CN105506692B - A kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof - Google Patents
A kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof Download PDFInfo
- Publication number
- CN105506692B CN105506692B CN201510962371.2A CN201510962371A CN105506692B CN 105506692 B CN105506692 B CN 105506692B CN 201510962371 A CN201510962371 A CN 201510962371A CN 105506692 B CN105506692 B CN 105506692B
- Authority
- CN
- China
- Prior art keywords
- admiro
- nickel
- deposition layer
- deposition
- rich phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- 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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Abstract
The invention belongs to electrochemical plating field, and in particular to a kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof.Porous anti-corrosion nickel-rich phase admiro deposition layer, by pulse current method, it is about 5~30 microns that electro-deposition, which is obtained with porous surface pattern zn-ni alloy depositses, aperture, in hydrosulphate admiro bath system.Pure nickel phase is rich in the present invention in zn-ni alloy depositses, decay resistance is good, and the field such as protection of iron structure has good application value in briny environment.
Description
Technical field
The invention belongs to electrochemical plating field, and in particular to a kind of porous anti-corrosion nickel-rich phase admiro deposition layer and
Its preparation method.
Background technology
Seawater is a kind of salinity between 32~37 ‰, natural strong electrolytic solution of the pH value between 7.9~8.4, therefore,
Electrochemical reaction occurs for iron structure in briny environment and surrounding medium and too corroded.Electrochemical plating is one
The steel protection measure commonly used in kind marine environment, the bianry alloy that wherein zinc is formed with iron group metal, i.e. zinc-nickel, zinc-iron, zinc
Cobalt alloy etc., it is widely used because its is attractive in appearance fine and close.
In numerous Zn-based plating layers, zn-ni alloy depositses are firmly combined with substrate, and simple with solution composition, toxicity
It is low, it is easy to maintain the advantages of.The corrosion resisting property of admiro increases with the increase of coating nickel content, corrosion resistance, it was reported that nickeliferous
The higher zn-ni alloy depositses corrosion resistance of amount can reach 5~6 times of same thickness zinc coating.The alloy coat has good simultaneously
Solderable and machinability, almost without hydrogen embrittlement, and be firmly combined with matrix.
However, the zn-ni alloy depositses nickel content prepared under conventional DC power supply is low, mostly zinc-rich phase admiro plates
Layer, when it is applied in marine environment, still enough protection can not be provided for iron structure, it is necessary to safeguard often, band
Come the huge wasting of resources and economic loss.
The content of the invention
It is a kind of present invention aims at providing for above-mentioned zn-ni alloy depositses the presence in terms of corrosion resisting property the problem of
Porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof.
To achieve the above object, the present invention takes following technical scheme to implement：
A kind of porous anti-corrosion nickel-rich phase admiro deposition layer, by pulse current method, in hydrosulphate admiro
It is about 5~30 microns that electro-deposition, which is obtained with porous surface pattern zn-ni alloy depositses, aperture, in bath system.
The pulse current average value used is 80~100mA/cm2, peak value is 160~200mA/cm2；The pulse electricity used
Stream pulse frequency is 25~50Hz.
The hydrosulphate admiro bath system, wherein composition and its mass fraction are：35~40g/L
ZnSO4·7H2O, 35~40g/L NiSO4With 80~85g/L Na2SO4；PH value is 2.0~2.5；Wherein, ZnSO4·7H2O with
NiSO4Mass ratio be 1:1.
A kind of porous anti-corrosion nickel-rich phase admiro deposition layer preparation method, by pulse current method, in hydrosulphate
To the porous pattern zn-ni alloy depositses of substrate surface electro-deposition to be protected in admiro bath system.
Specifically, by pulse current method, using steel to be protected as pulse power negative pole, using pure nickel piece as the pulse power just
Pole, steel to be protected and pure nickel piece system are immersed in sulfate admiro bath system under stirring condition, sunk by pulse
Product is by zn-ni alloy depositses electro-deposition in steel surface to be protected.
