CN101122036A - High-strength high-plasticity nano nickel and its plating solvent and preparation method - Google Patents
High-strength high-plasticity nano nickel and its plating solvent and preparation method Download PDFInfo
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- CN101122036A CN101122036A CNA2007100095092A CN200710009509A CN101122036A CN 101122036 A CN101122036 A CN 101122036A CN A2007100095092 A CNA2007100095092 A CN A2007100095092A CN 200710009509 A CN200710009509 A CN 200710009509A CN 101122036 A CN101122036 A CN 101122036A
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Abstract
The invention provides a high strength and high plasticity nano nickel, and a bath solution and a preparation method of the nano nickel. The bath solution consists of nickel sulfamic acid, manganese chloride, nickel chlorite, boric acid, sodium dodecyl sulfate and saccharin; the preparation method is to adopt a DC current deposition method to conduct electric deposition in a nickel aminosulfonate alloy to prepare the nano nickel. The tensile strength of the nano nickel prepared by the invention is 1200 to 1300MPa, the total elongation at break is 12 to 13percent, and the grain size range of the nano nickel is between 10 and 100mm. Compared with the nano nickel prepared by traditional melting methods, the nano nickel prepared by the invention has obviously higher strength, and obviously improved plasticity compared with the general nano nickel prepared by the currently reported electric deposition methods. The invention has advantages of adoption of nickel sulfamic acid as the main salt, has low stress, quite large current capable of being added in plating, easiness in obtaining good plating layer surface quality, etc. The invention is applicable in preparing high strength and high plasticity nano nickel with high efficiency.
Description
Technical field
The invention belongs to field of nanometer material technology, more specifically relate to a kind of high-strength high-plasticity nano nickel and plating bath thereof and preparation method.
Background technology
Compare with congruent tradition micron crystalline metal material, nano metal material has very high intensity and hardness.People carry out a large amount of research to nano material is synthetic with the preparation method, propose several different methods.Wherein electro-deposition method has that technology is simple, the nano material density height of equipment less investment, preparation, realizes advantage such as block production easily.With the improvement of common watt type nickel plating solution process, add a small amount of additive (asccharin, tonka bean camphor etc.), electrodepositable obtains nanometer nickel, the characteristics of this nanometer nickel are that grain-size is more even, average grain size is about 20nm, grain size distribution is narrower, generally at 15nm-40nm, have very high intensity, tensile strength is generally all more than 1000MPa, but its plasticity very low (tensile elongation is generally less than 5%), there is not tangible work hardening, cause that easily distortion is concentrated, be difficult to the plastic working moulding, accidental overload may cause early fracture during military service.This has had a strong impact on the processing and the application of nano metal material.Therefore improve the plasticity of nano metal material, the processing and the safe and reliable application of nano metal material had great importance.In recent years, it is found that micron crystalline substance-nanocrystalline mixed structure can keep obviously improving plasticity under the high-intensity prerequisite.In the galvanic deposit nano metal,, must carry out low-temperature annealing, but must strictly control annealing temperature and time, be difficult to practical application in order to obtain this tissue.
Summary of the invention
The purpose of this invention is to provide a kind of high-strength high-plasticity nano nickel and plating bath thereof and preparation method, novel electroplate liquid formulation of the present invention, by suitable electrodeposition technology, can obtain a kind of nanometer crystal microstructure of uniqueness in the deposition attitude, its grain size range is bigger, and between 10nm-100nm, the nanometer nickel with this tissue has very high intensity and plasticity simultaneously, and the preparation method is simple, and is workable.
The plating bath of high-strength high-plasticity nano nickel of the present invention is characterized in that: the system component of described plating bath is: nickel sulfamic acid (Ni (SO
3NH
2)
24H2O) 400g/L-600g/L, Manganous chloride tetrahydrate (MnCl
24H2O) 10g/L-50g/L, nickelous chloride (NiCl
26H2O) 10g/L-40g/L, boric acid (H
3BO
3) 30g/L-50g/L, sodium lauryl sulphate (C
12H
25SO
4Na) 0.05g/L-0.1g/L, asccharin (C
6H
5COSO
2NH
2) 2g/L-5g/L.
