CN103149197A - Atomic vapor sampling method and device based on electro-deposition and electro-heat - Google Patents
Atomic vapor sampling method and device based on electro-deposition and electro-heat Download PDFInfo
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- CN103149197A CN103149197A CN2013100716394A CN201310071639A CN103149197A CN 103149197 A CN103149197 A CN 103149197A CN 2013100716394 A CN2013100716394 A CN 2013100716394A CN 201310071639 A CN201310071639 A CN 201310071639A CN 103149197 A CN103149197 A CN 103149197A
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Abstract
The invention discloses an atomic vapor sampling method and an atomic vapor sampling device based on electro-deposition and electro-heat. The atomic vapor sampling method based on the electro-deposition and the electro-heat is characterized in that a sample enters an electrolysis cavity; elements to be detected are deposited on heating wires under the electrolysis effect, and waste liquid is discharged; the heating wires are heated for drying the electrolysis cavity under the assistance of carrier gas and are gradually heated until high-temperature evaporation and atomization are completed; and the carrier gas loads substances to be detected and atomic vapor to the next step. The elements to be detected are elements capable of forming sediments on the surface of an electrode under the electrolysis effect. The atomic vapor sampling method and device based on the electro-deposition and electro-heat provided by the invention can be used for realizing the enrichment and separation of the substances to be detected; the sensitivity can be effectively improved, the matrix interference is reduced, and the memory effect is reduced; and the atomic vapor sampling method and device based on the electro-deposition and electro-heat provided by the invention has no need of a desolvation device, has small size and is beneficial to miniaturization and portability of the instrument.
Description
Technical field
The present invention relates to electro-deposition-Electrothermal Atomic steam sample injection method and device, belong to the instrument analysis technology field.
Background technology
It is " bottleneck " that the sensitivity of restriction atomic spectroscopy improves that sample is introduced technology always, is the most active and most important research field in the atomic spectrometry determination development.Mainly comprise now pneumatic nebulization method, ultrasonic atomizatio method, hot atomization, outstanding slurry atomization, high-pressure atomization method and electron spray method etc.The pneumatic nebulization method mainly has obvious defect at aspects such as nebulization efficiency, anti-high salt ability and memory effects; The ultrasonic atomizatio cost is higher, and matrix effect is larger, and molten backup system must be arranged, and is unfavorable for instrument miniaturization; Hot atomization has higher nebulization efficiency, but matrix effect is serious, has must possess to assist to remove dissolving device, is unfavorable for instrument miniaturization; Outstanding slurry atomization requires particle to wash and evenly; High-pressure atomization requires to provide high pressure, and at present during low discharge effect bad, be unfavorable for instrument miniaturization.
Electro-deposition refers to that simple metal ion or complexation of metal ions form the process of metal or alloy coating at material surface by the galvanochemistry approach.These processes are carried out under certain electrolyte and operating conditions, and the complexity of metal electrodeposition and sedimental form are relevant with the character of plated metal, also depend on the factors such as electrolytical composition, pH value, temperature, current density.Set an appropriate sedimentation potential according to element to be measured, can realize separating with the element that is less than this sedimentation potential, the element that is less than this sedimentation potential is still in liquid, and the element deposition that is greater than this sedimentation potential has arrived electrode surface.
Electric heating evaporation is large electric current by resistance heating, and when temperature acquires a certain degree, the on-gaseous material gasification of being heated around conductor, will make the material on every side excited atom that is heated if temperature continues to raise.Different gasification substances, atomization temperature difference, possess certain separating power.
At present, the report for ultimate analysis atomic vapour sample introduction is not also arranged by electro-deposition-electric heating.It is having broad application prospects aspect atomic spectrum sample introduction, particularly the miniaturization of analytical instrument and aspect linearize.
Summary of the invention
goal of the invention:for solving the problems of the technologies described above, the purpose of this invention is to provide electro-deposition-Electrothermal Atomic steam sample injection method and device, the sample that electro-deposition-electroheat technology is applied to atomic spectroscopy is introduced.
technical scheme:for reaching above-mentioned technique effect, the present invention adopts following technical scheme:
A kind of based on electro-deposition Electrothermal Atomic steam sample injection method, described sample injection method comprises the following steps:
A. determinand solution is passed in chamber, carrier gas slowly passes in chamber with 0 ~ 100ml/min, and two electrodes are connected with direct supply by wire, and the heating wire two ends are connected with DC power cathode by wire; Open the direct supply electrolysis, until cut off the power supply after the complete electrolytic deposition of determinand, waste liquid is discharged;
B. carrier gas is passed in chamber with 10 ~ 2000ml/min, the heating wire two ends are connected with the electric heating power positive cathode respectively by wire, the opening power heating, be warming up to solvent boiling point ± 50 ℃, low temperature drying by heating wire;
C. after drying, carrier gas is passed into 5 ~ 500ml/min, heating wire is rapidly heated to determinand volatilization temperature ± 300 ℃;
D. carrier gas is passed into 0 ~ 100ml/min, heating wire is warming up to rapidly to determinand evaporation or excitation temperature ± 500 ℃;
E. carrier gas is passed into 3 ~ 1000ml/min, after device signal stabilization to be detected, deenergization;
F. carrier gas is passed into 30 ~ 6000ml/min, be cooled to 20 ~ 200 ℃.
In described step a, when adopting the potentiostatic method electrolysis, direct supply voltage is-10V ~+10V; While adopting the galvanostatic method electrolysis, the direct supply electric current is 0.2A ~ 5A; In step b, the electric heating supply voltage is 220V, and electric current is 50HZ.Described carrier gas is at least one and hydrogen 0 ~ 10% combination gas in helium, argon gas, neon and nitrogen.The complete electrolytic deposition of described determinand is: voltage jump, electric current are close to 0 or to set electrolysis time be 5 ~ 50 minutes.
A kind of based on electro-deposition Electrothermal Atomic steam sampling device, comprise the insulation evaporation cavity, evaporation cavity is provided with injection port 3 and exhausr port 4, described evaporation cavity inside is provided with heating wire 6, described heating wire 6 two ends are connected with wire 2 respectively through the chamber wall, on relative two the chamber walls of described evaporation cavity, are respectively equipped with an electrode 1; When electrolysis: described two electrodes 1 are connected with direct supply by wire, and described heating wire 6 two ends are connected with DC power cathode by wire 2; When heating: described heating wire 6 two ends are connected with the electric heating power positive cathode respectively by wire 2.
Described cavity also is provided with air admission hole, with injection port, forms gas distribution system, and described air admission hole is a plurality of, forms even gas distribution system.Described heating wire material is tungsten, molybdenum, platinum or tantalum, and described electrode material is gold-plated or platinum plating; Described insulation evaporation cavity consists of heat proof material, and the insulation heat proof material is simple glass, pyroceram, quartz or ceramic.
In the inventive method: in step a, the slow intermittently purpose of air inlet is to stir; The purpose heated up in step b is to accelerate the volatilization of solvent, and the purpose of the quick air inlet of carrier gas is to take away water vapor, reduction carrier gas to the impact heated up and the volatile matter of taking away generation; The purpose heated up in step c is to guarantee that obviously volatilization and determinand are not taken out of discharge cavity to determinand fast; The purpose heated up in steps d is to make determinand form steam part of atoms/ionization; the purpose that carrier gas slowly enters is to allow determinand form in chamber to fill the air effect enter material concentration and the seed electrons number in discharge cavity with raising; the purpose that in step e, carrier gas slowly enters is to carry gas to be measured to enter discharge cavity; the purpose that is cooled to lower temperature in step f is to guarantee that heating wire changes oxidation by air, and the purpose that carrier gas enters fast is protection heating wire oxidation and accelerates the heating wire cooling.Enrichment completes in electrolysis stage, under the effect of electric current, by liquid phase, becomes solid phase or gas phase.Separation completes in electrolysis and electric heating evaporation stage, and different materials has different decomposition voltages and gasification temperature.
The present invention, by electrolysis and electroheat technology combination, is applied to the sample introduction of plasma generator.Wherein electric heating comprises electric heating evaporation and electric atomizing.Wherein electrolysis and electroheat technology combination are present, and heating wire as electrolysis electrode, plays electric action in electrolytic process, in the electric heating process, plays heating functioin.These parts generate heat under the effect of power supply, realize in chamber drying and determinand is vaporized, atomization.
beneficial effect:
1. method provided by the invention can substitute the metal hydride objects system, and for the difficult element that forms hydride of other difficult volatilizations provides a kind of good method, without any reagent, do not produce waste liquid.
The present invention by effluent discharge after liquid electrolysis enrichment to be measured, dry electrolyte chamber, realize that liquid to be measured goes molten, save dissolving device, volume is little, has realized the miniaturization of instrument, for the miniaturization of atomic spectroscopy instrument, portablely provide strong technical foundation;
3. the present invention has the concentration and separation effect, in electrolytic process, by adopting appropriate voltage, realizes initial gross separation and the enrichment of determinand, in the electric heating process, by appropriate air inlet and heating mode, further realizes separation and the enrichment of determinand.At the determinand volatilization temperature near excitation temperature, the carrier gas intake velocity is 0 or approaches 0, forms and fills the air effect, increases the testing concentration that enters next stage, increase first stage ionization efficiency, can effectively improve sensitivity, reduce the matrix interference and reduce memory effect.The condensation rate of determinand is very high, has further improved sensitivity.Through one-level atomization, can effectively reduce the next stage condition of work, improve next stage atomization/Ionization Efficiency.
The accompanying drawing explanation
Fig. 1 is the structural representation of electro-deposition-Electrothermal Atomic steam sampling device.
Fig. 2 is base plate vertical view in Fig. 1.
Wherein: 1. electrode, 2. wire, 3. injection port, 4. exhausr port, 5. base plate, 6. heating wire, 7,8. insulated cavity wall.
Embodiment
below in conjunction with drawings and Examples, the present invention is described in detail:
A kind of electro-deposition Electrothermal Atomic of the present invention steam sampling device as shown in Figure 1, comprise the evaporation cavity formed by insulated cavity wall 7,8 and base plate 5, evaporation cavity is provided with injection port 3 and exhausr port 4, described evaporation cavity inside is provided with heating wire 6, described heating wire 6 two ends are connected with wire 2 respectively through the chamber wall, on relative two the chamber walls of described evaporation cavity, are respectively equipped with an electrode 1; When electrolysis: described two electrodes 1 are connected with direct supply by wire, and described heating wire 6 two ends are connected with DC power cathode by wire 2; When heating: described heating wire 6 two ends are connected with the electric heating power positive cathode respectively by wire 2.
Embodiment 1: as shown in Figure 1, evaporation cavity is comprised of pyroceram 7,8 and pyroceram base plate 5, injection port 3 and exhausr port 4, form gas handling system, gold,platinized electrolysis electrode 1 is at the plate two ends, and tungsten filament heating wire 6 two ends connect wire 2 through base plate 5, and opposite is exhausr port 4.By injection port fluid injection, discharge opeing, but air admission hole passes into carrier gas heating electric source, be the feedback current power supply, can realize that the precision of temperature is controlled.
By standard solution Cr(Cr
3+) from injection port 3 enters, the combination gas of argon gas 95% and hydrogen 5% is entered by injection port 3 with 15ml/min, lower electrolysis is stirred in carrier gas, adopt potentiostatic electrodeposition, sedimentation potential is-1.3V, now two electrodes 1 connect DC power anode by wire, heating wire 6 two ends connect DC power cathode by wire 2, setting electrolysis time is 30 minutes, waste liquid is discharged by injection port 3, heating wire 6 two ends connect respectively 220V alternating-current power supply ground wire and live wire by wire 2 afterwards, heating wire 6 is heated to 100 ± 10 ℃, carrier gas simultaneously passes into the speed of 100ml/min, after dry, heating wire 6 heats up, carrier gas passes into 10ml/min speed, stopped for 30 seconds to 1750 ℃, carrier gas speed is zero, then heating wire 6 is rapidly heated to 2800 ℃, afterwards with the logical carrier gas of 50ml/min, the signal stabilization for the treatment of the next stage stops heating afterwards, continuation is with the logical carrier gas of 3000ml/min, until heating wire is cooled to 50 ℃ of target temperatures.
Wherein the Cr sample solution is by [product IDs number] 107346[production code member] the GSBG62017-90[Chinese] chromium Cr, standard value: 1000ppm, matrix: 10%HCl (crome metal, trivalent) dilution obtains.
This apparatus structure is simple, easy for installation, in the situation that do not go dissolving device to realize well going molten effect, obviously enrichment determinand, effectively reduced chaff interference, be very beneficial for the miniaturization of sampling device.
Embodiment 2: as shown in Figure 1, evaporation cavity is comprised of quartz 7,8 and pyroceram base plate 5, and injection port 3 and exhausr port 4 form gas handling system, and gold,platinized electrolysis electrode 1 is at the plate two ends, and tungsten filament heating wire 6 two ends connect wires 2 through base plate 5, and opposite is exhausr port 4.
Implementation process is: by standard solution Cd
2+from injection port 3 enters, enter stirring under electrolysis with 20ml/min by injection port 3 at 96% helium and 4% hydrogen mixed gas carrier gas, adopt galvanostatic deposition, electric current is 2A, now electrolysis electrode 1 connects DC power anode by wire, heating wire 6 connects DC power cathode by wire 2, after completing enrichment to determinand, now sedimentation potential transits to suddenly lower current potential at-1.0V, waste liquid is discharged by injection port 3, heating wire 6 connects respectively 220V alternating-current power supply ground wire and live wire by wire afterwards, PID controls temperature, be heated to 100 ± 10 ℃, carrier gas simultaneously passes into the speed of 150ml/min, after dry, heating wire 10 heats up, carrier gas passes into 20ml/min speed, stopped for 40 seconds to 280 ℃, carrier gas speed is zero, then be rapidly heated to 800 ℃, with the logical carrier gas of 80ml/min, the signal stabilization for the treatment of the next stage stops heating afterwards, continuation is with the logical carrier gas of 1500ml/min, until heating wire is cooled to 30 ℃ of target temperatures.
Cd wherein
2+sample solution is by [product IDs number] 98072[production code member] the GSB04-1721-2004[Chinese] cadmium standard solution [product specification] 50mL/ bottle standard value: 1000 μ g/ml dilutions obtain.
Claims (7)
1. one kind based on electro-deposition Electrothermal Atomic steam sample injection method, and it is characterized in that: described sample injection method comprises the following steps:
A. determinand solution is passed in chamber, carrier gas slowly passes in chamber with 0 ~ 100ml/min, and two electrodes are connected with direct supply by wire, and the heating wire two ends are connected with DC power cathode by wire; Open the direct supply electrolysis, until cut off the power supply after the complete electrolytic deposition of determinand, waste liquid is discharged;
B. carrier gas is passed in chamber with 10 ~ 2000ml/min, the heating wire two ends are connected with the electric heating power positive cathode respectively by wire, the opening power heating, be warming up to solvent boiling point ± 50 ℃, low temperature drying by heating wire;
C. after drying, carrier gas is passed into 5 ~ 500ml/min, heating wire is rapidly heated to determinand volatilization temperature ± 300 ℃;
D. carrier gas is passed into 0 ~ 100ml/min, heating wire is warming up to rapidly to determinand evaporation or excitation temperature ± 500 ℃;
E. carrier gas is passed into 3 ~ 1000ml/min, after device signal stabilization to be detected, deenergization;
F. carrier gas is passed into 30 ~ 6000ml/min, be cooled to 20 ~ 200 ℃.
2. method according to claim 1: it is characterized in that: in described step a, when adopting the potentiostatic method electrolysis, direct supply voltage is-10V ~+10V; While adopting the galvanostatic method electrolysis, the direct supply electric current is 0.2A ~ 5A; In described step b, the electric heating supply voltage is 220V, and electric current is 50HZ.
3. method according to claim 1: it is characterized in that: described carrier gas is at least one and hydrogen 0 ~ 10% combination gas in helium, argon gas, neon and nitrogen.
4. method according to claim 1: it is characterized in that: the complete electrolytic deposition of described determinand is: voltage jump, electric current are close to 0 or to set electrolysis time be 5 ~ 50 minutes.
