CN102534585B - Preparation method of Al-Ag alloy powder plated with silver chemically - Google Patents
Preparation method of Al-Ag alloy powder plated with silver chemically Download PDFInfo
- Publication number
- CN102534585B CN102534585B CN201210011252.5A CN201210011252A CN102534585B CN 102534585 B CN102534585 B CN 102534585B CN 201210011252 A CN201210011252 A CN 201210011252A CN 102534585 B CN102534585 B CN 102534585B
- Authority
- CN
- China
- Prior art keywords
- silver
- powder
- alloy powder
- concentration
- alloy
- 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.)
- Active
Links
Images
Abstract
The invention relates to a preparation method of Al-Ag alloy powder plated with silver chemically, belonging to the technical field of chemical plating. The method comprises the following steps of: taking Al-Ag alloy powder, corroding the Al-Ag alloy powder by a NaOH solution and washing; placing the alloy powder into a silver nitrate solution with a certain concentration to perform a precursor replacement reaction under room temperature and constant pressure; separating the powder out and placing the powder into a chemically silver-plating reducing liquid, and dropwise adding the silver-ammonia solution into the reducing liquid under an ultrasonic condition, wherein the reducing liquid consists of glucose, thiocarbamide, tartaric acid and absolute ethyl alcohol, and silver salt is a silver-ammonia solution; performing washing and vacuum drying after completing plating; and carrying out heat treatment on the silver-plated powder obtained in the above step under a vacuum condition at 240-600 DEG C for 2 hours, and finally, obtaining the Al-Ag powder with complete and uniform silver layer coating and good electrical conductivity. The process is simple and easy to operate, and the cost and energy consumption are reduced.
Description
Technical field
The present invention relates to the method for Al alloy powder surface clad silver, be specifically related to a kind of on Al alloy powder surface directly by the method clad metal silver of electroless plating, obtain the preparation method of silver-colored metallized aluminum alloy powder, belong to the electroless plating technology field.
Background technology
Argent has the characteristics such as good electroconductibility and ornamental, germ resistance, weldability, reflective, solidity to corrosion, in fields such as aerospace, optics instrument, radio communication equipment, laser, have a wide range of applications, but silver has easy migration, the shortcoming such as expensive simultaneously, and this has restricted silver-colored use to a certain extent.At other materials matrix surface coated with silver, both can save ag material, and can show the property of argent, and can give full play to the effect of bi-material, thereby the coated with silver material becomes the focus that people pay close attention to.The silver-colored coating material of having reported at present is of a great variety, as silver-plated copper powder can be used as electric slurry, electrode materials, catalyzer and electromagnetic shielding material etc.; Silver-plated nickel powder is as the stopping composition of elastic resin system, and the production high-performance radio-frequency is disturbed and the electromagnetic interference shield conductive spacer, and some other products that require to have excellent conductive performance; Silver-plated thick film circuit material, electrical condenser, packing ring and the sealing material of can be used as of hollow or solid glass microsphere surface; Silvered aluminum powder, as a kind of functional properties conductivity filler, can make an addition to it coating, tackiness agent, printing ink, plastics, rubber, is widely used in the fields such as electrically conducting coating, electromagnetic shielding material, absorbing material, anti-electrostatic.With other silver coating materials, compare, the advantage such as silvered aluminum powder has that light weight, cost are lower, good corrosion resistance, look shallow, have and decorate and high reflection double effects.
The Al powder is amphoteric metal, with other metallographic phase comparatively speaking, the plating difficulty is large.At present the preparation method of the silvered aluminum powder of report mainly contains three kinds, a kind of be the Al powder after the overactivation sensitization, adopt redox reaction directly to carry out chemical silvering, the method gained powder homogeneity is not fine, and pretreatment technology is loaded down with trivial details.Another kind is that the Al powder carries out electroless copper after surface preparation, more silver-plated by replacement(metathesis)reaction, covers layer of copper in the alloy powder silver layer that the method makes, and the copper stratification changes in silver-plated process, very easily oxidized; Also having a kind of method is to have the material of catalytic activity at Al powder surface coating one deck polyamines or other, then carry out chemical silvering on the active substance surface, this method pretreatment technology is loaded down with trivial details, and the gained powder is the Al-X-Ag composite powder, has good integrity.