The preparation method of high-strength high-plasticity nano nickel of the present invention is characterized in that: described preparation method is: adopt high purity low-sulfur electrolytic nickel as anode, polishing Stainless Steel sheet is a negative electrode, and with the method preparation of dc electrodeposition, preparation process is:
(1) according to described electroplate liquid formulation preparation plating bath;
(2) anode pre-treatment;
(3) negative electrode pre-treatment;
(4) direct current deposition method prepares high-strength high-plasticity nano nickel coating; The processing parameter of described galvanic deposit is: current density 5A/dm
2-20A/dm
2, negative electrode and anodic area are than 1: 3-1: 10, and bath temperature is controlled between 50 ℃-70 ℃, and the plating bath pH value is controlled between the 3-4, adopts magnetic agitation, and galvanic deposit is to needed nickel layer thickness;
(5) high-strength high-plasticity nano nickel coating aftertreatment.
High-strength high-plasticity nano nickel of the present invention is characterized in that: the grain-size of described nanometer nickel is between 10nm-100nm, and average grain size is 25nm-27nm, and thickness reaches more than the 200 μ m-300 μ m; The coating surface light of described nanometer nickel, hardness are HV550-HV600, and tensile strength is between 1000MPa-1300MPa, and the fracture percentage of total elongation is 10%-13%.
Remarkable advantage of the present invention is: adopt novel electroplate liquid formulation, adopting nickel sulfamic acid is main salt, has low-stress, it is bigger that plating can apply electric current, obtain good advantages such as coating surface quality easily,, can obtain a kind of nanometer crystal microstructure of uniqueness in the deposition attitude by suitable electrodeposition technology, its grain size range is bigger, between 10nm-100nm.Nanometer nickel with this tissue has very high intensity and plasticity simultaneously, substantially exceed the intensity and the plasticity of the pure nanometer nickel and the micron crystalline substance-nanocrystalline mixed structure nanometer nickel of present bibliographical information, and the preparation method is simple, and is workable.
Description of drawings
Fig. 1 is a nanometer nickel coating transmission electron microscope micro-organization chart, and wherein, (a) part is a nanometer nickel coating transmission electron microscope microstructure, and (b) part is the selected area electron diffraction spectrum.
Fig. 2 is nanometer nickel stress strain curve figure of the present invention.
Embodiment
The present invention is the method that adopts dc electrodeposition, galvanic deposit nanometer nickel in the nickel sulfamic acid system.Plating bath consist of nickel sulfamic acid, Manganous chloride tetrahydrate, nickelous chloride, boric acid, sodium lauryl sulphate, asccharin.Specific implementation method of the present invention is as follows:
1. preparation plating bath, the composition of plating bath is: nickel sulfamic acid (Ni (SO
3NH
2)
24H
2O) 400g/L-600g/L, Manganous chloride tetrahydrate (MnCl
24H
2O) 10g/L-50g/L, nickelous chloride (NiCl
26H
2O) 10g/L-40g/L, boric acid (H
3BO
3) 30g/L-50g/L, sodium lauryl sulphate (C
12H
25SO
4Na) 0.05g/L-0.1g/L, asccharin (C
6H
5COSO
2NH
2) 2g/L-5g/L.
2. anode is selected high purity low-sulfur sheet nickel for use, place to go nickel plate oxide on surface before the galvanic deposit, when serious hole surface occurring on nickel plate surface for reusable nickel plate, use grinder buffing, milling machine processing to make it have even curface, should be able to demonstrate the silvery white gloss of metallic nickel after the oil of place to go.
3. negative electrode uses polishing Stainless Steel sheet (can use the polishing Stainless Steel sheet of selling on the market that is used to decorate).Before the plating, use nonconducting adhesive plaster (can use daily scotch tape) will be back to the stainless steel substrates surface encapsulation of anode one side, simultaneously the submergence acetone oil removing time is 10min over against anodic, the functional quality mark is that the hydrochloric acid soln of 10%-15% carries out activation treatment afterwards, and the time is 3min-5min.
4. the anode of immersion plating bath is controlled at more than 3 times with the area ratio of negative electrode, area is decided on the capacity of concrete galvanic deposit coating bath than the upper limit, annode area is big more, more little by the current density on the anode, anode nickel consumption is even more, help the stable of deposition process, obtain good coating surface quality.The temperature of plating bath is controlled between 40 ℃-70 ℃, and PH is controlled between the 3-4, uses magnetic agitation.Connect the direct current electrode position power supply, the nickel plate connects anode, and stainless steel substrates connects negative electrode.The current density that electroplating process applies is 5A/dm
2-20A/dm
2The big plating bath of main salt solubility can use the current density of increase.Electroplating time depends on actual need and decides.At 10A/dm
2Down, deposit thickness can reach 200 μ m-240 μ m in 3 hours.
5. after electroplating end, take out the Stainless Steel sheet, clean with flushing with clean water, dry up.
6. adopt mechanical process that coating is never embroidered on the steel plate and strip down, can obtain nanometer nickel.Can use emery wheel carefully to polish when peeling off and remove the metal that coating is wrapped in Stainless Steel sheet edge, to take off coating, speed should be slower during polishing, avoids fricative heat that coating is heated, and the coating temperature is above 100 ℃.
Embodiment 1
1. the composition of plating bath is: nickel sulfamic acid (Ni (SO
3NH
2)
24H
2O) 500g/L, Manganous chloride tetrahydrate (MnCl
24H
2O) 15g/L, nickelous chloride (NiCl
26H
2O) 20g/L, boric acid (H
3BO
3) 30g/L, sodium lauryl sulphate (C
12H
25SO
4Na) 0.1g/L, asccharin (C
6H
5COSO
2NH
2) 2g/L.
2. electrodeposition condition: current density 8A/dm
2, the pH value of plating bath is controlled at 3.5-4, and temperature is controlled at 60 ℃, magnetic agitation.Anode is selected high-purity low-sulfur nickel plate (purity is 99.9%) for use, and negative electrode is selected the Stainless Steel sheet of electropolishing for use, and immersion liquid negative and positive area ratio is 1: 3.Use thionamic acid and basic carbonate nickel solution to regulate the pH value of plating bath in the electrodeposition process.The coating that thickness is 200 μ m is obtained in galvanic deposit, peels off coating with mechanical process afterwards.
Experimental result
1) the transmission electron microscope microstructure as shown in Figure 1.(b) part is the selected area electron diffraction spectrum among the figure, and spot is round distribution, is typical nanocrystalline feature, and grain size range is bigger, approximately the 10nm-100 nanometer.
2) the sedimentary nanometer nickel stress strain curve of institute as shown in Figure 2.As can be seen from Fig. 2, tensile strength is 1290MPa, and the fracture percentage of total elongation is 13%.
Claims (7)
1. the plating bath of a high-strength high-plasticity nano nickel, it is characterized in that: the system component of described plating bath is: thionamic acid nickel (SO
3NH
2)
24H
2O 400g/L-600g/L, Manganous chloride tetrahydrate MnCl
24H
2O 10g/L-50g/L, nickelous chloride NiCl
26H
2O 10g/L-40g/L, boric acid H
3BO
330g/L-50g/L, sodium lauryl sulphate C
12H
25SO
4Na 0.05g/L-0.1g/L, asccharin C
6H
5COSO
2NH
22g/L-5g/L.
2. the preparation method of a high-strength high-plasticity nano nickel as claimed in claim 1, it is characterized in that: described preparation method is: adopt high purity low-sulfur electrolytic nickel as anode, polishing Stainless Steel sheet is a negative electrode, and with the method preparation of dc electrodeposition, preparation process is:
(1) according to described electroplate liquid formulation preparation plating bath;
(2) anode pre-treatment;
(3) negative electrode pre-treatment;
(4) direct current deposition method prepares high-strength high-plasticity nano nickel coating; The processing parameter of described galvanic deposit is: current density 5A/dm
2-20A/dm
2, negative electrode and anodic area are than 1: 3-1: 10, and bath temperature is controlled between 50 ℃-70 ℃, and the plating bath pH value is controlled between the 3-4, adopts magnetic agitation, is electroplated to needed nickel coating thickness;
(5) high-strength high-plasticity nano nickel coating aftertreatment.
3. the preparation method of a kind of high-strength high-plasticity nano nickel according to claim 2, it is characterized in that: described anode pre-treatment is: remove nickel plate oxide on surface, when serious hole surface occurring on nickel plate surface for reusable nickel plate, use grinder buffing, milling machine processing to make it have even curface, should be able to demonstrate the silvery white gloss of metallic nickel after the removal oil.
4. the preparation method of a kind of high-strength high-plasticity nano nickel according to claim 2, it is characterized in that: described negative electrode pre-treatment is: use nonconducting adhesive plaster will be back to the stainless steel substrates surface encapsulation of anode one side, simultaneously the submergence acetone oil removing time is 10min over against anodic, the functional quality mark is that the hydrochloric acid soln of 10%-15% carries out activation treatment afterwards, and the time is 3min-5min.
5. the preparation method of a kind of high-strength high-plasticity nano nickel according to claim 2, it is characterized in that: the aftertreatment of described nanometer nickel coating is: electroplate finish after, take out the Stainless Steel sheet, clean with flushing with clean water, dry up; Adopt mechanical process that coating is never embroidered on the steel plate and strip down, can obtain nanometer nickel.
6. the preparation method of a kind of high-strength high-plasticity nano nickel according to claim 5, it is characterized in that: described mechanical process is peeled off to using emery wheel carefully to polish and is removed the metal that coating is wrapped in Stainless Steel sheet edge, to take off coating, speed should be slower during polishing, avoids fricative heat that coating is heated.
7. one kind as claim 1,2,3,4,5 or 6 described high-strength high-plasticity nano nickels, and it is characterized in that: the grain-size of described nanometer nickel is between 10nm-100nm, and average grain size is 25nm-27nm, and thickness reaches 200 μ m-300 μ m; The coating surface light of described nanometer nickel, hardness are HV550-HV600, and tensile strength is between 1000MPa-1300MPa, and the fracture percentage of total elongation is 10%-13%.
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|---|---|---|---|
| CN200710009509A CN100588748C (en) | 2007-09-12 | 2007-09-12 | High-strength high-plasticity nano nickel and its plating solvent and preparation method |
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|---|---|---|---|
| CN200710009509A CN100588748C (en) | 2007-09-12 | 2007-09-12 | High-strength high-plasticity nano nickel and its plating solvent and preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN101122036A true CN101122036A (en) | 2008-02-13 |
| CN100588748C CN100588748C (en) | 2010-02-10 |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534703A (en) * | 2012-01-05 | 2012-07-04 | 北京工业大学 | Method for preparing nano/micron crystal composite structure pure copper |
| CN103726086A (en) * | 2013-04-22 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Electroplating device and preparation method for carbon fiber shielding paper with nanometer nickel coating |
| CN104862747A (en) * | 2015-06-10 | 2015-08-26 | 北京科技大学 | Method for preparing high-plasticity electroformed nickel by employing chloride-free plating solution |
| CN109342234A (en) * | 2018-11-26 | 2019-02-15 | 杨凌美畅新材料股份有限公司 | A kind of detection method of nickel sulfamic acid system plating solution deposition layer hardness |
| CN113005490A (en) * | 2021-03-16 | 2021-06-22 | 昆明理工大学 | Method for improving corrosion performance of nanocrystalline nickel through heat treatment |
| CN114586121A (en) * | 2019-10-24 | 2022-06-03 | 日进材料股份有限公司 | Nickel foil for manufacturing thin film capacitor and method for manufacturing same |
| CN115369270A (en) * | 2022-08-15 | 2022-11-22 | 金昌镍都矿山实业有限公司 | Forming method of electroplating anode nickel ball |
-
2007
- 2007-09-12 CN CN200710009509A patent/CN100588748C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102534703A (en) * | 2012-01-05 | 2012-07-04 | 北京工业大学 | Method for preparing nano/micron crystal composite structure pure copper |
| CN103726086A (en) * | 2013-04-22 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Electroplating device and preparation method for carbon fiber shielding paper with nanometer nickel coating |
| CN104862747A (en) * | 2015-06-10 | 2015-08-26 | 北京科技大学 | Method for preparing high-plasticity electroformed nickel by employing chloride-free plating solution |
| CN109342234A (en) * | 2018-11-26 | 2019-02-15 | 杨凌美畅新材料股份有限公司 | A kind of detection method of nickel sulfamic acid system plating solution deposition layer hardness |
| CN114586121A (en) * | 2019-10-24 | 2022-06-03 | 日进材料股份有限公司 | Nickel foil for manufacturing thin film capacitor and method for manufacturing same |
| CN113005490A (en) * | 2021-03-16 | 2021-06-22 | 昆明理工大学 | Method for improving corrosion performance of nanocrystalline nickel through heat treatment |
| CN115369270A (en) * | 2022-08-15 | 2022-11-22 | 金昌镍都矿山实业有限公司 | Forming method of electroplating anode nickel ball |
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| Publication number | Publication date |
|---|---|
| CN100588748C (en) | 2010-02-10 |
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