CN108360028B - Ni/ZrO preparation by using double pulses2Method for preparing binary gradient functional material - Google Patents

Ni/ZrO preparation by using double pulses2Method for preparing binary gradient functional material Download PDF

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CN108360028B
CN108360028B CN201810156833.5A CN201810156833A CN108360028B CN 108360028 B CN108360028 B CN 108360028B CN 201810156833 A CN201810156833 A CN 201810156833A CN 108360028 B CN108360028 B CN 108360028B
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zro
double
copper sheet
copper substrate
electrolyte
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CN108360028A (en
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葛文
李佳梅
靳一帆
周玉杰
周飞杨
梅思雨
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China University of Geosciences
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/562Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18Electroplating using modulated, pulsed or reversing current
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces

Abstract

The invention discloses a method for preparing Ni/ZrO by utilizing double pulses2The method of the binary gradient functional material comprises the steps of preparing electrolyte, pretreating a copper substrate to obtain a copper sheet to be plated, and sealing one surface of the copper sheet; taking a copper sheet as a cathode, taking a nickel plate as an anode, connecting the cathode and the anode with a double-pulse power supply, putting the copper sheet into a plating tank, wherein the unsealed surface of the copper sheet is opposite to the nickel plate, adding the electrolyte prepared in the step S1 into the plating tank, and controlling the temperature of the electrolyte to be 40 ℃ and the pH value to be 4 +/-0.1; starting a double-pulse power supply and setting electrodeposition; post-processing to obtain Ni/ZrO2A binary gradient functional material. The preparation method is simple, low in cost, low in pollution and suitable for large-scale and large-scale production; Ni/ZrO produced by the invention2The binary gradient functional material is flat, corrosion resistant, small in crystal grain, uniform and compact in surface.

Description

Ni/ZrO preparation by using double pulses2Method for preparing binary gradient functional material
Technical Field
The invention relates to the technical field of functional materials, in particular to a method for utilizingDouble-pulse preparation of Ni/ZrO2A method of binary gradient functional material.
Background
Metal corrosion is a spontaneous, ubiquitous phenomenon in nature. The corrosion of metal materials is widely existed in various fields, the loss caused by the corrosion is very large, particularly in a damp and hot marine environment, steel is easy to be corroded by salt fog, tide and the like, serious electrochemical corrosion is generated, huge economic loss can be caused, safety accidents are more easily caused, and the rigorous requirements of material use in special environments are continuously improved due to the vigorous development of modern scientific and industrial technologies such as aviation, energy, navigation and the like. The mechanical strength, heat resistance, durability and service life of common ceramic, metal and composite materials are difficult to meet the requirements, and functionally graded materials are produced at the same time.
At present, the preparation methods of the functional gradient material mainly comprise a vapor deposition method (PVD, CVD), a plasma spraying method, a powder metallurgy method, a self-propagating high-temperature combustion synthesis method, an electrodeposition method and the like, but each method has inevitable defects. The vapor deposition method can prepare a large-size sample, but the synthesis rate is low, the thickness of the prepared material is low, and the requirement on equipment is high; the physical vapor deposition method has low deposition rate and the distribution of the material can not be continuously controlled; the temperature of the powder metallurgy method is high, not only energy is consumed, but also the material structure and the component gradient have the defects of non-uniformity and difficult control; the self-propagating high-temperature combustion synthesis method has high production efficiency, low investment and high product purity, but has complex preparation conditions, high temperature and easy splashing, in addition, large-scale production cannot be carried out in many preparation modes due to overhigh cost, heavy pollution and the like, and the functionally graded material still cannot generally enter the lives of people.
Disclosure of Invention
In view of the above, the embodiment of the invention provides a method for preparing Ni/ZrO with flatness, corrosion resistance, small crystal grains, uniform and compact surface by using double pulses2A method of binary gradient functional material.
Embodiments of the present invention provide a method for utilizing double pulsesPreparation of Ni/ZrO2A method of binary gradient functional materials comprising the steps of:
s1, preparing electrolyte and selecting NiSO4·6H2O and NiCl2·6H2O as main salt ion electrolyte, NaCl and Na2SO4As supporting electrolyte, H3BO3And HCOONa as a buffer, saccharin as an additive, and ZrO added2
S2, preprocessing a copper substrate to obtain a copper sheet to be plated, and sealing one surface of the copper sheet;
s3, taking the copper sheet processed in the step S2 as a cathode, taking a nickel plate as an anode, connecting the cathode and the anode with a double-pulse power supply, putting the copper sheet into a plating bath, wherein the unclosed surface of the copper sheet is opposite to the nickel plate, adding the electrolyte prepared in the step S1 into the plating bath, and the temperature and the pH value of the electrolyte are respectively 4 +/-0.1 and 40 ℃;
s4, starting the double-pulse power supply, setting parameters of the double-pulse power supply to carry out electrodeposition, and stirring electroplating liquid in the electrodeposition process;
s5, post-treating the copper sheet after electrodeposition to obtain Ni/ZrO2A binary gradient functional material.
Further, in the step S1, NiSO4·6H2O is 280g/L, NiCl2·6H2O is 40g/L, H3BO330g/L, saccharin 0.5g/L, ZrO2The amount of (B) is 5 g/L.
Further, in step S2, the specific method of the copper substrate pretreatment is:
s1.1, firstly, polishing a copper substrate by using coarse abrasive paper, then polishing the copper substrate by using fine abrasive paper, and polishing and washing the copper substrate along the same direction;
s1.2, deoiling and washing the copper substrate;
s1.3, carrying out strong etching on the copper substrate, and washing;
s1.4, neutralizing and washing the copper substrate;
s1.5, carrying out weak etching on the copper substrate and washing.
Further, 70g/L of sodium hydroxide, 70g/L of sodium carbonate, 30g/L of trisodium phosphate and 4mL/L of detergent OP-10 are selected for oil removal, the temperature is 70-90 ℃, and the time is 20-30 min; the strong etching is performed by using 90% concentrated hydrochloric acid, 4g/L urotropine and 10% deionized water at room temperature for 50 s; the neutralization treatment is carried out for 10s by using 40g/L sodium carbonate, and the weak etching is carried out for 5-10 s by using 20mL of 1.84g/L sulfuric acid.
Further, in step S4, the parameters of the double pulse power supply are: forward duty ratio of 10-80% and forward current density of 1-2.5 A.dm-2The current density of the current is 1/10, and the forward working time and the reverse working time are 12 ms.
Compared with the prior art, the preparation method is simple, low in cost, small in pollution and suitable for large-scale and large-scale production; Ni/ZrO produced by the invention2The binary gradient functional material is flat, corrosion resistant, small in crystal grain, uniform and compact in surface.
Drawings
FIG. 1 shows a method for preparing Ni/ZrO by using double pulses2A schematic diagram of an apparatus used in a method for binary gradient functional materials.
FIG. 2 shows a method for preparing Ni/ZrO by using double pulses2A flow chart of a method for binary gradient functional materials.
FIG. 3 shows Ni/ZrO obtained by different forward duty ratios, forward current densities, forward periods, reverse duty ratios and reverse periods in the embodiment of the present invention2XRD spectrum of the binary gradient functional material.
FIG. 4 shows different concentrations of ZrO in examples of the present invention2Preparation of the electroplating solution to obtain Ni/ZrO2XRD spectrum of the binary gradient functional material.
FIG. 5 is a structural diagram of XRD measurement after 400 ℃ hot corrosion in an example of the present invention.
FIG. 6 is a structural diagram of XRD measurement after 500 ℃ hot corrosion in an example of the present invention.
FIG. 7 is a structural diagram of XRD measurement after 600 ℃ high temperature corrosion in an example of the present invention.
FIG. 8 shows different ZrO layers in examples of the present invention2Addition of Ni/ZrO2Tafel polarization curve of functionally graded coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.
Example 1
The embodiment of the invention provides a method for preparing Ni/ZrO by using double pulses2A method of binary gradient functional material.
The invention uses a double-pulse electrodeposition device, as shown in figure 1, comprising an electrolytic tank 1, wherein the electrolytic tank 1 is a cuboid made of glass, the electrolytic tank 1 is arranged in a constant-temperature water tank 2, electrolyte is arranged in the electrolytic tank 1, a cathode electrode 3, an anode electrode 4 and an electric stirrer 6 are arranged in the electrolyte, the cathode electrode 3 and the anode electrode 4 are connected with a double-pulse power supply 5, and the electric stirrer 6 is positioned in the middle of the electrolytic tank 1. The double-pulse power supply 5 is responsible for providing rectangular wave type double-pulse current, the electric stirrer 6 controls the stirring speed in the reaction process, and the constant-temperature water tank 2 controls the temperature of the electrolyte.
Referring to fig. 2, the method specifically includes the following steps:
s1, preparing electrolyte and selecting NiSO4·6H2O and NiCl2·6H2O as main salt ion electrolyte, NaCl and Na2SO4As supporting electrolyte, H3BO3And HCOONa as a buffer, saccharin as an additive, and ZrO added2
Preferably, NiSO4·6H2O is 280g/L, NiCl2·6H2O is 40g/L, H3BO330g/L, sodium dodecyl sulfate 0.1g/L, saccharin 0.5g/L, ZrO2The amount of (B) is 0-40g/L, and 0g/L is not selected.
S2, pretreating a copper substrate to obtain a copper sheet to be plated, and specifically:
s1.1, firstly, polishing a copper substrate by using coarse abrasive paper, then polishing the copper substrate by using fine abrasive paper, and polishing and washing the copper substrate along the same direction;
s1.2, degreasing the copper substrate, namely selecting 70g/L of sodium hydroxide, 70g/L of sodium carbonate, 30g/L of trisodium phosphate and 4mL/L of detergent OP-10, wherein the temperature is 70-90 ℃, and the time is 20-30 min; washing;
s1.3, carrying out strong etching on a copper substrate, selecting 90% concentrated hydrochloric acid, 4g/L urotropine and 10% deionized water, and keeping the temperature at room temperature for 50 s; washing;
s1.4, neutralizing the copper substrate, selecting 40g/L sodium carbonate for 10s, and washing;
s1.5, carrying out weak etching on the copper substrate, and washing with 20mL of 1.84g/L sulfuric acid for 5-10 s.
Sealing one surface of the pretreated copper sheet, and sticking the surface by using an adhesive tape;
s3, taking the copper sheet processed in the step S2 as a cathode, taking a nickel plate as an anode, connecting the cathode and the anode with a double-pulse power supply, putting the copper sheet into a plating bath, controlling the unclosed surface of the copper sheet to be opposite to the nickel plate, adding the electrolyte prepared in the step S1 into the plating bath, and controlling the temperature of the electrolyte to be 40 ℃ through a constant-temperature water tank, wherein the pH value of the electrolyte is 4 +/-0.1;
s4, starting the double-pulse power supply, setting parameters of the double-pulse power supply for electrodeposition, wherein the parameters of the double-pulse power supply are preferably as follows: forward duty ratio of 10-80% and forward current density of 1-2.5 A.dm-2Forward period is 2-8ms, reverse duty ratio is 20-80%, reverse period is 1-4ms, reverse current density is 1/10 of the forward current density, forward working time and reverse working time are 12ms, electroplating solution is stirred in the electrodeposition process, and stirring speed in the reaction process is controlled to be 300r/min through an electric stirrer 6;
s5, post-treating the copper sheet after electrodeposition to obtain Ni/ZrO2A binary gradient functional material.
Designing an orthogonal test of double-pulse parameters, selecting five factors of a forward duty ratio, a forward current density, a forward period, a reverse duty ratio and a reverse period, and designing an orthogonal experimental table L by taking four horizontal values for each factor as shown in figure 316(45) Orthogonal experiments were performed, with the factors and levels of the orthogonal experimental design shown in Table 1 and the double pulse parameters shown in Table 2Orthogonal test table, the same parameters are selected for the rest.
TABLE 1
TABLE 2
1. For the prepared Ni/ZrO2Structural representation and corrosion resistance test of binary gradient functional material coating, and prepared Ni/ZrO2The plating layers of the binary gradient functional materials are all of face-centered cubic structures (fcc), the main crystal planes are oriented to (111) and (200), and the orientation advantage of the (200) plane is more obvious; the Scherrer formula is used for calculating the grain sizes of different crystal face orientations of the crystal face, and the double-pulse parameter pair nano Ni/ZrO is discussed2The influence of the coating organization structure of the binary gradient functional material, in order to obtain crystal grains with smaller grain size, the optimal parameters of the double-pulse power supply are as follows: positive duty cycle gamma+20%, reverse duty cycle gamma-60%, forward current density J+1.0A/dm2Reverse period T-3ms, forward period T+4 ms; by range analysis, with Ni/ZrO2The average grain size of the binary gradient functional material coating is used as a judgment index to obtain five parameter pairs of Ni/ZrO of the double-pulse electroplating power supply2The order of influence of the grain size of the functionally graded coating is: forward duty cycle > reverse duty cycle > forward current density > reverse period > forward period.
2. Investigation of the addition of ZrO at different concentrations2Preparation of Ni/ZrO from the electroplating solution2And (3) selecting the same parameters for the rest of the functionally graded coating samples, and determining the tissue structure of the samples by XRD (X-ray diffraction) and discussing the change rule of the tissue structure of the coating as shown in figure 4: from reducing composite electroplated layer grain sizeFrom the aspect of inches, the higher the composite amount of the nanoparticles is, the better the composite amount is, but (as the addition amount of zirconia is increased, Ni/ZrO2The grain size of the functionally graded coating tends to decrease and then increase); Ni/ZrO2The functional gradient coating has fine crystal grains and nano ZrO2The characteristics of uniform particle distribution and the like all contribute to the improvement of the corrosion resistance of the plating layer, as shown in table 3.
TABLE 3
3. After studying different high-temperature corrosion temperatures (400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃) for continuous high temperature 12h, the structure of the high-temperature corrosion is measured by XRD, and the Ni/ZrO of different high-temperature corrosion temperature pairs is discussed2The effect of the texture of the functionally graded coating, as shown in FIGS. 5-7 and tables 4-6, Table 4 is Ni/ZrO after oxidation at 400 deg.C2Grain size of functionally graded coating, Ni/ZrO after 500 ℃ Oxidation, Table 52Grain size of functionally graded coatings, Ni/ZrO after 600 ℃ Oxidation, Table 62Grain size of functionally graded coating.
TABLE 4
TABLE 5
TABLE 6
After high-temperature oxidation at 400, 500 and 600 ℃, the preferred orientation planes of the plating layer are (111) and (200), and the orientation advantage of the (200) plane is more obvious. Ni/ZrO after high temperature2Ni/ZrO grain size of functionally graded coating at general ratio to normal temperature2The grain size of the functionally graded coating is large and with increasing temperature, Ni/ZrO2The average grain size of the functionally graded coating is gradually increased; grain size ratio Ni/ZrO of pure nickel coating2The grain size of the functionally gradient coating is large. Ni/ZrO with increasing zirconia addition2The grain size of the functionally graded coating tends to decrease first and then increase. After high-temperature oxidation at 400, 500 and 600 ℃, the addition amount of zirconia is 30g/L, namely Ni/ZrO2The average grain size of the functionally graded coating was the smallest, 24.9, 25.45 and 26.05nm, respectively. After the pure nickel coating is oxidized at the high temperature of 700 ℃, no obvious crystal face orientation exists, and Ni/ZrO2The preferred orientation planes of the functionally gradient coating are (111) plane and (200) plane, and the orientation advantage of the (200) plane is more obvious. After 800 deg.C, the pure nickel coating is oxidized into NiO, Ni/ZrO2Although the functional gradient plating layer also has NiO characteristic peaks, the preferred orientation planes of the plating layer are (111) and (200), and the orientation advantage of the (200) plane is more obvious. Average grain size change following nano ZrO at high temperature2The compounding amount of the particles is firstly reduced and then increased, which is in line with the analysis of the compounding amount of the nano particles in the composite electroplated layer at normal temperature. When nano ZrO2The addition amount of the particles is too high, and agglomeration is generated among nano particles, so that Ni/ZrO is generated2The functionally graded coating has a loose structure, low high-temperature corrosion resistance and high-temperature oxidation tendency, so that the grain size is larger at high temperature than at normal temperature.
4. ZrO with different concentrations is added by adopting muffle furnace high-temperature test to measure2Ni/ZrO of2The high-temperature corrosion resistance of the functionally graded coating is characterized in that the surface appearance of the coating before and after corrosion is observed by adopting SEM: Ni/ZrO before high temperature corrosion2The flatness of the functional gradient coating is superior to that of a pure Ni coating, even the flatness is enlarged by 3000 timesUnder the condition, the pure nickel Ni coating is still flat and has no obvious defects, and after high-temperature corrosion, the pure nickel Ni coating firstly generates local cavitation along with the temperature rise, and is finally completely oxidized, the structure is loose, and different ZrO layers are formed2Addition of Ni/ZrO2The Tafel polarization curve of the functionally graded coating is shown in FIG. 8.
Ni/ZrO preparation by double-pulse electrodeposition method2Coating of binary gradient functional material, gradient direction ZrO2The content of (A) is gradually increased from 0 to 34.99 percent (mass fraction); the addition of zirconium oxide can make Ni/ZrO2The plating layer is more smooth, and the corrosion resistance is greatly improved; Ni/ZrO prepared by double pulse electrodeposition under the same process parameters2Compared with a pure nickel plating layer, the functionally graded plating layer has the advantages of finer crystal grains, more uniform and compact surface of the plating layer and greatly improved corrosion resistance.
Example 2
The present embodiment differs from embodiment 1 only in that the parameters of the double pulse power supply are: average current density in forward direction of 1A/dm2The forward duty cycle is 40%, the forward operation time is 12ms, the reverse duty cycle is 60%, and the reverse operation time is 12ms, the rest is basically the same as that of the embodiment 1
Scanning the prepared material by an electron microscope, and observing the dark color and compact structure close to the copper sheet through the section appearance; near the surface of the coating, the color is brighter, the holes are larger, and ZrO is2The particle distribution becomes gradually dense from top to bottom. The results of the Scanning Electron Microscope (SEM) section morphology, section element distribution diagram and EDS (electron-beam spectroscopy) component analysis of the section A, B and C point are combined to judge that the ZrO content of 0-34.99% can be prepared by the double-pulse electrodeposition method2Ni/ZrO of2And (4) functionally gradient coating.
Example 3
This example differs from example 1 only in that ZrO2The addition amount of (A) is 5g/L, and the parameters of the double-pulse power supply are as follows: forward duty ratio of 10% and forward current density of 1A dm-2Forward cycle 3ms, reverse duty cycle 20%, reverse cycle 1ms, and the remainder is substantially the same as in embodiment 1.
Example 4
The present example is different from example 1 only in that the amount of zirconia added was 30g/L, and the rest was substantially the same as example 1.
The preparation method is simple, low in cost, low in pollution and suitable for large-scale and large-scale production; Ni/ZrO produced by the invention2The binary gradient functional material is flat, corrosion resistant, small in crystal grain, uniform and compact in surface.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (3)

1. Ni/ZrO preparation by using double pulses2The method for preparing the binary gradient functional material is characterized by comprising the following steps of:
s1, preparing electrolyte and selecting NiSO4·6H2O and NiCl2·6H2O as main salt ion electrolyte, NaCl and Na2SO4As supporting electrolyte, H3BO3And HCOONa as a buffer, saccharin as an additive, and ZrO added2Wherein, NiSO4·6H2O is 280g/L, NiCl2·6H2O is 40g/L, H3BO330g/L, saccharin 0.5g/L, ZrO2The addition amount of (A) is 30 g/L;
s2, preprocessing a copper substrate to obtain a copper sheet to be plated, and sealing one surface of the copper sheet;
s3, taking the copper sheet processed in the step S2 as a cathode, taking a nickel plate as an anode, connecting the cathode and the anode with a double-pulse power supply, putting the copper sheet into a plating bath, wherein the unclosed surface of the copper sheet is opposite to the nickel plate, adding the electrolyte prepared in the step S1 into the plating bath, and the temperature and the pH value of the electrolyte are respectively 4 +/-0.1 and 40 ℃;
s4, starting the double-pulse power supply, setting parameters of the double-pulse power supply to carry out electrodeposition, and stirring electroplating solution in the electrodeposition processThe parameters are as follows: forward duty ratio of 20% and forward current density of 1A dm2The forward period is 4ms, the reverse duty ratio is 60%, the reverse period is 3ms, the reverse current density is 1/10 of the forward current density, and the forward working time and the reverse working time are 12 ms;
s5, post-treating the copper sheet after electrodeposition to obtain Ni/ZrO2A binary gradient functional material.
2. Ni/ZrO production by means of double pulses according to claim 12The method for preparing the binary gradient functional material is characterized in that in the step S2, the concrete method for preprocessing the copper substrate is as follows:
s1.1, firstly, polishing a copper substrate by using coarse abrasive paper, then polishing the copper substrate by using fine abrasive paper, and polishing and washing the copper substrate along the same direction;
s1.2, deoiling and washing the copper substrate;
s1.3, carrying out strong etching on the copper substrate, and washing;
s1.4, neutralizing and washing the copper substrate;
s1.5, carrying out weak etching on the copper substrate and washing.
3. Ni/ZrO production by means of double pulses according to claim 22The method for preparing the binary gradient functional material is characterized in that 70g/L of sodium hydroxide, 70g/L of sodium carbonate, 30g/L of trisodium phosphate and 4mL/L of detergent OP-10 are selected for oil removal, the temperature is 70-90 ℃, and the time is 20-30 min; the strong etching is performed by using 90% concentrated hydrochloric acid, 4g/L urotropine and 10% deionized water at room temperature for 50 s; the neutralization treatment is carried out for 10s by using 40g/L sodium carbonate, and the weak etching is carried out for 5-10 s by using 20mL of 1.84g/L sulfuric acid.
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