CN102936015A - Preparation method of silica gel microspheres - Google Patents
Preparation method of silica gel microspheres Download PDFInfo
- Publication number
- CN102936015A CN102936015A CN2012104806342A CN201210480634A CN102936015A CN 102936015 A CN102936015 A CN 102936015A CN 2012104806342 A CN2012104806342 A CN 2012104806342A CN 201210480634 A CN201210480634 A CN 201210480634A CN 102936015 A CN102936015 A CN 102936015A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- preparation
- gel microball
- uniform
- silicon sol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a preparation method of silica gel microspheres, which comprises the following steps: mixing template agent, hydrochloric acid and tetraethylorthosilicate (TEOS) to form a uniformly dispersed water-phase silica sol; crushing and dispersing the water-phase silica sol by jet suspension polymerization to form water drops with uniform size, forming a uniform W/O suspension in an oil phase, and heating the silica sol for polymerization to obtain the silica gel composite microspheres with uniform particle size; and firing the silica gel composite microspheres at high temperature to remove the template, thereby obtaining the porous silica gel microspheres. The silica gel microspheres prepared by the method disclosed by the invention have the advantages of uniform particle size, controllable microsphere size and controllable pore size, and have potential application value in liquid phase chromatography and biological separation engineering.
Description
Technical field:
The present invention relates to silica gel microball and make field, particularly a kind of preparation method of silica gel microball.
Background technology:
In recent years, silica gel microball shows tempting application prospect in the Application Areass such as high performance liquid chromatography and bioseparation engineering, in order to satisfy its application requiring, be current research exploitation and one of hot subject of using to the particle diameter of silica gel microball and the research of size distribution thereof.
The method of prior art synthesized silicon rubber microballoon mainly contains sol-gel method and silicate cement solution.
The metal content of the silica gel microball of water glass hydrolysis method preparation is higher, and its application is limited by very large.Adopt traditional sol-gel method can prepare the tens monodispersity silica gel microballs to the hundreds of nanometer.But, remain a difficult point for the preparation of the monodispersity silica gel microball of micro-meter scale.
United States Patent (USP) (US3782075) discloses a kind of polymkeric substance for preparing the porous silica gel microballoon and has induced the heap method.At first prepare water silica sol, then mix copolymerization complex microsphere under acidic conditions with urea formaldehyde.Remove organism through high temperature and form the porous silica gel microballoon.
Chinese patent (CN200810202772.8) discloses a kind of preparation method of mesoporous silica gel microballoon, and take quaternary cationics as template, under alkaline condition, sol-gel method prepares the mesoporous silica gel microballoon.
United States Patent (USP) (US3857924) discloses the method that a kind of emulsion polymerization prepares the porous silica gel microballoon.At first process polysilicate solution with cation exchange material, with decationize; Process to remove inorganic acid radical with anion-exchange material again; Then letex polymerization and the formation silica gel microball that in organic phase, condenses.
Chinese patent (CN1124715) discloses a kind of preparation method of porous silicon dioxide microsphere, namely adopt the cell walls of biomass cells or cytolemma as template, to contain compound of silicate class and pore-creating agent adds, and be dispersed in the aqueous phase system, by two stage hydrolytic condensation and gelation reaction, be prepared into particle diameter at 1~200 micron porous silica microballoon, but its size distribution is wider.
Even by above-mentioned improvement, the silica gel microball size that described method prepares is heterogeneity very still.Therefore, the preparation method who inquires into a kind of monodispersity silica gel microball is key issue to be solved.
Summary of the invention:
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of method that adopts the jet flow suspension polymerization to prepare the monodispersity silica gel microball.Described method has overcome popular response can not synthesize the silica gel microball of homogeneous and the defective that prepared silica gel microball exists in performance thereof.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions: a kind of preparation method of silica gel microball, may further comprise the steps: (1) prepares jet flow suspension polymerization device: described jet flow suspension polymerization device comprises polymerization reaction kettle, water storage tank and nozzle, water storage tank upper end links to each other with nitrogengas cylinder through the first variable valve, and links to each other through the nozzle of the second variable valve with the reactor upper end; Water storage tank upper end is equipped with tensimeter and motor, and the driven by motor agitator rotates;
(2) template, hydrochloric acid and tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol; Described mixing and stirring are preferably finished in the water storage tank;
(3) add stablizer and whiteruss in the stirring-type reactor, dispersed with stirring forms uniform oil-phase solution;
(4) add suitable pressure, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(5) rising temperature, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(6) get dried silica gel complex microsphere high temperature sintering and remove template, obtain the silica gel microball of porous.
Preferably, template preferably is comprised of one or more chain polymer in the described step (2); Described template is preferably segmented copolymer, polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate, polymethyl acrylate, polyvinyl acetate (PVA), poly (glycidyl methacrylate) or derivatives thereof.
Preferably, stablizer is one or more tensio-active agent in the described step (3), and described tensio-active agent is Span80, Tween40 or its mixture preferably.
Preferably, the temperature of polyreaction is 60~80 ℃ in the described step (5), preferred 75 ℃.
Preferably, the high temperature sintering temperature of complex microsphere is 600~1000 ℃ in the described step (6), preferred 800 ℃.
Preferably, the particle diameter of the middle silica gel microball of described step (6) is in 1.7 microns~100 micrometer ranges; The pore size of silica gel microball exists
In the scope.
Compared with prior art, usefulness of the present invention is: the silica gel microball uniform particle diameter of preparation method's preparation of this silica gel microball, and size is adjustable; The aperture of the silica gel microball of preparation is adjustable; Preparation technology is simple, be easy to industrialization.
Embodiment:
Describe the present invention below by embodiment.
Embodiment one:
(1) with 3.0g PEG20,000,6.0g0.1M hydrochloric acid and 30g tetraethoxy (TEOS) mix, and fully stirs, and forms homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Span80 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.2MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 5 μ m porous silica gel microballoons.The aperture is
Embodiment two:
(1) 3.0g polyvinyl alcohol, 6.0g0.1M hydrochloric acid and 30g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Span80 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.1MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 10 μ m porous silica gel microballoons.The aperture is
Embodiment three
(1) 6.0g polymethylmethacrylate, 7.0g0.1M hydrochloric acid and 50g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Tween40 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.1MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 10 μ m porous silica gel microballoons.The aperture is
Embodiment four:
(1) 10.0g segmented copolymer F127 (E0106P070E0106), 7.0g0.1M hydrochloric acid and 50g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Tween40 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.1MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 10 μ m porous silica gel microballoons.The aperture is
Embodiment five:
(1) 10.0g segmented copolymer F127 (E0106P070E0106), 3.0g polyoxyethylene glycol (PEG20,000), 7.0g0.1M hydrochloric acid and 50g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Tween40 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.1MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 10 μ m porous silica gel microballoons.The aperture is
Embodiment six:
(1) 10.0g segmented copolymer F127 (E0106P070E0106), 3.0g polyoxyethylene glycol (PEG20,000), 7.0g0.1M hydrochloric acid and 50g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Tween40 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.05MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 20 μ m porous silica gel microballoons.The aperture is
Embodiment seven:
(1) 10.0g segmented copolymer F127 (E0106P070E0106), 3.0g polyoxyethylene glycol (PEG20,000), 7.0g0.1M hydrochloric acid and 50g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Tween40 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.2MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 5 μ m porous silica gel microballoons.The aperture is
Embodiment eight:
(1) 10.0g segmented copolymer F127 (E0106P070E0106), 7.0g0.1M hydrochloric acid and 50g tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol;
(2) in the stirring-type reactor, add 20g Tween40 and 980g whiteruss, behind the stirring 30min, disperse to form uniform oil-phase solution, keep stirring velocity to 200rpm;
(3) add suitable pressure, make the pressure in the oil phase storage tank keep 0.2MPa, open the second variable valve, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(4) raise 75 ℃, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(5) get dried silica gel complex microsphere and put into High Temperature Furnaces Heating Apparatus, be warming up to piecemeal 800 ℃, keep this temperature calcination 6h, obtain at last 5 μ m porous silica gel microballoons, the aperture is
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (6)
1. the preparation method of a silica gel microball may further comprise the steps:
(1) prepare jet flow suspension polymerization device:
Described jet flow suspension polymerization device comprises polymerization reaction kettle, water storage tank and nozzle, and water storage tank upper end links to each other with nitrogengas cylinder through the first variable valve, and links to each other through the nozzle of the second variable valve with the reactor upper end; Water storage tank upper end is equipped with tensimeter and motor, and the driven by motor agitator rotates;
(2) template, hydrochloric acid and tetraethoxy (TEOS) are mixed, fully stir, form homodisperse water silicon sol; Described mixing and stirring are preferably finished in the water storage tank;
(3) add stablizer and whiteruss in the stirring-type reactor, dispersed with stirring forms uniform oil-phase solution;
(4) add suitable pressure, described water silicon sol is entered by nozzle dispersion form uniform w/o type suspension in the described oil-phase solution;
(5) rising temperature, the silicon sol polymerization can obtain the silica gel complex microsphere of uniform particle diameter;
(6) get dried silica gel complex microsphere high temperature sintering and remove template, obtain the silica gel microball of porous.
2. the preparation method of silica gel microball according to claim 1 is characterized in that, template preferably is comprised of one or more chain polymer in the described step (2); Described template is preferably segmented copolymer, polyvinyl alcohol, polyoxyethylene glycol, polymethylmethacrylate, polymethyl acrylate, polyvinyl acetate (PVA), poly (glycidyl methacrylate) or derivatives thereof.
3. the preparation method of silica gel microball according to claim 1 is characterized in that, stablizer is one or more tensio-active agent in the described step (3), and described tensio-active agent is Span80, Tween40 or its mixture preferably.
4. the preparation method of silica gel microball according to claim 1 is characterized in that, the temperature of polyreaction is 60~80 ℃ in the described step (5), preferred 75 ℃.
5. the preparation method of silica gel microball according to claim 1 is characterized in that, the high temperature sintering temperature of complex microsphere is 600~1000 ℃ in the described step (6), preferred 800 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012104806342A CN102936015A (en) | 2012-11-23 | 2012-11-23 | Preparation method of silica gel microspheres |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2012104806342A CN102936015A (en) | 2012-11-23 | 2012-11-23 | Preparation method of silica gel microspheres |
Publications (1)
Publication Number | Publication Date |
---|---|
CN102936015A true CN102936015A (en) | 2013-02-20 |
Family
ID=47694951
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2012104806342A Pending CN102936015A (en) | 2012-11-23 | 2012-11-23 | Preparation method of silica gel microspheres |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102936015A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105600789A (en) * | 2015-12-28 | 2016-05-25 | 南京众力盛强新材料科技有限公司 | Millimeter-scale porous silica ball and preparation method thereof |
CN106215909A (en) * | 2016-07-29 | 2016-12-14 | 苏州知益微球科技有限公司 | A kind of monodisperse porous silica gel chromatographic column filling material and preparation method thereof |
CN107474302A (en) * | 2017-08-22 | 2017-12-15 | 成都新柯力化工科技有限公司 | A kind of phenoplasts foaming agent and preparation method with toughening functions |
CN108249451A (en) * | 2018-03-15 | 2018-07-06 | 东莞市真思电子有限公司 | A kind of synthesizing preparation method in situ of virtual acoustic material |
CN108851213A (en) * | 2018-08-06 | 2018-11-23 | 江西中烟工业有限责任公司 | A kind of cigarette filter tip and preparation method thereof containing bulky grain solid-state perfume (or spice) pearl |
CN110482558A (en) * | 2019-09-06 | 2019-11-22 | 无锡迈科为生物科技有限公司 | A kind of preparation method of silicon dioxide microsphere |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1715182A (en) * | 2005-05-30 | 2006-01-04 | 同济大学 | A kind of micron order SiO 2The preparation method of gas gel small ball |
CN1944251A (en) * | 2006-10-30 | 2007-04-11 | 复旦大学 | Synthetic method for porous silicon dioxide hollow micro ball |
CN101298335A (en) * | 2008-03-21 | 2008-11-05 | 太原理工大学 | Hollow mesopore molecular sieve big ball and preparation thereof |
CN102504077A (en) * | 2011-11-17 | 2012-06-20 | 无锡中德伯尔生物技术有限公司 | Preparation method of quantum dot polymer microspheres |
-
2012
- 2012-11-23 CN CN2012104806342A patent/CN102936015A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1715182A (en) * | 2005-05-30 | 2006-01-04 | 同济大学 | A kind of micron order SiO 2The preparation method of gas gel small ball |
CN1944251A (en) * | 2006-10-30 | 2007-04-11 | 复旦大学 | Synthetic method for porous silicon dioxide hollow micro ball |
CN101298335A (en) * | 2008-03-21 | 2008-11-05 | 太原理工大学 | Hollow mesopore molecular sieve big ball and preparation thereof |
CN102504077A (en) * | 2011-11-17 | 2012-06-20 | 无锡中德伯尔生物技术有限公司 | Preparation method of quantum dot polymer microspheres |
Non-Patent Citations (1)
Title |
---|
刘辉等: "阴离子-非离子混合模板剂法制备有序介孔硅胶微球及其性能研究", 《中国药科大学学报》, vol. 41, no. 3, 31 March 2010 (2010-03-31), pages 263 - 267 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105600789A (en) * | 2015-12-28 | 2016-05-25 | 南京众力盛强新材料科技有限公司 | Millimeter-scale porous silica ball and preparation method thereof |
CN106215909A (en) * | 2016-07-29 | 2016-12-14 | 苏州知益微球科技有限公司 | A kind of monodisperse porous silica gel chromatographic column filling material and preparation method thereof |
CN107474302A (en) * | 2017-08-22 | 2017-12-15 | 成都新柯力化工科技有限公司 | A kind of phenoplasts foaming agent and preparation method with toughening functions |
CN108249451A (en) * | 2018-03-15 | 2018-07-06 | 东莞市真思电子有限公司 | A kind of synthesizing preparation method in situ of virtual acoustic material |
CN108851213A (en) * | 2018-08-06 | 2018-11-23 | 江西中烟工业有限责任公司 | A kind of cigarette filter tip and preparation method thereof containing bulky grain solid-state perfume (or spice) pearl |
CN108851213B (en) * | 2018-08-06 | 2020-12-29 | 江西中烟工业有限责任公司 | Cigarette filter rod containing large-particle solid aromatic beads and preparation method thereof |
CN110482558A (en) * | 2019-09-06 | 2019-11-22 | 无锡迈科为生物科技有限公司 | A kind of preparation method of silicon dioxide microsphere |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102936015A (en) | Preparation method of silica gel microspheres | |
CN103342991B (en) | Composite nanocapsule phase-change material and preparation method thereof | |
CN103588920B (en) | Novel preparation method for monodisperse porous polymer nano microcapsule | |
CN103359740A (en) | Preparation method of silica shear thickening liquid | |
CN103496724B (en) | The preparation method of a kind of nano alumina sol and gel | |
CN102120585B (en) | Preparation method of SiO2 micro-nanosphere and micro-reaction system | |
CN103254888A (en) | Clean-water carrying fracturing supporting agent and preparation method | |
CN103936018A (en) | Method for preparing hydrophobic SiO2 aerogel by virtue of normal pressure drying | |
CN102502667B (en) | Large-pore-diameter large-window three-dimensionally communicated ordered mesoporous material and preparation method thereof | |
CN107833645B (en) | Preparation method of thorium-based mixed oxide ceramic microspheres | |
CN105110343B (en) | Method for rapid preparation of monodisperse ordered mesoporous silicon oxide hollow sphere | |
CN109574021A (en) | A method of Metaporous silicon dioxide material is prepared by template of hydroxyethyl cellulose | |
CN104386700B (en) | A kind of method of preparing mesoporous silicon dioxide micro-sphere | |
CN104909378A (en) | Preparation method of monodisperse porous silicon dioxide microspheres | |
CN102674379A (en) | Hollow mesoporous silicon dioxide nano particles and method for preparing same | |
CN102344517B (en) | Polymer microballoons and preparation method thereof | |
CN107010955B (en) | A kind of preparation method of the ceramic microsphere of thorium oxide | |
CN102249251A (en) | Method for preparing amorphous ultrafine silicon oxide by hydrothermal method | |
CN105060308A (en) | Method for preparing regular-appearance silicon dioxide aerogel particles | |
CN103964449B (en) | Constant pressure and dry technology is utilized to prepare the method for silica aerogel microballoon fast | |
CN103788385A (en) | Method for preparing hydrogel photonic crystal granules by using spray-drying method | |
CN109133144A (en) | A kind of preparation method of monodisperse ultra-small grain size ceria nano-crystalline | |
CN103613147A (en) | Preparation method of La0.7Sr0.3CoO3 perovskite composite | |
CN102755880B (en) | Method for preparing high-purity silica packing through sol-gel process | |
CN102527305A (en) | Preparation method of spherical beta-cyclodextrin/ melamine resin phase change energy storage materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
DD01 | Delivery of document by public notice |
Addressee: Suzhou Knowledge & Benefit Sphere Tech. Co., Ltd. Document name: Decision of Rejection |
|
C12 | Rejection of a patent application after its publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130220 |