CN111850619A - Preparation method and application of hollow gold product - Google Patents
Preparation method and application of hollow gold product Download PDFInfo
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- CN111850619A CN111850619A CN202010729014.2A CN202010729014A CN111850619A CN 111850619 A CN111850619 A CN 111850619A CN 202010729014 A CN202010729014 A CN 202010729014A CN 111850619 A CN111850619 A CN 111850619A
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
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Abstract
The invention relates to the field of electroforming, in particular to a preparation method and application of a hollow gold product. The method comprises the steps of copper plating on a mold core, electroforming of K gold, mold core removal and post-treatment to obtain the hollow gold product. The applicant provides a method for preparing hollow gold products, which can prepare hollow gold products with various shapes and light weight, can be widely applied to various fields such as ornaments, electronics, clocks and the like, can improve the hardness and corrosion resistance of the hollow gold products by reasonably designing parameters of electroforming solution and electroforming K gold, can obtain products with smooth and bright surfaces, can enlarge the range of gold content of the gold products, can obtain hollow gold products with 9-22K, and can improve the processing stability.
Description
Technical Field
The invention relates to the field of electroforming, in particular to a preparation method and application of a hollow gold product.
Background
In recent years, due to the rapid development of internet technology, aspects of social economy and people's life have been completely embedded in platforms based on the internet. The commodities in all walks of life and most regions on the global village can be displayed in front of the people through the Internet, and the substances are rich and convenient in the current society. The daily needs of modern people are more and more, and in this background, the price of single consumer products must be reduced to a certain degree to be possibly selected by the public. The gold ornaments are particularly outstanding in the aspect of contradiction because of the precious metal materials. In addition, the expanded live broadcast cargo carrying economy is increased day by day, and when a consumer selects commodities on a live broadcast platform, price intervals have decisive influence on the commodities. In order to enable the gold jewelry to still meet the selection and the demand of consumers under the modern internet economy, the production of three-dimensional and light hollow gold products is the current development direction.
In the conventional process for preparing the hollow gold product, because the hollow gold product needs to be subjected to treatment such as demolding, higher requirements are put on the stability in the electroforming process of the hollow gold product, the hardness, the corrosion resistance and the like of the hollow gold product, and the appearance of the product can be influenced due to subsequent treatment such as decoppering.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a hollow gold product, which comprises the steps of core copper plating, gold electroforming, core removal and post treatment, and the hollow gold product is obtained.
In the preferable technical scheme of the invention, in the copper plating of the mold core, the mold core is subjected to electrolysis and water washing, and then sequentially subjected to alkaline copper plating and bright copper electroforming to obtain the pre-plated mold core.
In the electroforming of the K gold, a pre-plated mold core is put into electroforming solution for electroforming to obtain a prefabricated product.
As a preferable technical scheme, the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 50-130 g/L of main salt, 15-40 g/L of main complexing agent and the balance of deionized water, wherein the main salt comprises gold salt.
As a preferred embodiment of the present invention, the main salt further includes a copper salt.
As a preferable technical scheme, the current density of the electroformed K gold is 0.3-0.45 ASD, and the temperature is 60-70 ℃.
In a preferred technical scheme of the invention, in the demolding core, 2 convection holes are drilled in the prefabricated product, and the prefabricated product is heated until the mold core is melted and flows out of the convection holes to obtain a crude product.
As a preferable technical scheme, the post-treatment sequentially comprises copper removal and heat treatment, wherein in the copper removal, the crude product is placed in an acid solution at the temperature of 70-85 ℃ for 1-3 hours and then washed with water.
As a preferable technical scheme, the temperature of the heat treatment is 700-800 ℃.
The invention provides an application of the preparation method of the hollow gold product, which is used for preparing ornaments, electronics and watches.
Compared with the prior art, the invention has the following beneficial effects: the applicant provides a method for preparing hollow gold products, which can prepare hollow gold products with various shapes and light weight, can be widely applied to various fields such as ornaments, electronics, clocks and the like, can improve the hardness and corrosion resistance of the hollow gold products by reasonably designing parameters of electroforming solution and electroforming K gold, can obtain products with smooth and bright surfaces, can enlarge the range of gold content of the gold products, can obtain hollow gold products with 9-22K, and can improve the processing stability.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a preparation method of a hollow gold product, which comprises the steps of copper plating on a mold core, electroforming of K gold, mold core removal and post-treatment to obtain the hollow gold product.
Copper plating on mould core
The material of the mold core used in the invention is low-melting point alloy, and the mold core can be prepared by methods such as centrifugal casting and the like, and is not particularly limited. The melting point temperature of the low-melting-point alloy used in the invention is generally 80-200 ℃, the melt is eutectic low-melting-point alloy which is formed by taking elements such as bismuth, cadmium, tin, lead, dysprosium and indium in a certain proportion as main components, and the invention does not specifically limit the material of the mold core and is a well-known mold core material in the field.
In one embodiment, in the copper plating of the mold core, the mold core is subjected to electrolysis and water washing, and then subjected to alkaline copper plating and bright copper electroforming in sequence to obtain the pre-plated mold core.
Before electroforming, such as nickel plating, chromium plating, silver plating, gold plating and the like, copper plating is needed for priming, repairing worn parts, preventing local carburization and improving conductivity. The alkaline copper plating can be cyanide copper plating or cyanide-free alkaline copper plating, is not particularly limited, is a well-known alkaline copper plating method in the field, and as an example, in the alkaline copper plating, a mold core is placed in cyanide copper electroforming solution and is electroformed at 45-60 ℃ and the current density of 0.5-4 ASD; the copper cyanide electroforming solution is well known in the art, is not particularly limited, and is prepared by taking the following components in mass concentration as raw materials: 50-70 g/L cuprous cyanide, 70-100 g/L sodium cyanide, 1-3 g/L sodium hydroxide, 20-30 g/L potassium sodium tartrate and the balance of deionized water.
Bright copper means copper having a copper content of 99.95% or more, which is obtained by electrocasting from an electrocasting solution and is reddish and bright. The applicant obtains high filling degree, low internal stress and ductility and good leveling property by sequentially performing alkaline copper plating and bright copper electroforming, and can avoid mechanical grinding and polishing processes. The method for electroforming the bright copper is not particularly limited, and as an example, in the bright copper electroforming, a mold core plated with copper in an alkaline manner is placed in bright copper electroforming liquid, and the electroplating is carried out at the temperature of 10-30 ℃ and the current density of 0.5-4 ASD, so that a pre-plated mold core is obtained; the bright copper electroforming solution is not particularly limited, and is a bright copper electroforming solution well known in the field, and the bright copper electroforming solution is prepared by taking the following components in mass concentration as an example: 200-220 g/L copper sulfate, 60-70 g/L sulfuric acid, 0.0005-0.003 g/L thiazolidinone, 0.02-0.08 g/L hydrochloric acid, 0.05-0.2 g/L sodium dodecyl sulfate and the balance of water.
Electroforming of gold
Gold K (or gold kaiki) is an alloy of gold and other metals. The term "K" of K gold is written in the foreign language "Karat", and the complete expression is Karat gold (i.e. K gold), and "AU" or "G" is a symbol used internationally to indicate gold purity (i.e. gold content). The K gold ornaments are characterized by less gold consumption, low cost, capability of being prepared into various colors, improved hardness and difficult deformation and abrasion. The K gold is divided into 24K gold, 22K gold, 18K gold, 9K gold and the like according to the content of the gold. The metering method of the K gold comprises the following steps: pure gold is 24K (i.e. 100% gold content) and the gold content of 1K is about 4.166%. The gold K system is the international popular gold metering standard, expressed as K value and converted from pure gold 24K, and the relation of K number and gold content is that Au wt% isK/24 multiplied by 100%, and the gold content per K is 4.166% as specified by national standard GB 11887-89.
In one embodiment, in the electroforming of the K gold, the pre-plated core is put into the electroforming solution for electroforming to obtain the preform.
Preferably, the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 50-130 g/L of main salt, 15-40 g/L of main complexing agent and the balance of deionized water, wherein the main salt comprises gold salt; further, the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 50-130 g/L of main salt, 15-40 g/L of main complexing agent, 10-40 g/L, pH g/5-20 g/L of auxiliary complexing agent and the balance of deionized water, wherein the main salt comprises gold salt.
In one embodiment, the primary salts of the present invention further comprise copper salts; further, the main salt comprises a gold salt and a copper salt, and the weight ratio is (0.07-0.11): 1.
preferably, the gold salt of the present invention is selected from one of potassium aurous cyanide, sodium aurous cyanide and ammonium aurous cyanide.
More preferably, the copper salt is selected from one of copper sulfate, cupric halide, copper sulfamate, copper methane sulfonate, cupric acetate, basic cupric carbonate and cuprous cyanide.
The gold plating layer has wide application in jewelry, clocks and electronic components, can be used as a gold coating layer of a hollow gold product, but a single gold plating layer has the problems of wear resistance and the like.
The applicant finds that the concentration of the main salt and the proportion of the copper salt and the gold salt in the main salt have great influence on the working stability of the electroforming solution and the appearance of a plating layer, and when the proportion of the copper salt and the gold salt is too large or too small, the precipitation of relatively less metal can be correspondingly and obviously inhibited, although a plating layer with larger or smaller gold content can be obtained, the surface of the gold-coated layer is rough, and the brightness is poor, so that the applicant selects a proper main complexing agent through a large number of experiments to obtain the gold-coated layer with wide-range gold content and simultaneously improve the brightness and the smoothness of the gold-coated layer.
Further preferably, the main complex of the present invention is selected from one or more of cyanide, phosphate, sulfonate, and sulfate.
Examples of cyanides include, but are not limited to, sodium cyanide, ammonium cyanide, potassium cyanide.
As examples of phosphates, including, but not limited to, hydroxyethylidene diphosphate, ethylenediamine tetramethylene phosphate, aminotrimethylene phosphate, methylene diphosphate; the phosphate can be one of potassium salt, sodium salt and ammonium salt of phosphoric acid; in a preferred embodiment, the phosphate according to the invention comprises hydroxyethylidene diphosphate and ethylenediaminetetramethylenephosphate in a weight ratio of 1: (1-2).
Examples of the sulfonate include, but are not limited to, alkylsulfonates, and there may be exemplified methylenedisulfonates such as sodium methylenedisulfonate and potassium methylenedisulfonate, 1, 4-butanedisulfonates such as sodium 1, 4-butanedisulfonate, potassium 1, 4-butanedisulfonate, methanesulfonate, 2-hydroxypropylsulfonate; alkyl benzene sulfonate, for example, sodium dodecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, sodium octadecylbenzene sulfonate; an alkenyl sulfonate; an alkynyl sulfonate; the sulfonate can be one of potassium salt, sodium salt and ammonium salt of sulfonic acid; in a preferred embodiment, the sulfonate of the present invention comprises an alkyl sulfonate and an alkyl benzene sulfonate in a weight ratio of 1: (0.1 to 0.5); further, the alkyl sulfonate of the present invention is methylene disulfonate and/or 1, 4-butanedisulfonate.
Examples of sulfates include, but are not limited to, magnesium sulfate, sodium sulfate, potassium sulfate, ammonium sulfate.
Still further preferably, the primary complex of the present invention comprises cyanide.
Still further preferably, the host complex of the present invention further comprises a phosphate; further, the weight ratio of the cyanide to the phosphate is 1: (0.1-0.2).
Still further preferably, the host complex of the present invention further comprises a sulfonate; further, the weight ratio of the cyanide to the sulfonate is 1: (0.05-0.1).
In one embodiment, the co-complexing agent of the present invention is selected from one or more of alcohol co-complexing agents, fatty acid co-complexing agents, and nitrogen-containing co-complexing agents.
Examples of alcohol co-complexing agents include, but are not limited to, glycerol, polyethylene glycol, sorbitol, gluconate, sucrose, xylitol, mannitol.
Examples of co-complexing agents for fatty acids include, but are not limited to, citric acid, malic acid, tartaric acid.
Examples of nitrogen-containing co-complexing agents include, but are not limited to, sodium ethylenediaminetetraacetate, ethylenediamine, pyridine-2-carboxylic acid, triethanolamine, iminodiacetic acid; in a preferred embodiment, the nitrogen-containing auxiliary agent comprises triethanolamine and iminodiacetic acid in a weight ratio of (1-6): (1-6).
Preferably, the co-complexing agent of the present invention is a nitrogen-containing co-complexing agent.
The pH buffer is not particularly limited in the present invention, and examples thereof include ammonium chloride, ammonium sulfate, boric acid, acetic acid, propionic acid, oxalic acid, succinic acid, lactic acid, glycolic acid, tartaric acid, boric acid, sodium acetate, sodium tetraborate, sodium oxalate, sodium citrate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate.
In one embodiment, the raw materials for preparing the electroforming solution of the invention further comprise a hardening agent.
In one embodiment, the hardening agent of the present invention is one selected from halogen salts, sulfates, sulfonates of thallium, tellurium, selenium, zinc; further, the mass concentration of the hardening agent is 0.1-4 g/L.
In one embodiment, the raw materials for preparing the electroforming solution of the invention further comprise an auxiliary agent.
The present invention is not particularly limited to the additives, and may be those known in the art, and may include, for example, stress-relieving agents, accelerators, stabilizers, brighteners.
As examples of stress relieving agents, there may be mentioned, but not limited to, at least one of sodium o-benzoylsulfonimide, bisbenzenesulfonimide, sodium propenyl sulfonate, sodium propynyl sulfonate; the nickel ion stabilizer is selected from: disodium ethylene diamine tetraacetate, tetrasodium ethylene diamine tetraacetate, sodium potassium tartrate and sodium alginate; in one embodiment, the stress relieving agent has a mass concentration of 0.01 to 0.1 g/L.
Examples of accelerators include, but are not limited to, hydrofluoric acid, sodium fluoride, potassium fluoride, ammonium fluoride; in one embodiment, the mass concentration of the accelerator is 2-12 g/L.
As examples of stabilizers, including, but not limited to, thiourea; a thiourea derivative; a thiocyanate salt; acetic acid compounds of lead, antimony, bismuth; nitric acid compounds of lead, antimony, bismuth; water-soluble organic matter containing-SH functional group; in one embodiment, the mass concentration of the stabilizer is 0.01 to 1 g/L.
Examples of brighteners include, but are not limited to, potassium sulfamate, benzylidene acetone, saccharin, 2, 3-bis (2-pyridyl) pyrazine, 3- (3-pyridyl) -acrylic acid, 3- (4-imidazolyl) -acrylic acid, 3-pyridyl carboxymethanesulfonic acid, 2- (pyridyl) -4-ethanesulfonic acid, 1- (3-sulfopropyl) -pyridinebetaine, 1- (3-sulfopropyl) -isoquinolinebetaine, tetrahydrothiazolinone; in one embodiment, the mass concentration of the brightener is 0.01-2 g/L.
In a preferred embodiment, the electroformed K gold has a current density of 0.3 to 0.45ASD, a temperature of 60 to 70 ℃ and a time of 10 to 15 hours.
In a more preferred embodiment, in the electroformed K gold, the rotation speed is 50 to 200 rpm; furthermore, the rotation speed of electroforming is 50-100 rpm.
The applicant adds phosphate and cyanide of multi-coordination sites to act together to form a multi-layer complex structure with copper salt and gold salt, and selects proper phosphate to adjust the binding force with the copper salt and the gold salt, so that a hollow gold product with high gold content can be obtained under the conditions of lower temperature, current density and the like; the applicant can realize a hollow gold product with high copper content by regulating and controlling a larger rotating speed condition, and reduce the generation of hydrogen and byproducts, and the applicant finds that when sulfonate is added, the complex structure at a higher rotating speed can be stabilized by inserting the complex structure and adsorbing the complex structure on the surface, the phenomena of precipitation caused by the action of impurities and main salt and the like are reduced, the continuous working stability of electroforming is improved, the crystallization compactness is promoted, the glossiness and the performances of wear resistance, hardness, corrosion resistance and the like of the product are improved, and the damage to the surface of the product in the subsequent demolding and copper removing processes is reduced.
Demoulding core
In one embodiment, the inventive release core is formed by drilling 2 convection holes in the preform, heating the preform until the core melts and flows out of the convection holes to form a crude product.
Preferably, in the demolding core, the preform is drilled with 2 convection holes, the core is melted by heating to 160-200 ℃ and flows out of the convection holes to obtain a crude product.
More preferably, the diameter of the convection hole is 0.5-1 mm.
Post-treatment
In one embodiment, the post-treatment of the present invention comprises copper removal and heat treatment in that order.
Preferably, in the copper removal, the crude product is placed in an acid solution at the temperature of 70-85 ℃ for 1-3 hours and then washed with water.
More preferably, the acidic solution of the present invention comprises an acid and water in a weight ratio of 1: (0.5-2).
The acid is not specifically limited in the present invention, and is well known in the art, and there may be mentioned organic acids including, but not limited to, oxalic acid, succinic acid, malic acid, salicylic acid, sorbic acid, anhydrous citric acid; inorganic acids, including, but not limited to, sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid. In one embodiment, the acid is nitric acid.
Further preferably, the temperature of the heat treatment is 700-800 ℃.
The invention provides an application of the preparation method of the hollow gold product, which is used for preparing ornaments, electronics and watches.
Examples
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.45ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 70g/L of main salt, 25g/L of main complexing agent, 20g/L, pH g of auxiliary complexing agent, 10g/L of buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.07: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 2: 5, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 2
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.4ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 95g/L of main salt, 30g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.08: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 4: 3, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 3
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 12h at the current density of 0.4ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 95g/L of main salt, 30g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.08: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 4: 3, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 4
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 15h at the current density of 0.4ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 95g/L of main salt, 30g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.08: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 4: 3, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 5
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 15h at the current density of 0.38ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 95g/L of main salt, 30g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.08: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 4: 3, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 6
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.35ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 95g/L of main salt, 30g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.08: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 4: 3, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 7
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.3ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 110g/L of main salt, 35g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.11: 1, the main complex is cyanide, the cyanide is potassium cyanide, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 3: 4, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 8
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.45ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 70g/L of main salt, 25g/L of main complexing agent, 20g/L, pH g of auxiliary complexing agent, 10g/L of buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.07: 1, the main complex is cyanide and phosphonate, and the weight ratio of the cyanide to the phosphonate is 1: 0.1, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 2, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 2: 5, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 9
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.3ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 110g/L of main salt, 35g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.11: 1, the main complex is cyanide and phosphonate, and the weight ratio of the cyanide to the phosphonate is 1: 0.2, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 1, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 3: 4, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 10
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.45ASD, the temperature of 65 ℃ and the rotating speed of 100rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 70g/L of main salt, 25g/L of main complexing agent, 20g/L, pH g of auxiliary complexing agent, 10g/L of buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.07: 1, the main complex is cyanide and phosphonate, and the weight ratio of the cyanide to the phosphonate is 1: 0.1, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 2, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 2: 5, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 11
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.45ASD, the temperature of 65 ℃ and the rotating speed of 100rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 70g/L of main salt, 25g/L of main complexing agent, 20g/L, pH g of auxiliary complexing agent, 10g/L of buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.07: 1, the main complex is cyanide, phosphonate and sulfonate, and the weight ratio of the main complex to the sulfonate is 1: 0.1: 0.1, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 2, the sulfonate is potassium 1, 4-butanedisulfonate and sodium hexadecylbenzene sulfonate, and the weight ratio is 1: 0.2; the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 2: 5, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 12
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.3ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 110g/L of main salt, 35g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.11: 1, the main complex is cyanide, phosphonate and sulfonate, and the weight ratio of the main complex to the sulfonate is 1: 0.2: 0.05, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 1, the sulfonate is potassium 1, 4-butanedisulfonate and sodium hexadecylbenzene sulfonate, and the weight ratio is 1: 0.5; the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 3: 4, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 13
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.3ASD, the temperature of 65 ℃ and the rotating speed of 50rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 110g/L of main salt, 35g/L of main complexing agent, 10g/L of auxiliary complexing agent 35g/L, pH buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.11: 1, the main complex is cyanide and phosphonate, and the weight ratio of the cyanide to the phosphonate is 1: 0.2, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium aminotrimethylene phosphonate in a weight ratio of 1: 1, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 3: 4, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 14
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.45ASD, the temperature of 65 ℃ and the rotating speed of 200rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 70g/L of main salt, 25g/L of main complexing agent, 20g/L, pH g of auxiliary complexing agent, 10g/L of buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.07: 1, the main complex is cyanide and phosphonate, and the weight ratio of the cyanide to the phosphonate is 1: 0.1, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 2, the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 2: 5, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Example 15
The embodiment provides a preparation method of a hollow gold product, which comprises the following steps:
copper plating on a mold core: carrying out electrolysis and water washing on the mold core, and then sequentially carrying out alkaline copper plating and bright copper electroforming to obtain a pre-plated mold core;
electroforming K gold: putting the mold core into electroforming solution, electroforming for 10h at the current density of 0.45ASD, the temperature of 65 ℃ and the rotating speed of 100rpm to obtain a prefabricated product;
demolding: drilling 2 upper and lower convection holes with the diameter of 0.8 mm on the prefabricated product, heating to 200 ℃ in an oven to melt the alloy and flow out of the convection holes to obtain a crude product;
and (3) post-treatment: and (2) placing the crude product in an acid solution at 80 ℃ for 2h, washing with water, and then carrying out heat treatment at 750 ℃ to obtain a hollow gold product, wherein the acid solution comprises nitric acid and water in a weight ratio of 1: 1;
the preparation raw materials of the electroforming solution comprise the following components in mass concentration: 70g/L of main salt, 25g/L of main complexing agent, 20g/L, pH g of auxiliary complexing agent, 10g/L of buffering agent, 1g/L of hardening agent and the balance of deionized water; the main salt comprises aurous potassium cyanide and cuprous cyanide, and the weight ratio is 0.07: 1, the main complex is cyanide, phosphonate and sulfonate, and the weight ratio of the main complex to the sulfonate is 1: 0.1: 0.1, the cyanide is potassium cyanide, and the phosphonate is potassium hydroxyethylidene diphosphonate and potassium ethylene diamine tetra methylene phosphonate, wherein the weight ratio of the potassium cyanide to the potassium ethylene diamine tetra methylene phosphonate is 1: 2, the sulfonate is sodium methanesulfonate and sodium hexadecylbenzene sulfonate, and the weight ratio is 1: 0.2; the co-complexing agent is triethanolamine and iminodiacetic acid, and the weight ratio is 2: 5, the pH buffering agent is dipotassium hydrogen phosphate, and the hardening agent is zinc sulfate.
Evaluation of Performance
1. The content of gold: the gold-clad layer of the hollow gold product prepared by the preparation method of the hollow gold product provided in the example was tested for gold and copper contents according to GB11887-2012, and the results are shown in table 1.
2. Brightness: the surface brightness of the hollow gold product prepared by the preparation method of the hollow gold product provided in the embodiment is observed and evaluated, wherein the level 1 is a small amount of scorch, the level 2 is complete fogging, the level 3 is most fogging, the level 4 is partial brightening, the level 5 is most brightening, the level 6 is full brightening and slightly uneven, and the level 7 is full brightening and flat results are shown in table 1.
3. Stability: according to the preparation method of the hollow gold product provided by the embodiment, continuous electroforming is carried out until the electroforming solution generates precipitation, and the time of the precipitation is recorded to evaluate the stability, wherein the 5-grade time is 2400min or more, the 4-grade time is 2000min or more and less than 2400min, the 3-grade time is 1500min or more and less than 2000min, the 2-grade time is 1000min or more and 1500min or less, the 1-grade time is 1000min or less, the larger the precipitation time is, the better the stability is, and the result is shown in table 1.
Table 1 performance characterization test
4. And (3) performance testing: the hollow gold product prepared by the preparation method of the hollow gold product provided in the embodiment is subjected to thickness and vickers hardness tests, and artificial sweat tests:
the artificial sweat testing method comprises the following steps: suspending the hollow gold product in an artificial sweat solution, standing at 40 +/-2 ℃ for 72h, testing the corrosion degree of the surface of the product, and if the corrosion area is less than 1.5mm, marking the product as qualified, and if the corrosion area exceeds 1.5mm, marking the product as failed; the formula of the artificial sweat solution comprises the following components: 20g/L of sodium chloride, 17.5g/L of ammonia chloride, 5g/L of urea, 2.5g/L of acetic acid and 15g/L of lactic acid, and then adding sodium hydroxide until the pH value of the solution reaches 4.7;
the results are shown in Table 2, wherein the results of the artificial sweat tests performed in examples 1-11 are acceptable.
Table 2 characterization test of properties
The test results in tables 1-2 show that the preparation method of the hollow gold product provided by the invention can be used for the hollow gold product with smooth surface and good gloss, and has good performances such as hardness and corrosion resistance, and the products with different gold contents can be obtained by the method provided by the invention, and can be used in the fields of various ornaments, electronics, clocks and the like, so that the application range is expanded.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The preparation method of the hollow gold product is characterized by comprising the steps of copper plating on a mold core, electroforming of K gold, mold core removal and post-treatment to obtain the hollow gold product.
2. The method for preparing a hollow gold product according to claim 1, wherein in the step of plating the core with copper, the core is subjected to electrolysis and water washing, and then subjected to alkaline copper plating and bright copper electroforming in sequence to obtain the pre-plated core.
3. The method according to claim 2, wherein the pre-plating core is electroformed in an electroforming solution to obtain a preform.
4. The method for producing a hollow gold article according to claim 3, wherein the raw material for producing the electroforming solution comprises the following components in mass concentration: 50-130 g/L of main salt, 15-40 g/L of main complexing agent and the balance of deionized water, wherein the main salt comprises gold salt.
5. The method of claim 4, wherein the main salt further comprises a copper salt.
6. The method for producing a hollow gold product according to claim 3, wherein the electroformed K gold has a current density of 0.3 to 0.45ASD and a temperature of 60 to 70 ℃.
7. The method of any one of claims 3 to 6, wherein the core-removing core is formed by drilling 2 convection holes in the preform, heating the preform until the core is melted and flows out of the convection holes to obtain a crude product.
8. The method for preparing a hollow gold product according to claim 7, wherein the post-treatment comprises copper removal and heat treatment in sequence, and in the copper removal, the crude product is washed with water after being placed in an acid solution at 70-85 ℃ for 1-3 h.
9. The method for producing a hollow gold article according to claim 8, wherein the heat treatment temperature is 700 to 800 ℃.
10. Use of the method according to any one of claims 1 to 9 for the production of a hollow gold article, for the production of an ornament, an electronic article, or a timepiece.
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| CN113026059A (en) * | 2021-03-02 | 2021-06-25 | 深圳市永达锐国际科技有限公司 | Electroforming process of 22K hard gold jewelry |
| CN114525556A (en) * | 2022-02-25 | 2022-05-24 | 王文荣 | Tungsten-containing alloy coated with gold casting layer and preparation method thereof |
| CN114686939A (en) * | 2022-03-28 | 2022-07-01 | 中国地质大学（武汉） | High-precision hard gold and production method thereof |
| CN114836794A (en) * | 2021-06-25 | 2022-08-02 | 深圳市铭轩珠宝首饰有限公司 | Gold-copper alloy electroforming process and application thereof |
| CN114875456A (en) * | 2021-06-25 | 2022-08-09 | 深圳市铭轩珠宝首饰有限公司 | Copper-gold composite gold-coating method and application thereof |
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2020
- 2020-07-27 CN CN202010729014.2A patent/CN111850619A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113026059A (en) * | 2021-03-02 | 2021-06-25 | 深圳市永达锐国际科技有限公司 | Electroforming process of 22K hard gold jewelry |
| CN114836794A (en) * | 2021-06-25 | 2022-08-02 | 深圳市铭轩珠宝首饰有限公司 | Gold-copper alloy electroforming process and application thereof |
| CN114875456A (en) * | 2021-06-25 | 2022-08-09 | 深圳市铭轩珠宝首饰有限公司 | Copper-gold composite gold-coating method and application thereof |
| CN114836794B (en) * | 2021-06-25 | 2024-01-30 | 深圳市铭轩珠宝首饰有限公司 | Gold-copper alloy electroforming process and application thereof |
| CN114875456B (en) * | 2021-06-25 | 2024-03-08 | 深圳市铭轩珠宝首饰有限公司 | Copper-gold composite gold coating method and application thereof |
| CN114525556A (en) * | 2022-02-25 | 2022-05-24 | 王文荣 | Tungsten-containing alloy coated with gold casting layer and preparation method thereof |
| CN114686939A (en) * | 2022-03-28 | 2022-07-01 | 中国地质大学（武汉） | High-precision hard gold and production method thereof |
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