CN100412232C - Method for chemical plating nickel-boron alloy on magnesium alloy surface - Google Patents
Method for chemical plating nickel-boron alloy on magnesium alloy surface Download PDFInfo
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- CN100412232C CN100412232C CNB2006100053305A CN200610005330A CN100412232C CN 100412232 C CN100412232 C CN 100412232C CN B2006100053305 A CNB2006100053305 A CN B2006100053305A CN 200610005330 A CN200610005330 A CN 200610005330A CN 100412232 C CN100412232 C CN 100412232C
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Abstract
The present invention discloses a method for chemically plating nickel-boron alloy on a magnesium alloy surface, which relates to a technique for chemically plating nickel-boron alloy on the surface of AZ91D magnesium alloy. The present invention provides a technique method which has the advantages of low technique cost, simple operation and is favorable for environment; in addition, the technique method can obtain a chemical plating nickel-boron alloy plating layer with excellent performance on the surface of AZ91D magnesium alloy. The present invention comprises the following steps: washing in alkali; washing the AZ91D magnesium alloy in water after the AZ91D magnesium alloy is treated in a solution composed of sodium carbonate, sodium phosphate and triton X-100; washing in acid; washing the AZ91D magnesium alloy in water after the AZ91D magnesium alloy is treated in a solution composed of glacial acetic acid and sodium nitrate; chemically plating; after the AZ91D magnesium alloy is washed in the alkali and the acid, washing the AZ91D magnesium alloy in water to obtain a nickel-boron alloy plating layer after being chemically plated in a chemical plating solution composed of nickel acetate, sodium borohydride, ethylene diamine, sodium hydroxide and compound additive; drying the AZ91D magnesium alloy plated with the nickel-boron alloy plating layer.
Description
Technical field
The present invention relates to a kind of AZ91D chemical plating nickel-boron alloy on magnesium alloy surface technology.
Background technology
That magnesium alloy has is in light weight, shock absorption and thermal diffusivity height, casting and excellent cutting performance, electromagnetic immunity barrier height, and antifatigue, nontoxic, nonmagnetic, advantage such as crackle proneness is low and recyclable, be successfully applied to numerous areas such as traffic, computer, communication, consumer electrical equipment, defence and military.But the solidity to corrosion of magnesium is relatively poor, and this is the bottleneck that the restriction magnesium alloy elicits latent faculties.On the other hand, because the hardness of magnesium alloy is low, wear resistance is poor, has therefore restricted a large amount of uses of magnesium alloy.For solidity to corrosion and the wear resistance that improves magnesium alloy, it is carried out suitable surface modification is necessary.
Electroless plating has that thickness of coating is even, chemical stability good, any surface finish is smooth, workable, method simply is easy to control, can obtain uniform coating on complex-shaped foundry goods, the performance of coating can advantage such as regulate according to different needs.At present, the research of magnesium alloy surface chemical plating is also fewer, and great majority research concentrates on the chemical plating Mi-P alloy, and there are the following problems for the technology that these researchs obtain:
(1) contain the compound of chromium and fluorine in pre-treatment and the chemical plating fluid, to environment harmful (Surface and CoatingsTechnology, 2004,179:124-134).
(2) adopt fluorochemical activation direct chemical plating Ni-P bonding force not high (patent CN02144834.5), need preplating in order to improve bonding force, cause technology loaded down with trivial details (Corrosion Science, 2004,46:1467-1477).
(3) processing requirement strictness, the pH value changes narrow, difficult in maintenance (Metal Finishing, 1998,3:12-18).
Electroless Plating Ni-B alloy is to utilize borane reducing agent hydride or amido borine, make that the nickel ion in the nickel salt is reduced into metallic nickel in the plating bath, and deposit on the sample surfaces, the boron atom that reductive agent decomposition is simultaneously produced can dissolve in the nickel, has formed the supersaturated solid solution of boracic.For iron, copper etc. the metal and the alloy thereof of katalysis are arranged, can directly deposit the Ni-B alloy (Surface andCoatings Technology, 2000,124:201-209).Electroless Plating Ni-B alloy is a kind of good functional coating, and its contact resistance is approaching with silver, is a kind of good in silvering and contact material; And has good solderability and melting welding ability, good bonding and electroconductibility; The coating hardness height, after heat treatment its hardness can be up to 1160HV, and is more taller than hard chromium; Excellent and the chemical plating Mi-P alloy of wear resistance, after heat treatment, its wear resistance surpasses hard chrome.
