CN103184581A - Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method - Google Patents
Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method Download PDFInfo
- Publication number
- CN103184581A CN103184581A CN2013100913443A CN201310091344A CN103184581A CN 103184581 A CN103184581 A CN 103184581A CN 2013100913443 A CN2013100913443 A CN 2013100913443A CN 201310091344 A CN201310091344 A CN 201310091344A CN 103184581 A CN103184581 A CN 103184581A
- Authority
- CN
- China
- Prior art keywords
- nano titanium
- titanium oxide
- polysulfonamides
- spinning
- electrostatic spinning
- 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
Images
Abstract
The invention belongs to the technology of nano fiber preparation and particularly relates to a method for preparing polysulfonamide/nanometer TiO2 composition fiber by an electrostatic spinning method. The method comprises the following steps: firstly placing dry nano titanium dioxide into a N, N'-Dimethylacetamide, sealing and carrying out ultrasonic vibration; then dissolving mixed solution into spinning stock solution containing 10 to 15 wt percent, stirring, sealing and carrying out ultrasonic vibration; and then obliquely pouring the prepared polysulfonamide/ nano titanium dioxide composite spinning solution into a static silk-spinning machine for static spinning. The added proportioning of the nano titanium dioxide, the N,N'-Dimethylacetamide and the spinning stock solution is 1 g to 12-9 ml to 100-900 g. The composite nano fiber prepared by the invention remarkably overcomes the defect that the uvioresistant performance of the polysulfonamide is poor, and the preparation device for the composition fiber is simple, low in cost and strong in adjustment and control of the preparation technology.
Description
Technical field
The invention belongs to the nanofiber technology of preparing, particularly a kind of method of electrostatic spinning prepares the method for polysulfonamides/nano titanium oxide composite fibre.
Background technology
Method of electrostatic spinning is polymeric spray static stretch spinning method, and is completely different with conventional method, is to utilize the high-tension electricity field force that charged solution is sprayed the final a kind of spinning process that obtains nanofiber that stretches.Electrostatic spinning is simple with its manufacturing installation, spinning is with low cost, can spin advantages such as substance classes is various, technology is controlled, has become one of main path of effective preparation nano-fiber material.Electrostatic spinning technique has prepared the abundant nanofiber of kind, comprise organic, organic/inorganic is compound and inorganic nano-fiber, utilize the diameter of fiber of this method preparation than low one to two order of magnitude of fiber of solution spinning or melt spinning method preparation, and specific fiber surface is long-pending big, the porosity height has received a lot of researchers' concern and electrostatic spinning fiber has been widely used in various fields such as bio-medical material, filtration and protection, catalysis, the energy, photoelectricity, food engineering, cosmetics.
Polysulfonamides has another name called fragrant sulfone synthetic fibre, Han You – NHOC in the polysulfonamides molecule, and-SO2-and phenyl ring functional group, so this polymer has very strong heat-resisting quantity, high temperature dimensional stability.In addition, in anti-flammability, aspects such as dyeability also show excellent characteristic, are widely used in the civil and military field, as high-temperature-resistant filtering material, friction honeybee material, protective article, electrically insulating material, cellular structural material etc.Yet there is serious defective in polysulfonamides, and namely anti-ultraviolet property is poor.
Nano titanium oxide also claims nanometer titanium dioxide, can absorb ultraviolet ray, can reflect again, scatters ultraviolet, can also see through visible light, is superior performance, extremely rising physical shielding ultraviolet protective agent.The strong anti-uv-ray of nano titanium oxide is because it has high refractivity and high photolytic activity.The big titanium dioxide nanoparticle of particle diameter to the isolation of long-wavelength region ultraviolet ray (320-400nm) and medium wave district ultraviolet ray (280-320nm) based on reflection and scattering, the little nano titanium oxide of particle diameter to the ultraviolet isolation in medium wave district to be absorbed as the master.
Summary of the invention
The purpose of this invention is to provide the method that a kind of method of electrostatic spinning prepares polysulfonamides/nano titanium oxide composite fibre, the employed equipment of this preparation method is simple, the technology Modulatory character is strong, with low cost, and the diameter of the composite fibre of preparing has excellent anti-uv-ray between 250nm-350nm.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method of electrostatic spinning prepares the method for polysulfonamides/nano titanium oxide composite fibre, and its step comprises:
(1) nano titanium oxide with drying places N, in N '-dimethylacetylamide, and sealing, sonic oscillation; Then mixed liquor is held in the spinning solution of the polysulfonamides that contains 10-15wt%, stirring, sealing, sonic oscillation get final product;
(2) polysulfonamides/nano titanium oxide composite spinning liquid inclination that makes in the step (1) is poured into and carried out electrostatic spinning in the electrostatic spinning machine.
