CN1793436A - Process for directly electroplating on surface of aluminium or aluminium alloy - Google Patents
Process for directly electroplating on surface of aluminium or aluminium alloy Download PDFInfo
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- CN1793436A CN1793436A CN 200510032435 CN200510032435A CN1793436A CN 1793436 A CN1793436 A CN 1793436A CN 200510032435 CN200510032435 CN 200510032435 CN 200510032435 A CN200510032435 A CN 200510032435A CN 1793436 A CN1793436 A CN 1793436A
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Abstract
The invention relates to a aluminum and its alloy surface direct electroplating method. Its features are that the aluminum alloy is no need special pre-processing before electroplating; it is put in bath after chemical polishing; the bath is added complexation film removing film; electroplating is adopted direct current or impulse current; the pulse frequency is 50-100Hz; duty factor is 10%-30%; current density is 2-8A/dm<SUP>2</SUP>. The formed plating layer is uniform and compact. The plating layer and the aluminum foundation base have good binding power. The invention overcomes the defect of cockamamie steps, forward product quality and bad plating layer binding in traditional aluminum and its alloy electroplating. It is simple and convenient aluminum and its alloy surface processing method satisfied their high quality surface processing and performance demand.
Description
Technical field
The invention relates to a kind of on aluminium and aluminum alloy surface the method for Direct Electroplating nickel.Particularly, aluminium of the present invention and aluminium alloy electric nickel plating technology need not to carry out special pre-treatment to aluminum alloy materials, can directly electroplate in plating bath, obtain coating.
Background technology
Aluminium and alloy thereof are one of most widely used metals, have good conductivity, conduct heat fast, light specific gravity, specific tenacity height, be easy to characteristics such as moulding.But aluminium and alloy thereof exist again hardness low, not wear-resisting, easily take place intergranular corrosion, be difficult for shortcomings such as welding, influence its range of application and work-ing life.Aluminium and alloy thereof can be given protection-decoration and other functionalized use after electroplating, can increase the service life and the broadened application scope.
Phenomenons such as electroplating more much more difficultly than electroplating on other metal on aluminium and the alloy thereof, mainly is because easily generation peeling and decortication between coating and the matrix, and bonding force is bad.Tracing it to its cause is that the avidity of 1. aluminium and oxygen is very strong, so total surface has oxide film, and the electroconductibility of oxide film is bad, has a strong impact on combining of coating and matrix; 2. aluminium is very active, and replacement(metathesis)reaction easily takes place in plating, and the displacement layer that this reaction produces and the bonding force of matrix are very poor; 3. the coefficient of expansion of aluminium is big than metals such as nickel, copper; 4. between the aluminium base and coating hydrogen occlusion is often arranged, easily bubbling.For above-mentioned reasons, Direct Electroplating becomes very difficult on aluminium and aluminium alloy.
At present, aluminium and plating on aluminium alloy mainly adopt special pre-treating process, comprise electroplating process such as secondary soaking zinc, chemical nickel plating, anodic oxidation.Though aforesaid method is helpful really to improving binding force of cladding material, the pre-treatment process steps is loaded down with trivial details, and quality product is wayward, and production cost is higher.In these methods, anonizing is because the coating that obtains mainly carries out bonded by the mechanical snap effect, and its bonding force is subjected to certain restriction, and cost is higher simultaneously, so use few; The chemically coated nickel method pre-treatment step is loaded down with trivial details, and quality product is wayward, and cost is higher, so use also wideless; It is commonplace that the secondary soaking zinc method is used, and its electroplating technology flow process is: oil removing → washing → etch → washing → bright dipping → wash → soak zinc → wash → move back and soak zinc → washing → plating zinc → washing → second time.Still there is tangible deficiency in this technology: the one, and complex steps is unfavorable for the actual production operation; The 2nd, for composition difference, aluminium alloy that structure is different, the bonding force of the coating that obtains often differs greatly; The 3rd, which kind of aluminium alloy no matter adopts the bonding force of coating that this technology obtains and substrate all not too high, and range of application is restricted.
