CN105419776A - Preparation method for nano-particles with metal-carbon core-shell structures - Google Patents
Preparation method for nano-particles with metal-carbon core-shell structures Download PDFInfo
- Publication number
- CN105419776A CN105419776A CN201510618792.3A CN201510618792A CN105419776A CN 105419776 A CN105419776 A CN 105419776A CN 201510618792 A CN201510618792 A CN 201510618792A CN 105419776 A CN105419776 A CN 105419776A
- Authority
- CN
- China
- Prior art keywords
- metal
- preparation
- carbon core
- shell structure
- structure nanoparticles
- 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
Abstract
The invention discloses a preparation method for nano-particles with metal-carbon core-shell structures. The preparation method comprises the steps of: firstly adding a metal target into an organic solution; introducing inert gas; ablating the metal target by using a laser device under a stirring condition; then adding the obtained laser-ablated product into a sulfuric acid solution; introducing the inert gas; heating and stirring the solution; and cooling the solution to obtain the nano-particles with metal-carbon core-shell structures. The preparation method disclosed by the invention is simple in process, fast, good in repeatability and green and pollution-free; and the obtained nano-particles with metal-carbon core-shell structures are high in purity and uniform in shape, carbon fluorescence is enhanced, and the nano-particles can be regulated.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of metal-carbon Core-shell Structure Nanoparticles.
Background technology
Carbon point, as a kind of nano-luminescent material, has excitation wavelength and emission wavelength is tunable, good biocompatibility, toxicity are low, the resistance to photobleaching of fluorescent stabilization and unglazed scintillation etc. are excellent fluorescence property.By strengthening carbon point fluorescence intensity, enhancing surface Raman can be applied to, strengthen photo detector signal and bio-imaging.
At present, the method preparing fluorescent carbon point mainly comprises electrochemical process, microwave process for synthesizing, hydrothermal method and laser ablation method.Document (H.T.Li, X.D.He, Z.H.Kang, H.Huang, Y.Liu, J.L.Liu, S.Y.Lian, C.H.A.Tsang, X.B.YangandS.T.Lee, Angew.Chem., Int.Ed., 2010,49,4430) adopt electrochemical process to peel off graphite cellular layer and prepare fluorescent carbon point, the fluorescent carbon point purity of preparation is high, and size is controlled, and productive rate is high, but this preparation method's energy consumption is large, cost is high and can produce alkaline waste liquor, easily causes environmental pollution.Document (X.H.Wang, K.G.Qu, B.L.Xu, J.S.RenandX.G.Qu, J.Mater.Chem., 2011,21,2445.) adopt microwave process for synthesizing one step to prepare fluorescent carbon point in, the method does not need surface passivator, gentleness, low cost, but carbon quantum dot pattern and grain size wayward.Document (J.M.Wei, X.Zhang, Y.Z.Sheng, J.M.Shen, P.Huang, S.K.Guo, J.Q.Pan, B.T.Tao, B.X.Feng, New.J.Chem., 2014,38,906.) hydrothermal method is adopted to prepare fluorescent carbon point, this carbon point shows good light stability, and fluorescence quantum yield is high, but carbon quantum dot particle diameter prepared by this method is wayward.Document (K.Habiba, V.I.Makarov, J.Avalos, M.J.F.Guinel, B.R.WeinerandG.Morell, Carbon, 2013,64,341-350.) adopt laser ablation method to prepare fluorescent carbon point, experimentation is pollution-free fast, and product purity is high, but particle size is wayward, carbon quantum dot fluorescent yield is low.At present, existing also do not exist can fast, Green synthesis fluorescent carbon quantum dot, and strengthen carbon quantum dot ultra-violet light-emitting and regulate the simple and easy method strengthening carbon point fluorescence intensity.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and the preparation method providing a kind of metal-carbon Core-shell Structure Nanoparticles, the method preparation technology is simple, quick, reproducible, green non-pollution; The metal-carbon Core-shell Structure Nanoparticles purity obtained is high, pattern is homogeneous, carbon Fluorescence Increasing and controllable.
A preparation method for metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, adds to metal targets in organic solution, passes into rare gas element, carries out ablation under agitation, obtain the colloidal solution of metal-carbon Core-shell Structure Nanoparticles with laser apparatus to metal targets;
Step 2, adds in sulphuric acid soln by the colloidal solution of step 1 gained metal-carbon Core-shell Structure Nanoparticles, passes into rare gas element, heated and stirred, cooling, namely obtains the colloidal solution of the metal-carbon core shell nanoparticles of different metal core volume.
As the further improvement of foregoing invention, described metal targets is Ti, Al, Cr, Mn, Pd or Sn, purity >=99.99%.
As the further improvement of foregoing invention, described organic solution is ethanol solution.
As the further improvement of foregoing invention, the ablation process of step 1 is carried out in quartz container.
As the further improvement of foregoing invention, in step 1, stir speed (S.S.) is 80 ~ 90rpm.
As the further improvement of foregoing invention, the optical maser wavelength that in step 1, laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
As the further improvement of foregoing invention, in step 2, sulphuric acid soln concentration is 5v/v%.
As the further improvement of foregoing invention, in step 2, the volume of sulphuric acid soln accounts for 0 ~ 50% of laser ablation product and sulphuric acid soln cumulative volume.
As the further improvement of foregoing invention, in step 2, Heating temperature is 70 DEG C, and stirring velocity is 300rpm, and churning time is 15min.
The principle of the invention is: laser beam acts on the metal targets in organic solvent, the target plane of incidence is heated even to be evaporated, under sufficiently high laser flux, METAL HEATING PROCESS face is converted into high temperature, high pressure, highdensity plasma body, under suitable condensing condition, plasma plume brightness generation cancellation, define metal nanoparticle, meanwhile, C-O key in organic solvent molecule and C-C key rupture in metal plasma body feathers brightness cancellation process, the carbon atom broken to form can be coated on surfaces of metal nanoparticles, thus define the carbon coating layer of surface of metal particles, obtain the nano particle of metal-carbon nucleocapsid structure, with acid, product is etched further again, metallic core and acid react, volume reduces gradually, carbon shell then can not react, due between metal and carbon shell surface interaction, that is, as distance d<5nm between the two, transmission ofenergy can be got back to ground state to metal with radiationless form by the carbon fluorescence of excited state, shows as the quenching effect of metal pair fluorescent emission.As 5nm<d<20nm, metal unbound electron regular motion and produce surface plasma body resonant vibration under the external electromagnetic field action of certain frequency, greatly strengthen the electromagnetic field of particle periphery, and this surperficial local Electromagnetic enhancement makes the molecule activation on metallic surface, launching efficiency improves, carbon shell Fluorescence Increasing.Therefore, by adding the difference of acid amount, the size of metallic core volume can be regulated, and then regulate carbon point fluorescence.
Compared with prior art, its remarkable advantage is: the first in the present invention, and preparation technology of the present invention is simple, quick, reproducible, Product size is little, green non-pollution; The second, the present invention utilizes the surface interaction between metallic core and carbon shell, enhances metal-carbon particle fluorescence, and realizes the adjustable of Fluorescence Increasing intensity; 3rd, the core-shell structured nanomaterials purity that the present invention obtains is high, pattern is homogeneous, good stability, and metal-carbon particle fluorescence strengthens and controllable.
Accompanying drawing explanation
Fig. 1 is the TEM figure of CrC Core-shell Structure Nanoparticles prepared by invention example 1;
Fig. 2 is the PL figure of CrC Core-shell Structure Nanoparticles prepared by invention example 1;
Fig. 3 is the TEM figure in the CrC Core-shell Structure Nanoparticles acid etch process of invention example 1 preparation;
Fig. 4 is the TEM figure after the CrC Core-shell Structure Nanoparticles acid etch process of invention example 1 preparation;
Fig. 5 is the PL figure of the different acid etch degree of CrC Core-shell Structure Nanoparticles prepared by invention example 1;
Fig. 6 is the carbon point Fluorescence Increasing factor graph of embodiment 1, embodiment 2, embodiment 3 gained metal-carbon Core-shell Structure Nanoparticles.
Embodiment
Embodiment 1
The preparation method of metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, by metal targets Cr(purity >=99.99%) add in ethanolic soln, pass into argon gas, under 80 ~ 90rpm agitation condition, with laser apparatus, ablation is carried out to metal targets, obtain laser ablation product;
Step 2, added in 5v/v% sulphuric acid soln by step 1 gained laser ablation product, pass into argon gas, under 70 DEG C of conditions, 300rpm stirring reaction 15min, is cooled to room temperature, obtains final product.
