CN103276389A - Aluminium oxide and zirconium diboride reinforced aluminum matrix in-situ composite and preparation method thereof - Google Patents
Aluminium oxide and zirconium diboride reinforced aluminum matrix in-situ composite and preparation method thereof Download PDFInfo
- Publication number
- CN103276389A CN103276389A CN2013102478418A CN201310247841A CN103276389A CN 103276389 A CN103276389 A CN 103276389A CN 2013102478418 A CN2013102478418 A CN 2013102478418A CN 201310247841 A CN201310247841 A CN 201310247841A CN 103276389 A CN103276389 A CN 103276389A
- Authority
- CN
- China
- Prior art keywords
- particle
- aluminum
- matrix
- zirconium diboride
- preparation
- 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.)
- Granted
Links
Images
Abstract
The invention relates to an aluminium oxide and zirconium diboride reinforced aluminum matrix in-situ composite and a preparation method thereof. A ZrO2 particle and a B or B2O3 particle are mixed and ball-milled, the mixed particle formed after ball-milling is added into a matrix, a particle filling area of the matrix is processed through stirring friction, the rotating speed, the travel speed, the downward-pressing quantity, the inclination angle, the processing times of a stirring tool are 600-3000 r/min, 30-60 mm/min, 0.05-0.6 mm, 0-3 degrees, and 3-8 respectively, and during the processing process, ZrO2 and B or B2O3 particle is in chemical reaction with the aluminium matrix jointly to finally obtain the aluminium oxide and zirconium diboride reinforced aluminum matrix in-situ composite. In the aluminium matrix composite, the AL2O3 and ZrB2 particle subjected to in-situ synthesis have higher hardness and thermal stability, so that the composite has higher high-temperature-resistance abrasion performance.
Description
Technical field
The present invention relates to the method for preparing aluminum-based composite material field, particularly synthetic (the Al of a kind of agitating friction processing original position
2O
3+ ZrB
2) method of particle enhanced aluminum-based composite material.
Background technology
Aluminum matrix composite has advantages such as specific tenacity height, specific modulus height, thermal conductivity height, thermal expansivity be low, high temperature resistant, wear-resistant, occupies critical role in manufacturing fields such as aerospace, automobiles.Compare with the fiber reinforcement aluminum matrix composite, particle enhanced aluminum-based composite material has advantages such as isotropy, preparation are simple relatively, cost is cheap relatively, is the emphasis of metal current based composites area research.
Particle enhanced aluminum-based composite material preparation at present mainly comprises liquid state, solid-state, semi-solid state, deposition and the synthetic five kinds of complete processings of original position.Compare with other several technologies, in-situ synthesis prepares particle to be strengthened golden aluminum matrix composite and have the following advantages: (1) original position generates and strengthens the body heat stable mechanical property; (2) strengthen body and basal body interface is pollution-free and bonding strength is high; (3) it is tiny and be evenly distributed in the matrix to strengthen body; (4) strengthening the body size is not subjected to initially to add particle size and limits.
Find through the literature search to prior art, Zhu and state etc. were " Powder Technology " (2012 years, the 217th volume, the 401-408 page or leaf) " the Microstructure and high temperature wear of aluminum matrix composites fabricated by reaction from Al-ZrO that delivers
2-B elemental powders ", propose to adopt the synthetic (Al of heat release disperse reaction (XD) method in this article
2O
3+ ZrB
2) particle enhanced aluminum-based composite material, concrete grammar is: with Al powder, B powder and ZrO
2Powder is for making raw material, ball milling, briquetting, reacting by heating generation Al in vacuum oven
2O
3And ZrB
2Particle studies show that such matrix material has higher high temperature wear resistant performance.Its deficiency is: synthetic particle is at micron order, and particle is thicker, and reaction needs to carry out the production cost height under vacuum and high temperature (800 ℃).