Summary of the invention
The objective of the invention is at complex steps, poor, the more high shortcoming of production cost of binding force of cladding material in the existing aluminium alloy electric coating technology, a kind of method of aluminum or aluminum alloy directly electroplating on surface is provided, and this method need not special pre-treatment, and step is simple, binding force of cladding material is good, and cost is lower.
Method of the present invention comprises step specific as follows:
1) pre-treatment: comprise mechanical pretreatment and chemical rightenning;
2) electronickelling: in plating bath, adopt direct current or pulse current method, aluminium alloy is carried out Direct Electroplating; Add complexing and remove film in electroplate liquid, its concentration is controlled at 20～40g/L.
Described pre-treatment comprises mechanical pretreatment and chemical rightenning, and purpose is for the grease of removing workpiece surface and oxide film.The present invention can adopt sandblast and sand paper grinding to carry out mechanical pretreatment.Chemical polishing also can adopt other acidic chemical polishing treatment solutions to carry out polished finish except adopting following basic chemical polishing liquid described in the invention, equally also can reach polishing effect preferably.
All need wash after described each operation steps.
Chemical brightening solution of the present invention adopts following prescription:
NaOH 100～400g/L；
NaNO
3 200～550g/L；
CoSO
4 1～20g/L；
75～95℃；
1～5min。
In the electronickelling, the working parts strap tele-release is gone in the plating tank to electroplate.Plating bath is formed: main salt, conducting salt, buffer reagent, complexing remove film, and the pH value of solution value is controlled at 3.0～5.0.The present invention adopts direct current or pulse current method (P.C.), pulse-repetition 50～100Hz, work ratio 10%～30%, current density 2～8A/dm
2, 20～50 ℃ of temperature.
Plating bath is formed:
Main salt is one or both in single nickel salt, the nickelous chloride, and concentration is 60～120g/L.
Conducting salt is one or both in nickelous chloride, the sodium-chlor, and its concentration is 30～50g/L.
Buffer reagent is a boric acid, 20～30g/L.
Complexing removes a kind of or composite that film can be in Sodium Fluoride, ammonium bifluoride, Trisodium Citrate, Tripotassium Citrate, sodium tartrate, Seignette salt, disodium ethylene diamine tetraacetate, the Sunmorl N 60S.Complexing removes the film total concn and is controlled at 20～40g/L.
The contriver finds under study for action, adds complexing in the plating bath of the present invention and removes film, has both played the effect of complex ni-ion, can improve the plating bath covering power, improve the anode dissolution performance, increase the cathode current density that allows, crystal grain thinning makes coating more even, fine and close; Complexing simultaneously removes the oxide film that film can be removed aluminum alloy material surface, obviously improves the bonding force of coating and matrix, and the effective complexing dissolved aluminum ion of energy, prevents that it from producing adverse influence to electroplating process.By effective use that complexing removes film, the present invention has overcome the shortcoming of traditional aluminium and aluminium alloy electric nickel plating technology, can obtain the good coating of bonding force, has simplified pre-treatment step again greatly.Method of the present invention is that a kind of new mode has been opened up in electronickelling on the aluminum or aluminum alloy, and no longer stay in only is improvement to the relevant condition in the former technology in the past.Make that the technological process of electronickelling has obtained maximum simplification on the aluminum or aluminum alloy, prove absolutely also that by test of many times method of the present invention is effectively, feasible.
Technology of the present invention has following advantage:
1. Direct Electroplating nickel method of the present invention, without soaking complicated pre-treatment step such as zinc, anodic oxidation, electroless plating, technological operation is simple, and quality product is easy to control.Because processing step of the present invention can farthest be simplified, required energy consumption also can drop to minimum.
2. Direct Electroplating nickel method of the present invention, the complexing of adding in the plating bath removes film, can remove the oxide thin layer film that is present in aluminum alloy surface effectively, improve the bonding force of coating and matrix greatly, solved aluminium and aluminium alloy coating and basal body binding force difference and problem such as the coating peeling that causes and bubbling in electroplating process.
3. the nickel layer that adopts the present invention to make, thicknesses of layers is even, and is strong with basal body binding force, and solidity to corrosion is good.
4. Direct Electroplating nickel method of the present invention, it is low that its electrolytic solution has the solution total concn, long service life, yield rate height, characteristics such as energy consumption is low.
5. raw material of the present invention is easy to get, and cost is low, is easy to suitability for industrialized production.
Embodiment
The following embodiment of the invention is intended to illustrate the present invention rather than limitation of the invention.
Embodiment 1
Direct Electroplating nickel on the fine aluminium
Sample adopts the L3 commercial-purity aluminium, and concrete steps are as follows:
1. pre-treatment.Adopt NaOH 250g/L, NaNO
3460g/L, CoSO
4The chemical brightening solution that 1g/L forms carries out chemical rightenning to sample.80～95 ℃ of temperature, time 2min; Washing.
2. Direct Electroplating nickel.The charged plating tank of putting into of sample after pre-treatment is electroplated.Electroplate liquid consists of: NiSO
460g/L; Boric acid 25g/L; NaCl 50g/L; Trisodium Citrate 5g/L; NaF 5g/L; Seignette salt 10g/L; PH value 4.5.Adopt pulse current method, power frequency 50Hz; Work is than 30%; Current density 2A/dm
2Electroplating time 20min; Room temperature.Washing; Dry up.
Quality of coating: even, smooth, fine and close; Thickness of coating 12 μ m.
The sample bonding force adopts following method to detect:
(1) on sample, draws the parallel to each other and staggered cut (forming the grid of 1mm * 1mm) that reaches substrate deeply, use the wire brush friction surface again, do not see coating peeling obscission with the steel knife point;
(2) clamp sample one with pincer pliers and bring in back bending Qu Wuci, fracture until print, fracture both sides coating combines closely with substrate, does not see the peeling obscission;
(3) adopt thermal cycling test, plating piece is incubated 1 hour under 220 ℃ of conditions, take out back chilling in cold water, coating peeling obscission is not seen in round-robin test 40 times.
Detected result shows: binding force of cladding material is good.
Embodiment 2
Direct Electroplating nickel on the duralumin
Sample adopts the LY-12 duralumin, and concrete steps are as follows:
1. mechanical pretreatment: adopt sandblast or sand paper to grind, remove deburring, firm oxide compound, extruding with lubricator, cutting wet goods foreign matter, reduce surfaceness; Washing;
2. chemical rightenning: adopt NaOH 300g/L, NaNO
3500g/L, CoSO
4The chemical brightening solution that 2g/L forms carries out chemical rightenning to sample.80～95 ℃ of temperature, time 3min; Washing;
3. Direct Electroplating nickel: the charged plating tank of putting into of the sample after pre-treatment, electroplate.Electroplate liquid consists of: NiSO
470g/L; NiCl
250g/L; Boric acid 20g/L; Disodium ethylene diamine tetraacetate 10g/L; Ammonium bifluoride 5g/L; Sodium tartrate 10g/L; PH value 4.0.Adopt direct current electrode position, current density 8A/dm
2Electroplating time 20min; Room temperature.Washing; Dry up.
Quality of coating: even, smooth, fine and close; Thickness of coating 15 μ m.
The sample bonding force adopts following method to detect:
(1) on sample, draws the parallel to each other and staggered cut (forming the grid of 1mm * 1mm) that reaches substrate deeply, use the wire brush friction surface again, do not see coating peeling obscission with the steel knife point;
(2) adopt thermal cycling test, plating piece is incubated 1 hour under 300 ℃ of conditions, take out back chilling in cold water, coating peeling obscission is not seen in round-robin test 40 times;
Detected result shows: binding force of cladding material is good.
Embodiment 3
Direct Electroplating nickel on the cast aluminium alloy
Sample adopts the ZL-108 cast aluminium alloy, and concrete steps are as follows:
1. mechanical pretreatment: adopt sandblast and sand paper to grind, remove deburring, firm oxide compound, extruding with lubricator, cutting wet goods foreign matter, reduce surfaceness; Washing;
2. chemical rightenning: adopt NaOH 300g/L, NaNO
3520g/L, CoSO
4The chemical brightening solution that 5g/L forms carries out chemical rightenning to sample.80～95 ℃ of temperature, time 3min; Washing;
3. Direct Electroplating nickel: the charged plating tank of putting into of the sample after pre-treatment, electroplate.Electroplate liquid consists of: NiSO
480g/L; NiCl
220g/L; Boric acid 30g/L; NaCl 30g/L; Sodium Fluoride 10g/L; Sodium tartrate 15g/L; Trisodium Citrate 15g/L; PH value 3.5; Adopt pulse current method, power frequency 100Hz; Work is than 10%; Current density 3A/dm
2Electroplating time 20min; Room temperature.Washing; Dry up.
Quality of coating: even, smooth, fine and close; Thickness of coating 16 μ m.
The sample bonding force adopts following method to detect:
(1) on sample, draws the parallel to each other and staggered cut (forming the grid of 1mm * 1mm) that reaches substrate deeply, use the wire brush friction surface again, do not see coating peeling obscission with the steel knife point;
(2) adopt thermal cycling test, plating piece is incubated 1 hour under 300 ℃ of conditions, take out back chilling in cold water, coating peeling obscission is not seen in round-robin test 40 times.
Detected result shows: binding force of cladding material is good.
Claims (8)
1. the method for an aluminum or aluminum alloy directly electroplating on surface is characterized in that:
Operation as follows:
1) pre-treatment: comprise mechanical pretreatment and chemical rightenning;
2) electronickelling: in plating bath, adopt direct current or pulse current method, aluminium alloy is carried out Direct Electroplating; Add complexing and remove film in electroplate liquid, its concentration is controlled at 20～40g/L.
2, the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 1 is characterized in that: it is in Sodium Fluoride, ammonium bifluoride, Trisodium Citrate, Tripotassium Citrate, sodium tartrate, Seignette salt, disodium ethylene diamine tetraacetate, the Sunmorl N 60S one or more that complexing removes film.
3, the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 1, it is characterized in that: current density is controlled at 2～8A/dm
220～50 ℃ of temperature adopt pulse current method, and pulse-repetition is controlled at 50～100Hz, and work is than 10%～30%.
4. the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 1 is characterized in that: described electroplating bath components also comprises main salt, conducting salt, buffer reagent, and the pH value of solution value is controlled at 3.0～5.0.
5. the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 4 is characterized in that: main salt is one or both in single nickel salt, the nickelous chloride in the plating bath, and its concentration is controlled at 60～120g/L.
6. the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 4 is characterized in that: conducting salt is one or both in nickelous chloride, the sodium-chlor in the plating bath, and its concentration is controlled at 30～50g/L.
7. the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 4 is characterized in that: buffer reagent is a boric acid in the plating bath, and its concentration is controlled at 20～30g/L.
8, the method for a kind of aluminum or aluminum alloy directly electroplating on surface according to claim 1 is characterized in that: described mechanical pretreatment is that sandblast and sand paper grind; Described chemical brightening solution composition comprises: sodium hydroxide 100～400g/L, SODIUMNITRATE 200～550g/L, rose vitriol 1～20g/L; The chemical rightenning temperature is controlled at 70～95 ℃, treatment time 1～5min.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100324355A CN100467675C (en) | 2005-11-25 | 2005-11-25 | Process for directly electroplating on surface of aluminium or aluminium alloy |
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|---|---|---|---|
| CNB2005100324355A CN100467675C (en) | 2005-11-25 | 2005-11-25 | Process for directly electroplating on surface of aluminium or aluminium alloy |
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| CN100467675C CN100467675C (en) | 2009-03-11 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101826675A (en) * | 2010-02-10 | 2010-09-08 | 株洲永盛电池材料有限公司 | Material for shell of connector and preparation method thereof |
| CN101899695A (en) * | 2010-07-30 | 2010-12-01 | 福建师范大学 | Method for preparing nickel-plated aluminum tab by two-step electroplating |
| CN101638770B (en) * | 2009-06-26 | 2011-04-13 | 深圳市杰瑞表面技术有限公司 | Method for improving aluminum solderability of vacuum coating film |
| CN102330130A (en) * | 2011-11-02 | 2012-01-25 | 沈阳飞机工业（集团）有限公司 | Process method for preplating nickel on surface of minuteness aluminum wire before copper plating |
| CN105063702A (en) * | 2015-07-31 | 2015-11-18 | 广东欧珀移动通信有限公司 | Surface processing method for aluminum alloy part and aluminum alloy product |
| CN105256341A (en) * | 2015-10-28 | 2016-01-20 | 安徽恒源煤电股份有限公司 | Electroplate liquid usable for scaffolds made of multiple materials |
| CN105586615A (en) * | 2016-01-21 | 2016-05-18 | 华南理工大学 | Method for pulse pre-nickeling of surface of magnesium alloy |
| CN108315783A (en) * | 2018-02-09 | 2018-07-24 | 中南大学 | In the method that flexible metal manganese is electroplated in aluminium surface |
| CN111024685A (en) * | 2019-12-02 | 2020-04-17 | 四川渝邻汽车零部件有限公司 | Detection solution and aluminum piston bonding force detection method |
| CN111674491A (en) * | 2020-05-12 | 2020-09-18 | 宁波吉胜铸业有限公司 | Aluminum shell for vehicle |
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2005
- 2005-11-25 CN CNB2005100324355A patent/CN100467675C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101638770B (en) * | 2009-06-26 | 2011-04-13 | 深圳市杰瑞表面技术有限公司 | Method for improving aluminum solderability of vacuum coating film |
| CN101826675A (en) * | 2010-02-10 | 2010-09-08 | 株洲永盛电池材料有限公司 | Material for shell of connector and preparation method thereof |
| CN101826675B (en) * | 2010-02-10 | 2012-05-09 | 株洲永盛电池材料有限公司 | Material for shell of connector and preparation method thereof |
| CN101899695A (en) * | 2010-07-30 | 2010-12-01 | 福建师范大学 | Method for preparing nickel-plated aluminum tab by two-step electroplating |
| CN102330130A (en) * | 2011-11-02 | 2012-01-25 | 沈阳飞机工业（集团）有限公司 | Process method for preplating nickel on surface of minuteness aluminum wire before copper plating |
| CN105063702A (en) * | 2015-07-31 | 2015-11-18 | 广东欧珀移动通信有限公司 | Surface processing method for aluminum alloy part and aluminum alloy product |
| CN105256341A (en) * | 2015-10-28 | 2016-01-20 | 安徽恒源煤电股份有限公司 | Electroplate liquid usable for scaffolds made of multiple materials |
| CN105586615A (en) * | 2016-01-21 | 2016-05-18 | 华南理工大学 | Method for pulse pre-nickeling of surface of magnesium alloy |
| CN108315783A (en) * | 2018-02-09 | 2018-07-24 | 中南大学 | In the method that flexible metal manganese is electroplated in aluminium surface |
| CN108315783B (en) * | 2018-02-09 | 2019-10-29 | 中南大学 | In the method for aluminium surface plating flexible metal manganese |
| CN111024685A (en) * | 2019-12-02 | 2020-04-17 | 四川渝邻汽车零部件有限公司 | Detection solution and aluminum piston bonding force detection method |
| CN111674491A (en) * | 2020-05-12 | 2020-09-18 | 宁波吉胜铸业有限公司 | Aluminum shell for vehicle |
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|---|---|
| CN100467675C (en) | 2009-03-11 |
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Assignee: Changsha Haida Aluminum Co., Ltd. Assignor: Hunan University Contract fulfillment period: 2009.10.9 to 2015.10.8 contract change Contract record no.: 2009430000243 Denomination of invention: Process for directly electroplating on surface of aluminium or aluminium alloy Granted publication date: 20090311 License type: Exclusive license Record date: 20091216 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.10.9 TO 2015.10.8; CHANGE OF CONTRACT Name of requester: CHANGSHA HAIDA ALUMINUM PRODUCTS CO., LTD. Effective date: 20091216 |
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