CN103938231A - Gold electroplating method and hard gold preparation method - Google Patents
Gold electroplating method and hard gold preparation method Download PDFInfo
- Publication number
- CN103938231A CN103938231A CN201410077259.6A CN201410077259A CN103938231A CN 103938231 A CN103938231 A CN 103938231A CN 201410077259 A CN201410077259 A CN 201410077259A CN 103938231 A CN103938231 A CN 103938231A
- Authority
- CN
- China
- Prior art keywords
- gold
- salt
- liquid
- plating
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/02—Tubes; Rings; Hollow bodies
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Abstract
The present invention discloses a gold electroplating method and a hard gold preparation method. The hard gold preparation method comprises: electroplating a gold layer on a core shaft formed from a low melting point material; and forming a hole penetrating through the electroplating layer until reaching the core shaft, melting the core shaft, and discharging out from the hole. The hard gold preparation method is characterized in that the method for electroplating the gold layer on the core shaft comprises: adopting the core shaft as a cathode, and electroplating in a cyanide-free electroplating solution containing a gold sulfite solution, a phosphate, a hydrophosphate, an alkali metal sulfite, a hardening agent and a complexing agent. According to the present invention, the gold sulfite solution in the cyanide-free electroplating solution for forming the gold layer has good stability, and the gold product obtained from the cyanide-free electroplating solution has high hardness and has great industrial application prospects.
Description
Technical field
The present invention relates to a kind of method of gold and a kind of preparation method of hard gold of electroplating.
Background technology
Along with the raising day by day of people's living standard, gold product is more and more subject to consumers in general's favor.At present, the gold product of producing by the mode of electroplating is more and more.Wherein, in electroplating process, electroplate liquid used is mainly the solution that contains potassium auric cyanide.But potassium auric cyanide belongs to highly toxic substance, not only in the production process of gold product, can to work the mischief to the healthy of producer, and to produce the pollution of waste liquid to environment in order reducing, also need to spend a large amount of expenses with process for producing waste liquid.
In order to overcome the above-mentioned defect that contains potassium auric cyanide electroplate liquid, in recent years, also there is the solution that Some Enterprises employing contains sulfurous acid gold liquid (sulfurous acid gold potassium and/or gold sodium sulfide) to substitute the solution that contains potassium auric cyanide as electroplate liquid, to prepare gold product.But, due to the less stable of sulfurous acid gold potassium and gold sodium sulfide, in electroplating process, very easily separate out, thereby affected the stability of electroplating process and the performance of gold product.In addition, the hardness of the gold product obtaining as electroplate liquid using sulfurous acid gold potassium and/or gold sodium sulfide is lower, can make like this to make gold product that purity is higher particularly when thousand pure golds, easily deform, cave in, in use very easily damage, thereby how improving the stability of the electroplate liquid that contains sulfurous acid gold liquid and obtaining the plating gold that hardness is higher is the technical problem that current yellow Manufacturing Technology is needed solution badly.
Summary of the invention
To the object of the invention is existingly to contain the sulfurous acid gold electroplate liquid poor stability of liquid and the lower defect of gold product hardness of acquisition in order overcoming, and a kind of method of plating gold and a kind of preparation method of hard gold who adopts stable cyanideless electro-plating liquid to obtain the gold product that hardness is higher to be provided.
In order to realize foregoing invention object, the invention provides a kind of method of electroplating gold, wherein, the method comprises electroplates the cyanideless electro-plating liquid that contains sulfurous acid gold liquid, phosphoric acid salt, hydrophosphate, alkali sulfite metal-salt, stiffening agent and complexing agent.
In addition, the present invention also provides a kind of preparation method of hard gold, and the method comprises:
In the mandrel being formed by the low melting material Gold plated Layer that powers on;
Form and arrive the hole of described mandrel through electrolytic coating, and described mandrel is melted to discharge by described hole; It is characterized in that, comprise taking described mandrel as negative electrode in the power on method of Gold plated Layer of described mandrel, in the cyanideless electro-plating liquid that contains sulfurous acid gold liquid, phosphoric acid salt, hydrophosphate, alkali sulfite metal-salt, stiffening agent and complexing agent, electroplate.
The present inventor finds by further investigation, above-mentioned several materials contained in described cyanideless electro-plating liquid are used in conjunction with, not only can show the stability that improves described cyanideless electro-plating liquid Central Asia auric sulfate liquid, electroplating process is steadily carried out, but also can improve the hardness of gold product, have prospects for commercial application.
A preferred embodiment of the invention, when described stiffening agent is the mixture of antimonic salt and selenium salt, and the weight ratio of described antimonic salt and selenium salt is while being 0.25-1:1, can further improve the hardness of gained gold product.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the concrete preparation method of the one of described hard gold provided by the invention.
Description of reference numerals
10-mandrel; 11-silicon rubber mould; 12-scavenging solution; 13-copper plating bath; 14-electroplate liquid; 15-nickel-plating liquid; 20-hanger.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The method of plating gold provided by the invention comprises electroplates the cyanideless electro-plating liquid that contains sulfurous acid gold liquid, phosphoric acid salt, hydrophosphate, alkali sulfite metal-salt, stiffening agent and complexing agent.
The present invention is not particularly limited the content of each component in above-mentioned cyanideless electro-plating liquid, for example, described sulfurous acid gold liquid with respect to 10g in gold element, described phosphatic content can be 100-200 gram, the content of described hydrophosphate can be 50-200 gram, the content of described alkali sulfite metal-salt can be 30-120 gram, and the content of described stiffening agent can be 0.01-2 gram, and the content of described complexing agent can be 0.01-5 gram.Preferably, described sulfurous acid gold liquid with respect to 10g in gold element, described phosphatic content is 150-200 gram, the content of described hydrophosphate is 80-120 gram, the content of described alkali sulfite metal-salt is 40-100 gram, the content of described stiffening agent is 0.5-1.5 gram, and the content of described complexing agent is 2-5 gram.
As a rule, described cyanideless electro-plating liquid also contains water.The consumption of described water can be that the routine of this area is selected, as long as can guarantee electroplating process smoothly, for example, the consumption of described water can make described cyanideless electro-plating liquid taking 1L as benchmark, content taking the described sulfurous acid gold liquid of gold element can, as 8-20g, be preferably 9-12g.
According to the present invention, described sulfurous acid gold liquid can be for existing various without cyanogen and can electroplate the material that contains sulfite ion and gold ion that obtains gold product, and its specific examples includes but not limited to: one or more in sulfurous acid gold potassium, gold sodium sulfide and sulfurous acid gold ammonium.But because described sulfurous acid gold ammonium can produce poisonous ammonia in electroplating process, therefore, described sulfurous acid gold liquid is particularly preferably sulfurous acid gold potassium and/or gold sodium sulfide.
According to the present invention, described phosphoric acid salt, hydrophosphate and alkali sulfite metal-salt can be all that the routine of this area is selected.For example, described phosphoric acid salt can be potassiumphosphate and/or sodium phosphate.Described hydrophosphate can be selected from one or more in potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC.Described alkali sulfite metal-salt can be potassium sulfite and/or S-WAT.
Described stiffening agent can be the existing various materials that can improve plating gold product hardness, be preferably antimonic salt and/or selenium salt, the more preferably mixture of antimonic salt and selenium salt, adopts this stiffening agent that simultaneously contains antimonic salt and selenium salt can further improve the hardness of gold product.In the time that described stiffening agent is the mixture of antimonic salt and selenium salt, the weight ratio of described antimonic salt and selenium salt is particularly preferably 0.25-1:1.In addition, the example of described antimonic salt includes but not limited to: one or more in sodium antimony tartrate, antimonypotassium tartrate, sodium antimonate and potassium antimonate.The example of described selenium salt includes but not limited to: one or more in sodium thiosulfate, seleno potassium sulfate, Sodium Selenite and potassium selenite.
Described complexing agent can be for the existing various compounds that can form with gold ion complexing ion, for example, can be selected from one or more in sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine.
The present invention is not particularly limited the condition of described plating, as long as can obtain gold product, as a rule, the condition of described plating can comprise: the temperature of electroplate liquid is 40-60 DEG C, and the pH value of electroplate liquid is 6-8, and cathode current density is 0.1-1A/dm
2, electroplating time is 8-20 hour.The method that the pH value of described electroplate liquid is controlled in above-mentioned scope is known to the skilled person, and for example, adds acidic substance or alkaline matter in described electroplate liquid in the past.Described acidic substance can be for example one or more in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid etc.Described alkaline matter can be for example one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, ammoniacal liquor etc.The consumption of above-mentioned acidic substance and alkaline matter is to be adjusted to the pH value of described electroplate liquid in above-mentioned scope and to be as the criterion, and therefore not to repeat here.
In addition, the preparation method of hard gold provided by the invention comprises:
In the mandrel being formed by the low melting material Gold plated Layer that powers on;
Form and arrive the hole of described mandrel through electrolytic coating, and described mandrel is melted to discharge by described hole; It is characterized in that, comprise taking described mandrel as negative electrode in the power on method of Gold plated Layer of described mandrel, in the cyanideless electro-plating liquid that contains sulfurous acid gold liquid, phosphoric acid salt, hydrophosphate, alkali sulfite metal-salt, stiffening agent and complexing agent, electroplate.
The cyanideless electro-plating liquid adopting in the preparation method of described hard gold is identical with component and the content of the cyanideless electro-plating liquid adopting in the method for above-mentioned plating gold, and therefore not to repeat here.
Described mandrel mainly plays the effect of forming mould, thereby not only can obtain the gold product of different shape, and the gold product obtaining after described mandrel is removed is hollow structure, thereby can show gold consumption used while reducing the gold product of producing same size, reduce production cost.In the present invention, described " low melting point " refers to that fusing point, not higher than 200 DEG C, is preferably 60-130 DEG C.The material of the mandrel of described low melting point can be sn-bi alloy and/or wax.Wherein, in described sn-bi alloy, the weight ratio of described tin and bismuth can be 0.5-1.5:1.The example of described wax includes but not limited to: one or more in beeswax, mineral wax (as montanin wax, ceresine, paraffin) and petroleum wax etc.The size and shape of the gold product that the size and shape of described mandrel can obtain as required carries out choose reasonable, and therefore not to repeat here.
In addition, because described sn-bi alloy is when the high temperature stripping, can corrode gold, therefore, before described mandrel powers on Gold plated Layer, preferably first on described mandrel, electroplate the first bronze medal layer, and then on described the first bronze medal layer, electroplate described gold layer, and after described mandrel being melted and discharge, remove described the first bronze medal layer.In addition,, as the optional mode of another kind, described mandrel also can be electroplating after the first bronze medal layer, remove before electrogilding layer.While removing described mandrel, can adopt the discharge of the auxiliary described low melting material of vibration.
According to the present invention, in the time that described mandrel or the first bronze medal layer power on Gold plated Layer, the condition of described plating can comprise conventionally: the temperature of electroplate liquid is 40-60 DEG C, and the pH value of electroplate liquid is 6-8, and cathode current density is 0.1-1A/dm
2, electroplating time is 8-20 hour.In addition, the thickness of the described gold layer of formation can be 50-150 μ m, is preferably 100-130 μ m.
According to the present invention; before the preparation method of described hard gold is also included in and forms described hole; first on described gold layer, electroplate successively the second bronze medal layer and nickel dam; and after described mandrel being melted and discharge, remove described the second bronze medal layer and nickel dam; can prevent like this gold layer " dissolving ", thereby play a protective role.In the concrete preparation process of described hard gold, the method that forms described the first bronze medal layer generally includes described low melting material (as sn-bi alloy and/or wax, in the time being wax, conventionally need on the surface of wax, be coated with conductive oil) as negative electrode, using phosphorized copper as anode, in copper-contained electroplating liquid, electroplate.The method that forms described the second bronze medal layer generally includes using the goods that are electroplate with gold layer as negative electrode, using phosphorized copper as anode, electroplating containing in copper electrolyte.The copper-contained electroplating liquid adopting in the process of above-mentioned twice copper electroplating layer can be selected for the routine of this area, and therefore not to repeat here.
The plating condition that forms described the first bronze medal layer can be identical or different with the plating condition that forms described the second bronze medal layer, and comprise independently of one another: the temperature of electroplate liquid can be 15-35 DEG C, the pH value of electroplate liquid can be 0.1-0.5, and cathode current density can be 0.5-5A/dm
2, electroplating time can be 30-60 minute.In addition, the thickness of the described first bronze medal layer of formation can be 40-60 micron, is preferably 45-55 micron; The thickness of described the second bronze medal layer forming can be 40-60 micron, is preferably 45-55 micron.Described the first bronze medal layer is preferably bright and smooth, and it is also bright and smooth can making so the follow-up gold layer obtaining.
According to the present invention, the method that forms described nickel dam generally includes using the goods that are electroplate with the second bronze medal layer as negative electrode, using metallic nickel as anode, containing electroplating in nickel electrolyte.The described routine that can be this area containing nickel electrolyte is selected, and therefore not to repeat here.The plating condition that forms described nickel dam can comprise conventionally: the temperature of electroplate liquid is 35-50 DEG C, and the pH value of electroplate liquid is 3.5-5, and cathode current density is 2-4A/dm
2, electroplating time is 10-20 minute.In addition, the thickness of the described nickel dam of formation can be 5-20 micron, is preferably 5-10 micron.
In addition, can adopt existing the whole bag of tricks to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam, for example, can, after described mandrel is removed, the gold prefabricated component of acquisition be immersed in dilute nitric acid solution.The concentration of described dilute nitric acid solution can be for example 5-10mol/L.
According to a kind of embodiment of the present invention, as shown in Figure 1, the preparation method of described hard gold comprises: the mandrel 10 that rotational casting is formed by low melting point alloy in silicon rubber mould 11, again described mandrel 10 is placed in cylinder to remove thorn or any joint line, then mandrel 10 is connected on the hanger 20 of plating rack, and cleans in electrolysis and/or ultrasonic cleaning solution 12.If the fusing point of mandrel 10 is lower than the temperature of electroplate liquid that forms gold layer, need on mandrel 10, form the first bronze medal layer, that is, clean mandrel 10 is transferred to the electroplating of going forward side by side in copper plating bath 13, to form the first bronze medal layer on the surface at mandrel 10.Described the first bronze medal layer should be bright and smooth, is also bright and smooth thereby make the gold layer of follow-up formation.(be electroplate with the first bronze medal layer or be not electroplate with the first bronze medal layer) mandrel 10 is placed in to the electroplate liquid 14 that contains sulfurous acid gold liquid and electroplates, form gold layer, then the product obtaining is placed in to copper plating bath 13 and electroplates, to form the second bronze medal layer on gold layer.Preferably, after forming the second bronze medal layer, the product obtaining is placed in to nickel-plating liquid 15 and electroplates, to form nickel dam on the second bronze medal layer.After completing plating, the product obtaining is removed from fixture 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 DEG C, the mandrel 10 of low melting point melts and flows out from hole.Then be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam removing product after the mandrel 10 of low melting point again, only retain gold layer, thereby obtain gold product.
Above-mentioned each plating step all can be implemented by traditional way, for example, can will comprise that described mandrel 10 is electrically connected to the negative electrode of direct supply by hanger 20 and inserts in corresponding electroplate liquid with the product of the associated metal level forming afterwards, anode is connected to the positive terminal of direct supply and inserts in corresponding electroplate liquid.
In addition, the preparation method of described hard gold also comprises and adopts the modes such as welding, sandblast and polishing to process to become jewelry piece the gold product of removing after residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam.
Below will describe the present invention by embodiment.
Preparation example 1
This preparation example is used for illustrating cyanideless electro-plating liquid provided by the invention and preparation method thereof.
At 60 DEG C, by taking gold element consumption as the gold sodium sulfide of 10 grams, 200 grams of potassiumphosphates, 100 grams of potassium phosphate,monobasics, 50 grams of S-WATs, 0.5 gram of sodium antimony tartrate, 0.5 gram of Sodium Selenite and 5 grams of sodium ethylene diamine tetracetates are dissolved in 1L water, obtain cyanideless electro-plating liquid Z1.Measure stability and the electroconductibility of cyanideless electro-plating liquid Z1 by cyclic voltammetry, cathodic polarization curve and cathode efficiency method.Result shows, the stability of cyanideless electro-plating liquid Z1 is high, only has very a small amount of gold ion automatic reduction, and electroconductibility is very good, and cathode efficiency maintains more than 90%.
Preparation example 2
This preparation example is used for illustrating cyanideless electro-plating liquid provided by the invention and preparation method thereof.
At 40 DEG C, by taking gold element consumption as the sulfurous acid gold potassium of 10 grams, 180 grams of sodium phosphates, 80 grams of disodium-hydrogens, 40 grams of potassium sulfites, 0.2 gram of antimonypotassium tartrate, 0.3 gram of sodium thiosulfate and 2 grams of thiocarbamides are dissolved in 1L water, obtain cyanideless electro-plating liquid Z2.According to the method for preparation example 1, stability and the electroconductibility of cyanideless electro-plating liquid Z2 are tested.Result shows, the stability of cyanideless electro-plating liquid Z2 is high, there is no gold ion automatic reduction, and electroconductibility is better but lower than cyanideless electro-plating liquid Z1, and cathode efficiency maintains more than 90%.
Preparation example 3
This preparation example is used for illustrating cyanideless electro-plating liquid provided by the invention and preparation method thereof.
At 45 DEG C, by taking gold element consumption as the gold sodium sulfide of 10 grams, 150 grams of potassiumphosphates, 120 grams of potassium primary phosphates, 100 grams of S-WATs, 0.5 gram of sodium antimonate, 1 gram of potassium selenite and 5 grams of Sulfothiorine are dissolved in 1L water, obtain cyanideless electro-plating liquid Z3.According to the method for preparation example 1, stability and the electroconductibility of cyanideless electro-plating liquid Z3 are tested.Result shows, cyanideless electro-plating liquid Z3 stability is very high, there is no gold ion automatic reduction, and electroconductibility is very good, and cathode efficiency maintains more than 90%.
Preparation example 4
This preparation example is used for illustrating cyanideless electro-plating liquid provided by the invention and preparation method thereof.
Prepare cyanideless electro-plating liquid according to the method for preparation example 1, different, described sodium antimony tartrate substitutes with the Sodium Selenite of identical weight part, obtains cyanideless electro-plating liquid Z4.According to the method for preparation example 1, stability and the electroconductibility of cyanideless electro-plating liquid Z4 are tested.Result shows, the stability of cyanideless electro-plating liquid Z4 is high, only has very a small amount of gold ion automatic reduction, and electroconductibility is better but lower than cyanideless electro-plating liquid Z1, and cathode efficiency maintains more than 90%.
Contrast preparation example 1
This contrast preparation example is for illustrating cyanideless electro-plating liquid of reference and preparation method thereof.
Prepare cyanideless electro-plating liquid according to the method for preparation example 4, different, described potassiumphosphate substitutes with the potassium phosphate,monobasic of identical weight part, obtains reference cyanideless electro-plating liquid DZ1.According to the method for preparation example 1, stability and the electroconductibility of reference cyanideless electro-plating liquid DZ1 are tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ1 is low, poorly conductive, and cathode current density only can reach 80%.
Contrast preparation example 2
This contrast preparation example is for illustrating cyanideless electro-plating liquid of reference and preparation method thereof.
Prepare cyanideless electro-plating liquid according to the method for preparation example 4, different, described potassium phosphate,monobasic substitutes with the potassiumphosphate of identical weight part, obtains reference cyanideless electro-plating liquid DZ2.According to the method for preparation example 1, the stability of reference cyanideless electro-plating liquid DZ2 is tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ2 is low, poorly conductive, and cathode current density only can reach 80%.
Contrast preparation example 3
This contrast preparation example is for illustrating cyanideless electro-plating liquid of reference and preparation method thereof.
Method according to contrast preparation example 1 is prepared cyanideless electro-plating liquid, different, and described potassium phosphate,monobasic substitutes with the gold sodium sulfide of identical weight part, obtains reference cyanideless electro-plating liquid DZ3.According to the method for preparation example 1, stability and the electroconductibility of reference cyanideless electro-plating liquid DZ3 are tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ3 is low, poorly conductive, and cathode current density only can reach 75%.
Embodiment 1
This embodiment is for illustrating the preparation method of plating gold provided by the invention and hard gold.
As shown in Figure 1, in silicon rubber mould 11, by low melting point tin bismuth alloy, (weight ratio of tin and bismuth is 52:48 to rotational casting, the mandrel 10 forming down together), again described mandrel 10 is placed in cylinder to remove thorn or any joint line, then mandrel 10 is connected on the hanger 20 of plating rack, and cleans in ultrasonic cleaning solution 12.Then clean mandrel 10 is transferred to the mixture of the copper sulfate of copper plating bath 13(200g/L and the sulfuric acid of 70g/L, lower with) in the electroplating of going forward side by side, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 DEG C, the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the first bronze medal layer of 50 microns.Then the mandrel 10 that is electroplate with the first bronze medal layer is placed in to the cyanideless electro-plating liquid Z1 that contains sulfurous acid gold liquid and electroplates, wherein, plating condition comprises that the temperature of cyanideless electro-plating liquid Z1 is 60 DEG C, and the pH value of cyanideless electro-plating liquid Z1 is 8, and cathode current density is 0.8A/dm
2, electroplating time is 8 hours, formation thickness is the gold layer of 130 microns.Then the product that is electroplate with gold layer is placed in to copper plating bath 13 and electroplates, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 DEG C, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the second bronze medal layer of 50 microns.Then the product that is electroplate with the second bronze medal layer is placed in to the mixture of boric acid, the sodium sulfate of 100g/L and the single nickel salt of 100g/L of nickel-plating liquid 15(20g/L, down together), electroplate, wherein, plating condition comprises that the temperature of nickel-plating liquid 15 is 45 DEG C, the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, formation thickness is the nickel dam of 10 microns.After completing plating, the product obtaining is removed from hanger 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 DEG C, the axle center 10 of low melting point is melted and is flowed out from hole.Then be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam removing product after the axle center 10 of low melting point again, thereby only retained the gold product of gold layer.Through sclerometer calibrating, the hardness of this gold product is 130Hv, and golden purity is 99.96% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Embodiment 2
This embodiment is for illustrating the preparation method of plating gold provided by the invention and hard gold.
As shown in Figure 1, the mandrel 10 that rotational casting is formed by low melting point tin bismuth alloy in silicon rubber mould 11, again described mandrel 10 is placed in cylinder and stings or any joint line to remove, then mandrel 10 is connected on the hanger 20 of plating rack, and clean in ultrasonic cleaning solution 12.Then clean mandrel 10 is transferred to the electroplating of going forward side by side in copper plating bath 13, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 DEG C, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the first bronze medal layer of 50 microns.Then the mandrel 10 that is electroplate with the first bronze medal layer is placed in to the cyanideless electro-plating liquid Z2 that contains sulfurous acid gold liquid and electroplates, wherein, plating condition comprises that the temperature of cyanideless electro-plating liquid Z2 is 40 DEG C, and the pH value of cyanideless electro-plating liquid Z2 is 6, and cathode current density is 0.2A/dm
2, electroplating time is 16 hours, formation thickness is the gold layer of 100 microns.Then the product that is electroplate with gold layer is placed in to copper plating bath 13 and electroplates, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 DEG C, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the second bronze medal layer of 50 microns.Then the product that is electroplate with the second bronze medal layer is placed in to nickel-plating liquid 15 and electroplates, wherein, plating condition comprises that the temperature of nickel-plating liquid 15 is 45 DEG C, and the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, formation thickness is the nickel dam of 10 microns.After completing plating, the product obtaining is removed from hanger 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 DEG C, the axle center 10 of low melting point is melted and is flowed out from hole.Then be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam removing product after the axle center 10 of low melting point again, thereby only retained the gold product of gold layer.Assay through sclerometer, the hardness of this gold product is 135Hv, and golden purity is 99.92% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Embodiment 3
This embodiment is for illustrating the preparation method of plating gold provided by the invention and hard gold.
As shown in Figure 1, the mandrel 10 that rotational casting is formed by low melting point tin bismuth alloy in silicon rubber mould 11, again described mandrel 10 is placed in cylinder and stings or any joint line to remove, then mandrel 10 is connected on the hanger 20 of plating rack, and clean in ultrasonic cleaning solution 12.Then clean mandrel 10 is transferred to the electroplating of going forward side by side in copper plating bath 13, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 DEG C, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the first bronze medal layer of 50 microns.Then the mandrel 10 that is electroplate with the first bronze medal layer is placed in to the cyanideless electro-plating liquid Z3 that contains sulfurous acid gold liquid and electroplates, wherein, plating condition comprises that the temperature of cyanideless electro-plating liquid Z3 is 45 DEG C, and the pH value of cyanideless electro-plating liquid Z3 is 7, and cathode current density is 0.3A/dm
2, electroplating time is 12 hours, formation thickness is the gold layer of 120 microns.Then the product that is electroplate with gold layer is placed in to copper plating bath 13 and electroplates, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 DEG C, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the second bronze medal layer of 50 microns.Then the product that is electroplate with the second bronze medal layer is placed in to nickel-plating liquid 15 and electroplates, wherein, plating condition comprises that the temperature of nickel-plating liquid 15 is 45 DEG C, and the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, formation thickness is the nickel dam of 10 microns.After completing plating, the product obtaining is removed from hanger 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 DEG C, the axle center 10 of low melting point is melted and is flowed out from hole.Then be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam removing product after the axle center 10 of low melting point again, thereby only retained the gold product of gold layer.Assay through sclerometer, the hardness of this gold product is 145Hv, and golden purity is 99.95% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Embodiment 4
This embodiment is for illustrating the preparation method of plating gold provided by the invention and hard gold.
Electroplate gold and carry out the preparation of hard gold according to the method for embodiment 1, different, described cyanideless electro-plating liquid Z1 substitutes with cyanideless electro-plating liquid Z4, is only retained the gold product of gold layer.Through sclerometer calibrating, the hardness of this gold product is 102Hv, and golden purity is 99.94% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Embodiment 5
This embodiment is for illustrating the preparation method of plating gold provided by the invention and hard gold.
Electroplate gold and carry out the preparation of hard gold according to the method for embodiment 4, different is, in preparation process, do not comprise the step that forms the second bronze medal layer and nickel dam, but directly the product forming after the first bronze medal layer and gold layer is bored a hole to remove low melting point axle center 10, and be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer removing product after the axle center 10 of low melting point, thereby only retained the gold product of gold layer.Through sclerometer calibrating, the hardness of this gold product is 90Hv, and golden purity is 99.92% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Embodiment 6
This embodiment is for illustrating the preparation method of gold product provided by the invention.
Electroplate gold and carry out the preparation of hard gold according to the method for embodiment 3, different, in the time forming mandrel 10, low melting point tin bismuth alloy is substituted by the paraffin of same volume, obtains gold product.Through sclerometer calibrating, the hardness of this gold product is 142Hv, and golden purity is 99.93% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Comparative example 1
This comparative example is for illustrating the plating gold of reference and the preparation method of hard gold.
Electroplate gold and carry out the preparation of hard gold according to the method for embodiment 1, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ1.Assay through sclerometer, the hardness of the gold product that employing the method obtains is only 90Hv, and golden purity is 98.97% through the calibrating of fire examination method, rough, fails to meet product standard requirement.
Comparative example 2
This comparative example is for illustrating the plating gold of reference and the preparation method of hard gold.
Electroplate gold and carry out the preparation of hard gold according to the method for embodiment 1, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ2.Assay through sclerometer, the hardness of the gold product that employing the method obtains is only 70Hv, and golden purity is 98.51% through the calibrating of fire examination method, rough, fails to meet product standard requirement.
Comparative example 3
This comparative example is for illustrating the plating gold of reference and the preparation method of hard gold.
Electroplate gold and carry out the preparation of hard gold according to the method for embodiment 1, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ3.Assay through sclerometer, the hardness of the gold product that employing the method obtains is only 70Hv, and golden purity is 98.45% through the calibrating of fire examination method, and surface irregularity, fails to meet product standard requirement.
As can be seen from the above results, the stability of the cyanideless electro-plating liquid Central Asia auric sulfate liquid that forms gold layer provided by the invention is fine, and the gold product being obtained by this cyanideless electro-plating liquid has very high hardness, has prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a method of electroplating gold, is characterized in that, the method comprises electroplates the cyanideless electro-plating liquid that contains sulfurous acid gold liquid, phosphoric acid salt, hydrophosphate, alkali sulfite metal-salt, stiffening agent and complexing agent.
2. method according to claim 1, wherein, in described cyanideless electro-plating liquid, described sulfurous acid gold liquid with respect to 10g in gold element, described phosphatic content is 100-200 gram, and the content of described hydrophosphate is 50-200 gram, and the content of described alkali sulfite metal-salt is 30-120 gram, the content of described stiffening agent is 0.01-2 gram, and the content of described complexing agent is 0.01-5 gram.
3. method according to claim 1 and 2, wherein, described cyanideless electro-plating liquid also contains water, and taking the described cyanideless electro-plating liquid of 1L as benchmark, taking the content of the described sulfurous acid gold liquid of gold element as 8-20g.
4. method according to claim 1 and 2, wherein, described sulfurous acid gold liquid is sulfurous acid gold potassium/gold sodium sulfide; Described phosphoric acid salt is potassiumphosphate and/or sodium phosphate; Described hydrophosphate is selected from one or more in potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC; Described alkali sulfite metal-salt is potassium sulfite and/or S-WAT; Described stiffening agent is antimonic salt and/or selenium salt; Described complexing agent is selected from one or more in sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine.
5. method according to claim 4, wherein, described stiffening agent is the mixture of antimonic salt and selenium salt, and the weight ratio of described antimonic salt and selenium salt is 0.25-1:1.
6. method according to claim 4, wherein, described antimonic salt is selected from one or more in sodium antimony tartrate, antimonypotassium tartrate, sodium antimonate and potassium antimonate; Described selenium salt is selected from one or more in sodium thiosulfate, seleno potassium sulfate, Sodium Selenite and potassium selenite.
7. method according to claim 1 and 2, wherein, the condition of described plating comprises: the temperature of electroplate liquid is 40-60 DEG C, and the pH value of electroplate liquid is 6-8, and cathode current density is 0.1-1A/dm
2, electroplating time is 8-20 hour.
8. a preparation method for hard gold, the method comprises:
In the mandrel being formed by the low melting material Gold plated Layer that powers on;
Form and arrive the hole of described mandrel through electrolytic coating, and described mandrel is melted to discharge by described hole; It is characterized in that, comprise taking described mandrel as negative electrode in the power on method of Gold plated Layer of described mandrel, in the cyanideless electro-plating liquid that contains sulfurous acid gold liquid, phosphoric acid salt, hydrophosphate, alkali sulfite metal-salt, stiffening agent and complexing agent, electroplate.
9. preparation method according to claim 8, wherein, in described cyanideless electro-plating liquid, described sulfurous acid gold liquid with respect to 10g in gold element, described phosphatic content is 100-200 gram, and the content of described hydrophosphate is 50-200 gram, and the content of described alkali sulfite metal-salt is 30-120 gram, the content of described stiffening agent is 0.01-2 gram, and the content of described complexing agent is 0.01-5 gram.
10. preparation method according to claim 8 or claim 9, wherein, described cyanideless electro-plating liquid also contains water, and taking the described cyanideless electro-plating liquid of 1L as benchmark, taking the content of the described sulfurous acid gold liquid of gold element as 8-20g.
11. preparation methods according to claim 8 or claim 9, wherein, described sulfurous acid gold liquid is sulfurous acid gold potassium/gold sodium sulfide; Described phosphoric acid salt is potassiumphosphate and/or sodium phosphate; Described hydrophosphate is selected from one or more in potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC; Described alkali sulfite metal-salt is potassium sulfite and/or S-WAT; Described stiffening agent is antimonic salt and/or selenium salt; Described complexing agent is selected from one or more in sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine.
12. methods according to claim 11, wherein, described stiffening agent is the mixture of antimonic salt and selenium salt, and the weight ratio of described antimonic salt and selenium salt is 0.25-1:1.
13. methods according to claim 11, wherein, described antimonic salt is selected from one or more in sodium antimony tartrate, antimonypotassium tartrate, sodium antimonate and potassium antimonate; Described selenium salt is selected from one or more in sodium thiosulfate, seleno potassium sulfate, Sodium Selenite and potassium selenite.
14. methods according to claim 8 or claim 9, wherein, the condition of described plating comprises: the temperature of electroplate liquid is 40-60 DEG C, and the pH value of electroplate liquid is 6-8, and cathode current density is 0.1-1A/dm
2, electroplating time is 8-20 hour.
15. methods according to claim 8 or claim 9, wherein, described low melting material is sn-bi alloy and/or wax.
16. methods according to claim 15, wherein, described low melting material is sn-bi alloy, and the method is also included in described mandrel and powers on before Gold plated Layer, first on described mandrel, electroplate the first bronze medal layer, and then on described the first bronze medal layer, electroplate described gold layer, and after described mandrel being melted and discharge, remove described the first bronze medal layer.
Method described in 17. according to Claim 8 or 16 wherein, before the method is also included in and forms described hole, is first electroplated successively the second bronze medal layer and nickel dam, and after described mandrel being melted and discharge, is removed described the second bronze medal layer and nickel dam on described gold layer.
18. methods according to claim 17, wherein, the thickness of described the first bronze medal layer is 30-60 micron, and the thickness of described gold layer is 50-150 micron, and the thickness of described the second bronze medal layer is 30-60 micron, and the thickness of described nickel dam is 5-20 micron.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410077259.6A CN103938231B (en) | 2014-03-04 | 2014-03-04 | Gold electroplating method and hard gold preparation method |
| HK15100759.4A HK1200505A1 (en) | 2014-03-04 | 2015-01-23 | Gold electroplating method and hard gold preparation method |
| PCT/CN2015/073546 WO2015131795A1 (en) | 2014-03-04 | 2015-03-03 | Gold electroplating method and hard gold preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410077259.6A CN103938231B (en) | 2014-03-04 | 2014-03-04 | Gold electroplating method and hard gold preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103938231A true CN103938231A (en) | 2014-07-23 |
| CN103938231B CN103938231B (en) | 2015-04-01 |
Family
ID=51186092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410077259.6A Active CN103938231B (en) | 2014-03-04 | 2014-03-04 | Gold electroplating method and hard gold preparation method |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN103938231B (en) |
| HK (1) | HK1200505A1 (en) |
| WO (1) | WO2015131795A1 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862752A (en) * | 2015-06-12 | 2015-08-26 | 深圳市联合蓝海投资有限公司 | Modified cyanide-free gold plating solution and application thereof as well as preparation method of hard gold |
| WO2015131795A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海科技开发有限公司 | Gold electroplating method and hard gold preparation method |
| WO2015131796A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and use therefor |
| CN106637307A (en) * | 2017-01-04 | 2017-05-10 | 中国地质大学（武汉） | Additive for cyanide-free electroforming technology of gold |
| CN106757202A (en) * | 2016-12-30 | 2017-05-31 | 深圳市联合蓝海科技开发有限公司 | A kind of gold product and preparation method thereof |
| CN106929889A (en) * | 2017-05-09 | 2017-07-07 | 句容市博远电子有限公司 | A kind of cyanideless electro-plating liquid and preparation method thereof |
| CN107028305A (en) * | 2016-11-30 | 2017-08-11 | 陈哲 | A kind of processing method of hollow gold ornaments |
| CN107059070A (en) * | 2017-04-21 | 2017-08-18 | 深圳市金玉福珠宝首饰有限公司 | A kind of electroforming process of karat gold ornaments |
| CN107419129A (en) * | 2017-06-26 | 2017-12-01 | 南京市产品质量监督检验院 | A kind of hard gold and preparation method thereof |
| CN107684202A (en) * | 2016-08-03 | 2018-02-13 | 周生生珠宝金行有限公司 | Pure gold and its manufacture method |
| CN109628962A (en) * | 2019-01-21 | 2019-04-16 | 南京市产品质量监督检验院 | A kind of preparation method of no cyanogen 18k gold ornaments |
| CN109913912A (en) * | 2019-04-02 | 2019-06-21 | 深圳市昊扬电铸技术开发有限公司 | A kind of electroforming solution for gold without cyanogen electroforming process |
| CN110106537A (en) * | 2019-06-26 | 2019-08-09 | 浙江金卓首饰有限公司 | A kind of preparation method of the electroforming solution being used to prepare the hard gold of 3D and the hard gold of 3D |
| CN110129843A (en) * | 2019-06-05 | 2019-08-16 | 深圳市华乐珠宝首饰有限公司 | A kind of hard golden mirror photoelectricity casting process of no cyanogen |
| CN110230079A (en) * | 2015-01-16 | 2019-09-13 | 哈钦森技术股份有限公司 | Golden electroplating solution and method |
| CN110226820A (en) * | 2019-07-03 | 2019-09-13 | 深圳国韵黄金文化有限公司 | A kind of machine carves the preparation process of hard gold |
| CN110607539A (en) * | 2019-09-29 | 2019-12-24 | 深圳市金久缘珠宝有限公司 | Processing technology of gold jewelry |
| CN113699563A (en) * | 2021-08-24 | 2021-11-26 | 深圳市联合蓝海黄金材料科技股份有限公司 | Production method of hard gold round ball |
| CN114016096A (en) * | 2021-10-22 | 2022-02-08 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electroplated 18K rose gold liquid, preparation method and application thereof, and preparation method of 18K rose gold coating |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112410773B (en) * | 2020-11-02 | 2022-11-25 | 山东恒银珠宝有限公司 | Gold antique finishing method and antique gold |
| CN113046790A (en) * | 2021-02-04 | 2021-06-29 | 德诚珠宝集团有限公司 | Electroforming liquid for gold cyanide-free electroforming process and electroforming process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109517A (en) * | 1995-02-24 | 1995-10-04 | 清华大学 | Electromoulding liquid for cyanogen-free electromoulding K gold product |
| CN1494606A (en) * | 2001-02-28 | 2004-05-05 | ƽ | Bath for galvanic deposition of gold and gold alloys, and use thereof |
| JP2008115449A (en) * | 2006-11-07 | 2008-05-22 | Ne Chemcat Corp | Non-cyanogen-based gold electroplating bath for forming gold bump or gold wiring |
| CN101560676A (en) * | 2009-04-24 | 2009-10-21 | 武汉金凰珠宝股份有限公司 | Method for electroforming hard gold product |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86106568A (en) * | 1986-10-08 | 1987-04-22 | 孙启旺 | The method of forming of housing artwork |
| CN102845889B (en) * | 2012-10-18 | 2014-07-30 | 范社强 | Craft flower with gold and silver layers and preparation method of craft flower |
| CN102862440B (en) * | 2012-10-18 | 2015-06-03 | 范社强 | Silver or gold and silver peony prepared by fresh flower and preparation process thereof |
| CN103938231B (en) * | 2014-03-04 | 2015-04-01 | 深圳市联合蓝海科技开发有限公司 | Gold electroplating method and hard gold preparation method |
| CN103938232B (en) * | 2014-03-04 | 2015-04-01 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and application thereof |
| CN104047037B (en) * | 2014-06-16 | 2015-06-03 | 深圳市联合蓝海科技开发有限公司 | Hardener |
-
2014
- 2014-03-04 CN CN201410077259.6A patent/CN103938231B/en active Active
-
2015
- 2015-01-23 HK HK15100759.4A patent/HK1200505A1/en unknown
- 2015-03-03 WO PCT/CN2015/073546 patent/WO2015131795A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109517A (en) * | 1995-02-24 | 1995-10-04 | 清华大学 | Electromoulding liquid for cyanogen-free electromoulding K gold product |
| CN1494606A (en) * | 2001-02-28 | 2004-05-05 | ƽ | Bath for galvanic deposition of gold and gold alloys, and use thereof |
| JP2008115449A (en) * | 2006-11-07 | 2008-05-22 | Ne Chemcat Corp | Non-cyanogen-based gold electroplating bath for forming gold bump or gold wiring |
| CN101560676A (en) * | 2009-04-24 | 2009-10-21 | 武汉金凰珠宝股份有限公司 | Method for electroforming hard gold product |
Non-Patent Citations (1)
| Title |
|---|
| 张允诚等: "《电镀手册第2版》", 31 July 1997, 国防工业出版社 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015131795A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海科技开发有限公司 | Gold electroplating method and hard gold preparation method |
| WO2015131796A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and use therefor |
| CN110230079B (en) * | 2015-01-16 | 2022-03-11 | 哈钦森技术股份有限公司 | Gold plating solution and method |
| CN110230079A (en) * | 2015-01-16 | 2019-09-13 | 哈钦森技术股份有限公司 | Golden electroplating solution and method |
| CN104862752B (en) * | 2015-06-12 | 2016-02-17 | 深圳市联合蓝海投资控股集团有限公司 | The preparation method of modification cyanogen-less gold liquid and application and hard gold |
| WO2016197662A1 (en) * | 2015-06-12 | 2016-12-15 | 深圳市联合蓝海投资控股集团有限公司 | Modified cyanide-free gold plating solution and use thereof as well as preparation method for hard gold |
| CN104862752A (en) * | 2015-06-12 | 2015-08-26 | 深圳市联合蓝海投资有限公司 | Modified cyanide-free gold plating solution and application thereof as well as preparation method of hard gold |
| CN107684202A (en) * | 2016-08-03 | 2018-02-13 | 周生生珠宝金行有限公司 | Pure gold and its manufacture method |
| CN107028305A (en) * | 2016-11-30 | 2017-08-11 | 陈哲 | A kind of processing method of hollow gold ornaments |
| CN106757202A (en) * | 2016-12-30 | 2017-05-31 | 深圳市联合蓝海科技开发有限公司 | A kind of gold product and preparation method thereof |
| CN106637307A (en) * | 2017-01-04 | 2017-05-10 | 中国地质大学（武汉） | Additive for cyanide-free electroforming technology of gold |
| CN107059070A (en) * | 2017-04-21 | 2017-08-18 | 深圳市金玉福珠宝首饰有限公司 | A kind of electroforming process of karat gold ornaments |
| CN106929889A (en) * | 2017-05-09 | 2017-07-07 | 句容市博远电子有限公司 | A kind of cyanideless electro-plating liquid and preparation method thereof |
| CN107419129A (en) * | 2017-06-26 | 2017-12-01 | 南京市产品质量监督检验院 | A kind of hard gold and preparation method thereof |
| CN107419129B (en) * | 2017-06-26 | 2019-07-23 | 南京市产品质量监督检验院 | A kind of hard gold and preparation method thereof |
| CN109628962A (en) * | 2019-01-21 | 2019-04-16 | 南京市产品质量监督检验院 | A kind of preparation method of no cyanogen 18k gold ornaments |
| CN109913912A (en) * | 2019-04-02 | 2019-06-21 | 深圳市昊扬电铸技术开发有限公司 | A kind of electroforming solution for gold without cyanogen electroforming process |
| CN110129843A (en) * | 2019-06-05 | 2019-08-16 | 深圳市华乐珠宝首饰有限公司 | A kind of hard golden mirror photoelectricity casting process of no cyanogen |
| CN110106537A (en) * | 2019-06-26 | 2019-08-09 | 浙江金卓首饰有限公司 | A kind of preparation method of the electroforming solution being used to prepare the hard gold of 3D and the hard gold of 3D |
| CN110226820A (en) * | 2019-07-03 | 2019-09-13 | 深圳国韵黄金文化有限公司 | A kind of machine carves the preparation process of hard gold |
| CN110607539A (en) * | 2019-09-29 | 2019-12-24 | 深圳市金久缘珠宝有限公司 | Processing technology of gold jewelry |
| CN113699563A (en) * | 2021-08-24 | 2021-11-26 | 深圳市联合蓝海黄金材料科技股份有限公司 | Production method of hard gold round ball |
| CN113699563B (en) * | 2021-08-24 | 2023-01-03 | 深圳市联合蓝海黄金材料科技股份有限公司 | Production method of hard gold round ball |
| CN114016096A (en) * | 2021-10-22 | 2022-02-08 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electroplated 18K rose gold liquid, preparation method and application thereof, and preparation method of 18K rose gold coating |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015131795A1 (en) | 2015-09-11 |
| CN103938231B (en) | 2015-04-01 |
| HK1200505A1 (en) | 2015-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103938231B (en) | Gold electroplating method and hard gold preparation method | |
| CN103938232B (en) | Cyanide-free electroplating solution and application thereof | |
| CN104047037B (en) | Hardener | |
| CN104862752B (en) | The preparation method of modification cyanogen-less gold liquid and application and hard gold | |
| CA2883815A1 (en) | Plating solution and plating process for multi-layer cyanide-free plating copper-tin alloy coating, and coins made by the process | |
| CN103668369A (en) | Electric plating method capable of improving anti-corrosion performance of metal element | |
| CN104544801B (en) | A kind of preparation method of gold ornament | |
| CN102021613A (en) | Electrolyte composition | |
| CN102677116A (en) | Method for dipulse preplating non-cyanide alkaline copper on ferro matrix | |
| CN110284166A (en) | A kind of electro-deposition method preparing foam nickel-molybdenum alloy | |
| CN110885996A (en) | Hardware surface treatment process and hardware | |
| TW201428143A (en) | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids | |
| EP2877615B1 (en) | Electrodeposition process of nickel-cobalt coatings with dendritic structure | |
| CN103911638A (en) | Cobalt nickel phosphorus-silicon carbide electroplating solution and electroplating method | |
| CN109321956A (en) | A kind of method of Ni―Ti anode coating production and coating reparation | |
| CN105132980B (en) | A kind of lead silver alloy anode surface recombination ceramic film film build method | |
| CN204174298U (en) | A kind of supplementary anode for Acidic zinc-nickel alloy plating | |
| US20190368065A1 (en) | Coatings containing nickel-tungsten plating layers and methods for the production thereof | |
| CN105154931A (en) | Platinum electroplating solution comprising dihydrogen dinitrosulfatoplatinate and electroplating method adopting platinum electroplating solution | |
| CN104372389A (en) | Cobalt-tungsten-nickel alloy electroplating solution and preparation method thereof | |
| CN105506689B (en) | Battery steel shell made from a kind of battery steel shell duplex nickel plating technique and the technique | |
| KR20110041424A (en) | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals | |
| CN1978711A (en) | Method for preparing alloy coating | |
| JP6543526B2 (en) | Electroplating bath for forming porous cage-like copper plating film and method for forming porous cage-like copper plating film using the same | |
| RU2133305C1 (en) | Electrolyte for brilliant nickel plating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1200505 Country of ref document: HK |
|
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1200505 Country of ref document: HK |
|
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 518020 floor 7, warehouse 7, Sungang, No. 1007, Bao'an North Road, Sunxi community, Sungang street, Luohu District, Shenzhen, Guangdong Patentee after: Shenzhen United Blue Ocean Applied Materials Technology Co.,Ltd. Patentee after: SHENZHEN UNITED BLUEOCEAN NEW TECHNOLOGY Co.,Ltd. Address before: 518019 area a, 7 / F, building 3, petrochemical industrial zone, North Cuizhu Road, Luohu District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN UNITED BLUEOCEAN TECHNOLOGY DEVELOPMENT Co.,Ltd. Patentee before: SHENZHEN UNITED BLUEOCEAN NEW TECHNOLOGY Co.,Ltd. |