5. one kind based on electro-deposition Electrothermal Atomic steam sampling device, it is characterized in that: comprise the insulation evaporation cavity, evaporation cavity is provided with injection port (3) and exhausr port (4), described evaporation cavity inside is provided with heating wire (6), described heating wire (6) two ends are connected with wire (2) respectively through the chamber wall, on relative two the chamber walls of described evaporation cavity, are respectively equipped with an electrode (1); During electrolysis: described two electrodes (1) are connected with direct supply by wire, and described heating wire (10) two ends are connected with DC power cathode by wire (2); During heating: described heating wire (10) two ends are connected with the electric heating power positive cathode respectively by wire (2).
6. device according to claim 5: it is characterized in that: described cavity also is provided with air admission hole, with injection port, forms gas distribution system, and described air admission hole is a plurality of, forms even gas distribution system.
7. device according to claim 5: it is characterized in that: described heating wire (10) material is tungsten, molybdenum, platinum or tantalum, and described electrode material is gold-plated or platinum plating; Described insulation evaporation cavity consists of heat proof material, and the insulation heat proof material is simple glass, pyroceram, quartz or ceramic.
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| US5978082A (en) * | 1997-02-05 | 1999-11-02 | Hitachi, Ltd. | Atomic absorptiometer and a metal specimen atomic vapor generation apparatus used in the atomic absorotiometer |
| CN201107273Y (en) * | 2007-11-28 | 2008-08-27 | 成都理工大学 | Atomic fluorescent spectrometer |
| CN101482497A (en) * | 2009-02-19 | 2009-07-15 | 成都理工大学 | On-line electro-chemistrical separation and concentration tungsten filament electric heating atom absorption detection apparatus |
| CN101694469A (en) * | 2009-11-12 | 2010-04-14 | 中国海洋大学 | Guiding deposition strengthening method for detecting ions in water through laser-induced breakdown spectroscopy |
| CN102338745A (en) * | 2010-07-15 | 2012-02-01 | 北京吉天仪器有限公司 | Electro-thermal vaporization atomic fluorescence spectrometry method and spectrometer used for determining cadmium |
| CN203216852U (en) * | 2013-03-06 | 2013-09-25 | 河海大学 | Atomic vapor sampling device based on electrodeposition and electric heating |
-
2013
- 2013-03-06 CN CN2013100716394A patent/CN103149197A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5978082A (en) * | 1997-02-05 | 1999-11-02 | Hitachi, Ltd. | Atomic absorptiometer and a metal specimen atomic vapor generation apparatus used in the atomic absorotiometer |
| CN201107273Y (en) * | 2007-11-28 | 2008-08-27 | 成都理工大学 | Atomic fluorescent spectrometer |
| CN101482497A (en) * | 2009-02-19 | 2009-07-15 | 成都理工大学 | On-line electro-chemistrical separation and concentration tungsten filament electric heating atom absorption detection apparatus |
| CN101694469A (en) * | 2009-11-12 | 2010-04-14 | 中国海洋大学 | Guiding deposition strengthening method for detecting ions in water through laser-induced breakdown spectroscopy |
| CN102338745A (en) * | 2010-07-15 | 2012-02-01 | 北京吉天仪器有限公司 | Electro-thermal vaporization atomic fluorescence spectrometry method and spectrometer used for determining cadmium |
| CN203216852U (en) * | 2013-03-06 | 2013-09-25 | 河海大学 | Atomic vapor sampling device based on electrodeposition and electric heating |
Non-Patent Citations (2)
| Title |
|---|
| WALTER LUND ET AL.: ""The application of electrodeposition techniques to flameless atomic absorption spectrometry:Part Ⅱ.Determination of cadmium in sea water"", 《ANALYTICA CHIMICA ACTA》, vol. 72, no. 1, 30 September 1974 (1974-09-30), pages 57 - 62 * |
| 胡子文等: ""电沉积-钨丝电热原子吸收光谱法测定水样中的铅"", 《分析实验室》, vol. 29, no. 2, 28 February 2010 (2010-02-28), pages 42 - 44 * |
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Application publication date: 20130612 |