At present, also do not plate the document and the patent report of Ni-B alloy both at home and abroad about magnesium alloy chemical.With the Electroless Plating Ni-B alloy phase ratio of other base material such as iron, copper and alloy thereof, the Electroless Plating Ni of magnesium alloy-B alloy is difficulty comparatively, is applicable to that the general chemistry plating bath of base material such as iron and steel is not suitable for magnesium alloy.The AZ91D magnesium alloy is to use maximum diecast magnesium alloys at present, mainly has following difficult point at AZ91D Mg alloy surface direct chemical plating Ni-B alloy:
(1) the AZ91D magnesium alloy is by two phase composites, and main body is a α phase (Mg) and intermetallic compound β (Mg mutually
17Al
12), make the sample surfaces current potential not wait, forming microbattery is the major cause that the AZ91D magnesium alloy is difficult to plating.
(2) the Mg alloy is active, and loose MgO can form rapidly at alloy surface, hinders metal refining and substrate to form metallic bond.
(3) traditional general selective chlorination nickel of chemical nickel plating or single nickel salt are main salt, and most of plating bath has corrosion to magnesium, is particularly containing Cl
-, SO
42-Salts solution in, the erosion rate of Mg is bigger; Under the unstress state, Mg-Al-Zn is that the erosion rate of alloy is Cl in the different anions medium
-＞SO
4 2-＞NO
3 -＞Ac
-＞CO
3 2-Existing magnesium alloy surface chemical plating Ni-P alloy generally adopts basic nickel carbonate.But the price of basic nickel carbonate is too high, and the cost of electroless plating is multiplied; Basic nickel carbonate is water insoluble in addition, must use hydrofluoric acid dissolution earlier before preparation, and dissolution process is time-consuming, also can produce environmental pollution, reduces production efficiency; The another one problem of using basic nickel carbonate to do the nickel salt existence is that bath life is short, when cause is replenished nickel in the plating bath life-time service, must increase fluorinion concentration in the plating bath, and the solubility of fluorides of nickel is very little, finally in the electroless plating process, generate precipitation, cause nickel to replenish, bath life shortens.
(4) hydrolysis easily takes place in the sodium borohydride as reductive agent in Electroless Plating Ni-B alloy in acid and neutral solution, for fear of hydrolysis and obtain higher sedimentation rate, must make plating bath keep strong basicity, and in the alkaline medium of pH＞11, the Mg surface can form the Mg (OH) of insoluble
2Film influences combining of coating and substrate.
Summary of the invention
It is low, simple to operate, environmentally friendly that purpose of the present invention aims to provide a kind of technology cost, can be in the processing method of the Electroless Plating Ni-B alloy layer of AZ91D Mg alloy surface obtained performance excellence.
Its step of the present invention is as follows:
Step 1: alkali cleaning, at 60～75 ℃ and add under the ultrasonic wave condition, magnesium alloy is put into by 15～20gL
-1Yellow soda ash, 15～20gL
-1Sodium phosphate, 5～10mLL
-1Handle 10～15min in the solution that Triton X-100 (OP-10) is formed, take out the back and use water rinse, remove the greasy dirt on surface and the impurity of absorption, described magnesium alloy is the AZ91D magnesium alloy;
Step 2: pickling, in room temperature and adding under the ultrasonic wave condition, will put into by 15～25mLL through the magnesium alloy after step 1 is handled
-1Glacial acetic acid (36%), 35～50gL
-1Handle 0.5～1.5min in the solution that SODIUMNITRATE is formed, take out the back and use water rinse, remove the oxide compound of surface porosity and the residual alkaline matter that neutralizes;
Step 3: electroless plating, under 80～90 ℃, will put into by 35～40gL through the magnesium alloy after alkali cleaning and the cleanup acid treatment
-1Nickelous acetate, 0.55～0.6gL
-1Sodium borohydride, 50～55mlL
-1Quadrol, 30～60gL
-1Electroless plating 2～3h in the chemical plating solution that sodium hydroxide and composite additive are formed takes out the back water rinse, obtains the Ni-B alloy layer; Described composite additive comprises 5～8gL
-1P-TOLUENE SULFO ACID 99's sodium, 2～6gL
-1Propanedioic acid, 30～60mgL
-1Sulphosalicylic acid;
Step 4: the magnesium alloy that will be coated with the Ni-B alloy layer is under 150～180 ℃, and 30～45min is handled in oven dry, to remove surface-moisture.
The present invention has at first adopted special acid cleaning process, need not preplating and can obtain the bottom that one deck has catalytic activity at the AZ91D Mg alloy surface, and this technology cost is low, simple to operate, does not contain chromium and fluorine cpd, and is environmentally friendly; The second, adopting the salt of weak acid nickel acetate is main salt, has both avoided Cl in the plating bath
-, SO
4 2-A large amount of existence to the corrosion of magnesium, also avoided using the variety of problems of basic nickel carbonate, obtained good deposition effect; The 3rd, by in chemical plating fluid, adding composite additive, make and preferentially carry out in the situation deposit reaction of plating bath pH＞11, avoided the substrate alkaline etching, obtained well behaved coating, coating has high surface hardness, good bonding force and corrosion resisting property.But and chemical plating fluid operating restraint wide (pH＞12.8), by adding the plating continuously of each main component, good actual application prospect is arranged.
Description of drawings
Fig. 1 is the AZ91D Mg alloy surface pattern (SEM, * 500) after alkali cleaning is handled.
Fig. 2 is the AZ91D Mg alloy surface pattern (SEM, * 1000) after cleanup acid treatment.
Fig. 3 is the AZ91D Mg alloy surface pattern (SEM, * 1000) after Electroless Plating Ni-B handles.
Fig. 4 is the AZ91D magnesium alloy cross section pattern (SEM, * 3000) after Electroless Plating Ni-B handles.
Fig. 5 is the AZ91D magnesium alloy XRD structural analysis that Electroless Plating Ni-B handles the back and do not have to handle.In Fig. 5, X-coordinate be 2Theta (°), ordinate zou is Counts; A is Mg, and B is Mg
17Al
12
Fig. 6 is deposition Ni-B coating and the AZ91D magnesium alloy electrokinetic potential scanning polarization curve in 3.5% sodium chloride solution that does not deposit Ni-B coating.In Fig. 6, X-coordinate is I (log (A)), and ordinate zou is E (mv Vs.SCE).
Fig. 7 is the AZ91D Mg alloy surface pattern (SEM, * 1500) after Electroless Plating Ni-B handles among the embodiment 2.
Embodiment
Embodiment 1
1) alkali cleaning, under the room temperature, (1L) adds yellow soda ash (15g), sodium phosphate (15g), OP-10 (5mL) successively in deionized water, wait to dissolve complete post-heating to 75 ℃, the AZ91D magnesium alloy sample that will be processed into 10mm * 10mm * 2mm size is put into the lasting ultrasonic stirring of this soda-wash solution, takes out behind the processing 15min.Under the room temperature, put into and take out after the mobile deionized water cleans 2min.AZ91D magnesium alloy sample surfaces pattern after the processing is seen Fig. 1, shows through obtaining the AZ91D magnesium alloy mechanical polishing surface of cleaning after the alkali cleaning.
2) pickling, under the room temperature, (1L) adds 36% Glacial acetic acid (18mL), SODIUMNITRATE (36g) successively in deionized water, and the AZ91D magnesium alloy after will handling through alkali cleaning is put into this Acidwash solution and is continued ultrasonic stirring, handles after 75 seconds and takes out.Under the room temperature, the AZ91D magnesium alloy put into take out after the mobile deionized water cleans 2min.AZ91D magnesium alloy sample surfaces pattern (SEM after the processing, * 1000) see Fig. 2, show the rete that obtains to have mesh-like structure after overpickling at the AZ91D Mg alloy surface, this rete and substrate are adhered to closely, increase surperficial roughness, helped the machinery wedging of chemical plating.
3) Electroless Plating Ni-B, under the room temperature, (700mL) adds nickelous acetate (37g) in deionized water, after treating dissolving fully, stir and add quadrol (50mL) down, to be cooledly after room temperature, under agitation add composite additive, be followed successively by: P-TOLUENE SULFO ACID 99's sodium (5g), propanedioic acid (2g), sulphosalicylic acid (30mg), treat under agitation to add sodium hydroxide (40g) after the dissolving fully, wait to dissolve complete back and add sodium borohydride (0.55g), add deionized water at last, be heated to 85 ℃ of constant temperature to 1L, to put into this constant temperature solution through the AZ91D magnesium alloy after the above-mentioned processing, under agitation condition, take out behind the processing 2h.Under the room temperature, the AZ91D magnesium alloy that is coated with Ni B coating put into take out after the mobile deionized water cleans 2min.
4) oven dry is put into the AZ91D magnesium alloy at last and is taken out after 180 ℃ of baking ovens are dried 30min.Be coated with the AZ91D Mg alloy surface pattern (SEM of Ni-B coating, * 1000) and cross section pattern (SEM, * 3000) see Fig. 3 and Fig. 4 respectively, show that Electroless Plating Ni-B coating is by tightly packed the forming of born of the same parents' shape deposited particles, whole coating surface is smooth, fine and close, smooth, coating and substrate have the mechanical snap feature, in conjunction with tight.Plating is handled the back and is not had the AZ91D magnesium alloy XRD surface structure analysis of processing to see Fig. 5 through Ni-B, show that Electroless Plating Ni-B coating is amorphous alloy (the XRD spectrum has tangible bag shape diffraction peak), the coating results of elemental analyses shows, by quality than coating consist of Ni 93.75%, B 6.25%.
Below provide the performance of embodiment 1 gained coating.
1, coating bonding properties:
A, qualified by the bonding force of mensuration coating of the scratch method among the standard GB 5270-85 and matrix.
B, qualified by the bonding force of mensuration coating of the thermal shock method among standard GB/T 13913-92 and matrix.
C, carry out bonding strength experiment, record the bonding force＞45MPa of coating and substrate by ASTM-F1044.
2, corrosion resistance coating:
Experimental system is a 3.5%NaCl solution, and used medicine sodium-chlor is analytical pure, and solution uses the redistilled water preparation.Adopt three-electrode system, saturated calomel electrode is reference electrode (SCE), and platinized platinum is a supporting electrode, and the working electrode working area is 10mm * 10mm, the non-working surface epoxy encapsulation.Adopt electrokinetic potential sweep measurement polarization curve, sweep velocity is 0.1mVs
-1Begin scanning from relative corrosion potential-0.15V, to the passive film puncture, till corrosion current sharply increases.Fig. 6 is seen in the AZ91D magnesium alloy that deposits Ni-B coating after treatment and do not deposit Ni-B coating electrokinetic potential scanning polarization curve contrast in 3.5% sodium chloride solution, show that the Ni-B coating that this technology obtains has good corrosion resisting property, the corrosion current of AZ91D magnesium alloy in 3.5% sodium chloride solution that has deposited Ni-B coating is than little nearly 2 orders of magnitude of the AZ91D magnesium alloy that does not deposit Ni-B coating, corrosion potential improves 1000mV, and experimental result is listed in table 1.
Table 1
3, other performance of coating:
Other performance of coating sees Table 2.
Table 2
1) alkali cleaning, under the room temperature, (1L) adds yellow soda ash (20g), sodium phosphate (20g), OP-10 (10mL) successively in deionized water, waits to dissolve complete post-heating to 60 ℃, AZ91D magnesium alloy sample is put into this soda-wash solution continue ultrasonic stirring, take out behind the processing 10min.Under the room temperature, the AZ91D magnesium alloy after handling put into take out after the mobile deionized water cleans 4min.
2) pickling is with embodiment 1.
3) Electroless Plating Ni-B, under the room temperature, after (700mL) adding nickelous acetate (38g) is treated dissolving fully in deionized water, stir and add quadrol (52mL) down, to be cooledly after room temperature, under agitation add composite additive, be followed successively by: P-TOLUENE SULFO ACID 99's sodium (6g), propanedioic acid (3g), sulphosalicylic acid (50mg), treat under agitation to add sodium hydroxide (28g) after the dissolving fully, wait to dissolve complete back and add sodium borohydride (0.56g), add deionized water at last to 1L, be heated to 85 ℃ of constant temperature, the AZ91D magnesium alloy after handling is put into this constant temperature solution, agitation condition takes out after handling 3h down.Under the room temperature, the AZ91D magnesium alloy behind Electroless Plating Ni-B put into take out after the mobile deionized water cleans 4min.
4) oven dry is with embodiment 1.
AZ91D Mg alloy surface pattern (SEM, * 1500) after Electroless Plating Ni-B handles is seen Fig. 7, shows Electroless Plating Ni-B coating by tightly packed the forming of born of the same parents' shape deposited particles, and whole coating surface is smooth, fine and close, smooth.
Below provide the performance of gained coating.
1, coating bonding properties:
Testing method and experimental result are with embodiment 1.
2, corrosion resistance coating:
Testing method and experimental result are with embodiment 1.
3, other performance of coating:
Other performance of coating sees Table 3.
Table 3
Embodiment 3
1) alkali cleaning is with embodiment 1.
2) pickling, under the room temperature, (1L) adds 36% Glacial acetic acid (22mL), SODIUMNITRATE (45g) successively in deionized water, the AZ91D magnesium alloy after handling put into this solution continue ultrasonic stirring, handles after 30 seconds and takes out, washed with de-ionized water.
3) Electroless Plating Ni-B, under the room temperature, (700mL) adds nickelous acetate (40g) in deionized water, after treating dissolving fully, stir and add quadrol (55mL) down, the to be cooled stirring after the room temperature adds composite additive down, be followed successively by: P-TOLUENE SULFO ACID 99's sodium (8g), propanedioic acid (6g), sulphosalicylic acid (60mg), treat under agitation to add sodium hydroxide (48g) after the dissolving fully, wait to dissolve complete back and add sodium borohydride (0.6g), add deionized water at last to 1L, be heated to 80 ℃ of constant temperature, AZ91D magnesium alloy is after treatment put into this constant temperature solution, and agitation condition takes out washed with de-ionized water after handling 3h down
4) oven dry will be taken out after the AZ91D magnesium alloy after Electroless Plating Ni-B handles is put into 150 ℃ of baking oven oven dry 45min.
The gained coating performance is with embodiment 1.
Embodiment 4
1) alkali cleaning is with embodiment 1.
2) pickling, under the room temperature, (1L) adds 36% Glacial acetic acid (20mL), SODIUMNITRATE (40g) successively in deionized water, the AZ91D magnesium alloy after handling put into this Acidwash solution continue ultrasonic stirring, handles after 60 seconds and takes out, washed with de-ionized water.
3) Electroless Plating Ni-B, under the room temperature, after (700mL) adding nickelous acetate (40g) is treated dissolving fully in deionized water, stir and add quadrol (55mL) down, the to be cooled stirring after the room temperature adds composite additive down, be followed successively by: P-TOLUENE SULFO ACID 99's sodium (6g), propanedioic acid (4g), sulphosalicylic acid (40mg), treat under agitation to add sodium hydroxide (44g) after the dissolving fully, wait to dissolve complete back and add sodium borohydride (0.6g), add deionized water at last to 1L, be heated to 85 ℃ of constant temperature, the AZ91D magnesium alloy after handling is put into this constant temperature solution, agitation condition takes out washed with de-ionized water after handling 2h down.
4) oven dry is with embodiment 1.
The gained coating performance is with embodiment 1.
1) alkali cleaning, under the room temperature, (1L) adds yellow soda ash (18g), sodium phosphate (18g), OP-10 (8mL) successively in deionized water, wait to dissolve complete post-heating to 70 ℃, the AZ91D magnesium alloy is put into this soda-wash solution continue ultrasonic stirring, take out washed with de-ionized water behind the processing 10min
2) pickling is with embodiment 1.
3) Electroless Plating Ni-B, under the room temperature, after (700mL) adding nickelous acetate (38g) is treated dissolving fully in deionized water, stir and add quadrol (52mL) down, the to be cooled stirring after the room temperature adds composite additive down, be followed successively by: P-TOLUENE SULFO ACID 99's sodium (5g), propanedioic acid (2g), sulphosalicylic acid (30mg), treat under agitation to add sodium hydroxide (36g) after the dissolving fully, wait to dissolve complete back and add sodium borohydride (0.57g), add deionized water at last to 1L, be heated to 85 ℃ of constant temperature, AZ91D magnesium alloy is after treatment put into this constant temperature solution, agitation condition takes out washed with de-ionized water after handling 2.5h down.
4) oven dry is with embodiment 1.
The gained coating performance is with embodiment 1.
Claims (3)
1. the method for chemical plating nickel-boron alloy on magnesium alloy surface is characterized in that its step is as follows:
Step 1: alkali cleaning, at 60～75 ℃ and add under the ultrasonic wave condition, magnesium alloy is put into soda-wash solution handle 10～15min, take out the back water rinse;
Step 2: pickling, in room temperature and adding under the ultrasonic wave condition, will put into Acidwash solution through the magnesium alloy after step 1 is handled and handle 0.5～1.5min, take out the back and uses water rinse, Acidwash solution is by 15～25mLL
-1Glacial acetic acid and 35～50gL
-1SODIUMNITRATE form, wherein the concentration of Glacial acetic acid is 36%;
Step 3: electroless plating, under 80～90 ℃, will put into chemical plating solution electroless plating 2～3h through the magnesium alloy after alkali cleaning and the cleanup acid treatment, take out the back water rinse, obtain the Ni-B alloy layer, chemical plating solution is by 35～40gL
-1Nickelous acetate, 0.55～0.6gL
-1Sodium borohydride, 50～55mlL
-1Quadrol, 30～60gL
-1Sodium hydroxide and composite additive are formed, and composite additive comprises 5～8gL
-1P-TOLUENE SULFO ACID 99's sodium, 2～6gL
-1Propanedioic acid, 30～60mgL
-1Sulphosalicylic acid;
Step 4: the magnesium alloy that will be coated with the Ni-B alloy layer is put into baking oven under 150～180 ℃, and 30～45min is handled in oven dry.
2. the method for chemical plating nickel-boron alloy on magnesium alloy surface as claimed in claim 1 is characterized in that described magnesium alloy is the AZ91D magnesium alloy.
3. the method for chemical plating nickel-boron alloy on magnesium alloy surface as claimed in claim 1 is characterized in that described soda-wash solution is by 15～20gL
-1Yellow soda ash, 15～20gL
-1Sodium phosphate, 5～10mLL
-1Triton X-100 is formed.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775606A (en) * | 2010-03-09 | 2010-07-14 | 哈尔滨工程大学 | Nickel plating process method of magnesium alloy |
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| CN100366579C (en) * | 2006-09-22 | 2008-02-06 | 北京工业大学 | Preparation method of alloy cladding type TiB2 powder |
| CN101423948B (en) * | 2007-10-30 | 2011-09-07 | 比亚迪股份有限公司 | ZA magnesium alloy chemical pre-processing method |
| CN111118480B (en) * | 2020-01-14 | 2022-02-11 | 常州大学 | Chemical plating solution for low-temperature chemical plating of Ni-B binary alloy layer and chemical plating method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039450A (en) * | 1988-06-09 | 1990-02-07 | 联合工艺公司 | Contain ethylene thiourea, can plate the electroless nickel plating-B solution composition of tool abrasion coating |
| JPH06192846A (en) * | 1992-12-25 | 1994-07-12 | Taiho Kogyo Co Ltd | Ni-b electrolees-plating solution, plating bath or replenishing solution and plating method |
| US20040144285A1 (en) * | 2002-10-04 | 2004-07-29 | Enthone Inc. | Process and electrolytes for deposition of metal layers |
-
2006
- 2006-01-13 CN CNB2006100053305A patent/CN100412232C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039450A (en) * | 1988-06-09 | 1990-02-07 | 联合工艺公司 | Contain ethylene thiourea, can plate the electroless nickel plating-B solution composition of tool abrasion coating |
| JPH06192846A (en) * | 1992-12-25 | 1994-07-12 | Taiho Kogyo Co Ltd | Ni-b electrolees-plating solution, plating bath or replenishing solution and plating method |
| US20040144285A1 (en) * | 2002-10-04 | 2004-07-29 | Enthone Inc. | Process and electrolytes for deposition of metal layers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775606A (en) * | 2010-03-09 | 2010-07-14 | 哈尔滨工程大学 | Nickel plating process method of magnesium alloy |
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