CN102336387B - Quartz micro-needle array tip spherical shell microstructure and preparation method thereof - Google Patents
Quartz micro-needle array tip spherical shell microstructure and preparation method thereof Download PDFInfo
- Publication number
- CN102336387B CN102336387B CN201110304710.XA CN201110304710A CN102336387B CN 102336387 B CN102336387 B CN 102336387B CN 201110304710 A CN201110304710 A CN 201110304710A CN 102336387 B CN102336387 B CN 102336387B
- Authority
- CN
- China
- Prior art keywords
- micro
- needle array
- spherical shell
- tip
- quartz
- 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.)
- Expired - Fee Related
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000010453 quartz Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229920006254 polymer film Polymers 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012943 hotmelt Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 230000005622 photoelectricity Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000011257 shell material Substances 0.000 description 37
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- KLULSCKBRGQDOY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;toluene Chemical compound CC(=C)C(O)=O.CC1=CC=CC=C1 KLULSCKBRGQDOY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a quartz micro-needle array tip spherical shell microstructure and a preparation method thereof. The quartz micro-needle array tip spherical shell microstructure consists of a quartz micro-needle array and a spherical shell positioned at the tip of a micro-needle, wherein the diameter of the micro-needle is 2 to 200mu m, and the spherical shell is solid or hollow. The preparation method comprises the following steps of: coating a layer of polymer film on the surface of the tip of the quartz micro-needle; processing under the appropriate condition to make the polymer film form a spherical microstructure at the tip of the micro-needle; coating a layer of organic, inorganic or metal film on the surface of the spherical microstructure to obtain a quartz micro-needle array tip solid spherical shell microstructure; and removing a polymer material in a shell layer by a solvent soaking method or a firing method and the like to obtain a quartz micro-needle array tip hollow spherical shell microstructure. The quartz micro-needle array tip spherical shell microstructure is novel, is easy to prepare and can be applied to fields of biology, optics, photo-electricity, information and the like.
Description
Technical field
The present invention relates to a kind of quartz micro-needle array tip spherical shell microstructure and preparation method thereof, belong to material microstructure and preparing technical field thereof.
Background technology
Novel Microstructure will excite new function and performance, and every field realizes application in fields such as biology, optics, photoelectricity, information etc.Introduce the spheroid micro-structural of various material at the tip of quartz micro needle array (Chinese patent ZL 200710134575.2), application can be obtained in a lot of fields.Such as, because very thin quartz micro needle can accomplish the aciculiform from several microns of uniform shrinkage to most advanced and sophisticated tens nanometers, if in its most advanced and sophisticated preparation diameter hundreds of nanometers to the microballoon of several microns, then the resonator system of a mechanics can be formed, can be used for the research and apply of micro-nano mechanics.If be electric or magnetic response at the micro-sphere material of needle-shaped tip, then in this system, single microballoon or microballoon and microballoon also can be applicable in electric or magnetic device the characteristic of electric field, magnetic responsiveness.At present, the preparation of quartz micro-needle array tip spherical shell microstructure is technological difficulties, needs to seek new technology of preparing and method obtains quartz micro-needle array tip spherical shell microstructure.
Summary of the invention
The object of this invention is to provide a kind of quartz micro-needle array tip spherical shell microstructure, make this fine structure material can obtain extensive use in fields such as biology, optics, photoelectricity, information.Another object of the present invention is to provide the preparation method of this fine structure material.
In order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A kind of quartz micro-needle array tip spherical shell microstructure, is made up of quartz micro needle array and the spherical shell be positioned on micropin tip; The diameter of described micropin bottom is 2-200 μm, and described spherical shell is solid or hollow.
Described spherical shell material is organic and inorganic or one or more combination in metal material.
The preparation method of quartz micro-needle array tip spherical shell microstructure of the present invention, comprises the following steps:
(1) bottom diameter be the quartz micro needle array tip surface of 2 ~ 200 μm by spray, flood, dip, method or its combination such as spin coating, the polymethyl methacrylate (PMMA) of coated one deck 50nm ~ 50 μm thickness, polystyrene (PS) or rosin etc. are by organic solvent dissolution or the little thin polymer film of the rear viscosity of heating;
(2) polymer is made to form spherical micro-structural at micropin tip by hot melt, solvent vapo(u)r process or its method process of combining the quartz micro needle array of coated polymer;
(3) by this spherical micro-structure surface by chemical plating, plating, sol-gal process, sputtering, coating, or more method any combination, coated a layer thickness is the organic and inorganic or metallic film of 10nm ~ 50 μm, obtains the solid spherical shell micro-structural of quartz micro needle array tip;
(4) removed the polymeric material of shell inside by the method such as solvent soaking or calcination, obtain quartz micro needle array tip hollow ball shell micro-structural.
Compared with prior art, its remarkable advantage is in the present invention: (1) can obtain novel quartz micro-needle array tip spherical shell microstructure; (2) with low cost, without the need to large-scale instrument, simple and reliable process.
Accompanying drawing explanation
Fig. 1 be quartz micro-needle array tip spherical shell microstructure of the present invention prepare schematic diagram.Wherein, step 1): quartz micro needle array tip coated polymer; Step 2): it is spherical that felicity condition process makes polymer be formed; Step 3): spherome surface carries out coated; Step 4): remove spherical shell interior polymeric thing.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The quartz micro needle array used in the present embodiment utilizes the method described in patent ZL20071 0134575.2 obtained.
Embodiment 1: the rosin dipping coated one deck 1 μm of thickness on the quartz micro needle array tip surface that diameter is 10 μm, then heat-treat at 110 DEG C, namely polymer forms spherical micro-structural at micropin tip.Then this spherical micro-structure surface is sputtered one deck Ag films, obtain quartz micro needle array tip solid ping-pong ball shell micro-structural; Or removed the rosin of shell inside by alcohol immersion, obtain quartz micro needle array tip hollow silver spherical shell micro-structural.
Embodiment 2: the rosin passing through the coated one deck 50nm thickness of dipping on the quartz micro needle array tip surface that diameter is 2 μm, then heat-treat at 130 DEG C, namely polymer forms spherical micro-structural at micropin tip.After this spherical micro-structure surface is sputtered the gold thin film that a layer thickness is 10nm, obtain quartz micro needle array tip gold solid spherical shell micro-structural; Or soaked the rosin removing shell inside by acetone, obtain quartz micro needle array tip hollow gold goal shell micro-structural.
Embodiment 3: the polymethyl methacrylate at diameter being quartz micro needle array tip surface coated one deck of spin coating 50 μm of thickness of 200 μm, chloroform steam treatment makes polymer form spherical micro-structural at micropin tip.This spherical micro-structure surface is prepared by sol-gal process the silica membrane that a layer thickness is 50 μm, obtains the solid spherical shell micro-structural of quartz micro needle array tip silica; Or the polymethyl methacrylate of shell inside is removed in 400 DEG C of calcinings, obtains quartz micro needle array tip hollow silica ball shell micro-structural.
Embodiment 4: diameter be 125 μm quartz micro needle array tip surface by dipping the polystyrene (PS) of coated one deck 10nm ~ 50 μm thickness, by hot melt process make polymer micropin tip formed spherical micro-structural.Be the thin nickel metal film of 10 μm by the coated a layer thickness of chemical plating by this spherical micro-structure surface, obtain the solid spherical shell micro-structural of quartz micro needle array tip nickel; Or removed the polystyrene of shell inside by solvent soaking, obtain quartz micro needle array tip nickel hollow ball shell micro-structural.
Embodiment 5: the quartz micro needle array tip surface at diameter being 40 μm, by the polymethyl methacrylate (PMMA) of the coated one deck of dipping 5 μm of thickness, makes polymer form spherical micro-structural at micropin tip by chloroform steam treatment.Be the chromium metallic film of 2 μm by the coated a layer thickness of plating by this spherical micro-structure surface, obtain the solid spherical shell micro-structural of quartz micro needle array tip chromium; Or soaked the polymethyl methacrylate removing shell inside by chloroform, obtain quartz micro needle array tip chromium hollow ball shell micro-structural.
Embodiment 6: the quartz micro needle array tip surface at diameter being 30 μm, by the polyethylene glycol of the coated one deck of dipping 5 μm of thickness, makes it form spherical micro-structural at micropin tip by 110 DEG C of heat treatments.Be the polymethyl methacrylate of 2 μm by coated a layer thickness of mode of dipping polymethyl methacrylate toluene solution by this spherical micro-structure surface, obtain the solid spherical shell micro-structural of quartz micro needle array tip polymethyl methacrylate; Or by soaking the polyethylene glycol removing shell inside in water, obtain quartz micro needle array tip polymethyl methacrylate hollow ball shell micro-structural.
Embodiment 7: the quartz micro needle array tip surface at diameter being 8 μm, by the polystyrene (PS) of the coated one deck of spin coating 1 μm of thickness, makes polymer form spherical micro-structural at micropin tip by chloroform steam treatment.Be the titanium deoxid film of 2 μm by the coated a layer thickness of sol-gal process by this spherical micro-structure surface, obtain the solid spherical shell micro-structural of quartz micro needle array tip titanium dioxide; Or removed the polystyrene of shell inside by 400 DEG C of calcinations, obtain quartz micro needle array tip titanium dioxide hollow ball shell micro-structural.
Claims (5)
1. a preparation method for quartz micro-needle array tip spherical shell microstructure, is characterized in that, said method comprising the steps of:
(1) at bottom diameter be the thin polymer film of quartz micro needle array tip Surface coating one deck 50nm ~ 50 μm thickness of 2 ~ 200 μm;
(2) by the quartz micro needle array of coated polymer hot melt, solvent vapo(u)r process, or more Combination of Methods condition under process make polymer micropin tip formed spherical micro-structural;
(3) by the coated a layer thickness of this spherical micro-structure surface be the organic and inorganic or metallic film of 10nm ~ 50 μm, obtain the solid spherical shell micro-structural of quartz micro needle array tip;
(4) in the structure of step (3), remove the polymeric material of shell inside further by solvent soaking or calcination method, obtain quartz micro needle array tip hollow ball shell micro-structural.
2. the preparation method of a kind of quartz micro-needle array tip spherical shell microstructure according to claim 1, is characterized in that the coated combination of one or more adopted in spraying, dipping or spin coating method described in step (1).
3. the preparation method of a kind of quartz micro-needle array tip spherical shell microstructure according to claim 1, is characterized in that the material of the thin polymer film described in step (1) is by the little polymer of viscosity after organic solvent dissolution or heating.
4. the preparation method of a kind of quartz micro-needle array tip spherical shell microstructure according to claim 3, is characterized in that described polymer adopts polymethyl methacrylate or polystyrene.
5. the preparation method of a kind of quartz micro-needle array tip spherical shell microstructure according to claim 1, it is characterized in that the method for coating described in step (3) be chemical plating, plating, sol-gal process, sputtering, coating, or more any combination of method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110304710.XA CN102336387B (en) | 2011-10-10 | 2011-10-10 | Quartz micro-needle array tip spherical shell microstructure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110304710.XA CN102336387B (en) | 2011-10-10 | 2011-10-10 | Quartz micro-needle array tip spherical shell microstructure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102336387A CN102336387A (en) | 2012-02-01 |
| CN102336387B true CN102336387B (en) | 2015-04-08 |
Family
ID=45512399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110304710.XA Expired - Fee Related CN102336387B (en) | 2011-10-10 | 2011-10-10 | Quartz micro-needle array tip spherical shell microstructure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102336387B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838078A (en) * | 2012-09-17 | 2012-12-26 | 无锡英普林纳米科技有限公司 | Suspended disk array microstructure and preparation method thereof |
| CN103569958A (en) * | 2013-11-12 | 2014-02-12 | 无锡英普林纳米科技有限公司 | Preparation method of spindle-shaped micron/submicron quartz rod array |
| CN108275646B (en) * | 2018-01-30 | 2020-10-09 | 北京理工大学 | Low-adhesion end effector for micro-operation and manufacturing method thereof |
| CN112807561A (en) * | 2021-01-26 | 2021-05-18 | 上海烨映微电子科技股份有限公司 | Microneedle structure and method for producing same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002050584A2 (en) * | 2000-12-21 | 2002-06-27 | Biovalve Technologies, Inc. | Microneedle array systems |
| JP2005063798A (en) * | 2003-08-11 | 2005-03-10 | Japan Science & Technology Agency | Cone-shaped microstructure and its manufacturing method |
| CA2613596A1 (en) * | 2005-06-27 | 2007-01-04 | Applied Thin Films, Inc. | Aluminum phosphate based microspheres |
| KR101261466B1 (en) * | 2009-07-17 | 2013-05-10 | 한국전자통신연구원 | The method for manufacturing hallow micro needle structures |
| TWI396845B (en) * | 2009-11-13 | 2013-05-21 | Nat Univ Tsing Hua | Single molecule detection platform, the manufacturing method thereof and the method using the same |
-
2011
- 2011-10-10 CN CN201110304710.XA patent/CN102336387B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102336387A (en) | 2012-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Botanical‐inspired 4D printing of hydrogel at the microscale | |
| Medina‐Sánchez et al. | Swimming microrobots: Soft, reconfigurable, and smart | |
| CN106644189B (en) | Pliable pressure sensor and preparation method thereof | |
| CN102336387B (en) | Quartz micro-needle array tip spherical shell microstructure and preparation method thereof | |
| Tang et al. | Mechano-regulated surface for manipulating liquid droplets | |
| Hu et al. | Magnetic soft micromachines made of linked microactuator networks | |
| Lee et al. | Fabrication of patterned nanofibrous mats using direct-write electrospinning | |
| US9610580B2 (en) | Magnetically tunable microstructured surfaces | |
| Xia et al. | Use of electroless silver as the substrate in microcontact printing of alkanethiols and its application in microfabrication | |
| Zhou et al. | Magnetoresponsive surfaces for manipulation of nonmagnetic liquids: Design and applications | |
| Chen et al. | Fabrication of polymer nanopeapods in the nanopores of anodic aluminum oxide templates using a double-solution wetting method | |
| CN107416762B (en) | Silicon nano-pore structure and manufacturing method thereof | |
| Chen et al. | Hierarchical structures by wetting porous templates with electrospun polymer fibers | |
| Liu et al. | Magnetically Powered Annelid‐Worm‐Like Microswimmers | |
| Bai et al. | A review of smart superwetting surfaces based on shape‐memory micro/nanostructures | |
| Zheng et al. | Salvinia-effect-inspired “sticky” superhydrophobic surfaces by meniscus-confined electrodeposition | |
| Gallego-Perez et al. | Versatile methods for the fabrication of polyvinylidene fluoride microstructures | |
| Sun et al. | Simple and affordable way to achieve polymeric superhydrophobic surfaces with biomimetic hierarchical roughness | |
| EP2941638A1 (en) | Sensor, method for forming the same, and method of controlling the same | |
| Kumar et al. | Straightforward and precise approach to replicate complex hierarchical structures from plant surfaces onto soft matter polymer | |
| Sun et al. | Ingenious humidity-powered micro-worm with asymmetric biped from single hydrogel | |
| Peethan et al. | Laser‐Assisted Tailoring of Surface Wettability‐Fundamentals and Applications: A Critical Review | |
| Li et al. | Static and dynamic hydrophobic properties of honeycomb structured films via breath figure method | |
| Zhang et al. | Robust underwater air layer retention and restoration on salvinia-inspired self-grown heterogeneous architectures | |
| Xin et al. | Rapid and multimaterial 4d printing of shape‐morphing micromachines for narrow micronetworks traversing |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170721 Address after: 510640 Guangdong City, Tianhe District Province, No. five, road, public education building, unit 371-1, unit 2401 Patentee after: Guangdong Gaohang Intellectual Property Operation Co., Ltd. Address before: 214192 No. three, No. 99, Furong Road, Wuxi, Jiangsu Patentee before: Wuxi Imprint Nano Technology Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Guiju Inventor before: Ge Haixiong Inventor before: Chen Yanfeng Inventor before: Yuan Changsheng Inventor before: Lu Minghui |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170927 Address after: 274300, 169, North Village, administrative village, San San village, Huanggang Town, Heze, Shandong, Shanxian County Patentee after: Li Guiju Address before: 510640 Guangdong City, Tianhe District Province, No. five, road, public education building, unit 371-1, unit 2401 Patentee before: Guangdong Gaohang Intellectual Property Operation Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150408 Termination date: 20171010 |