CN106245070B - A method of combination plating solution and electroplating nickel on surface of magnesium alloy for magnesium alloy plating nickel - Google Patents
A method of combination plating solution and electroplating nickel on surface of magnesium alloy for magnesium alloy plating nickel Download PDFInfo
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- CN106245070B CN106245070B CN201610919745.7A CN201610919745A CN106245070B CN 106245070 B CN106245070 B CN 106245070B CN 201610919745 A CN201610919745 A CN 201610919745A CN 106245070 B CN106245070 B CN 106245070B
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- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/16—Acetylenic compounds
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1806—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by mechanical pretreatment, e.g. grinding, sanding
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1837—Multistep pretreatment
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
- C23C28/025—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only with at least one zinc-based layer
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- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
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Abstract
The invention discloses a kind of combination nickel plating baths for magnesium alloy plating nickel, for the aqueous solution of following density component, wherein, nickel sulfate, soluble fluoride, ammonium citrate, saccharin sodium, benzene sulfinic acid sodium salt, Isosorbide-5-Nitrae-butynediols, lauryl sodium sulfate and pH adjusting agent.Furthermore, the present invention also provides a kind of methods of electroplating nickel on surface of magnesium alloy, including being mechanically polished to magnesium alloy, surface degreasing, alkali cleaning, pickling, activation processing, single or multiple electroless zinc platings and in the combination nickel plating bath carry out electronickelling processing, obtain the magnesium alloy that electroplating surface has nickel.Various magnesium alloy substrates are suitable for using combination nickel plating bath of the present invention and nickel plating process, and the matrix of plating piece obtained is higher with binding force of cladding material, corrosion resisting property is more preferable, the straight and even beauty in plating piece surface.
Description
Technical field
The present invention relates to a kind of magnesium alloy plating nickel technical fields of chrome-free acid-wash activation, and in particular to one kind is closed for magnesium
The combination plating solution of golden electronickelling, and the method that Mg alloy surface nickel plating is carried out using the combination plating solution.
Background technique
Magnesium is one of the most abundant light metal alloy of reserves on the earth, and the specific gravity of magnesium is 1.74g/cm3, only aluminium 2/3,
The 2/5 of titanium;Magnesium alloy is lighter than aluminium alloy 36%, lighter than kirsite 73%, lighter than steel by 77%.Magnesium has specific strength, specific stiffness height,
Thermal conductivity is good, and has that good electromagnetic shielding, damping and amortization, damping, machinability and processing cost are low, add
The advantages that work energy is only the 70% of aluminium alloy and is easily recycled.The specific strength of magnesium alloy is higher than aluminium alloy and steel, slightly below compares
The highest fibre reinforced plastics of intensity;Specific stiffness is suitable with aluminium alloy and steel, is much higher than fibre reinforced plastics;Wear-resisting property is than low
Carbon steel is much better, has been more than pack alloy A380." Chinese magnesium alloy industry market prediction is reported with investment strategy planning application
Prediction " it is 2015 estimated, global magnesium alloy market is 6,000,000 tons, and annual average compound growth rate (CAGR) is 20%~25% (wherein
Contain the application of the vehicles, 3C, aerospace and field of medicine and chemical technology magnesium alloy), also referred to as " 21 century most develops
With the green engineering material of application potential ".
However, the electrode potential due to magnesium is lower, chemical activity is relatively high.Magnesium alloy is in moist atmosphere Sulphur Contaminated Environment sea
Severe electrochemical corrosion can be all generated in foreign air, such situation seriously reduces the application advantage of magnesium-alloy material, and
Platform is limited its application strongly.In view of the disadvantages described above of magnesium alloy, corrosion resistance must be used under its many application environment
The preferable metal or alloy of energy is as its protective layer.Numerous known, magnesium alloy is more difficult plating compared with other alloys as substrate, therefore
Its surface directly carries out plating or chemical plating is all extremely difficult.
