CN217351575U - Coating structure of neodymium iron boron zinc-plating chromium-free passivation - Google Patents
Coating structure of neodymium iron boron zinc-plating chromium-free passivation Download PDFInfo
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- CN217351575U CN217351575U CN202220539370.2U CN202220539370U CN217351575U CN 217351575 U CN217351575 U CN 217351575U CN 202220539370 U CN202220539370 U CN 202220539370U CN 217351575 U CN217351575 U CN 217351575U
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Abstract
The utility model discloses a coating structure of neodymium iron boron zinc-plating chromium-free passivation, including the neodymium iron boron base member and the citrate nickel precoating layer, pyrophosphate copperite layer, galvanizing coat and the silane chromium-free passivation layer of preparing in proper order from inside to outside on the neodymium iron boron base member. The utility model discloses a neodymium iron boron zinc-plating does not have cladding material structure of chromium passivation carries out neutral salt fog test 240h according to GB/T10125 and adds 2012 "artificial atmosphere corrosion test salt fog test" and plates a surface and do not have white corrosive substance and generate. The plating layer structure has the advantages of environment-friendly preparation process and good corrosion resistance.
Description
Technical Field
The utility model belongs to the technical field of metal surface treatment, concretely relates to neodymium iron boron zinc-plating does not have cladding material structure of chromium passivation.
Background
Neodymium iron boron materials have been widely used for preparing high magnetic magnets. The surface of the neodymium iron boron substrate is porous, and the material has high chemical activity. In the prior art, protective layers such as a zinc coating, a nickel coating, a copper-nickel-chromium combined coating, a nickel-copper-nickel combined coating and the like are prepared on the surface of neodymium iron boron, but the coatings cannot effectively protect the neodymium iron boron matrix from being corroded. At present, after the neodymium iron boron magnets sold in the market are placed indoors for two years, the phenomena of pitting corrosion, bubbling and even coating falling can occur on the surfaces of some products.
Disclosure of Invention
In order to solve the problem that the corrosion resistance of the neodymium iron boron plated part is poor, the utility model provides a plating layer structure of neodymium iron boron zinc plating chromium-free passivation. In order to achieve the purpose, the utility model adopts the following technical scheme:
a neodymium iron boron zinc plating chromium-free passivation coating structure comprises a neodymium iron boron base body, and a citrate pre-nickel plating layer, a pyrophosphate copper plating layer, a zinc coating and a silane chromium-free passivation layer which are sequentially prepared from inside to outside on the neodymium iron boron base body;
the silane chromium-free passivation layer is prepared by adopting a solvent type silane chromium-free passivator.
Preferably, the thickness of the silane chromium-free passivation layer is 0.6-1.2 mu m.
Preferably, the thickness of the citrate pre-plated nickel layer is 1-10 μm.
Preferably, the pyrophosphate copper plating layer has a thickness of 5 to 12 μm.
Preferably, the thickness of the zinc coating is 5-15 μm.
The surface of the neodymium iron boron substrate has more pores, the substrate is directly galvanized, and the plating solution can be immersed into the pores on the surface of the substrate. When the acid galvanizing process is adopted for galvanizing, the acid galvanizing solution can slowly corrode the substrate and the plating layer, and finally, bubbling or pitting corrosion occurs at the position of a pore. When the alkaline galvanizing process is adopted for galvanizing, the alkaline plating solution can corrode a galvanizing layer, so that pitting corrosion occurs at the positions of pores. The utility model discloses a nickel coating is preplated in citrate nickel plating technology preparation, and neutral citrate nickel plating solution is very little to the corrosive action of neodymium iron boron base member and galvanizing coat, can not destroy base member and cladding material. The citrate nickel plating solution has higher deep plating capability, and the adoption of the citrate nickel plating process for pre-plating nickel is also beneficial to hole sealing of the neodymium iron boron matrix. Pyrophosphate copper plating is carried out on the pre-plated nickel layer, and then zinc plating is carried out, so that higher binding force can be formed among the plating layers. The pyrophosphate copper plating layer is galvanized, the galvanized layer is an anode plating layer, a higher potential difference exists between the two plating layers, and the pyrophosphate copper plating layer can effectively prevent corrosive media from corroding towards the direction of the substrate.
Compared with the prior art, the utility model discloses following beneficial effect has:
1. the utility model discloses a neodymium iron boron zinc plating chromium-free passivation coating structure, which can effectively overcome the technical defects that a zinc coating prepared on the surface of a neodymium iron boron matrix in the prior art is easy to blister and has point corrosion;
2. the zinc coating is passivated by adopting the silane chromium-free passivation process, so that the zinc coating is green and environment-friendly;
3. the utility model adopts the silane chromium-free passivation technology to passivate the zinc coating, and the corrosion resistance of the zinc coating is higher than that of the prior trivalent chromium passivation technology.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, do not constitute a limitation of the invention, and in which:
FIG. 1 is a schematic diagram of the structure of the plating layer in examples 1, 2 and 3 of the present invention.
Detailed Description
The invention will be described in detail with reference to the drawings and specific embodiments, which are used to explain the invention, but not as a limitation thereof.
The utility model provides a coating structure of neodymium iron boron galvanizing chromium-free passivation, includes the neodymium iron boron base member and citrate pre-nickel plating layer, pyrophosphate copper plating layer, galvanizing coat and the silane chromium-free passivation layer of preparing from inside to outside in proper order on the neodymium iron boron base member.
Carrying out oil removal, rust removal and activation treatment on a neodymium iron boron workpiece substrate according to the existing pretreatment process, and then sequentially preparing a citrate pre-plated nickel layer, a pyrophosphate copper-plated layer, a zinc-plated layer and a silane chromium-free passivation layer.
The thickness of the citrate pre-plated nickel layer is 1-10 mu m, and the citrate pre-plated nickel layer is prepared by adopting the existing citrate nickel plating process.
Preferably, the citrate nickel plating process comprises the following steps: 180-250 g/L nickel sulfate hexahydrate, 10-12 g/L sodium chloride, 30-35 g/L boric acid, 30-40 g/L magnesium sulfate, 7.0-7.2 of pH value, 50-60 ℃ of temperature and 1-1.5A/cm of cathode current density 2 The yin movement is 4 to 6 m/min.
The pyrophosphate copper plating layer is 5-12 mu m thick and is prepared by adopting the existing pyrophosphate copper plating process.
The thickness of the zinc coating is 5-15 mu m, and the zinc coating is prepared by adopting the existing zinc coating process.
Preferably, the galvanizing process adopts a DETRONZIN 401 potassium chloride galvanizing process developed by Guangzhou ultra-Pont chemical industry Co., Ltd: 50-70 g/L of zinc chloride, 180-220 g/L of potassium chloride, 25-35 g/L of boric acid, 0.8-1.5 mL/L of DETRONZIN 401 brightener, 25-35 mL/L of DETRONZIN 401 softener, temperature of 15-30 ℃, pH value of 4.8-5.6 and cathode current density of 1-4A/dm 2 The cathode is moved 3-5 m/min.
Preferably, the galvanizing process adopts a DETRONZIN 406 low-foam potassium chloride galvanizing process developed by ultra-nation chemical industry: 50-70 g/L of zinc chloride, 180-220 g/L of potassium chloride, 25-35 g/L of boric acid, 0.8-1.5 mL/L of DETRONZIN 406 brightener, 25-35 mL/L of DETRONZIN 406 softener, 15-30 ℃, 4.8-5.6 of pH value and 1-4A/dm of cathode current density 2 Moderate air agitation.
Preferably, the galvanizing process adopts a DETRONZIN 240 alkaline galvanizing process in ultra-high chemical industry: 8-10 g/L of zinc ions, 120-140 g/L of sodium hydroxide, 6-10 mL/L of 240 BASE auxiliary agent, 1-2 mL/L of 240 BRI brightening agent, 3-5 mL/L of 240 PURIFIER 1 purifying agent, 5-7 mL/L of 240 PURIFIER 2 purifying agent, 20-30 ℃ of plating bath temperature and 1-2.5A/dm of cathode current density 2 。
The thickness of the silane chromium-free passivation layer is 0.6-1.2 mu m, and the silane chromium-free passivation layer is prepared by adopting a solvent type silane chromium-free passivator.
Preferably, the silane passivation layer is prepared by a zinc procico Z-Caot 888 FL chromium-free passivator in ultra-high chemical engineering, and the passivation process is as follows: the zinc PRODICO Z-Caot 888 FL passivator is a solvent type, is used as a stock solution, is operated at room temperature, is passivated for 30-90 s, and is baked at 80-100 ℃ for 18-25 min.
Preferably, the silane passivation layer is prepared by using a zinc Zeccoat-825 chromium-free passivator in the ultra-high chemical industry: the zinc ZECCOAT-825 chromium-free passivator is a solvent type, is used as a stock solution, is operated at room temperature, is passivated for 30-90 s, and is baked for 20-25 min at 70-90 ℃.
Example 1:
as shown in fig. 1, a coating structure of neodymium iron boron zinc plating chromium-free passivation comprises a neodymium iron boron base body 1, and a citrate pre-nickel plating layer 2, a pyrophosphate copper plating layer 3, a zinc plating layer 4 and a silane chromium-free passivation layer 5 which are sequentially prepared from inside to outside on the neodymium iron boron base body 1.
The thickness of the citrate pre-nickel plating layer 2 is 4 μm, and the citrate pre-nickel plating layer is prepared by adopting the existing citrate nickel plating process: 200g/L of nickel sulfate hexahydrate, 10g/L of sodium chloride, 30g/L of boric acid, 30g/L of magnesium sulfate, pH =7.2, temperature 50 ℃, and cathode current density 1A/cm 2 The cathode was moved 5 m/min.
The pyrophosphate copper plating layer 3 is 8 mu m thick and is prepared by adopting the existing pyrophosphate copper plating process.
The thickness of the zinc coating 4 is 10 μm, and the DETRONZIN 401 potassium chloride galvanizing process developed by the ultra-high chemical industry is adopted: 60g/L of zinc chloride, 200g/L of potassium chloride, 30g/L of boric acid and 1mL/L of DETRONZIN 401 brightenerDETRONZIN 401 softener 30mL/L, temperature 25 ℃, pH =5.2, cathode current density 2A/dm 2 The cathode was moved 4 m/min.
The thickness of the silane chromium-free passivation layer 5 is 0.8 mu m, the silane chromium-free passivation layer is prepared by adopting a zinc Cuctte PRODICO Z-Caot 888 FL chromium-free passivator in the ultra-high-level chemical industry, and the passivation process is as follows: the zinc-based PRODICO Z-Caot 888 FL passivator is solvent-based, used as stock solution, operated at room temperature, passivated for 60s, and baked at 90 deg.C for 20 min.
The operation of the embodiment is divided into the following steps:
1. pretreatment: the workpiece base 1 is subjected to a pretreatment process of "alkaline chemical degreasing → water washing → sulfuric acid pickling → water washing → alkaline cathodic electrolytic degreasing → water washing → alkaline anodic electrolytic degreasing → water washing → acid salt activation → water washing".
2. Pre-nickel plating: after pretreatment of the workpiece, a pre-plated nickel layer 2 is prepared according to a citrate nickel plating process.
3. Pyrophosphate copper plating: and (3) pre-plating nickel on the workpiece, and then preparing the pyrophosphate copper plating layer 3 according to a pyrophosphate copper plating process.
4. And (3) potassium chloride galvanization: after the pyrophosphate of the workpiece is plated with copper, a zinc coating 4 is prepared according to a potassium chloride galvanizing process.
5. Chromium-free passivation: after the workpiece is galvanized, preparing a silane chromium-free passivation layer 5 by 'bright dipping of dilute nitric acid with the volume fraction of 1% → washing → film removal of sodium hydroxide solution with the mass fraction of 5% → washing → drying → silane chromium-free passivation → blowing off the passivation solution remained at the bottom of the rack-plated workpiece by high-pressure air → baking and curing'.
Example 2:
as shown in fig. 1, a coating structure of neodymium iron boron zinc plating chromium-free passivation comprises a neodymium iron boron base body 1, and a citrate pre-nickel plating layer 2, a pyrophosphate copper plating layer 3, a zinc plating layer 4 and a silane chromium-free passivation layer 5 which are sequentially prepared from inside to outside on the neodymium iron boron base body 1.
The thickness of the citrate pre-nickel plating layer 2 is 6 μm, and the citrate pre-nickel plating layer is prepared by adopting the existing citrate nickel plating process: 180g/L of nickel sulfate hexahydrate, 10g/L of sodium chloride, 30g/L of boric acid, 30g/L of magnesium sulfate, pH =7.0, temperature 55 ℃, and cathode current density of 1A/cm 2 The cathode was moved 5 m/min.
The pyrophosphate copper plating layer 2 is 8 mu m thick and is prepared by adopting the existing pyrophosphate copper plating process.
The thickness of the zinc coating 3 is 12 μm, and the DETRONZIN 406 low-foam potassium chloride galvanizing process developed by ultra-high chemical engineering is adopted: 60g/L of zinc chloride, 200g/L of potassium chloride, 30g/L of boric acid, 1mL/L of DETRONZIN 406 brightener, 30mL/L of DETRONZIN 406 softener, 200 ℃ of temperature, 5.0 of pH value and 1-4A/dm of cathode current density 2 Moderate air agitation.
The thickness of the silane chromium-free passivation layer 4 is 0.8 mu m, the silane chromium-free passivation layer is prepared by adopting a zinc Cuctte PRODICO Z-Caot 888 FL chromium-free passivator in the ultra-high-level chemical industry, and the passivation process is as follows: the zinc-based PRODICO Z-Caot 888 FL passivator is solvent-based, used as stock solution, operated at room temperature, passivated for 60s, and baked at 90 deg.C for 20 min.
The operation of the embodiment is divided into the following steps:
1. pretreatment: the workpiece base 1 is subjected to a pretreatment process of "alkaline chemical degreasing → water washing → sulfuric acid pickling → water washing → alkaline cathodic electrolytic degreasing → water washing → alkaline anodic electrolytic degreasing → water washing → acid salt activation → water washing".
2. Pre-nickel plating: after the pretreatment of the workpiece, a pre-plated nickel layer 2 is prepared according to a citrate nickel plating process.
3. Pyrophosphate copper plating: and (3) pre-plating nickel on the workpiece, and then preparing the pyrophosphate copper plating layer 3 according to a pyrophosphate copper plating process.
4. And (3) potassium chloride galvanization: after the pyrophosphate of the workpiece is plated with copper, a zinc coating 4 is prepared according to a potassium chloride galvanizing process.
5. Chromium-free passivation: after the workpiece is galvanized, preparing a silane chromium-free passivation layer 5 by 'nitric acid brightening with volume fraction of 1% → washing → sodium hydroxide solution film removal with mass fraction of 5% → washing → drying → silane chromium-free passivation → blowing off the passivation solution remained at the bottom of the rack-plated workpiece by high-pressure air → baking and curing'.
Example 3:
as shown in fig. 1, a coating structure of neodymium iron boron zinc plating chromium-free passivation comprises a neodymium iron boron base body 1, and a citrate pre-nickel plating layer 2, a pyrophosphate copper plating layer 3, a zinc plating layer 4 and a silane chromium-free passivation layer 5 which are sequentially prepared from inside to outside on the neodymium iron boron base body 1.
The thickness of the citrate pre-nickel plating layer 2 is 3 μm, and the citrate pre-nickel plating layer is prepared by adopting the existing citrate nickel plating process: 220g/L nickel sulfate hexahydrate, 12g/L sodium chloride, 32g/L boric acid, 32g/L magnesium sulfate, pH =7.1, temperature 58 ℃, cathode current density 1A/cm 2 The cathode was moved 5 m/min.
The pyrophosphate copper plating layer 2 is 10 mu m thick and is prepared by adopting the existing pyrophosphate copper plating process.
The thickness of the zinc coating 3 is 10 μm, and the alkaline zinc plating process of DETRONZIN 240 in ultra-high chemical industry is adopted: 9g/L of zinc ions, 130g/L of sodium hydroxide, 8mL/L of 240 BASE auxiliary agent, 1.5mL/L of 240 BRI brightening agent, 4mL/L of 240 PURIFIER 1 purifying agent, 6mL/L of 240 PURIFIER 2 purifying agent, 25 ℃ of plating bath temperature and 2A/dm of cathode current density 2 。
The thickness of the silane chromium-free passivation layer 4 is 0.8 mu m, and the silicon-based chromium-free passivation agent is prepared by adopting a zinc ZeCCOAT-825 chromium-free passivation agent in ultra-high chemical industry: the zinc ZECCOAT-825 chromium-free passivator is a solvent type, is used as a stock solution, is operated at room temperature, has the passivating time of 60s, and is baked for 22min at 80 ℃.
The operation of the embodiment is divided into the following steps:
1. pretreatment: the workpiece base 1 is subjected to a pretreatment of "alkaline chemical degreasing → water washing → sulfuric acid pickling → water washing → alkaline cathodic electrolytic degreasing → water washing → alkaline anodic electrolytic degreasing → water washing → acid salt activation → water washing".
2. Pre-nickel plating: after pretreatment of the workpiece, a pre-plated nickel layer 2 is prepared according to a citrate nickel plating process.
3. Pyrophosphate copper plating: and (3) pre-plating nickel on the workpiece, and then preparing the pyrophosphate copper plating layer 3 according to a pyrophosphate copper plating process.
4. Cyanide-free alkaline zinc plating: after the pyrophosphate of the workpiece is plated with copper, a zinc coating 4 is prepared according to the DETRONZIN 240 alkaline zinc plating process.
5. Chromium-free passivation: after the workpiece is galvanized, preparing a silane chromium-free passivation layer 5 by 'nitric acid brightening with a volume fraction of 1%' washing → sodium hydroxide solution film removal with a mass fraction of 5% 'washing → drying → silane chromium-free passivation → blowing off the passivation solution remained at the bottom of the rack-plated workpiece by high-pressure air → baking and curing'.
The neodymium iron boron zinc-plating chromium-free passivated plating layer structures prepared in the embodiments 1, 2 and 3 are subjected to a neutral salt spray test 240h according to GB/T10125-. The utility model discloses the cladding material structure of chromium-free passivation of neodymium iron boron galvanization of preparation carries out the time ratio GB/T34491 that neutral salt fog does not produce white rust and says that 48h of the colored passivation neutral salt fog test of galvanizing coat that criteria stipulates of sintered neodymium iron boron surface coating begin the corrosion 5 times.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the above embodiments are only applicable to help understand the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, the specific implementation manner and the application range may be changed. In general, nothing in this specification should be construed as limiting the invention.
Claims (5)
1. The utility model provides a coating structure of neodymium iron boron zinc-plating no chromium passivation which characterized in that: the neodymium iron boron base body is sequentially provided with a citrate pre-nickel-plating layer, a pyrophosphate copper-plating layer, a zinc-plating layer and a silane chromium-free passivation layer from inside to outside;
the silane chromium-free passivation layer is prepared by adopting a solvent type silane chromium-free passivator.
2. The coating structure of neodymium iron boron zinc-plating chromium-free passivation of claim 1, characterized in that: the thickness of the silane chromium-free passivation layer is 0.6-1.2 mu m.
3. The coating structure of neodymium iron boron zinc-plating chromium-free passivation of claim 1, characterized in that: the thickness of the citrate pre-plated nickel layer is 1-10 mu m.
4. The coating structure of neodymium iron boron zinc-plating chromium-free passivation of claim 1, characterized in that: the pyrophosphate copper plating layer is 5-12 μm thick.
5. The coating structure of neodymium iron boron zinc-plating chromium-free passivation of claim 1, characterized in that: the thickness of the zinc coating is 5-15 mu m.
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