CN105463534B - A kind of nano compound electroplating liquid, its preparation method and Zinc alloy electroplating part - Google Patents

A kind of nano compound electroplating liquid, its preparation method and Zinc alloy electroplating part Download PDF

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CN105463534B
CN105463534B CN201510945964.8A CN201510945964A CN105463534B CN 105463534 B CN105463534 B CN 105463534B CN 201510945964 A CN201510945964 A CN 201510945964A CN 105463534 B CN105463534 B CN 105463534B
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zinc alloy
zinc
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coating
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CN105463534A (en
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刘委明
陈国贵
王从敏
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Zhejiang Weixing Industrial Development Co Ltd
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Zhejiang Weixing Industrial Development Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/58Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/02Slide fasteners

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Abstract

The invention provides a kind of nano compound electroplating liquid, include the component of following concentration:Cuprous cyanide:23~26g/L, zinc cyanide:10~12g/L, Cymag:43~51g/L, sodium carbonate:25~35g/L, sodium potassium tartrate tetrahydrate:10~20g/L, ammonium chloride:4~8g/L, Nano-meter SiO_22:1~4g/L, surplus are water.Nano-meter SiO_22Addition make the increase of cathodic polarization degree, and prevent growing up for Cu Zn alloy grains, coating is more refined and closely, reduce sedimentary voidage, the metal-based compound coating of particle enhancing is formd, so as to improve the corrosion resistance of coating.Test result indicates that the corrosion current of coating of the present invention is greatly lowered, illustrate that the corrosion resistance of the nano-composite plate in the present invention is significantly improved compared with Cu Zn alloy layers.Present invention also offers a kind of preparation method of nano compound electroplating liquid and Zinc alloy electroplating part.

Description

A kind of nano compound electroplating liquid, its preparation method and Zinc alloy electroplating part
Technical field
The invention belongs to electroplating technology, more particularly to a kind of nano compound electroplating liquid, its preparation method and kirsite Plated item.
Background technology
The fusing point of kirsite is low, can be cast into variously-shaped complicated part, and the piece surface being cast into is smooth, causes Close, accurate size, and processing charges is cheap, production efficiency is high, is and produces in batches, thus is made using Zinc alloy die-casting process Part at home and abroad have developed rapidly, and commercial Application is also more and more extensive.
Although zinc alloy diecasting has above-mentioned all the advantages, poor chemical stability of its material itself, hold in atmosphere It is vulnerable to oxidation and loses the gloss on surface, to improve its anti-corrosive properties and decoration performance must just carries out surface coating processing.By More than the zinc alloy diecasting based on light industrial goods, cosmetic requirement is higher, therefore uses electroplating technology more, is met using coating Above-mentioned requirements.
But zinc alloy diecasting chemical stability is poor, acid is met, alkali all easily dissolves, therefore can neither adopted in electroplating technology Strong acid etch can not be used with highly basic oil removing, electroplating solution is also needed to select the technical recipe for approaching neutrality, is otherwise possible to It is dissolved in the solution, metathesis occurs with the metal of current potential calibration, so as to influences the adhesion of coating and to pollute plating molten Liquid.
Publication No. CN 101012569A Chinese patent discloses a kind of direct copper non-cyanide plating of zinc alloy casting die Method, this method are electroplated using the electroplate liquid containing bivalent cupric ion to kirsite, obtain the zinc with simple substance copper coating Alloy.The good bonding strength of copper coating made from this method and kirsite matrix, still, corrosion resistance is poor.
The content of the invention
It is an object of the invention to provide a kind of nano compound electroplating liquid, its preparation method and Zinc alloy electroplating part, this hair The coating that the nano compound electroplating liquid of bright offer is formed has preferable decay resistance.
The present invention provides a kind of nano compound electroplating liquid, includes the component of following concentration:
Cuprous cyanide:23~26g/L, zinc cyanide:10~12g/L, Cymag:43~51g/L, sodium carbonate:25~35g/ L, sodium potassium tartrate tetrahydrate:10~20g/L, ammonium chloride:4~8g/L, SiO2:1~4g/L, surplus are water.
Preferably, the Nano-meter SiO_22Particle diameter be 10~20nm.
Preferably, the mass ratio of the cuprous cyanide and zinc cyanide is (2~2.5):1.
Preferably, the concentration of the cuprous cyanide is 24~25g/L.
Preferably, the cyaniding zinc concentration is 11~11.5g/L.
Preferably, the nano compound electroplating liquid also includes dispersant;
The dispersant includes PDDA and/or cetyl trimethylammonium bromide.
Preferably, the concentration of the PDDA is 5~50mg/L;
The concentration of the cetyl trimethylammonium bromide is 5~50mg/L.
The present invention provides a kind of preparation method of nano compound electroplating liquid, comprises the following steps:
By cuprous cyanide, zinc cyanide, Cymag, sodium carbonate, sodium potassium tartrate tetrahydrate, ammonium chloride and Nano-meter SiO_22Mixed with water, Obtain nano compound electroplating liquid;
Wherein, cuprous cyanide concentration is 23~26g/L in the nano compound electroplating liquid, and cyaniding zinc concentration is 10~12g/ L, sodium cyanide concentration are 43~51g/L, and concentration of sodium carbonate is 25~35g/L, and potassium tartrate na concn is 10~20g/L, chlorination Ammonium concentration is 4~8g/L, SiO2Concentration is 1~4g/L.
The present invention provides a kind of Zinc alloy electroplating part, by the zinc alloy diecasting in nano compound electroplating described above Plating obtains in liquid.
Preferably, the Zinc alloy electroplating part is the Zinc alloy electroplating part that surface has copper-nickel alloy tin coating.
The invention provides a kind of nano compound electroplating liquid, include the component of following concentration:Cuprous cyanide:23~26g/L, Zinc cyanide:10~12g/L, Cymag:43~51g/L, sodium carbonate:25~35g/L, sodium potassium tartrate tetrahydrate:10~20g/L, chlorination Ammonium:4~8g/L, Nano-meter SiO_22:1~4g/L, surplus are water.Nano-meter SiO_22Addition make the increase of cathodic polarization degree, and prevent Cu-Zn alloy grains are grown up, and coating is more refined and closely, are reduced sedimentary voidage, form particle enhancing Metal-based compound coating, so as to improve the corrosion resistance of coating.Test result indicates that the Cu-Zn-SiO in the present invention2Nanometer The I of composite depositecorrFor 15.0 × 10-6A/cm2, and do not add SiO2Cu-Zn alloy layers IcorrFor 109.52 × 10-6A/ cm2, the corrosion current of coating of the present invention is greatly lowered, and illustrates that the corrosion resistance of the nano-composite plate in the present invention is closed compared with Cu-Zn Gold plate is significantly improved.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the coating photo that the embodiment of the present invention 1 obtains;
Fig. 2 is the Tafel polarization curves of the embodiment of the present invention 1 and comparative example 1;
Fig. 3 is the coating photo that the embodiment of the present invention 2 obtains;
Fig. 4 is the Tafel polarization curves of the embodiment of the present invention 2 and comparative example 1;
Fig. 5 is the coating photo that the embodiment of the present invention 3 obtains;
Fig. 6 is the Tafel polarization curves of the embodiment of the present invention 3 and comparative example 1;
Fig. 7 is the coating picture that the embodiment of the present invention 4 obtains;
Fig. 8 is the Tafel polarization curves of the embodiment of the present invention 4 and comparative example 1;
Fig. 9 is the coating photo that comparative example 1 of the present invention obtains.
Embodiment
The present invention provides a kind of nano compound electroplating liquid, includes the component of following concentration:
Cuprous cyanide:23~26g/L, zinc cyanide:10~12g/L, Cymag:43~51g/L, sodium carbonate:25~35g/ L, sodium potassium tartrate tetrahydrate:10~20g/L, ammonium chloride:4~8g/L, Nano-meter SiO_22:1~4g/L, surplus are water.
Electrodeposited coating made from nano compound electroplating liquid provided by the invention has preferable decay resistance.
In the present invention, the mass concentration of the cuprous cyanide is 23~26g/L, preferably 24~25g/L;The cyaniding The mass concentration of zinc is 10~12g/L, preferably 11~11.5g/L;The mass ratio of the cuprous cyanide and zinc cyanide is preferably (2~2.5):1, more preferably (2.1~2.4):1, be most preferably (2.2~2.3):1.The present invention is by optimizing in electrolyte Mass ratio between Cu, Zn content and Cu, Zn so that the content ratio of copper zinc maintains 80 in composite deposite:20~65:35 Between, i.e., Deposit appearance shows pale yellow to golden yellow ormolu color, and coating color relatively easily controls.
In the present invention, the mass concentration of the Cymag is 43~51g/L, preferably 44~50g/L, more preferably 45 ~49g/L;The mass concentration of the sodium carbonate is preferably 25~35g/L, more preferably 26~34g/L, most preferably 27~ 33g/L;The mass concentration of the sodium potassium tartrate tetrahydrate is 10~20g/L, preferably 12~18g/L, more preferably 13~17g/L; The mass concentration of the ammonium chloride is 4~8g/L, preferably 5~7g/L.
In the present invention, the mass concentration of the nano silicon is 1~4g/L, preferably 2~3g/L;The nanometer The particle diameter of silica is preferably 10~20nm, more can be preferably 12~18nm, most preferably 13~17nm, the most preferably 14 ~16nm.The present invention adds nano silicon in the electrolyte, makes the degree of polarization of negative electrode increase, prevents simultaneously Cu-Zn alloy grains are grown up, and the alloy layer formed it into more refines and closely, reduces sedimentary voidage, shape Into the metal-based compound coating of particle enhancing, corrosion resistance greatly improves compared to simple ormolu coating.
Nano compound electroplating liquid in the present invention preferably also includes dispersant, and the dispersant preferably includes poly dimethyl two Allyl ammonium chloride (PDDA) and/or cetyl trimethylammonium bromide (CTAB).
Wherein, the CTAB is cationic surface active agent, and it carries a large amount of positive charge groups after dissociating, and can around inhale Attached a large amount of SiO for carrying opposite charges2, intergranular repulsion is added, reaches scattered purpose, while dissociates the small ion come The ionic strength of decentralized medium is changed, so as to change the thickness of electric double layer, enhance the stability of electric double layer, make to receive Rice SiO2Easily it is co-deposited to form composite deposite with metal ion;The PDDA is cation type polymer electrolyte, its from Polymer macromolecule after solution can effectively obstruct the reunion of nano particle using the space steric effect of itself, and carry largely just Charge groups, it can around adsorb a large amount of SiO for carrying opposite charges2, intergranular repulsion is added using electrostatic stabilization mechanism, Reach scattered purpose, make Nano-meter SiO_22Easily it is co-deposited to form composite deposite with metal ion.In the present invention, the PDDA Mass concentration be 5~50mg/L, preferably 10~45mg/L, more preferably 15~40mg/L, most preferably 20~35mg/L; The mass concentration of the CTAB is 5~50mg/L, preferably 10~45mg/L, more preferably 15~40mg/L, most preferably 20 ~35mg/L.
Present invention also offers a kind of preparation method of nano compound electroplating liquid, comprise the following steps:
By cuprous cyanide, zinc cyanide, Cymag, sodium carbonate, sodium potassium tartrate tetrahydrate, ammonium chloride and Nano-meter SiO_22Mixed with water, Obtain nano compound electroplating liquid above.The present invention is preferably by cuprous cyanide, zinc cyanide, Cymag, sodium carbonate, potassium tartrate Sodium, ammonium chloride and water are prepared to obtain the first mixed solution, then take a small amount of mixed solution to be mixed with dispersant and silica To the second mixed solution, rear ultrasonic disperse is stirred, finally the second mixed solution is added in the first mixed solution, received Rice composite plating solution.Obtained nano compound electroplating liquid is nano compound electroplating liquid described above according to the method described above, wherein Cuprous cyanide, zinc cyanide, Cymag, sodium carbonate, sodium potassium tartrate tetrahydrate, ammonium chloride, the species and quality of silica and dispersant Concentration and cuprous cyanide, zinc cyanide, Cymag, sodium carbonate, sodium potassium tartrate tetrahydrate, chlorination in nano compound electroplating liquid described above Ammonium, silica are consistent with mass concentration with the species of dispersant, will not be repeated here.
Present invention also offers a kind of Zinc alloy electroplating part, by the zinc alloy diecasting in nano combined electricity described above Plating obtains in plating solution.
In the present invention, the zinc ingot metal used in the zinc alloy diecasting is 4# kirsites;The zinc alloy diecasting is preferred There is the Zinc alloy electroplating part of copper-nickel alloy tin coating for surface;The Coating composition on the Zinc alloy electroplating part surface and each composition Content is respectively:Copper 50~60%, tin 30~40%, the zinc of remainder 10% or so.Specifically, in an embodiment of the present invention, The present invention can use the slider of zipper fastener of zinc alloy diecasting to be electroplated.
The present invention preferably electroplates to the zinc alloy diecasting by the following method:
By nano compound electroplating liquid above, anode is added in the electroplating bath of ormolu plate, to adjust temperature control Device makes between temperature maintains 30~35 DEG C in groove, adjusts plating solution pH between 11.5~12 by pH meter, regulation current valve makes The current density for being passed through electroplate liquid is 0.17~0.92A/dm2, then by the zinc alloy diecasting for needing to electroplate with the side of rack plating Formula, which is put into plating in electroplating bath and obtains surface attachment, Cu-Zn-SiO2The Zinc alloy electroplating part of composite galvanized coating.
In the present invention, the copper and 20 of 60~80% mass fractions is preferably included in the ormolu plate as anode The zinc of~40% mass fraction, the zinc of copper and 30% mass fraction more preferably including 70% mass fraction.
The invention provides a kind of nano compound electroplating liquid, include the component of following concentration:Cuprous cyanide:23~26g/L, Zinc cyanide:10~12g/L, Cymag:43~51g/L, sodium carbonate:25~35g/L, sodium potassium tartrate tetrahydrate:10~20g/L, chlorination Ammonium:4~8g/L, SiO2:1~4g/L;The SiO2Particle diameter be 10~20nm.Nano-meter SiO_22Addition make cathodic polarization degree Increase, and growing up for Cu-Zn alloy grains is prevented, coating is more refined and closely, reduce sedimentary voidage, formed The metal-based compound coating of particle enhancing, so as to improving the corrosion resistance of coating.
Present invention also offers a kind of Zinc alloy electroplating part, using zinc alloy diecasting as ground, zinc alloy diecasting is loose It is porous, Cu-Zn-SiO that is not corrosion-resistant, but being prepared using the nano compound electroplating liquid in the present invention2Composite galvanized coating can be very Good protection base material, improves its corrosion resistance.
In addition, the raw materials used source of the present invention is wide, prepare simply, cost is low, and the nano-composite plate of gained is as protection Decorative coating can be applied to multiple fields.
The present invention in the nano compound electroplating liquid after copper sheet (10*1cm) oil removing activation in the present invention will electroplate To Cu-Zn-SiO2Nano-composite plate, then it is made into working electrode, electrode area 0.5cm2, using three electrode bodies System's test, SCE are reference electrode, and Pt pieces are to electrode, and measuring technology is the Tafel polarization curves in electrochemical workstation, is surveyed Test solution is 5% salt solution, and the corrosion electric current density I of coating is calculated further according to Tafel linear extrapolation methodscorr, corrosion current is bigger It is more perishable, according to IcorrSize can more different coating corrosion resistance.As a result show, the Cu-Zn-SiO in the present invention2 The I of nano-composite platecorrFor 4.5 × 10-6A/cm2, and do not add SiO2Cu-Zn alloy layers IcorrFor 109.52 × 10- 6A/cm2, the corrosion current of coating of the present invention is greatly lowered, and illustrates the corrosion resistance of nano-composite plate in the present invention compared with Cu-Zn Alloy layer is significantly improved.
In order to further illustrate the present invention, with reference to embodiments to a kind of nano compound electroplating liquid provided by the invention, Its preparation method and Zinc alloy electroplating part are described in detail, but can not be understood as limiting the scope of the present invention.
In the examples below, PDDA is purchased from Aladdin reagent.
