CN101812705A - Ultrasonic processing method for enhancing size accuracy of micro-electroformed apparatus - Google Patents
Ultrasonic processing method for enhancing size accuracy of micro-electroformed apparatus Download PDFInfo
- Publication number
- CN101812705A CN101812705A CN 201010133989 CN201010133989A CN101812705A CN 101812705 A CN101812705 A CN 101812705A CN 201010133989 CN201010133989 CN 201010133989 CN 201010133989 A CN201010133989 A CN 201010133989A CN 101812705 A CN101812705 A CN 101812705A
- Authority
- CN
- China
- Prior art keywords
- micro
- electroformed
- electroforming
- substrate
- glue
- 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 ultrasonic processing method for enhancing the size accuracy of a micro-electroformed apparatus, belongs to the technical field of micro-manufacturing and particularly relates to a method for enhancing the size accuracy of the micro-electroformed apparatus. A process for manufacturing the micro-electroformed apparatus comprises the following processes: performing pretreatment on a nickel substrate, manufacturing a micro-electroformed rubber mold and performing micro-electroforming. In the process of manufacturing the micro-electroformed rubber mold, the nickel substrate coated with SU-8 rubber is fixed on an ultrasonic workbench after whirl coating, prebaking, photo-etching and after-baking are performed, is ultrasonically vibrated and developed to obtain the micro-electroformed rubber mold. The micro-electroformed rubber mold is soaked into electrotyping solution and is subjected to electro-deposition in a groove of the micro-electroformed rubber mold to form a nickel-electroformed layer. The SU-8 rubber is removed and vacuum annealing treatment is performed to eliminate residual stress. Due to the adoption of the method, the amount of the electrotyping solution absorbed by the SU-8 rubber in the electroforming process is reduced, swelling of the rubber mold is lowered and the size accuracy of the micro-electroformed apparatus is enhanced.
Description
Technical field
The invention belongs to the micro-fabrication technology field, particularly improve the method for size accuracy of micro-electroformed apparatus.
Background technology
The manufacturing field that has been widely used in micro elements such as micro sensor, microactrator and minisize mould based on little galvanoplastics of SU-8 glue UV-LIGA technology.In little electroforming process, SU-8 glue can absorb electroforming solution, causes the rubber moulding volumetric expansion, produces swelling effect, and metal construction and size differ even can reach 50% after the electroforming.The swelling of photoresist material rubber moulding has a strong impact on the controllability and the accuracy of electroformed apparatus scantlings of the structure.The error that PMMA colloid swelling is brought when reducing electroforming, magazine Mcirosystem Technologies proposed in the phase 116-119 page or leaf to carry out the method for electroforming at ambient temperature to reduce the rubber moulding swelling in 2002 the 8th, but reduce the electroforming temperature and not only influence the cast layer sedimentation velocity, but also the cast layer internal stress is increased, cast layer comes off easily.Magazine Journal of Micromechanics and Microengineering proposed a kind of scheme that increases the isolation strip around the rubber moulding figure in 2004 the 14th in the phase 1548-1557 page or leaf, in order to reduce on every side big area PMMA colloidal swelling to the influence of electroforming structure, this method is only effective to peripheral structure, and is inoperative for middle portion intensive, complex figure.The method that document 1,2 provides can be applied in little electroforming process of SU-8 rubber moulding, but equally also has above-mentioned problem.
The dimensional precision of little electroforming structure is lower, and is difficult to control the further raising that has restricted the micro element performance, how to reduce in the electroforming process, and the scale error that the rubber moulding swelling causes is a urgent problem during micro-electroformed apparatus is made.
Summary of the invention
The technical barrier that the present invention will solve is deficiency and the application limit that overcomes above-mentioned existing method, proposes the little electroforming rubber moulding of a kind of reduction swelling, to improve the novel method of size accuracy of micro-electroformed apparatus.This method is utilized supersound process SU-8 glue, can reduce in the electroforming process SU-8 glue to the absorbed dose of electroforming solution, reduces the rubber moulding swelling, thereby improves the dimensional precision of electroformed apparatus.
