CN115261966A

CN115261966A - Method for treating metal by using efficient cleaning agent

Info

Publication number: CN115261966A
Application number: CN202210963510.3A
Authority: CN
Inventors: 梁嘉晟
Original assignee: Wuxi Jizhi Electronic Technology Co ltd
Current assignee: Wuxi Jizhi Electronic Technology Co ltd
Priority date: 2022-08-11
Filing date: 2022-08-11
Publication date: 2022-11-01

Abstract

The invention provides a method for treating metal by using an efficient cleaning agent, which can effectively shorten the period of a surface treatment process and obtain a high-quality flat metal surface by using an efficient cleaning solution and a treatment process.

Description

Method for treating metal by using efficient cleaning agent

Technical Field

The invention designs a method for treating metal by using an efficient cleaning agent, and particularly relates to the field of aluminum alloy surface cleaning.

Technical Field

In nature, aluminum is the metal element with the highest content, 8.3 of the content of the occupied shell, aluminum and aluminum alloy products have the advantages of small specific gravity, good electric and thermal conductivity, high specific strength, high temperature resistance, corrosion resistance of various media, fatigue resistance, good light and heat reflection performance and the like, are typical light alloy materials, are widely applied to the fields of civil use, construction, mechanical manufacturing, science and technology, military, electronic and electrical equipment, transportation, aerospace, chemical industry and the like, and continuously develop scientific technology and industrial technology to provide higher requirements and standards for the surface quality of aluminum and aluminum alloy workpieces, particularly for the two aspects of the surface glossiness and the flatness of the workpieces, so that the aluminum and aluminum alloy workpieces can meet the use standards of industrial production and life, and the surfaces of the aluminum and aluminum alloy workpieces usually achieve the decorative effect of a sand surface or a mirror surface.

However, aluminum and aluminum alloy have low hardness and poor wear resistance, and aluminum alloy materials cause mechanical damage to workpieces during manufacturing and production, and generate defects such as pores, scratches, bruises, scratches and abrasion on the surfaces of aluminum and aluminum alloy workpieces. Due to the existence of the surface defects, the appearance and application value of the aluminum and aluminum alloy workpiece are greatly influenced, the surface smoothness and brightness of the aluminum and aluminum alloy workpiece are reduced, and the existence of the defects particularly influences the chemical stability of the workpiece, particularly obviously influences the corrosion resistance, local corrosion is often generated preferentially at the surface defects of the workpiece, and the service time of the workpiece is greatly shortened. Therefore, solving the problem of surface defects of aluminum and aluminum alloy products is a central focus of the continued development of the aluminum and aluminum alloy industry. To eliminate these surface defects and achieve high surface brightness and good decorative effects, aluminum and aluminum alloy workpieces are usually subjected to surface treatment.

Polishing techniques can be classified into mechanical polishing, electrochemical polishing (electropolishing), and chemical polishing according to their principles of action and process characteristics. The surface polishing treatment technology can be used for final treatment of the surface of the aluminum and aluminum alloy workpiece, and can also be used for final treatment of the surface of the aluminum and aluminum alloy workpiece

And the pretreatment processes of anodic oxidation and electroplating of the aluminum alloy. Each polishing method has the advantages and disadvantages of the polishing methods, the polishing modes are different, and the polishing effects of the treated aluminum and the treated aluminum alloy are different, which mainly reflects in four aspects of polishing process, polishing cost, workpiece surface finish and influence on atmospheric environment.

The mechanical polishing is to grind and roll the very fine polishing paste coated on the polishing disk and the surface of the workpiece to be processed under the action of external force, remove the convex part of the processed surface of the workpiece and enable the uneven surface to become flat and smooth. However, in the mechanical polishing process, a new crystal deformation layer is formed on the surface of the workpiece under the influence of factors such as extrusion, heat and the like, so that the surface structure of the workpiece is damaged, and the polished aluminum alloy workpiece still has problems and cannot meet the use requirements of products, such as insufficient surface smoothness of the polished workpiece, poor corrosion resistance and easy generation of stress corrosion or grain boundary corrosion. Although the surface of the workpiece after mechanical polishing can be sufficiently flat and bright, if such a workpiece is directly subjected to the anodic oxidation process, a high-quality film excellent in decorative effect cannot be obtained. In addition, mechanical polishing can only perform polishing treatment on some workpieces with simple appearance structures, and for decorative materials, precise parts and optical parts which have high requirements on the surface performance of the workpieces and have complex shapes, the mirror reflectivity and the surface flatness required by the workpieces cannot be achieved by only depending on mechanical polishing.

For example, CN105081941A discloses a mechanical polishing process for the inner wall of a stainless steel storage tank, which comprises the following steps:

1) Rough polishing: grinding, polishing or lapping the surface of a workpiece by using a No. 60-100 carborundum wheel to remove burrs, scratches, rust marks, oxide skin, welding bead excess height, welding beading, welding slag and the like on the surface, and removing a surface oxide layer to expose metallic luster;

2) Fine polishing: further processing the roughly polished surface by adopting an 80# carborundum grinding wheel and a thousand-blade wheel, removing scratches left during rough polishing, and generating a smooth to medium-brightness surface;

3) Fine polishing: polishing the surface of the stainless steel storage tank by using a 240# -320 # fiber wheel and a cloth wheel coated with polishing paste, further reducing the roughness of the surface of the stainless steel, and achieving the purpose of microcosmic leveling;

4) And (3) polishing detection: and (3) detecting by adopting a center line average value method, transversely moving the roughness detector on the surface of the stainless steel storage tank during detection, and recording the peak-valley variation amplitude.

