CN109128148A - A kind of preparation method of graphene aluminum matrix composite - Google Patents
A kind of preparation method of graphene aluminum matrix composite Download PDFInfo
- Publication number
- CN109128148A CN109128148A CN201810806220.1A CN201810806220A CN109128148A CN 109128148 A CN109128148 A CN 109128148A CN 201810806220 A CN201810806220 A CN 201810806220A CN 109128148 A CN109128148 A CN 109128148A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- matrix composite
- aluminum matrix
- metallic particles
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
Abstract
The present invention is a kind of preparation method of graphene aluminum matrix composite, belongs to field of nanometer material technology.A kind of preparation method of graphene aluminum matrix composite, comprising the following steps: after being stirred graphene oxide water solution and metallic particles at 0-30 DEG C, fast spraying drying is carried out by centrifugal spray drying tower, obtains the graphene aluminum matrix composite；Wherein, the metallic particles is aluminium powder or Al alloy powder.A kind of preparation method of graphene aluminum matrix composite of the present invention, provide it is a kind of it is environmental-friendly, can continuous mass production scheme, wherein control mixing temperature and rate of drying and drying temperature, the degree of oxidation of controllable metal powder, make the composite material low oxygen content of preparation, preparation cost minimizes, and can further enhance metallic matrix electric conductivity, meanwhile the preparation process can be used for industrialized production.
Description
Technical field
The invention belongs to field of nanometer material technology, and in particular to a kind of preparation method of graphene aluminum matrix composite.
Background technique
Graphene be one kind by carbon atom with sp2The honeycomb flat film that hybrid form is formed, thickness is in a nanometer
Hereinafter, graphene is the nano material that hitherto known world is most thin, most hard, Young's modulus is up to 1.01TPa, tension
Intensity is up to 130GPa, is more than 100 times of structural steel, and thermal coefficient is up to 5300W/mK, is much higher than copper, also above carbon nanometer
Pipe and diamond.Because graphene has minimum density, highest mechanical property, highest heating conduction and minimum heat swollen
Swollen performance, graphene are regarded as a kind of very promising reinforcement from birth.
Aluminum matrix composite has many advantages, such as high specific strength, high specific stiffness, and easily prepared and processing, therefore its hair
It opens up all especially prominent in entire field of metal matrix composite.Improve the research of resin and ceramic performance using graphene at present
The most extensively, but it is relatively fewer using the industrial application of graphene aluminum matrix composite.Main cause is multiple for graphene aluminium base
There is also two big technical bottlenecks for condensation material industrialized production: first is that the problem that graphene is evenly dispersed in aluminum substrate；Second is that
Existing laboratory process condition is harsh, complicated, and industrialized production is relatively difficult to achieve.
There is prior art CN104862508B it is found that being dispersed in alcohol liquid by graphene powder, by Al alloy powder
End is added in graphene solution, is packed into ball grinder and carries out mechanical ball mill, and mixed liquor is packed into beaker after a certain period of time by ball milling
It is placed in baking oven and dries, obtain graphene/aluminum alloy composite powder.But there is problems in that firstly, graphene is as powder
It is dispersed in alcohol liquid, graphene itself can occur to reunite or be overlapped in being dried to powder process, the graphene within three layers
The more difficult preparation of powder；Secondly, alcohol is defined as Class A binomial as inflammable explosive article, in the fire risk of production, to big rule
Mould production is promoted limited；Again, graphene ethanol solution is mixed by the way of mechanical ball mill with Al alloy powder, to steel ball
Material is more demanding, and it is poor to introduce the more and mixed effect of impurity；Last mixed alcohol liquid is placed in baking oven, is pacified
Full risk increases, and the ethyl alcohol evaporated in alcohol volatilization process has a certain impact to environment.
There is prior art CN105215353B it is found that metallic particles is added in graphene oxide water solution, metallic particles
It is mixed with graphene oxide and in-situ reducing occurs and reacted, obtain evenly dispersed metallic particles/graphene mixture；It is mixed to this
It closes object to be filtered by vacuum, is dried to obtain the Metal/grapheme composite material powder of redox graphene coating metal particles.
But the technology has the following problems: being related to aluminium gold metal particles and graphene slant acidity solution long-time room temperature for the method
Under mixing condition, a large amount of oxidation reaction can occur for aluminium gold metal particles, and the metallic aluminium prepared/graphene composite material powder contains
Oxygen amount is higher, fails to play humidification to material electric conductivity itself；In addition, metallic particles/graphene that this scheme uses is mixed
Liquid vacuumizing filtration drying means is closed, industrialized production can not be promoted effectively, and in vacuumizing filtration is dry, graphite
The part that alkene film fails cladding with metal ball body is easily reunited, and graphene enhancing metallic matrix fails to play efficient effect.
In view of this, the present invention proposes a kind of preparation method of graphene aluminum matrix composite, this method has been prepared low
The graphene aluminum matrix composite of oxygen content, promotes the electric conductivity of material, and solves continuous chemical industry mass production low efficiency
The problems such as.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of graphene aluminum matrix composite, which makes graphene
It is evenly dispersed in aluminum substrate, it is mixed at low temperature by graphene oxide water solution with aluminium powder, it is fast using spray drying technology
Fast wink-dry prepares the graphene aluminum matrix composite of low oxygen content, promotes the electric conductivity of material, further the company of solution
The problems such as continuous chemical industry mass production low efficiency.
To achieve the goals above, used technical solution are as follows:
A kind of preparation method of graphene aluminum matrix composite, comprising the following steps:
After graphene oxide water solution and metallic particles are stirred at 0-30 DEG C, by centrifugal spray drying tower into
Row fast spraying is dry, obtains the graphene aluminum matrix composite；
Wherein, the metallic particles is aluminium powder or Al alloy powder.
Further, the graphene aluminum matrix composite is made of metallic particles and graphene, and the metal
Grain is coated by graphene uniform.
Further, the mass ratio of the graphene oxide and metallic particles is 0.001-0.05:1.
Further, the metallic particles partial size is 1-100 μm.
Further, the mixing speed 150-300r/min, time 0.5-8h.
Further, the graphene oxide sheet diameter size is 50-300 microns, and 80% or more within 3 layers.
Further, the graphene oxide is the graphene oxide being prepared using hummers method is improved
Liquid.
Further, in the spray-drying process: charging rate 30-100rpm, inlet air temperature 120-200
DEG C, leaving air temp is 90-110 DEG C, and atomizer revolving speed is 10000-24000r/min.
Compared with prior art, the beneficial effects of the present invention are:
1, the preparation method of a kind of graphene aluminum matrix composite of the present invention, passes through graphene aqueous solution and aluminium powder
It mixes, is further decreased because of the aluminium powder oxidation in water phase mixed process at low temperature；Meanwhile mixed graphene coated aluminium powder
Slurry liquid reduces graphene aluminium-based powder composite in drying stage oxide minimum by centrifugal spray wink-dry moisture.
2, the preparation method of a kind of graphene aluminum matrix composite of the present invention passes through graphene oxide and aluminium powder
Water phase mixing, and using to mixed liquor centrifugal spray drying combination, designing the suitable process of centrifugal spray drying, including into
Air temperature, atomization disk rotating speed, wind speed etc., minimize the composite material oxygen content of preparation, preparation cost minimizes, simply
Preparation process condition provide feasibility as industrialized production.
3, the preparation method of a kind of graphene aluminum matrix composite of the present invention, passes through graphene oxide aqueous phase solution
It being quickly stirred under Al alloy powder low temperature, mixed liquor enters in centrifugal spray drying tower through peristaltic pump to be spray-dried,
Graphene aluminum-based powder material is obtained, this material can be widely applied to the field of powder metallurgy such as 3D printing, Electronic Packaging, the method
Low cost, safe and efficient is realized, extensive implementation is provided for industrialized production and possibility is provided.
Detailed description of the invention
Fig. 1 is graphene aluminum matrix composite stereoscan photograph prepared by the embodiment of the present invention 1.
Specific embodiment
In order to which the present invention is further explained, a kind of preparation method of graphene aluminum matrix composite, reaches expected invention mesh
, in conjunction with the preferred embodiment, to a kind of preparation method of graphene aluminum matrix composite proposed according to the present invention, tool
Body embodiment, structure, feature and its effect, detailed description is as follows.In the following description, different " embodiment " or " real
Apply example " refer to be not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can be by appointing
What suitable form combination.
Before elaborating a kind of preparation method of graphene aluminum matrix composite of the present invention, it is necessary to in the present invention
The raw material referred to and method etc. are described further, to reach better effect.
The raw material that the present invention uses are commercially available.
The graphene oxide liquid that graphene oxide is prepared using hummers method is improved in the present invention, piece diameter size
It is 50-300 microns, 80% or more within 3 layers；
Metallic particles in the present invention is aluminium powder or Al alloy powder, and grain diameter is 1-100 μm.
After having understood above-mentioned raw materials and method etc., below in conjunction with specific embodiment to a kind of graphene aluminium of the present invention
The preparation method of based composites is further described in detail:
Embodiment 1.
Specific steps are as follows:
(1) at 10 DEG C, the 2L graphene oxide water solution prepared (graphene oxide solid content is 4g/L) is placed in
It is stirred in glass kettle with low temperature oil bath collet, 2kg pure aluminium powder is taken to be added in graphene oxide water solution, in turning for 150r/min
Under speed, continue to stir lower 3h；
(2) by the graphene aluminium powder slurry in step (1) after mixing dispersion under low temperature stirring by peristaltic pump enter from
Heart spray drying tower, charging rate 45rpm, inlet air temperature are 150 DEG C, and leaving air temp is 100 DEG C, and atomizer revolving speed is
22000r/min obtains graphene aluminium-based powder composite, which is made of metallic particles and graphene,
And the metallic particles coats (as shown in Figure 1) by graphene uniform.
A kind of preparation method of graphene aluminum matrix composite described in the embodiment of the present invention provides a kind of environment friend
It is good, can continuous mass production scheme, wherein control mixing temperature and rate of drying and drying temperature, can control the oxygen of metal powder
Change degree makes the composite material low oxygen content of preparation, and preparation cost minimizes, and can further enhance metallic matrix electric conductivity
Can, meanwhile, which can be used for industrialized production.
Embodiment 2.
Specific steps are as follows:
(1) at 3 DEG C, the 5L graphene oxide water solution prepared (graphene oxide solid content is 2g/L) is placed in band
It is stirred in the glass kettle of low temperature oil bath collet, takes 3kg pure aluminium powder to be added in graphene oxide water solution, in the revolving speed of 200r/min
Under, continue to stir lower 5h；
(2) by the graphene aluminium powder slurry in step (1) after mixing dispersion under low temperature stirring by peristaltic pump enter from
Heart spray drying tower, charging rate 50rpm, inlet air temperature are 180 DEG C, and leaving air temp is 110 DEG C, and atomizer revolving speed is
24000r/min obtains graphene aluminium-based powder composite, which is made of metallic particles and graphene,
And the metallic particles is coated by graphene uniform.
A kind of preparation method of graphene aluminum matrix composite described in the embodiment of the present invention provides a kind of environment friend
It is good, can continuous mass production scheme, wherein control mixing temperature and rate of drying and drying temperature, can control the oxygen of metal powder
Change degree makes the composite material low oxygen content of preparation, and preparation cost minimizes, and can further enhance metallic matrix electric conductivity
Can, meanwhile, which can be used for industrialized production.
Embodiment 3.
Specific steps are as follows:
(1) at 2 DEG C, the 2L graphene oxide water solution prepared (graphene oxide solid content is 5g/L) is placed in band
It is stirred in the glass kettle of low temperature oil bath collet, takes 2kg pure aluminium powder to be added in graphene oxide water solution, in the revolving speed of 150r/min
Under, continue to stir lower 8h；
(2) by the graphene aluminium powder slurry in step (1) after mixing dispersion under low temperature stirring by peristaltic pump enter from
Heart spray drying tower, charging rate 60rpm, inlet air temperature are 120 DEG C, and leaving air temp is 110 DEG C, and atomizer revolving speed is
20000r/min obtains graphene aluminium-based powder composite, which is made of metallic particles and graphene,
And the metallic particles is coated by graphene uniform.
The raw material of embodiment 1-3 and product are subjected to oxygen content test, the results are shown in Table 1:
Table 1
As shown in Table 1, the oxygen content of the product of embodiment 1-3 preparation is more oxygen-containing than the product for preparing in air drying technique
Measure it is low, respectively low 43.02%, 38.55% and 39.55%, the oxygen content of product is substantially reduced.
A kind of preparation method of graphene aluminum matrix composite described in the embodiment of the present invention provides a kind of environment friend
It is good, can continuous mass production scheme, wherein control mixing temperature and rate of drying and drying temperature, can control the oxygen of metal powder
Change degree makes the composite material low oxygen content of preparation, and preparation cost minimizes, and can further enhance metallic matrix electric conductivity
Can, meanwhile, which can be used for industrialized production.
Embodiment 4.
Specific steps are as follows:
(1) at 30 DEG C, the 2L graphene oxide water solution prepared (graphene oxide solid content is 1g/L) is placed in
It is stirred in glass kettle with low temperature oil bath collet, takes 2kg Al alloy powder to be added in graphene oxide water solution, 300r/min's
Under revolving speed, continue to stir lower 0.5h；
(2) by the graphene aluminium powder slurry in step (1) after mixing dispersion under low temperature stirring by peristaltic pump enter from
Heart spray drying tower, charging rate 100rpm, inlet air temperature are 200 DEG C, and leaving air temp is 90 DEG C, and atomizer revolving speed is
18000r/min obtains graphene aluminium-based powder composite, which is made of metallic particles and graphene,
And the metallic particles is coated by graphene uniform.
A kind of preparation method of graphene aluminum matrix composite described in the embodiment of the present invention provides a kind of environment friend
It is good, can continuous mass production scheme, wherein control mixing temperature and rate of drying and drying temperature, can control the oxygen of metal powder
Change degree makes the composite material low oxygen content of preparation, and preparation cost minimizes, and can further enhance metallic matrix electric conductivity
Can, meanwhile, which can be used for industrialized production.
Embodiment 5.
Specific steps are as follows:
(1) at 0 DEG C, the 2L graphene oxide water solution prepared (graphene oxide solid content is 25g/L) is placed in
It is stirred in glass kettle with low temperature oil bath collet, 1kg pure aluminium powder is taken to be added in graphene oxide water solution, in turning for 250r/min
Under speed, continue to stir lower 6h；
(2) by the graphene aluminium powder slurry in step (1) after mixing dispersion under low temperature stirring by peristaltic pump enter from
Heart spray drying tower, charging rate 30rpm, inlet air temperature are 150 DEG C, and leaving air temp is 100 DEG C, and atomizer revolving speed is
10000r/min obtains graphene aluminium-based powder composite, which is made of metallic particles and graphene,
And the metallic particles is coated by graphene uniform, oxygen content 6892ppm.
A kind of preparation method of graphene aluminum matrix composite described in the embodiment of the present invention provides a kind of environment friend
It is good, can continuous mass production scheme, wherein control mixing temperature and rate of drying and drying temperature, can control the oxygen of metal powder
Change degree makes the composite material low oxygen content of preparation, and preparation cost minimizes, and can further enhance metallic matrix electric conductivity
Can, meanwhile, which can be used for industrialized production.
The above is only the preferred embodiment of the embodiment of the present invention, not makees any shape to the embodiment of the present invention
Limitation in formula, any simple modification to the above embodiments of technical spirit according to an embodiment of the present invention, equivalent variations
With modification, in the range of still falling within technical solution of the embodiment of the present invention.
Claims (8)
1. a kind of preparation method of graphene aluminum matrix composite, which comprises the following steps:
After graphene oxide water solution and metallic particles are stirred at 0-30 DEG C, carried out by centrifugal spray drying tower fast
Speed spray drying, obtains the graphene aluminum matrix composite；
Wherein, the metallic particles is aluminium powder or Al alloy powder.
2. preparation method according to claim 1, which is characterized in that wherein,
The graphene aluminum matrix composite is made of metallic particles and graphene, and the metallic particles is by graphene uniform
Cladding.
3. preparation method according to claim 1, which is characterized in that wherein,
The mass ratio of the graphene oxide and metallic particles is 0.001-0.05:1.
4. preparation method according to claim 1, which is characterized in that wherein,
The metallic particles partial size is 1-100 μm.
5. preparation method according to claim 1, which is characterized in that wherein,
The mixing speed 150-300r/min, time 0.5-8h.
6. preparation method according to claim 1, which is characterized in that wherein,
The graphene oxide sheet diameter size is 50-300 microns, and 80% or more within 3 layers.
7. preparation method according to claim 6, which is characterized in that wherein,
The graphene oxide is the graphene oxide liquid being prepared using hummers method is improved.
8. preparation method according to claim 1, which is characterized in that wherein,
In the spray-drying process: charging rate 30-100rpm, inlet air temperature are 120-200 DEG C, and leaving air temp is
90-110 DEG C, atomizer revolving speed is 10000-24000r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810806220.1A CN109128148A (en) | 2018-07-20 | 2018-07-20 | A kind of preparation method of graphene aluminum matrix composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810806220.1A CN109128148A (en) | 2018-07-20 | 2018-07-20 | A kind of preparation method of graphene aluminum matrix composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109128148A true CN109128148A (en) | 2019-01-04 |
Family
ID=64801495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810806220.1A Pending CN109128148A (en) | 2018-07-20 | 2018-07-20 | A kind of preparation method of graphene aluminum matrix composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109128148A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111515403A (en) * | 2020-05-18 | 2020-08-11 | 山东省科学院新材料研究所 | Method for preparing graphene reinforced aluminum matrix composite powder in short process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349846A (en) * | 2015-11-02 | 2016-02-24 | 唐山建华科技发展有限责任公司 | Preparation method of graphene/aluminum composite material |
| CN105385870A (en) * | 2015-11-02 | 2016-03-09 | 唐山建华科技发展有限责任公司 | Preparation method of graphene/aluminum composite material |
| CN106784828A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | A kind of layer type casting moulding Graphene metallic composite and preparation method |
| CN106744857A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 3D printing Graphene metallic composite, preparation method and application |
| CN107497377A (en) * | 2017-10-19 | 2017-12-22 | 山东大学 | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere |
| CN108117065A (en) * | 2017-12-14 | 2018-06-05 | 北京化工大学 | A kind of method that graphene is prepared using alternative current stripping |
-
2018
- 2018-07-20 CN CN201810806220.1A patent/CN109128148A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105349846A (en) * | 2015-11-02 | 2016-02-24 | 唐山建华科技发展有限责任公司 | Preparation method of graphene/aluminum composite material |
| CN105385870A (en) * | 2015-11-02 | 2016-03-09 | 唐山建华科技发展有限责任公司 | Preparation method of graphene/aluminum composite material |
| CN106784828A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | A kind of layer type casting moulding Graphene metallic composite and preparation method |
| CN106744857A (en) * | 2016-12-30 | 2017-05-31 | 尹宗杰 | 3D printing Graphene metallic composite, preparation method and application |
| CN107497377A (en) * | 2017-10-19 | 2017-12-22 | 山东大学 | A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere |
| CN108117065A (en) * | 2017-12-14 | 2018-06-05 | 北京化工大学 | A kind of method that graphene is prepared using alternative current stripping |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111515403A (en) * | 2020-05-18 | 2020-08-11 | 山东省科学院新材料研究所 | Method for preparing graphene reinforced aluminum matrix composite powder in short process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105821227B (en) | A kind of method for preparing graphene enhancing Cu-base composites | |
| CN107299237B (en) | A kind of CNTs/TiO2The method of nano composite powder Reinforced Cu-Base Composites | |
| CN105397103A (en) | Nano-silver/graphene composite material and preparation method thereof | |
| CN108559861A (en) | A method of preparing graphene reinforced aluminum matrix composites | |
| CN106495133A (en) | High heat conduction Flexible graphene method for manufacturing thin film | |
| CN104846228A (en) | Method for reinforcing metallic material by graphene | |
| CN106735249B (en) | A kind of niobium based composites and preparation method | |
| CN101864547B (en) | Preparation method of homodisperse carbon nano tube enhanced aluminium base composite material | |
| CN106825552B (en) | The preparation method of 3D printing graphene coated alloy powder composite material | |
| CN108455584A (en) | A kind of graphene aqueous slurry and preparation method thereof | |
| CN110157931B (en) | Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
| CN106566942B (en) | A kind of method for preparing High-performance graphene reinforced aluminum matrix composites | |
| CN110257662A (en) | A kind of copper-graphite alkene composite material and preparation method | |
| CN107987661A (en) | A kind of biomass graphene modified raw lacquer heavy antisepsis composite coating and preparation method thereof | |
| CN107267792A (en) | A kind of preparation method of graphene enhancing copper or copper alloy bar | |
| CN105036178A (en) | Preparation method of modified nano zinc oxide | |
| CN105585035B (en) | A kind of preparation method of hollow aluminum oxide microspheres | |
| CN104259472B (en) | A kind of organic composite of superfine sheet copper powder and preparation method thereof | |
| CN105088111A (en) | Preparation method of carbon nanotube reinforced aluminum matrix composite | |
| CN109128148A (en) | A kind of preparation method of graphene aluminum matrix composite | |
| CN102560455A (en) | Preparation method of ultra-thin tungsten film-coated diamond | |
| TW201307208A (en) | Micro-scaled flake silver particles and method for producing the same | |
| CN107452865B (en) | Gold nanoparticle-coated nanosheet structure Sb2Te3Method for manufacturing thermoelectric material | |
| CN108569721A (en) | A kind of MoS2@g-C3N4Core-shell nanospheres and preparation method thereof | |
| CN107460021B (en) | Preparation method of low-temperature graphene-based nano borate composite material |
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: 20190104 |
|
| RJ01 | Rejection of invention patent application after publication |