The agitating friction processing technology is a kind of solid-state processing method that forms in the development of friction Stir technical foundation.This technology prepares particle enhanced aluminum-based composite material and has following unique advantage: matrix material generation dynamic recrystallization forms tiny equiax crystal in (1) course of processing, and its mechanical property obviously improves; (2) course of processing is convenient to realize accurately control by regulating machined parameters; (3) the matrix material degree of depth can freely be selected by the length that changes stirring tool; (4) particle wild phase add-on can freely be adjusted by changing blind hole or groove dimensions and spacing in the matrix material; (5) course of processing does not produce obnoxious flavour, is a kind of radiationless, green energy conservation technology that noise is few.
Agitating friction processing original position synthetic technology is based on a kind of compound preparation technology on agitating friction processing technology and the original position synthetic technology basis, and its principle is to utilize that high temperature and violent viscous deformation make particle with the generation of matrix generation chemical reaction and disperses required enhanced granule in the agitating friction course of processing.This technology has agitating friction processing technology and original position synthetic technology advantage concurrently.
Chinese patent CN102021557A discloses a kind of aluminum alloy surface Al
2O
3+ TiB
2Compound coating and preparation method thereof at first, is left some dark 0.5mm～2mm that are in aluminum alloy surface, and wide be the groove of 0.5mm～2mm, and the filling ball milling is good in groove contains 30%～70%TiO
2, 30%～70%B
2O
3Mixed powder by agitating friction processing, makes TiO again
2And B
2O
3Mixed powder is evenly distributed in the upper layer of aluminium alloy, at last this upper layer is carried out induction heating, produces chemical reaction 3TiO
2+ 3B
2O
3+ 10Al=3TiB
2+ 5Al
2O
3, obtain Al
2O
3+ TiB
2Compound coating forms metallurgical bonding interface between coating and matrix.Chemical reaction occurs in after the agitating friction processing in this patent, and its deficiency is: need follow-up induction heating process that chemical reaction could take place after the agitating friction processing, processing step complexity, and TiO in the induction heating process
2And B
2O
3The particle contact is insufficient, is unfavorable for reacting completely and carries out.
Summary of the invention
The purpose of this invention is to provide a kind of aluminum oxide and zirconium diboride and strengthen aluminum-based in-situ composite materials and preparation method thereof.
The present invention takes technical scheme to be:
Aluminum oxide and zirconium diboride strengthen the preparation method of aluminum-based in-situ composite materials, comprise that step is as follows:
(1) with ZrO
2Particle mixes by mass ratio 11:2 with the B particle, or with ZrO
2Particle and B
2O
3Particle is pressed mass ratio 5:2 and is mixed, and composite grain is carried out ball milling;
(2) be matrix with fine aluminium or aluminium alloy plate, composite grain behind the ball milling is added in the matrix;
(3) agitating friction processing is carried out in the particles filled zone of matrix, the stirring tool speed of rotation is 600～3000r/min, and gait of march is 30～60mm/min, volume under pressure is 0.05～0.6mm, the pitch angle is 0～3 °, and the processing number of times is 3～8 times, ZrO in the course of processing
2, B or B
2O
3Chemical reaction takes place in particle and aluminum substrate jointly, finally obtains aluminum oxide and zirconium diboride and strengthens aluminum-based in-situ composite materials.
The described ball milling time of above-mentioned steps (1) is 1～10 hour, and rotating speed is 50～100r/min, and ratio of grinding media to material is 5-15:1.
ZrO
2The particle median size is that purity is 90～99.9%, B or B between 10nm～10 μ m
2O
3The particle median size is that purity is 90～99.9% between 10nm～100 μ m.
The mode that the described composite grain of above-mentioned steps (2) adds in the matrix has: (1) adds composite grain in groove or the blind hole, and tamps in matrix surface or inner open channels or blind hole; (2) method with spraying or coating adds matrix surface with composite grain.
Twice machine direction or sense of rotation are identical or opposite before and after the processing of above-mentioned steps (3).
