CN108914166A - A kind of electroforming manufacture craft of noble metal ebuche - Google Patents
A kind of electroforming manufacture craft of noble metal ebuche Download PDFInfo
- Publication number
- CN108914166A CN108914166A CN201810694580.7A CN201810694580A CN108914166A CN 108914166 A CN108914166 A CN 108914166A CN 201810694580 A CN201810694580 A CN 201810694580A CN 108914166 A CN108914166 A CN 108914166A
- Authority
- CN
- China
- Prior art keywords
- ebuche
- electroforming
- base
- gold
- components
- 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.)
- Pending
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
- C25D1/00—Electroforming
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Adornments (AREA)
Abstract
The present invention relates to a kind of electroforming manufacture crafts of gold ebuche, include the following steps：S1, using can be pressed into the metal alloy of hydrochloric acid or nitric acid or sulfuric acid chemically reactive with base in the identical grain pattern of upper and lower surface and symmetrical ebuche and carry out finishing processing to it；S2, along the symmetrical shaft position that base face symmetrical above and below is cut open in the ebuche uniformly being smeared a circle insulating oil；S3, it will finish and coat base in the ebuche of insulating oil and hang on the electroforming suspender in electroforming cylinder, electroformed deposit is carried out to base in components and forms layer of precious metal；S4, the ebuche for smearing insulating oil is successively immersed in nitric acid solution, removes base in components made of metal or metal alloy in sulfuric acid solution；S5, it polished the inner membrance and outer membrane of ebuche after the completion of electroforming, polished and press polish processing；S6, the ebuche handled well is cleaned up, can be prepared by gold ebuche.
Description
Technical field
The present invention relates to clock and watch technical field and the field of metal processing, and in particular to a kind of electricity of noble metal ebuche
Cast manufacture craft.
Background technique
With the continuous improvement of living standard and appreciation of arts level, wrist-watch have become it is a kind of it is noble with elegant, tradition with
Modern, the classical commodity with fashion, people have biggish promotion for wrist-watch decoration demand and have gradually been more than use demand,
The value of wrist-watch be not limited only to its use value and be more it whether can people bring fashion, appreciation and pleasure etc.
It enjoys, contains higher technological value, technique value, artistic value and reserve value, therefore the market of noble metal wrist-watch is got over
Hair grows, and more and more consumers buys the noble metal wrist-watch manufactured by gold material.
The important spare part that wreath/literal/indicator etc. is all wrist-watch is criticized, various informative, pattern is complicated, has stronger dress
Decorations effect.It retrieves, is found in existing wrist-watch production field by the prior art, zero, wrist-watches, batch wreath/literal/indicator etc.
Part is usually made by copper or other common metals using burn into cutting or stamping forming mode, and often primary
Energy corrosion or one components of punching press, working efficiency is low, on the other hand, also without finding any patent document record about gold
The manufacture craft of ebuche；The components such as batch wreath/literal/indicator for gold wrist-watch similarly can be by gold material
Material is made, and the components such as batch wreath/literal/indicator made of gold need finer processing to prevent gold material
Waste, if usually excessive or punching press can not enough lead to decorative pattern because of punching press using the stamping forming mode of existing press machine
Fuzzy, rough surface, the abrasion for causing unnecessary gold material, and the precision of stamping technology is not high enough, can not carry out it is more fine,
Complicated grain pattern processing.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the present invention is intended to provide a kind of electroforming of noble metal ebuche makes work
Skill makes identical two noble metal ebuches using the technique electroforming one-pass molding, substantially reduce process flow and
Time simplifies technique, meanwhile, the mode of electroforming can increase the hardness and toughness of noble metal ebuche, prevent by
Techniques damage caused by molding noble metal ebuche such as it is stamped or cut out.
Technical scheme is as follows：
1, a kind of electroforming manufacture craft of gold ebuche, includes the following steps：
It is S1, identical with upper and lower surface using that can be pressed into the metal alloy of hydrochloric acid or nitric acid or sulfuric acid chemically reactive
Base and finishing processing is carried out to it in grain pattern and symmetrical ebuche；
S2, along the symmetrical shaft position that base face symmetrical above and below is cut open in the ebuche uniformly being smeared a circle
Insulating oil；
S3, it will finish and coat base in the ebuche of insulating oil and hang on the electroforming suspender in electroforming cylinder,
Electroformed deposit is carried out to base in components and forms layer of precious metal；
S4, the ebuche after electroforming is successively immersed in nitric acid solution, removes metal in sulfuric acid solution or metal closes
Base in components made of gold；
S5, it polished the inner membrance and outer membrane of ebuche after the completion of electroforming, polished and press polish processing；
S6, the ebuche handled well is cleaned up, can be prepared by gold ebuche.
Wherein, the metal alloy is kirsite.
Wherein, finishing processing includes accurate grinding, oil removing, activation and cleaning in the step S1.
Wherein, the oil removing carries out alkali cleaning using sodium hydroxide or at least one of sodium phosphate or triethanolamine；The work
Change process carries out under the conditions of reversed polarity, electrolytic etching is carried out to base surface in ebuche, mechanically metal alloy system
At ebuche in base surface oxidation film removal.
Wherein, the process of base specifically includes following steps in the alloy ebuche of pressed metal in the step S1：
(1) purebred nothing will can be obtained after primary treatment with the metal alloy of hydrochloric acid or nitric acid or sulfuric acid chemically reactive
The raw material of impurity, and as the bottom material of base in production ebuche；
(2) it is injected after melting bottom material in the stainless steel ebuche compacting tool set to match with its size, and
It is suppressed by the mode of punching press, obtains base in ebuche；
(3) surface is carried out to components after being removed from the molds base in stamping forming ebuche and removes thorn, and gong
Fall rough surface deformation and rough part.
Wherein, the mold includes cope plate and lower template；The cope plate is identical with lower template size, lines flower
Sample is identical and two templates are symmetrical set, and matches with base in the components.
Wherein, the step S3 electroforming process specifically includes following steps：
(1) 0.03~0.2mol/L complexing agent, the monovalence gold with the complexing agent equimolar concentration are added in electroforming cylinder
Salt, the citric acid of 5~8mL/L, potassium citrate, disodium EDTA and pure water are configured to electroforming solution；
(2) base in ebuche is hung on the electroforming suspender in electroforming cylinder, makes in components base in electroforming
Electroforming is carried out according to certain rotational speed with electroforming suspender in the process；The revolving speed of the electroforming suspender is 30~35r/
Min, the electroforming time is 15~18h, using the recurrent pulse current of commutation；Positive peak current density is 2~3A/dm2, reversed peak
It is worth 3~5A/dm of current density2；
(3) cylinder is played after the completion of electroforming, drying machine drying is used to the ebuche after the completion of electroforming, drying temperature is
100~120 DEG C, drying time is 20~30min.
Wherein, the process of base specifically includes following steps in components made of the step S4 removal metal alloy：
(1) ebuche after electroforming is immersed in nitric acid and water volume ratio is 1:In 0.8~1.2 nitric acid solution；
The nitric acid mass fraction is 68%；Nitric acid solution temperature is maintained at 400~500 DEG C, and soaking time is 2~3h, every 30~
40min adds the once nitric acid solution with concentration, takes out after base dissolution in components and is cleared up using vibration of ultrasonic wave；
(2) components are immersed in the volume ratio of sulfuric acid and water is 1:In 0.9~1.3 sulfuric acid solution；The sulfuric acid
Mass fraction is 98%；Sulfuric acid solution temperature is maintained at 700~900 DEG C, and soaking time is 20~40min；
(3) sulfuric acid is dried after placing room temperature, is rinsed well with clear water, obtain zero, noble metal wrist-watch of electroforming formation
Part.
Wherein, bruting process uses sand needle to carry out surface frosted processing in the step S5；Burnishing process uses agate pen
Press polish is carried out to edge.
Wherein, the ebuche includes wrist-watch batch wreath, literal and pointer.
The present invention has the advantages that：
1, for the present invention using the hard golden ebuche light weight of electroforming process production, wear-resisting, the dimensional accuracy of components is good,
Appearance surfaces can reach desired finish, and components can also reach required hardness and toughness, on the other hand, electroforming process energy
It is enough to complete more fine grain pattern processing.
2, base in the symmetrical components of disjunctor is made using kirsite in the present invention, and base needs symmetrical cutting in components
Position at smear insulating oil, make antimere can not carry out electroforming so as to during electroformed deposit layer gold once at
Two groups of components of type can prevent from cutting instead of the process for separating components after electroforming by cutting while simplifying technique
Abrasion and impact caused by molding gold ebuche.
3, the present invention in successively using nitric acid solution and sulfuric acid solution immersion electroforming made of ebuche, by multiple
Addition nitric acid can guarantee that the reaction for removing kirsite sufficiently carries out, and completely remove the kirsite as template, improve noble metal
The purity of ebuche is the boiling temperature of nitric acid with nitric acid dousing temperature, and when the temperature is excessively high, base is possible to out in kirsite
Now boiling vaporization, electroforming layer gold may also be heated softenings, lead to electric casting deformation or even scrap；Electroforming part is immersed in dense sulphur again
In acid, the concentrated sulfuric acid can form passivating film in precious metal surface and play the role of passivation protection to noble metal ebuche.
4, the present invention carries out electroforming to it using reverse pulse electric current in electroforming process, during electroforming first
It exports one group of direct impulse and introduces one group of reverse impulse later.The main function of reverse impulse is to keep cathode surface metal ion dense
Degree gos up rapidly, and the concentration polarization that can reduce cathodic region improves the current density upper limit.Reverse pulse current also acts one
The effect of electropolishing has leveling effect to coating burr, and can be reduced the field trash in coating.In short, commutating pulse skill
Art can improve layer gold quality, obtain finer and close, the bright layer gold low with porosity.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of base in wrist-watch of the present invention batch wreath；
Fig. 2 is the sectional view of the present invention crowd wreath compacting tool set；
Fig. 3 is the scanning electron microscope for the golden skin surface that the embodiment of the present invention 3 makes；
Fig. 4 is the scanning electron microscope (SEM) photograph of the golden skin surface of comparative example production.
1, symmetry axis；2, cope plate；3, lower template.
Specific embodiment
To the present invention, the present invention is further illustrated with preferred embodiment with reference to the accompanying drawing.
Embodiment 1
A kind of electroforming manufacture craft of noble metal ebuche, includes the following steps：
S1, using can be pressed into the kirsite of nitric acid chemically reactive with the identical grain pattern of upper and lower surface and symmetrical hand
Base in table components (being as shown in Figure 1 base in batch wreath in the present invention with a kind of grain pattern) simultaneously carries out it to include accurate grind
It cuts, oil removing, the finishing processing of four steps of cleaning and activation；Firstly, using accurate grinding mode in ebuche
Base is polished；Secondly, carrying out alkali cleaning to base in components using sodium hydroxide；Then, it is carried out under the conditions of reversed polarity, to zero
Base surface carries out electrolytic etching in component, and base in components is connect to the anode of power supply, the plated pen that the libation at an ancient wedding ceremony expires activating solution is connected to power supply
Cathode, plated pen is contacted with base surface in components and relative motion, and under electric field action, base surface is dissolved and analysed in components
Oxygen out mechanically activates the removal of the oxidation film of zinc alloy surface, mentions for coating with collective intermetallic good combination
For advantage；Finally, utilizing base in ultrasonic activation cleaning ebuche；
S2, along the position for the symmetry axis 1 that base face symmetrical above and below is cut open in the ebuche uniformly can be smeared
One circle insulating oil；Electroforming can not be carried out in the place of oiling after enclosing insulating oil by smearing at symmetry axis, when by kirsite system
At ebuche in base be dissolved in acid and become liquid outflow when can be so that zero made of two electroforming symmetrical above and below
Part is directly separated, and one-pass molding no longer needs to cut it；
S3, it will finish and coat base in the ebuche of insulating oil and hang on the electroforming suspender in electroforming cylinder,
Electroformed deposit is carried out to base in components and forms layer of precious metal；
S4, the ebuche for smearing insulating oil is successively immersed in nitric acid solution, removes metal or gold in sulfuric acid solution
Belong to base in components made of alloy；Firstly, will coat, base in insulation ebuche will be immersed in nitric acid and water volume ratio is 1:
In 0.8 nitric acid solution；The nitric acid mass fraction is 68%；Nitric acid solution temperature is maintained at 400 DEG C, is the boiling temperature of nitric acid
Degree, if temperature is excessively high, base is possible to boiling vaporization occur in components, and electroforming layer gold may also be heated softening, leads to electroforming part
Deformation is even scrapped；Soaking time is 2h, every 30min plus once with the nitric acid solution of concentration, by repeatedly adding nitric acid energy
Enough reactions for guaranteeing removal kirsite sufficiently carry out, and completely remove the kirsite as template, improve noble metal ebuche
Purity；It is taken out after base dissolution in components and carries out internal cleaning using vibration of ultrasonic wave；Then, then by components impregnate
It is 1 in the volume ratio of sulfuric acid and water:In 0.9 sulfuric acid solution；The mass fraction of the sulfuric acid is 98%；Sulfuric acid solution temperature is protected
It holds at 700 DEG C, soaking time 20min；The concentrated sulfuric acid can form passivating film to noble metal ebuche in precious metal surface
Play the role of passivation protection.
S5, it polished the inner membrance and outer membrane of ebuche after the completion of electroforming, polished and press polish processing；Bruting process
Surface frosted processing is carried out using sand needle；Burnishing process carries out press polish to edge using agate pen；
S6, the ebuche handled well is cleaned up, can be prepared by gold ebuche.
Wherein, the process of base specifically includes following steps in the alloy ebuche of pressed metal in the step S1：It is first
First, the raw material of purebred free from admixture can will be obtained after primary treatment with the kirsite of nitric acid chemically reactive, and as
Make the bottom material of base in ebuche；Secondly, injecting the stainless steel wrist-watch to match with its size after bottom material is melted
In components compacting tool set, and the mode Jing Guo punching press is suppressed, and is obtained base in ebuche and (is illustrated in figure 2 this hair
Bright middle a kind of cross-sectional view of the compacting tool set of grain pattern)；The compacting tool set includes cope plate 2 and lower template 3；The cope plate 2
Identical with 3 size of lower template, lines style is identical and two templates are symmetrical set, and with base phase in the components
Match；Finally, carrying out surface except thorn to components after base in stamping forming ebuche is removed from the molds, and gong falls table
The coarse deformation in face and rough part.
Wherein, the step S3 electroforming process specifically includes following steps：Firstly, 0.03mol/L is added in electroforming cylinder
Complexing agent and the monovalence gold salt of the complexing agent equimolar concentration, the citric acid of 5mL/L, potassium citrate, ethylenediamine tetra-acetic acid two
Sodium salt and pure water are configured to electroforming solution；Secondly, base in ebuche is hung on the electroforming suspender in electroforming cylinder, make zero
Base carries out electroforming according to certain rotational speed with electroforming suspender during electroforming in component；The electroforming suspender
Revolving speed be 30r/min, the electroforming time be 15h, using the recurrent pulse current of commutation；Positive peak current density is 2A/dm2,
Inverse peak current density 3A/dm2；The anodic solution of reverse pulse current can make cathode surface gold ion mass concentration rapid
Go up, can reduce the concentration polarization in cathodic region, improve the current density upper limit, being conducive to the subsequent cathode current duty cycle makes
With high pulse current density, and high pulse current density makes the formation speed of nucleus be greater than the speed of growth of crystal,
Thus available finer and close coating；The anode spalling effect of reverse pulse current keeps the folder of organic impurities in coating attached big
It is big to reduce, thus cast layer purity is higher；On the other hand, the work of reverse pulse current plays the role of an electropolishing.Just
The cell structure that the formation of electroforming layer surface can be made raised to a certain degree to the duty cycle of pulse current, and reverse pulse current
It can make these cell structures that a degree of dissolution occur in the course of work, increase the Surface flat of electroforming layer surface further
Add；Finally, playing cylinder after the completion of electroforming, drying machine drying, drying temperature 100 are used to the ebuche after the completion of electroforming
DEG C, drying time 20min, drying can be formed again to ebuche；Finally, the ebuche measured is hard
Degree is 118HV.
Embodiment 2
A kind of electroforming manufacture craft of noble metal ebuche, includes the following steps：
S1, using can be pressed into the kirsite of nitric acid chemically reactive with the identical grain pattern of upper and lower surface and symmetrical hand
Base in table components (being as shown in Figure 1 base in batch wreath in the present invention with a kind of grain pattern) simultaneously carries out it to include accurate grind
It cuts, oil removing, the finishing processing of four steps of cleaning and activation；Firstly, using accurate grinding mode in ebuche
Base is polished；Alkali cleaning is carried out to base in components secondly, adopting sodium phosphate；Then, it is carried out under the conditions of reversed polarity, to components
Interior base surface carries out electrolytic etching, and base in components is connect to the anode of power supply, and the plated pen that the libation at an ancient wedding ceremony expires activating solution is connected to the negative of power supply
Pole, plated pen is contacted with base surface in components and relative motion, and under electric field action, base surface dissolves and oxygen is precipitated in components
Gas mechanically activates the removal of the oxidation film of zinc alloy surface, is provided with for coating with collective intermetallic good combination
Sharp condition；Finally, utilizing base in ultrasonic activation cleaning ebuche；
S2, along the position for the symmetry axis 1 that base face symmetrical above and below is cut open in the ebuche uniformly can be smeared
One circle insulating oil；Electroforming can not be carried out in the place of oiling after enclosing insulating oil by smearing at symmetry axis, when by kirsite system
At ebuche in base be dissolved in acid and become liquid outflow when can be so that zero made of two electroforming symmetrical above and below
Part is directly separated, and one-pass molding no longer needs to cut it；
S3, it will finish and coat base in the ebuche of insulating oil and hang on the electroforming suspender in electroforming cylinder,
Electroformed deposit is carried out to base in components and forms layer of precious metal；
S4, the ebuche for smearing insulating oil is successively immersed in nitric acid solution, removes metal or gold in sulfuric acid solution
Belong to base in components made of alloy；Firstly, will coat, base in insulation ebuche will be immersed in nitric acid and water volume ratio is 1:
In 1.2 nitric acid solution；The nitric acid mass fraction is 68%；Nitric acid solution temperature is maintained at 500 DEG C, is the boiling temperature of nitric acid
Degree, if temperature is excessively high, base is possible to boiling vaporization occur in components, and electroforming layer gold may also be heated softening, leads to electroforming part
Deformation is even scrapped；Soaking time is 3h, every 40min plus once with the nitric acid solution of concentration, by repeatedly adding nitric acid energy
Enough reactions for guaranteeing removal kirsite sufficiently carry out, and completely remove the kirsite as template, improve noble metal ebuche
Purity；It is taken out after base dissolution in components and carries out internal cleaning using vibration of ultrasonic wave；Then, then by components impregnate
It is 1 in the volume ratio of sulfuric acid and water:In 1.3 sulfuric acid solution；The mass fraction of the sulfuric acid is 98%；Sulfuric acid solution temperature is protected
It holds at 900 DEG C, soaking time 40min；The concentrated sulfuric acid can form passivating film to noble metal ebuche in precious metal surface
Play the role of passivation protection.
S5, it polished the inner membrance and outer membrane of ebuche after the completion of electroforming, polished and press polish processing；Bruting process
Surface frosted processing is carried out using sand needle；Burnishing process carries out press polish to edge using agate pen；
S6, the ebuche handled well is cleaned up, can be prepared by gold ebuche.
Wherein, the process of base specifically includes following steps in the alloy ebuche of pressed metal in the step S1：It is first
First, the raw material of purebred free from admixture can will be obtained after primary treatment with the kirsite of nitric acid chemically reactive, and as
Make the bottom material of base in ebuche；Secondly, injecting the stainless steel wrist-watch to match with its size after bottom material is melted
In components compacting tool set, and the mode Jing Guo punching press is suppressed, and is obtained base in ebuche and (is illustrated in figure 2 this hair
Bright middle a kind of cross-sectional view of the compacting tool set of grain pattern)；The compacting tool set includes cope plate 2 and lower template 3；The cope plate 2
Identical with 3 size of lower template, lines style is identical and two templates are symmetrical set, and with base phase in the components
Match；Finally, carrying out surface except thorn to components after base in stamping forming ebuche is removed from the molds, and gong falls table
The coarse deformation in face and rough part.
Wherein, the step S3 electroforming process specifically includes following steps：Firstly, 0.2mol/L network is added in electroforming cylinder
Mixture, citric acid, potassium citrate, disodium ethylene diamine tetraacetate with the monovalence gold salt of the complexing agent equimolar concentration, 8mL/L
Salt and pure water are configured to electroforming solution；Secondly, base in ebuche is hung on the electroforming suspender in electroforming cylinder, make zero
Base carries out electroforming according to certain rotational speed with electroforming suspender during electroforming in part；The electroforming suspender
Revolving speed is 35r/min, and the electroforming time is 18h, using the recurrent pulse current of commutation；Positive peak current density is 3A/dm2, instead
To peak current density 5A/dm2；The anodic solution of reverse pulse current can be such that cathode surface gold ion mass concentration returns rapidly
It rises, can reduce the concentration polarization in cathodic region, improve the current density upper limit, be conducive to subsequent cathode current duty cycle use
High pulse current density, and high pulse current density makes the formation speed of nucleus greater than the speed of growth of crystal, because
And available finer and close coating；The anode spalling effect of reverse pulse current keeps the folder of organic impurities in coating attached significantly
It reduces, thus cast layer purity is higher；On the other hand, the work of reverse pulse current plays the role of an electropolishing.It is positive
The cell structure that the duty cycle of pulse current can make the formation of electroforming layer surface raised to a certain degree, and the work of reverse pulse current
It can make these cell structures that a degree of dissolution occur during work, further increase the Surface flat of electroforming layer surface；
Finally, playing cylinder after the completion of electroforming, drying machine drying is used to the ebuche after the completion of electroforming, drying temperature is 120 DEG C, is dried
The dry time is 30min, and drying can be formed again to ebuche；Finally, the hardness of the ebuche measured is
117HV。
Embodiment 3
A kind of electroforming manufacture craft of noble metal ebuche, includes the following steps：
S1, using can be pressed into the kirsite of nitric acid chemically reactive with the identical grain pattern of upper and lower surface and symmetrical hand
Base in table components (being as shown in Figure 1 base in batch wreath in the present invention with a kind of grain pattern) simultaneously carries out it to include accurate grind
It cuts, oil removing, the finishing processing of four steps of cleaning and activation；Firstly, using accurate grinding mode in ebuche
Base is polished；Secondly, carrying out alkali cleaning to base in components using triethanolamine；Then, it is carried out under the conditions of reversed polarity, to zero
Base surface carries out electrolytic etching in component, and base in components is connect to the anode of power supply, the plated pen that the libation at an ancient wedding ceremony expires activating solution is connected to power supply
Cathode, plated pen is contacted with base surface in components and relative motion, and under electric field action, base surface is dissolved and analysed in components
Oxygen out mechanically activates the removal of the oxidation film of zinc alloy surface, mentions for coating with collective intermetallic good combination
For advantage；Finally, utilizing base in ultrasonic activation cleaning ebuche；
S2, along the position for the symmetry axis 1 that base face symmetrical above and below is cut open in the ebuche uniformly can be smeared
One circle insulating oil；Electroforming can not be carried out in the place of oiling after enclosing insulating oil by smearing at symmetry axis, when by kirsite system
At ebuche in base be dissolved in acid and become liquid outflow when can be so that zero made of two electroforming symmetrical above and below
Part is directly separated, and one-pass molding no longer needs to cut it；
S3, it will finish and coat base in the ebuche of insulating oil and hang on the electroforming suspender in electroforming cylinder,
Electroformed deposit is carried out to base in components and forms layer of precious metal；
S4, the ebuche for smearing insulating oil is successively immersed in nitric acid solution, removes metal or gold in sulfuric acid solution
Belong to base in components made of alloy；Firstly, will coat, base in insulation ebuche will be immersed in nitric acid and water volume ratio is 1:1
Nitric acid solution in；The nitric acid mass fraction is 68%；Nitric acid solution temperature is maintained at 450 DEG C, is the boiling temperature of nitric acid,
If temperature is excessively high, base is possible to boiling vaporization occur in components, and electroforming layer gold may also be heated softening, leads to electric casting deformation
Even scrap；Soaking time is 2.5h, can by repeatedly adding nitric acid every 35min plus once with the nitric acid solution of concentration
Guarantee that the reaction of removal kirsite sufficiently carries out, completely removes the kirsite as template, improve noble metal ebuche
Purity；It is taken out after base dissolution in components and carries out internal cleaning using vibration of ultrasonic wave；Then, then by components it is immersed in
The volume ratio of sulfuric acid and water is 1:In 1 sulfuric acid solution；The mass fraction of the sulfuric acid is 98%；Sulfuric acid solution temperature is maintained at
800 DEG C, soaking time 30min；The concentrated sulfuric acid can form passivating film in precious metal surface and play to noble metal ebuche
Passivation protection effect.
S5, it polished the inner membrance and outer membrane of ebuche after the completion of electroforming, polished and press polish processing；Bruting process
Surface frosted processing is carried out using sand needle；Burnishing process carries out press polish to edge using agate pen；
S6, the ebuche handled well is cleaned up, can be prepared by gold ebuche.
Wherein, the process of base specifically includes following steps in the alloy ebuche of pressed metal in the step S1：It is first
First, the raw material of purebred free from admixture can will be obtained after primary treatment with the kirsite of nitric acid chemically reactive, and as
Make the bottom material of base in ebuche；Secondly, injecting the stainless steel wrist-watch to match with its size after bottom material is melted
In components compacting tool set, and the mode Jing Guo punching press is suppressed, and is obtained base in ebuche and (is illustrated in figure 2 this hair
Bright middle a kind of cross-sectional view of the compacting tool set of grain pattern)；The compacting tool set includes cope plate 2 and lower template 3；The cope plate 2
Identical with 3 size of lower template, lines style is identical and two templates are symmetrical set, and with base phase in the components
Match；Finally, carrying out surface except thorn to components after base in stamping forming ebuche is removed from the molds, and gong falls table
The coarse deformation in face and rough part.
Wherein, the step S3 electroforming process specifically includes following steps：Firstly, 0.1mol/L network is added in electroforming cylinder
Mixture, citric acid, potassium citrate, disodium ethylene diamine tetraacetate with the monovalence gold salt of the complexing agent equimolar concentration, 6mL/L
Salt and pure water are configured to electroforming solution；Secondly, base in ebuche is hung on the electroforming suspender in electroforming cylinder, make zero
Base carries out electroforming according to certain rotational speed with electroforming suspender during electroforming in part；The electroforming suspender
Revolving speed is 33r/min, and the electroforming time is 16h, using the recurrent pulse current of commutation；Positive peak current density is 2.5A/dm2,
Inverse peak current density 4A/dm2；The anodic solution of reverse pulse current can make cathode surface gold ion mass concentration rapid
Go up, can reduce the concentration polarization in cathodic region, improve the current density upper limit, being conducive to the subsequent cathode current duty cycle makes
With high pulse current density, and high pulse current density makes the formation speed of nucleus be greater than the speed of growth of crystal,
Thus available finer and close coating；The anode spalling effect of reverse pulse current keeps the folder of organic impurities in coating attached big
It is big to reduce, thus cast layer purity is higher；On the other hand, the work of reverse pulse current plays the role of an electropolishing.Just
The cell structure that the formation of electroforming layer surface can be made raised to a certain degree to the duty cycle of pulse current, and reverse pulse current
It can make these cell structures that a degree of dissolution occur in the course of work, increase the Surface flat of electroforming layer surface further
Add；Finally, playing cylinder after the completion of electroforming, drying machine drying, drying temperature 110 are used to the ebuche after the completion of electroforming
DEG C, drying time 25min, drying can be formed again to ebuche；Finally, the ebuche measured is hard
Degree is 121HV.
Comparative example
A kind of electroforming manufacture craft of noble metal ebuche, includes the following steps：
A, using can with the kirsite of hydrochloric acid or nitric acid or sulfuric acid chemically reactive make model type；
B, the ebuche model type made of kirsite is hung on into the suspension of the electroforming in the electroforming cylinder for filling electroforming solution
On part, the revolving speed of electroforming suspender is 30r/min, and the electroforming time is 12h, using 1.5A/dm2Low current density carry out electricity
Casting, electroforming temperature are 40 DEG C；
C, at least one relief hole is bored in the model type that electroforming finishes；
D, the model type of drilling is put into hydrochloric acid, after so that model type and hydrochloric acid is generated chemical reaction and is dissolved completely in hydrochloric acid
Outflow；
E, after model type dissolves, electroformed deposit layer is washed with water.
Performance test
1, hardness determination：The test of sample Vickers hardness is using HVS-1000B type digital display microhardness testers measurement sample
Vickers hardness number.The test scope of micro Vickers used is 1~2967HV.Vickers hardness number and test force are divided by impression
The quotient of surface area is directly proportional.For same material, test force is bigger, indentation surface product bigger, sample hardness value and test force
Size is unrelated.According to GB/T4340.1-2009 (Vickers Hardness Test of Metallic Materials part 1：Test method) in regulation, test
Thickness degree at least should be 1.5 times of impression catercorner length.This test specimen is with a thickness of 0.2mm or so.When test force is
When 1.96N, impression is closer to ideal square.Therefore, 1.96N is chosen as test, and diamond is with sample time of contact
15s, each sample measure five times, and using the average value of five measurement results as measurement result, (five measurements are selected in different portions
Position).
2, appearance is tested：Using visually observing golden watch watchcase flatness.
3, sem test：It is observed using Zeiss AURIGA Compact field emission scanning electron microscope (SEM)
Cast the tissue topography on layer gold surface.
Test result is as follows：
Table 1
Table 2
Hardness is the important performance of the hard pure gold of electroforming, will affect the intensity, wearability and service life of golden wristwatch case, by
Tables 1 and 2 is it is found that the Vickers hardness of embodiment 1-3 (carries out electricity using direct current compared to comparative example in 120HV or so
Casting), it is significantly improved in hardness；Secondly, direct current gold cast layer is larger in the difference in hardness of different parts, standard deviation 12.72,
And each position hardness standard difference of commutating pulse gold cast layer is respectively 5.88,4.92 and 5.55, shows commutating pulse electric current electroforming
Relatively, difference is little for the hardness at each position of layer gold, reflects the goldc grains size and group of the layer gold of commutating pulse electric current electroforming
It is all relatively uniform to knit structure.
From the point of view of appearance is tested in conjunction with SEM map analysis, the gold ebuche of embodiment 1-3 production is real relative to comparison
Apply the gold ebuche surfacing of example；Meanwhile by the SEM of comparative example figure (Fig. 4) it is found that being carried out using direct current
Electroforming, resulting gold cast layer surface topography loosely, accumulate in spherical, tufted, and particulate interspaces are larger by goldc grains；Embodiment 3 uses
Commutating pulse electric current carries out electroforming, from the figure 3, it may be seen that the form of goldc grains and accumulation mode are changed, goldc grains is in two-dimensional layer
Shape growth accumulation, interlayer accumulation is close, and hole is few.
The above embodiment is a preferred embodiment of the present invention, can transport the manufacture craft of above-mentioned noble metal ebuche
For batch wreath, literal and indicator production of noble metal wrist-watch, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included in protection scope of the present invention.
Claims (10)
1. a kind of electroforming manufacture craft of gold ebuche, which is characterized in that include the following steps：
S1, using can be pressed into the metal alloy of hydrochloric acid or nitric acid or sulfuric acid chemically reactive with the identical grain pattern of upper and lower surface
And base and finishing processing is carried out to it in symmetrical ebuche；
S2, along can be by base face symmetrical above and below is cut open in the ebuche symmetry axis（1）Uniformly smear a circle in position
Insulating oil；
S3, it will finish and coat base in the ebuche of insulating oil and hang on the electroforming suspender in electroforming cylinder, to zero
Base carries out electroformed deposit and forms layer of precious metal in component；
S4, the ebuche after electroforming is successively immersed in nitric acid solution, removes metal or metal alloy system in sulfuric acid solution
At components in base；
S5, it polished the inner membrance and outer membrane of ebuche after the completion of electroforming, polished and press polish processing；
S6, the ebuche handled well is cleaned up, can be prepared by gold ebuche.
2. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：The metal alloy
For kirsite.
3. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：In the step S1
Finishing processing includes accurate grinding, oil removing, activation and cleaning.
4. a kind of electroforming manufacture craft of gold ebuche as claimed in claim 3, it is characterised in that：The oil removing uses
Sodium hydroxide or at least one of sodium phosphate or triethanolamine carry out alkali cleaning；The activation process carries out under the conditions of reversed polarity,
Electrolytic etching is carried out to base surface in ebuche, mechanically the oxygen on base surface in ebuche made of metal alloy
Change film removal.
5. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：In the step S1
The process of base specifically includes following steps in the alloy ebuche of pressed metal：
（1）Purebred free from admixture will can be obtained after primary treatment with the metal alloy of hydrochloric acid or nitric acid or sulfuric acid chemically reactive
Raw material, and as production ebuche in base bottom material；
（2）It injects in the stainless steel ebuche compacting tool set to match with its size, and passes through after bottom material is melted
The mode of punching press is suppressed, and base in ebuche is obtained；
（3）Surface is carried out except thorn to components after base in stamping forming ebuche is removed from the molds, and gong falls table
The coarse deformation in face and rough part.
6. a kind of electroforming manufacture craft of gold ebuche as claimed in claim 5, it is characterised in that：
The mold includes cope plate（2）And lower template（3）；The cope plate（2）And lower template（3）Size is identical, line
Road style is identical and two templates are symmetrical set, and matches with base in the components.
7. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：The step S3 electricity
Casting process specifically includes following steps：
（1）Be added in electroforming cylinder 0.03 ~ 0.2mol/L complexing agent, with the monovalence gold salt of the complexing agent equimolar concentration, 5 ~
Citric acid, potassium citrate, disodium EDTA and the pure water of 8mL/L is configured to electroforming solution；
（2）Base in ebuche is hung on the electroforming suspender in electroforming cylinder, makes in components base in the process of electroforming
According to certain rotational speed carry out electroforming with electroforming suspender；The revolving speed of the electroforming suspender is 30 ~ 35r/min,
The electroforming time is 15 ~ 18h, using the recurrent pulse current of commutation；Positive peak current density is 2 ~ 3A/dm2, inverse peak current
3 ~ 5A/dm of density2；
（3）Cylinder is played after the completion of electroforming, and drying machine drying used to the ebuche after the completion of electroforming, drying temperature is 100 ~
120 DEG C, drying time is 20 ~ 30min.
8. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：The step S4 is gone
Except the process of base in components made of metal alloy specifically includes following steps：
（1）It is 1 that base in insulation ebuche, which will be coated, and be immersed in nitric acid and water volume ratio:In 0.8 ~ 1.2 nitric acid solution；Institute
Stating nitric acid mass fraction is 68%；Nitric acid solution temperature is maintained at 400 ~ 500 DEG C, and soaking time is 2 ~ 3h, adds every 30 ~ 40min
Once with the nitric acid solution of concentration, takes out after base dissolution in components and cleared up using vibration of ultrasonic wave；
（2）It is 1 by the volume ratio that components are immersed in sulfuric acid and water:In 0.9 ~ 1.3 sulfuric acid solution；The quality of the sulfuric acid point
Number is 98%；Sulfuric acid solution temperature is maintained at 700 ~ 900 DEG C, and soaking time is 20 ~ 40min；
（3）Sulfuric acid is dried after placing room temperature, rinsed well with clear water, obtains the noble metal ebuche of electroforming formation.
9. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：In the step S5
Bruting process carries out surface frosted processing using sand needle；Burnishing process carries out press polish to edge using agate pen.
10. a kind of electroforming manufacture craft of gold ebuche as described in claim 1, it is characterised in that：The wrist-watch zero
Component includes wrist-watch batch wreath, literal and pointer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810694580.7A CN108914166A (en) | 2018-06-29 | 2018-06-29 | A kind of electroforming manufacture craft of noble metal ebuche |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810694580.7A CN108914166A (en) | 2018-06-29 | 2018-06-29 | A kind of electroforming manufacture craft of noble metal ebuche |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108914166A true CN108914166A (en) | 2018-11-30 |
Family
ID=64423293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810694580.7A Pending CN108914166A (en) | 2018-06-29 | 2018-06-29 | A kind of electroforming manufacture craft of noble metal ebuche |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108914166A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826698A (en) * | 2020-07-16 | 2020-10-27 | 深圳市联合蓝海黄金材料科技股份有限公司 | Method for preparing clock parts by using hard gold |
| CN111826686A (en) * | 2020-07-16 | 2020-10-27 | 深圳市联合蓝海黄金材料科技股份有限公司 | Method for preparing hard gold gyroscope flywheel bracket |
| CN114481231A (en) * | 2022-03-05 | 2022-05-13 | 弘福臻品(深圳)珠宝文化有限公司 | Reverse electroforming process for jewelry processing |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5578273A (en) * | 1978-12-07 | 1980-06-12 | Citizen Watch Co Ltd | Manufacture for decoration plate for watch |
| JPS5848687A (en) * | 1982-09-03 | 1983-03-22 | Citizen Watch Co Ltd | Production of dial and panel cover for timepiece |
| CN1341513A (en) * | 2001-08-22 | 2002-03-27 | 魏志凌 | Preparation method of surface tiling and veneering technology form |
| CN104532303A (en) * | 2015-01-30 | 2015-04-22 | 深圳市凡逅珠宝首饰有限公司 | Manufacturing method of hollow watch case or ornament |
| CN104593831A (en) * | 2015-01-26 | 2015-05-06 | 黄盛平 | Method for producing watch by virtue of 3D noble metal technique |
| CN105301945A (en) * | 2014-07-21 | 2016-02-03 | 斯沃奇集团研究和开发有限公司 | Electroform welding of an electroformed timepiece shell |
-
2018
- 2018-06-29 CN CN201810694580.7A patent/CN108914166A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5578273A (en) * | 1978-12-07 | 1980-06-12 | Citizen Watch Co Ltd | Manufacture for decoration plate for watch |
| JPS5848687A (en) * | 1982-09-03 | 1983-03-22 | Citizen Watch Co Ltd | Production of dial and panel cover for timepiece |
| CN1341513A (en) * | 2001-08-22 | 2002-03-27 | 魏志凌 | Preparation method of surface tiling and veneering technology form |
| CN105301945A (en) * | 2014-07-21 | 2016-02-03 | 斯沃奇集团研究和开发有限公司 | Electroform welding of an electroformed timepiece shell |
| CN104593831A (en) * | 2015-01-26 | 2015-05-06 | 黄盛平 | Method for producing watch by virtue of 3D noble metal technique |
| CN104532303A (en) * | 2015-01-30 | 2015-04-22 | 深圳市凡逅珠宝首饰有限公司 | Manufacturing method of hollow watch case or ornament |
Non-Patent Citations (1)
| Title |
|---|
| 编写组: "《电子设备金属腐蚀与防护技术》", 28 February 1988 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826698A (en) * | 2020-07-16 | 2020-10-27 | 深圳市联合蓝海黄金材料科技股份有限公司 | Method for preparing clock parts by using hard gold |
| CN111826686A (en) * | 2020-07-16 | 2020-10-27 | 深圳市联合蓝海黄金材料科技股份有限公司 | Method for preparing hard gold gyroscope flywheel bracket |
| CN114481231A (en) * | 2022-03-05 | 2022-05-13 | 弘福臻品(深圳)珠宝文化有限公司 | Reverse electroforming process for jewelry processing |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108914166A (en) | A kind of electroforming manufacture craft of noble metal ebuche | |
| CN101613845B (en) | Zirconium-base non-crystalline alloy compound material and preparation method | |
| CN102264952A (en) | Method of electrolytic ceramic coating for metal, electrolysis solution for electrolytic ceramic coating for metal, and metallic material | |
| Lechtman et al. | New perspectives on Moche metallurgy: techniques of gilding copper at Loma Negra, Northern Peru | |
| CN105862027A (en) | Surface treatment technique for aluminum alloy die casting | |
| CN108070899A (en) | A kind of non-crystaline amorphous metal local polishing technique | |
| CN102953114A (en) | Stainless steel product and preparation method thereof | |
| CN111286770B (en) | Composite material with high binding force | |
| CN106381482A (en) | Chemical plating solution for Ni-P plated layer and controllable preparation method of micro-nano mold | |
| US20190018323A1 (en) | HOROLOGICAL COMPONENT FORMED FROM AMAGNETIC BINARY CuNi ALLOY | |
| CN111411379B (en) | Low-stress nickel-phosphorus alloy roller for microstructure machining and electroplating process thereof | |
| CN108893759A (en) | A kind of hollow golden watch shell manufacture craft | |
| CN108941506A (en) | A kind of solid wristwatch case manufacture craft of noble metal | |
| JPS58177494A (en) | Anodically oxidizing bath for aluminum-clad part and anodic oxidation | |
| CN111593376A (en) | Method for electrodepositing bright copper | |
| CN104611735A (en) | Carbon nanotube composite chromium plating solution and electroplating method | |
| CN111826686A (en) | Method for preparing hard gold gyroscope flywheel bracket | |
| CN109852851A (en) | A kind of low wear rate material and preparation method thereof | |
| CN109097798B (en) | Manufacturing process of belt particles of hollow hard gold watch watchband | |
| CN114686939A (en) | High-precision hard gold and production method thereof | |
| Yeh et al. | Effect of pulse-reverse current on microstructure and properties of electroformed nickel–iron mold insert | |
| CN110693145A (en) | Electroforming-based gem inlaying process | |
| CN109056000A (en) | A kind of golden watch shell electroforming solution and its electroforming process | |
| CN108958005A (en) | A kind of gold wrist-watch batch wreath manufacture craft | |
| CN108907621A (en) | A kind of gold ebuche manufacture craft |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181130 |
|
| RJ01 | Rejection of invention patent application after publication |