In step 1, ablation process is carried out in quartz container; The optical maser wavelength that laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
In step 2, the volume of laser ablation product is 4mL, and the volume of sulphuric acid soln is followed successively by 0mL, 1mL, 1.3mL, 1.7mL, 2.7mL, 4mL.
Gained CrC Core-shell Structure Nanoparticles is carried out phenetic analysis, as shown in Figure 1, Figure 2, shown in Fig. 3, Fig. 4, Fig. 5.Result shows, the Core-shell Structure Nanoparticles purity of the carbon coated metal that the present invention obtains is high, pattern is homogeneous, and in acid etch process, carbon shell caves in, the hollow carbon shell for subsiding after having etched; As can be seen from PL, the fluorescence of gained nano particle is positioned at ultraviolet region.In addition, due to the surface interaction between metallic core and carbon shell, along with acid etch degree increases, carbon point fluorescence changes, and when sour volume is 40%, etching completes, remain hollow carbon shell, carbon point fluorescence is the most weak and no longer change, and achieves the controllable of carbon point Fluorescence Increasing and fluorescence intensity.
Embodiment 2
The preparation method of metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, by metal targets Ti(purity >=99.99%) add in ethanolic soln, pass into argon gas, under 80 ~ 90rpm agitation condition, with laser apparatus, ablation is carried out to metal targets, obtain laser ablation product;
Step 2, added in 5v/v% sulphuric acid soln by step 1 gained laser ablation product, pass into argon gas, under 70 DEG C of conditions, 300rpm stirring reaction 15min, is cooled to room temperature, obtains final product.
In step 1, ablation process is carried out in quartz container; The optical maser wavelength that laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
In step 2, the volume of laser ablation product is 4mL, and the volume of sulphuric acid soln is followed successively by 0mL, 1mL, 1.3mL, 1.7mL, 2.7mL, 4mL.
Carry out TEM and PL to sample to characterize, result is with embodiment 1.
Embodiment 3
The preparation method of metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, by metal targets Al(purity >=99.99%) add in ethanolic soln, pass into argon gas, under 80 ~ 90rpm agitation condition, with laser apparatus, ablation is carried out to metal targets, obtain laser ablation product;
Step 2, added in 5v/v% sulphuric acid soln by step 1 gained laser ablation product, pass into argon gas, under 70 DEG C of conditions, 300rpm stirring reaction 15min, is cooled to room temperature, obtains final product.
In step 1, ablation process is carried out in quartz container; The optical maser wavelength that laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
In step 2, the volume of laser ablation product is 4mL, and the volume of sulphuric acid soln is followed successively by 0mL, 1mL, 1.3mL, 1.7mL, 2.7mL, 4mL.
Carry out TEM and PL to sample to characterize, result is with embodiment 1.
Embodiment 4
The preparation method of metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, by metal targets Sn(purity >=99.99%) add in ethanolic soln, pass into argon gas, under 80 ~ 90rpm agitation condition, with laser apparatus, ablation is carried out to metal targets, obtain laser ablation product;
Step 2, added in 5v/v% sulphuric acid soln by step 1 gained laser ablation product, pass into argon gas, under 70 DEG C of conditions, 300rpm stirring reaction 15min, is cooled to room temperature, obtains final product.
In step 1, ablation process is carried out in quartz container; The optical maser wavelength that laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
In step 2, the volume of laser ablation product is 4mL, and the volume of sulphuric acid soln is followed successively by 0mL, 1mL, 1.3mL, 1.7mL, 2.7mL, 4mL.
Carry out TEM and PL to sample to characterize, result is with embodiment 1.
Embodiment 5
The preparation method of metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, by metal targets Mn(purity >=99.99%) add in ethanolic soln, pass into argon gas, under 80 ~ 90rpm agitation condition, with laser apparatus, ablation is carried out to metal targets, obtain laser ablation product;
Step 2, added in 5v/v% sulphuric acid soln by step 1 gained laser ablation product, pass into argon gas, under 70 DEG C of conditions, 300rpm stirring reaction 15min, is cooled to room temperature, obtains final product.
In step 1, ablation process is carried out in quartz container; The optical maser wavelength that laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
In step 2, the volume of laser ablation product is 4mL, and the volume of sulphuric acid soln is followed successively by 0mL, 1mL, 1.3mL, 1.7mL, 2.7mL, 4mL.
Carry out TEM and PL to sample to characterize, result is with embodiment 1.
Embodiment 6
The preparation method of metal-carbon Core-shell Structure Nanoparticles, comprises the following steps:
Step 1, by metal targets Pd(purity >=99.99%) add in ethanolic soln, pass into argon gas, under 80 ~ 90rpm agitation condition, with laser apparatus, ablation is carried out to metal targets, obtain laser ablation product;
Step 2, added in 5v/v% sulphuric acid soln by step 1 gained laser ablation product, pass into argon gas, under 70 DEG C of conditions, 300rpm stirring reaction 15min, is cooled to room temperature, obtains final product.
In step 1, ablation process is carried out in quartz container; The optical maser wavelength that laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
In step 2, the volume of laser ablation product is 4mL, and the volume of sulphuric acid soln is followed successively by 0mL, 1mL, 1.3mL, 1.7mL, 2.7mL, 4mL.
Carry out TEM and PL to sample to characterize, result is with embodiment 1.
Fig. 6 is the carbon point Fluorescence Increasing factor graph of embodiment 1, embodiment 2, embodiment 3 gained metal-carbon Core-shell Structure Nanoparticles, and as seen from the figure, preparation method of the present invention can strengthen the fluorescence of carbon point, and intensification factor can reach 3-5 doubly.
Claims (9)
1. a preparation method for metal-carbon Core-shell Structure Nanoparticles, is characterized in that: comprise the following steps:
Step 1, adds to metal targets in organic solution, passes into rare gas element, carries out ablation under agitation, obtain the colloidal solution of metal-carbon Core-shell Structure Nanoparticles with laser apparatus to metal targets;
Step 2, adds in sulphuric acid soln by the colloidal solution of step 1 gained metal-carbon Core-shell Structure Nanoparticles, passes into rare gas element, heated and stirred, cooling, namely obtains the colloidal solution of the metal-carbon core shell nanoparticles of different metal core volume.
2. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: described metal targets is Ti, Al, Cr, Mn, Pd or Sn, purity >=99.99%.
3. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: described organic solution is ethanol solution.
4. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: the ablation process of step 1 is carried out in quartz container.
5. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: in step 1, stir speed (S.S.) is 80 ~ 90rpm.
6. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, it is characterized in that: the optical maser wavelength that in step 1, laser apparatus is launched is 1064nm, the pulse duration is 10ns, voltage 400V, energy are 101mJ, and the ablation time is 3min.
7. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: in step 2, sulphuric acid soln concentration is 5v/v%.
8. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: in step 2, the volume of sulphuric acid soln accounts for 0 ~ 50% of the cumulative volume of laser ablation product and sulphuric acid soln.
9. the preparation method of metal-carbon Core-shell Structure Nanoparticles according to claim 1, is characterized in that: in step 2, Heating temperature is 70 DEG C, and stirring velocity is 300rpm, and churning time is 15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510618792.3A CN105419776A (en) | 2015-09-24 | 2015-09-24 | Preparation method for nano-particles with metal-carbon core-shell structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510618792.3A CN105419776A (en) | 2015-09-24 | 2015-09-24 | Preparation method for nano-particles with metal-carbon core-shell structures |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105419776A true CN105419776A (en) | 2016-03-23 |
Family
ID=55498328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510618792.3A Pending CN105419776A (en) | 2015-09-24 | 2015-09-24 | Preparation method for nano-particles with metal-carbon core-shell structures |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105419776A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587005A (en) * | 2016-10-21 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Multi-step carbonized high quantum efficiency carbon quantum dot and preparation method thereof |
| CN108767227A (en) * | 2018-05-29 | 2018-11-06 | 广州大学 | A kind of preparation method based on laser method carbon coating iron oxide anode material for lithium-ion batteries |
| CN111687425A (en) * | 2020-07-22 | 2020-09-22 | 广东工业大学 | Core-shell structure nano material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102601357A (en) * | 2012-03-14 | 2012-07-25 | 天津大学 | Laser processing method of carbon-coated metal micro-powder |
| CN104014800A (en) * | 2014-06-09 | 2014-09-03 | 天津大学 | Preparing method for controllably synthesizing monodisperse active metal nanoparticles through lasers |
-
2015
- 2015-09-24 CN CN201510618792.3A patent/CN105419776A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102601357A (en) * | 2012-03-14 | 2012-07-25 | 天津大学 | Laser processing method of carbon-coated metal micro-powder |
| CN104014800A (en) * | 2014-06-09 | 2014-09-03 | 天津大学 | Preparing method for controllably synthesizing monodisperse active metal nanoparticles through lasers |
Non-Patent Citations (2)
| Title |
|---|
| J.B. PARK ET AL.: "Synthesis of carbon-encapsulated magnetic nanoparticles by pulsed laser irradiation of solution", 《CARBON》 * |
| KAI-YANG NIU ET AL.: "Synthesis of carbon encapsulated nickel nanoparticles by laser ablation in liquid", 《APPLIED MECHANICS AND MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587005A (en) * | 2016-10-21 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Multi-step carbonized high quantum efficiency carbon quantum dot and preparation method thereof |
| CN108767227A (en) * | 2018-05-29 | 2018-11-06 | 广州大学 | A kind of preparation method based on laser method carbon coating iron oxide anode material for lithium-ion batteries |
| CN111687425A (en) * | 2020-07-22 | 2020-09-22 | 广东工业大学 | Core-shell structure nano material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| De et al. | A green and facile approach for the synthesis of water soluble fluorescent carbon dots from banana juice | |
| Wang et al. | Water-soluble and phosphorus-containing carbon dots with strong green fluorescence for cell labeling | |
| Tien et al. | Novel technique for preparing a nano-silver water suspension by the arc-discharge method | |
| Xu et al. | Ln3+ (Ln= Eu, Dy, Sm, and Er) ion-doped YVO4 nano/microcrystals with multiform morphologies: hydrothermal synthesis, growing mechanism, and luminescent properties | |
| Chen et al. | Multicolor upconversion NaLuF 4 fluorescent nanoprobe for plant cell imaging and detection of sodium fluorescein | |
| CN104031642B (en) | A kind of fluorescent carbon quantum dot and its preparation method and application | |
| US8529749B2 (en) | Electrochemical cell including a plasma source and method of operating the electrochemical cell | |
| CN105219384A (en) | A kind of preparation method of carbon quantum dot of yellow fluorescence of zine ion doping | |
| Zhang et al. | Synthesis of ultra-small BaLuF 5: Yb 3+, Er 3+@ BaLuF 5: Yb 3+ active-core–active-shell nanoparticles with enhanced up-conversion and down-conversion luminescence by a layer-by-layer strategy | |
| CN105419776A (en) | Preparation method for nano-particles with metal-carbon core-shell structures | |
| CN108101010B (en) | Preparation method of graphite phase carbon nitride quantum dots | |
| Qin et al. | Modification on populating paths of β-NaYF 4: Nd/Yb/Ho@ SiO 2@ Ag core/double-shell nanocomposites with plasmon enhanced upconversion emission | |
| Li et al. | Facile ionic-liquid-assisted electrochemical synthesis of size-controlled carbon quantum dots by tuning applied voltages | |
| Wang et al. | Multiple irradiation triggered the formation of luminescent LaVO4: Ln 3+ nanorods and in cellulose gels | |
| CN107815310A (en) | A kind of nitrogen, chlorine codope fluorescent carbon quantum dot preparation method | |
| CN106978170B (en) | A kind of preparation method of water-solubility fluorescent carbon quantum dot | |
| Liu et al. | Ultrafast photonics applications of zirconium carbide as a novel mode-locker for fiber lasers | |
| CN103771391A (en) | Preparation method of water-soluble carbon nanoparticles having fluorescent properties | |
| Gao et al. | Synthesis and luminescent properties of uniform monodisperse LuPO4: Eu3+/Tb3+ hollow microspheres | |
| Li et al. | Fabrication of core@ spacer@ shell Au nanorod@ mSiO 2@ Y 2 O 3: Er nanocomposites with enhanced upconversion fluorescence | |
| Jiu et al. | The synthesis and photoluminescence property of YPO4: Eu3+ hollow microspheres | |
| Zhang et al. | Synthesis of gold nanorod/neodymium oxide yolk/shell composite with plasmon-enhanced near-infrared luminescence | |
| Ma et al. | Raman scattering and plasmonic photocatalysis of single particles of NaYF 4: Yb, Er@ Ag under near-infrared laser excitation | |
| Xu et al. | Large-scale fabrication of porous YBO3 hollow microspheres with tunable photoluminescence | |
| Tao et al. | Preparation and upconversion luminescence of monodisperse Y2O2S: Yb/Ho-silica/aminosilane core-shell nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160323 |
|
| WD01 | Invention patent application deemed withdrawn after publication |