻率，提高溶解金属的扩散率，铝合金的表面粗糙度低，镜面效果好。
The invention provides an aluminum alloy processing solution. By configuring the solution containing perchloric acid, maleic acid, oxalic acid, rhodin, sulfosalicylic acid, butylene glycol, triethanolamine, phenylpropyltriazole, The electrolytic polishing solution of ethanol and water can effectively reduce the resistivity of the mucosa formed by the anodic dissolution process, improve the diffusivity of dissolved metals, and the surface roughness of the aluminum alloy is low, and the mirror effect is good.
Description
Technical Field
The invention relates to an aluminum alloy processing solution and a preparation method thereof, in particular to preparation of an electrochemical polishing solution for aluminum alloy.
Background
Electrochemical Polishing (electrochemical Polishing) is a commonly used titanium surface treatment technology which is emerging and developed after mechanical Polishing and chemical Polishing and is gradually mature. The technology can not only obviously reduce the micro-roughness of the surface of the titanium and titanium alloy material and improve the surface brightness, but also has no cutting force, heat and burrs in the polishing process and does not generate a residual strain layer and a phase change layer.
The basic polishing principle of electrochemical polishing is that after an electrochemical polishing system is energized with a certain polishing voltage and current density, a viscous film with high resistivity is generated on the surface of an anode workpiece, and the film thickness at different positions on the surface of the workpiece is different: the film layer at the microcosmic upper convex part of the surface is thinner, the resistance is smaller, the current density is higher, and the dissolution rate of the anode workpiece is high; in contrast, the film distribution at the microscopic lower recesses of the surface is thicker and the resistance is higher, so that the dissolution rate of the anode workpiece is lower than that at the upper projections of the surface. Because the thickness of the adhesive film and the current density are not consistent, the dissolving speed of the microcosmic convex part on the surface of the workpiece is higher than that of the concave part, and the roughness and the brightness of the metal surface are reduced and the polishing is realized along with the prolonging of the working time
In the progress of this polishing work, the combined effect of many factors has an effect on the polishing effect. Synthesis of
The difference in material properties, electropolishing solution formulations, and process parameters of the metal workpiece may occur at the surface of the metal workpiece
The course of the one or more chemical reactions:
(1) the anode metal is dissolved Me = Me under the combined action of electrical parameters and polishing solution2++2e-；
(2) A passive film Me +2OH is generated on the surface of the anode metal-=MeO+H2O+2e-；
(3) Evolution of gaseous oxygen 4OH-=O2+2H2O+4e-；
(4) Oxidation of active ingredients of electrochemical polishing solution on surface of metal workpiece
Therefore, the surface quality of the metal workpiece after the electrochemical polishing process is determined by the coordination of the four reaction processes.
In general, a conventional anode theoretical current-potential curve can be seen in "second edition of aluminum alloy anodization and surface treatment technology" zhushu fragrant edition, page 51, and a general electrochemical polishing process is divided into an AB section, a BC section, a CD section, and a DE section.
In the AB section, the anode current density is rapidly increased along with the increase of the potential, at the moment, the metal surface of the anode is in an active dissolved state, metal cations are diffused into the polishing solution to form hydrated ions, and the hydrated ions basically accord with the Tafel rule, namely Me = Me2++2e-。
At this stage: the micro-convex part on the surface of the anode metal has concentrated current and higher current density, the micro-convex part is dissolved firstly, metal atoms on the surface of the anode workpiece lose electrons to generate metal cations, the speed of the metal cations diffusing into the polishing solution is slightly higher than the speed of dissolving the base material, and the viscous film is not completely generated. In the process, because the viscous film is not completely generated, the electrochemical polishing is only in the active dissolution stage of the surface of the anode metal substrate, and the polishing effect is not achieved.
The anode potential increases significantly in the BC segment, but the anode current density decreases inversely with the increase in the anode potential becauseIn the AB stage, a great amount of hydrated ions are generated and gathered near the surface of the anode, the diffusion speed of the hydrated ions into the electrochemical polishing solution is lower than the metal dissolution speed of the surface of the anode substrate, anode concentration polarization is formed, in addition, oxides are generated on the surface of the substrate, the resistance of the oxides is higher, and the other reason for reducing the current density in the stage is that Me +2OH mainly occurs-=MeO+H2O+2e-。
In the BC section, the anode substrate continues to be dissolved, but the current density is not high enough and unstable, the anodic oxygen evolution reaction is difficult, and the mucosa is still in the generation stage, and the polishing effect is not achieved.
In the CD section, the current density of the anode is basically stable, theoretically belongs to a good electrochemical polishing stage and belongs to a current density stable area. In the process, oxide on the surface of the anode is basically generated completely, the dissolution of the metal substrate, the generation and the destruction of an oxide film are in a dynamic balance state so as to maintain the relatively stable state of current density, the metal surface is microscopically and gradually flattened in the stage, the difference of micro-concave and micro-convex positions is not large, a certain metal luster is presented, but a small amount of oxygen bubbles are attached to the surface of the substrate due to the weak oxygen evolution phenomenon, and the bubbles can prevent the smooth progress of electrochemical polishing. Therefore, the anode surface often has defects such as small spots and the like, and the brightness is not high although the anode surface has certain metal luster.
In the DE stage, the voltage is continuously increased, the oxygen evolution potential is reached, and the anode current density is rapidly increased along with the increase of the anode potential, and is mainly used for oxygen evolution. At this time, a large amount of bubbles are generated on the surface of the anode workpiece, but oxygen adheres to the surface of the workpiece due to insufficient pressure, so that electrochemical polishing is prevented from proceeding smoothly, and therefore, the surface of the anode often has defects such as large spots.
It is obvious that when the voltage is used for polishing in the CDE section and oxygen is released in the DE section, the polishing effect can be improved, therefore, the prior art generally performs electrochemical polishing at a certain voltage behind the D point, but the following technical problems still exist: the electropolishing of the adhesive film has the disadvantages of excessive resistance, increased time of voltage-current density CD section, difficulty in gas release, high energy consumption and poor polishing effect.
Disclosure of Invention
Based on the technical problems existing in the electrolytic polishing process: the invention provides an electrochemical polishing solution for aluminum alloy processing, which can effectively improve the electrochemical polishing efficiency, almost has no anode current density stable section in the electrolytic polishing process, can effectively obtain the optimal electrochemical polishing voltage through curve fitting, and improves the diffusion speed of metal ions in the polishing process, thereby effectively obtaining an aluminum alloy material with low roughness and high mirror surface effect.
An aluminum alloy processing solution comprises a complex acid, a corrosion inhibitor, a brightening agent, a viscosity regulator and an additive, wherein the complex acid is a mixture of perchloric acid, maleic acid and oxalic acid, the corrosion inhibitor is Rundin, the brightening agent is sulfosalicylic acid, the viscosity regulator is tetramethylene glycol, the additive is triethanolamine and benzotriazole, a solvent is ethanol and water, and the volume ratio of the perchloric acid to the maleic acid to the oxalic acid is 1: 11: 4,135 ml/L
If so: 3g/L
The sulfosalicylic acid: 2 g/L
The tetramethylene glycol: 190ml/L
The triethanolamine: 1 g/L
The benzotriazole: 1 g/L
The ethanol: 570 ml/L
The balance being deionized water.
Further, an aluminum alloy workpiece is used as an anode to be connected with a positive electrode of a direct current power supply, stainless steel is used as a cathode to be connected with a negative electrode of the direct current power supply, the electrolysis temperature is 27 ℃, the voltage is less than 81V, and the current density is less than 1.9A.cm-2Electrode spacing of 17mm
Further, the solution has a fitted functional relationship between voltage and current density during the electropolishing as follows:
a = 0.0105V + 0.0082, said 0 < V < 46;
A = 0.09e0.0369Vand the V is more than 46 and less than 81.
Further, the electrochemical polishing DC voltage is preferably 46 + -0.3V, and the polishing time is preferably 120 s.
Further, the aluminum alloy workpiece is subjected to surface pretreatment in advance.
Further, the preparation method of the aluminum alloy processing solution is characterized by comprising the following steps:
(1) adding water to a reaction vessel, and adding oxalic acid, perchloric acid and maleic acid thereto in this order;
(2) sequentially adding part of ethanol, tolbutate, sulfosalicylic acid, triethanolamine and benzotriazole into the mixed solution in the step (1), and uniformly mixing by magnetic stirring;
(3) and (3) supplementing the balance of ethanol, adding butylene glycol, and magnetically stirring and uniformly mixing to obtain the aluminum alloy processing solution for electrolytic polishing.
Generally, the electrochemical polishing solution mainly comprises an oxidizing acid and a conditioning agent, wherein the oxidizing acid mainly participates in the dissolution of the anode workpiece and forms a soluble salt with the main element of the polished metal sample, so that an oxide film is generated on the surface of the polished sample. Secondly, the conditioning agent component is an indispensable composition of the electrochemical polishing solution, but it does not directly participate in the electrochemical reaction, and is used for conditioning the polishing effect, such as the brightener for conditioning the polishing brightness.
The oxidizing acid is a compound acid and is a mixture of perchloric acid, maleic acid and oxalic acid; the regulators are corrosion inhibitors, viscosity regulators, additives and solutions.
Perchloric acid is used as a strong oxidant, is a main component of electrolytic polishing, is easy to obtain a better polishing effect, and is a conventional component.
The maleic acid and the oxalic acid are mainly used for dissolving soluble salts generated in the electrochemical polishing process, both the maleic acid and the oxalic acid are acid-type acidic solutions, metal ions dissolved from an anode can be effectively complexed, the diffusion speed of the metal ions is improved, the viscosity of the solution is reduced, the mucosal resistance of the solution on the surface of the anode is further reduced, the polishing effect is effectively improved, and in addition, the carboxyl groups on the maleic acid and the oxalic acid have the effect of complexing and dissolving metals and also have the effect of a corrosion inhibitor.
Corrosion inhibitor: the D is a mixture mainly comprising di-o-toluenethiourea, starch, salt and peregal, and particularly, the main effective component of the D is di-o-toluenethiourea with the dosage of 26 percent; the starch is used as a brightening agent in an amount of 17wt.%, the salt is used in an amount of 52% for improving the conductive effect and improving the current efficiency, and the peregal is used in an amount of 5% for improving the release rate of oxygen gas in the polishing solution. If D is used as a commercial component, the proportion is stable, the purchase is easy, and the preparation difficulty of the electrochemical polishing solution is reduced.
Brightening agent: sulfosalicylic acid is mainly used for improving the brightness of workpieces and reducing the surface roughness value.
Viscosity modifier: the butyl-ethylene glycol contains a plurality of hydroxyl groups, the viscosity of the butyl-ethylene glycol is high, the viscosity adjusting effect can be achieved, the polishing quality is improved, in the electrochemical polishing process, the butyl-ethylene glycol can generate an adsorption effect at the anode to form an adsorption film attached to the surface of a workpiece, and the electrochemical polishing is assisted. Along with the continuous proceeding of the electrochemical reaction, the micro-convex part is continuously dissolved, and the microscopic surface of the test piece is gradually smooth and bright.
Ethanol: the contained hydroxyl-OH can adjust the pH value of the polishing solution, play a role in inhibiting corrosion and improve the polishing quality.
Triethanolamine and benzotriazole are used as auxiliary complexing agents and are mainly used for improving the complexing effect of maleic acid, oxalic acid and anodic oxidation dissolved metal and effectively improving the diffusion speed of metal ions in the polishing solution.
Electrochemical polishing parameters:
(1) temperature: in the polishing process, the temperature directly influences the viscosity of the electrochemical polishing solution, the solution with low temperature has larger viscosity and small solution dispersing capacity, and the dissolution of the anode workpiece is too slow; within a certain temperature range, the higher the polishing temperature is, the lower the solution consistency is, the higher the moving speed of reactants and products is, and the dissolution speed of the anode metal workpiece can be correspondingly accelerated, so that better electrochemistry can be obtained at the momentAnd (5) polishing effect. However, when the temperature of the electrochemical polishing solution is too high, the activity of perchlorate ions is greatly enhanced, and the phenomenon of over-corrosion and even burning of the metal to be polished can be generated, and the temperature adopted by the invention is 27 DEGoAnd C, effectively balancing the electropolishing effect while considering viscosity.
(2) Electrode spacing: the electrode spacing is too small, the energy consumption is small, but the electrode spacing is not favorable for the diffusion of ions in the solution, and the solution temperature in a polishing area is easy to rise suddenly, so that the electrochemical polishing effect is seriously influenced; when the distance is too large, the required voltage is increased, and the energy consumption is increased.
(3) As mentioned above, if the low voltage is too low, the metal will not generate electropolishing effect, but only the anodic oxidation of aluminum material will occur, if the voltage is too low, the gas will be released very fast during electropolishing, the current density will increase and cause the temperature rise of the surrounding solution, the strong oxidation of perchloric acid will be rapidly increased along with the temperature rise, and further the corrosion and even burning phenomenon will occur.
(4) The polishing time of the invention is 120s, if the polishing time is less than 120s, the viscous film is not completely removed, so that the polishing process can not be carried out; when the time exceeds 120s, the oxidation corrosion of the surface of the sample is intensified, and even pits appear, so that the surface quality is seriously influenced, and the polishing effect is reduced.
Through the effective ratio to each composition of above-mentioned electrolytic polishing liquid, to the regulation of electrolysis parameter, can have the effectual stationary phase who avoids the electrochemical polishing process that obtains, effectual reduction energy consumption, through the linear fitting to voltage and current density, divide into two stages of V1 and V2 with the applied voltage, at 0~ V1 stage, voltage and current density are linear relation, and the function is: a. the1= 0.0105V1 + 0.0082， 0＜V1< 46, in the latter part of the function, partial polishing but no gas evolution takes place, in the V1-V2 part oxygen evolution takes place, the function of which is A2 = 0.09e0.0369V2， 46＜V2< 81, as shown in FIG. 1, FIG. 2, and FIG. 3, the polishing effect is most suitable when the electrochemical polishing DC voltage is 46 + -0.3V, and the substrate is effectively polished without generating any electricity to the substrateBurning or uneven polishing phenomena.
The beneficial technical effects are as follows:
(1) according to the invention, by preparing the electrolytic polishing solution containing perchloric acid, maleic acid and oxalic acid, such as n-butyl, sulfosalicylic acid, tetramethylene glycol, triethanolamine, benzotriazole, ethanol and water, the resistivity of a mucosa formed in the anode dissolving process can be effectively reduced, the diffusivity of dissolved metal is improved, namely a CD section in the electrolytic polishing process is effectively avoided, the voltage requirement of polishing is reduced, the oxygen evolution is performed at low pressure, the energy consumption is saved, and the polishing efficiency is effectively improved.
(2) The obtained aluminum alloy has low surface roughness and good mirror surface effect.
Drawings
FIG. 1 is a graph of voltage versus current density for example 1 of the present invention.
FIG. 2 shows that the voltage range 0 < V in example 1 of the present invention1< 46 voltage-current density graph.
FIG. 3 shows that the voltage range 46 < V in example 1 of the present invention2< 81 voltage-current density plot.
FIG. 4 is an SEM image of the aluminum alloy after polishing in example 1 of the present invention.
FIG. 5 is an SEM image of an aluminum alloy of the present invention.
FIG. 6 is an SEM photograph of the aluminum alloy of comparative example 1 of the present invention after polishing.
FIG. 7 is an SEM image of the aluminum alloy of comparative example 2 of the present invention after polishing.
FIG. 8 is an SEM photograph of the aluminum alloy of comparative example 3 of the present invention after polishing.
FIG. 9 is an SEM photograph of the aluminum alloy of comparative example 4 of the present invention after polishing.
Detailed Description
All the treatment modes of the aluminum alloy comprise electrochemical polishing pretreatment, electrochemical polishing treatment and electrochemical polishing post-treatment, wherein the electrochemical polishing solution is prepared by the following steps:
(1) adding water to a reaction vessel, and adding oxalic acid, perchloric acid and maleic acid thereto in this order;
(2) sequentially adding part of ethanol, tolbutate, sulfosalicylic acid, triethanolamine and benzotriazole into the mixed solution in the step (1), and uniformly mixing by magnetic stirring;
(3) and (3) supplementing the balance of ethanol, adding butylene glycol, and magnetically stirring and uniformly mixing to obtain the aluminum alloy processing solution for electrolytic polishing.
For the comparative example, where some of the ingredients were reduced, the supplement was made with ethanol.
Example 1
An aluminum alloy working solution, the composition of said solution being as follows:
the volume ratio of perchloric acid to maleic acid to oxalic acid is 1: 11: 4,135 ml/L;
if so: 3g/L;
sulfosalicylic acid: 2 g/L;
and (3) butylene glycol: 190ml/L;
triethanolamine: 1 g/L;
benzotriazole: 1 g/L;
ethanol: 570 ml/L;
the balance being deionized water.
An aluminum alloy workpiece is used as an anode to be connected with a direct current power supply anode, stainless steel is used as a cathode to be connected with a direct current power supply cathode, the electrolysis temperature is 27 ℃, the electrode spacing is 17mm, the electrochemical polishing direct current voltage is 46V, and the polishing time is 120 s.
Comparative example 1
An aluminum alloy working solution, the composition of said solution being as follows:
the volume ratio of perchloric acid to maleic acid to oxalic acid is 1, 8.43 ml/L;
if so: 3g/L;
sulfosalicylic acid: 2 g/L;
and (3) butylene glycol: 190ml/L;
triethanolamine: 1 g/L;
benzotriazole: 1 g/L;
ethanol: 570+126.56 ml/L;
the balance being deionized water.
An aluminum alloy workpiece is used as an anode to be connected with a direct current power supply anode, stainless steel is used as a cathode to be connected with a direct current power supply cathode, the electrolysis temperature is 27 ℃, the electrode spacing is 17mm, the electrochemical polishing direct current voltage is 46V, and the polishing time is 120 s.
Comparative example 2
An aluminum alloy working solution, the composition of said solution being as follows:
the volume ratio of perchloric acid to maleic acid to oxalic acid is 1: 11: 4,135 ml/L;
sulfosalicylic acid: 2 g/L;
and (3) butylene glycol: 190ml/L;
triethanolamine: 1 g/L;
benzotriazole: 1 g/L;
ethanol: 570 ml/L +3g;
the balance being deionized water.
An aluminum alloy workpiece is used as an anode to be connected with a direct current power supply anode, stainless steel is used as a cathode to be connected with a direct current power supply cathode, the electrolysis temperature is 27 ℃, the electrode spacing is 17mm, the electrochemical polishing direct current voltage is 46V, and the polishing time is 120 s.
Comparative example 3
An aluminum alloy working solution, the composition of said solution being as follows:
the volume ratio of perchloric acid to maleic acid to oxalic acid is 1: 11: 4,135 ml/L;
if so: 3g/L;
and (3) butylene glycol: 190ml/L;
triethanolamine: 1 g/L;
benzotriazole: 1 g/L;
ethanol: 570 ml/L +2g;
the balance being deionized water.
An aluminum alloy workpiece is used as an anode to be connected with a direct current power supply anode, stainless steel is used as a cathode to be connected with a direct current power supply cathode, the electrolysis temperature is 27 ℃, the electrode spacing is 17mm, the electrochemical polishing direct current voltage is 46V, and the polishing time is 120 s.
Comparative example 4
An aluminum alloy working solution, the composition of said solution being as follows:
the volume ratio of perchloric acid to maleic acid to oxalic acid is 1: 11: 4,135 ml/L;
if so: 3g/L;
sulfosalicylic acid: 2 g/L;
and (3) butylene glycol: 190ml/L;
triethanolamine: 1 g/L;
benzotriazole: 1 g/L;
ethanol: 570+190ml/L;
the balance being deionized water.
An aluminum alloy workpiece is used as an anode to be connected with a direct current power supply anode, stainless steel is used as a cathode to be connected with a direct current power supply cathode, the electrolysis temperature is 27 ℃, the electrode spacing is 17mm, the electrochemical polishing direct current voltage is 46V, and the polishing time is 120 s.
Comparative example 5
An aluminum alloy working solution, the composition of said solution being as follows:
the volume ratio of perchloric acid to maleic acid to oxalic acid is 1: 11: 4,135 ml/L;
if so: 3g/L;
sulfosalicylic acid: 2 g/L;
and (3) butylene glycol: 190ml/L;
ethanol: 570 ml/L +2g;
the balance being deionized water.
An aluminum alloy workpiece is used as an anode to be connected with a direct current power supply anode, stainless steel is used as a cathode to be connected with a direct current power supply cathode, the electrolysis temperature is 27 ℃, the electrode spacing is 17mm, the electrochemical polishing direct current voltage is 46V, and the polishing time is 120 s.
And (3) testing the glossiness: DR60A intelligent glossiness instrument with a reflection angle of 45oC。
And (3) roughness detection: TMR roughness tester, roughness of 5 blocks of area is averaged and regarded as the roughness result.
As shown in the above table, when no complex acid maleic acid and oxalic acid are added into the polishing solution, and no viscosity modifier is added, the polishing effect is very poor, which may be caused by that when the polishing voltage is 46V, the dissolved metal ions are limited, the anode surface mucosa resistance is large, and effective polishing cannot occur, wherein FIG. 4 shows that the aluminum alloy treated by the electrolytic polishing solution configured by the invention has extremely few surface irregularities and a good polishing effect, and is far better than the effect of SEM images of the aluminum alloy after polishing in FIG. 5, the aluminum alloy in FIG. 6 in comparative example 1, the aluminum alloy in FIG. 7 in comparative example 2, the aluminum alloy in FIG. 8 in comparative example 3, and the aluminum alloy in FIG. 9 in comparative example 4.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (6)
1. An aluminum alloy processing solution is characterized by comprising a complex acid, a corrosion inhibitor, a brightening agent, a viscosity regulator and an additive, wherein the complex acid is a mixture of perchloric acid, maleic acid and oxalic acid, the corrosion inhibitor is formol, the brightening agent is sulfosalicylic acid, the viscosity regulator is tetramethylene glycol, the additive is triethanolamine and benzotriazole, a solvent is ethanol and water, and the volume ratio of the perchloric acid to the maleic acid to the oxalic acid is 1: 11: 4,135 ml/L
If so: 3g/L;
the sulfosalicylic acid: 2 g/L;
the tetramethylene glycol: 190ml/L;
the triethanolamine: 1 g/L;
the benzotriazole: 1 g/L;
the ethanol: 570 ml/L;
the balance being deionized water.
2. The aluminum alloy processing solution as recited in claim 1, wherein the aluminum alloy workpiece is connected to a positive electrode of a DC power supply as an anode, and connected to a negative electrode of the DC power supply as a cathode, and the aluminum alloy workpiece is electrolyzed at a temperature of 27 ℃, a voltage of less than 81V, and a current density of less than 1.9A.cm-2And the electrode spacing is 17 mm.
3. An aluminum alloy working solution according to claim 2 wherein said solution is subjected to a voltage and current density fitting function during electropolishing as follows:
A1= 0.0105V1 + 0.0082， 0＜V1＜46；
A2 = 0.09e0.0369V2， 46＜V2＜81。
4. an aluminum alloy working solution according to claim 3, wherein the electrochemical polishing DC voltage is preferably 46. + -. 0.3V, and the polishing time is preferably 120 s.
5. An aluminum alloy working solution as set forth in claim 2, wherein the aluminum alloy workpiece is subjected to surface pretreatment beforehand.
6. The method of producing an aluminum alloy working solution as recited in any one of claims 1 to 5, comprising the steps of:
(1) adding water to a reaction vessel, and adding oxalic acid, perchloric acid and maleic acid thereto in this order;
(2) sequentially adding part of ethanol, tolbutate, sulfosalicylic acid, triethanolamine and benzotriazole into the mixed solution in the step (1), and uniformly mixing by magnetic stirring;
(3) and (3) supplementing the balance of ethanol, adding butylene glycol, and magnetically stirring and uniformly mixing to obtain the aluminum alloy processing solution for electrolytic polishing.
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