Embodiment 1
Preparation of nano composite plating solution:Wherein, cuprous cyanide concentration is 25g/L, and cyaniding zinc concentration is 11g/L, Cymag Concentration is 47g/L, concentration of sodium carbonate 30g/L, and potassium tartrate na concn is 10g/L, ammonium chloride concentration 6g/L, Nano-meter SiO_22 Particle size is 15 ± 5nm, Nano-meter SiO_22Concentration is 1g/L, and PDDA concentration is 5mg/L.
Compound method is:First configured by said components and be free of dispersant and Nano-meter SiO_22Copper zinc electroplate liquid (match somebody with somebody Method processed is with comparative example 1), then take a small amount of electroplate liquid to add dispersant, then add Nano-meter SiO_22Particle, stir 10min, mixing Ultrasonic disperse 60min afterwards, this is finally contained into dispersant and Nano-meter SiO_22A small amount of electroplate liquid of particle is added in original electroplate liquid Stir and produce Cu-Zn-SiO2Nano compound electroplating liquid.
The electroplate liquid that will be prepared, anode is added as in the electroplating bath of ormolu plate, regulation temperature controller makes in groove Temperature is 30 DEG C, and it is 11.6 to adjust plating solution pH by pH meter, and the current density that regulation current valve makes to be passed through electroplate liquid is 0.3A/ dm2, Zinc alloy slide fastener head is then put into plating in electroplating bath in a manner of rack plating and obtains Cu-Zn-SiO2Nano composite plating Layer.Coating is as shown in figure 1, Fig. 1 is the coating photo that the embodiment of the present invention 1 obtains.
The test of corrosion resistance of coating:Electro-deposition Cu-Zn-SiO after copper sheet (10*1cm) oil removing is activated2Nano-composite plate It is fabricated to working electrode, electrode area 0.5cm2, tested using three-electrode system, SCE is reference electrode, and Pt pieces are to electricity Pole, measuring technology be electrochemical workstation in Tafel polarization curves, test fluid is 5% salt solution, further according to Tafel straight lines outside Pushing manipulation calculates the corrosion electric current density I of coatingcorr, corrosion current is more big more perishable, according to IcorrSize can be than less With the corrosion resistance of coating.
Test result is bent in Fig. 2 as shown in Fig. 2 Fig. 2 is the Tafel polarization curves of the embodiment of the present invention 1 and comparative example 1 Line 1 is the coating Tafel polarization curves that comparative example 1 of the present invention obtains;Curve 2 obtains nano combined for the embodiment of the present invention 1 The Tafel polarization curves of coating.According to Fig. 2, Cu-Zn-SiO is measured by electrochemistry experiment2The I of nano-composite platecorrFor 15.0×10-6A/cm2, and do not add SiO2Cu-Zn alloy layers IcorrFor 109.52 × 10-6A/cm2, the former corrosion electricity Stream is greatly lowered, and illustrates Cu-Zn-SiO2The corrosion resistance of nano-composite plate is significantly improved compared with Cu-Zn alloy layers.
Embodiment 2
Prepare to obtain the nano compound electroplating liquid with matching as follows according to the method in embodiment 1:Cuprous cyanide concentration For 25g/L, cyaniding zinc concentration is 11g/L, sodium cyanide concentration 47g/L, concentration of sodium carbonate 30g/L, potassium tartrate na concn For 10g/L, ammonium chloride concentration 6g/L, Nano-meter SiO_22Particle size is 15 ± 5nm, Nano-meter SiO_22Concentration is 4g/L, PDDA concentration For 50mg/L.
The electroplate liquid that will be prepared, anode is added as in the electroplating bath of ormolu plate, regulation temperature controller makes in groove Temperature is 35 DEG C, and it is 12 to adjust plating solution pH by pH meter, and the current density that regulation current valve makes to be passed through electroplate liquid is 0.5A/dm2, Then Zinc alloy slide fastener head is put into plating in electroplating bath in a manner of rack plating and obtains Cu-Zn-SiO2Nano-composite plate.Plating Layer is as shown in figure 3, Fig. 3 is the coating photo that the embodiment of the present invention 2 obtains.
Method of testing according to coating corrosion resistance in embodiment 1 tests the corrosion resistant of nano-composite plate in the present embodiment Corrosion, as a result as shown in figure 4, Fig. 4 is the Tafel polarization curves of the embodiment of the present invention 2 and comparative example 1, in Fig. 4, curve 1 is this The coating Tafel polarization curves that invention comparative example 1 obtains;Curve 3 is the nano-composite plate that the embodiment of the present invention 2 obtains Tafel polarization curves.According to Fig. 4, Cu-Zn-SiO is measured by electrochemistry experiment2The I of nano-composite platecorrFor 91.7 × 10-6A/cm2, than the I of Cu-Zn alloy layercorrIt is small, illustrate Cu-Zn-SiO2Nano-composite plate has preferable corrosion resistance.
Embodiment 3
Prepare to obtain the nano compound electroplating liquid with matching as follows according to the method in embodiment 1:Cuprous cyanide concentration For 25g/L, cyaniding zinc concentration is 11g/L, sodium cyanide concentration 47g/L, concentration of sodium carbonate 30g/L, potassium tartrate na concn For 10g/L, ammonium chloride concentration 6g/L, Nano-meter SiO_22Particle size is 15 ± 5nm, Nano-meter SiO_22Concentration is 2g/L, PDDA concentration For 50mg/L.
The electroplate liquid that will be prepared, anode is added as in the electroplating bath of ormolu plate, regulation temperature controller makes in groove Temperature is 30 DEG C, and it is 12 to adjust plating solution pH by pH meter, and the current density that regulation current valve makes to be passed through electroplate liquid is 0.7A/dm2, Then Zinc alloy slide fastener head is put into plating in electroplating bath in a manner of rack plating and obtains Cu-Zn-SiO2Nano-composite plate.Plating Layer is as shown in figure 5, Fig. 5 is the coating photo that the embodiment of the present invention 3 obtains.
Method of testing according to coating corrosion resistance in embodiment 1 tests the corrosion resistant of nano-composite plate in the present embodiment Corrosion, as a result as shown in fig. 6, Fig. 6 is the Tafel polarization curves of the embodiment of the present invention 3 and comparative example 1, in Fig. 6, curve 1 is this The coating Tafel polarization curves that invention comparative example 1 obtains;Curve 4 is the nano-composite plate that the embodiment of the present invention 3 obtains Tafel polarization curves.According to Fig. 6, experiment measures Cu-Zn-SiO2The I of nano-composite platecorrFor 4.5 × 10-6A/cm2, than The I of Cu-Zn alloy layerscorrIt is small, illustrate Cu-Zn-SiO2Nano-composite plate has preferable corrosion resistance.
Embodiment 4
Prepare to obtain the nano compound electroplating liquid with matching as follows according to the method in embodiment 1:Cuprous cyanide concentration For 25g/L, cyaniding zinc concentration is 11g/L, sodium cyanide concentration 47g/L, concentration of sodium carbonate 30g/L, potassium tartrate na concn For 10g/L, ammonium chloride concentration 6g/L, Nano-meter SiO_22Particle size is ± 15 ± 5nm, Nano-meter SiO_22Concentration is 3g/L, and CTAB is dense Spend for 50mg/L.Coating is as shown in fig. 7, Fig. 7 is the coating photo that the embodiment of the present invention 4 obtains.
The electroplate liquid that will be prepared, anode is added as in the electroplating bath of ormolu plate, regulation temperature controller makes in groove Temperature is 35 DEG C, and it is 12 to adjust plating solution pH by pH meter, and the current density that regulation current valve makes to be passed through electroplate liquid is 0.2A/dm2, Then Zinc alloy slide fastener head is put into plating in electroplating bath in a manner of rack plating and obtains Cu-Zn-SiO2Nano-composite plate.
Method of testing according to coating corrosion resistance in embodiment 1 tests the corrosion resistant of nano-composite plate in the present embodiment Corrosion, as a result as shown in figure 8, Fig. 8 is the Tafel polarization curves of the embodiment of the present invention 4 and comparative example 1, in Fig. 8, curve 1 is this The coating Tafel polarization curves that invention comparative example 1 obtains;Curve 5 is the nano-composite plate that the embodiment of the present invention 4 obtains Tafel polarization curves.According to Fig. 8, experiment measures Cu-Zn-SiO2The I of nano-composite platecorrFor 79.5 × 10-6A/cm2, than The I of Cu-Zn alloy layerscorrIt is small, illustrate Cu-Zn-SiO2Nano-composite plate has preferable corrosion resistance.
Comparative example 1
Preparation of nano composite plating solution:Wherein, cuprous cyanide concentration is 25g/L, and cyaniding zinc concentration is 11g/L, Cymag Concentration is 47g/L, and concentration of sodium carbonate 30g/L, potassium tartrate na concn is 10g/L, ammonium chloride concentration 6g/L.
Compound method is:Required zinc cyanide is dissolved in sodium cyanide solution by calculating, is slowly added to cuprous cyanide, side Edged is stirred, and the sodium carbonate, ammonium chloride and sodium potassium tartrate tetrahydrate of metering are added after all dissolving, is filtered after stirring and dissolving, finally Constant volume obtains the copper zinc electroplate liquid of comparative example 1.
The electroplate liquid that will be prepared, anode is added as in the electroplating bath of ormolu plate, regulation temperature controller makes in groove Temperature is 30 DEG C, and it is 12 to adjust plating solution pH by pH meter, and the current density that regulation current valve makes to be passed through electroplate liquid is 0.7A/dm2, Then Zinc alloy slide fastener head is put into plating in electroplating bath in a manner of rack plating and obtains Cu-Zn-SiO2Nano-composite plate.Plating Layer is as shown in figure 9, Fig. 9 is the coating photo that comparative example 1 of the present invention obtains.As seen from Figure 9, the Cu- prepared with the present invention Zn-SiO2Nano-composite plate is not with adding SiO2Alloy layer color it is basically identical, Deposit appearance color is easy to keep stable.
Method of testing according to coating corrosion resistance in embodiment 1 tests the corrosion resistance of coating in the present embodiment, knot For fruit as shown in the curve 1 in Fig. 2, Fig. 4, Fig. 6 or Fig. 8, the curve 1 in Fig. 2,4,6 or 8 is the plating that comparative example 1 of the present invention obtains The Tafel polarization curves of layer.The Cu-Zn-SiO that embodiment 1~4 obtains it can be seen from Fig. 2,4,6 or 82Nano-composite plate IcorrThan the I of Cu-Zn alloy layers in this comparative examplecorrIt is small, illustrate Cu-Zn-SiO2Nano-composite plate has preferably resistance to Corrosion.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (8)

1. a kind of Zinc alloy electroplating part, by zinc alloy diecasting, rack plating obtains in nano compound electroplating liquid,
The nano compound electroplating liquid includes the component of following concentration:
Cuprous cyanide:23~26g/L, zinc cyanide:10~12g/L, Cymag:43~51g/L, sodium carbonate:25~35g/L, wine Stone acid potassium sodium:10~20g/L, ammonium chloride:4~8g/L, Nano-meter SiO_22:1~4g/L, surplus are water;
The nano compound electroplating liquid is made according to following steps:
By cuprous cyanide, zinc cyanide, Cymag, sodium carbonate, sodium potassium tartrate tetrahydrate, ammonium chloride and Nano-meter SiO_22Mix, received with water Rice composite plating solution.
2. Zinc alloy electroplating part according to claim 1, it is characterised in that the Nano-meter SiO_22Particle diameter be 10~20nm.
3. Zinc alloy electroplating part according to claim 1, it is characterised in that the mass ratio of the cuprous cyanide and zinc cyanide For (2~2.5):1.
4. Zinc alloy electroplating part according to claim 1, it is characterised in that the concentration of the cuprous cyanide is 24~25g/ L。
5. Zinc alloy electroplating part according to claim 1, it is characterised in that the cyaniding zinc concentration is 11~11.5g/ L。
6. the Zinc alloy electroplating part according to Claims 1 to 5 any one, it is characterised in that the nano compound electroplating Liquid also includes dispersant;
The dispersant includes PDDA and/or cetyl trimethylammonium bromide.
7. Zinc alloy electroplating part according to claim 6, it is characterised in that the PDDA Concentration is 5~50mg/L;
The concentration of the cetyl trimethylammonium bromide is 5~50mg/L.
8. Zinc alloy electroplating part according to claim 1, it is characterised in that the zinc alloy diecasting is that surface has in vain The Zinc alloy electroplating part of copper and tin coating.
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