Above-mentioned chemical reaction product is Al
2O
3And ZrB
2Particle, chemical equation is: 4Al+3ZrO
2+ 6B → 2Al
2O
3+ 3ZrB
2Or 10Al+3ZrO
2+ 3B
2O
3→ 5Al
2O
3+ 2ZrB
2The aluminum oxide of method for preparing and zirconium diboride strengthen aluminum-based in-situ composite materials.
Technique scheme of the present invention is compared with the prior art scheme and is had the following advantages: utilize the present invention to prepare in the aluminum matrix composite, original position synthesis particle Al
2O
3And ZrB
2All have high hardness and thermostability, make such matrix material have higher high temperature wear resistant performance.The present invention compares with patent CN102021557A, and chemical reaction occurs in the agitating friction course of processing, does not need follow-up heat-processed, save production cost, and in the agitating friction course of processing, ZrO
2, B and Al matrix sufficient reacting under the vigorous stirring effect.
Description of drawings
Fig. 1 is preparation method's agitating friction processing principle of work synoptic diagram of the present invention;
Fig. 2 makes the product shape appearance figure for the present invention;
Wherein, 1. aluminium sheet, 2. stirring tool, 3. particles filled zone, 4. aluminum matrix composite zone.
Embodiment
Further specify below in conjunction with embodiment.
Embodiment 1
Thick 6061 aluminium alloy plates of body material: 10mm.
Add particle: monoclinic zirconia (median size 80nm, purity 99.8%), amorphous boron (median size 500nm, purity is 96%).
ZrO
2Particle mixes by mass ratio 11:2 with the B particle, and composite grain is carried out ball milling; The ball milling time is 2 hours, and rotating speed is 80r/min, and ratio of grinding media to material is 15:1.
In aluminium sheet region intermediate processing three row's blind holes, hole depth and diameter are 4mm, and pitch of holes is 2mm.
Composite grain is poured in the volatile organic solvent behind the ball milling, mixes the back and adds in blind hole or the groove; Treat to fill again after the organic solvent volatilization, until tamping;
Agitating friction processing original position synthesis technologic parameter: speed of rotation 900r/min, gait of march 60mm/min, volume under pressure 0.1mm, 2.5 ° at pitch angle, the processing number of times is 5 times, 5 times all along identical direct of travel.
The material composite bed microhardness that makes is about 2.5 times of mother metals, and the high temperature wear resistant performance is 1.4 times of mother metals.
Embodiment 2
Thick 6061 aluminium alloy plates of body material: 10mm.
Add particle: monoclinic zirconia (median size 80nm, purity 99.8%), amorphous boron (median size 500nm, purity is 96%).
ZrO
2Particle mixes by mass ratio 11:2 with the B particle, and composite grain is carried out ball milling; The ball milling time is 3 hours, and rotating speed is 60r/min, and ratio of grinding media to material is 15:1.
In aluminium sheet region intermediate processing three row's blind holes, hole depth and diameter are 4mm, and pitch of holes is 2mm.
Composite grain is poured in the volatile organic solvent behind the ball milling, mixes the back and adds in blind hole or the groove; Treat to fill again after the organic solvent volatilization, until tamping;
Agitating friction processing original position synthesis technologic parameter: speed of rotation 1100r/min, gait of march 50mm/min, volume under pressure 0.2mm, 2 ° at pitch angle, the processing number of times is 6 times, 6 times all along identical direct of travel.
The material composite bed microhardness that makes is about 2.3 times of mother metals, and the high temperature wear resistant performance is 1.6 times of mother metals.
Embodiment 3
The thick aluminium sheet of body material: 10mm.
Add particle: monoclinic zirconia (median size 80nm, purity 99.8%), amorphous boron (median size 500nm, purity is 96%).
ZrO
2Particle mixes by mass ratio 11:2 with the B particle, and composite grain is carried out ball milling; The ball milling time is 8 hours, and rotating speed is 40r/min, and ratio of grinding media to material is 15:1.
In aluminium sheet region intermediate processing three row's blind holes, hole depth and diameter are 4mm, and pitch of holes is 2mm.
Composite grain is poured in the volatile organic solvent behind the ball milling, mixes the back and adds in blind hole or the groove; Treat to fill again after the organic solvent volatilization, until tamping;
Agitating friction processing original position synthesis technologic parameter: speed of rotation 600r/min, gait of march 40mm/min, volume under pressure 0.1mm, 2.5 ° at pitch angle, the processing number of times is 4 times, 4 times all along identical direct of travel.
The material composite bed microhardness that makes is about 2.1 times of mother metals, and the high temperature wear resistant performance is 1.5 times of mother metals.
Claims (6)
1. aluminum oxide and zirconium diboride strengthen the preparation method of aluminum-based in-situ composite materials, it is characterized in that, comprise that step is as follows:
(1) with ZrO
2Particle mixes by mass ratio 11:2 with the B particle, or with ZrO
2Particle and B
2O
3Particle is pressed mass ratio 5:2 and is mixed, and composite grain is carried out ball milling;
(2) be matrix with fine aluminium or aluminium alloy plate, composite grain behind the ball milling is added in the matrix;
(3) agitating friction processing is carried out in the particles filled zone of matrix, the stirring tool speed of rotation is 600～3000r/min, and gait of march is 30～60mm/min, volume under pressure is 0.05～0.6mm, the pitch angle is 0～3 °, and the processing number of times is 3～8 times, ZrO in the course of processing
2, B or B
2O
3Chemical reaction takes place in particle and aluminum substrate jointly, finally obtains aluminum oxide and zirconium diboride and strengthens aluminum-based in-situ composite materials.
2. aluminum oxide according to claim 1 and zirconium diboride strengthen the preparation method of aluminum-based in-situ composite materials, it is characterized in that the described ball milling time of step (1) is 1～10 hour, and rotating speed is 50～100r/min, and ratio of grinding media to material is 5-15:1.
3. aluminum oxide according to claim 1 and zirconium diboride strengthen the preparation method of aluminum-based in-situ composite materials, it is characterized in that described ZrO
2The particle median size is that purity is 90～99.9%, B or B between 10nm～10 μ m
2O
3The particle median size is that purity is 90～99.9% between 10nm～100 μ m.
4. aluminum oxide according to claim 1 and zirconium diboride strengthen the preparation method of aluminum-based in-situ composite materials, it is characterized in that, the mode that the described composite grain of step (2) adds in the matrix has: (1) is in matrix surface or inner open channels or blind hole, composite grain is added in groove or the blind hole, and tamp; (2) method with spraying or coating adds matrix surface with composite grain.
5. aluminum oxide according to claim 1 and zirconium diboride strengthen the preparation method of aluminum-based in-situ composite materials, it is characterized in that, twice machine direction or sense of rotation are identical or opposite before and after the processing of step (3).
6. aluminum oxide and the zirconium diboride of the described method preparation of claim 1 strengthen aluminum-based in-situ composite materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310247841.8A CN103276389B (en) | 2013-06-20 | 2013-06-20 | Aluminium oxide strengthens aluminum-based in-situ composite materials and preparation method thereof with zirconium diboride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310247841.8A CN103276389B (en) | 2013-06-20 | 2013-06-20 | Aluminium oxide strengthens aluminum-based in-situ composite materials and preparation method thereof with zirconium diboride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103276389A true CN103276389A (en) | 2013-09-04 |
| CN103276389B CN103276389B (en) | 2016-08-17 |
Family
ID=49058998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310247841.8A Expired - Fee Related CN103276389B (en) | 2013-06-20 | 2013-06-20 | Aluminium oxide strengthens aluminum-based in-situ composite materials and preparation method thereof with zirconium diboride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103276389B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451236A (en) * | 2014-11-07 | 2015-03-25 | 江苏大学 | In-situ preparation method of nano ZrB2 particle reinforced aluminum matrix composite |
| CN104674085A (en) * | 2015-02-02 | 2015-06-03 | 安徽省斯特嘉汽车零部件有限公司 | Preparation method of zirconium diboride reinforced 7A04 aluminium alloy hub |
| CN109234562A (en) * | 2018-10-31 | 2019-01-18 | 江苏大学 | A method of regulation prepares binary nanoparticles reinforced aluminum matrix composites in situ |
| CN109676328A (en) * | 2019-02-12 | 2019-04-26 | 黄山学院 | A kind of inclined-plane workpiece surface modification method and device |
| CN110042280A (en) * | 2019-06-05 | 2019-07-23 | 山东大学 | A kind of in-situ endogenic multiphase particle reinforced aluminum matrix composites and preparation method thereof |
| CN110666447A (en) * | 2019-09-02 | 2020-01-10 | 西安建筑科技大学 | Magnesium alloy material with mixed crystal structure and preparation method thereof |
| CN111531266A (en) * | 2020-05-07 | 2020-08-14 | 广东省焊接技术研究所（广东省中乌研究院） | Friction stir welding equipment and method for particle-reinforced gradient composite material |
| CN116121581A (en) * | 2023-01-17 | 2023-05-16 | 江苏大学 | Particle reinforced aluminum-based composite intermediate alloy, aluminum-based composite material and preparation methods thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6179776A (en) * | 1984-09-26 | 1986-04-23 | Agency Of Ind Science & Technol | Manufacture of composite pipe |
| CN1796036A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院金属研究所 | Method for preparing surface aluminium based composite material |
| CN101250700A (en) * | 2008-04-03 | 2008-08-27 | 清华大学 | Solid-state processing method for producing lamina profunda, agglomerate body, macrography spectrum composite material |
| CN102021557A (en) * | 2010-12-03 | 2011-04-20 | 湖北工业大学 | Al2O3 and TiB2 compound coating synthesized by aluminium alloy surface stirring rubbing processing and heating reaction and preparation method of Al2O3+TiB2 compound coating |
-
2013
- 2013-06-20 CN CN201310247841.8A patent/CN103276389B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6179776A (en) * | 1984-09-26 | 1986-04-23 | Agency Of Ind Science & Technol | Manufacture of composite pipe |
| CN1796036A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院金属研究所 | Method for preparing surface aluminium based composite material |
| CN101250700A (en) * | 2008-04-03 | 2008-08-27 | 清华大学 | Solid-state processing method for producing lamina profunda, agglomerate body, macrography spectrum composite material |
| CN102021557A (en) * | 2010-12-03 | 2011-04-20 | 湖北工业大学 | Al2O3 and TiB2 compound coating synthesized by aluminium alloy surface stirring rubbing processing and heating reaction and preparation method of Al2O3+TiB2 compound coating |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451236A (en) * | 2014-11-07 | 2015-03-25 | 江苏大学 | In-situ preparation method of nano ZrB2 particle reinforced aluminum matrix composite |
| CN104674085A (en) * | 2015-02-02 | 2015-06-03 | 安徽省斯特嘉汽车零部件有限公司 | Preparation method of zirconium diboride reinforced 7A04 aluminium alloy hub |
| CN109234562B (en) * | 2018-10-31 | 2020-12-18 | 江苏大学 | Method for preparing in-situ binary nanoparticle reinforced aluminum matrix composite material through regulation and control |
| CN109234562A (en) * | 2018-10-31 | 2019-01-18 | 江苏大学 | A method of regulation prepares binary nanoparticles reinforced aluminum matrix composites in situ |
| CN109676328A (en) * | 2019-02-12 | 2019-04-26 | 黄山学院 | A kind of inclined-plane workpiece surface modification method and device |
| CN109676328B (en) * | 2019-02-12 | 2023-11-21 | 黄山学院 | Inclined plane workpiece surface modification method and device |
| CN110042280A (en) * | 2019-06-05 | 2019-07-23 | 山东大学 | A kind of in-situ endogenic multiphase particle reinforced aluminum matrix composites and preparation method thereof |
| CN110042280B (en) * | 2019-06-05 | 2020-09-08 | 山东大学 | In-situ endogenous multiphase particle reinforced aluminum matrix composite material and preparation method thereof |
| CN110666447B (en) * | 2019-09-02 | 2021-07-27 | 西安建筑科技大学 | Magnesium alloy material with mixed crystal structure and preparation method thereof |
| CN110666447A (en) * | 2019-09-02 | 2020-01-10 | 西安建筑科技大学 | Magnesium alloy material with mixed crystal structure and preparation method thereof |
| CN111531266A (en) * | 2020-05-07 | 2020-08-14 | 广东省焊接技术研究所（广东省中乌研究院） | Friction stir welding equipment and method for particle-reinforced gradient composite material |
| CN111531266B (en) * | 2020-05-07 | 2021-08-31 | 广东省科学院中乌焊接研究所 | Friction stir welding equipment and method for particle-reinforced gradient composite material |
| CN116121581A (en) * | 2023-01-17 | 2023-05-16 | 江苏大学 | Particle reinforced aluminum-based composite intermediate alloy, aluminum-based composite material and preparation methods thereof |
| CN116121581B (en) * | 2023-01-17 | 2024-03-19 | 江苏大学 | Particle reinforced aluminum-based composite intermediate alloy, aluminum-based composite material and preparation methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103276389B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103276389A (en) | Aluminium oxide and zirconium diboride reinforced aluminum matrix in-situ composite and preparation method thereof | |
| CN102021557B (en) | Preparation method of Al2O3 and TiB2 compound coating synthesized by aluminium alloy surface stirring rubbing processing and heating reaction | |
| CN106676335B (en) | A kind of graphene aluminum silicon carbide composite material and preparation method thereof and its application | |
| CN101555137B (en) | (TiB2 plus TiC)/Ti3SiC2 multi-phase ceramic material and preparation method thereof | |
| US20180186700A1 (en) | Method for synthesizing high-purity ultrafine ZrC-SiC composite powder | |
| CN102618774B (en) | Manufacturing method of metal matrix nanocomposites with high toughness | |
| CN1982506B (en) | Electrolytic reduction of metal oxides such as titanium dioxide and process applications | |
| CN103540783B (en) | A kind of titanium aluminium carbon granule strengthens Zn Al Alloy Matrix Composites and pressureless sintering preparation method thereof | |
| KR101821220B1 (en) | Method for preparing titanium nitride-titanium diboride-cubic boron nitride composite | |
| CN105478777A (en) | Metal/ceramic gradient material and preparation method thereof | |
| CN102787252B (en) | Method for preparing TiB2 reinforced aluminium matrix composite in situ | |
| CN103073320B (en) | Preparation method for ZrB2-SiC (w) ceramic raw material | |
| CN104209498A (en) | Preparing method of interface modification layer of ceramic particle enhanced metal base composite material | |
| CN104498752A (en) | Preparation method of micro-nano particle reinforced aluminium matrix composite | |
| CN103484814A (en) | Preparation method of titanium boride based inorganic composite coating | |
| CN101913876A (en) | Method for preparing zirconium boride-tungsten titanium carbide self-lubricating composite ceramic material | |
| CN110744058A (en) | Preparation method for in-situ synthesis of copper-based composite material | |
| CN105272260A (en) | Unbonded-phase tungsten carbide composite material and preparation method thereof | |
| CN103898499A (en) | Method for preparing SiC/Al2O3 coating by using precursor conversion method | |
| CN103014492B (en) | A kind of Mo 2feB 2the preparation method of base thermal spraying alloy powder | |
| CN103305825B (en) | A kind of aluminum oxide and three calorize zirconiums strengthen base surface in-situ composite material and preparation method thereof | |
| CN106396688A (en) | Fast preparation method of TiB-TiC-TiB2-B4C composite ceramic | |
| CN105483487B (en) | A kind of Boral alloy composite materials containing zirconium and preparation method thereof | |
| CN109231990A (en) | A kind of preparation method of tungsten carbide-diamond composite | |
| CN105728715B (en) | A kind of coated SiO2The preparation method of/Al composite granules |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20200620 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |