CN1024569C - Solution and its process for chemical plating of corrosion resisting amorphous phosphorus-nickel alloy - Google Patents
Solution and its process for chemical plating of corrosion resisting amorphous phosphorus-nickel alloy Download PDFInfo
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- CN1024569C CN1024569C CN 89104018 CN89104018A CN1024569C CN 1024569 C CN1024569 C CN 1024569C CN 89104018 CN89104018 CN 89104018 CN 89104018 A CN89104018 A CN 89104018A CN 1024569 C CN1024569 C CN 1024569C
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- concentrated solution
- plating bath
- plating
- nickel
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Abstract
The present invention relates to chemical plating liquid and a method for obtaining an amorphous nickel-phosphorus alloy plating layer with high corrosion resistance. The molecular ratio of plating liquid composition of Ni<2+> to H2PO2<-> to complexing agent is 1.0:2.5:2.0, and the non-single complexing agent comprises at least one kind of multidentate ligand chelant which can form five-membered ring chelate and six-membered ring chelate with nickel ions. Plating liquid components are replenished and regulated in the mode of three kinds of concentrated solution, the plating temperature is 88 DEGC, and the pH value is 4.6.
Description
The invention belongs to the electroless plating technology field.
Known nickel-phosphorus alloy electroless plating is an out-phase surface autocatalyzed oxidation reduction reaction.Oxygenant is a nickel salt in the plating bath, and reductive agent is an inferior sodium phosphate.For obtaining the stable chemical plating fluid and the coating of practicality, must add complexing agent, stablizer, pH value buffer reagent etc. in the plating bath.Only add a kind of complexing agent in the nickel-phosphorus chemical plating bath before this, for example citric acid (United States Patent (USP) № 3597266,1971; English Patent № 1266729,1972), oxyacetic acid (United States Patent (USP) № 4600609,1986), and N '-(Japanese Patent 59-105870, United States Patent (USP) № 4636255,1987) such as hydroxyethylethylene diamine tri-acetic acid salt.Stablizer is a toxic agents, as Pb
2+Hg
2+Cd
2+And NaM
0O
3, (NH
2)
2CS etc. see that United States Patent (USP) № 2762723 adds the plating bath of single complexing agent, and as the plating bath of lactic acid or Padil complexing agent, plating speed is very fast, but the corrosion resisting property of coating is poor; Though be that the corrosion resistance of coating that obtains in the plating bath of complexing agent is better with the citric acid, sedimentation velocity is very slow.And, must add stablizer in the above-mentioned plating bath, otherwise bath stability is relatively poor, bath life is not long; Yet the adding of aforementioned stable agent causes plating defect easily, as the porosity increase etc., causes corrosion resistance coating to descend.Normally increase thickness of coating to satisfy the requirement of corrosion resisting property.
The corrosion resisting property that the nickel-phosphorus alloy electroless plating is led is relevant with the coating phosphorus content, in general, phosphorus content 11%(weight %) about corrosion resistance of coating the highest.Yet, the experiment proved that and come from the chemical Ni-plating layer that different plating baths are formed, though its phosphorus content identical (11%, the weight meter), but corrosion resisting property each other differs greatly.Complexing agent is more remarkable to the influence comparison coating phosphorus content and the thickness of coating of corrosion resistance of coating; It is relevant that this has deep effect with additives such as complexing agents for the microdistribution of the growth morphology of nickel-phosphorus alloy and phosphorus content.In addition, complexing agent chemical stability of self in plating bath also is one of influence factor, and complexing agent esterification tendency in the acidic bath of long-time heating is low, then bath stability and corrosion resistance coating height.
The objective of the invention is a kind of nickel chemical plating technology of researchdevelopment, make the chemical plating nickel-phosphorus alloy plating bath both have long work-ing life and rational sedimentation velocity, can obtain the coating of high anti-corrosion again.
For this reason, the present invention promptly contains two or more complexing agent, and has following molecular structural formula by adopting non-single complexing agent in chemical plating nickel-phosphorus alloy plating bath of the present invention:
In the formula:
R
1-H，-NH
2，-OH
R
2, R
3:-H ,-(CHm)-and COOH, m is the integer of 1-2,
N is the integer of 0-3.
The compound use of the present invention has in the complexing agent of above-mentioned molecular structural formula and contains a kind of multiple engaging ligand chelator that can form five-ring and six-membered ring chelate with nickel ion at least, be generally the saturated or undersaturated polycarboxylic acid salt that the hydrogen on the alpha-carbon atom is replaced by amido or hydroxyl, Trisodium Citrate for example, amino-succinic acid sodium etc., to reach existing rational sedimentation velocity and long bath life, can obtain the highest corrosion resisting property again.
Do not contain Pb in the nickel-phosphorus alloy chemical plating fluid of the present invention
2+, Hg
2+, Cd
2+In the toxic heavy metal ion, and be to use harmless chemical substance, as iodate, thioresorcin a pair of horses going side by side thiazole, fumaric acid etc. do not have tangible detrimentally affect as stablizer to the corrosion resisting property of coating.Add wetting agent in the plating bath and help the chemical nickel plating phosphorus solution and fully contact with the metallic surface, help the effusion of reaction product bubble hydrogen, the minimizing plating defect improves quality of coating.In sum, the high ni-resist phosphorus alloy of the present invention chemical plating fluid is composed as follows:
Component content (molconcentration, M)
NiSO
4·6H
2O 0.10～0.13
NaH
2PO
2.H
2O 0.25～0.33
Trisodium Citrate+amino-succinic acid sodium 0.16～0.26
NaAc 0.10～0.18
C
12H
25SO
4Na 20～30ppm
KIO
31～2ppm
H
2The O surplus
Another is characterised in that operating procedure the present invention, and particularly bath element replenishes inflation method.The chemical nickel-plating solution temperature has influence significantly for plating speed and coating phosphorus content, and solution temperature is low excessively, and sedimentation velocity is very slow; Temperature is too high, and bath stability and coating phosphorus content descend, and chemical nickel-plating solution operating temperature range of the present invention is 85～95 ℃.Similar with Temperature Influence, electroless nickel deposition speed is the exponential function of bath pH value, and one of operational condition of chemical nickel-plating solution of the present invention is pH4.2～5.0.In the aforesaid operations scope, chemical Ni-plating layer phosphorus content of the present invention is stabilized between 10～11%, and has rational sedimentation velocity.
Only manage the buffer reagent that contains q.s in the plating bath, because chemical plating nickel-phosphorus alloy is the process that bath pH value reduces, in the plating process, must add the pH value that alkaline matter is adjusted plating bath, to keep bath pH value in the operating restraint of regulation.In addition because workpiece take out of and in the acidic bath of long-time heating from esterification, therefore in fact complexing agent is consumptive in the plating process, must be replenished.Owing to exist the redox of vying each other to pay reaction on catalytic out-phase surface, reduction efficiency as the inferior sodium phosphate of reductive agent in the chemical nickel plating phosphorus solution is lower than 40%, therefore in order to obtain ideal coating, keeping the optimal molar ratio value of reactant single nickel salt and inferior sodium phosphate, ([Ni for example
2+]/[H
2PO
- 2Actual consumption ratio, for example [Ni must be pressed in]=0.4
2+]/[H
2PO
-1 2Additional single nickel salt and inferior sodium phosphate are added in]=0.3. in order correctly to state replenishing and adjusting of complicated multifactorial bath element, the present invention uses three kinds of raw material concentrated solution modes to replenish and adjusts plating bath. and concentrated solution A is made up of nickel salt and buffer reagent, concentrated solution B is made up of reductive agent, complexing agent, wetting agent and stablizer, concentrated solution C adjusts agent by reductive agent, complexing agent and pH and forms, with concentrated solution A and concentrated solution B preparation plating bath, replenish the adjustment plating bath with concentrated solution A and concentrated solution C, bath element and pH value are maintained in the optimum range automatically.The preferred composition of A, B, three kinds of concentrated solutions of C is: concentrated solution A contains NiSO
46H
2O1.5～2.0M, NaAc1.5～2.8M, concentrated solution B contains NaH
2PO
2.H
2O1.7～2.2M Trisodium Citrate+amino-succinic acid sodium 1.1～1.7M, C
12H
25O
4SNa130～330ppm, KIO
37～13ppm, concentrated solution C:NaH
2PO
2H
2O2.5～3.3M, Trisodium Citrate 0.1～0.5M, Na
2CO
3To pH value of solution=1.20.With concentrated solution A6.5%(volumeter) and concentrated solution B15.0%(volumeter) be preparation cost invention chemical plating nickel-phosphorus alloy plating bath, under optimum operation condition, promptly temperature is 88 ℃, pH=4.6, load slot 1dm
2/ l directly adds concentrated solution A and concentrated solution C with following speed in the work plating bath, concentrated solution A7.2 milliliter/liter/hour, concentrated solution C14.4 milliliter/liter/hour.
With method of the present invention operation with replenish when adjusting plating bath, do not toppling under the situation that any plating bath, plating speed is about 13 μ m/ hours, bath life still can reach the 6MTO(replacement cycle), i.e. 600 μ m/dm
2/ l.
Chemical plating nickel-phosphorus alloy bath stability height of the present invention, long service life; Under plating temperature, adjust plating bath, operate continuously, production efficiency height; Cost is low, P/C ratio height; The corrosion resistance of coating height.
For example, carbon steel work-piece is through electrochemical deoiling, electrolytic degreasing, acidic activated after, by carrying out electroless plating under the invention described above bath element and the operational condition.During plating continuously the mode of circulating filtration plating bath stir plating bath, per hour internal circulating load is 6～10 times of plating bath volume, and the mean pore size of filter bag or filter core is 3～5 μ m, the bright coating of acquisition, the analysis of X-ray diffraction spectra turns out to be amorphous phosphorus-nickel alloy, non magnetic, the coating of 25 μ m can anti-neutral salt spray test more than 1000 hours, in multiple corrosive medium, as seawater, caustic alkali, organic acid, the solidity to corrosion in the dilute hydrochloric acid is better than the Cr18Ni9 stainless steel.Coating is after 400 ℃ of thermal treatment, and hardness can reach 900～1000HV100, has high abrasion resistance properties.
Amorphous phosphorus-nickel alloy coating by plating bath of the present invention and method are obtained meets following relevant specification and standard:
ISO4527 1987(E) autocatalysis nickel-phosphorus alloy coating specification and test method
The ASTM656-79 engineering is with autocatalytic nickel-standard method on the metal
MIL-C-26074C, 1985 chemical Ni-plating layer requirements
Claims (8)
1, a kind of water-soluble acid plating bath of electroless plating amorphous phosphorus-nickel alloy, form by nickel salt, inferior sodium phosphate, buffer reagent, wetting agent, nontoxic stability and complexing agent, it is characterized in that complexing agent wherein is by the following complex compound of two or more structural formula, and wherein at least a be the multiple engaging ligand chelator that can form five-ring or six-ring with nickel ion, the structure of this complex compound is:
In the formula: R
1:-H.-NH
2-OH
R
2, R
3:-H ,-(CH
m)
nCOOH, m are 1 or 2, and n is 0～3 integer.
2, plating bath described in the claim (1), buffer reagent wherein is a sodium-acetate, and wetting agent is a sodium lauryl sulphate, and non-toxic stabilizer is iodate, thioresorcin a pair of horses going side by side thiazole, fumaric acid.
3, the described plating bath of claim (1), the ligand _ mixture of nibbling wherein is citric acid, amino-succinic acid more.
4, the described plating bath of claim (1), it is characterized in that by single nickel salt 0.1～0.13M inferior sodium phosphate 0.25～0.33M, sodium-acetate 0.1～0.18M, sodium lauryl sulphate 20～30ppm, Potassium Iodate 1～2ppm and citric acid and amino-succinic acid mixed twine mixture 0.16～0.26m form.
5, a kind of preparation, replenish and adjust method as the described plating bath of claim (1), it is characterized in that: (1) preparation concentrated solution A, B, C, concentrated solution A is made up of nickel salt and buffer reagent, concentrated solution B is made up of reductive agent, complexing agent, wetting agent and stablizer, concentrated solution C is by reductive agent, and complexing agent and pH adjust agent and form; (2) get concentrated solution A and B obtain solution; (3) get concentrated solution A and C and replenish the adjustment plating bath.
6, a kind of as the said method of claim (5), the preferred component of its A, B, three kinds of concentrated solutions of C is: concentrated solution A contains NiSO
4.6H
2O1.5～2.0M, NaAc1.5～2.8M, concentrated solution B contains NaH
2PO
2.H
2O1.7～2.2M, Trisodium Citrate+amino-succinic acid sodium 1.1～1.7M, C
12H
25SO
4Na130～330ppm, KIO
37～13ppm, concentrated solution C contains NaH
2PO
2.H
2O2.5～3.3M, Trisodium Citrate 0.1～0.5M, pH=12.
7, a kind of as the said method of claim (5), get concentrated solution A6.5%(volumeter) and concentrated solution B15%(volumeter) the preparation plating bath, best operating condition is 88 ℃ of groove temperature, pH4.6, load slot 1dm
2/ L.
8, a kind of as the said method of claim 6, directly in the work plating bath, add concentrated solution A and concentrated solution C with following speed, concentrated solution A7.2 milliliter/liter/hour, concentrated solution C14.4 milliliter/liter/hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89104018 CN1024569C (en) | 1989-06-15 | 1989-06-15 | Solution and its process for chemical plating of corrosion resisting amorphous phosphorus-nickel alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89104018 CN1024569C (en) | 1989-06-15 | 1989-06-15 | Solution and its process for chemical plating of corrosion resisting amorphous phosphorus-nickel alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040398A CN1040398A (en) | 1990-03-14 |
| CN1024569C true CN1024569C (en) | 1994-05-18 |
Family
ID=4855396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89104018 Expired - Fee Related CN1024569C (en) | 1989-06-15 | 1989-06-15 | Solution and its process for chemical plating of corrosion resisting amorphous phosphorus-nickel alloy |
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| Country | Link |
|---|---|
| CN (1) | CN1024569C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191205B (en) * | 2007-12-21 | 2010-05-19 | 天津大学 | High corrosion resistance nickel-tin-phosphorus alloy plating liquid |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034882C (en) * | 1992-09-29 | 1997-05-14 | 中国科学院金属腐蚀与防护研究所 | Bellows used in expansion joint and flexible metal tubing |
| CN1049019C (en) * | 1996-01-30 | 2000-02-02 | 中国科学技术大学 | Method for preparing metal nickel film by gamma ray irradiation |
| CN1073644C (en) * | 1999-09-24 | 2001-10-24 | 华南理工大学 | Chemical nickel plating solution |
| CN102051605B (en) * | 2009-10-30 | 2012-07-04 | 海洋王照明科技股份有限公司 | Method for anti-corrosive surface treatment of aluminum or aluminum alloy product |
| CN103774126B (en) * | 2014-02-24 | 2016-01-20 | 哈尔滨工业大学 | Electricimpulse improves the method for Ni-P Chemical Plating Layer thickness |
| US10006126B2 (en) * | 2014-10-27 | 2018-06-26 | Surface Technology, Inc. | Plating bath solutions |
| CN111020540B (en) * | 2019-12-05 | 2022-04-01 | 光山白鲨针布有限公司 | Medium-phosphorus chemical nickel plating solution and application |
-
1989
- 1989-06-15 CN CN 89104018 patent/CN1024569C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191205B (en) * | 2007-12-21 | 2010-05-19 | 天津大学 | High corrosion resistance nickel-tin-phosphorus alloy plating liquid |
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| Publication number | Publication date |
|---|---|
| CN1040398A (en) | 1990-03-14 |
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