CN101429350A - Method for producing nano-organic/inorganic composite atom resistant oxygen coating - Google Patents
Method for producing nano-organic/inorganic composite atom resistant oxygen coating Download PDFInfo
- Publication number
- CN101429350A CN101429350A CNA2007101243725A CN200710124372A CN101429350A CN 101429350 A CN101429350 A CN 101429350A CN A2007101243725 A CNA2007101243725 A CN A2007101243725A CN 200710124372 A CN200710124372 A CN 200710124372A CN 101429350 A CN101429350 A CN 101429350A
- Authority
- CN
- China
- Prior art keywords
- coating
- solution
- atomic
- preparation
- coupling agent
- 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
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a method for preparing a nanometer organic/inorganic composite anti-atomic oxygen coating solution. The method comprises the following steps: tetraethyl orthosilicate, nanometer monox, nanometer alumina and a silane coupling agent (such as KH560) in certain proportion are mixed, are added with certain amount of ethanol as a solvent and are subjected to mechanical stirring through a magnetic stirrer; in the stirring process, proper amount of deionized water and inorganic acid are added into the mixture; and after certain time, the obtained solution is kept stand for a period of time so as to obtain the nanometer organic/inorganic composite anti-atomic oxygen coating solution. The solution can be used for coating the surface of polyimide through dip coating, brushing, pull spraying or rotary coating so as to obtain a coating layer. The obtained coating has the anti-atomic oxygen performance and can be used in an aerostat of a low orbit space.
Description
Technical field
Atomic-oxygen resistant coating solution, atomic-oxygen resistant coating preparation, the protection of space low orbit flyer anti-atomic oxygen
Background technology
The space material majority of using does not have the ability of opposing atomic oxygen erosion at present.When improving material property, applying protective coating on its surface is a convenient valid approach.But strict to the coating performance that use in the space, specifically comprise: (1) can provide good anti-atomic oxygen to corrode and the ability of uv-radiation, and should not change the fundamental property of body material; (2) not only thin but also light and firm with matrix bond; (3) there are not defective, pore and slight crack; (4) has good counter-bending and antistrip performance; (5) when Low Earth Orbit space environment long-term exposure, can keep stability; (6) has very low volatility and should satisfy the vacuum exhaust requirement; (7) technology of preparation coating satisfies with low cost and the efficient height, and easily expands on the large-size workpiece.
During space shuttle flight, the testing data that obtains after exposing under the Low Earth Orbit space environment shows that organosilyl erosion rate is than low 1～2 order of magnitude of polyimide in early days.Organic silicon coating and atomic oxygen reaction lose organic composition and form silicon oxide.Because density increases, coatingsurface shrinks, and has produced a microcosmic vesicular structure, can not stop oxidation.The fragility that inorganic coating has, mismatch in coefficient of thermal expansion and because the shortcomings such as change of the surface topography that the atomic oxygen sapping causes.
In recent years along with sol-gel technique this technology of widespread use in inorganic materials, glass, pottery, light coatings art has obtained bigger development, with organic and inorganic materials by the compound elite clone that obtains more suitably of sol-gel technique in material field at present, especially on material surface is handled.
Therefore synthesizing the compound coating of the organic-inorganic that possesses the excellent anti atomic oxygen by sol-gel method is a convenient and tangible approach.
Summary of the invention
Purpose of the present invention provides the method that a kind of composite atomic-oxygen resistant coating solution is synthetic and atomic-oxygen resistant coating prepares over against the problems referred to above.Adopt sol-gel method to prepare organic/inorganic composite atom resistant oxygen coating, promptly adopt tetraethoxy, nano silicon oxide, nano aluminium oxide and silane coupling agent raw material, obtain atomic-oxygen resistant coating by the collosol and gel approach.