In the described step (1), nano titanium oxide, N, the adding proportioning of N '-dimethylacetylamide and spinning solution is 1g:12-19mL:100-900g.Preferably, nano titanium oxide, N, the adding proportioning of N '-dimethylacetylamide and spinning solution is 1g:14-17mL:105-850g.
In the described step (1), nano titanium oxide is rutile-type, and purity is 95-99%, and particle diameter is 30-50nm.
In the described step (1), the sonic oscillation time is 0.5-1.5 hour.
In the described step (1), the content of the polysulfonamides in the spinning solution is 12wt%.
In the described step (2), the angle of inclination that polysulfonamides/nano titanium oxide composite spinning liquid tilts to pour in the electrostatic spinning machine is the 10-40 degree; The flow velocity of this composite spinning liquid is 0.08-0.2mL/h.
The process conditions of the electrostatic spinning in the described step (2) are that electrostatic pressure 20-35kV, rotation rotating speed 35-45rpm, acceptance are apart from 10-20 centimetre.Preferably, the process conditions of the electrostatic spinning in the described step (2) are that electrostatic pressure is that 28kV, rotation rotating speed are 42rpm, accepts 15 centimetres of distances.
Nano titanium oxide belongs to n molded breadth bandgap semiconductor material, and its electronic structure is to be made of the conduction band, and the unoccupied orbital of no electronics has formed this conduction band with the valence band that is full of electronics, exists the forbidden band wide.When being subjected to energy more than or equal to the irradiation of the light of this energy gap, nano-TiO
2Can absorb the ability of this photon, then the electronics on the valence band is excited, and transits to conduction band.Valence band formed the hole and formed electron-hole pair owing to lacking electronics this moment, had created the chance with other electronics or hole-recombination, so made nano-TiO
2Ultraviolet ray had absorption preferably.In addition, it has reflection, scattering process preferably to ultraviolet ray, so, in the preparation process of polysulfonamides fibre, added nano-TiO
2, make the composite fibre of preparation also have anti-uv-ray and heat-resisting quantity preferably, widened the scope of application of composite fibre.
Compared with prior art, beneficial effect of the present invention is: 1, the present invention joins nano titanium oxide in the polysulfonamides, adopt method of electrostatic spinning to prepare composite nano fiber, significantly improved the defective of the anti-ultraviolet property difference of polysulfonamides itself, the diameter of the polysulfonamides that obtains/nano titanium oxide composite fibre is between 250nm-350nm, has significant anti-uv-ray, excellent heat-resisting quantity.2, the preparation facilities of described polysulfonamides/nano titanium oxide composite fibre is simple, with low cost, and preparation technology's Modulatory character is strong.
Description of drawings
Fig. 1 is the scanning electron microscope diagram sheet of embodiment 2 prepared nano-composite fibers.
Fig. 2 is the diameter of the composite fibre that adopts method of electrostatic spinning and wet spinning process and prepare and the contrast schematic diagram of specific area.
The specific embodiment
Below in conjunction with embodiment, the invention will be further described:
Experimental raw: CP level N, N '-dimethylacetylamide (DMAC); The spinning solution that contains the polysulfonamides (PSA) of 12wt%; Nano titanium oxide, this nano titanium oxide are rutile-type, and particle diameter is 30-50nm, and purity is 99%.
Laboratory apparatus: electrostatic spinning machine, FA1104A type ten thousand/balance weighing apparatus, KQ-700 type ultrasonic cleaner, 79-1 type magnetic force heating stirrer, WD-5000 type electric drying oven with forced convection.
Embodiment 1
(1) preparation of polysulfonamides/nano titanium oxide composite spinning liquid:
With nano titanium oxide (nano-TiO
2) put into and carry out drying in the drying box, to remove moisture.Measure the N of 1mL with graduated cylinder, N '-dimethylacetylamide (DMAC) solvent places beaker, weighs in the balance to get the dry good nano-TiO of 0.061g
2Be poured in the beaker and with glass bar and stir, it is tentatively mixed with the DMAC solvent, then this beaker is sealed and puts into the ultrasonic cleaner sonic oscillation with preservative film and made mixed liquor (during sonic oscillation, guaranteeing that the water level in the ultrasonic cleaner is higher than the liquid level groove of DMAC in the beaker) in 0.5 hour; Pour 50g at the preliminary good mixed liquor of sonic oscillation and contain nano-TiO
2Be the PSA spinning solution of 12wt%, and with the magnetic force heating stirrer it stirred 0.5 hour that seal with preservative film finishing after, and put it in the ultrasonic cleaner, sonic oscillation is 1.5 hours again, make nano-TiO
2Particle can well be dispersed in the PSA spinning solution, can make polysulfonamides/nano titanium oxide composite spinning liquid.
(2) preparation of polysulfonamides/nano titanium oxide composite fibre:
Polysulfonamides/nano titanium oxide composite spinning the liquid that obtains in the step (1) is spent the syringe that electrostatic spinning machine is injected at inclinations angle continuously with 30, and the volume of syringe is 20mL, and the syringe needle internal diameter in the syringe is 1.2mm, and flow velocity is 0.1mL/h; The receiver of this electrostatic spinning machine is the swing roller of a ground connection, and the needle point of the syringe of this electrostatic spinning machine is 15cm apart from the distance of swing roller, and the rotating speed of swing roller is 42rpm.The electrostatic pressure of the HV generator of described electrostatic spinning machine is 28kV, and power-on can prepare and contain nano-TiO
2Polysulfonamides/nano titanium oxide composite fibre for 1wt%.
Embodiment 2
With nano-TiO in the step among the embodiment 1 (1)
2Addition is adjusted into 0.186g, and the addition of DMAC is adjusted into 3mL, and other conditions are constant, can prepare and contain nano-TiO
2Polysulfonamides/nano titanium oxide composite fibre for 3wt%.Fig. 1 is the scanning electron microscope diagram sheet of the prepared nano-composite fiber of present embodiment, and as can be seen from Figure, titanium dioxide nanoparticle is embedded in the surface of fiber.
Embodiment 3
With nano-TiO in the step among the embodiment 1 (1)
2Addition be adjusted into 0.316g, the addition of DMAC is adjusted into 5mL, other conditions are constant, can prepare to contain nano-TiO
2Polysulfonamides/nano titanium oxide composite fibre for 5wt%.
Embodiment 4
With nano-TiO in the step among the embodiment 1 (1)
2Addition be adjusted into 0.452g, the addition of DMAC is adjusted into 7mL, other conditions are constant, can prepare to contain nano-TiO
2Polysulfonamides/nano titanium oxide composite fibre for 7wt%.
The ultraviolet ray transmissivity contrast test:
Polysulfonamides/nano titanium oxide the composite fibre that makes among above-mentioned 4 embodiment is made the tunica fibrosa that length is 5cm * 5cm * 0.1cm, with Labsphere UV-1000F (U.S.) type textiles uvioresistant tester, test its ultraviolet ray transmissivity.Test as a comparison, with the polysulfonamides/nano titanium oxide composite spinning liquid that makes in above-described embodiment, adopt wet spinning process to prepare polysulfonamides/nanometer titanium dioxide fiber, and be made into the tunica fibrosa that length is 5cm * 5cm * 0.1cm, test its ultraviolet percent of pass, test condition: the test wave-length coverage is 250nm～450nm, absorbance is 0～2.5A, sweep time≤5s, data break are 1nm, and the sample beam diameter is 10mm.Concrete data are shown in Table 1:
The anti-ultraviolet property comparison sheet of the composite cellulosic membrane of two kinds of spinning process preparations of table 1()
From table, can obviously find out, adopt same composite spinning liquid, the tunica fibrosa that the ultraviolet percent of pass of the tunica fibrosa that electro-spinning obtains fully obtains fully than wet method spinning low illustrate that the polysulfonamides/nano titanium oxide composite fibre that utilizes method of electrostatic spinning to prepare has more excellent uvioresistant usefulness.
The principle of wet spinning is to utilize nitrogen pressure with PSA/nano-TiO
2Spinning solution extrudes from spinneret orifice and forms thread, and thread solidifies the formation as-spun fibre in coagulating bath.In this process, because spinneret orifice is little, so a part of nano-TiO
2Particle causes volume to become big because reunion takes place, and finally can't squeeze out from spinneret orifice along with PSA solution, namely finally causes being present in the nano-TiO on the as-spun fibre
2Content reduces.And the principle of utilizing electrospinning process to prepare fiber is taken out long drawing-down for having squeezed out back recycling high-pressure electrostatic field force from big spinneret orifice at spinning solution with jet, finally forms fiber, therefore the nano-TiO in mixed liquor
2Particle is loss not, finally all will be present in the surperficial or inner of fiber.Therefore, contain same amount nano-TiO in use
2During the spinning solution of particle, utilize the nano-TiO in the fiber of method of electrostatic spinning preparation
2Content higher, so static spins PSA/nano-TiO
2Fiber shows more outstanding uvioresistant usefulness.
Fig. 2 is for adopting the polysulfonamides/nano titanium oxide composite spinning liquid that makes among above-mentioned 4 embodiment, two kinds of fibre diameters that make with method of electrostatic spinning and wet spinning process and specific area comparison schematic diagram.As can be seen from Figure 2, with respect to wet method spin PSA/nano-TiO
2Fiber, static spins PSA/nano-TiO
2Fiber has than minor diameter, than bigger serface, under the same terms, can absorb more content ultraviolet rays, therefore utilizes the fiber of method of electrostatic spinning preparation to show more excellent anti-ultraviolet property.
Above-described embodiment is interpreted as only being used for explanation the present invention and is not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Claims (9)
1. a method of electrostatic spinning prepares the method for polysulfonamides/nano titanium oxide composite fibre, and its step comprises:
(1) nano titanium oxide with drying places N, in N '-dimethylacetylamide, and sealing, sonic oscillation; Then mixed liquor is dissolved in the spinning solution of the polysulfonamides that contains 10-15wt%, stirring, sealing, sonic oscillation get final product;
(2) polysulfonamides/nano titanium oxide composite spinning liquid inclination that makes in the step (1) is poured into and carried out electrostatic spinning in the electrostatic spinning machine.
2. method of electrostatic spinning according to claim 1 prepares the method for polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: in the described step (1), nano titanium oxide, N, the adding proportioning of N '-dimethylacetylamide and spinning solution is 1g:12-19mL:100-900g.
3. method of electrostatic spinning according to claim 2 prepares the method for polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: in the described step (1), nano titanium oxide, N, the adding proportioning of N '-dimethylacetylamide and spinning solution is 1g:14-17mL:105-850g.
4. method of electrostatic spinning according to claim 1 prepares the method for polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: in the described step (1), nano titanium oxide is rutile-type, and purity is 95-99%, and particle diameter is 30-50nm.
5. method of electrostatic spinning according to claim 1 prepares the method for polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: in the described step (1), the sonic oscillation time is 0.5-1.5 hour.
6. method of electrostatic spinning according to claim 1 prepares the method for polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: in the described step (1), the content of the polysulfonamides in the spinning solution is 12wt%.
7. method of electrostatic spinning according to claim 1 prepares the method for polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: in the described step (2), the angle of inclination that polysulfonamides/nano titanium oxide composite spinning liquid tilts to pour in the electrostatic spinning machine is the 10-40 degree; The flow velocity of this composite spinning liquid is 0.08-0.2mL/h.
8. static according to claim 1 spins the preparation method of polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: the process conditions of the electrostatic spinning in the described step (2) are that electrostatic pressure 20-35kV, rotation rotating speed 35-45rpm, acceptance are apart from 10-20 centimetre.
9. static according to claim 8 spins the preparation method of polysulfonamides/nano titanium oxide composite fibre, it is characterized in that: the process conditions of the electrostatic spinning in the described step (2) are, electrostatic pressure is that 28kV, rotation rotating speed are 42rpm, accepts 15 centimetres of distances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100913443A CN103184581A (en) | 2013-03-21 | 2013-03-21 | Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100913443A CN103184581A (en) | 2013-03-21 | 2013-03-21 | Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103184581A true CN103184581A (en) | 2013-07-03 |
Family
ID=48676015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100913443A Pending CN103184581A (en) | 2013-03-21 | 2013-03-21 | Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103184581A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506761A (en) * | 2016-01-19 | 2016-04-20 | 浙江理工大学 | Centrifugal spinning preparation method of silicon dioxide and polystyrene micro-nano fiber membrane |
| CN109666977A (en) * | 2019-02-25 | 2019-04-23 | 牟富书 | A kind of anti-bacterial fibre preparation method |
| CN111249927A (en) * | 2020-02-24 | 2020-06-09 | 上海工程技术大学 | Meta-aramid/polysulfonamide/silicon dioxide composite air filter membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113857A1 (en) * | 2007-04-11 | 2010-05-06 | National University Of Singapore | Fibers for decontamination of chemical and biological agents |
| CN102504537A (en) * | 2011-11-16 | 2012-06-20 | 上海工程技术大学 | Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof |
| CN102505351A (en) * | 2011-11-16 | 2012-06-20 | 上海大学 | Method for preparing polysulfonamide separating films by aid of electrostatic spinning |
| CN102969471A (en) * | 2012-10-24 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | High-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm |
-
2013
- 2013-03-21 CN CN2013100913443A patent/CN103184581A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100113857A1 (en) * | 2007-04-11 | 2010-05-06 | National University Of Singapore | Fibers for decontamination of chemical and biological agents |
| CN102504537A (en) * | 2011-11-16 | 2012-06-20 | 上海工程技术大学 | Anti-ultraviolet polysulfone amide/titanium dioxide nano-composite material and preparation method thereof |
| CN102505351A (en) * | 2011-11-16 | 2012-06-20 | 上海大学 | Method for preparing polysulfonamide separating films by aid of electrostatic spinning |
| CN102969471A (en) * | 2012-10-24 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | High-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506761A (en) * | 2016-01-19 | 2016-04-20 | 浙江理工大学 | Centrifugal spinning preparation method of silicon dioxide and polystyrene micro-nano fiber membrane |
| CN105506761B (en) * | 2016-01-19 | 2017-11-24 | 浙江理工大学 | A kind of centrifugal spinning preparation method of silica/polystyrene micro/nano-fibre film |
| CN109666977A (en) * | 2019-02-25 | 2019-04-23 | 牟富书 | A kind of anti-bacterial fibre preparation method |
| CN111249927A (en) * | 2020-02-24 | 2020-06-09 | 上海工程技术大学 | Meta-aramid/polysulfonamide/silicon dioxide composite air filter membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102344685B (en) | Method for preparing nano cellulose microfibril reinforced polymer composite material | |
| Moghaddam et al. | Preparation of calcium alginate microcapsules containing n-nonadecane by a melt coaxial electrospray method | |
| Kim et al. | Preparation of submicron‐scale, electrospun cellulose fibers via direct dissolution | |
| CN101921410B (en) | Method for preparing cellulose microspheres | |
| Qi et al. | Electrospinning of cellulose‐based fibers from NaOH/urea aqueous system | |
| CN106283268B (en) | A kind of preparation method of cellulose/calcium alginate blended fiber | |
| CN101928996A (en) | Preparation method of fibrous membrane with super hydrophobic multi-stage nanometer structure | |
| CN106929929B (en) | A kind of preparation method of the cellulose spin dope for electrostatic spinning | |
| CN105970485A (en) | Polyimide-zirconium dioxide composite nanofiber membrane and preparation method thereof | |
| CN102660798B (en) | Method for performing coaxial electrostatic blending on polyvinylpyrrolidone(PVP)/chitosan (CS)/Fe3O4 nano fiber film | |
| CN103184581A (en) | Method for preparing polysulfonamide/nanometer TiO2 composition fiber by electrostatic spinning method | |
| CN105672014A (en) | Preparation method of super-hydrophobic magnetic nano-crystalline cellulose paper | |
| CN101724929B (en) | Method for preparing cellulose/nanometer titanium dioxide blending material in ionic liquid solvent | |
| CN101967697B (en) | Method for preparing biodegradable solid-solid phase transition nano fibers or fiber membranes | |
| WO2014065747A1 (en) | Method of spinning fibres or extrusion, and the products obtained | |
| CN103225115B (en) | Electrostatic spinning technique is utilized to prepare the method for nano-porous materials | |
| CN104480560A (en) | Electrostatic spinning solution of polyvinylidene fluoride and preparation method of electrostatic spinning solution | |
| CN103816843A (en) | Preparation method of uniformly-sized regenerated cellulose microspheres | |
| CN105780299B (en) | Preparation method of supermolecule adsorption filter screen | |
| CN104262642A (en) | Method for dissolving cellulose in aqueous solution of NaOH/thiourea at normal temperature | |
| CN113046925B (en) | Polyvinylidene fluoride superfine nanofiber membrane and preparation method thereof | |
| CN103184579A (en) | Preparation method of electrospun polysulfonamide/multi-wall carbon nano tube complex fiber | |
| CN108654406A (en) | It is a kind of to cross M in drainage3+Micro/nano fibrous membrane material and preparation method thereof | |
| CN106048761A (en) | Encapsulated and networked regenerated cellulose phase-change fiber and preparation method thereof | |
| Mao et al. | Effects of coagulation conditions on properties of multifilament fibers based on dissolution of cellulose in NaOH/urea aqueous solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130703 |