CN103233253B - Black Mn-Fe-P-B composite plating solution as well as using method and film layer formed by solution - Google Patents
Black Mn-Fe-P-B composite plating solution as well as using method and film layer formed by solution Download PDFInfo
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- CN103233253B CN103233253B CN201310198532.6A CN201310198532A CN103233253B CN 103233253 B CN103233253 B CN 103233253B CN 201310198532 A CN201310198532 A CN 201310198532A CN 103233253 B CN103233253 B CN 103233253B
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Abstract
The invention discloses a black Mn-Fe-P-B composite plating solution as well as a using method and a film layer formed by the solution. The plating solution includes the following components: main salts consisting of 80grams/liter-90 grams/liter of manganous dihydrogen phosphate, 20 grams/liter-40 grams/liter of fluoborate and 150 grams/liter -200 grams/liter of ferric sulfate, additives consisting of 3 grams/liter-5 grams/liter of glycine, 1 gram/liter -3 grams/liter of peregalO-20 and 0.5 gram/liter -1 gram/liter of dodecyl sulfonate, a pH regulating gent including sulfuric acid for regulating the pH value to 2-4, wherein the fluoborate is potassium fluoborate, sodium fluoborate or complex thereof, the dodecyl sulfonate is potassium dodecyl sulfate, sodium dodecyl sulfate or complex thereof. The process conditions are as follows: the temperature condition is normal temperature, the single pulse current with pulse width is 100 microseconds and period of 1000 microseconds are selected, wherein the average current density range is 5A/dm<2>-10A/dm<2>, and the voltage range is 5V-15V, and the electroplating time is 5 minutes to 10 minutes. The obtained film layer can be used for replacing a nickel-black chromium electroplating process in environments.
Description
Technical field
The invention belongs to field of surface treatment, be specifically related to the rete of a kind of black Mn-Fe-P-B composite plating bath, using method and formation thereof.
Background technology
On February 13rd, 2003, European Union has issued " waste electronic andelectrical equipment instruction " and " using some Hazardous Substances Directive about restriction in electronic electric equipment ".The former came into force from August 13rd, 2004, and the 10 large classes being to the effect that exported to European Union totally 99 kinds of electronic and electrical equipments reclaim and processing costs will be born by manufacturer oneself; Latter came into force from 1 day July in 2006, mainly forbid the electronic and electrical equipment selling leaded, mercury, cadmium, sexavalent chrome, poly-6 kinds of objectionable impuritiess such as dibromodiphenyl ether and poly-bromo biphenyl to European Union, this instruction will relate to 8 large classes totally 64 kinds of products, simultaneously, because nickel is to the harm of human body skin, therefore the nickel content of product surface is also subject to strict control.
The objectionable impuritiess such as chromium, cadmium, nickel all can cause huge harm to environment and problem in the industrial production of product, use procedure and offal treatment, but due to the excellent properties of chromium plating, nickel layer, still be widely used in current industrial production, and be difficult to be substituted completely.
Summary of the invention
The object of the invention is the shortcoming and defect existed to overcome prior art, and providing one to be applicable to metallic surface, and technique is simple, with low cost, environmental protection, black Mn-Fe-P-B composite plating bath that plated film bonding force is good.
Another object of the present invention is to provide a kind of using method utilizing above-mentioned composite plating bath to form plated film in metallic surface.
3rd object of the present invention is to provide the rete that a kind of above-mentioned using method is formed.
For realizing first object of the present invention, technical scheme of the present invention is that this bath composition comprises following component:
Phosphate dihydrogen manganese 80 ~ 100 grams per liter;
Fluoroborate 20 ~ 40 grams per liter;
Ferric sulfate 150 ~ 200 grams per liter;
PH value is 2-4;
Solute is water.
Further setting also includes additive, and this additive includes:
Glycine 3 ~ 5 grams per liter; Paregal O-20 1 ~ 3 grams per liter; Dodecane sulfonate 0.5 ~ 1 grams per liter.
Further setting is described dodecyl sulfate is dodecyl sulphate potassium, sodium lauryl sulphate or its compound.
Further setting is described fluoroborate is Sodium tetrafluoroborate, potassium fluoborate or its compound.