Method of the present invention has been utilized organic and inorganic advantage performance.Organo silane coupling agent has good film forming properties in forming coating, forms the film with controllable thickness, smooth surface, and leakless produces.Inorganic part, the final hydrolysis of tetraethoxy forms the network structure of silicon-dioxide, has firm intensity, nano silicon oxide, nano aluminium oxide are then because crystallization is abundant, hardness is firm, make coating have impact-resistant performance, the defective of pliability and thickness is then remedied by the formation of organic moiety.Adopt the compound supercoat of organic-inorganic why can play a protective role; established silicon-dioxide of sol-gel method and nano silicon oxide and nano aluminium oxide constitute the protective layer of anti-atomic oxygen; uniform thin film coating with organosilicon formation; make organosilicon obtain protection to a certain extent; when a small amount of organosilicon structure is subjected to the atomic oxygen attack; siloxane bond has formed new silicon-dioxide again; many again protective layers newly, so the amount that the organic moiety in the organosilicon is lost because of the atomic oxygen attack then is reduced to minimum.The silicon-dioxide that forms by sol-gel method; nano silicon oxide; nano aluminium oxide; the silicon-dioxide that forms under the atomic oxygen bombardment with organosilicon has constituted the fine and close silicon-dioxide and the cross-linked layer of aluminum oxide together; attached to the surface, quaternary silicon has higher Thermodynamically stable valence state securely, does not react with atomic oxygen; hinder atomic oxygen and be penetrated into surface of polymer material, this has also just reached the good result of coating protection.
The invention provides the method that a kind of composite atomic-oxygen resistant coating solution is synthetic and atomic-oxygen resistant coating prepares, wherein the atomic-oxygen resistant coating solution manufacturing method is: the synthesis material of the solution that the preparation coating is used adopts tetraethoxy, nano silicon oxide, nano aluminium oxide and silane coupling agent, wherein the part by weight of tetraethyl silicate is 20 to 80%, the part by weight of nano silicon oxide is 2 to 10%, particle diameter is the 10-80 nanometer, the part by weight of nano aluminium oxide is 0 to 8%, particle diameter is the 10-80 nanometer, silane coupling agent adopts any in the following silane coupling agent: KH550, KH560, KH570, part by weight are 10 to 50%.Solvent adopts ethanol, and consumption of ethanol is tetraethoxy, nano silicon oxide, nano aluminium oxide and silane coupling agent total amount 1 to 100 times.Add deionized water 1-10%.Add mineral acid be in the following mineral acid any: hydrochloric acid, acetic acid, its consumption is 0.1～5% of total amount.The pH value scope is controlled at 4 to 10.Mixed reaction process adopts machinery or magnetic agitation, and churning time was at 30 to 500 minutes.
Behind the solution left standstill 30 to 300 minutes, pour in the container and seal, after 30 to 60 hours, solution is used for coating.Coating adopts the crystal pulling method preparation, and pull rate is 5 to 15cm/ minutes, and lifting number of times is 1 to 20 time, and lifting the gap is 2 to 10 minutes.After 5 to 40 minutes, put into heat treatment furnace at air drying, temperature is 80 to 150 ℃, and heat treatment time is 10 to 100 minutes.
Adopt the atomic-oxygen resistant coating of method preparation of the present invention to have very high anti-atomic oxygen characteristic.Reach 5.4 * 10 through the total irradiation of atomic oxygen
20/ cm
2Irradiation experiment shows that the sample of atomic-oxygen resistant coating protection is arranged, behind the atomic oxygen pre-irradiation, and the Electronic Speculum pattern indistinction of its scanning.The back not damaged is being shone on surface after promptly handling through supercoat through atomic oxygen.
Embodiment
Implement will be further understood that the present invention from following illustrative.