The technical solution used in the present invention is a kind of SU-8 glue 2 to be carried out supersound process, to improve the method for size accuracy of micro-electroformed apparatus, comprises making and little electroforming process of ni substrate 1 pre-treatment, little electroforming rubber moulding.It is characterized in that, in the process of making little electroforming rubber moulding, after whirl coating, preceding baking, photoetching and the back baking, the ni substrate 1 that scribbles SU-8 glue 2 is fixed on the ultrasonic workbench 7, utilize ultrasonic US to carry out vibration treatment, and then develop.The making step of micro-electroformed apparatus is as follows:
A. earlier ni substrate 1 is carried out mechanical grinding and polishing, the surface roughness Ra of polishing back ni substrate 1 is less than 0.04 μ m, then, utilize acetone and dehydrated alcohol that ni substrate 1 was carried out ultrasonic cleaning each 20 minutes successively, after washing with deionized water again, dry up with nitrogen, put into 120 ℃ of oven-baked about 60 minutes;
B. after treating that ni substrate 1 is cooled to room temperature, apply SU-8 glue 2 in its surface rotation, in order to improve the planarization of glue-line, after whirl coating finished, first level left standstill from smooth about 30 minutes, puts into baking oven again and carries out preceding baking, 65 ℃ were dried by the fire 40～60 minutes before this, and then 85 ℃ were dried by the fire 40～60 minutes;
C. after treating that the gluing ni substrate is cooled to room temperature, place it on the lithography machine, cover mask plate 3, by hard contact, ultraviolet (UV) irradiation exposure, figure on the realization mask plate 3 then, carries out the back baking with the gluing ni substrate after the exposure to the transfer of SU-8 glue 2,85 ℃ of back baking temperature, 1.5～3 minutes back baking time;
D. in order to reduce in the electroforming process SU-8 glue to the absorbed dose of electroforming solution, reduce the swelling of glued membrane, thereby improve the dimensional precision of micro-electroformed apparatus, after treating that the gluing ni substrate is cooled to room temperature, carry out supersound process, be fixed on the ultrasonic workbench 7, coated face up, supersound process 5～10 minutes, ultrasonic frequency 20kHz, power 100～150W;
E. ni substrate can heating up in the supersound process process, need be cooled to room temperature after, utilize the SU-8 glue developing solution to develop again, be not subjected to the colloid dissolving of light-struck position after the development, raceway groove 4 occurs, thereby obtain little electroforming rubber moulding;
F. little electroforming rubber moulding is immersed in the electroforming solution, in the raceway groove 4 of little electroforming rubber moulding, realize galvanic deposit, form nickel cast layer 5;
G. electroforming is good device immerses and is equipped with in the beaker of SU-8 glue glue-dispenser Remove PG, place the ultrasonic cleaning machine to remove photoresist, 80～90 ℃ of bath temperatures, with the micro-electroformed apparatus after removing photoresist with deionized water rinsing after, put into vacuum oven, treat that the perfect vacuum degree reaches 10
-3Behind the Pa, be heated to 350～400 ℃, keep about 90 minutes after, furnace cooling is to remove unrelieved stress.
The invention has the beneficial effects as follows: overcome deficiency and application limit that the size accuracy of micro-electroformed apparatus methods are improved in low temperature electroforming and increase isolation strip etc., utilize when making rubber moulding and ultrasonic SU-8 glue is handled, reduce in the electroforming process SU-8 glue to the absorbed dose of electroforming solution, reduce the swelling of rubber moulding, improve the dimensional precision of micro-electroformed apparatus.
Description of drawings
Fig. 1 is an exposure process, and Fig. 2 is the supersound process operation, and Fig. 3 is a developing procedure, and Fig. 4 is little electroforming process, and Fig. 5 is a postprocessing working procedures.Wherein: the 1-ni substrate, 2-SU-8 glue, the 3-mask plate, the 4-raceway groove, 5-nickel cast layer, the UV-UV-light, US-is ultrasonic.
Fig. 6 is the supersound process synoptic diagram.Wherein: 6-gluing substrate, 7-ultrasonic workbench, 8-ultrasonic amplitude transformer, the ultrasonic generating unit of 9-.
