CN105463534A - Nano-composite electroplating solution, preparing method of nano-composite electroplating solution and zinc alloy electroplated part - Google Patents
Nano-composite electroplating solution, preparing method of nano-composite electroplating solution and zinc alloy electroplated part Download PDFInfo
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- CN105463534A CN105463534A CN201510945964.8A CN201510945964A CN105463534A CN 105463534 A CN105463534 A CN 105463534A CN 201510945964 A CN201510945964 A CN 201510945964A CN 105463534 A CN105463534 A CN 105463534A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The invention provides a nano-composite electroplating solution. The nano-composite electroplating solution is prepared from, by concentration, 23-26 g/L of cuprous cyanide, 10-12 g/L of zinc cyanide, 43-51 g/L of sodium cyanide, 25-35 g/L of sodium carbonate, 10-20 g/L of sodium potassium tartrate tetrahydrate, 4-8 g/L of ammonium chloride, 1-4 g/L of nano SiO2 and the balance water. By adding the nano SiO2, the degree of polarization of the cathode is increased, and growth of Cu-Zn alloy grains is prevented, so that a coating is more refined and compact, the porosity of a deposited layer is decreased, the particle-reinforced metal-based composite coating is formed, and accordingly the corrosion resistance of the coating is improved. It is indicated through test results that the corrosion current of the coating is greatly decreased, and it is proved that the corrosion resistance of the nano-composite coating is obviously improved compared with a Cu-Zn alloy coating. The invention further provides a preparing method of the nano-composite electroplating solution and a zinc alloy electroplated part.
Description
Technical field
The invention belongs to electroplating technology field, particularly relate to a kind of nano compound electroplating liquid, its preparation method and Zinc alloy electroplating part.
Background technology
The fusing point of zinc alloy is low, the part of different shape complexity can be cast into, the piece surface be cast into is smooth, fine and close, size is accurate, and processing charges is cheap, production efficiency is high, be and produce in batches, thus utilize Zinc alloy die-casting process to make part and develop very fast at home and abroad, industrial application is also more and more extensive.
Although zinc alloy diecasting has above-mentioned all advantages, the poor chemical stability of its material own, is easily oxidized in atmosphere and is lost the gloss on surface, be improved its preservative property and decorate properties just must carry out surface-coated process.Because zinc alloy diecasting is main mainly with light industrial goods, cosmetic requirement is higher, therefore adopts electroplating technology more, utilizes coating to meet above-mentioned requirements.
But zinc alloy diecasting chemical stability is poor, chance acid, alkali are all easily dissolved, therefore highly basic oil removing can not be adopted in electroplating technology can not to adopt strong acid etch, electroplating solution also needs to select the technical recipe close to neutral, otherwise just likely dissolved in the solution, with the metal generation metathesis of current potential calibration, thus affect the bonding force of coating and pollute electroplating solution.
Publication number is a kind of method that the Chinese patent of CN101012569A discloses direct copper non-cyanide plating of zinc alloy casting die, and the method adopts the electroplate liquid containing bivalent cupric ion to electroplate zinc alloy, obtains the zinc alloy with elemental copper coating.The good bonding strength of the copper coating that the method obtains and zinc alloy matrix, but erosion resistance is poor.
Summary of the invention
The object of the present invention is to provide a kind of nano compound electroplating liquid, its preparation method and Zinc alloy electroplating part, the coating that nano compound electroplating liquid provided by the invention is formed has good corrosion resistance nature.
The invention provides a kind of nano compound electroplating liquid, comprise the component of following concentration:
Cuprous cyanide: 23 ~ 26g/L, zinc cyanide: 10 ~ 12g/L, sodium cyanide: 43 ~ 51g/L, sodium carbonate: 25 ~ 35g/L, Seignette salt: 10 ~ 20g/L, ammonium chloride: 4 ~ 8g/L, SiO
2: 1 ~ 4g/L, surplus is water.
Preferably, described Nano-meter SiO_2
2particle diameter be 10 ~ 20nm.
Preferably, the mass ratio of described cuprous cyanide and zinc cyanide is (2 ~ 2.5): 1.
Preferably, the concentration of described cuprous cyanide is 24 ~ 25g/L.
Preferably, described cyaniding zinc concentration is 11 ~ 11.5g/L.
Preferably, described nano compound electroplating liquid also comprises dispersion agent;
Described dispersion agent comprises Poly Dimethyl Diallyl Ammonium Chloride and/or cetyl trimethylammonium bromide.
Preferably, the concentration of described Poly Dimethyl Diallyl Ammonium Chloride is 5 ~ 50mg/L;
The concentration of described cetyl trimethylammonium bromide is 5 ~ 50mg/L.
The invention provides a kind of preparation method of nano compound electroplating liquid, comprise the following steps:
By cuprous cyanide, zinc cyanide, sodium cyanide, sodium carbonate, Seignette salt, ammonium chloride and Nano-meter SiO_2
2mix with water, obtain nano compound electroplating liquid;
Wherein, in described nano compound electroplating liquid, cuprous cyanide concentration is 23 ~ 26g/L, and zinc cyanide concentration is 10 ~ 12g/L, sodium cyanide concentration is 43 ~ 51g/L, and concentration of sodium carbonate is 25 ~ 35g/L, and soluble tartrate na concn is 10 ~ 20g/L, ammonium chloride concentration is 4 ~ 8g/L, SiO
2concentration is 1 ~ 4g/L.
The invention provides a kind of Zinc alloy electroplating part, electroplated in nano compound electroplating liquid mentioned above by described zinc alloy diecasting and obtain.
Preferably, described 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, comprise the component of following concentration: cuprous cyanide: 23 ~ 26g/L, zinc cyanide: 10 ~ 12g/L, sodium cyanide: 43 ~ 51g/L, sodium carbonate: 25 ~ 35g/L, Seignette salt: 10 ~ 20g/L, ammonium chloride: 4 ~ 8g/L, Nano-meter SiO_2
2: 1 ~ 4g/L, surplus is water.Nano-meter SiO_2
2add cathodic polarization degree increased, and prevent growing up of Cu-Zn alloy grain, make coating refinement and closely more, decrease settled layer voidage, define the metal-based compound coating of particle reinforce, thus improve the erosion resistance of coating.Experimental result shows, the Cu-Zn-SiO in the present invention
2the I of nano-composite plate
corrbe 15.0 × 10
-6a/cm
2, and do not add SiO
2the I of Cu-Zn alloy layer
corrbe 109.52 × 10
-6a/cm
2, the corrosion current of coating of the present invention greatly reduces, and the solidity to corrosion that the nano-composite plate in the present invention is described comparatively Cu-Zn alloy layer is significantly improved.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the coating photo that the embodiment of the present invention 1 obtains;
Fig. 2 is the Tafel polarization curve 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 curve 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 curve 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 curve 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 invention provides a kind of nano compound electroplating liquid, comprise the component of following concentration:
Cuprous cyanide: 23 ~ 26g/L, zinc cyanide: 10 ~ 12g/L, sodium cyanide: 43 ~ 51g/L, sodium carbonate: 25 ~ 35g/L, Seignette salt: 10 ~ 20g/L, ammonium chloride: 4 ~ 8g/L, Nano-meter SiO_2
2: 1 ~ 4g/L, surplus is water.
The electrolytic coating that nano compound electroplating liquid provided by the invention obtains has good corrosion resistance nature.
In the present invention, the mass concentration of described cuprous cyanide is 23 ~ 26g/L, is preferably 24 ~ 25g/L; The mass concentration of described zinc cyanide is 10 ~ 12g/L, is preferably 11 ~ 11.5g/L; The mass ratio of described cuprous cyanide and zinc cyanide is preferably (2 ~ 2.5): 1, is more preferably (2.1 ~ 2.4): 1, most preferably is (2.2 ~ 2.3): 1.The present invention is by the content of Cu, Zn in optimization electrolytic solution and the mass ratio between Cu, Zn, the content of copper zinc in composite deposite ratio is made to maintain between 80:20 ~ 65:35, namely Deposit appearance presents pale yellow to golden yellow copper zinc alloy color, and coating color relatively easily controls.
In the present invention, the mass concentration of described sodium cyanide is 43 ~ 51g/L, is preferably 44 ~ 50g/L, is more preferably 45 ~ 49g/L; The mass concentration of described sodium carbonate is preferably 25 ~ 35g/L, is more preferably 26 ~ 34g/L, most preferably is 27 ~ 33g/L; The mass concentration of described Seignette salt is 10 ~ 20g/L, is preferably 12 ~ 18g/L, is more preferably 13 ~ 17g/L; The mass concentration of described ammonium chloride is 4 ~ 8g/L, is preferably 5 ~ 7g/L.
In the present invention, the mass concentration of described nano silicon is 1 ~ 4g/L, is preferably 2 ~ 3g/L; The particle diameter of described nano silicon is preferably 10 ~ 20nm, more can be preferably 12 ~ 18nm, most preferably be 13 ~ 17nm, is the most preferably 14 ~ 16nm.The present invention adds nano silicon in described electrolytic solution, the degree of polarization of negative electrode is increased, prevent growing up of Cu-Zn alloy grain simultaneously, the alloy layer making it be formed more refinement and closely, decrease settled layer voidage, define the metal-based compound coating of particle reinforce, solidity to corrosion improves greatly compared to simple copper zinc alloy coating.
Nano compound electroplating liquid in the present invention preferably also comprises dispersion agent, and described dispersion agent preferably includes Poly Dimethyl Diallyl Ammonium Chloride (PDDA) and/or cetyl trimethylammonium bromide (CTAB).
Wherein, described CTAB is cationic surfactant, with a large amount of positive charge group after its dissociation, around can adsorb in a large number with the SiO of opposite charges
2, add intergranular repulsion, reach dispersion object, dissociation small ion out makes the ionic strength of dispersion medium change simultaneously, thus changes the thickness of electrostatic double layer, enhances the stability of electrostatic double layer, makes Nano-meter SiO_2
2easier and metal ion codeposition forms composite deposite; Described PDDA is cation type polymer ionogen, and the polymer macromolecule after its dissociation utilizes the space steric effect of self effectively can intercept the reunion of nano particle, and with a large amount of positive charge group, around can adsorb in a large number with the SiO of opposite charges
2, utilize electrostatic stabilization mechanism to add intergranular repulsion, reach dispersion object, make Nano-meter SiO_2
2easier and metal ion codeposition forms composite deposite.In the present invention, the mass concentration of described PDDA is 5 ~ 50mg/L, is preferably 10 ~ 45mg/L, is more preferably 15 ~ 40mg/L, most preferably is 20 ~ 35mg/L; The mass concentration of described CTAB is 5 ~ 50mg/L, is preferably 10 ~ 45mg/L, is more preferably 15 ~ 40mg/L, most preferably is 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, sodium cyanide, sodium carbonate, Seignette salt, ammonium chloride and Nano-meter SiO_2
2mix with water, obtain nano compound electroplating liquid above.The preparation of cuprous cyanide, zinc cyanide, sodium cyanide, sodium carbonate, Seignette salt, ammonium chloride and water is preferably obtained the first mixing solutions by the present invention, then take a morsel mixing solutions and dispersion agent and silicon-dioxide is mixed to get the second mixing solutions, be uniformly mixed rear ultrasonic disperse, finally the second mixing solutions is added in the first mixing solutions, obtain nano compound electroplating liquid.Nano compound electroplating liquid obtained is according to the method described above nano compound electroplating liquid mentioned above, wherein kind and the mass concentration of cuprous cyanide, zinc cyanide, sodium cyanide, sodium carbonate, Seignette salt, ammonium chloride, silicon-dioxide and dispersion agent are consistent with the kind of cuprous cyanide, zinc cyanide, sodium cyanide, sodium carbonate, Seignette salt, ammonium chloride, silicon-dioxide and dispersion agent in nano compound electroplating liquid mentioned above and mass concentration, do not repeat them here.
Present invention also offers a kind of Zinc alloy electroplating part, electroplated in nano compound electroplating liquid mentioned above by described zinc alloy diecasting and obtain.
In the present invention, the zinc ingot metal that described zinc alloy diecasting is used is 4# zinc alloy; Described zinc alloy diecasting is preferably the Zinc alloy electroplating part that surface has copper-nickel alloy tin coating; The Coating composition on described Zinc alloy electroplating part surface and the content of each composition is respectively: copper 50 ~ 60%, tin 30 ~ 40%, the zinc of remaining about 10%.Concrete, in an embodiment of the present invention, the present invention can adopt the slider of zipper fastener of zinc alloy diecasting to electroplate.
The present invention preferably electroplates described zinc alloy diecasting by the following method:
By nano compound electroplating liquid above, add in plating tank that anode is copper zinc alloy plate, temperature regulator is regulated to make temperature in groove maintain between 30 ~ 35 DEG C, regulate plating solution pH between 11.5 ~ 12 by pH meter, regulate current valve to make the current density passing into electroplate liquid be 0.17 ~ 0.92A/dm
2, then namely obtain surface attachment have Cu-Zn-SiO by needing the zinc alloy diecasting of plating to put into plating tank plating in the mode of rack plating
2the Zinc alloy electroplating part of composite galvanized coating.
In the present invention, described as preferably including the copper of 60 ~ 80% massfractions and the zinc of 20 ~ 40% massfractions in the copper zinc alloy plate of anode, more preferably comprise the copper of 70% massfraction and the zinc of 30% massfraction.
The invention provides a kind of nano compound electroplating liquid, comprise the component of following concentration: cuprous cyanide: 23 ~ 26g/L, zinc cyanide: 10 ~ 12g/L, sodium cyanide: 43 ~ 51g/L, sodium carbonate: 25 ~ 35g/L, Seignette salt: 10 ~ 20g/L, ammonium chloride: 4 ~ 8g/L, SiO
2: 1 ~ 4g/L; Described SiO
2particle diameter be 10 ~ 20nm.Nano-meter SiO_2
2add cathodic polarization degree increased, and prevent growing up of Cu-Zn alloy grain, make coating refinement and closely more, decrease settled layer voidage, define the metal-based compound coating of particle reinforce, thus improve the erosion resistance of coating.
Present invention also offers a kind of Zinc alloy electroplating part, be ground with zinc alloy diecasting, zinc alloy diecasting is loose porous, not corrosion-resistant, but adopts Cu-Zn-SiO prepared by the nano compound electroplating liquid in the present invention
2composite galvanized coating can be good at protecting base material, improves its erosion resistance.
In addition, the raw materials used source of the present invention is wide, and preparation is simple, and cost is low, and the nano-composite plate of gained can be applicable to multiple field as protecting decorative coating.
Carry out plating in nano compound electroplating liquid in the present invention after copper sheet (10*1cm) oil removing activates by the present invention and obtain Cu-Zn-SiO
2nano-composite plate, is then made into working electrode, and electrode area is 0.5cm
2, adopt three-electrode system test, SCE is reference electrode, and Pt sheet is to electrode, and measuring technology is the Tafel polarization curve in electrochemical workstation, and test fluid is 5% salt solution, then calculates the corrosion electric current density I of coating according to Tafel straight-line extrapolation method
corr, corrosion current is more large more perishable, according to I
corrsize can the solidity to corrosion of more different coating.Result shows, the Cu-Zn-SiO in the present invention
2the I of nano-composite plate
corrbe 4.5 × 10
-6a/cm
2, and do not add SiO
2the I of Cu-Zn alloy layer
corrbe 109.52 × 10
-6a/cm
2, the corrosion current of coating of the present invention greatly reduces, and the solidity to corrosion that the nano-composite plate in the present invention is described comparatively Cu-Zn alloy layer is significantly improved.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of nano compound electroplating liquid provided by the invention, its preparation method and Zinc alloy electroplating part being described in detail, but can not limiting the scope of the present invention being understood as.
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 zinc cyanide concentration is 11g/L, and sodium cyanide concentration is 47g/L, and concentration of sodium carbonate is 30g/L, and soluble tartrate na concn is 10g/L, and ammonium chloride concentration is 6g/L, Nano-meter SiO_2
2particle size is 15 ± 5nm, Nano-meter SiO_2
2concentration is 1g/L, PDDA concentration is 5mg/L.
Compound method is: first configure not containing dispersion agent and Nano-meter SiO_2 by said components proportioning
2copper zinc electroplate liquid (compound method is with comparative example 1), then the electroplate liquid that takes a morsel adds dispersion agent, then adds Nano-meter SiO_2
2particle, stirs 10min, and ultrasonic disperse 60min after mixing, finally contains dispersion agent and Nano-meter SiO_2 by this
2a small amount of electroplate liquid of particle adds and to stir in original electroplate liquid and to obtain Cu-Zn-SiO
2nano compound electroplating liquid.
By the electroplate liquid prepared, add in plating tank that anode is copper zinc alloy plate, regulate temperature regulator to make temperature in groove be 30 DEG C, regulate plating solution pH to be 11.6 by pH meter, regulate current valve to make the current density passing into electroplate liquid be 0.3A/dm
2, then Zinc alloy slide fastener head is put into plating tank plating in the mode of rack plating and namely obtains Cu-Zn-SiO
2nano-composite plate.As shown in Figure 1, Fig. 1 is the coating photo that the embodiment of the present invention 1 obtains to coating.
The test of corrosion resistance of coating: by galvanic deposit Cu-Zn-SiO after copper sheet (10*1cm) oil removing activation
2nano-composite plate is made into working electrode, and electrode area is 0.5cm
2, adopt three-electrode system test, SCE is reference electrode, and Pt sheet is to electrode, and measuring technology is the Tafel polarization curve in electrochemical workstation, and test fluid is 5% salt solution, then calculates the corrosion electric current density I of coating according to Tafel straight-line extrapolation method
corr, corrosion current is more large more perishable, according to I
corrsize can the solidity to corrosion of more different coating.
As shown in Figure 2, Fig. 2 is the Tafel polarization curve of the embodiment of the present invention 1 and comparative example 1 to test result, and in Fig. 2, curve 1 is the coating Tafel polarization curve that comparative example 1 of the present invention obtains; Curve 2 is the Tafel polarization curve of the nano-composite plate that the embodiment of the present invention 1 obtains.According to Fig. 2, record Cu-Zn-SiO by electrochemistry experiment
2the I of nano-composite plate
corrbe 15.0 × 10
-6a/cm
2, and do not add SiO
2the I of Cu-Zn alloy layer
corrbe 109.52 × 10
-6a/cm
2, the former corrosion current greatly reduces, and Cu-Zn-SiO is described
2the solidity to corrosion of nano-composite plate comparatively Cu-Zn alloy layer is significantly improved.
Embodiment 2
The nano compound electroplating liquid with following proportioning is obtained: cuprous cyanide concentration is 25g/L, and zinc cyanide concentration is 11g/L, and sodium cyanide concentration is 47g/L according to the method preparation in embodiment 1, concentration of sodium carbonate is 30g/L, soluble tartrate na concn is 10g/L, and ammonium chloride concentration is 6g/L, Nano-meter SiO_2
2particle size is 15 ± 5nm, Nano-meter SiO_2
2concentration is 4g/L, PDDA concentration is 50mg/L.
By the electroplate liquid prepared, add in plating tank that anode is copper zinc alloy plate, regulate temperature regulator to make temperature in groove be 35 DEG C, regulate plating solution pH to be 12 by pH meter, regulate current valve to make the current density passing into electroplate liquid be 0.5A/dm
2, then Zinc alloy slide fastener head is put into plating tank plating in the mode of rack plating and namely obtains Cu-Zn-SiO
2nano-composite plate.As shown in Figure 3, Fig. 3 is the coating photo that the embodiment of the present invention 2 obtains to coating.
The erosion resistance of nano-composite plate in the present embodiment is tested according to the testing method of coating erosion resistance in embodiment 1, result as shown in Figure 4, Fig. 4 is the Tafel polarization curve of the embodiment of the present invention 2 and comparative example 1, in Fig. 4, curve 1 is the coating Tafel polarization curve that comparative example 1 of the present invention obtains; Curve 3 is the Tafel polarization curve of the nano-composite plate that the embodiment of the present invention 2 obtains.According to Fig. 4, record Cu-Zn-SiO by electrochemistry experiment
2the I of nano-composite plate
corrbe 91.7 × 10
-6a/cm
2, than the I of Cu-Zn alloy layer
corrlittle, Cu-Zn-SiO is described
2nano-composite plate has good solidity to corrosion.
Embodiment 3
The nano compound electroplating liquid with following proportioning is obtained: cuprous cyanide concentration is 25g/L, and zinc cyanide concentration is 11g/L, and sodium cyanide concentration is 47g/L according to the method preparation in embodiment 1, concentration of sodium carbonate is 30g/L, soluble tartrate na concn is 10g/L, and ammonium chloride concentration is 6g/L, Nano-meter SiO_2
2particle size is 15 ± 5nm, Nano-meter SiO_2
2concentration is 2g/L, PDDA concentration is 50mg/L.
By the electroplate liquid prepared, add in plating tank that anode is copper zinc alloy plate, regulate temperature regulator to make temperature in groove be 30 DEG C, regulate plating solution pH to be 12 by pH meter, regulate current valve to make the current density passing into electroplate liquid be 0.7A/dm
2, then Zinc alloy slide fastener head is put into plating tank plating in the mode of rack plating and namely obtains Cu-Zn-SiO
2nano-composite plate.As shown in Figure 5, Fig. 5 is the coating photo that the embodiment of the present invention 3 obtains to coating.
The erosion resistance of nano-composite plate in the present embodiment is tested according to the testing method of coating erosion resistance in embodiment 1, result as shown in Figure 6, Fig. 6 is the Tafel polarization curve of the embodiment of the present invention 3 and comparative example 1, in Fig. 6, curve 1 is the coating Tafel polarization curve that comparative example 1 of the present invention obtains; Curve 4 is the Tafel polarization curve of the nano-composite plate that the embodiment of the present invention 3 obtains.According to Fig. 6, experiment records Cu-Zn-SiO
2the I of nano-composite plate
corrbe 4.5 × 10
-6a/cm
2, than the I of Cu-Zn alloy layer
corrlittle, Cu-Zn-SiO is described
2nano-composite plate has good solidity to corrosion.
Embodiment 4
The nano compound electroplating liquid with following proportioning is obtained: cuprous cyanide concentration is 25g/L, and zinc cyanide concentration is 11g/L, and sodium cyanide concentration is 47g/L according to the method preparation in embodiment 1, concentration of sodium carbonate is 30g/L, soluble tartrate na concn is 10g/L, and ammonium chloride concentration is 6g/L, Nano-meter SiO_2
2particle size is ± 15 ± 5nm, Nano-meter SiO_2
2concentration is 3g/L, CTAB concentration is 50mg/L.As shown in Figure 7, Fig. 7 is the coating photo that the embodiment of the present invention 4 obtains to coating.
By the electroplate liquid prepared, add in plating tank that anode is copper zinc alloy plate, regulate temperature regulator to make temperature in groove be 35 DEG C, regulate plating solution pH to be 12 by pH meter, regulate current valve to make the current density passing into electroplate liquid be 0.2A/dm
2, then Zinc alloy slide fastener head is put into plating tank plating in the mode of rack plating and namely obtains Cu-Zn-SiO
2nano-composite plate.
The erosion resistance of nano-composite plate in the present embodiment is tested according to the testing method of coating erosion resistance in embodiment 1, result as shown in Figure 8, Fig. 8 is the Tafel polarization curve of the embodiment of the present invention 4 and comparative example 1, in Fig. 8, curve 1 is the coating Tafel polarization curve that comparative example 1 of the present invention obtains; Curve 5 is the Tafel polarization curve of the nano-composite plate that the embodiment of the present invention 4 obtains.According to Fig. 8, experiment records Cu-Zn-SiO
2the I of nano-composite plate
corrbe 79.5 × 10
-6a/cm
2, than the I of Cu-Zn alloy layer
corrlittle, Cu-Zn-SiO is described
2nano-composite plate has good solidity to corrosion.
Comparative example 1
Preparation of nano composite plating solution: wherein, cuprous cyanide concentration is 25g/L, and zinc cyanide concentration is 11g/L, and sodium cyanide concentration is 47g/L, and concentration of sodium carbonate is 30g/L, and soluble tartrate na concn is 10g/L, and ammonium chloride concentration is 6g/L.
Compound method is: be dissolved in sodium cyanide solution by calculating by required zinc cyanide, slowly add cuprous cyanide, limit edged stirs, and adds the sodium carbonate of metering, ammonium chloride and Seignette salt after all dissolving, filter after stirring and dissolving, last constant volume obtains the copper zinc electroplate liquid of comparative example 1.