Adopt the method that tetraethoxy, nano silicon oxide, nano aluminium oxide and silane coupling agent (as KH570) composite atomic-oxygen resistant coating solution are synthetic and atomic-oxygen resistant coating prepares
Embodiment 1
Proportioning raw materials is: ethanol, 50 grams, tetraethoxy 10 grams, nano silicon oxide 0.5 gram, nano aluminium oxide 0.3 gram, KH-570,5 grams, deionized water 1 gram, acetic acid 0.1 gram.Mix the back and stirred 200 minutes, with solution left standstill after 100 minutes, pour in the container and seal, after 40 hours, pour out part solution and be used for coating with magnetic stirrer.Coating adopts the crystal pulling method preparation, and pull rate is 10cm/ minute, and lifting number of times is 10 times, and lifting the gap is 5 minutes.After 20 minutes, put into heat treatment furnace at air drying, temperature is 120 ℃, and heat treatment time is 60 minutes.Reach 5.4 * 10 through the total irradiation of atomic oxygen
20/ cm
2Irradiation experiment shows that the sample of atomic-oxygen resistant coating protection is arranged, behind the atomic oxygen pre-irradiation, and the Electronic Speculum pattern indistinction of its scanning.The back not damaged is being shone on surface after promptly handling through supercoat through atomic oxygen.
Embodiment 2
Proportioning raw materials is: ethanol, 20 grams, tetraethoxy 10 grams, nano silicon oxide 0.2 gram, nano aluminium oxide 0.1 gram, KH-570,5 grams, deionized water 1 gram, acetic acid 0.2 gram.Mix the back and stirred 400 minutes, with solution left standstill after 30 minutes, pour in the container and seal, after 30 hours, pour out part solution and be used for coating with magnetic stirrer.Coating adopts the crystal pulling method preparation, and pull rate is 5cm/ minute, and lifting number of times is 2 times, and lifting the gap is 2 minutes.After 10 minutes, put into heat treatment furnace at air drying, temperature is 85 ℃, and heat treatment time is 20 minutes.Reach 5.4 * 10 through the total irradiation of atomic oxygen
20/ cm
2Irradiation experiment shows that the sample of atomic-oxygen resistant coating protection is arranged, behind the atomic oxygen pre-irradiation, and the Electronic Speculum pattern indistinction of its scanning.The back not damaged is being shone on surface after promptly handling through supercoat through atomic oxygen.
Embodiment 3
Proportioning raw materials is: ethanol, 200 grams, tetraethoxy 10 grams, nano silicon oxide 0.7 gram, nano aluminium oxide 0.0 gram, KH-570,2 grams, deionized water 1 gram, hydrochloric acid 0.1 gram.Mix the back and stirred 80 minutes, with solution left standstill after 240 minutes, pour in the container and seal, after 40 hours, pour out part solution and be used for coating with magnetic stirrer.Coating adopts the crystal pulling method preparation, and pull rate is 8cm/ minute, and lifting number of times is 15 times, and lifting the gap is 8 minutes.After 40 minutes, put into heat treatment furnace at air drying, temperature is 140 ℃, and heat treatment time is 80 minutes.Reach 5.4 * 10 through the total irradiation of atomic oxygen
20/ cm
2Irradiation experiment shows that the sample of atomic-oxygen resistant coating protection is arranged, behind the atomic oxygen pre-irradiation, and the Electronic Speculum pattern indistinction of its scanning.The back not damaged is being shone on surface after promptly handling through supercoat through atomic oxygen.
Embodiment 4
Proportioning raw materials is: ethanol, 500 grams, tetraethoxy 10 grams, nano silicon oxide 0.1 gram, nano aluminium oxide 0.3 gram, KH-570,7 grams, deionized water 1 gram, acetic acid 0.3 gram.Mix the back and stirred 600 minutes, with solution left standstill after 150 minutes, pour in the container and seal, after 60 hours, pour out part solution and be used for coating with magnetic stirrer.Coating adopts the crystal pulling method preparation, and pull rate is 15cm/ minute, and lifting number of times is 20 times, and lifting the gap is 10 minutes.After 30 minutes, put into heat treatment furnace at air drying, temperature is 130 ℃, and heat treatment time is 50 minutes.Reach 5.4 * 10 through the total irradiation of atomic oxygen
20/ cm
2Irradiation experiment shows that the sample of atomic-oxygen resistant coating protection is arranged, behind the atomic oxygen pre-irradiation, and the Electronic Speculum pattern indistinction of its scanning.The back not damaged is being shone on surface after promptly handling through supercoat through atomic oxygen.
Embodiment 5
Proportioning raw materials is: ethanol, 50 grams, tetraethoxy 10 grams, nano silicon oxide 0.5 gram, nano aluminium oxide 0.1 gram, KH-570,8 grams, deionized water 1 gram, acetic acid 0.1 gram.Mix the back and stirred 100 minutes, with solution left standstill after 100 minutes, pour in the container and seal, after 50 hours, pour out part solution and be used for coating with magnetic stirrer.Coating adopts the crystal pulling method preparation, and pull rate is 10cm/ minute, and lifting number of times is 10 times, and lifting the gap is 5 minutes.After 5 minutes, put into heat treatment furnace at air drying, temperature is 100 ℃, and heat treatment time is 90 minutes.Reach 5.4 * 10 through the total irradiation of atomic oxygen
20/ cm
2Irradiation experiment shows that the sample of atomic-oxygen resistant coating protection is arranged, behind the atomic oxygen pre-irradiation, and the Electronic Speculum pattern indistinction of its scanning.The back not damaged is being shone on surface after promptly handling through supercoat through atomic oxygen.
Claims (9)
1, a kind of method for preparing the composite atomic-oxygen resistant coating solution is characterized in that: tetraethoxy, nano silicon oxide, nano aluminium oxide and silane coupling agent compound solution are used for the preparation of atomic-oxygen resistant coating.
2, according to the described preparation method of claim 1, it is characterized in that: the part by weight of the synthesis material tetraethyl silicate of the solution that the preparation coating is used is 20 to 80%.
3, according to the described preparation method of claim 1, it is characterized in that: the part by weight of the synthesis material nano silicon oxide of the solution that the preparation coating is used is 2 to 10%, and particle diameter is the 10-80 nanometer.The part by weight of nano aluminium oxide is 0 to 8%, and particle diameter is the 10-80 nanometer.The part by weight of silane coupling agent is 10 to 50%.Silane coupling agent comprises KH550, KH560, KH570.
4, according to the described preparation method of claim 1, it is characterized in that: solvent adopts ethanol, and consumption of ethanol is tetraethoxy, nano silicon oxide, nano aluminium oxide and silane coupling agent total amount 1 to 100 times.
5, according to the described preparation method of claim 1, it is characterized in that: its add mineral acid be in the following mineral acid any: hydrochloric acid, acetic acid, its consumption is 0.1～5% of total amount.
6, according to the described preparation method of claim 1, it is characterized in that: the amount of adding deionized water is 1～10%.
7, according to the described preparation method of claim 1, it is characterized in that: film and adopt spraying, or dip-coating, or brush, or crystal pulling method, or revolve to cover and be coated with.
8, according to the described preparation method of claim 1, it is characterized in that: the coating that is coated is through Temperature Treatment, and temperature range is 80 to 250 ℃.
9, described according to Claim 8 preparation method is characterized in that: when heat-treated, the treatment time is 10-100 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101243725A CN101429350A (en) | 2007-11-08 | 2007-11-08 | Method for producing nano-organic/inorganic composite atom resistant oxygen coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101243725A CN101429350A (en) | 2007-11-08 | 2007-11-08 | Method for producing nano-organic/inorganic composite atom resistant oxygen coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101429350A true CN101429350A (en) | 2009-05-13 |
Family
ID=40644994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101243725A Pending CN101429350A (en) | 2007-11-08 | 2007-11-08 | Method for producing nano-organic/inorganic composite atom resistant oxygen coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101429350A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275350A (en) * | 2011-05-10 | 2011-12-14 | 上海交通大学 | Namometer SiO2-doped polymer laminated film and preparation method thereof |
| CN103709797A (en) * | 2013-12-27 | 2014-04-09 | 深圳市嘉达高科产业发展有限公司 | Inorganic overcoat resin and preparation method thereof |
| CN106397807A (en) * | 2016-08-30 | 2017-02-15 | 兰州空间技术物理研究所 | Composite protection coating for atomic oxygen |
| CN106497194A (en) * | 2016-11-25 | 2017-03-15 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN108892979A (en) * | 2018-06-19 | 2018-11-27 | 张文霞 | One kind is for environment friendly heat resistant refractory coating and preparation method thereof |
| CN109627976A (en) * | 2018-12-18 | 2019-04-16 | 浙江大学自贡创新中心 | A kind of preparation of inorganic waste particulate coating material and application method |
| CN110144057A (en) * | 2019-04-25 | 2019-08-20 | 上海空间电源研究所 | Space polyimide material surface atom oxygen protective coating and preparation method thereof |
| CN111303761A (en) * | 2020-03-07 | 2020-06-19 | 东南大学 | Long-acting self-repairing super-hydrophobic ceramic coating and preparation method and application thereof |
| CN115521640A (en) * | 2022-03-03 | 2022-12-27 | 中国科学院上海硅酸盐研究所 | Atomic oxygen resisting micro-nano porous coating and preparation method thereof |
| CN115558904A (en) * | 2022-10-11 | 2023-01-03 | 兰州空间技术物理研究所 | Antistatic composite atomic oxygen protective coating for space |
| US20230068922A1 (en) * | 2020-11-10 | 2023-03-02 | Luyang Energy-Saving Materials Co., Ltd. | High-temperature nano-composite coating and preparation method thereof, and small bag flexible packaging coating |
| CN115746368A (en) * | 2021-12-08 | 2023-03-07 | 中国科学院上海硅酸盐研究所 | Polymer surface anti-atomic oxygen/ultraviolet-intercepting modified film layer and preparation method and application thereof |
| CN115785592A (en) * | 2021-12-08 | 2023-03-14 | 中国科学院上海硅酸盐研究所 | Secondary surface mirror based on surface modified fluoroplastic film and preparation method and application thereof |
-
2007
- 2007-11-08 CN CNA2007101243725A patent/CN101429350A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275350A (en) * | 2011-05-10 | 2011-12-14 | 上海交通大学 | Namometer SiO2-doped polymer laminated film and preparation method thereof |
| CN102275350B (en) * | 2011-05-10 | 2013-11-06 | 上海交通大学 | Namometer SiO2-doped polymer laminated film and preparation method thereof |
| CN103709797A (en) * | 2013-12-27 | 2014-04-09 | 深圳市嘉达高科产业发展有限公司 | Inorganic overcoat resin and preparation method thereof |
| CN106397807A (en) * | 2016-08-30 | 2017-02-15 | 兰州空间技术物理研究所 | Composite protection coating for atomic oxygen |
| CN106497194A (en) * | 2016-11-25 | 2017-03-15 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN106497194B (en) * | 2016-11-25 | 2018-10-30 | 北京建筑大学 | A kind of composite coating of preventing metal corrosion and preparation method thereof |
| CN108892979A (en) * | 2018-06-19 | 2018-11-27 | 张文霞 | One kind is for environment friendly heat resistant refractory coating and preparation method thereof |
| CN109627976A (en) * | 2018-12-18 | 2019-04-16 | 浙江大学自贡创新中心 | A kind of preparation of inorganic waste particulate coating material and application method |
| CN110144057A (en) * | 2019-04-25 | 2019-08-20 | 上海空间电源研究所 | Space polyimide material surface atom oxygen protective coating and preparation method thereof |
| CN111303761A (en) * | 2020-03-07 | 2020-06-19 | 东南大学 | Long-acting self-repairing super-hydrophobic ceramic coating and preparation method and application thereof |
| CN111303761B (en) * | 2020-03-07 | 2022-01-25 | 东南大学 | Long-acting self-repairing super-hydrophobic ceramic coating and preparation method and application thereof |
| US20230068922A1 (en) * | 2020-11-10 | 2023-03-02 | Luyang Energy-Saving Materials Co., Ltd. | High-temperature nano-composite coating and preparation method thereof, and small bag flexible packaging coating |
| US11926762B2 (en) * | 2020-11-10 | 2024-03-12 | Luyang Energy-Saving Materials Co., Ltd. | High-temperature nano-composite coating and preparation method thereof, and small bag flexible packaging coating |
| CN115746368A (en) * | 2021-12-08 | 2023-03-07 | 中国科学院上海硅酸盐研究所 | Polymer surface anti-atomic oxygen/ultraviolet-intercepting modified film layer and preparation method and application thereof |
| CN115785592A (en) * | 2021-12-08 | 2023-03-14 | 中国科学院上海硅酸盐研究所 | Secondary surface mirror based on surface modified fluoroplastic film and preparation method and application thereof |
| CN115746368B (en) * | 2021-12-08 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Atomic oxygen resistant/ultraviolet blocking modified film layer on polymer surface as well as preparation method and application thereof |
| CN115785592B (en) * | 2021-12-08 | 2023-10-20 | 中国科学院上海硅酸盐研究所 | Secondary surface mirror based on surface modified fluoroplastic film and preparation method and application thereof |
| CN115521640A (en) * | 2022-03-03 | 2022-12-27 | 中国科学院上海硅酸盐研究所 | Atomic oxygen resisting micro-nano porous coating and preparation method thereof |
| CN115558904A (en) * | 2022-10-11 | 2023-01-03 | 兰州空间技术物理研究所 | Antistatic composite atomic oxygen protective coating for space |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101429350A (en) | Method for producing nano-organic/inorganic composite atom resistant oxygen coating | |
| US9982140B2 (en) | Inorganic-organic hybrid oxide polymer and manufacturing method thereof | |
| Wang et al. | Sol–gel coatings on metals for corrosion protection | |
| CN104910656B (en) | A kind of method that super-hydrophobic silica powder and super-hydrophobic coat are prepared with compound silicon source | |
| Balasubramanian et al. | Titania powder modified sol-gel process for photocatalytic applications | |
| CN108585948B (en) | Method for modifying surface of alumina-based ceramic fiber | |
| Shilova | Synthesis and structure features of composite silicate and hybrid TEOS-derived thin films doped by inorganic and organic additives | |
| CN103965776B (en) | A kind of high temperature resistant heat insulation anticorrosive coating | |
| CN109502987B (en) | Method for preparing high-hardness anti-reflection film based on hollow silicon oxide | |
| US20080245260A1 (en) | Particular nanostructured material, as protective coating for metallic surfaces | |
| US20090202815A1 (en) | Use of a nanostructured material, as protective coating of metal surfaces | |
| CN102492339A (en) | Preparation method for high-wave permeability super-hydrophobic moisture-proofing coating for antenna housing material | |
| CN111534162B (en) | Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof | |
| JP2010209337A (en) | Uniformly dispersed photocatalyst coating liquid, method for producing the same, and photocatalytically active composite material obtained by using the same | |
| JPH11502262A (en) | Method for producing ceramic thick film by sol-gel coating method | |
| KR102040964B1 (en) | A coating composition manufacturing method of silica aerogel for radon mitigation | |
| CN105789339A (en) | Perovskite solar cell nano silicon dioxide coating liquid and application thereof | |
| CN110669363B (en) | Preparation method of transparent super-hydrophobic coating | |
| CN104072781A (en) | Perhydropolysilazane with controllable ratio of SiH2 to SiH1 in molecular structure, hydrophobic transparent high-hardness coating prepared by perhydropolysilazane and synthesis method of perhydropolysilazane | |
| CN113337214B (en) | Oxygen barrier coating and preparation method thereof | |
| CN110157225B (en) | Preparation method of graphene-antibacterial antifouling anticorrosion composite coating on metal surface | |
| CN101817980A (en) | Sol-gel preparation method of silica-based superhydrophobic thin films | |
| CN105176394A (en) | Organic and inorganic coating material based on sol-gel technique and preparation method thereof | |
| US7781064B2 (en) | Substrate coated with a coating | |
| CN109280389A (en) | A kind of preparation method of Nano silver grain Composite silicone resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090513 |