CN115449890A - Electrolytic stripping liquid for stripping nitride coating, electrolytic stripping method and application - Google Patents
Electrolytic stripping liquid for stripping nitride coating, electrolytic stripping method and application Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 38
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title claims description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002077 nanosphere Substances 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 25
- 229910000997 High-speed steel Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 9
- 229910010037 TiAlN Inorganic materials 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007733 ion plating Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000009991 scouring Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- -1 carboxylic ester salt Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 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
- C25F3/02—Etching
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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)
- ing And Chemical Polishing (AREA)
Abstract
The invention relates to an electrolytic stripping solution for stripping nitride coatings, an electrolytic stripping method and application. The electrolytic stripping liquid is used for electrochemical stripping, can effectively improve stripping efficiency, can ensure that current is uniformly distributed as much as possible, effectively reduces the defect generation rate of the surface of a workpiece, and obtains a high-quality surface.
Description
Technical Field
The invention relates to an electrolytic stripping liquid for stripping a nitride coating, an electrolytic stripping method and application, and belongs to the field of surface treatment.
Background
The service life of the metal cutter can be prolonged by coating a nitride coating on the surface of the metal cutter, the cutting edge and the coating on the surface of the cutting edge are worn after the cutter is used for a period of time, and the metal cutter can be used again only by polishing, recoating and recoating; stripping the original coating on the surface of the cutter to facilitate the next coating;
how to efficiently and stably peel a hard film from a substrate without damaging the substrate body as much as possible is a problem that needs to be faced in industrial mass production.
The existing stripping methods applied in large scale include chemical stripping and electrochemical stripping.
The chemical stripping has the advantages of good consistency for removing the surface coating of the special-shaped cutter shape, easy control of stripping strength and the like. The chemical stripping is that a cutter coating is subjected to a dissolution reaction by using a specific chemical solution, and the whole stripping process consumes a long time and has high requirements on reaction temperature due to the use of a pure soaking mode.
Electrochemical de-coating: the main technical characteristic of electrochemical de-coating is that the coating on the surface of the substrate is selectively dissolved (the coating is in an active dissolving area, and the substrate is in a stable and passive area) by applying a proper polarization potential in an electrolytic circuit due to the fact that the coating metal element and the substrate have different electrochemical characteristics.
In the conventional electrolytic stripping formula, in order to ensure the stripping efficiency, a large proportion of electrolyte is added into the formula, and higher electrolytic voltage and higher current density are applied. In this way, when the film layer is peeled off, overlarge current is locally generated, and irregularly distributed large-size depressions are generated on the surface of the substrate, so that the substrate is damaged.
The multilayer structure design of the nanometer multilayer nitride hard film is formed by alternately superposing a plurality of different nitride monolayers, so that the substrate is more easily damaged or the de-coating efficiency is low due to unreasonable de-coating process parameters in the de-coating process.
The Chinese invention patent application CN201010150010 discloses a stripping solution containing acid, an accelerator and a corrosion inhibitor, which is chemically stripped, and a workpiece is contacted with the stripping solution in a spraying and soaking mode to dissolve a titanium nitride film layer, wherein the method takes 0.5-2 hours, takes long time and has low efficiency.
Chinese patent application CN102234835a discloses an electrochemical stripping method for stripping titanium carbide by using two stripping solutions with different formulations, aiming at the difference of carbon content of titanium carbide coating at different thicknesses, which comprises preparing a stripping solution formulation containing hydroxides with different concentrations, a first stripping solution: 5-100 g/L sodium hydroxide; second stripping liquid: 50-300 g/L sodium hydroxide. The electrolytic strength is controlled, and the nondestructive removal of the matrix coating is realized; however, the process method adopts two times of electrolysis, and the operation is relatively time-consuming.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide an electrolytic stripping solution for stripping nitride coatings, so as to effectively strip nitride coatings and avoid the generation of surface defects of substrates as much as possible; the second purpose of the invention is to provide an electrolytic stripping method for stripping nitride coating; the invention also aims to provide the application of the nano carbon spheres in removing the nitride coating by an electrochemical de-coating method, and the nano carbon spheres are dispersed in the electrolyte.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the electrolytic stripping liquid for stripping the nitride coating comprises water-soluble hydroxide, a complexing agent, nano carbon spheres (CNBS), an anionic surfactant and water.
According to the invention, the nano carbon spheres are introduced into the electrolytic stripping solution and assisted with the anionic surfactant, so that the nano carbon spheres are uniformly and stably dispersed in the electrolytic stripping solution, specifically, under the action of the anionic surfactant, a layer of polar adsorption film completely wrapping spheres is formed on the surface of CNBS, the polarity of the surface of CNBS is increased, and the nano carbon spheres are far away from the nano carbon spheres due to electrostatic repulsion, so that a uniform and stable suspension system is formed. Therefore, on one hand, the conductivity of the electrolytic stripping solution can be effectively improved, the resistance of the electrolytic stripping solution is reduced, the current distribution in the electrolytic stripping solution is more uniform in the electrolytic stripping process, and the CNBS with electronegativity generates a certain enrichment effect in an anode reaction zone under the driving of an electric field; on the other hand, in the electrolytic stripping process, hard metal cations stripped from the surface of the workpiece react with anions in the electrolytic stripping liquid to form flocculent complexes, so that the electrolytic efficiency of the area is influenced.
Furthermore, the concentration of the nano carbon spheres is 1 to 25g/L, preferably 2 to 15g/L, and more preferably 2 to 8g/L.
Further, the concentration of the anionic surfactant is 1 to 50g/L, preferably 4 to 30g/L, and more preferably 4 to 16g/L.
Further, the particle size of the nano carbon spheres is 20-800nm, preferably 50-700nm, and more preferably 100-600nm.
Further, the carbon nanospheres are modified carbon nanospheres, the surfaces of the modified carbon nanospheres contain hydroxyl functional groups, and preferably, the content of the hydroxyl functional groups is more than or equal to 4wt%.
Further, the anionic surfactant is sodium dodecyl benzene sulfonate, sodium hexadecyl sulfonate and fatty alcohol polyether-n carboxylic ester salt, and is preferably sodium dodecyl benzene sulfonate.
Further, the concentration of the water-soluble hydroxide is 10 to 200g/L, preferably 50 to 200g/L.
Further, the concentration of the complexing agent is 10 to 100g/L, preferably 50 to 80g/L.
Preferably, the water-soluble hydroxide is a water-soluble alkali metal hydroxide, and the water-soluble alkali metal hydroxide comprises one or more of sodium hydroxide and potassium hydroxide.
Preferably, the complexing agent comprises one or more of monoethanolamine, sodium ethylene diamine tetracetate (ETDDA-4 Na) and tartaric acid, and more preferably, the complexing agent is one of sodium ethylene diamine tetracetate and tartaric acid.
Optionally, the nitride coating is a nitride coating on a cutting tool (e.g., a milling cutter, a band saw blade, etc.). Optionally, the base body of the tool is one or more of high-speed steel, stainless steel and alloy steel.
Optionally, the coating is a nitride single layer coating or a nano-multilayer nitride coating.
Optionally, the preparation method of the electrolytic stripping coating liquid comprises the following steps:
(1) Weighing quantitative deionized water according to the requirement, then sequentially adding the required CNBS and anionic surfactant into the deionized water, heating to 25-45 ℃, carrying out ultrasonic vibration for 15-45 minutes, and carrying out manual auxiliary stirring for 2-5 times, wherein each time lasts for 0.5-3min, so as to obtain uniformly and stably dispersed CNBS dispersion liquid;
(2) Adding a small amount of water-soluble hydroxide into the CNBS dispersion liquid for multiple times, and stirring until the water-soluble hydroxide is completely dissolved to obtain a mixed liquid;
(3) When the temperature of the mixed solution is cooled to below 60 ℃, weighing a quantitative complexing agent and stirring until the complexing agent is dissolved;
(4) And (4) using deionized water to fix the volume to a target volume to obtain the electrolytic stripping solution.
The electrolytic stripping method for removing the nitride coating is characterized in that the electrolytic stripping liquid is used as electrolyte, and electrochemical stripping treatment is carried out on a workpiece to be stripped of the nitride coating; preferably, the electrochemical de-coating treatment time is 1-15min.
Optionally, the electrolytic stripping solution is stirred during the electrochemical stripping treatment to enhance the scouring effect.
Optionally, when the electrochemical stripping treatment is carried out, the electrolytic stripping liquid is stirred clockwise; the workpiece is fixed on the anode, and the anode is controlled to rotate anticlockwise; to further enhance the scouring effect.
Optionally, the stirring speed of the electrolytic stripping liquid is 80-220r/min, and further 100-200r/min; the rotation speed of the workpiece is 20-55 r/min, and further 20-30r/min.
Optionally, when the electrochemical de-coating treatment is carried out, controlling the temperature of the electrolytic de-coating liquid to be 45-60 ℃; preferably, the control direct current voltage is 4-12V.
Optionally, when the electrochemical de-coating treatment is performed, the cathode plate is made of one of graphite and red copper; the anode is made of brass, and the surface of the anode is plated with a nickel layer with the thickness of 4-8 microns. Optionally, the anode and cathode have a pole separation of 10-30mm.
The application of the nano carbon spheres in removing the nitride coating by an electrochemical back-coating method disperses the nano carbon spheres in the electrolyte. Thus, the nitride coating can be removed uniformly and rapidly in the electrochemical stripping process, and the damage to the matrix is avoided.
Optionally, the nano carbon spheres have a particle size of 20-800nm, preferably 50-700nm, more preferably 100-600nm.
The electrolytic stripping liquid is used for electrochemical stripping, can effectively improve stripping efficiency, enables current to be distributed as uniformly as possible, effectively reduces the defect generation rate of the surface of a workpiece, and obtains a high-quality surface.
Drawings
FIG. 1 is an SEM image (a) and a TEM image (b) of a nanocarbon sphere of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. In each of the examples and comparative examples, the Carbon Nanospheres (CNBS) used were obtained from nying gikka nanotechnology co ltd and were manufactured in the following types: solid carbon spheres JCSC-99-550-COOH.
Example 1
A. Sample providing plated nitride coating
A polished surface of a sample (size 35 mm. Times.10 mm) of high speed steel (W2 Mo9Cr4VCo8, long An You titanium metal materials, inc., dongguan) was plated with a nitride coating layer having a thickness of 4.7 μm with a bonding layer of CrN and a functional layer of TiAlN as a sample using an arc ion plating apparatus (Shenyang Willd vacuum technology, inc.).
B. Providing electrolytic stripping coating liquid
The preparation method of the electrolytic stripping solution is shown in table 1.
TABLE 1
According to Table 2, 10L of the electrolytic stripping solution was prepared in accordance with Table 1 and used.
TABLE 2
| Name (R) | NaOH | ETDDA-4Na | DBS | CNBS | Deionized water |
| Concentration of | 115g/L | 60g/L | 8g/L | 4.0g/L | Allowance of |
C. Nitride coating removal
Putting the electrolytic stripping solution into an electrolytic bath, and heating and keeping the temperature at 45-60 ℃; fixing a sample on an anode (the anode is matched with a motor for driving the anode to rotate); starting an electrolysis stirring pump and a motor, wherein the stirring speed of the electrolysis stripping liquid is 100r/min; the rotation speed of the anode was 20r/min. Keeping the interelectrode potential at 4.5V/cm;
the electrolytic bath is characterized in that a bath body of the electrolytic bath is made of PP materials, and a quartz heating pipe is arranged on the side wall of the bath body and used for heating electrolyte; the tank body is internally provided with a cathode and an anode, and the distance between the cathode and the anode is 15mm. Surface observations were made every 80 s.
Through observation, after 400s, the TiAlN and CrN coatings on the sample block are completely removed, and the high-speed steel matrix body is exposed; no corrosion pits are found on the surface of the base material.
Comparative example 1
Example 1 was repeated with the only difference that: the concentration of DBS in the electrolytic stripping liquid is 0, namely DBS is not added.
After electrolytic stripping treatment for 400s, visual sampling observation shows that TiAlN and CrN coatings on the sample block are not completely stripped off, and the local part of the high-speed steel sample substrate is in black and gray; no corrosion pits are found on the surface of the base material; and further adding electrolysis de-coating treatment time for 160s, then sampling and observing, wherein local black and gray of the high-speed steel sample matrix disappears, but fine corrosion pits appear on the surface of the base material.
Comparative example 2
Example 1 was repeated with the only difference that: the concentration of CNBS in the electrolytic stripping liquid is 0, namely CNBS is not added.
After electrolytic stripping treatment for 400s, visual sampling observation shows that TiAlN and CrN coatings on the sample block are not completely stripped off, and the local part of the high-speed steel sample substrate is in black and gray; no corrosion pits are found on the surface of the base material; and further adding the electrolytic stripping treatment time for 320s, and then sampling and observing, wherein the local black and gray color of the matrix of the high-speed steel sample disappears, but the surface of the base material has corrosion pits.
Comparative example 3
Example 1 was repeated with the only difference that: stirring the electrolytic stripping solution at the speed of 0r/min; the rotating speed of the workpiece is 0r/min, namely the workpiece and the electrolyte do not move relatively.