Plating solution mixing speed is 200~800rpm in the deposition process.It is preferred that plating solution mixing speed is in deposition process
200rpm。
The beneficial effects of the present invention are：
By the present invention in that with pulse current method, optimal current density be prepared under optimal pulse frequency it is porous anti-corrosion
Nickel-rich phase admiro deposition layer, makes deposition layer possess good corrosion resistance, the sea water resistance for improving ferrous materials
Corrosion life has major application meaning；It is characterized in particular in：
(1) deposition layer surface possesses porous pattern in the present invention, and aperture is about 5~30 microns, and disposable load is other
Material, gain performance；
(2) deposition layer is rich in pure nickel phase due to the application of pulsed deposition process in the present invention, increase effectively coating
Corrosion potential, strengthen corrosion resisting property；
(3) deposition layer of the present invention can set deposition layer thickness and structure according to application environment and substrate service life, protect
Hinder structure service life；
(4) the smooth densification of deposition layer in the present invention, Dark grey surface is presented, is favorably improved the attractive in appearance of substrate, can use
In the steel construction for having particular/special requirement；
(5) deposition layer is firmly combined with substrate in the present invention, compared to customary DC deposition layer, is possessed more excellent
Corrosion resisting property；
(6) deposition layer provides a kind of anti-corrosion protection side of the reinforcing to iron structure in briny environment in the present invention
Method.
Brief description of the drawings
Fig. 1 is that porous anti-corrosion nickel-rich phase admiro deposition layer (a) provided in an embodiment of the present invention is closed with common zinc-nickel
The optical photograph of golden deposition layer (b).
Fig. 2 is 100 times (a) and 1000 of porous anti-corrosion nickel-rich phase admiro deposition layer provided in an embodiment of the present invention
(b) stereoscan photograph again.
Fig. 3 is that porous anti-corrosion nickel-rich phase admiro deposition layer (a) provided in an embodiment of the present invention is closed with common zinc-nickel
The X ray crystal diffraction collection of illustrative plates of golden deposition layer (b)；Wherein, 1 pure zinc phase character crystal diffraction peak is represented；2 represent admiro
Phase character crystal diffraction peak；3 represent pure nickel phase character crystal diffraction peak.
Fig. 4 is that porous anti-corrosion nickel-rich phase admiro deposition layer (a) provided in an embodiment of the present invention is closed with common zinc-nickel
Golden deposition layer (b) electrochemical impedance spectrogram in 3.5%NaCl solution.
Fig. 5 is that porous anti-corrosion nickel-rich phase admiro deposition layer (a) provided in an embodiment of the present invention is closed with common zinc-nickel
Golden deposition layer (b) polarization curve in 3.5%NaCl solution.
Embodiment
Below by way of specific embodiment, the invention will be further described, contributes to one of ordinary skill in the art more
It is fully understood by the present invention, but do not limit the invention in any way.
Embodiment 1：
Porous anti-corrosion nickel-rich phase admiro deposition layer preparation method
1) acid sulfuric acid admiro bath system is prepared, by 35g ZnSO4·7H2O、35g NiSO4With 80g Na2SO4
It is dissolved in 1L distilled water, with 1mol/L H2SO4It is 2 to adjust pH value, and standby is S1；By 40g ZnSO4·7H2O、40g NiSO4With
85g Na2SO4It is dissolved in 1L distilled water, with 1mol/L H2SO4It is 2.5 to adjust pH value, and standby is S2.
2) 20# carbon steel coupons working surface is polished step by step to 2000# with SiC aqueous phases sand paper, ultrasonic wave is clear in absolute ethyl alcohol
10min is washed, it is standby as steel matrix to be protected thoroughly to remove steel disc surface and oil contaminant and impurity；
3) use Gamary Reference 3000 to be used as the pulse power, connected with the steel to be protected after being handled in step 2)
DC power cathode is connect, DC power anode is connected with the pure nickel piece of identical size.It is immersed in the sulfuric acid of step 1) preparation
In admiro bath system S1, in average current density 80mA/cm2, peak value 160mA/cm2Under, pulse frequency 25Hz, stirring
Pulsed deposition 10min is carried out under speed 200rpm, obtains porous anti-corrosion nickel-rich phase admiro deposition layer AE1；Submerged
In sulfuric acid admiro bath system S1 prepared by step 1), in average current density 100mA/cm2, peak value 200mA/cm2
Under, pulse frequency 25Hz, mixing speed 600rpm carry out pulsed deposition 10min, obtain porous anti-corrosion nickel-rich phase admiro electricity
Sedimentary AE2.It is immersed in the sulfuric acid admiro bath system S2 of step 1) preparation, in average current density 100mA/
cm2, peak value 200mA/cm2Under, pulse frequency 50Hz, mixing speed 800rpm carry out pulsed deposition 10min, obtain porous anti-corrosion
Nickel-rich phase admiro deposition layer AE3.