Chemical polishing and electrochemical polishing are similar, and both rely on the etching action of special chemical reagents on the surface of a workpiece

Selectively dissolving the rugged region, and under the condition of a certain temperature and time, etching off the oxide layer and the crystal deformation layer on the surface, thereby eliminating the grinding marks on the surface and leveling the etching. The surface glossiness of the workpiece after chemical polishing is improved, the surface roughness is reduced, the chemical stability is improved, the light and heat reflecting capacity is enhanced, and the like. But compared with electrochemical polishing, the chemical polishing has the advantages of less equipment fund, no need of power supply equipment and corresponding clamps, simple equipment, simple operation, high production efficiency, capability of effectively processing parts which are thin tubes, have deep holes, and have small sizes and complex shapes. Because most of aluminum and aluminum alloys have no special requirements in use occasions, the requirements of daily industry and life on the surface glossiness and the flatness can be met, and the chemical polishing process is completely sufficient. The chemical polishing is suitable for the aluminum and aluminum alloy products, other products such as copper, nickel, titanium and alloy products thereof, and even workpieces comprising steel, silver and the like, and can improve the smoothness of the surface of the material by using a chemical polishing process or an electrochemical polishing process.

For example, CN102277575A discloses a chemical polishing solution for aluminum products and a preparation method thereof, relating to a chemical polishing solution. The chemical polishing solution for the aluminum product has the advantages of less yellow smoke, low pollution, no nitric acid and the like, and the polishing quality can reach the level of the traditional 'three-acid' process by the nitrate-improved 'three-acid' polishing process, and the environmental pollution caused by the release of nitrogen oxides can be reduced. The raw materials of the coating comprise sulfuric acid, phosphoric acid, boric acid, a passivating agent, a fog-inhibiting brightener, citric acid, tartaric acid and water. The method comprises the specific steps of adding all solid raw materials into water, dissolving, sequentially adding phosphoric acid and sulfuric acid, cooling the solution, and transferring to a volumetric flask for constant volume. The using method comprises the following steps: heating the chemical polishing solution of the aluminum product to 95-110 ℃; immersing the dried and clean aluminum product to be polished into the chemical polishing solution of the aluminum product, treating for 30-100 s, and taking out; and immersing the taken aluminum product to be polished into nitric acid to polish for 25-120 s, and cleaning to finish polishing the aluminum product.

Electrochemical polishing (also called electropolishing) refers to a surface finishing technique in which the anode of a metal workpiece is dissolved in a certain electrolyte to reduce the surface roughness and improve the brightness of the metal workpiece, thereby producing a certain metal luster. The specific process is as follows: the workpiece to be treated is taken as an anode, insoluble metal is taken as a cathode (a lead plate or a stainless steel plate is mostly adopted), then the cathode and the anode are placed in electrolytic bath solution, a direct current power supply is turned on to start polishing, and the anode which is selective to the surface of the aluminum and aluminum alloy workpiece is dissolved in the polishing process, so that the surface of the workpiece with higher glossiness and smoother surface is obtained. Electrochemical polishing techniques have been developed over decades to improve the properties of metal surfaces without changing the properties of the bulk of the workpiece. Metals and alloys become more flat, smooth, and more corrosion resistant after electrochemical polishing, which dissolves particles produced by mechanical polishing.

For example, CN110846710A discloses an electrochemical polishing method for the surface of copper material, comprising the following steps: preparing a polishing solution; soaking a copper material to be polished into a polishing solution, and turning on a power supply to polish; wherein, preparing the polishing solution comprises: calculating the dosage of each solute according to the total volume of the solution to be prepared, wherein the solutes comprise phosphoric acid, glycerol, thiourea and polyoxyethylene alkanolamide; according to the calculation result, weighing phosphoric acid and glycerol, introducing the phosphoric acid and the glycerol into a corrosion-resistant container, adding water until the total volume is reached, and stirring and dissolving to obtain a first intermediate solution; according to the calculation result, weighing thiourea, adding the thiourea into the first intermediate solution, and stirring and dissolving to obtain a second intermediate solution; and measuring polyoxyethylene alkanolamide according to the calculation result, adding the polyoxyethylene alkanolamide into the second intermediate solution, and uniformly stirring to obtain the polishing solution. The invention can improve the surface roughness of the copper precision part from Ra0.4 mu m to Ra0.2 mu m so as to meet the use requirement of a vacuum electronic device.

Compared with chemical polishing and mechanical polishing, the electrochemical polishing has the advantages that (1) high surface smoothness can be obtained; (2) high polishing precision can be obtained; (3) the operation environment is good, and the metal loss is small; (4) low energy consumption; (5) can process workpieces of any shape and size; (6) the polishing speed is independent of the physical and mechanical properties of the metal; (7) the production efficiency can be greatly improved; (g) The physical and mechanical properties, the physical and chemical properties and the service performance of the surface of the metal part can be improved; (9) the operation technology is easy to master; (10) the application range is wide.

Disclosure of Invention

Based on the introduction of polishing, the invention provides a method for treating metal by using an efficient cleaning agent, wherein the cleaning agent is used as an electrochemical polishing electrolyte, can effectively polish a metal substrate, and can obtain a metal surface with low roughness, high flatness, good corrosion resistance and good stability.

The method for treating metal by using high-efficiency cleaning agent is characterized by that said cleaning agent is formed from polyalcohol, perchloric acid, polyalcohol amine, mercapto sulfonyl ionic compound and pyridinium salt compound.

The polyalcohol is one of dipropylene glycol, glycerol or butanediol.

The polyalcohol amine is selected from one of diisopropanolamine, triisopropanolamine or triethanolamine.

The sulfydryl sulfonyl ionic compound is selected from one of thiazolinyl dithio propane sodium sulfonate, dimethyl dithio carbonyl propane sodium sulfonate and 3- (benzothiazole-2-sulfydryl) -propane sodium sulfonate.

The pyridinium salt compound is one selected from 1-ethyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, 3- (4-tert-butyl 1-pyridyl) propanesulfonate or 3- (1-pyridyl) propanesulfonate.

And applying a power supply between the metal anode and the inert metal cathode to clean the anode metal by taking the metal as the anode, taking the inert metal as the cathode and taking the cleaning agent as electrolyte.

The cleaning process comprises the following steps:

(1) Starting a direct current power supply: the current density is 3-5A/cm ² Polishing for 5-7min at 20-25 deg.C and a polar distance of 15-20mm;

(2) Turning on a millisecond pulse power supply: the forward pulse current density is 2-3mA/cm ² The forward pulse width is 100-150ms, the forward duty ratio is 10-15%, the pulse number is 5-10, and the reverse pulse current density is 2-3mA/cm ² Pulse width is 150-170ms, reverse duty ratio is 10-15%, pulse number is 1, temperature is 20-25 ℃, time is 2-3min;

(3) Turning on a microsecond pulse power supply: the forward pulse current density is 1-2mA/cm ² The width of the forward pulse is 50-100 mu s, the duty ratio of the forward pulse is 10-15%, the pulse number is 10-15, the current density of the reverse pulse is 1-2mA/cm < 2 >, the width of the reverse pulse is 50-100 mu s, the duty ratio of the reverse pulse is 10-15%, the pulse number is 1, the temperature is 13-15 ℃, and the time is 0.5-1min;

further, the content of the polyol is 30-65vol.%, the content of the perchloric acid is 3-5vol.%, the content of the polyalcohol amine is 10-15ml/L, the content of the mercapto sulfonyl ionic compound is 3-5g/L, and the content of the pyridinium salt compound is 1.5-3g/L.

Further, the metal is stainless steel, aluminum alloy or titanium alloy, preferably aluminum alloy.

Further, a step (1) and a step (2) are provided, and an intermittent step is arranged between the step (2) and the step (3): turning off the power supply, and turning on stirring at the speed of 200-300rpm and the temperature of 17-23 deg.C for 2-3min.

Further, after the step (3), post-treatment is performed: turning off the power supply, washing with absolute ethyl alcohol, purging in inert atmosphere and drying.

Furthermore, the inert atmosphere is nitrogen or argon, the temperature is 35-40 ℃, and the time is 1-2h.

The cleaning solution of the present invention is composed of polyol, perchloric acid, polyalcohol amine, sulfydryl sulfonyl ionic compound, pyridinium salt compound, and the balance of ethanol is supplemented, and is a standard deionized water cleaning system, generally speaking, the components of the polishing solution are complex, and the types of the polishing solutions suitable for each material are different, and no specific formula is provided, and most of the polishing solutions need to be tested and searched, but the types of the components are roughly divided into three parts, namely, polishing base solution, oxidant and various additives, the oxidant is the most important component, and the electrochemical polishing solution mainly comprises three main types, namely, acid-acid systems, such as concentrated sulfuric acid-concentrated phosphoric acid, and the like; acid-alcohol systems, such as concentrated sulfuric acid-methanol/ethanol, and the like; alcohol-salt systems such as ethylene glycol-chloride salts and the like. Each polishing solution system cannot meet all requirements, has certain advantages and disadvantages, and does not have a completely ideal polishing solution system. Acid-acid systems mostly adopt strong acid such as concentrated sulfuric acid and concentrated phosphoric acid, and although the polishing quality is good and the polishing efficiency is high, the corrosivity is strong, the reaction process is not easy to control, and danger is easy to occur in the using process. In an acid-alcohol system, alcohol is generally volatile and is not easy to store, and the alcohol and the acid are easy to react to generate lipid, so that the operation process has high requirements on environment and the like. Although most of the alcohol-salt systems have no pollution to the environment, the polishing efficiency is low due to low corrosivity and oxidizability, the production cost is high, the requirements on a polishing device and the like in the polishing process are high, and the alcohol-salt system is mainly a polyol-perchloric acid system, and perchloric acid is used as an oxidizing agent and is the most important component in the polishing solution. It can dissolve metal alloy, generate soluble salt and generate passive film on the surface of test piece. The polyhydric alcohol is used as a solvent to dissolve soluble salts generated by the anode, and simultaneously, carboxyl and hydroxyl contained in the soluble salts can play a corrosion inhibition role.