By consulting literatures it is found that cyanide electroplating bottoming or direct electroless plating technique are closed for magnesium after the leaching zinc of DOW company
Gold surface protection is relatively mature.And the dip galvanizing technique process of DOW company exploitation are as follows: surface treatment activation leaching zinc cyaniding plating
Copper chemical plating nickel-phosphorus alloy.There are a large amount of CrO3- environmental pollutions are serious in acid cleaning process in this process;Cyanide electroplating bottoming
When, containing cyanides such as a large amount of copper cyanider potassium cyanide Cymags in plating solution, nonhazardous post-processing is many and diverse, and pertinent literature shows
Its technique is not applicable to the higher magnesium alloy of aluminium content.And by the way of chemical plating nickel-phosphorus alloy, technique is more simple, plating solution
In be free of cyanide, gradually favored, but the binding force of its coating and matrix be not so good as DOW technique production plating piece.
Corrosion stability of magnesium alloy can it is poor, soak zinc after corrosion resisting property increase, if but zinc-impregnating layer there are small defects, electronickelling
When the pH of solution system is lower in the process, easy acceleration matrix corrosion, therefore prior art multiselect weakly acidic pH or alkaline electro-nickel
Solution.Such as:
" the plating handbook third edition " discloses a kind of citrate nickel plating process, as follows with when method:
NiSO4·7H2O | 120g/L~180g/L |
Sodium citrate | 150g/L~230g/L |
NiCl2·7H2O | 10g/L~15g/L |
Magnesium sulfate (MgSO4) | 10g/L~20g/L |
pH | 6.6~7.0 |
Temperature | 35 DEG C~40 DEG C |
Cathode-current density | 0.5A/dm2~1.2A/dm2 |
Movable cathode | 18 times/min~25 time/min |
The electronickelling electronickelling formula of liquid and technique plating layer porosity obtained are higher, cannot form effective ni-resist
Layer.
In addition, " the plating handbook third edition " also discloses the formula and method of a kind of pyrophosphate nickel plating, it is as shown in the table:
The electronickelling electronickelling formula of liquid and the coating of technique are more crisp, and binding force is poor.
For another example, the prior art also includes the type electronickelling and technique of following table:
The coating that the electronickelling electronickelling formula of liquid and technique obtain is more crisp, easily burns.
Existing electronickelling formula is easily burnt during magnesium alloy plating, and porosity is excessively high, and coating brittleness is big etc. asks
Topic, more has formula that cannot form effective anticorrosion layer.
Summary of the invention
It is easy to burn to solve prior art electronickelling, is difficult to the problems such as electronickelling obtained, the present invention provides one kind
Combination plating solution for magnesium alloy plating nickel.In addition, the present invention also provides a kind of magnesium alloy tables using the combination plating solution
The method of face electronickelling is solved by carrying out the embodiments such as pickling, activation, dip galvanizing technique and electronickelling formula to magnesium alloy
Problem above, and then the associativity of plating material coating and substrate is improved, improve the compactness of electroplating of plating piece, improve corrosion resistance.
A kind of combination nickel plating bath for magnesium alloy plating nickel is the aqueous solution of following density component, wherein
Preferably, the pH of the combination nickel plating bath is 5.5~6.5.
The present invention has acid combination nickel plating bath using described, is conducive to plating and forms fine and close and matrix to combine
The nickel coating that power is strong, corrosion resistance is strong.Combination nickel plating bath of the present invention overcomes the acid of existing technical staff's common cognition
Property under the conditions of electronickelling easily make matrix corrosion, the technology that need to be carried out under neutral or basic conditions misread.
Preferably, the soluble fluoride is potassium fluoride, sodium fluoride, lithium fluoride, at least one in ammonium acid fluoride
Kind.
The pH adjusting agent is preferably water-soluble alkaline compound, preferably, pH adjusting agent is ammonium hydroxide.For example, logical
The pH for crossing the ammonium hydroxide adjustment combination nickel plating bath is 5.5~6.5.
The present invention also provides a kind of pair of environment is more friendly, various magnesium alloy substrates are applicable in, matrix is in conjunction with coating
Li Genggao, pre-plating layer corrosion resisting property is more preferable, and the magnesium alloy chromium-free of the straight and even beauty in plating piece surface is without the magnesium alloy of the low sour usage amount of cyanogen
The method of electroplating nickel on surface.
The method of the electroplating nickel on surface of magnesium alloy, by by the zinc-plated magnesium alloy in surface in the combination nickel plating bath
Solution atmosphere in electronickelling, obtain the magnesium alloy of plating nickel on surface.