By the electroplate liquid prepared, add in plating tank that anode is copper zinc alloy plate, regulate temperature regulator to make temperature in groove be 30 DEG C, regulate plating solution pH to be 12 by pH meter, regulate current valve to make the current density passing into electroplate liquid be 0.7A/dm
2, then Zinc alloy slide fastener head is put into plating tank plating in the mode of rack plating and namely obtains Cu-Zn-SiO
2nano-composite plate.As shown in Figure 9, Fig. 9 is the coating photo that comparative example 1 of the present invention obtains to coating.As seen from Figure 9, with Cu-Zn-SiO prepared by the present invention
2nano-composite plate with do not add SiO
2alloy layer color basically identical, Deposit appearance color is easy to keep stable.
The erosion resistance of coating in the present embodiment is tested according to the testing method of coating erosion resistance in embodiment 1, result is as shown in the curve 1 in Fig. 2, Fig. 4, Fig. 6 or Fig. 8, and the curve 1 in Fig. 2,4,6 or 8 is the Tafel polarization curve of the coating that comparative example 1 of the present invention obtains.As can be seen from Fig. 2,4,6 or 8, the Cu-Zn-SiO that embodiment 1 ~ 4 obtains
2the I of nano-composite plate
corrthan the I of Cu-Zn alloy layer in this comparative example
corrlittle, Cu-Zn-SiO is described
2nano-composite plate has good solidity to corrosion.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a nano compound electroplating liquid, comprises the component of following concentration:
Cuprous cyanide: 23 ~ 26g/L, zinc cyanide: 10 ~ 12g/L, sodium cyanide: 43 ~ 51g/L, sodium carbonate: 25 ~ 35g/L, Seignette salt: 10 ~ 20g/L, ammonium chloride: 4 ~ 8g/L, Nano-meter SiO_2
2: 1 ~ 4g/L, surplus is water.
2. nano compound electroplating liquid according to claim 1, is characterized in that, described Nano-meter SiO_2
2particle diameter be 10 ~ 20nm.
3. nano compound electroplating liquid according to claim 1, is characterized in that, the mass ratio of described cuprous cyanide and zinc cyanide is (2 ~ 2.5): 1.
4. nano compound electroplating liquid according to claim 1, is characterized in that, the concentration of described cuprous cyanide is 24 ~ 25g/L.
5. nano compound electroplating liquid according to claim 1, is characterized in that, described cyaniding zinc concentration is 11 ~ 11.5g/L.
6. the nano compound electroplating liquid according to Claims 1 to 5 any one, is characterized in that, described nano compound electroplating liquid also comprises dispersion agent;
Described dispersion agent comprises Poly Dimethyl Diallyl Ammonium Chloride and/or cetyl trimethylammonium bromide.
7. nano compound electroplating liquid according to claim 6, is characterized in that, the concentration of described Poly Dimethyl Diallyl Ammonium Chloride is 5 ~ 50mg/L;
The concentration of described cetyl trimethylammonium bromide is 5 ~ 50mg/L.
8. a preparation method for nano compound electroplating liquid, comprises the following steps:
By cuprous cyanide, zinc cyanide, sodium cyanide, sodium carbonate, Seignette salt, ammonium chloride and Nano-meter SiO_2
2mix with water, obtain nano compound electroplating liquid;
Wherein, in described nano compound electroplating liquid, cuprous cyanide concentration is 23 ~ 26g/L, and zinc cyanide concentration is 10 ~ 12g/L, sodium cyanide concentration is 43 ~ 51g/L, and concentration of sodium carbonate is 25 ~ 35g/L, and soluble tartrate na concn is 10 ~ 20g/L, ammonium chloride concentration is 4 ~ 8g/L, SiO
2concentration is 1 ~ 4g/L.
9. a Zinc alloy electroplating part, electroplates in the nano compound electroplating liquid obtained at the nano compound electroplating liquid described in claim 1 ~ 7 any one or preparation method according to claim 8 obtain by zinc alloy diecasting.
10. Zinc alloy electroplating part according to claim 9, is characterized in that, described Zinc alloy electroplating part is the Zinc alloy electroplating part that surface has copper-nickel alloy tin coating.
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