The polyalcohol and the polyalcohol amine are added simultaneously, the polyalcohol amine is selected from one of diisopropanolamine, triisopropanolamine or triethanolamine, the polyalcohol amine is alkalescent and can be a complexing agent or a leveling agent, and mucosa can be generated on the surface and adsorbed on the surface to help polishing and gradually flatten the surface.

The composition of the sulfydryl sulfonyl ionic compound and the pyridinium salt compound has the technical effect of synergistic leveling and brightening, and the sulfydryl sulfonyl ionic compound is selected from one of thiazolinyl dithiopropane sodium sulfonate, dimethyl dithiocarbonyl propane sodium sulfonate and 3- (benzothiazole-2-sulfydryl) -propane sodium sulfonate; the pyridinium salt compound is one of 1-ethyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, 3- (4-tert-butyl 1-pyridyl) propanesulfonate or 3- (1-pyridyl) propanesulfonate, and three pyridinium salt compounds have the following structural formulas:

；

；

theoretically, in the metal polishing process, after the metal immersed in the electrolyte is electrified, electrons are lost at the anode, the metal is dissolved in the electrolyte in the form of ions, and the reaction formula is Al → 3Al ³⁺ +3e; in this process it is desirable that the aluminium ions leave the surface as quickly as possible; then the metal loses electrons, OH-ions do electromigration movement under the action of the electric field force, so that a large amount of local OH-ions are accumulated on the goldIn the vicinity of the anode, hydrolysis and precipitation reaction occur, i.e. Al occurs ³⁺ +3OH ^- →Al(OH) ₃ Based on the above theory, the pyridinium salts of the present invention all have a C = N structure and are amphiphilic compounds, under the current condition, one end of an anion is adsorbed on the surface of an anode to neutralize the anion therein, and metal ions released during the polishing dissolution process, such as aluminum ions, significantly form a repulsive interaction with nitrogen-containing positive charges to accelerate Al hydrolysis ³⁺ The metal ions enter into the electrolyte from the surface of the dissolved metal, and the rejected aluminum ions are very easy to hydrolyze with water to form hydroxide particles, which affect the polishing effect, and in order to prevent excessive hydrolysis of the aluminum ions, the metal ions (Al) entering into the solution ³⁺ ) The compound can be combined with C-S = O and N = C-S in a sulfydryl sulfonyl device, unshared electron pairs in the functional groups are filled in empty orbits of metal ions to realize a strong adsorption effect with the metal ions, so that the deposition of metal is avoided, in addition, sulfydryl sulfonyl ionic compounds and pyridinium salt compounds have rich annular structures, the adsorption conjugation effect is obvious, a mucosa structure is formed on the surface, the rapid corrosion of convex parts and the slow corrosion of concave parts are controlled, the leveling and brightening effects are finally obtained, the two are not enough, if the pyridinium salt is lacked, the metal ions cannot be effectively moved and diffused away from the metal surface, and if the sulfydryl sulfonyl ionic compounds are lacked, the metal ions cannot be effectively prevented from being hydrolyzed, as shown in attached figures 1 and 2.

Another important reason for the excellent surface treatment effect obtained by the cleaning agent for treating the metal surface is the electrochemical electrolysis parameter, the electrochemical polishing power supply mainly adopted in the prior art is a direct current power supply or a pulse power supply, a direct current-pulse treatment mode is adopted, and a millisecond-level-first and micron-level-second electrochemical treatment process is adopted.

The method comprises the steps of taking a substrate to be treated as an anode, adding the cleaning agent prepared in the preparation process, and then carrying out anode electrochemical polishing, wherein the metal to be treated is stainless steel, aluminum alloy or titanium alloy, preferably aluminum alloy, and the metal can be subjected to various surface pretreatments including but not limited to oil removal and degreasing, acid pickling and activation, sand blasting, grinding, polishing and the like.

The method comprises the steps of firstly carrying out direct-current electrolytic polishing on a substrate, wherein in the initial stage of the direct-current electrolytic polishing, due to the fact that the roughness degrees of the surfaces of parts are different, namely, the roughness of the metal surface is staggered, electrolyte is adsorbed on the metal surface and oxidation reaction occurs, a viscous liquid film generated at a convex part is smaller than the thickness of the viscous liquid film generated at a concave part, the viscous liquid film at the convex part is greatly impacted by power lines and stirred by liquid, and in addition, the convex part is closer to a cathode, the electric field intensity is large, electrons are easily lost according to the principle of point discharge, and positive charges are highly concentrated at the convex part. Since the anions around the anode preferentially react with the cations at the protrusions, the metal forming the protrusions dissolves at a faster rate than the depressions. For the direct current electrolytic polishing, the obvious concave-convex structure on the metal surface has obvious and rapid flattening effect, the whole process is rough and rapid, and the efficiency is rapid although the fineness is insufficient, as shown in figure 3.

Direct current electrolysis conditions: the current density is 3-5A/cm ² Polishing for 5-7min at 20-25 deg.C and inter-polar distance of 15-20mm; wherein, the current density has the biggest influence on the DC electrolytic polishing process and is the energy source for polishing. Too large or too small a current density can adversely affect polishing. When the current density is too small, the polished surface is always in a dissolving stage, the surface roughness is large, no metal luster exists, and the polishing effect is small. When the current density is too large, the reaction is violent, the heat generation is more, the oxidability of perchloric acid is enhanced along with the rise of the temperature, the surface material is more corroded and removed, and the surface brightness is enhanced. Meanwhile, oxygen precipitation on the surface of the anode is increased, and the phenomena of uneven polishing and excessive polishing of the surface can occur due to the stirring of gas. In addition, the inter-electrode distance during electrochemical polishing is larger than that during electrolytic machining, and the purpose of ensuring more uniform dissolution of metal in the polishing process is mainly achieved, so that a better polishing effect is achieved. When the interelectrode distance is too small, the diffusion of the reactant is inconvenient, the temperature of the polishing solution rises quickly, and the heat dissipation is poor. When the interelectrode distance is too large, the current densityThe reduction and the polishing effect are not obvious, and the final optimized reaction condition is that the current density is 3-5A/cm ² The polishing time is 5-7min, the temperature is 20-25 ℃, the inter-polar distance is 15-20mm, and compared with pulse electrolysis, the direct current electrolytic polishing has the advantages of large current density, long time and capability of quickly obtaining a flat surface.

The roughness of the metal surface treated by direct current electrolytic polishing is about 5-10 μm, the polishing precision is obviously insufficient, the main reasons may be that the direct current voltage is constant, the removal of polishing products and heat is difficult, and the products are accumulated on the surface of the anode, so that the roughness of the surface of a workpiece is increased, and further the surface quality is poor.

Then, pulse processing is carried out:

(2) Turning on a millisecond pulse power supply: the forward pulse current density is 2-3mA/cm ² The forward pulse width is 100-150ms, the forward duty ratio is 10-15%, the pulse number is 5-10, and the reverse pulse current density is 2-3mA/cm ² The pulse width is 150-170ms, the reverse duty ratio is 10-15%, the pulse number is 1, the temperature is 20-25 ℃, and the time is 2-3min.

(3) Intermittent step: turning off the power supply, and turning on stirring at the speed of 200-300rpm and the temperature of 17-23 deg.C for 2-3min.

(4) Turning on a microsecond pulse power supply: the forward pulse current density is 1-2mA/cm ² The forward pulse width is 50-100 mus, the forward duty ratio is 10-15%, the pulse number is 10-15, the reverse pulse current density is 1-2mA/cm < 2 >, the reverse pulse width is 50-100 mus, the reverse duty ratio is 10-15%, the pulse number is 1, the temperature is 13-15 ℃, and the time is 0.5-1min.

Compared with direct current chemical polishing, the surface roughness of the polished surface of the pulse current electrochemical polishing is greatly reduced, and theoretically, pressure waves can be generated in the electrode gap at the moment of electrifying, bubbles can be generated in the electrode gap due to the action of the pressure waves, and the surface of the anode is corroded. At the moment of power failure, bubbles are suddenly expanded and combined, and the anode product is flushed and rolled away, so that the phenomenon of poor surface roughness caused by the fact that the surface product is not in time to be removed is effectively reduced. Generally, the narrower the pulse width of the pulse current, the higher the frequency, and the more beneficial the improvement of the convection field, because the smaller the pulse width, the higher the frequency, the faster the electrolyte renewal speed in the gap, and the more obvious the impact effect of the pressure wave, and the more beneficial the improvement of the surface quality.

Based on the consideration, the invention adopts a periodic reversing pulse power supply, the periodic reversing pulse is formed by adding one or more reverse pulses after a group of forward pulses, the migration of an anode product can be further accelerated, and then a high polishing effect is obtained, in the pulse stage, firstly, a relatively high current is used for carrying out long-time millisecond-level anode polishing, the obtained metal surface roughness is about 400-600nm, then, a relatively low current is used for carrying out short-time microsecond-level anode polishing, the obtained metal surface roughness is about 50-150nm, compared with the mode of directly carrying out microsecond-level periodic reversing pulse electrochemical treatment, the same polishing effect is obtained, the polishing time can be shortened by 3/4, the polishing effect is greatly satisfied, and the polishing effect is shown in figure 4.

Advantageous technical effects

(1) The invention effectively prepares the cleaning solution, particularly the sulfydryl sulfonyl ionic compound and the pyridinium salt compound, and has direct influence on the roughness, high flatness and glossiness of the metal surface treatment.

(2) According to the invention, the metal surface is treated by direct current, millisecond pulse and microsecond pulse, so that the working hour consumption is effectively reduced and the loss is reduced on the premise of ensuring low roughness, high gloss and low corrosion amount of the metal surface.

Drawings

FIG. 1 is a drawing of an aluminum alloy after treatment of comparative example 1 of the present invention.

FIG. 2 is a drawing of an aluminum alloy of comparative example 2 of the present invention after treatment.

FIG. 3 is a drawing of an aluminum alloy of comparative example 3 of the present invention after treatment.

FIG. 4 is a drawing of an aluminum alloy after treatment in example 2 of the present invention.