After the electrolytic stripping treatment is carried out for 420s, visual sampling observation is carried out, the TiAlN and CrN coatings on the sample block are not completely stripped, and the local part of the high-speed steel sample substrate is in black and gray; no corrosion pits are found on the surface of the base material; and further adding electrolysis de-coating treatment time for 160s, then sampling and observing, wherein local black and gray of the high-speed steel sample matrix disappears, but fine corrosion pits appear on the surface of the base material.
Example 2
A. Sample providing plated nitride coating
A nitride coating with the thickness of 3.8 microns is coated on a polished surface of a sample (the size is 35mm multiplied by 10 mm) of high-speed steel (W2 Mo9Cr4VCo8, the length of the Dongguan is An You titanium metal material limited) by using an arc ion plating device (Shenyang Williard vacuum technology limited), a bonding layer of the nitride coating is TiAlN, a functional layer is prepared by alternately stacking and depositing the TiAlN and the CrAlN, and the modulation ratio is as follows: 1:2 with a modulation period of 9.6nm as a sample.
B. Providing electrolytic stripping coating liquid
10L of the electrolytic stripping solution was prepared in accordance with Table 3 and Table 1, and was used.
TABLE 3
| Name (R) | NaOH | ETDDA-4Na | DBS | CNBS | Deionized water |
| Concentration of | 130g/L | 48g/L | 6g/L | 3.0g/L | Balance of |
C. Nitride coating remover
Putting the electrolytic stripping solution into an electrolytic bath, and heating and keeping the temperature at 45-60 ℃; fixing a sample on an anode (the anode is matched with a motor for driving the anode to rotate); starting the electrolytic stirring pump and the motor, wherein the stirring speed of the electrolytic stripping liquid is 100r/min, and the rotation speed of the anode is 20r/min. Keeping the interelectrode potential at 5.4V/cm and the reaction time at 280s;
the electrolytic bath is characterized in that a bath body of the electrolytic bath is made of PP materials, and a quartz heating pipe is arranged on the side wall of the bath body and used for heating electrolyte; the tank body is internally provided with a cathode and an anode, and the distance between the cathode and the anode is 15mm.
Through observation, the TiAlN and CrAlN coatings on the sample block are completely removed, and the high-speed steel matrix body is exposed; no corrosion pits are found on the surface of the base material.
Example 3
A. Sample providing plated nitride coating
A nitride coating with a thickness of 5.2 microns was plated on a polished surface of a sample (size 35mm x 10 mm) of high speed steel (W2 Mo9Cr4VCo8, length An You titanium metal materials, inc., dongguan) with an arc ion plating apparatus (Shenyang Williade vacuum technology, inc.), the bonding layer of the nitride coating was CrAlN, the functional layer was AlCrBN and CrAlN alternately stacked and deposited, and the modulation ratio was: 1:1 with a modulation period of 12.1nm, was used as a sample.
B. Providing electrolytic stripping coating liquid
10L of the electrolytic stripping solution was prepared in accordance with Table 4 and Table 1, and was used.
TABLE 4
| Name (R) | NaOH | ETDDA-4Na | DBS | CNBS | Deionized water |
| Concentration of | 170g/L | 48g/L | 5g/L | 2.5g/L | Balance of |
C. Nitride coating removal
Putting the electrolytic stripping solution into an electrolytic bath, and heating and preserving the temperature to be between 45 and 60 ℃; fixing a sample on an anode (the anode is matched with a motor for driving the anode to rotate); starting an electrolytic stirring pump and a motor, wherein the stirring speed of the electrolytic stripping liquid is 100r/min; the rotation speed of the anode was 20r/min. Keeping the interelectrode potential at 6V/cm and the reaction time at 380s;
the electrolytic cell is characterized in that a cell body of the electrolytic cell is made of PP materials, and a quartz heating pipe is arranged on the side wall of the cell body and used for heating electrolyte; the tank body is internally provided with a cathode and an anode, and the distance between the cathode and the anode is 25mm.
Observing, completely removing the AlCrBN and CrAlN coatings on the sample block, and exposing a high-speed steel matrix body; no corrosion pits are found on the surface of the base material.
Example 4
A. Sample providing plated nitride coating
A polished surface of high speed steel (W2 Mo9Cr4VCo8, long An You titanium materials of Dongguan, ltd.) (sample size 35mm x 10 mm) was coated with a nitride coating having a thickness of 3.4 μm, which was prepared by alternately stacking and depositing a bonding layer of AlTiN and a functional layer of AlTiN and AlCrSiN in a modulation ratio of: 3:1 with a modulation period of 11.6nm, as a sample.
B. Providing electrolytic stripping coating liquid
10L of the electrolytic stripping solution was prepared in accordance with Table 5 and Table 1, and was used.