4) DJS-292E type potentiostats are used, are adjusted under constant current mode, with the steel to be protected after processing in step 2)
DC power cathode is connected, DC power anode is connected with the pure nickel piece of identical size.It is immersed in the sulphur of step 1) preparation
In sour admiro bath system S1, in current density 80mA/cm2, 10min is deposited under mixing speed 200rpm, is obtained common
Admiro deposition layer AC1；It is immersed in the sulfuric acid admiro bath system S1 of step 1) preparation, in current density
100mA/cm2, 10min is deposited under mixing speed 600rpm, obtains common admiro deposition layer AC2.It is immersed in step
In the rapid sulfuric acid admiro bath system S2 1) prepared, in current density 100mA/cm2, deposit under mixing speed 800rpm
10min, obtain common admiro deposition layer AC3.
5) after the completion of electro-deposition, the steel disc plated is taken out, surface is rinsed residual electroplate liquid 2~3 times with redistilled water, done
It is dry.Its optical photograph is as shown in Figure 1.
Can be observed by figure, porous anti-corrosion nickel-rich phase admiro deposition layer surface compact is smooth in Fig. 1 a light,
And common admiro deposition layer rough surface in Fig. 1 b, and have obvious bubbling, combined with substrate insecure.
Embodiment 2
Porous anti-corrosion nickel-rich phase admiro deposition layer pattern and structural analysis
The porous anti-corrosion nickel-rich phase admiro deposition layer AE2 prepared in embodiment 1 and common admiro electricity is heavy
Lamination AC2 is scanned electron microscope observation and X ray crystallographic analysis, and its result is as shown in Figure 2 and Figure 3.
Fig. 2 a electron microscope observations, the nickel-rich phase admiro deposition layer surface topography under 100 times of display, Ke Yifa
Now typical porous pattern, deposition layer surface show the uniform original shape aperture of rule.Pattern is amplified to 1000 times,
Such as Fig. 2 b, the diameter of circular aperture is measured, its pore size is about 5~30 microns.
The characteristic diffraction peak (peak 2) of stronger admiro is shown in Fig. 3 a X ray crystal diffraction peak, but is occurred simultaneously
The characteristic diffraction peak (peak 3) of pure nickel phase, illustrate the component of its nickel-rich phase；And except the feature of stronger admiro in Fig. 3 b
Diffraction maximum, it have also appeared the characteristic diffraction peak (peak 1) of pure zinc phase.Thus, it is possible to which illustrate can be effective by preparation method of the present invention
Increase the nickel phase content inside admiro deposition layer.
Embodiment 3：
Porous anti-corrosion nickel-rich phase admiro deposition layer corrosion resisting property evaluation
The porous anti-corrosion nickel-rich phase admiro deposition layer AE3 prepared in embodiment 1 and common admiro electricity is heavy
Lamination AC3 is immersed in 3.5%NaCl solution, is carried out electro-chemical test analysis, is assessed its corrosion resisting property.Corrosion resisting property is tested
Method is：
1) using deposition layer as working electrode, platinum electrode is that salt bridge connection saturated calomel electrode (SCE) is reference to electrode
Electrode, using 3.5%NaCl solution as working media, it is assembled into three-electrode system；
2) under the OCP (OCP) of deposition layer, electrochemical impedance spectrogram test is carried out, test parameter is：It is sinusoidal
Wave voltage disturbance 10mV (rms), test forcing frequency scope 105~10-2Hz.Test result such as Fig. 4.
3) after stable system, dynamic potential polarization curve test is carried out, test parameter is：Test voltage scope+0.5V vs
OCP~-0.5V vs OCP, sweep speed 0.167mV/s.Test result is shown in Fig. 5.
Held by porous anti-corrosion nickel-rich phase admiro deposition layer AE3 (a) in electrochemical impedance spectroscopy nyquist diagram in Fig. 4
Anti- arc radius significantly increases, and can reach more than 3 times of common admiro deposition layer AC3 (b) capacitive reactance arc radius, illustrates that it is rotten
Erosion speed substantially reduces, and corrosion resisting property greatly improves.
By showing the dynamic potential polarization curve of two class zn-ni alloy depositses, porous anti-corrosion nickel-rich phase admiro electricity in Fig. 5
The more common admiro deposition layer AC3 (b) of sedimentary AE3 (a) corrosion potentials has shuffled about 400mV, under corrosion current
About 1 order of magnitude drops, and corrosion resisting property is significantly raised；Put down in addition, obvious oxygen diffusion occurs in the cathode branch in a polarization curves
Platform, it is the rate-determining steps of corrosion reaction to illustrate negative electrode oxygen diffusing step；And do not occur oxygen diffusion platform in b polarization curves, say
Bright cathode reaction speed is fast, and corrosion rate is fast.
In a word, electrochemical means are passed through, it can be deduced that conclusion, porous anti-corrosion nickel-rich phase admiro deposition layer is than common
Admiro deposition layer corrosion resisting property significantly improves.
Claims (5)
- A kind of 1. porous anti-corrosion nickel-rich phase admiro deposition layer, it is characterised in that：By pulse current method, in hydrosulphate It is 5~30 microns that electro-deposition, which is obtained with porous surface pattern zn-ni alloy depositses, aperture, in admiro bath system；The pulse current average value used is 80~100mA/cm2, peak value is 160~200mA/cm2；The pulse current arteries and veins used It is 25~50Hz to rush frequency；The hydrosulphate admiro bath system, wherein composition and its mass fraction are：35~40g/L ZnSO4· 7H2O, 35~40g/L NiSO4With 80~85g/L Na2SO4；PH value is 2.0~2.5；Wherein, ZnSO4·7H2O and NiSO4's Mass ratio is 1:1.
- A kind of 2. porous anti-corrosion nickel-rich phase admiro deposition layer preparation method described in claim 1, it is characterised in that： By pulse current method, to the porous pattern zinc-nickel of substrate surface electro-deposition to be protected in hydrosulphate admiro bath system Alloy layer.
- 3. according to the porous anti-corrosion nickel-rich phase admiro deposition layer preparation method described in claim 2, it is characterised in that： By pulse current method, using steel to be protected as pulse power negative pole, using pure nickel piece as pulse power positive pole, by steel to be protected with Pure nickel piece system is immersed in sulfate admiro bath system under stirring condition, by pulsed deposition by zn-ni alloy depositses Electro-deposition is in steel surface to be protected.
- 4. according to the porous anti-corrosion nickel-rich phase admiro deposition layer preparation method described in claim 3, it is characterised in that： Plating solution mixing speed is 200~800rpm in the deposition process.
- 5. according to the porous anti-corrosion nickel-rich phase admiro deposition layer preparation method described in claim 4, it is characterised in that： Plating solution mixing speed is 200rpm in deposition process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510962371.2A CN105506692B (en) | 2015-12-17 | 2015-12-17 | A kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510962371.2A CN105506692B (en) | 2015-12-17 | 2015-12-17 | A kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105506692A CN105506692A (en) | 2016-04-20 |
| CN105506692B true CN105506692B (en) | 2017-12-26 |
Family
ID=55714981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510962371.2A Active CN105506692B (en) | 2015-12-17 | 2015-12-17 | A kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105506692B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112522747B (en) * | 2020-11-19 | 2022-01-07 | 瑞声科技（南京）有限公司 | Preparation method of upper cover plate of vapor chamber and vapor chamber |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4351713A (en) * | 1979-08-22 | 1982-09-28 | Thomas Steel Strip Corp. | Electro-co-deposition of corrosion resistant nickel/zinc alloys onto steel substrates |
| JPS57164999A (en) * | 1981-04-03 | 1982-10-09 | Kawasaki Steel Corp | Production of steel plate electroplated zinc-nickel alloy with highly corrosion resistant |
| JPS5925994A (en) * | 1982-07-31 | 1984-02-10 | Sumitomo Metal Ind Ltd | Continuous zn alloy electroplating method |
| JPH08127892A (en) * | 1994-11-01 | 1996-05-21 | Nippon Steel Corp | Production of zinc-nickel alloy plated steel sheet |
| US8048285B2 (en) * | 2005-05-11 | 2011-11-01 | The Boeing Company | Low hydrogen embrittlement zinc/nickel plating for high strength steels |
| CN102677109B (en) * | 2012-05-31 | 2015-10-21 | 南京工程学院 | Tank for sewage gas surface thickness adjustable γ crystal formation zinc-nickel alloy preparation method |
| CN103451693B (en) * | 2013-07-29 | 2015-08-26 | 山东建筑大学 | A kind of alkaline zinc-nickel alloy pulse plating method of nickel stable content |
-
2015
- 2015-12-17 CN CN201510962371.2A patent/CN105506692B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105506692A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Han et al. | A study on pulse plating amorphous Ni–Mo alloy coating used as HER cathode in alkaline medium | |
| Qiao et al. | Effects of deposition temperature on electrodeposition of zinc–nickel alloy coatings | |
| CN103215614B (en) | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer | |
| CN101532153B (en) | Amorphous nano-alloy plating layer of electrodeposition nickel-based series, electroplating liquid and electroplating process | |
| Zhang et al. | Electrodeposition of high corrosion resistance Cu/Ni–P coating on AZ91D magnesium alloy | |
| Sasaki et al. | Electrodeposition of Binary Iron‐Group Alloys | |
| Baldwin et al. | The corrosion resistance of electrodeposited zinc-nickel alloy coatings | |
| CN102260891A (en) | Method for electrodepositing nanocrystalline nickel-cobalt alloy by double-pulse | |
| Badawy et al. | Electrodeposited Zn-Ni alloys as promising catalysts for hydrogen production-preparation, characterization and electro-catalytic activity | |
| Shao et al. | Structure and properties of composite Ni–Co–Mn coatings on metal interconnects by electrodeposition | |
| Shivakumara et al. | Influence of additives on electrodeposition of bright Zn-Ni alloy on mild steel from acid sulphate bath | |
| Pecequilo et al. | Study of copper electrodeposition mechanism from a strike alkaline bath prepared with 1-hydroxyethane-1, 1-diphosphonic acid through cyclic voltammetry technique | |
| Rashwan et al. | Electrodeposition and characterization of thin layers of Zn–Co alloys obtained from glycinate baths | |
| Liu et al. | Electrodeposition of Al on AZ31 magnesium alloy in TMPAC-AlCl3 ionic liquids | |
| Bindra et al. | The effect of base metal ions on the electrochemical and structural characteristics of electrodeposited gold films | |
| CN105506692B (en) | A kind of porous anti-corrosion nickel-rich phase admiro deposition layer and preparation method thereof | |
| Ivanov et al. | Corrosion resistance of compositionally modulated multilayered Zn–Ni alloys deposited from a single bath | |
| Assaf et al. | The effect manganese concentration on the corrosion resistance and physical properties of Zn-Ni-Mn alloy films produced by electrodeposition | |
| Birlik et al. | Influence of bath composition on the structure and properties of nickel coatings produced by electrodeposition technique | |
| Kim et al. | Effects of plating conditions on the microstructure of 80Sn 20Pb electrodeposits from an organic sulphonate bath | |
| CN103572339B (en) | A kind of method at surface of low-carbon steel electroplated Ni-Mn alloy | |
| CN102324276B (en) | Production process of copper coated aluminum-magnesium bimetallic conductor | |
| CN106906498A (en) | A kind of graphene oxide zinc composite plating solution and its preparation method and application | |
| Zheng et al. | Mechanisms of triethanolamine on copper electrodeposition from 1-hydroxyethylene-1, 1-diphosphonic acid electrolyte | |
| Liu et al. | Effect of nickel pre-plating on the plating of Zn-Ni alloy coating on stainless steel substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |