CN107164791A - Silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology - Google Patents
Silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology Download PDFInfo
- Publication number
- CN107164791A CN107164791A CN201710427598.6A CN201710427598A CN107164791A CN 107164791 A CN107164791 A CN 107164791A CN 201710427598 A CN201710427598 A CN 201710427598A CN 107164791 A CN107164791 A CN 107164791A
- Authority
- CN
- China
- Prior art keywords
- silver
- graphite
- graphite composite
- test group
- plating
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention belongs to field of electroplating, more particularly to silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology.The invention provides silver/graphite composite silver plating liquor, including：Water miscible Ag-containing compound, succimide, potassium pyrophosphate, graphite and Tween 80, the present invention are solved the current coating performance obtained using silver/graphite composite electrodeposition and are difficult to the technological deficiency for reaching power equipment needs.The silver/graphite composite deposite that silver/graphite composite silver plating liquor disclosed by the invention and preparation method thereof and electrodeposition technology are obtained has good surface topography, Cross Section Morphology, Coating composition and institutional framework.
Description
Technical field
The invention belongs to field of electroplating, more particularly to silver/graphite composite silver plating liquor and preparation method thereof and electro-deposition work
Skill.
Background technology
High voltage isolator is one of most power transmission and transforming equipment of usage amount in power system, is also important control and guarantor
Protection unit, its operation conditions whether normal relation to whole power network safety and stably.Operate failure, Insulator detection, conduction
Loop is overheated and corrosion is 4 subject matters reflected during current disconnecting switch is run.
Selecting copper the dynamic and static contact material of country's disconnecting switch at present, good conductive surface is typically carried out for guarantee more
Silver-plated process, i.e., make anode with fine silver plate, and copper contact makees negative electrode, and electro-deposition is carried out under cyaniding plant of silver system.But with electricity
The construction of fast development, particularly super-pressure, extra high voltage line and intelligent grid that power is built, the use longevity of common silver coating
Life has been difficult the actual demand for meeting the power transmission and transforming equipments such as high voltage isolator, and common silver coating matter is soft, wears no resistance, resistance
The problems such as color and not strong automatical cleaning ability, is urgently to be resolved hurrily.Moreover, cyanide is severe toxicity, to ecological environment and the health of producers
There is great harm, while the technology and cost requirement to liquid waste processing are higher.
At present, there is scholar to propose to prepare silver/graphite composite using new silver plating solution, but there remains silver/stone
Graphite is not attached in composite deposite well in black composite deposite, causes the technical problem of composite deposite hydraulic performance decline.
The content of the invention
In view of this, silver/graphite composite silver plating liquor disclosed by the invention and preparation method thereof and electrodeposition technology can have
Effect is solved the current coating performance obtained using silver/graphite composite electrodeposition and is difficult to reach that the technology of power equipment needs lacks
Fall into.
Present invention also offers silver/graphite composite silver plating liquor, including：Water miscible Ag-containing compound, succimide,
Potassium pyrophosphate, graphite and Tween 80.
Preferably, above-mentioned silver/graphite composite silver plating liquor includes following component：
Less preferred, above-mentioned silver/graphite composite silver plating liquor, including following component：
More preferably, above-mentioned silver/graphite composite silver plating liquor, including following component：
Preferably, above-mentioned water miscible Ag-containing compound is silver nitrate.
Wherein, the solvent of silver/graphite composite silver plating liquor of the invention is water.
It is more highly preferred to, the solvent of the silver/graphite composite silver plating liquor is deionized water.
The invention also discloses the preparation method of silver/graphite composite silver plating liquor, comprise the following steps：
1) water miscible Ag-containing compound, succimide and potassium pyrophosphate are mixed, obtains mixed solution；
2) by step 1) mixed solution mixed with graphite and Tween 80, dissolve graphite in ultrasound condition, obtain silver/stone
Black composite silver plating liquor.
Preferably, the graphite is the graphite after removal of impurities.
Preferably, step 1) PH of the mixed solution is 8.5-10.5.
Less preferred, step 1) PH of the mixed solution is 9-10.
More preferably, step 1) PH of the mixed solution is 9.
The invention also discloses a kind of electrodeposition technology, comprise the following steps：
1) silver/graphite composite silver plating liquor) is prepared；
2)) copper sheet and silver plate are set；
3)) by step 2) copper sheet and silver plate be placed in step 1) silver/graphite composite silver plating liquor in carry out electro-deposition, obtain
To silver/graphite composite plating bath.
Preferably, the current density of the electro-deposition is 0.2-0.7A/dm2。
Less preferred, the current density of the electro-deposition is 0.3-0.6A/dm2。
More preferably, the current density of the electro-deposition is 0.5A/dm2。
Preferably, the mixing speed of the electro-deposition is 800-1400r/min.
Less preferred, the mixing speed of the electro-deposition is 1000-1200r/min.