Embodiment
Below in conjunction with technical scheme and accompanying drawing, describe the concrete embodiment of the present invention in detail.
Example: electroforming linear pattern micro-mould on ni substrate 1, ni substrate 1 is of a size of 63 * 63mm, collinear is of a size of wide 100 μ m on the mask plate 3, long 20mm, and the concrete steps of making this mould are as follows: 1, ni substrate pre-treatment: the mechanical grinding, polishing and the surface cleaning that comprise ni substrate 1.The surface roughness Ra of polishing back ni substrate 1 is less than 0.04 μ m.The surface cleaning idiographic flow is as follows:
(1) ni substrate 1 is placed acetone, ultrasonic cleaning 20 minutes;
(2) use dehydrated alcohol instead, ultrasonic cleaning 20 minutes;
(3) after deionized water washes, dry up, put into 120 ℃ of oven-baked 60 minutes with nitrogen.2, whirl coating and preceding baking: after treating that ni substrate 1 is cooled to room temperature, applying model in its surface rotation is 2015 SU-8 glue 2, whirl coating thickness 70 μ m, in order to improve the planarization of glue-line, whirl coating finishes the first level in back and leaves standstill from smooth 30 minutes, put into baking oven again and carry out preceding baking, 65 ℃ were dried by the fire 40 minutes before this, and then 85 ℃ were dried by the fire 40 minutes.
3, exposure and back baking: after treating that the gluing ni substrate is cooled to room temperature, place it on the lithography machine, cover mask plate 3, by hard contact, ultraviolet (UV) irradiation exposure, the figure on the realization mask plate 3 is seen accompanying drawing 1 to the transfer of SU-8 glue 2, then, gluing ni substrate after the exposure is carried out the back baking, 85 ℃ of back baking temperature, 1.5 minutes back baking time.
4, supersound process: after treating that gluing ni substrate 6 is cooled to room temperature, be fixed on the ultrasonic workbench 7, coated face utilizes ultrasonic US to carry out vibration treatment 5 minutes up, ultrasonic frequency 20kHz, and power 150W sees accompanying drawing 2 and accompanying drawing 6.
5, develop: substrate can heating up in the supersound process process, utilizes the SU-8 glue developing solution to develop again after need being cooled to room temperature, is not subjected to the colloid dissolving of light-struck position after the development, raceway groove 4 occurs, thereby obtains little electroforming rubber moulding, sees accompanying drawing 3.
6, little electroforming: little electroforming rubber moulding is immersed in the electroforming solution, in the raceway groove 4 of little electroforming rubber moulding, realize galvanic deposit, form nickel cast layer 5, see accompanying drawing 4.The prescription of electroforming solution is nickel sulfamic acid 360g/L, nickelous chloride 5g/L, boric acid 50g/L, electroforming solution pH value 3.5,50 ℃ of electroforming temperature, current density 2A/dm
2
7, aftertreatment: comprise successively and remove SU-8 glue 2 and vacuum annealing.Detailed process is: the device that electroforming is good immerses and is equipped with in the beaker of SU-8 glue glue-dispenser Remove PG, places the ultrasonic cleaning machine to remove photoresist, 80 ℃ of bath temperatures; Micro-electroformed apparatus after removing photoresist is put into vacuum oven after with deionized water rinsing, treat that the perfect vacuum degree reaches 10
-3Behind the Pa, be heated to 350 ℃, keep furnace cooling after 90 minutes,, see accompanying drawing 5 to remove unrelieved stress.
Adopt the present invention to propose, utilize the ultrasonic method that SU-8 glue is handled when making little electroforming rubber moulding, can reduce that SU-8 glue reduces the swelling of rubber moulding to the absorbed dose of electroforming solution in the electroforming process, thereby improve the dimensional precision of micro-electroformed apparatus.When other processing parameters were identical, the mould that utilizes the rubber moulding electroforming after the supersound process to go out had improved 25% than the dimensional precision without supersound process.
Claims (1)
1. ultrasonic processing method that improves size accuracy of micro-electroformed apparatus, it is characterized in that, in the process of making little electroforming rubber moulding, after whirl coating, preceding baking, photoetching and the back baking, the ni substrate (1) that will scribble SU-8 glue (2) is fixed to and carries out the ultrasonic vibration processing on the ultrasonic workbench (5), and then develop, the concrete making step of micro-electroformed apparatus is as follows:
A. earlier ni substrate (1) is carried out mechanical grinding and polishing, the surface roughness Ra of polishing back ni substrate (1) is less than 0.04 μ m, then, utilize acetone and dehydrated alcohol that ni substrate (1) was carried out ultrasonic cleaning respectively each 20 minutes successively, after washing with deionized water again, dry up with nitrogen, put into 120 ℃ of oven-baked about 60 minutes;
B. after treating that ni substrate (1) is cooled to room temperature, apply SU-8 glue (2) in its surface rotation, in order to improve the planarization of glue-line, after whirl coating finished, first level left standstill from smooth about 30 minutes, puts into baking oven again and carries out preceding baking, 65 ℃ were dried by the fire 40～60 minutes before this, and then 85 ℃ were dried by the fire 40～60 minutes;
C. after treating that the gluing ni substrate is cooled to room temperature, place it on the lithography machine, cover mask plate (3), by hard contact, ultraviolet (UV) irradiation exposure, figure on the realization mask plate (3) then, carries out the back baking with the gluing ni substrate after the exposure to the transfer of SU-8 glue (2), 85 ℃ of back baking temperature, 1.5～3 minutes back baking time;
D. in order to reduce in the electroforming process SU-8 glue to the absorbed dose of electroforming solution, reduce the swelling of glued membrane, thereby improve the dimensional precision of micro-electroformed apparatus, after treating that the gluing ni substrate is cooled to room temperature, carry out supersound process, be fixed on the ultrasonic workbench (7), coated face up, supersound process 5～10 minutes, ultrasonic frequency 20kHz, power 100～150W;
E. ni substrate can heating up in the supersound process process, need be cooled to room temperature after, utilize the SU-8 glue developing solution to develop again, be not subjected to the colloid dissolving of light-struck position after the development, raceway groove (4) occurs, thereby obtain little electroforming rubber moulding;
F. little electroforming rubber moulding is immersed in the electroforming solution, in the raceway groove (4) of little electroforming rubber moulding, realize galvanic deposit forming nickel cast layer (5);
G. electroforming is good device immerses and is equipped with in the beaker of SU-8 glue glue-dispenser Remove PG, place the ultrasonic cleaning machine to remove photoresist, 80～90 ℃ of bath temperatures, with the micro-electroformed apparatus after removing photoresist with deionized water rinsing after, put into vacuum oven, treat that the perfect vacuum degree reaches 10
-3Behind the Pa, be heated to 350～400 ℃, keep about 90 minutes after, furnace cooling is to remove unrelieved stress.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101339895A CN101812705B (en) | 2010-03-25 | 2010-03-25 | Ultrasonic processing method for enhancing size accuracy of micro-electroformed apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101339895A CN101812705B (en) | 2010-03-25 | 2010-03-25 | Ultrasonic processing method for enhancing size accuracy of micro-electroformed apparatus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101812705A true CN101812705A (en) | 2010-08-25 |
| CN101812705B CN101812705B (en) | 2012-02-29 |
Family
ID=42620068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101339895A Expired - Fee Related CN101812705B (en) | 2010-03-25 | 2010-03-25 | Ultrasonic processing method for enhancing size accuracy of micro-electroformed apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101812705B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102494833A (en) * | 2011-12-16 | 2012-06-13 | 淮阴工学院 | Mini-type pressure sensor based on SU-8 polymer |
| CN102618893A (en) * | 2012-04-20 | 2012-08-01 | 大连理工大学 | Method for adjusting micro electroforming current density to improve casting layer interface bonding strength |
| CN103088374A (en) * | 2013-02-27 | 2013-05-08 | 大连理工大学 | Ultrasound-assisted electroforming method for improving thickness uniformity of micro-electroforming coating |
| CN103205785A (en) * | 2012-01-16 | 2013-07-17 | 昆山允升吉光电科技有限公司 | A film stripping process |
| CN103436923A (en) * | 2013-05-28 | 2013-12-11 | 大连理工大学 | Method for increasing interfacial bonding strength between SU-8 photoresist and metal substrate by ultrasound |
| CN105603468A (en) * | 2015-12-21 | 2016-05-25 | 大连理工大学 | Method for preparing high-density microfine nickel column array on metal nickel substrate |
| CN106099650A (en) * | 2016-08-01 | 2016-11-09 | 安徽贝莱电子科技有限公司 | A kind of production technology of radar discharging rod |
| CN107177866A (en) * | 2017-04-28 | 2017-09-19 | 大连理工大学 | The method that micro- radio frequency T-shaped power splitter is prepared in metallic substrates |
| CN108560024A (en) * | 2018-05-11 | 2018-09-21 | 大连理工大学 | Reduce the million sound auxiliary electrocasting method of micro- electroformed layer residual stress |
| CN114150350A (en) * | 2021-11-09 | 2022-03-08 | 北京工业大学 | Preparation method of corrosion-resistant and hydrophobic micro-nano part |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424433A (en) * | 1980-05-15 | 1984-01-03 | Inoue-Japax Research Incorporated | Method and apparatus for electrically machining a conductive workpiece with isotropic ultrasonic-waves radiation |
| JP2001254193A (en) * | 2000-01-07 | 2001-09-18 | Citizen Watch Co Ltd | Method of manufacturing electrocast parts |
| CN1482282A (en) * | 2003-07-03 | 2004-03-17 | 上海交通大学 | Process method of pore based on photolithograph |
| CN1715973A (en) * | 2005-05-19 | 2006-01-04 | 上海交通大学 | Method for preparing metal base micro machinery optical fiber position clip |
| CN1986011A (en) * | 2006-12-08 | 2007-06-27 | 中国科学院上海微系统与信息技术研究所 | Miniature needle array for medicine transmission and its making process |
| CN101276159A (en) * | 2008-04-25 | 2008-10-01 | 大连理工大学 | Apparatus and method of polymer photoresist ultrasonic ageing effect |
-
2010
- 2010-03-25 CN CN2010101339895A patent/CN101812705B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424433A (en) * | 1980-05-15 | 1984-01-03 | Inoue-Japax Research Incorporated | Method and apparatus for electrically machining a conductive workpiece with isotropic ultrasonic-waves radiation |
| JP2001254193A (en) * | 2000-01-07 | 2001-09-18 | Citizen Watch Co Ltd | Method of manufacturing electrocast parts |
| CN1482282A (en) * | 2003-07-03 | 2004-03-17 | 上海交通大学 | Process method of pore based on photolithograph |
| CN1715973A (en) * | 2005-05-19 | 2006-01-04 | 上海交通大学 | Method for preparing metal base micro machinery optical fiber position clip |
| CN1986011A (en) * | 2006-12-08 | 2007-06-27 | 中国科学院上海微系统与信息技术研究所 | Miniature needle array for medicine transmission and its making process |
| CN101276159A (en) * | 2008-04-25 | 2008-10-01 | 大连理工大学 | Apparatus and method of polymer photoresist ultrasonic ageing effect |
Non-Patent Citations (2)
| Title |
|---|
| 《光学精密工程》 20080315 杜立群等 后烘温度对SU-8光刻胶热溶胀性及内应力的影响 , 第03期 2 * |
| 《压电与声光》 20081015 杜立群等 UV-LIGA工艺中SU-8光刻胶的热溶胀性研究 , 第05期 2 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102494833A (en) * | 2011-12-16 | 2012-06-13 | 淮阴工学院 | Mini-type pressure sensor based on SU-8 polymer |
| CN103205785A (en) * | 2012-01-16 | 2013-07-17 | 昆山允升吉光电科技有限公司 | A film stripping process |
| CN102618893A (en) * | 2012-04-20 | 2012-08-01 | 大连理工大学 | Method for adjusting micro electroforming current density to improve casting layer interface bonding strength |
| CN103088374A (en) * | 2013-02-27 | 2013-05-08 | 大连理工大学 | Ultrasound-assisted electroforming method for improving thickness uniformity of micro-electroforming coating |
| CN103436923A (en) * | 2013-05-28 | 2013-12-11 | 大连理工大学 | Method for increasing interfacial bonding strength between SU-8 photoresist and metal substrate by ultrasound |
| CN103436923B (en) * | 2013-05-28 | 2015-12-23 | 大连理工大学 | The method of ultrasonic raising SU-8 photoresist material and metal base interface bond strength |
| CN105603468A (en) * | 2015-12-21 | 2016-05-25 | 大连理工大学 | Method for preparing high-density microfine nickel column array on metal nickel substrate |
| CN106099650A (en) * | 2016-08-01 | 2016-11-09 | 安徽贝莱电子科技有限公司 | A kind of production technology of radar discharging rod |
| CN107177866A (en) * | 2017-04-28 | 2017-09-19 | 大连理工大学 | The method that micro- radio frequency T-shaped power splitter is prepared in metallic substrates |
| CN107177866B (en) * | 2017-04-28 | 2019-03-05 | 大连理工大学 | The method of micro- radio frequency T shape power splitter is prepared in metallic substrates |
| CN108560024A (en) * | 2018-05-11 | 2018-09-21 | 大连理工大学 | Reduce the million sound auxiliary electrocasting method of micro- electroformed layer residual stress |
| CN108560024B (en) * | 2018-05-11 | 2019-08-09 | 大连理工大学 | Reduce the million sound auxiliary electrocasting method of micro- electroformed layer residual stress |
| CN114150350A (en) * | 2021-11-09 | 2022-03-08 | 北京工业大学 | Preparation method of corrosion-resistant and hydrophobic micro-nano part |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101812705B (en) | 2012-02-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101812705B (en) | Ultrasonic processing method for enhancing size accuracy of micro-electroformed apparatus | |
| CN103436923B (en) | The method of ultrasonic raising SU-8 photoresist material and metal base interface bond strength | |
| CN106736306B (en) | Metal shell of electronic product and surface treatment method thereof | |
| JP5968741B2 (en) | Method for forming laminated aperture reticulated polishing pad | |
| CN103576450B (en) | The method preparing nanometer grade thickness thin film and structure in curved substrate | |
| CN103276435B (en) | Micro-nano processing method for aluminum/aluminum alloy surface and aluminum/ aluminum alloy structure | |
| CN205430880U (en) | Electromagnetic shield piece is used to wireless charging | |
| CN104191320A (en) | Ultrasonic control shear thickening and polishing method and device | |
| CN102732916B (en) | A kind of fast electric casting process | |
| CN105603468B (en) | The method that highly dense fine nickel cylindrical-array is prepared in metal nickel substrate | |
| CN103088374A (en) | Ultrasound-assisted electroforming method for improving thickness uniformity of micro-electroforming coating | |
| DE602005012630D1 (en) | Process for producing a lithographic printing plate | |
| JP2010538468A5 (en) | ||
| JP2013067001A (en) | Method of forming open-network polishing pad | |
| JP2009506538A5 (en) | ||
| CN111014959A (en) | Bionic surface preparation method based on laser impact imprinting technology | |
| CN105665368A (en) | Surface cleaning treatment method for aluminum alloy workpiece | |
| CN102618893A (en) | Method for adjusting micro electroforming current density to improve casting layer interface bonding strength | |
| CN106544705A (en) | The manufacture method of the micro- replica metal micro structure of precise electrotyping | |
| CN110592622B (en) | Ultrasonic potential activation method for improving bonding strength of electroforming metal film substrate interface | |
| CN108560024B (en) | Reduce the million sound auxiliary electrocasting method of micro- electroformed layer residual stress | |
| CN103951936B (en) | A kind of can the preparation method of shape-memory material of physics self-repairing super hydrophobic characteristic | |
| CN103985948A (en) | Low-loss manufacturing method of quartz probe | |
| CN105253852A (en) | Manufacturing method of template of micro-nano composite structure | |
| CN101430385B (en) | Improved spring leaf production technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| 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: 20120229 Termination date: 20150325 |
|
| EXPY | Termination of patent right or utility model |