For realizing second goal of the invention of the present invention, technical scheme of the present invention comprises the following steps:
(1) by the workpiece of metal material through oil removing, scale removal, activates and cleans up;
(2), under normal temperature condition, the metal material workpiece after step (1) process is put into plating solution as claimed in claim 1, electroplates according to following processing condition; Processing parameter is:
With the workpiece of metallic substance for negative electrode, with ZGMn18 manganese steel for anode material, temperature condition is normal temperature, selects pulsewidth≤200 μ s, and the cycle is the monopulse square wave current of 1000 μ s, its average current density scope 5 ~ 10A/dm
2, voltage range 5 ~ 15V, electroplating time is 5 ~ 10 minutes;
(3) electroplated rear taking-up clean and dry or dry.
Further setting is also provided with between described step (1) (2) to carry out copper coating treatment process to the workpiece of metal material, and the metal material of this workpiece is active metal or active metal alloy.As Mg, Al etc. and alloy thereof.
Further setting is that in described step (2), processing condition are: temperature condition is normal temperature, selects pulsewidth to be 100 μ s, and the cycle is the monopulse square wave current of 1000 μ s, its average current density scope 6 ~ 8A/dm
2, voltage range 8 ~ 12V, electroplating time is 5 ~ 10 minutes.
Further setting is the sedimentation velocity of rete is 2 ~ 3 μm/min.
Realizing the 3rd goal of the invention technical scheme of the present invention is that membranous layer ingredient consists of:
Mn:45 ~ 60wt%; Fe:25 ~ 35wt%; P:10 ~ 20wt%; B:2 ~ 5wt%; Other elements: 2 ~ 5%.These other elements are conventional impurity element.
Principle of the present invention is in plating process, by square topped pulse moment strong current density 50 ~ 100A/dm
2chemical bond in phosphate ion, fluoroboric acid ion destroys by the surging force of effect, ionizes out P
5+and B
3+, simultaneously under its strong impact force effect and electric field action, make P
5+and B
3+together with Fe
3+and Mn
2+jointly deposit at the workpiece surface as negative electrode, composition Mn-Fe-P-B alloy layer.
The reaction of main generation is as follows:
PO
5 3-+ 10H
+→ P
5++ 5H
2under O(strong current density impact condition)
BO
3 3-+ 6H
+→ B
3++ 3H
2under O(strong current density impact condition)
Mn
2++2e
-→Mn
Fe
3++3e
-→Fe
B
3++3e
-→B
P
5++5e
-→P
By the environmentally friendly rete that formula of the present invention and technique obtain, detect it according to national standard, each Performance Detection of rete is as follows:
Hardness 486HV
0.1; (examination criteria: GB/T4340.4-2009 Vickers Hardness Test of Metallic Materials)
Blackness is 1 grade; (adopting nigrometer to detect)
It is 1 grade with the bonding force of matrix (or copper plate); (examination criteria: the method for inspection of SJ 1282-1977 metal plating bonding force)
Resistance to neutral salt spray test (NSS) can reach 150h.(examination criteria: GB/T 10125-1997 artificial atmosphere corrosion test salt-fog test)
Above-mentioned formula of the present invention, in conjunction with the specific processing parameter of the present invention, only at immediate current density>=50A/dm
2shi Caineng obtains the rete of highly corrosion resistant ability and high binding ability, due to current density>=50A/dm
2time, film deposition excessive velocities, and technique is not easy to control, so select Square wave pulses electric current, reduces energy consumption, improve technique controllability and to film quality management and control ability.
Advantage of the present invention:
The invention discloses a kind of black Mn-Fe-P-B composite plating bath and using method thereof, achieve the technique of replacement nickel plating-black chromium in metallic surface.This black Mn-Fe-P-B composite plating bath reaches the performance of black chromium plating, and have chromium plating liquid incomparable have advantage:
(1) hypotoxicity.The starting material adopted are generally recognized as safe or low harmful toxic matter, avoid hexavalent chromium environmental pollution and to the able-bodied infringement of workman, improve production environment.
(2) can electroplate at normal temperatures, reach the advantage of energy-conserving and environment-protective.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Fig. 1 Mn-Fe-P-B composite deposite 200 times of enlarged views;
Fig. 2 electroplating technology route map of the present invention.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
embodiment 1
The present invention adopts the following step can obtain adhesion 1 grade at 45# steel workpiece successively, and the neutral salt spray test (NSS) that the 10125-1997 of resistance to GB/T standard performs can reach the Mn-Fe-P-B plated film of 131 hours:
A (), by the workpiece of 45# steel matter through oil removing, scale removal, activates and cleans up;
B () configures containing phosphate dihydrogen manganese 80 ~ 100 grams per liter, potassium fluoborate 20 ~ 40 grams per liter, ferric sulfate 150 ~ 200 grams per liter, glycine 3 ~ 5 grams per liter, paregal O-20 1 ~ 3 grams per liter, sodium laurylsulfonate 0.5 ~ 1 grams per liter, between sulphur acid for adjusting pH to 3 ~ 4; Be: temperature condition is normal temperature select pulsewidth to be 100 μ s in processing condition by workpiece, the cycle is the single-pulse current of 1000 μ s, its average current density 7A/dm
2, voltage 8.6V, electroplating time is 10 minutes.
C () has been electroplated rear taking-up and has been cleaned and dry.
embodiment 2
The present invention adopts the following step can obtain adhesion 1 grade at Zl101 workpiece successively, and the neutral salt spray test (NSS) that the 10125-1997 of resistance to GB/T standard performs can reach the Mn-Fe-P-B plated film of 124 hours:
A (), by the workpiece of Zl101 through oil removing, scale removal, activates and cleans up;
B () adopts acid copper sulfate electroplating technology, workpiece is implemented preplating 30min and cleans up;
C () configures containing phosphate dihydrogen manganese 80 ~ 100 grams per liter, potassium fluoborate 20 ~ 40 grams per liter, ferric sulfate 150 ~ 200 grams per liter, glycine 3 ~ 5 grams per liter, paregal O-20 1 ~ 3 grams per liter, sodium laurylsulfonate 0.5 ~ 1 grams per liter, between sulphur acid for adjusting pH to 3 ~ 4; Be: temperature condition is normal temperature select pulsewidth to be 100 μ s in processing condition by workpiece, the cycle is the single-pulse current of 1000 μ s, its average current density 7A/dm
2, voltage 8.6V, electroplating time is 10 minutes.
D () has been electroplated rear taking-up and has been cleaned and dry.
The black coating uniformly with metalluster that the present embodiment is formed in metallic surface, film hardness is 486HV
0.1, neutral salt spray test (NSS) the duration 124h that the 10125-1997 of resistance to GB/T standard performs.
The plated film rete that the present embodiment is processed is tested through German Brooker wavelength dispersion fluorescence spectrophotometer, and its composition is as following table
table 1 Coating composition content
| Composition | Content (%) | Remarks |
| Mn | 50.13 | |
| Fe | 28.26 | |
| P | 15.63 | |
| B | 3.25 | |
| Trace element | 2.71 |
Claims (7)
1. a black Mn-Fe-P-B composite plating bath, is characterized in that: comprise following component:
Phosphate dihydrogen manganese 80 ~ 100 grams per liter;
Fluoroborate 20 ~ 40 grams per liter;
Ferric sulfate 150 ~ 200 grams per liter;
PH value is 2-4;
Solute is water;
Also include additive, this additive includes:
Glycine 3 ~ 5 grams per liter; Paregal O-20 1 ~ 3 grams per liter; Dodecane sulfonate 0.5 ~ 1 grams per liter.
2. a kind of black Mn-Fe-P-B composite plating bath according to claim 1, is characterized in that: described fluoroborate is Sodium tetrafluoroborate, potassium fluoborate or its compound.
3. black Mn-Fe-P-B composite plating bath forms a using method for plated film in metallic surface, it is characterized in that comprising the following steps:
(1) by the workpiece of metal material through oil removing, scale removal, activates and cleans up;
(2), under normal temperature condition, the metal material workpiece after step (1) process is put into plating solution as claimed in claim 1, electroplates according to following processing condition; Processing parameter is:
With the workpiece of metallic substance for negative electrode, with ZGMn18 manganese steel for anode material, temperature condition is normal temperature, selects pulsewidth≤200 μ s, and the cycle is the monopulse square wave current of 1000 μ s, its average current density scope 5 ~ 10A/dm
2, voltage range 5 ~ 15V, electroplating time is 5 ~ 10 minutes;
(3) electroplated rear taking-up clean and dry or dry.
4. a kind of black Mn-Fe-P-B composite plating bath according to claim 3 forms the using method of plated film in metallic surface, it is characterized in that: be also provided with between described step (1) (2) and carry out copper coating treatment process to the workpiece of metal material, the metal material of this workpiece is Mg, Al and alloy thereof.
5. a kind of black Mn-Fe-P-B composite plating bath according to claim 3 forms the using method of plated film in metallic surface, it is characterized in that: in described step (2), processing condition are: temperature condition is normal temperature, pulsewidth is selected to be 100 μ s, cycle is the monopulse square wave current of 1000 μ s, its average current density scope 6 ~ 8A/dm
2, voltage range 8 ~ 12V, electroplating time is 5 ~ 10 minutes.
6. a kind of black Mn-Fe-P-B composite plating bath according to claim 3 forms the using method of plated film in metallic surface, it is characterized in that: the sedimentation velocity of rete is 1 ~ 3 μm/min.
7. the rete that the using method that black Mn-Fe-P-B composite plating bath forms plated film in metallic surface is as claimed in claim 3 formed, is characterized in that: membranous layer ingredient consists of:
Mn:45 ~ 60wt%; Fe:25 ~ 35wt%; P:10 ~ 20wt%; B:2 ~ 5wt%; Other elements: 2 ~ 5%.
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|---|---|---|---|
| CN201310198532.6A CN103233253B (en) | 2013-05-23 | 2013-05-23 | Black Mn-Fe-P-B composite plating solution as well as using method and film layer formed by solution |
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|---|---|---|---|
| CN201310198532.6A CN103233253B (en) | 2013-05-23 | 2013-05-23 | Black Mn-Fe-P-B composite plating solution as well as using method and film layer formed by solution |
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| CN103233253B true CN103233253B (en) | 2015-04-22 |
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| CN104911640A (en) * | 2015-06-17 | 2015-09-16 | 黄惠娟 | Electroplating liquid for electroplating treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2319260A (en) * | 1996-11-16 | 1998-05-20 | Bassey Johnson Udofot | Electrodeposition of Fe-Mn alloys |
| US5965002A (en) * | 1997-11-12 | 1999-10-12 | Udofot; Bassey J. | Elecrodeposition of manganese and other hard to deposit metals |
| CN1473963A (en) * | 2002-08-07 | 2004-02-11 | 赵红玲 | Iron-manganese alloy plating liquid and method for plating parts |
| RU2241074C1 (en) * | 2003-07-28 | 2004-11-27 | Курская государственная сельскохозяйственная академия им. проф. И.И. Иванова | Method for electrolytic deposition of iron/manganese/ phosphorus alloy |
| CN101600813A (en) * | 2007-02-02 | 2009-12-09 | 魁北克水电公司 | Unformed Fe 100-a-bP aM bAlloy Foil and preparation method thereof |
-
2013
- 2013-05-23 CN CN201310198532.6A patent/CN103233253B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2319260A (en) * | 1996-11-16 | 1998-05-20 | Bassey Johnson Udofot | Electrodeposition of Fe-Mn alloys |
| US5965002A (en) * | 1997-11-12 | 1999-10-12 | Udofot; Bassey J. | Elecrodeposition of manganese and other hard to deposit metals |
| CN1473963A (en) * | 2002-08-07 | 2004-02-11 | 赵红玲 | Iron-manganese alloy plating liquid and method for plating parts |
| RU2241074C1 (en) * | 2003-07-28 | 2004-11-27 | Курская государственная сельскохозяйственная академия им. проф. И.И. Иванова | Method for electrolytic deposition of iron/manganese/ phosphorus alloy |
| CN101600813A (en) * | 2007-02-02 | 2009-12-09 | 魁北克水电公司 | Unformed Fe 100-a-bP aM bAlloy Foil and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王玲玲等.化学沉积Ni—Fe—P及Ni—Fe—P—B合金膜的结构和显微硬度.《湖南大学学报(自然科学版)》.2001,第28卷(第6期), * |
| 碱性条件下Fe-P-B合金电镀;周晓荣等;《材料保护》;20091031;第42卷(第10期);第37-39、44页 * |
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