Detailed Description

The preparation methods of the cleaning agents in examples 1 to 3 of the present invention and the comparative example were as follows:

(1) Mixing polyalcohol amine and polyalcohol at 5-10 deg.C, and stirring;

(2) Continuously stirring, keeping the temperature stable, slowly adding perchloric acid, and uniformly stirring;

(3) Continuously stirring, simultaneously adding the sulfydryl sulfonyl ionic compound and the pyridinium salt compound, slowly heating to the normal temperature, and continuously stirring for 1-2h to obtain the cleaning agent.

If the above components are not contained, part of the components are deleted adaptively.

Example 1

The method for treating the metal by using the efficient cleaning agent comprises the following steps of using a polyol, perchloric acid, polyalcohol amine, a sulfydryl sulfonyl ionic compound and a pyridinium salt compound, wherein the content of the polyol is 30vol.%, the content of the perchloric acid is 3vol.%, the content of the polyalcohol amine is 10ml/L, the content of the sulfydryl sulfonyl ionic compound is 3g/L, the content of the pyridinium salt compound is 1.5g/L, and the balance is deionized water.

The polyol is selected from dipropylene glycol.

The polyalcohol amine is selected from diisopropanolamine.

The mercapto sulfonyl ionic compound is selected from thiazolinyl dithio propane sodium sulfonate.

The pyridinium salt compound is selected from 3- (4-tertiary butyl 1-pyridyl) propane sulfonate.

The cleaning process comprises the following steps:

(1) Starting a direct current power supply: current density 3A/cm ² The polishing time is 5min, the temperature is 20 ℃, and the inter-polar distance is 15mm.

(2) Intermittent step: turning off the power supply, and turning on the stirring at the stirring speed of 200rpm and the stirring temperature of 17 ℃ for 2min.

(3) Turning on a millisecond pulse power supply: the forward pulse current density is 2mA/cm ² The forward pulse width is 100ms, the forward duty cycle is 10%, the pulse number is 5, and the reverse pulse current density is 2mA/cm ² The pulse width is 150ms, the reverse duty cycle is 10%, the pulse number is 1, the temperature is 20 ℃, and the time is 2min.

(4) Intermittent step: turning off the power supply, and turning on the stirring at the stirring speed of 200rpm and the stirring temperature of 17 ℃ for 2min.

(5) Turning on a microsecond pulse power supply: the forward pulse current density is 1mA/cm ² The forward pulse width was 50. Mu.s, the forward duty ratio was 10%, the pulse number was 10, and the reverse pulse current density was 1mA/cm ² The pulse width is 50 mus, the forward duty ratio is 10%, the pulse number is 1, the temperature is 13 ℃, and the time is 0.5min.

The method comprises the following steps: turning off the power supply, washing with absolute ethyl alcohol, blowing and drying in inert atmosphere, wherein the inert atmosphere is nitrogen or argon, the temperature is 35 ℃, and the time is 1h.

Example 2

The method for treating the metal by using the efficient cleaning agent comprises the following steps of using a polyol, perchloric acid, polyalcohol amine, a sulfydryl sulfonyl ionic compound and a pyridinium salt compound, wherein the content of the polyol is 55vol.%, the content of the perchloric acid is 4vol.%, the content of the polyalcohol amine is 12.5ml/L, the content of the sulfydryl sulfonyl ionic compound is 4g/L, the content of the pyridinium salt compound is 2g/L, and the balance is deionized water.

The polyalcohol is one of glycerol.

The polyalcohol amine is one selected from triisopropanolamine.

The mercapto sulfonyl ionic compound is selected from one of dimethyl dithio carbonyl propane sodium sulfonate.

The pyridinium salt compound is selected from 1-ethyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide.

And applying a power supply between the metal anode and the inert metal cathode to clean the metal anode by taking the metal as the anode, taking the inert metal as the cathode and taking the cleaning agent as electrolyte.

The cleaning process comprises the following steps:

(1) Starting a direct current power supply: current density 4A/cm ² The polishing time was 6min, the temperature 23 ℃ and the interpolar distance 17mm.

(2) Intermittent step: turning off the power supply, starting stirring at the speed of 250rpm and the temperature of 20 ℃ for 2.5min.

(3) Turning on a millisecond pulse power supply: the forward pulse current density is 2.5mA/cm ² The forward pulse width was 125ms, the forward duty cycle was 12.5%, the pulse number was 8, and the reverse pulse current density was 2.5mA/cm ² The reverse pulse width is 160ms, the reverse duty cycle is 12.5%, the pulse number is 1, the temperature is 23 ℃, and the time is 2.5min.

(4) Intermittent step: turning off the power supply, starting stirring at the speed of 250rpm and the temperature of 20 ℃ for 2.5min.

(5) Turning on a microsecond pulse power supply: the forward pulse current density is 1.5mA/cm ² The forward pulse width was 75. Mu.s, the forward duty cycle was 12.5%, the pulse number was 13, the reverse pulse current density was 1.5mA/cm2, the reverse pulse width was 75. Mu.s, the reverse duty cycle was 12.5%, the pulse number was 1, the temperature was 14 ℃, and the time was 0.75min.

The method comprises the following steps: turning off the power supply, washing with absolute ethyl alcohol, blowing and drying in inert atmosphere, wherein the inert atmosphere is nitrogen or argon, the temperature is 38 ℃, and the time is 1.5h.

