CN104630850A - Co element modified electrodeposition nano composite coating and preparation method thereof - Google Patents
Co element modified electrodeposition nano composite coating and preparation method thereof Download PDFInfo
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- CN104630850A CN104630850A CN201510057056.5A CN201510057056A CN104630850A CN 104630850 A CN104630850 A CN 104630850A CN 201510057056 A CN201510057056 A CN 201510057056A CN 104630850 A CN104630850 A CN 104630850A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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Abstract
The invention relates to a Co element modified electrodeposition nano composite coating and a preparation method thereof. The composite coating is a NiCo-Zr composite coating layer, wherein NiCo is of a nano-crystalline cubic solid solution phase structure. The preparation method comprises the following steps: (1) adding deionized water, nickel sulfate, nickel chloride, boric acid, cobalt sulfate and Zr particles into an electroplating bath to prepare an electroplating solution; (2) performing ultrasonic vibration on the prepared electroplating solution for 10-60 minutes, and then magnetically stirring for 2-5 hours; (3) putting polished and cleaned cathode and anode into the electroplating solution and connecting a power supply; and (4) starting a magnetic stirrer, setting the stirring speed as 300 r/min, switching on the power source, starting electroplating, depositing for 1-2 hours, and taking out a sample after depositing. Compared with the prior art, the nano composite coating provided by the invention is relatively small in surface roughness, relatively high in hardness and relatively high in corrosion resistance.
Description
Technical field
The present invention relates to a kind of novel nano-composite plate synthesis technique, compound coating of in particular a kind of galvanic deposit cobalt improvement and preparation method thereof.
Background technology
Electrodeposit metals base composite coating is because having higher hardness, and good corrosion resistance nature and good wear resistance, be widely used as the material modified or decorative material of microelectronic device surface.Gained electrolytic coating must have following feature: good bonding force, enough thickness, suitable mechanical property (hardness and intensity), heat resistanceheat resistant disturbance performance and corrosion resistance.Ni-based composite galvanized coating is due to its good processibility, and higher hardness, the advantages such as good abrasion resistance and higher corrosion resistance, obtain application on microelectronic device.
Pure nickel electrolytic coating is widely used in microelectronic device, encapsulation and decoration industry.But nickel coating is due to its lower hardness, poor wear resistance, poor antioxidant property and corrosion resistance limit it and apply further.In recent years, large quantity research is devoted to high rigidity, the nickel based metal base composite electric coating of high resistance against wear performance and improved corrosion performance.Such as, in electroplating process, add different inert particle (SiC, Al
2o
3, TiO
2, Y
2o
3, CeO
2deng) and metallic particles (Cr, Al and Ti), form Ni-SiC, Ni-Al
2o
3, Ni-TiO
2, Ni-Y
2o
3, Ni-Al, Ni-Cr composite electrodeposition material.
Research of coming in shows, Co element adds the Ni base composite electric coating composite galvanized coating that to be formed with NiCo alloy be metal matrix, such as NiCo-SiC, NiCo-Al
2o
3, NiCo-TiO
2.The NiCo base composite cladding formed has higher hardness, better wear resistance, good high-temperature stability.
In general, although more to the research of Ni-based composite galvanized coating at present, form NiCo-Zr matrix material by galvanic deposit and have not been reported.
Summary of the invention
Object of the present invention be exactly provide a kind of to overcome defect that above-mentioned prior art exists and reduce Coating Surface Roughness, galvanic deposit nano-composite plate and preparation method thereof that the Co element that increases corrosion resistance improves.
Object of the present invention can be achieved through the following technical solutions: the galvanic deposit nano-composite plate that a kind of Co element improves, and it is characterized in that, this composite deposite is NiCo-Zr compound coating, wherein NiCo be nanocrystalline, cube solid solution phase structure.
Described solid solution phase is NiCo phase, and this NiCo phase structure is the soluble solids that Co atom replaces the formation of Ni atom.
The grain size of described composite deposite is 31nm, and surfaceness is 120nm, and hardness is 498Hv, and corrosion current is 0.263 μ A/cm
2.
A preparation method for the galvanic deposit nano-composite plate that Co element improves, it is characterized in that, the method comprises the following steps:
(1) in electrolytic plating pool, add deionized water, single nickel salt, nickelous chloride, boric acid, rose vitriol, Zr particle, is made into electroplate liquid; Described single nickel salt, nickelous chloride, boric acid, rose vitriol, the weight ratio of Zr particle is 10 ~ 15:1 ~ 3:1 ~ 2:0.5 ~ 1.5:0.5 ~ 1.5; The add-on of described deionized water is make the concentration of rose vitriol be 0.01 ~ 0.05g/ml;
(2) the electroplate liquid vibration of ultrasonic wave 10 ~ 60min will configured, magnetic agitation 2 ~ 5h subsequently;
(3) negative electrode after polishing, cleaning be placed in electroplate liquid with anode and be connected power supply;
(4) start magnetic stirring apparatus, stirring velocity is set to 300 rpms; Switch on power, start plating, deposition 1 ~ 2h, terminate to take out sample.
Single nickel salt described in step (1), nickelous chloride, boric acid, rose vitriol, the weight ratio of Zr particle is 12:2:1.5:1:1; The add-on of described deionized water is make the concentration of rose vitriol be 0.02g/ml.
Step (1) single nickel salt purity is 99.9%, and the purity of nickelous chloride is 99.9%, and the purity of boric acid is 99.9%, and the purity of rose vitriol is the size of 99.9%, Zr particle is 1 μm, and purity is 99.9%;
The pH value of described electroplate liquid is adjusted to 4.2 by sodium hydroxide.
The vibrations time described in step (2) is 30min, and the magnetic agitation time is 4h.
Negative electrode described in step (3) is stainless steel film, and size is 15mm × 10mm, and thickness is 2mm; Described anode is nickel sheet, and size is 15mm × 10mm, and thickness is 1mm, and the distance between negative electrode and anode is 2cm.
The current density of the power supply described in step (4) is set to 4A/dm
2.
Compared with prior art, present invention achieves the NiCo phase of solid solution, Co element add refinement crystal grain; The solid solution phase formed and grain refining add the hardness of composite deposite, and its hardness is up to 498Hv; The refinement of crystal grain reduces the surfaceness of coating, and roughness size is 120nm; The reduction of surfaceness adds the corrosion resistance of coating.This high rigidity, the surfaceness of reduction and higher corrosion resistance add the through engineering approaches range of application of electroplated Ni Co-Zr compound coating, and at microelectronic device, mould and ornamental industry tool have good application prospect.
Accompanying drawing explanation
Fig. 1 is plating schematic diagram of the present invention;
Fig. 2 is the NiCo-Zr compound coating of galvanic deposit and the XRD diffracting spectrum of Ni-Zr coating as a comparison;
Fig. 3 is the NiCo-Zr compound coating of galvanic deposit and the grain size of Ni-Zr coating as a comparison;
Fig. 4 is that the NiCo-Zr compound coating of galvanic deposit and the surface atom of Ni-Zr coating as a comparison try hard to sheet;
Fig. 5 is the NiCo-Zr compound coating of galvanic deposit and the hardness of Ni-Zr coating as a comparison;
Fig. 6 is the NiCo-Zr compound coating of galvanic deposit and the polarization curve of Ni-Zr coating as a comparison.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
As shown in Figure 1, the preparation method of a kind of galvanic deposit nano-composite plate of the present embodiment, comprises the following steps:
(1) in beaker 1, single nickel salt 60g is added, nickelous chloride 10g, boric acid 7.5g, rose vitriol 5g, Zr particle 2.5g, deionized water 250mL;
(2) ultrasonic dissolved vibration of liquid 30 minutes, uses magnetic agitation solution 4 hours subsequently
(3) utilize sodium hydroxide solution to adjust the pH value to 4.2 of solution, open magnetic agitation 2, stir speed (S.S.) 300 rpms;
(4) anode 3 of the nickel sheet after polishing, cleaning and stainless steel substrate being connected with the mains respectively and negative electrode 4;
(5) switch on power 5, start plating, deposit 1 hour, take off sample, cleaning;
As shown in Figures 2 and 3, the sample of the present embodiment deposit N iCo-Zr detects analysis through XRD and obtains, and galvanic deposit compound NiCo-Zr coating comprises the NiCo phase 6 of solid solution, and the grain size of matrix NiCo phase is 31nm;
As shown in Figure 4, surface topography AFM checks display, and the surfaceness of NiCo-Zr composite deposite is 120nm, and the Ni-Zr composite deposite of comparison ratio is little.
As shown in Figure 5, analyze by the hardness of dimensional microstructure sclerometer to NiCo-Zr and contrast Ni-Zr electrodeposited composite coatings, load be 200g, NiCo-Zr coating hardness be the hardness of 498Hv, Ni-Zr coating be 340Hv.
As shown in Figure 6, study with the corrosion resistance of polarization experiment to the Ni-Zr electrodeposited composite coatings of NiCo-Zr and contrast, sweep velocity is that 1MV is per second, can obtain, and the corrosion current of NiCo-Zr composite deposite is less, is 0.263 μ A/cm
2, the corrosion current of Ni-Zr composite deposite is as a comparison 0.552 μ A/cm
2.
Embodiment 2
A preparation method for the galvanic deposit nano-composite plate that Co element improves, the method comprises the following steps:
(1) in electrolytic plating pool, add deionized water, single nickel salt, nickelous chloride, boric acid, rose vitriol, Zr particle, is made into electroplate liquid; Described single nickel salt, nickelous chloride, boric acid, rose vitriol, the weight ratio of Zr particle is 10:1:1:0.5:0.5; The add-on of described deionized water is make the concentration of rose vitriol be 0.01g/ml; Single nickel salt purity is 99.9%, and the purity of nickelous chloride is 99.9%, and the purity of boric acid is 99.9%, and the purity of rose vitriol is the size of 99.9%, Zr particle is 1 μm, and purity is 99.9%;
(2) the electroplate liquid vibration of ultrasonic wave 10min will configured, magnetic agitation 5h subsequently; The pH value of electroplate liquid is adjusted to 4.2 by sodium hydroxide.
(3) negative electrode after polishing, cleaning be placed in electroplate liquid with anode and be connected power supply; Described negative electrode is stainless steel film, and size is 15mm × 10mm, and thickness is 2mm; Described anode is nickel sheet, and size is 15mm × 10mm, and thickness is 1mm, and the distance between negative electrode and anode is 2cm.
(4) start magnetic stirring apparatus, stirring velocity is set to 300 rpms; Switch on power, the current density of power supply is set to 4A/dm
2, start plating, deposition 1h, terminate to take out sample.
Gained Co element improve galvanic deposit nano-composite plate be NiCo-Zr compound coating, wherein NiCo be nanocrystalline, cube solid solution phase structure.The grain size of described composite deposite is 31nm, and surfaceness is 120nm, and hardness is 498Hv, and corrosion current is 0.263 μ A/cm
2.
Embodiment 3
A preparation method for the galvanic deposit nano-composite plate that Co element improves, the method comprises the following steps:
(1) in electrolytic plating pool, add deionized water, single nickel salt, nickelous chloride, boric acid, rose vitriol, Zr particle, is made into electroplate liquid; Described single nickel salt, nickelous chloride, boric acid, rose vitriol, the weight ratio of Zr particle is 15:3:2:1.5:1.5; The add-on of described deionized water is make the concentration of rose vitriol be 0.05g/ml; Single nickel salt purity is 99.9%, and the purity of nickelous chloride is 99.9%, and the purity of boric acid is 99.9%, and the purity of rose vitriol is the size of 99.9%, Zr particle is 1 μm, and purity is 99.9%;
(2) the electroplate liquid vibration of ultrasonic wave 60min will configured, magnetic agitation 2h subsequently; The pH value of electroplate liquid is adjusted to 4.2 by sodium hydroxide.
(3) negative electrode after polishing, cleaning be placed in electroplate liquid with anode and be connected power supply; Described negative electrode is stainless steel film, and size is 15mm × 10mm, and thickness is 2mm; Described anode is nickel sheet, and size is 15mm × 10mm, and thickness is 1mm, and the distance between negative electrode and anode is 2cm.
(4) start magnetic stirring apparatus, stirring velocity is set to 300 rpms; Switch on power, the current density of power supply is set to 4A/dm
2, start plating, deposition 2h, terminate to take out sample.
Gained Co element improve galvanic deposit nano-composite plate be NiCo-Zr compound coating, wherein NiCo be nanocrystalline, cube solid solution phase structure.The grain size of described composite deposite is 31nm, and surfaceness is 120nm, and hardness is 498Hv, and corrosion current is 0.263 μ A/cm
2.
Claims (10)
1. Co element improve a galvanic deposit nano-composite plate, it is characterized in that, this composite deposite is NiCo-Zr compound coating, wherein NiCo be nanocrystalline, cube solid solution phase structure.
2. the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 1, it is characterized in that, described solid solution phase is NiCo phase, and this NiCo phase structure is the soluble solids that Co atom replaces the formation of Ni atom.
3. the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 1, it is characterized in that, the grain size of described composite deposite is 31nm, and surfaceness is 120nm, and hardness is 498Hv, and corrosion current is 0.263 μ A/cm
2.
4. a preparation method for the galvanic deposit nano-composite plate improved as the Co element as described in arbitrary in claims 1 to 3, it is characterized in that, the method comprises the following steps:
(1) in electrolytic plating pool, add deionized water, single nickel salt, nickelous chloride, boric acid, rose vitriol, Zr particle, is made into electroplate liquid; Described single nickel salt, nickelous chloride, boric acid, rose vitriol, the weight ratio of Zr particle is 10 ~ 15:1 ~ 3:1 ~ 2:0.5 ~ 1.5:0.5 ~ 1.5; The add-on of described deionized water is make the concentration of rose vitriol be 0.01 ~ 0.05g/ml;
(2) the electroplate liquid vibration of ultrasonic wave 10 ~ 60min will configured, magnetic agitation 2 ~ 5h subsequently;
(3) negative electrode after polishing, cleaning be placed in electroplate liquid with anode and be connected power supply;
(4) start magnetic stirring apparatus, stirring velocity is set to 300 rpms; Switch on power, start plating, deposition 1 ~ 2h, terminate to take out sample.
5. the preparation method of the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 4, it is characterized in that, the single nickel salt described in step (1), nickelous chloride, boric acid, rose vitriol, the weight ratio of Zr particle is 12:2:1.5:1:1; The add-on of described deionized water is make the concentration of rose vitriol be 0.02g/ml.
6. the preparation method of the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 4, it is characterized in that, step (1) single nickel salt purity is 99.9%, the purity of nickelous chloride is 99.9%, the purity of boric acid is 99.9%, the purity of rose vitriol is the size of 99.9%, Zr particle is 1 μm, and purity is 99.9%.
7. the preparation method of the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 4, it is characterized in that, the pH value of described electroplate liquid is adjusted to 4.2 by sodium hydroxide.
8. the preparation method of the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 4, it is characterized in that, the vibrations time described in step (2) is 30min, and the magnetic agitation time is 4h.
9. the preparation method of the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 4, it is characterized in that, the negative electrode described in step (3) is stainless steel film, and size is 15mm × 10mm, and thickness is 2mm; Described anode is nickel sheet, and size is 15mm × 10mm, and thickness is 1mm, and the distance between negative electrode and anode is 2cm.
10. the preparation method of the galvanic deposit nano-composite plate of a kind of Co element improvement according to claim 5, it is characterized in that, the current density of the power supply described in step (4) is set to 4A/dm
2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113201780A (en) * | 2021-04-28 | 2021-08-03 | 西安建筑科技大学 | Nickel-base super-hydrophobic nano CeO2Composite material of composite coating and preparation method thereof |
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|---|---|---|---|---|
| CN101532151A (en) * | 2009-04-22 | 2009-09-16 | 合肥工业大学 | Electric deposition nickel pottery plating solution and preparing method thereof |
| CN102605402A (en) * | 2012-03-28 | 2012-07-25 | 东南大学 | Preparation method of wear-resistant toughened composite ceramic layer on surface of aluminum alloy product |
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2015
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Patent Citations (2)
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|---|---|---|---|---|
| CN101532151A (en) * | 2009-04-22 | 2009-09-16 | 合肥工业大学 | Electric deposition nickel pottery plating solution and preparing method thereof |
| CN102605402A (en) * | 2012-03-28 | 2012-07-25 | 东南大学 | Preparation method of wear-resistant toughened composite ceramic layer on surface of aluminum alloy product |
Non-Patent Citations (4)
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|---|
| FEI CAI等: "Effects of Co contents on the microstructures and properties of the electrodeposited NiCo-Zr composite coatings", 《MATERIALS RESEARCH BULLETIN》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201780A (en) * | 2021-04-28 | 2021-08-03 | 西安建筑科技大学 | Nickel-base super-hydrophobic nano CeO2Composite material of composite coating and preparation method thereof |
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Application publication date: 20150520 |