More preferably, the mixing speed of the electro-deposition is 1200r/min.
Preferably, the plating temperature of the electro-deposition of the electro-deposition is 20-60 DEG C.
Less preferred, the plating temperature of the electro-deposition is 30-50 DEG C.
More preferably, the plating temperature of the electro-deposition is 40 DEG C.
Preferably, the electrodeposition time of the electro-deposition is 30-120min.
Less preferred, the electrodeposition time of the electro-deposition is 60-120min.
More preferably, the electrodeposition time of the electro-deposition is 120min.
The silver/graphite composite silver plating liquor that the present invention is provided, including water miscible Ag-containing compound, succimide, Jiao
Potassium phosphate, graphite and Tween 80, the stone under the specific components scope and specific preparation method and specific electro-deposition method
Ink can be equably mechanically embedding among silver/graphite composite deposite, and its obtained silver/graphite composite deposite all has good table
Face pattern, Cross Section Morphology, Coating composition and institutional framework, the performance energy of the of the invention silver/graphite composite deposite prepared
Reach current power equipment needs.
In addition, the invention also discloses a kind of electrodeposition technology, compared to traditional hot-working method, due to hot-working side
Method needs to carry out under the hot conditions more than 500 DEG C, so expensive production equipment is needed, and electricity disclosed by the invention
Depositing operation is processed using silver/graphite composite silver plating liquor, it is not necessary to hot conditions, and operation temperature can directly at room temperature
Carry out, relatively low is required to production equipment, therefore, the investment cost of the electrodeposition technology is few, required equipment is simple and easily controllable.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described.
Fig. 1 shows influence of the silver nitrate concentration to plating speed；
Fig. 2 shows influence of the sub- amide concentration of fourth two to plating speed；
Fig. 3 shows influence of the potassium pyrophosphate concentration to plating speed；
Fig. 4 shows influence of the pH value to plating speed；
Fig. 5 shows the outward appearance of anode silver plate under different pH value；
Fig. 6 shows influence of the graphite addition to thickness of coating；
Fig. 7 shows influence of the graphite addition to coating surface morphology；
Fig. 8 shows influence of the current density to thickness of coating；
Fig. 9 shows influence of the current density to coating surface morphology；
Figure 10 shows influence of the mixing speed to thickness of coating；
Figure 11 shows influence of the mixing speed to coating surface morphology；
Figure 12 shows influence of the plating temperature to thickness of coating；
Figure 13 shows influence of the plating temperature to coating surface morphology；
Figure 14 shows influence of the electrodeposition time to thickness of coating；
Figure 15 shows influence of the electrodeposition time to coating surface morphology；
Figure 16 shows the surface topography of silver coating and silver/graphite composite deposite；
Figure 17 shows the Cross Section Morphology of silver coating and silver/graphite composite deposite；
Figure 18 shows silver-plated layer surface and silver/graphite composite surface coating energy spectrum analysis；
Figure 19 shows that silver coating is distributed with silver/graphite composite deposite surface silver and carbon；
Figure 20 shows the XRD spectrum of silver coating and silver/graphite composite deposite.
Embodiment
The invention provides silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology, it can effectively solve to work as
The coating performance that preceding utilization silver/graphite composite electrodeposition is obtained is difficult to the technological deficiency for reaching power equipment needs.
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
Wherein, the raw material and reagent of following examples are commercially available.
Embodiment 1
AgNO3It is the main salt in plating solution, for providing Ag+, main salt concentration is increased or decreased in plating solution, all can be heavy to electricity
Product process and the quality of silver coating have direct influence.
Test group 1：10g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 2：20g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 3：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 4：40g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 5：50g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 6：60g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the silver plating solution of~test group 6, the parameter of electro-deposition is uniformly set to current density：0.5A/dm2；Mixing speed：1200r/
min；Plating temperature：30℃.
Table 1 is the influence that silver nitrate concentration changes the silver coating outward appearance prepared to silver plating solution, and Fig. 1 becomes for silver nitrate concentration
Change the influence to plating speed.Work as AgNO3When concentration is relatively low, limiting current density is low, and the speed of electro-deposition is slower, the outward appearance of silver coating
Gray.With AgNO in plating solution3The rise of concentration, the enhancing of plating solution electric conductivity, current efficiency and limiting current density are improved, silver
Sedimentation rate accelerate, the outward appearance of coating is also effectively improved, and becomes uniform, light.But work as AgNO3Concentration is higher than 50g/L
When, plating solution is unstable, and silver-colored sedimentation rate is too fast, causes Deposit appearance to become coarse.Because the speed of growth of nucleus is big
In the nucleation rate of silver, cause crystallization thick, be presented as the coarse of silver coating outward appearance.The quality and electricity for considering silver coating are sunk
Product speed, AgNO3Deposit appearance is also effectively improved when concentration is 30-40g/L, becomes uniform, light.
The silver nitrate concentration of table 1 changes the influence to silver coating outward appearance
| Group | Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 | Test group 6 |
| Silvering outward appearance # | Grey, brightless # | Half light # | Bright # | Bright # | Edge roughness # | Coarse # |
Embodiment 2
Succimide is the complexing agent in plating solution, and complexing agent has stable plating solution, improves plating solution covering power and plates energy
Power and crystal grain thinning, the effect for improving quality of coating.
Test group 1：30g/L silver nitrates, 30g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 2：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 3：30g/L silver nitrates, 90g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 4：30g/L silver nitrates, 120g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 5：30g/L silver nitrates, 150g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the silver-colored plating liquor of~test group 5, the parameter of electro-deposition is uniformly set to current density：0.5A/dm2；Mixing speed：1200r/
min；Plating temperature：30℃.
Succimide produces anion and Ag under alkaline environment+Coordination.As shown in table 2, succimide concentration compared with
When low, silver coating outward appearance prepared by silver plating liquid is not bright, in canescence, when succimide concentration reaches 90g/L, outside coating
Sight becomes uniform, light.Fig. 2 is influence of the succimide change in concentration to plating speed, there it can be seen that as succinyl is sub-
The increase of amine concentration, electrodepositing speed has been lifted but unobvious, therefore, when succimide concentration is 90g/L, outside coating
Sight becomes uniform, light.
Influence of the sub- amide concentration of 2 fourth of table two to Deposit appearance
| Group | Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 |
| Silvering outward appearance # | Canescence # | Half light # | Bright # | Bright # | Bright # |
Embodiment 3
Potassium pyrophosphate is made to also serve as conducting salt while auxiliary complex-former in the plating solution, can effectively improve the conduction of plating solution
Ability, its change in concentration is to quality of coating also important.
Test group 1：30g/L silver nitrates, 60g/L succimides, 0g/L potassium pyrophosphates, pH value：9, silver plating solution is made；
Test group 2：30g/L silver nitrates, 60g/L succimides, 30g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 3：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 4：30g/L silver nitrates, 60g/L succimides, 90g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid；
Test group 5：30g/L silver nitrates, 60g/L succimides, 120g/L potassium pyrophosphates, pH value：9, it is made silver-plated molten
Liquid.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the silver plating solution of~test group 5, the parameter of electro-deposition is uniformly set to current density：0.5A/dm2；Mixing speed：1200r/
min；Plating temperature：30℃.
As shown in table 3, when not adding potassium pyrophosphate, silver coating prepared by silver plating liquid is second-rate, and outward appearance is grey, no
Silver coating quality is progressively improved after light, addition potassium pyrophosphate, and when potassium pyrophosphate concentration is 90g/L, coating is uniform, light
It is bright.Simultaneously from figure 3, it can be seen that the change of potassium pyrophosphate concentration influences little to electrodepositing speed, in summary factor, burnt
When the concentration of potassium phosphate is 90g/L, coating is uniform, light.
Influence of the potassium pyrophosphate concentration of table 3 to silvering outward appearance
| Group | Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 |
| Silvering outward appearance # | Grey, brightless # | Grey, brightless # | Half light # | Bright # | Bright # |
Embodiment 4
The pH value of silver plating liquid is adjusted using potassium hydroxide, pH value influences very on the stability of plating solution and the quality of coating
Greatly.
Test group 1：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：8.5, it is made silver-plated molten
Liquid；
Test group 2：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9.0, it is made silver-plated molten
Liquid；
Test group 3：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：9.5, it is made silver-plated molten
Liquid；
Test group 4：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：10.0, it is made silver-plated
Solution；
Test group 5：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：10.5, it is made silver-plated
Solution.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the silver-colored plating liquor of~test group 5, the parameter of electro-deposition is uniformly set to current density：0.5A/dm2；Mixing speed：1200r/
min；Plating temperature：30℃.
Because the complexing of silver ion and the sub- acid amides of fourth two is occurred mainly in alkaline solution, when pH value is less than 8.5,
Silver ion is not coordinated completely, and muddy or taupe precipitation occurs in plating solution.The pH value of plating solution is improved, electrodepositing speed increase is silver-plated
Silver coating outward appearance prepared by liquid becomes bright, uniform.But succimide with pH value rise it is easier hydrolyze, cause electricity
Sedimentation rate declines.When experiment discovery pH value is 10.5, anodic passivity is serious, and coffee-like powdered precipitation occurs in silver plate surface
Thing, such as Fig. 5 b) shown in, now the surface of gained coating also becomes coarse, and considering pH value should be between 9.0~10.0
Preferably.When configuring silver plating solution, potassium hydroxide 40g/L is added, silver plating liquid pH stable is 9.0 or so, therefore the present invention takes hydrogen
Potassium application rate is aoxidized in 40g/L.
Influence of the table 4pH values to silvering outward appearance
| Group | Test group 1 | Test group 2 | Test group 3 | Test group 4 | Test group 5 |
| Silvering outward appearance # | Half light # | Bright # | Bright # | Bright # | Coarse # |
Embodiment 5
Test group 1：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 5g/L graphite, 0.5g/L are told
Temperature -80, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor；
Test group 2：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 10g/L graphite, 1g/L tweens-
80th, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor；
Test group 3：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 20g/L graphite, 2g/L tweens-
80th, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor；
Test group 4：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 30g/L graphite, 3g/L tweens-
80th, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor；
Test group 5：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 40g/L graphite, 4g/L tweens-
80th, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the silver/graphite composite silver plating liquor of~test group 5, carry out composite electrodeposition and prepare silver/graphite composite deposite, compound electric
The parameter of deposition is uniformly set to current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electro-deposition
Time 30min.
Fig. 6 is influence of the change of graphite quality concentration in plating solution to thickness of coating.It can be seen that silver/graphite
The thickness of composite deposite reaches most with the increase first increases and then decreases of graphite quality concentration in plating solution under conditions of 30g/L
Big value.The surface microscopic topographic of corresponding silver/graphite composite deposite as shown in fig. 7, therefrom more can intuitively find out silver/
The change of content of graphite in graphite composite deposite.When graphite quality concentration is 5g/L, the graphite particulate suspended in plating solution is less,
The quantity of graphite for depositing to cathode surface by suction-operated is accordingly less.It is defeated with the increase of graphite quality concentration in plating solution
The graphite particulate for sending and adsorbing in negative electrode increases, and graphite is electrically conductive particles, and silver can be deposited directly to the surface of graphite particulate,
So increasing electrodepositing speed, the thickness of silver/graphite composite deposite is increased.But graphite quality concentration be 10g/L~
During 20g/L, silver/graphite composite deposite is still more loose, such as Fig. 7 b), c) shown in, loose porous silver/graphite composite deposite is difficult
For use as contact material.Silver/graphite composite deposite such as Fig. 7 d prepared during graphite quality concentration 30g/L) shown in, now
Silver/graphite composite deposite is comparatively dense, and matrix surface is equably grown in coralliform.The quality for continuing to increase graphite particulate is dense
Degree, the thickness of silver/graphite composite deposite reduces on the contrary.This is primarily due to graphite particulate concentration in plating solution and is unfavorable for greatly very much disperseing
So as to cause the reunion of graphite particulate, while the mutual steric effect of particulate is controlled the diffusive migration of particulate, negative electrode
The graphite particulate that surface can be adsorbed is limited, so as to influence electrodepositing speed, the thickness of silver/graphite composite deposite is accordingly reduced.
Therefore, during composite electrodeposition, the addition of the graphite particulate in plating solution is unsuitable too high.
Embodiment 6
Test group 1 is to test group 6：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 20g/L graphite,
2g/L Tween-80s, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the composite silver plating liquor of~test group 6, carry out composite electrodeposition and prepare silver/graphite composite deposite.
The parameter of composite electrodeposition is set to：
Test group 1：Current density：0.1A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 2：Current density：0.2A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 3：Current density：0.3A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 4：Current density：0.4A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 5：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 6：Current density：0.6A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min。
Fig. 8 is influence of the current density change to thickness of multiple plating.It can be seen that current density is multiple to silver/graphite
The influence for closing thickness of coating is larger, and with the increase of current density, silver/graphite thickness of multiple plating substantially increases, but electric current is close
Degree reaches 0.5A/dm2Afterwards, the increased trend of thickness has slowed down.Fig. 9 is silver/graphite composite deposite under different current densities
Surface topography map.Under low current density, cathode overpotential is smaller, and active surface sites are few, coating nucleus formation probability it is small,
Form that speed is slow, the graphite particulate for being adsorbed onto cathode surface is difficult to be realized by silver cladding in time and is co-deposited, Fig. 9 a) in can be clear
See the graphite flake layer for being embedded in coating but not coated completely, now corresponding silver/graphite thickness of multiple plating it is smaller and
Graphite particulate content is less in coating.As current density increases, the polarization enhancing of negative electrode increases deposition overpotential, silver
Sedimentation rate accelerate, while can effectively coated graphite particulate, the thickness and consistency of silver/graphite composite deposite gradually increase
Plus, such as Fig. 9 b)~e) shown in.However, current density is not the bigger the better, at higher current densities, concentration polarization is serious, silver from
The speed that son is diffused near negative electrode is less than its depletion rate, and electrodepositing speed increase is smaller, and the increase of thickness of coating slows down.One
Denier current density oversteps the extreme limit current density, and negative electrode increased dramatically liberation of hydrogen speed due to famine discharge metal ion, cloudy
Extremely neighbouring pH value rises rapidly, and current efficiency reduction, silver/graphite composite deposite pattern becomes coarse or even occurs burning, sends out
The phenomenon such as black.Consider, control electric current density is 0.5A/dm2, now silver/graphite composite deposite is more smooth, densification.
Embodiment 7
Test group 1 is to test group 5：40g/L silver nitrates, 90g/L succimides, 40g/L potassium pyrophosphates, 20g/L graphite,
2g/L Tween-80s, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the composite silver plating liquor of~test group 5, carry out composite electrodeposition and prepare silver/graphite composite deposite.
The parameter of composite electrodeposition is set to：
Test group 1：Current density：0.5A/dm2；Mixing speed：600r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 2：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 3：Current density：0.5A/dm2；Mixing speed：1000r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 4：Current density：0.5A/dm2；Mixing speed：1200r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 5：Current density：0.5A/dm2；Mixing speed：1400r/min；Plating temperature：30 DEG C, electrodeposition time
30min。
Stirring has very important effect for composite electrodeposition.Stirring can accelerate the motion of graphite particulate,
Prevent occurring reuniting in electrodeposition process and settle, so that graphite particulate is evenly distributed in coating, while stirring can also have
Effect alleviates the concentration polarization near negative electrode, it is ensured that higher electrodepositing speed and quality of coating.Figure 10 is mixing speed change pair
The influence of silver/graphite thickness of multiple plating.It can be seen that the thickness of silver/graphite composite deposite is first with the increase of mixing speed
Reduce after increase, as shown in figure 11, silver/graphite composite deposite first becomes fine and close and then gone out again composite deposite pattern correspondingly
Existing loose porous phenomenon.Because when mixing speed is relatively low, graphite particulate can not it is fully dispersed in the plating solution, can be defeated
The graphite particulate for sending and being adsorbed onto cathode surface is less, and the thickness of silver/graphite composite deposite is smaller and surface porosity out-of-flatness, such as
Figure 11 a), b) shown in.With the increase of mixing speed, the movement rate increase of silver ion and graphite particulate, graphite particulate is defeated
The probability for sending and being adsorbed onto cathode surface is greatly increased, and deposition of the silver on graphite particulate surface is accelerated, silver/graphite composite deposite
Thickness increases therewith, and content of graphite also gradually increases in coating, while coating becomes smooth, densification, such as Figure 11 c), d) shown in.
But mixing speed is unsuitable excessive, and liquid stream and particulate are too strong to the souring of cathode surface when speed of agitator is excessive, and graphite is micro-
Grain has difficulty adhering to cathode surface or is easily washed desorption in the graphite particulate that cathode surface is in weakly stable state, is unfavorable for
Graphite particulate content is reduced in the co-deposition of silver and graphite, silver/graphite composite deposite, and thickness of coating declines therewith, the matter of coating
Amount is also relatively poor, such as Figure 11 e) shown in.In summary, it is 1200r/min to control mixing speed.
Embodiment 8
Test group 1 is to test group 5：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 20g/L graphite,
2g/L Tween-80s, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the composite silver plating liquor of~test group 5, carry out composite electrodeposition and prepare silver/graphite composite deposite.
The parameter of composite electrodeposition is set to：
Test group 1：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：20 DEG C, electrodeposition time
30min；
Test group 2：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 3：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：40 DEG C, electrodeposition time
30min；
Test group 4：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：50 DEG C, electrodeposition time
30min；
Test group 5：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：60 DEG C, electrodeposition time
30min。
Influence of the plating temperature to silver/graphite composite deposite is as shown in figure 12, with the rise of temperature, the thickness of composite deposite
Degree first increases to be reduced afterwards, and maximum is reached at 50 DEG C.When temperature is relatively low, rise temperature is conducive to migration and the stone of silver ion
The motion of black particulate, makes silver ion and the graphite particulate increase of arrival cathode surface, current efficiency and limiting current density increase,
Electrodeposition rate is accelerated, so that the thickness and content of graphite of coating are increased, silver/graphite composite deposite is also increasingly caused
It is close, such as Figure 13 a)~c) shown in.Figure 13 d), e) be respectively 50 DEG C and silver/graphite composite deposite at 60 DEG C pattern, therefrom can be with
When finding out that temperature reaches more than 50 DEG C, the crystallization of deposition of silver starts thicker, and silver/graphite composite deposite becomes coarse, thickness of coating
Also begin to decline.Because when temperature is too high, silver ion and graphite particulate movement rate are further speeded up, and cathode surface is difficult to
The silver ion and graphite particulate of high-speed motion are adsorbed, the souring of particle is added, so as to cause coating to become loose, thickness is plated
Degree declines, while the reduction of cathodic polarization make it that the crystallization of silver/graphite composite deposite is thick.In addition, temperature is too high so that plating solution is waved
Hair is serious, have impact on the content of plating solution active ingredient, the superposition of these multiple factors causes the performance of silver/graphite composite deposite
It is deteriorated.Therefore 40 DEG C of selection is plating temperature, and now the thickness and surface topography of silver/graphite composite deposite are preferable.
Embodiment 9
Test group 1 is to test group 5：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 20g/L graphite,
2g/L Tween-80s, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
After the composite silver plating liquor of~test group 5, carry out composite electrodeposition and prepare silver/graphite composite deposite.
The parameter of composite electrodeposition is set to：
Test group 1：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
10min；
Test group 2：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
30min；
Test group 3：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
60min；
Test group 4：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
90min；
Test group 5：Current density：0.5A/dm2；Mixing speed：800r/min；Plating temperature：30 DEG C, electrodeposition time
120min。
Figure 14 is influence of the change of electrodeposition time to silver/graphite thickness of multiple plating.It can be seen that electricity is heavy
Influence of the product time to thickness of coating is larger, linearly increases with the extension thickness of coating of electrodeposition time.Electro-deposition 60min
Thickness of coating is 10.5um, and electro-deposition 120min thickness of coating can reach 24um or so.Under Fig. 3-19 is different electrodeposition times
The surface topography of silver/graphite composite deposite.Figure 15 a), b) be respectively electro-deposition 10min, 30min coating morphology, now adsorb
And the quantity of graphite deposited in coating is less, composite deposite is loose porous, and electrodeposition time reaches that composite deposite starts after 60min
Become fine and close.But it is not that the longer the better for electrodeposition time, experiment finds the long composite deposite marginal surface meeting of electrodeposition time
There is fold peeling even obscission, Simultaneous Electrodeposition overlong time is also unfavorable for graphite particulate and deposited in cathode surface, because
It is difficult to long-time suspended dispersed in the plating solution for graphite particulate, part graphite particulate is precipitated to plating solution bottom gradually as time went on
Portion, so as to cause the content of graphite in silver/graphite composite deposite to reduce.In summary, the time of electro-deposition should be strictly controlled, really
Protect and obtain silver/graphite composite deposite of good performance.
Embodiment 10
Test group 1：40g/L silver nitrates, 90g/L succimides, 90g/L potassium pyrophosphates, 30g/L graphite, 3g/L tweens-
80th, potassium hydroxide：40g/L, ultrasound 1h after being sufficiently stirred for, is made silver/graphite composite silver plating liquor.
Silver plating solution：30g/L silver nitrates, 60g/L succimides, 60g/L potassium pyrophosphates, pH value：8.5, it is made silver-plated
Layer.
The copper sheet substrate and silver strip that carry out oil removing, polishing, ultrasonic wave cleaning, alkali cleaning and pickling are placed in above-mentioned test group 1
Composite silver plating liquor and silver plating solution after, carry out composite electrodeposition prepare silver/graphite composite deposite and silver plating solution.
The parameter of composite electrodeposition is set to：Test group：Current density：0.5A/dm2；Mixing speed：1200r/min；Apply
Plate temperature：40 DEG C, electrodeposition time 120min.
Figure 16 is the surface topography of silver coating and silver/graphite composite deposite.As can be seen from Figure 16, silver-plated layer surface is non-
Ordinary light is slided, smooth and densification.Silver/graphite composite deposite rough surface is in coralliform structure, and comparing will more dredge for silver coating
Pine, but its surface has no obvious burr and crackle.Figure 17 is the Cross Section Morphology of silver coating and silver/graphite composite deposite, equally may be used
Found out with contrasting, the more smooth densification in surface of silver coating, and silver/graphite composite deposite is then more loose, but itself and matrix
It is well combined, junction does not have any gap and hole.
In order to determine the main component of coating, Surface scan analysis is carried out to coating surface, EDS scanning results are shown in Figure 18.Figure
It is 18a) energy spectrum analysis of silver coating, Ag constituent contents are 100%, illustrates prepared silver coating without any impurity.Figure 18 b)
For the energy spectrum analysis of silver/graphite composite deposite, contained essential element is Ag elements and C element.The content of wherein C element reaches
7.01%, preliminary proof is that graphite particulate has been entered in composite deposite.Figure 19 is what silver/graphite composite deposite Surface scan was measured
The distribution map of Ag elements and C element, it can be seen that Ag elements and C element are evenly distributed in silver/graphite composite deposite, from
And it is more uniform to prove that graphite particulate is deposited in composite deposite, this is beneficial to obtain good coating performance.
Embodiment 11
Silver/graphite composite deposite and silver coating prepared by the test group 1 and silver plating solution of embodiment 10 carries out XRD points
Analysis, specifies the heterogeneous microstructure of material.Figure 20 is the XRD spectrum of silver coating and silver/graphite composite deposite.Figure 20 a) in five
Diffraction maximum position corresponds to (111), (200), (220), (311) and (222) crystal face of fine silver, the position of these diffraction maximums respectively
Collection of illustrative plates is characterized with the fine silver of face-centred cubic structure to match, the crystallization of silver coating shows (111) face preferential growth.In Figure 20 b)
Amplifier section can see, and occur in that a C (002) in the XRD spectrum of silver/graphite composite deposite in the position of 2 θ=26.55 °
Peak, it is believed that be the diffraction maximum of graphite.Because graphite particle mass fraction shared in composite deposite is very low, so this spreads out
Penetrate peak very weak.From the point of view of comprehensive two XRD spectrums, prepared silvering purity is higher, and adds graphite particle and do not change silver
Crystal structure, silver-colored selecting excellence evaluation is still (111) face.
Above example is silver/graphite composite silver plating liquor that the present invention is provided and preparation method thereof and electrodeposition technology system
The performance test analysis of standby obtained silver/graphite composite deposite and silver coating, including surface topography, Cross Section Morphology, Coating composition,
Institutional framework and growth mechanism, using silver/graphite composite silver plating liquor disclosed by the invention and preparation method thereof and electro-deposition
Technique can effectively be solved the current coating performance obtained using silver/graphite composite electrodeposition and be difficult to reach power equipment
The good conductive that needs, fastness, the technological deficiency of anti-corrosion and wear-resisting ability.The silver/graphite composite silver plating that the present invention is provided
The silver/graphite composite deposite that solution and preparation method thereof and electrodeposition technology are prepared has the surface shape of good coating
Looks, Cross Section Morphology, Coating composition, institutional framework and growth mechanism.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. silver/graphite composite silver plating liquor, it is characterised in that including：Water miscible Ag-containing compound, succimide, burnt phosphorus
Sour potassium, graphite and Tween 80.
2. silver/graphite composite silver plating liquor according to claim 1, it is characterised in that including following component：
3. silver/graphite composite silver plating liquor according to claim 2, it is characterised in that including following component：
4. the preparation method of silver/graphite composite silver plating liquor, it is characterised in that including：
1) water miscible Ag-containing compound, succimide and potassium pyrophosphate are mixed, obtains mixed solution；
2) by step 1) mixed solution mixed with graphite and Tween 80, dissolve graphite in ultrasound condition, obtain silver/graphite answer
Close silver-colored plating liquor.
5. preparation method according to claim 4, it is characterised in that the graphite is the graphite after removal of impurities.
6. preparation method according to claim 4, it is characterised in that step 1) PH of the mixed solution is 8.5-
10.5。
7. a kind of electrodeposition technology, it is characterised in that including：
1) silver/graphite composite silver plating liquor) is prepared；
2)) copper sheet and silver plate are set；
3)) by step 2) copper sheet and silver plate be placed in step 1) silver/graphite composite silver plating liquor in carry out electro-deposition, obtain
Silver/graphite composite deposite.
8. electrodeposition technology according to claim 7, it is characterised in that the current density of the electro-deposition is 0.2-
0.7A/dm2。
9. electrodeposition technology according to claim 7, it is characterised in that the mixing speed of the electro-deposition is 800-
1400r/min。
10. electrodeposition technology according to claim 7, it is characterised in that the plating temperature of the electro-deposition of the electro-deposition
For 20-60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710427598.6A CN107164791A (en) | 2017-06-08 | 2017-06-08 | Silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710427598.6A CN107164791A (en) | 2017-06-08 | 2017-06-08 | Silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107164791A true CN107164791A (en) | 2017-09-15 |
Family
ID=59826003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710427598.6A Pending CN107164791A (en) | 2017-06-08 | 2017-06-08 | Silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107164791A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267124A (en) * | 2018-10-19 | 2019-01-25 | 西安西电电气研究院有限责任公司 | A kind of silver coated graphite composite deposite and preparation method thereof |
| CN109440146A (en) * | 2018-11-28 | 2019-03-08 | 广东电网有限责任公司 | A kind of silver based on no cyanogen system-titanium carbide composite deposite and preparation method thereof |
| CN110983393A (en) * | 2019-12-27 | 2020-04-10 | 广东电网有限责任公司电力科学研究院 | Silver-niobium carbide composite coating and preparation method thereof |
| CN111705340A (en) * | 2019-03-18 | 2020-09-25 | 同和金属技术有限公司 | Composite plated article and method of making same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321049A (en) * | 1976-08-11 | 1978-02-27 | Mitsubishi Electric Corp | Low cyanide* high speed electroosilver plating solution |
| JPS5625992A (en) * | 1979-08-06 | 1981-03-12 | Shinko Electric Ind Co Ltd | Silver plating bath composition |
| CN101032750A (en) * | 2007-04-06 | 2007-09-12 | 深圳市危险废物处理站 | Method of producing sheet shaped silver-plated copper powder |
| CN101256903A (en) * | 2008-03-20 | 2008-09-03 | 上海交通大学 | Silver-graphitic electrical contact composite plating layer and method of preparing the same |
| CN105821465A (en) * | 2016-05-09 | 2016-08-03 | 南昌航空大学 | Preparation method for silver and graphene composite coating of cyanide-free system |
-
2017
- 2017-06-08 CN CN201710427598.6A patent/CN107164791A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321049A (en) * | 1976-08-11 | 1978-02-27 | Mitsubishi Electric Corp | Low cyanide* high speed electroosilver plating solution |
| JPS5625992A (en) * | 1979-08-06 | 1981-03-12 | Shinko Electric Ind Co Ltd | Silver plating bath composition |
| CN101032750A (en) * | 2007-04-06 | 2007-09-12 | 深圳市危险废物处理站 | Method of producing sheet shaped silver-plated copper powder |
| CN101256903A (en) * | 2008-03-20 | 2008-09-03 | 上海交通大学 | Silver-graphitic electrical contact composite plating layer and method of preparing the same |
| CN105821465A (en) * | 2016-05-09 | 2016-08-03 | 南昌航空大学 | Preparation method for silver and graphene composite coating of cyanide-free system |
Non-Patent Citations (3)
| Title |
|---|
| 方景礼: "《电镀添加剂理论与应用》", 30 April 2006, 国防工业出版社 * |
| 王丽丽: "无氰电沉积Ag-C合金", 《沈阳工业大学硕士学位论文》 * |
| 王立维: "分散剂对电沉积Ag/C复合层腐蚀性能的影响", 《材料保护》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267124A (en) * | 2018-10-19 | 2019-01-25 | 西安西电电气研究院有限责任公司 | A kind of silver coated graphite composite deposite and preparation method thereof |
| CN109440146A (en) * | 2018-11-28 | 2019-03-08 | 广东电网有限责任公司 | A kind of silver based on no cyanogen system-titanium carbide composite deposite and preparation method thereof |
| CN111705340A (en) * | 2019-03-18 | 2020-09-25 | 同和金属技术有限公司 | Composite plated article and method of making same |
| CN110983393A (en) * | 2019-12-27 | 2020-04-10 | 广东电网有限责任公司电力科学研究院 | Silver-niobium carbide composite coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107164791A (en) | Silver/graphite composite silver plating liquor and preparation method thereof and electrodeposition technology | |
| CN106283134B (en) | A kind of rare earth improvement Brush Plating silver plating liquid and its preparation process and application method | |
| Karwas et al. | Influence of boric acid on electrodeposition and stripping of Ni‐Zn alloys | |
| Nikolić et al. | Comparative morphological and crystallographic analysis of copper powders obtained under different electrolysis conditions | |
| CN109183102A (en) | A kind of Decentralized Impulse electro-plating method of heavy powder | |
| CN105714360A (en) | Alkaline graphene-nickel electroplating liquid, and preparation method and application thereof | |
| CN111074317B (en) | Surface treatment method of copper foil and copper foil material | |
| CN102051657A (en) | Preparation method of nano Sn/SiC composite plating | |
| Zhong et al. | Preparation of core-shell structured cobalt coated tungsten carbide composite powders by intermittent electrodeposition | |
| CN106048672B (en) | It is a kind of neutral without cyanogen Brush Plating silver plating liquid and its preparation process and application method | |
| CN104846417A (en) | Method for preparing Ni/CeO2 composite hydrogen evolution electrode | |
| CN108866586B (en) | Electroplating solution for electrodepositing ferrochromium alloy in trivalent chromium system and preparation method thereof | |
| CN102978679A (en) | Neodymium-iron-boron magnet nickel electroplating solution and use method thereof | |
| CN112952052B (en) | Preparation method of zinc/carbon nanotube foam composite material | |
| CN102534652A (en) | Preparation method for titanium base tin-doped lead dioxide electrode | |
| CN114622238B (en) | Preparation and application of transition metal-based hydrogen and oxygen evolution dual-functional electrode | |
| Xu et al. | Preparation and Electrocatalytic Activity of Nanocrystalline Ni–Mo–Co Alloy Electrode for Hydrogen Evolution | |
| CN111676498B (en) | Preparation method of cuprous oxide electrode | |
| CN109989080B (en) | Method for preparing high-tin bronze corrosion-resistant film on surface of steel by polyhydroxy ionic liquid electrodeposition | |
| CN110665509B (en) | FeNi with dendritic crystal morphology3Preparation method and application of phase electrocatalyst powder | |
| CN113445097A (en) | Fiber mesh-shaped magnesium oxide film and preparation method and application thereof | |
| CN107012485B (en) | A kind of electrolyte for making ultra-fine Fe-Ni alloy catalyst for ultrasound-electro-deposition coupling | |
| CN102367587B (en) | Method for treating excessive carbonate in cyanogens-containing gold plating solution | |
| CN107630240B (en) | Electroplate liquid of steel and iron parts cyanideless electro-plating tin bronze and preparation method thereof and electro-plating method | |
| CN111636090A (en) | Nickel-polytetrafluoroethylene coating and wear-resistant anti-static coil needle containing same |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170915 |