Example 3

The method for treating metal by using the efficient cleaning agent comprises the following steps of using the efficient cleaning agent to treat metal, wherein the efficient cleaning agent consists of polyol, perchloric acid, polyalcohol amine, sulfydryl sulfonyl ionic compounds and pyridinium compounds, the content of the polyol is 65vol.%, the content of the perchloric acid is 5vol.%, the content of the polyalcohol amine is 15ml/L, the content of the sulfydryl sulfonyl ionic compounds is 5g/L, the content of the pyridinium compounds is 3g/L, and the balance is deionized water.

The polyhydric alcohol is one selected from butanediol.

The polyalcohol amine is selected from triethanolamine.

The sulfydryl sulfonyl ionic compound is one of 3- (benzothiazole-2-sulfydryl) -propane sodium sulfonate.

The pyridinium salt compound is one selected from 3- (1-pyridyl) propanesulfonate.

Taking the metal as an anode, taking the inert metal as a cathode and taking the cleaning agent as electrolyte, and applying a power supply between the metal anode and the inert metal cathode to clean the anode metal; .

The cleaning process comprises the following steps:

(1) Starting a direct current power supply: current density 5A/cm ² The polishing time was 7min, the temperature was 25 ℃ and the interpolar distance was 20mm.

(2) Intermittent step: turning off the power supply, starting stirring at the speed of 300rpm and the temperature of 23 ℃ for 3min.

(3) Turning on a millisecond pulse power supply: the forward pulse current density is 3mA/cm ² The forward pulse width was 150ms, the forward duty cycle was 15%, the pulse number was 10, and the reverse pulse current density was 3mA/cm ² The pulse width is 170ms, the reverse duty cycle is 15%, the pulse number is 1, the temperature is 25 ℃, and the time is 3min.

(4) Intermittent step: turning off the power supply, and turning on stirring at the speed of 200-300rpm and the temperature of 17-23 deg.C for 2-3min.

(5) Turning on a microsecond pulse power supply: the forward pulse current density is 2mA/cm ² The forward pulse width was 100. Mu.s, the forward duty cycle was 15%, the pulse number was 15, the reverse pulse current density was 2mA/cm2, the reverse pulse width was 100. Mu.s, the reverse duty cycle was 15%, the pulse number was 1, the temperature was 15 ℃, and the time was 1min.

And (3) post-treatment: turning off the power supply, washing with absolute ethyl alcohol, blowing and drying in inert atmosphere, wherein the inert atmosphere is nitrogen or argon, the temperature is 40 ℃, and the time is 2 hours.

Comparative example 1

The method for treating metal by using the efficient cleaning agent comprises the following steps of preparing a polyol, perchloric acid and a polyalcohol amine compound, wherein the polyol content is 55vol.%, the perchloric acid content is 4vol.%, the polyalcohol amine content is 12.5ml/L, and the balance is deionized water.

The polyalcohol is one of glycerol.

The polyalcohol amine is one selected from triisopropanolamine.

The cleaning process comprises the following steps:

(1) Starting a direct-current power supply: current density 4A/cm ² The polishing time was 6min, the temperature 23 ℃ and the interpolar distance 17mm.

Comparative example 2

The method for treating the metal by using the efficient cleaning agent comprises the following steps of preparing a polyol, perchloric acid, polyalcohol amine and a sulfydryl sulfonyl ionic compound, wherein the content of the polyol is 55vol.%, the content of the perchloric acid is 4vol.%, the content of the polyalcohol amine is 12.5ml/L, the content of the sulfydryl sulfonyl ionic compound is 4g/L, and the balance is deionized water.

The polyalcohol is one of glycerol.

The polyalcohol amine is one selected from triisopropanolamine.

The mercapto sulfonyl ionic compound is one selected from sodium dimethyl dithio carbonyl propane sulfonate.

The cleaning process comprises the following steps:

(5) Microsecond pulse power supply is started: the forward pulse current density is 1.5mA/cm ² The forward pulse width was 75. Mu.s, the forward duty cycle was 12.5%, the pulse number was 13, the reverse pulse current density was 1.5mA/cm2, the reverse pulse width was 75. Mu.s, the reverse duty cycle was 12.5%, the pulse number was 1, the temperature was 14 ℃, and the time was 0.75min.

The method comprises the following steps: turning off the power supply, washing with absolute ethyl alcohol, purging and drying in inert atmosphere of nitrogen or argon at 38 ℃ for 1.5h.

Comparative example 3

The polyalcohol is one of glycerol.

The polyalcohol amine is one selected from triisopropanolamine.

The cleaning process comprises the following steps:

(1) Starting a direct-current power supply: current density 4A/cm ² The polishing time is 10min, the temperature is 23 ℃, and the inter-polar distance is 17mm.

(2) And (3) post-treatment: turning off the power supply, washing with absolute ethyl alcohol, blowing and drying in inert atmosphere, wherein the inert atmosphere is nitrogen or argon, the temperature is 38 ℃, and the time is 1.5h.

Comparative example 4

The polyalcohol is one of glycerol.

The polyalcohol amine is one selected from triisopropanolamine.

The cleaning process comprises the following steps:

(1) Turning on a millisecond pulse power supply: the forward pulse current density is 2.5mA/cm ² The forward pulse width was 125ms, the forward duty cycle was 12.5%, the pulse number was 8, and the reverse pulse current density was 2.5mA/cm ² The reverse pulse width is 160ms, the reverse duty cycle is 12.5%, the pulse number is 1, the temperature is 23 ℃, and the time is 13min.