In the present invention, it is electroplated in the combination nickel plating bath, wherein the temperature of electronickelling process is preferably 50~60
℃。
During the electronickelling, the system pH of electronickelling process is 5.5~6.5;Preferably 6.
The current density of electronickelling is 1.25~1.5A/dm2;Preferably 1.5Adm-2。
In the present invention, the combination nickel plating bath is mutually cooperateed with, then cooperates the electroplating technology, further can effectively be kept away
Exempt from occur burning situation in electroplating process, the binding force of nickel coating and magnesium alloy substrates is big, and the porosity and coating of nickel coating are crisp
Property is small, and plated layer compact, corrosion resistance greatly promote.
Further preferably, the initial current density of electronickelling process is 5Adm-2, 2~5min of time.
For magnesium as a kind of very active metal, electrode potential is -2.358V, and the electrode potential of nickel is -0.25V, two
Person's potential difference is too big, and nickel is difficult to directly deposit in Mg alloy surface.The electrode potential of zinc is -0.76V, between magnesium nickel,
It is zinc-plated to the surface of magnesium alloy before electronickelling, to deposit one layer of zinc in Mg alloy surface, be conducive to electronickelling, improve nickel
Electroplating effect, improve the performance of plating piece obtained.
In the present invention, except the combination nickel plating bath to electronickelling process and in addition to electroplating technology improves, also to electroless zinc plating liquid and
Technique is improved.
Preferably, the process that the surface of magnesium alloy is zinc-plated are as follows: electroless zinc plating will be immersed in by pretreated magnesium alloy
The zinc-plated processing of surface chemistry is carried out in liquid, then washes to obtain the zinc-plated magnesium alloy in surface;The electroless zinc plating liquid is following dense
Spend the aqueous solution of component:
ZnSO430~60g/L;
Water-soluble 100~180g/L of pyrophosphate;
Na2CO35g/L;
3~15g/L of soluble fluoride;
The pH value of the zinc-plated treatment process of surface chemistry is 10.2~10.4;Temperature is zinc-plated 5~12min in 70~80 DEG C.
In the electroless zinc plating liquid, preferably, soluble fluoride is LiF, concentration is preferably 3~15g/L;Or water
Dissolubility fluoride is NaF, and concentration is 5~10g/L;Or soluble fluoride is KF, concentration is preferably 7~15g/L.
In the electroless zinc plating liquid, the water-soluble pyrophosphate is preferably Na4P2O7Or K4P2O7。
Further preferably, the zinc-plated process in the surface of magnesium alloy are as follows: the electroless zinc plating liquid is the component of following concentration
Aqueous solution:
The pH value of the zinc-plated treatment process of surface chemistry is 10.2~10.4;Temperature is zinc-plated 12min in 75 DEG C.
Preferably, zinc-plated processing process circulation in surface carries out repeatedly.
The inventors discovered that carrying out repeating to soak zinc under the conditions of the surface zinc-plated processing, be conducive to improve matrix (magnesium
Alloy) surface zinc-impregnating layer uniformity and combine effect;And then be conducive to improve the compactness of the nickel coating of plating piece obtained
With anti-corrosion effect.
Further preferably, surface zinc-plated processing process circulation carries out 2~3 times.
In the present invention, preferably magnesium alloy is pre-processed before the zinc-plated processing of surface, the pretreated process packet of magnesium alloy
Include the polishing sequentially carried out, oil removing, alkali cleaning, pickling, activation step.
Before magnesium alloy nickel plating, the processing such as surface polishing oil removing acid pickling and rust removing Surface Activated Chemical leaching zinc are carried out to improve base
The binding force of body and coating.In the present invention, to magnesium alloy carry out pretreatment can be used it is well-known to those skilled in the art existing
Technology.
A kind of method of preferred electroplating nickel on surface of magnesium alloy of the invention, specifically includes the following steps:
Step (1): mechanical polishing
Step (2): surface degreasing, alkali cleaning are carried out to the magnesium alloy after polishing;
Step (3): it after step (2) processing, then carries out pickling, be activated;
Step (4): the magnesium alloy after step (3) activation carries out chemical leaching under the electroless zinc plating liquid and treatment process
Zinc processing;
Step (5): selectively circulation carries out step (4);
Step (6);By the magnesium alloy after step (4) or step (5) surface zinc-plated processing in the combination nickel plating bath
Electronickelling processing is carried out, the magnesium alloy that electroplating surface has nickel is obtained.
In step (1), matrix (magnesium alloy) is preferably used into 240#, 400#, 600#, 800#, 1000#, 1200# sand paper successively
Ultrasonic oscillation after polishing.
In step (2): carrying out surface degreasing to the material after polishing can be selected general deoiling method, for example, by using ability
The organic solvents such as acetone known to field technique personnel or trichloro ethylene carry out ultrasonic oscillation oil removing.
In step (2), alkali washing process be may be, for example:
(a): Na2CO315g/L, Na3PO4·12H2O 15g/L, OP-10 3mL/L, time: 10~30min, temperature: 60
~70 DEG C.
Or (b): NaOH50~60g/L, Na2CO3·10H220~25g/L of O, lauryl sodium sulfate 0.5g/L, the time:
2~10min, temperature: 75 DEG C.
Or preferably (c): Na2CO315g/L, Na3PO4·12H2O 15g/L, OP-10 1~3mL/L, Na2SiO3
20g/L, time: 10min, temperature: 60~70 DEG C.
The alkali cleaning time selectively can be adjusted according to magnesium alloy type, surface pollution degree etc. in actual production, had reached
Desired cleaning effect.
After the completion of the alkali cleaning processing of step (2), the acid pickling step of step (3) is carried out, matrix surface oxygen is removed by pickling
Change layer, attachment mechanical detritus, have been inserted into the impurity (exogenous impurity, sand grains, passivating film) of matrix, expose magnesium alloy substrate
Come.Acid cleaning process can use following scheme according to magnesium alloy materials:
For further improve preparation plating piece effect, the present invention also provides a kind of solution of preferred pickling and operations
Technique:
H3PO4240~250mL/L;
HNO310~15mL/L;
0.20~0.3g/L of thiocarbamide;
Temperature: 20~30 DEG C;
Time: 30~50s.
Further preferably, the solution and operating procedure of acid cleaning process are as follows: H3PO4242mL/L;HNO312mL/L;Thiocarbamide
0.25g/L;Temperature: 25 DEG C;Time: 40s.
It is activated again after pickling, further removes matrix surface oxide, and its surface is made to form one layer of fluoride ion
Compound so that its surface is more advantageous to the progress of leaching zinc reaction so that matrix be prevented to be immersed liquid zinc corrosion.Activating ligand below
Side and technique can be applied in the present invention, the activation for substrate:
In addition, aluminium-containing alloy can be activated with HF (70%) 220mL/L, other alloys are activated with HF (70%) 54mL/L.
Step (4) soaks zinc
Described in magnesium alloy after activation carries out under the electroless zinc plating liquid and technological parameter of magnesium alloy of the present invention again
The zinc-plated process in surface.
Step (4) is a chemical zincation process.In the present invention, preferably step (4) circulation is carried out repeatedly, further
Improve leaching zinc effect.
After step (6), step (4) or step (5) electroless zinc plating, then in the combination nickel plating bath atmosphere described in progress
Electronickelling processing, final obtained surface is coated with the magnesium alloy plating piece of nickel.
The method of the present invention is applicable in existing all kinds of magnesium alloys, for example, more applicable magnesium alloy is AZ91D, AZ80, AZ61
Deng.
Advantages of the present invention:
Using chrome-free acid-wash technique of the invention, carrying out activation leaching zinc can be uniform in matrix surface acquisition thickness, in conjunction with
The strong zinc-impregnating layer of power, the nickel coating even compact corrosion resistance for then carrying out electronickelling acquisition on this surface is high, for implementing to be electroplated
Or it is a good guarantee that chemical plating, which more has the subsequent plating layer of decorative effect,.The present invention is mainly to pickling, chemical zincation, plating
The solution and technique of nickel are improved;The improvement, which can effectively avoid in electroplating process, there is burning situation, nickel coating with
The binding force of magnesium alloy substrates is big, and the porosity and coating brittleness of nickel coating are small, and plated layer compact, corrosion resistance greatly promote.
In addition, metallic precoating layer of the invention has the ability of good conductive, thermally conductive and anti-electromagnetic interference, chromium ion pair is also avoided
It is seriously polluted caused by environment, is a kind of environmentally friendly pretreating process.Low in raw material price in present invention process, can
Production cost is reduced, is increased economic efficiency.Pretreating process of the invention is simple, and solution easily configures, process stabilizing, is suitable for each
The pretreatment of kind magnesium alloy plating chemical plating.
Detailed description of the invention
Fig. 1 is the photo figure of the magnesium alloy after 1 step of embodiment (5) activation;
Fig. 2 is the photo figure of the magnesium alloy after 1 step of embodiment (7) secondary soaking zinc;
Fig. 3 is the digital photograph figure of the magnesium alloy after 1 step of embodiment (8) electronickelling;
Fig. 4 is the sectional view of the magnesium alloy nickel after 1 step of embodiment (8) electronickelling;
Fig. 5 is the SEM microscopic appearance figure of the nickel coating of the magnesium alloy after 1 step of embodiment (8) electronickelling;
Fig. 6 is different leaching zinc mode rear surface Zn content comparison diagrams;
Fig. 7 is XRD material phase analysis figure after embodiment 1AZ91D magnesium alloy substrate and step (8) nickel plating;
Fig. 8 is 1 electroless nickel layer Surface scan surface composition measurement chart of embodiment;
Fig. 9 is condition pulse 1000Hz, duty ratio be 80% in the case where embodiment 1 made from after electronickelling
AZ91D magnesium alloy plating nickel layer polarization curve;
Figure 10 is condition pulse 1000Hz, duty ratio be 40% in the case where embodiment 1 made from after electronickelling
AZ91D magnesium alloy plating nickel layer polarization curve;
Figure 11 is condition pulse 1000Hz, duty ratio be 60% in the case where embodiment 1 made from after electronickelling
AZ91D magnesium alloy plating nickel layer polarization curve;
Figure 12 is condition pulse 1000Hz, duty ratio be 100% in the case where embodiment 1 made from after electronickelling
AZ91D magnesium alloy plating nickel layer polarization curve.
Specific embodiment
Below in conjunction with example, the present invention will be further described.
Material AZ91D magnesium alloy, specific implementation step are as follows:
One, preprocessing part one
Step (1): mechanical polishing successively polishes matrix with 240#, 400#, 600#, 800#, 1000#, 1200# sand paper.
Sample goes flash removed oxide skin to reduce surface roughness, and washes surface residual debris.
Step (2): ultrasonic oil removal soaked in absolute ethyl alcohol ultrasonic oscillation temperature: room temperature time: 30min.
Step (3): alkali cleaning
Solution allocation and operating condition are as follows: Na2CO3 40g/L Na3PO4 10g/L Na2SiO320g/L OP emulsifier
65 DEG C of times of 3mL/L temperature: 30min.
Step (4): pickling
Solution allocation and operating condition are as follows: H3PO4 242mL/L HNO312mL/L thiocarbamide 0.25g/L temperature: 25 DEG C
Time: 40s.
Step (5): activation
Solution allocation and operating condition are as follows: H3PO4 25mL/L K4P2O7 76g/LKF7g/L Na2CO315g/L temperature
Degree: 55 DEG C of times: 4min.Digital photograph such as Fig. 1;As shown in Figure 1, sample after activation surfacing, oxide-free residual;
Step (6): leaching zinc
Solution allocation and operating condition are as follows: ZnSO4 50g/L K4P2O7 174g/LNa2CO35g/L LiF11g/L tune
Section pH value of solution is 10.2~10.4 temperature: 75 DEG C of times: 15min
Step (7): it repeats leaching zinc: repeating step 6 and operate once.Digital photograph such as Fig. 2;As shown in Figure 2, sample after leaching zinc
Surface forms one layer of fine and close zinc-impregnating layer;
Two, preprocessing part two
Step (8): electronickelling
Solution allocation and operating condition are as follows: NiSO4·6H2O 120g/L NH4HF2 40g/L(NH4)3C6H5O7 10g/L
Saccharin sodium 2g/L benzene sulfinic acid sodium salt 0.5g/L, Isosorbide-5-Nitrae-butynediols 0.3g/L.Ammonium hydroxide 40mL/L lauryl sodium sulfate
0.1g/L temperature: 50~60 DEG C of magnetic agitations: 20r/min pulsewidth: 1ms duty ratio: 80% current density: 1.25Adm-2When
Between: it is 6 that 1.5h ammonium hydroxide, which adjusts pH value,.Initial current density is 5Adm-2, time 2min.Digital photograph such as Fig. 3
Fig. 4 is the sectional view of the magnesium alloy nickel after the present embodiment electronickelling;It is scanned by Fig. 4 electronickelling specimen cross section line
Test analysis would know that plating thickness is about 30 μm, and can obtain solution plating speed is about 0.33 μm/min, while knowing that plating solution has
Good depth capability, coating and matrix are well combined.
Fig. 5 is the SEM microscopic appearance figure of the nickel coating of the magnesium alloy after the present embodiment electronickelling;It would know that, be electroplated by Fig. 5
The institutional framework of nickel layer is fine and close.
Fig. 6 is different leaching zinc mode rear surface Zn content comparison diagrams, i.e. the table of the sample of step (6) and step (7) leaching zinc
The comparison diagram of face Zn content.More uniform zinc-impregnating layer can be obtained in sample surfaces by repeating leaching zinc as shown in Figure 6.
In addition, by the magnesium alloy and nickel coating XRD object phase of Fig. 7 and the nickel plating plane scan constituent analysis of Fig. 8, wherein Fig. 8
(a) be partially nickel coating surface scan figure, (b) of Fig. 8 partially pass through for the elemental analysis figure of superficial layer as seen from the figure
The present invention obtains the uniform nickel coating of a composition of layer in AZ91D Mg alloy surface.
Fig. 9~Figure 12 is condition pulse 1000Hz, the AZ91D magnesium alloy plating under different duty after embodiment electronickelling
Nickel layer polarization curve;By Fig. 9~Figure 12 it is found that the corrigendum of gained corrosion of coating current potential, corrosion in the case where duty ratio is 80%
Electric current is smaller, i.e., corrosion resisting property is more preferable.In addition, as shown in Figure 9, the nickel coating corrosion potential obtained through the invention is-
0.055v, relative to (Yang H, Guo X, Chen X, et al.A homogenisation pre-treatment in document
for adherent and corrosion-resistant Ni electroplated coatings on Mg-alloy
AZ91D [J] .Corrosion Science, 2014,79 (2): 41-49.) nickel coating corrosion potential has in -0.2V to -0.3V
The current potential of corrigendum, while polarization current is opposite with an order of magnitude small in document, that is, has higher corrosion resisting property.
In addition, to progress thermal shock and file test made from the embodiment of the present invention, comply fully with standard GB/T/
The requirement of T13913-92.
Claims (10)
1. a kind of combination nickel plating bath for magnesium alloy plating nickel, which is characterized in that it is the aqueous solution of following density component,
In,
100 ~ 200g/L of nickel sulfate;
5 ~ 60g/L of soluble fluoride;
2.5 ~ 30g/L of ammonium citrate;
1 ~ 3g/L of saccharin sodium;
0.5 ~ 1g/L of benzene sulfinic acid sodium salt;
Isosorbide-5-Nitrae -0.3 ~ 0.5g/L of butynediols;
0.1 ~ 0.2g/L of lauryl sodium sulfate;
30 ~ 50mL/L of pH adjusting agent;
The pH of the combination nickel plating bath is 5.5 ~ 6.5.
2. being used for the combination nickel plating bath of magnesium alloy plating nickel as described in claim 1, which is characterized in that the combination nickel plating
The pH of liquid is 6.
3. being used for the combination nickel plating bath of magnesium alloy plating nickel as claimed in claim 1 or 2, which is characterized in that described is water-soluble
Property fluoride be at least one of potassium fluoride, sodium fluoride, lithium fluoride, ammonium acid fluoride;PH adjusting agent is ammonium hydroxide.
4. a kind of method of electroplating nickel on surface of magnesium alloy, which is characterized in that by by the zinc-plated magnesium alloy in surface in claim 1
Electronickelling in the solution atmosphere of ~ 3 described in any item combination nickel plating baths, obtains the magnesium alloy of plating nickel on surface.
5. the method for electroplating nickel on surface of magnesium alloy as claimed in claim 4, which is characterized in that the zinc-plated mistake in the surface of magnesium alloy
Journey are as follows: the progress zinc-plated processing of surface chemistry in electroless zinc plating liquid will be immersed in by pretreated magnesium alloy, then wash to obtain table
The zinc-plated magnesium alloy in face;The electroless zinc plating liquid is the aqueous solution of following density component:
ZnSO430~60g/L;
Water-soluble 100 ~ 180g/L of pyrophosphate;
Na2CO35g/L;
3 ~ 15g/L of soluble fluoride;
The pH value of the zinc-plated treatment process of surface chemistry is 10.2 ~ 10.4;Temperature is zinc-plated 5 ~ 12min in 70 ~ 80 DEG C.
6. the method for electroplating nickel on surface of magnesium alloy as claimed in claim 5, which is characterized in that surface zinc-plated processing process circulation
It carries out multiple.
7. the method for electroplating nickel on surface of magnesium alloy as claimed in claim 5, which is characterized in that the preprocessing process packet of magnesium alloy
Include the polishing sequentially carried out, oil removing, alkali cleaning, pickling, activation step.
8. the method for electroplating nickel on surface of magnesium alloy as claimed in claim 7, which is characterized in that the solution of acid cleaning process and operation
Technique are as follows:
H3PO4240~250mL/L ;
HNO310~15mL/L ;
0.20 ~ 0.3g/L of thiocarbamide;
Temperature: 20 ~ 30 DEG C;
Time: 30 ~ 50s.
9. such as the method for the described in any item electroplating nickel on surface of magnesium alloy of claim 4 ~ 7, which is characterized in that electronickelling process
Temperature is 50 ~ 60 DEG C;The system pH of electronickelling process is 5.5 ~ 6.5.
10. the method for electroplating nickel on surface of magnesium alloy as claimed in claim 9, which is characterized in that the current density of electronickelling is
1.25~1.5A/dm2。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1208886A (en) * | 1966-10-28 | 1970-10-14 | M & T Chemicals Inc | Improvements in or relating to electrolytic nickel plating |
CN101021009A (en) * | 2007-03-09 | 2007-08-22 | 湖南大学 | Nickel pre-coating process and nickel pre-coating solution for magnesium alloy surface |
CN101280445A (en) * | 2008-05-16 | 2008-10-08 | 广州杰赛科技股份有限公司 | Electroplating process for surface of magnesium alloy motorcycle hub |
JP2015212417A (en) * | 2014-04-25 | 2015-11-26 | キーソウ ドクトル ブリンクマン ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディトゲゼルシャフト | Electrolytic bath for precipitation of bright nickel layer, mixture for use in electrolytic bath for precipitation of bright nickel layer and production method of article having bright nickel layer |
CN105780073A (en) * | 2016-04-21 | 2016-07-20 | 江门市瑞期精细化学工程有限公司 | Backing method for cyanide-free nickel electroplating on magnesium-lithium alloy |
-
2016
- 2016-10-21 CN CN201610919745.7A patent/CN106245070B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1208886A (en) * | 1966-10-28 | 1970-10-14 | M & T Chemicals Inc | Improvements in or relating to electrolytic nickel plating |
CN101021009A (en) * | 2007-03-09 | 2007-08-22 | 湖南大学 | Nickel pre-coating process and nickel pre-coating solution for magnesium alloy surface |
CN101280445A (en) * | 2008-05-16 | 2008-10-08 | 广州杰赛科技股份有限公司 | Electroplating process for surface of magnesium alloy motorcycle hub |
JP2015212417A (en) * | 2014-04-25 | 2015-11-26 | キーソウ ドクトル ブリンクマン ゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディトゲゼルシャフト | Electrolytic bath for precipitation of bright nickel layer, mixture for use in electrolytic bath for precipitation of bright nickel layer and production method of article having bright nickel layer |
CN105780073A (en) * | 2016-04-21 | 2016-07-20 | 江门市瑞期精细化学工程有限公司 | Backing method for cyanide-free nickel electroplating on magnesium-lithium alloy |
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