TABLE 5
| Name (R) | NaOH | ETDDA-4Na | DBS | CNBS | Deionized water |
| Concentration of | 170g/L | 48g/L | 4g/L | 2g/L | Balance of |
C. Nitride coating removal
Putting the electrolytic stripping solution into an electrolytic bath, and heating and keeping the temperature at 45-60 ℃; fixing a sample on an anode (the anode is matched with a motor for driving the anode to rotate); starting an electrolysis stirring pump and a motor, wherein the stirring speed of the electrolysis stripping liquid is 100r/min; the autorotation speed of the anode is 20r/min, the interpolar potential is kept at 6V/cm, and the reaction time is 440s;
the electrolytic bath is characterized in that a bath body of the electrolytic bath is made of PP materials, and a quartz heating pipe is arranged on the side wall of the bath body and used for heating electrolyte; the tank body is internally provided with a cathode and an anode, and the distance between the cathode and the anode is 20mm.
Through observation, the AlTiN and AlCrSiN coatings on the sample block are completely removed, and the high-speed steel matrix body is exposed; no corrosion pits are found on the surface of the base material.
In conclusion, the electrolytic stripping solution can be used for efficiently removing the multi-element (Al, cr, si, ti, B and other elements) nitride hard film on the surface of a high-speed steel workpiece, and the removing process is relatively uniform and stable without generating corrosion pits.
The foregoing examples are set forth to illustrate the present invention more clearly and are not to be construed as limiting the scope of the invention, which is defined in the appended claims to which the invention pertains, as modified in all equivalent forms, by those skilled in the art after reading the present invention.
Claims (9)
1. The electrolytic stripping liquid for stripping the nitride coating is characterized by comprising water-soluble hydroxide, a complexing agent, nano carbon spheres, an anionic surfactant and water.
2. The electrolytic stripping solution as claimed in claim 1, wherein the concentration of the carbon nanospheres is 1 to 25g/L, preferably 2 to 15g/L, and more preferably 2 to 8g/L.
3. The electrolytic stripping solution according to claim 1, wherein the concentration of the anionic surfactant is 1 to 50g/L, preferably 4 to 30g/L, and more preferably 4 to 16g/L.
4. The electrolytic stripping solution according to any one of claims 1 to 3, wherein the nano carbon spheres have a particle size of 20 to 800nm, preferably 50 to 700nm, more preferably 100 to 600nm.
5. The electrolytic stripping solution as claimed in any one of claims 1 to 3, wherein the nanocarbon spheres are modified nanocarbon spheres, the surfaces of the modified nanocarbon spheres contain hydroxyl functional groups, and preferably, the content of the hydroxyl functional groups is more than or equal to 4wt%.
6. Electrolytic stripping solution according to any of claims 1 to 3, characterized in that the anionic surfactant is sodium dodecylbenzene sulfonate, sodium hexadecyl sulfonate, fatty alcohol polyether-n-carboxylate, preferably sodium dodecylbenzene sulfonate.
7. The electrolytic stripping solution according to any one of claims 1 to 3, characterized in that the concentration of the water-soluble hydroxide is 10 to 200g/L, preferably 50 to 200g/L; the concentration of the complexing agent is 10-100 g/L, preferably 50-80 g/L; preferably, the water-soluble hydroxide is a water-soluble alkali metal hydroxide, and the water-soluble alkali metal hydroxide comprises one or more of sodium hydroxide and potassium hydroxide; preferably, the complexing agent comprises one or more of monoethanolamine, sodium ethylene diamine tetracetate and tartaric acid.
8. An electrolytic stripping method for removing nitride coatings, which is characterized in that the electrolytic stripping liquid as claimed in any one of claims 1 to 7 is used as an electrolyte, and the workpiece to be stripped is subjected to electrochemical stripping treatment; preferably, the electrochemical de-coating treatment time is 1-15min; preferably, the electrolyte is stirred during the electrochemical stripping treatment.
9. The application of the nano carbon spheres in removing the nitride coating by an electrochemical back-coating method is characterized in that the nano carbon spheres are dispersed in electrolyte; preferably, the nano carbon spheres have a particle size of 20-800nm.
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| CN202211151079.9A CN115449890A (en) | 2022-09-21 | 2022-09-21 | Electrolytic stripping liquid for stripping nitride coating, electrolytic stripping method and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211151079.9A CN115449890A (en) | 2022-09-21 | 2022-09-21 | Electrolytic stripping liquid for stripping nitride coating, electrolytic stripping method and application |
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