(3) Turning on a microsecond pulse power supply: the forward pulse current density is 1.5mA/cm ² The forward pulse width was 75. Mu.s, the forward duty cycle was 12.5%, the pulse number was 13, the reverse pulse current density was 1.5mA/cm2, the reverse pulse width was 75. Mu.s, the reverse duty cycle was 12.5%, the pulse number was 1, the temperature was 14 ℃, and the time was 7.4min.

And (3) post-treatment: turning off the power supply, washing with absolute ethyl alcohol, purging and drying in inert atmosphere of nitrogen or argon at 38 ℃ for 1.5h.

Surface roughness: respectively selecting 3 different regions on the surface of the sample for detection by an RSE3000 surface roughness meter, and averaging the roughness of the 3 regions to obtain a test result "

Surface glossiness: using aluminum material as sample, detecting and selecting 45 ^o The reflection angle, measured according to GB8807-88, is measured on the surface gloss of the test specimens.

TABLE 1

As shown in the above table, the roughness of the surface of the aluminum alloy obtained by the base solution + mercaptosulfonyl + pyridinium salt in the example 2 of the present invention is 53nm, the glossiness is 81.3%, and the corrosion amount of the product is small, in contrast, if the electrolyte is changed under the same electrolysis parameters, such as the mercaptosulfonyl + pyridinium salt in the comparative example 1 and the pyridinium salt in the comparative example 2, it can be seen that the electrolyte has a significant influence on the glossiness and the roughness of the product, which is ten times order of magnitude, and mainly the additive has a significant influence on the migration and diffusion of the generated oxidized particles in the electroplating solution. Comparative examples 3-4 are the same electrolyte, different electrolysis parameters, and if only direct current electrolysis is used, the polishing degree and the glossiness can not meet the requirements of low roughness and high metal luster in industry. The millisecond and microsecond pulse times of comparative example 3 were adjustable compared to directly pulsing, and by adjusting the time parameters of comparative example 3, a surface roughness effect consistent with example 2 was obtained. Although a high mirror effect can be obtained, the time consumption, the loss consumption, and the equipment load are significantly higher than those of embodiment 2 of the present invention.

Finally, it should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for treating metal by using a high-efficiency cleaning agent is characterized in that the cleaning agent consists of polyol, perchloric acid, polyalcohol amine, sulfydryl sulfonyl ionic compound and pyridinium salt compound;

the polyalcohol is one of dipropylene glycol, glycerol or butanediol,

the polyalcohol amine is one of diisopropanolamine, triisopropanolamine or triethanolamine

The mercapto sulfonyl ionic compound is one of thiazolinyl dithio propane sodium sulfonate, dimethyl dithio carbonyl propane sodium sulfonate and 3- (benzothiazole-2-mercapto) -propane sodium sulfonate;

the pyridinium salt compound is one of 1-ethyl-3-methylpyridinium bis (trifluoromethylsulfonyl) imide, 3- (4-tert-butyl 1-pyridyl) propanesulfonate or 3- (1-pyridyl) propanesulfonate;

taking the metal as an anode, taking the inert metal as a cathode and taking the cleaning agent as electrolyte, and applying a power supply between the metal anode and the inert metal cathode to clean the anode metal;

the cleaning process comprises the following steps:

(1) Starting a direct current power supply: the current density is 3-5A/cm ² Polishing for 5-7min at 20-25 deg.C and inter-polar distance of 15-20mm;

(3) Turning on a microsecond pulse power supply: the forward pulse current density is 1-2mA/cm ² The forward pulse width is 50-100 mus, the forward duty cycle is 10-15%, the pulse number is 10-15, the reverse pulse current density is 1-2mA/cm2, the reverse pulse width is 50-100 mus, the reverse duty cycle is 10-15%, the pulse number is1, the temperature is 13-15 ℃, and the time is 0.5-1min;

the method for treating metal with cleaning agent as claimed in claim 1, wherein the content of said polyhydric alcohol is 30-65vol.%, the content of perchloric acid is 3-5vol.%, the content of said polyalcohol amine is 10-15ml/L, the content of said mercapto sulfonyl ionic compound is 3-5g/L, and the content of said pyridinium salt compound is 1.5-3g/L.

2. The method for preparing a metal surface cleaning agent according to claim 1, wherein the metal is stainless steel, aluminum alloy or titanium alloy, preferably aluminum alloy.

3. The method for treating metal by using the efficient cleaning agent as claimed in claim 1, wherein the step (1) and the step (2) are carried out, and an intermittent step is arranged between the step (2) and the step (3): turning off the power supply, and turning on stirring at the speed of 200-300rpm and the temperature of 17-23 deg.C for 2-3min.

4. The method for treating metal by using the efficient cleaning agent as claimed in claim 1, wherein the step (3) is followed by post-treatment: turning off the power supply, washing with absolute ethyl alcohol, purging in inert atmosphere and drying.

5. The method for treating metal by using the efficient cleaning agent as claimed in claim 4, wherein the inert atmosphere is nitrogen or argon, the temperature is 35-40 ℃, and the time is 1-2 hours.