Summary of the invention
Problem to be solved by this invention is the intermediate layer that overcomes above-mentioned existence, and it is raw material that a kind of Al-Ag of take alloy powder is provided, and directly carries out the preparation method of chemical silvering on its surface, and the method facility simple to operate, energy consumption are low.
The preparation method of Al-Ag powdered alloy chemical silvering, is characterized in that, mainly comprises the following steps:
1) preparation of Al-Ag alloy powder: adopt the standby Al-Ag alloy powder of vacuum atomizing legal system; Then Al-Ag powdered alloy pre-treatment: get the Al-Ag alloy powder, the NaOH solution corrosion that is 0.005-0.03wt% by concentration, washing;
2) the Al-Ag alloy powder is silver-plated: under the room temperature condition of normal pressure, alloy powder is placed in to silver nitrate solution and carries out forerunner's replacement(metathesis)reaction; After displacement 30min, this powder is separated, be placed in the chemical silvering reduced liquid, this reduced liquid is comprised of glucose, thiocarbamide, tartrate, dehydrated alcohol, and silver salt is silver ammino solution, during under ultrasound condition, silver ammino solution dropwise splashes into reduced liquid; After plating finishes, washing, vacuum-drying;
3) the silver-plated powder last processing of Al-Ag alloy powder silvering powder: to step 3) obtained is heat-treated, vacuum condition or protection of inert gas, 240-600 ℃, 2h.
Step 1) in preferably in the Al-Ag alloy powder silver content be 0.5-10wt%; Step 2) in, silver nitrate solution concentration is preferably 10wt%, concentration 27g/L, the concentration 2mg/L of thiocarbamide, the tartaric concentration 4g/L of preferred glucose in reduced liquid; The preferred 50g/L of silver ammino solution concentration; When silver ammino solution splashes in reduced liquid, pH is 11.5-12.5, temperature 25-35 ℃, reaction 20-50min.
Technical solution of the present invention is: powder carries out the processing of deoxidation film, has also reached the effect of alligatoring simultaneously, makes the effective collision area of powder and silver salt increase, and has increased the contact surface between coating and base material; Then carry out forerunner's replacement(metathesis)reaction, after forerunner's replacement(metathesis)reaction, the surface coated skim silver of alloy powder particle has self-catalysis, can directly carry out chemical silvering, powder after silver-plated is heat-treated, can increase the sticking power of silver layer, make silver layer homogenizing more simultaneously, reduce resistivity.Flow process as shown in Figure 1.
The invention has the advantages that: select the Al-Ag alloy powder as silver-plated matrix, in forerunner's replacement process, alloy powder is interior in metastable Ag
2al is conducive to mutually the forming core of surperficial cenotype silver particle and grows up, and simultaneously, due to the enrichment of most of impurity atoms at grain boundaries, has caused crystal boundary and intergranule that potential difference is arranged, and forms microbattery, is conducive to the carrying out of forerunner's replacement(metathesis)reaction.In addition, after powdered alloy adopts the NaOH solution corrosion, both reach the effect of removing oxide film, increased again the contact surface between coating and base material, be conducive to improve the bonding strength of coating.And after forerunner's replacement ag plating, the silver on alloy powder surface has self-catalysis, does not need to activate sensitization, just can directly carry out chemical silvering, the powder after silver-plated is heat-treated, improve sticking power and the homogeneity of silver layer.Finally obtain the Al-Ag powder that the silver layer coating is complete evenly, conductivity is good.The simple easy handling of technique, reduced cost and energy consumption.
The accompanying drawing explanation
Fig. 1 is reaction principle schema of the present invention;
Fig. 2 be atomization produce be spherical Al-Ag alloy powder figure;
Fig. 3 is the Al-Ag alloy powder back scattering figure that atomization is produced;
Fig. 4 is the Al-Ag powder after forerunner's replacement ag plating, and surface coats skim silver;
Al-Ag alloy powder after Fig. 5 electroless plating, surface coats complete, even, fine and close, smooth;
When Fig. 6 is forerunner's replacement ag plating, the silver layer deposition morphology of different time, at first silver layer starts enrichment figure from grain boundaries;
When Fig. 7 is electroless plating, due to silver-colored self-catalysis, silver continues deposition, and there is no silver-colored place, and silver layer does not continue the figure of deposition.
Embodiment
Explain in detail the present invention below in conjunction with drawings and Examples, but the present invention is not limited to following examples.
Following examples reaction principle schema is shown in Fig. 1, and the spherical Al-Ag alloy powder that is that atomization is produced is shown in Fig. 2, and its back scattering figure is shown in Fig. 3, alloy phase Ag
2al is distributed in grain boundaries; Al-Ag powder after forerunner's replacement ag plating, its surface coats skim silver, sees Fig. 4; Al-Ag alloy powder after electroless plating, surface coats complete, even, fine and close, smooth, sees Fig. 5; During forerunner's replacement ag plating, the silver layer deposition morphology of different time, at first silver layer starts enrichment from grain boundaries, sees Fig. 6; Forerunner's replacement(metathesis)reaction 15min, carry out the silver layer deposition morphology of electroless plating, and during electroless plating, due to silver-colored self-catalysis, silver continues deposition, and there is no silver-colored place, and silver layer does not continue deposition, sees Fig. 7.
Embodiment 1
1) preparation of Al-Ag alloy powder: the powdered alloy that the spray silver content is 1wt%.
2) pre-treatment of Al-Ag alloy powder: get the 2g alloy powder, the NaOH solution corrosion that is 0.02wt% by concentration, see while having micro bubble to separate out, and the alloy powder after the striping alligatoring is washed 3 times with deionized water rapidly.
3) Al-Ag alloy powder contracted payment: under the room temperature condition of normal pressure, alloy powder is placed in to the silver nitrate solution that concentration is 10wt% and carries out forerunner's replacement(metathesis)reaction; After displacement 30min, this powder is separated, be placed in the chemical silvering reduced liquid of 100ml, this reduced liquid is comprised of glucose (27g/L), thiocarbamide (2mg/L), tartrate (4g/L), dehydrated alcohol etc., silver salt is silver ammino solution (50g/L), in under ultrasound condition, the silver ammino solution of 50ml dropwise being splashed into to reduced liquid, its pH is 11.5,30 ℃ of temperature, reaction 20min; After plating finishes, washing, vacuum-drying.
4) the last processing of Al-Ag alloy powder silvering powder: silver-plated powder is heat-treated, and temperature is 300 ℃, 400 ℃, 500 ℃ or 600 ℃, under vacuum condition, and insulation 2h.
Embodiment 2
1) preparation of Al-Ag alloy powder: the powdered alloy that the spray silver content is 3wt%.
2) pre-treatment of Al-Ag alloy powder: get the 4g alloy powder, the NaOH solution corrosion that is 0.03wt% by concentration, see while having micro bubble to separate out, and the alloy powder after the striping alligatoring is washed 3 times with deionized water rapidly.
3) Al-Ag alloy powder contracted payment: under the room temperature condition of normal pressure, alloy powder is placed in to the silver nitrate solution that concentration is 5wt% and carries out forerunner's replacement(metathesis)reaction; After displacement 30min, this powder is separated, be placed in the chemical silvering reduced liquid of 100ml, this reduced liquid is comprised of glucose (27g/L), thiocarbamide (2mg/L), tartrate (4g/L), dehydrated alcohol etc., silver salt is silver ammino solution (50g/L), in under ultrasound condition, the silver ammino solution of 50ml dropwise being splashed into to reduced liquid, its pH is 12,30 ℃ of temperature, reaction 30min; After plating finishes, washing, vacuum-drying.
4) the last processing of Al-Ag alloy powder silvering powder: silver-plated powder is heat-treated, and temperature is respectively 300 ℃, 400 ℃, 500 ℃ or 600 ℃, under vacuum condition, and insulation 2h.
Embodiment 3
1) preparation of Al-Ag alloy powder: the powdered alloy that the spray silver content is 5wt%.
2) pre-treatment of Al-Ag alloy powder: get the 3g alloy powder, the NaOH solution corrosion that is 0.02wt% by concentration, see while having micro bubble to separate out, and the alloy powder after the striping alligatoring is washed 3 times with deionized water rapidly.
3) Al-Ag alloy powder contracted payment: under the room temperature condition of normal pressure, alloy powder is placed in to the silver nitrate solution that concentration is 10wt% and carries out forerunner's replacement(metathesis)reaction; After displacement 40min, this powder is separated, be placed in the chemical silvering reduced liquid of 100ml, this reduced liquid is comprised of glucose (27g/L), thiocarbamide (2mg/L), tartrate (4g/L), dehydrated alcohol etc., silver salt is silver ammino solution (50g/L), in under ultrasound condition, the silver ammino solution of 50ml dropwise being splashed into to reduced liquid, its pH is 11.5,35 ℃ of temperature, reaction 30min; After plating finishes, washing, vacuum-drying.
4) the last processing of Al-Ag alloy powder silvering powder: silver-plated powder is heat-treated, and temperature is respectively 300 ℃, 400 ℃, 500 ℃ or 600 ℃, under vacuum condition, and insulation 2h.
The resistivity of powder in the present embodiment, the resistivity before and after the silver-plated Al-Ag powdered alloy thermal treatment that the matrix silver content is 5wt%, through Overheating Treatment, powder resistivity descends gradually, and thermal treatment temp is higher, and resistivity is lower, specifically in Table 1.
Embodiment 4
1) preparation of Al-Ag alloy powder: the powdered alloy that the spray silver content is 5wt%.
2) pre-treatment of Al-Ag alloy powder: get the 3g alloy powder, the NaOH solution corrosion that is 0.02wt% by concentration, see while having micro bubble to separate out, and the alloy powder after the striping alligatoring is washed 3 times with deionized water rapidly.
3) Al-Ag alloy powder contracted payment: under the room temperature condition of normal pressure, alloy powder is placed in to the silver nitrate solution that concentration is 8wt% and carries out forerunner's replacement(metathesis)reaction; After displacement 40min, this powder is separated, be placed in the chemical silvering reduced liquid of 100ml, this reduced liquid is comprised of glucose (27g/L), thiocarbamide (2mg/L), tartrate (4g/L), dehydrated alcohol etc., silver salt is silver ammino solution (50g/L), in under ultrasound condition, the silver ammino solution of 50ml dropwise being splashed into to reduced liquid, its pH is 11.5,35 ℃ of temperature, reaction 30min; After plating finishes, washing, vacuum-drying.
4) the last processing of Al-Ag alloy powder silvering powder: silver-plated powder is heat-treated, and temperature is respectively 300 ℃, 400 ℃, 500 ℃ or 600 ℃, under vacuum condition, and insulation 2h.
Embodiment 5
1) preparation of Al-Ag alloy powder: the powdered alloy that the spray silver content is 9wt%.
2) pre-treatment of Al-Ag alloy powder: get the 2g alloy powder, the NaOH solution corrosion that is 0.025wt% by concentration, see while having micro bubble to separate out, and the alloy powder after the striping alligatoring is washed 3 times with deionized water rapidly.
3) Al-Ag alloy powder contracted payment: under the room temperature condition of normal pressure, alloy powder is placed in to the silver nitrate solution that concentration is 10wt% and carries out forerunner's replacement(metathesis)reaction; After displacement 40min, this powder is separated, be placed in the chemical silvering reduced liquid of 100ml, this reduced liquid is comprised of glucose (27g/L), thiocarbamide (2mg/L), tartrate (4g/L), dehydrated alcohol etc., silver salt is silver ammino solution (50g/L), in under ultrasound condition, the silver ammino solution of 50ml dropwise being splashed into to reduced liquid, its pH is 11.5,25 ℃ of temperature, reaction 35min; After plating finishes, washing, vacuum-drying.
4) the last processing of Al-Ag alloy powder silvering powder: silver-plated powder is heat-treated, and temperature is respectively 300 ℃, 400 ℃, 500 ℃ or 600 ℃, under vacuum condition, and insulation 2h.
Claims (2)
1.Al-Ag the preparation method of powdered alloy chemical silvering, is characterized in that, comprises the following steps:
(1) preparation of Al-Ag alloy powder: adopt the standby Al-Ag alloy powder of vacuum atomizing legal system; Then Al-Ag powdered alloy pre-treatment: get the Al-Ag alloy powder, the NaOH solution corrosion that is 0.005-0.05wt% by concentration, washing;
(2) the Al-Ag alloy powder is silver-plated: under the room temperature condition of normal pressure, alloy powder is placed in to silver nitrate solution and carries out forerunner's replacement(metathesis)reaction; After displacement 30min, this powder is separated, be placed in the chemical silvering reduced liquid, this reduced liquid is comprised of glucose, thiocarbamide, tartrate, dehydrated alcohol, and silver salt is silver ammino solution, during under ultrasound condition, silver ammino solution dropwise splashes into reduced liquid; After plating finishes, washing, vacuum-drying;
(3) the last processing of Al-Ag alloy powder silvering powder: the silver-plated powder that step (3) is obtained is heat-treated, vacuum condition or protection of inert gas, 240-600 ℃, 2h;
In step (1), Al-Ag alloy powder silver content is 0.5-10wt%.
2. according to the method for claim 1, it is characterized in that, in step (2), silver nitrate solution concentration is 10wt%, the concentration 2mg/L of the concentration 27g/L of glucose, thiocarbamide, tartaric concentration 4g/L in reduced liquid; The preferred 50g/L of silver ammino solution concentration; When silver ammino solution splashes in reduced liquid, pH is 11.5-12.5, temperature 25-35 ℃, reaction 20-50min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210011252.5A CN102534585B (en) | 2012-01-15 | 2012-01-15 | Preparation method of Al-Ag alloy powder plated with silver chemically |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210011252.5A CN102534585B (en) | 2012-01-15 | 2012-01-15 | Preparation method of Al-Ag alloy powder plated with silver chemically |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102534585A CN102534585A (en) | 2012-07-04 |
| CN102534585B true CN102534585B (en) | 2014-01-01 |
Family
ID=46342576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210011252.5A Active CN102534585B (en) | 2012-01-15 | 2012-01-15 | Preparation method of Al-Ag alloy powder plated with silver chemically |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102534585B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104005010B (en) * | 2014-04-14 | 2016-03-02 | 北京工业大学 | A kind of conductive filler material preparation method of silver-colored alclad powdered alloy |
| CN111531168A (en) * | 2020-04-08 | 2020-08-14 | 西安工程大学 | Preparation method of silver-coated aluminum material for electromagnetic shielding |
| CN114932218B (en) * | 2022-05-30 | 2023-08-04 | 暨南大学 | Method for reducing evaporation of 3D printing zinc powder to form zinc-silver alloy through chemical silver plating |
| CN114700489B (en) * | 2022-06-07 | 2022-08-12 | 天津德恒永裕金属表面处理有限公司 | Preparation process of silver-coated aluminum powder and silver-coated aluminum powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425783A (en) * | 2002-12-31 | 2003-06-25 | 西安理工大学 | High temperature resistant anti-oxidant base metal copper-silver alloy composition and its producing method |
| 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 |
| CN101439305A (en) * | 2008-01-08 | 2009-05-27 | 北京科技大学 | Composite material using nano inorganic powder as surface with autocatalytic activity and preparation method thereof |
| CN102248159A (en) * | 2011-07-26 | 2011-11-23 | 北京工业大学 | Preparation method of silver-coated aluminum powder |
-
2012
- 2012-01-15 CN CN201210011252.5A patent/CN102534585B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425783A (en) * | 2002-12-31 | 2003-06-25 | 西安理工大学 | High temperature resistant anti-oxidant base metal copper-silver alloy composition and its producing method |
| 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 |
| CN101439305A (en) * | 2008-01-08 | 2009-05-27 | 北京科技大学 | Composite material using nano inorganic powder as surface with autocatalytic activity and preparation method thereof |
| CN102248159A (en) * | 2011-07-26 | 2011-11-23 | 北京工业大学 | Preparation method of silver-coated aluminum powder |
Non-Patent Citations (6)
| Title |
|---|
| 嵇永康等..镀金及金合金.《贵金属和稀有金属电镀》.化学工业出版社,2009,(第1版),第51页.. * |
| 嵇永康等。.镀金及金合金.《贵金属和稀有金属电镀》.化学工业出版社,2009,(第1版),第51页。. |
| 徐锐.铜-银、镍-银核-壳型双金属粉及锆酸钙包覆镍粉的研制.《 中国博士学位论文全文数据库》.2010,全文。. |
| 李传友等..化学镀法制备Ag/Al复合粉末.《功能材料》.2010,第41卷(第9期),第1525-1528页. * |
| 李传友等。.化学镀法制备Ag/Al复合粉末.《功能材料》.2010,第41卷(第9期),第1525-1528页. |
| 铜-银、镍-银核-壳型双金属粉及锆酸钙包覆镍粉的研制;徐锐;《 中国博士学位论文全文数据库》;20100315;全文。 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102534585A (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105273689A (en) | Novel multi-element structure composite conductive filling material | |
| CN102534585B (en) | Preparation method of Al-Ag alloy powder plated with silver chemically | |
| CN102311233B (en) | Surface chemical plating treatment process for hollow glass microsphere, plated metal hollow glass microsphere and application thereof | |
| CN102328076A (en) | Preparation method of silver coated copper powder for electronic slurry | |
| CN102212801B (en) | Chemical silvering method for PS (polystyrene) microspheres | |
| CN102407329B (en) | Method for preparing nickel-silver coreshell structure nanoparticles | |
| CN103469182B (en) | Palladium-free chemical copper-plating method on graphite nanosheet surface | |
| CN108118528B (en) | Flexible conductive textile | |
| CN105063580B (en) | A kind of preparation method of electromagnetic shielding material conductive rubber nickel coated graphite powder | |
| CN109423636B (en) | Preparation method of secondary silver-plated high-conductivity filler | |
| CN105603477B (en) | A kind of ABS plastic electro-coppering pretreatment process | |
| CN109957144B (en) | Preparation method of conductive filler with silver-plated surface | |
| CN101469075B (en) | Method for preparing two-sided polyimide / silver compound film | |
| CN102672168B (en) | Preparation method for core-shell structural nickel-silver bimetallic powder | |
| CN105225768B (en) | A kind of preparation method of the flexible silver-plated functional particles conducting film of sandwich structure | |
| CN102936726A (en) | Multiple-layer metallization processing method for epoxy resin package electronic component surface | |
| CN103491716A (en) | Pattern electrically conductive circuit structure and forming method thereof | |
| CN104164784B (en) | Preparation method of composite fiber with high thermal conductivity through coating graphene on chemical fiber surface | |
| CN103008675A (en) | Preparation method of nickel coated copper composite powder | |
| CN103103590A (en) | Direct-electroplating conductive liquid and preparation method thereof | |
| CN106435541B (en) | A kind of aluminum grain refiner and preparation method thereof based on titanium carbonitride | |
| CN102858084B (en) | Flexible base material and preparation method thereof | |
| CN111763930B (en) | Non-palladium activated copper plating process and sensitizer and activator thereof | |
| CN101974741B (en) | Method for performing chemical plating on surface of polytetrafluoroethylene thin film | |
| CN114105494B (en) | Coupling agent compounded ionic nickel palladium-free activation solution and method for preparing conductive basalt fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |