WO2013109588A1 - Zinc oxide sulfur sensors and methods of manufacture thereof - Google Patents
Zinc oxide sulfur sensors and methods of manufacture thereof Download PDFInfo
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- WO2013109588A1 WO2013109588A1 PCT/US2013/021676 US2013021676W WO2013109588A1 WO 2013109588 A1 WO2013109588 A1 WO 2013109588A1 US 2013021676 W US2013021676 W US 2013021676W WO 2013109588 A1 WO2013109588 A1 WO 2013109588A1
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- zinc oxide
- sulfur
- sensor
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- microstructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/26—Oils; viscous liquids; paints; inks
- G01N33/28—Oils, i.e. hydrocarbon liquids
- G01N33/2835—Oils, i.e. hydrocarbon liquids specific substances contained in the oil or fuel
- G01N33/287—Sulfur content
Definitions
- This disclosure relates generally to sensors for detecting sulfur concentrations in liquids. More specifically, this disclosure relates to improved zinc oxide sulfur sensors for measuring sulfur concentrations in liquids and methods of manufacturing improved zinc oxide sulfur sensors that may be used by operators in the field. Background
- a sensor determines a sulfur concentration in a liquid.
- the disclosed sensor may include a substrate that is at least partially coated with zinc oxide. Further, the zinc oxide may have a crystal lattice structure that is oriented in the (002) plane.
- a sulfur concentration detection system in another example, includes a sensor that may include a working electrode including a substrate coated with zinc oxide.
- the zinc oxide may include microstructures that have crystal lattice structures oriented in the (002) plane.
- the sensor may also include a reference electrode.
- the detection system may also include a current source and a voltage detector, wherein the current source may be connected to the working electrode and the voltage detector may be connected to the reference and working electrodes.
- a method for determining a sulfur concentration in a liquid includes exposing the liquid to a sulfur sensor.
- the sensor may include a working electrode including a substrate, a conductive material and zinc oxide microstructures protruding from the substrate. At least some of the zinc oxide microstructures may have a crystal lattice structure oriented in the (002) plane.
- the sulfur sensor may also include a reference electrode.
- the method further includes applying a constant current to the substrate, monitoring a voltage between the working and reference electrodes and correlating the voltage to a sulfur concentration in the liquid.
- FIG. 1 is a cross-sectional illustration of zinc oxide microstructures on a substrate as disclosed herein.
- FIG. 2 is a schematic illustration of one method of open circuit potential measurement whereby a disclosed sensor is at least partially submerged in a liquid to be measured and is connected to a working electrode, which is connected to a potentiometer which, in turn, is connected to a reference electrode that is at least partially in the liquid.
- FIG. 3 graphically illustrates the ability of a disclosed zinc oxide sensor to adsorb sulfur until the sulfur concentration reaches a certain value, which is indicative of the concentration of sulfur and the liquid.
- FIG. 4 graphically illustrates x-ray diffraction spectrums for seven different zinc oxide coatings (A-G) that were generated using either different precursors and/or different reaction conditions.
- FIG. 5 is a scanning electron microscope (SEM) photograph illustrating microstructures of sample A of FIG. 4 and FIG. 6 graphically illustrates the lack of adsorption of sulfur compounds onto the microstructures shown in the photograph of FIG. 5.
- SEM scanning electron microscope
- FIG. 7 is a SEM photograph of the microstructures of sample B of FIG. 4 and FIG. 8 graphically illustrates the ability of the microstructures of sample B to adsorb sulfur compounds onto the microstructures of sample B when the sulfur is at a concentration of about 350 ppm.
- FIG. 9 is a SEM photograph of the microstructures of sample G of FIG. 4 and FIG. 10 graphically illustrates the ability of the microstructures of sample G to adsorb sulfur compounds at least when the sulfur is at a
- FIG. 11 graphically illustrates the ability of the zinc oxide coating disposed on a copper substrate as shown in the photograph of FIG. 12 to adsorb sulfur compounds in a liquid at concentrations ranging from 1 ppm to 350 ppm.
- FIG. 13 graphically illustrates the ability of a disclosed zinc oxide coating on a stainless steel substrate as shown in FIG. 14 to adsorb sulfur compounds in a liquid at concentrations ranging from 15 ppm to 3600 ppm.
- FIG. 15 shows two SEM photographs of different magnifications of a zinc oxide coating that includes rod-like or ribbon-like microstructures that protrude upwardly from the substrate.
- FIGS. 16 and 17 are SEM photographs illustrating the preparation of two zinc oxide coatings at different manifold temperatures, wherein the manifold temperature for the coating of FIG. 16 is 200°C while the manifold temperature for the coating of FIG. 17 is 300°C, thereby establishing that an increased manifold temperature of FIG. 17 produces rod- like or ribbonlike upwardly protruding microstructures and wherein the lower manifold temperature of FIG. 16 produces shorter and rounder microstructures.
- FIGS. 18 and 19 illustrate the effect of reaction time on the microstructures of the zinc oxide coatings wherein the rod-like structures of FIG. 18 have an average thickness of about 0.7 microns and were prepared over a two hour reaction time while the thicker microstructures of FIG. 19 have an average thickness of about 1 micron and were prepared over a 3.5 hour reaction time.
- FIG. 20 graphically illustrates the ability of the coating shown in FIG. 18 to adsorb and detect sulfur at a concentration of 5 ppm in about 100 seconds and the ability to adsorb and detect sulfur at a concentration of about 386 ppm in about 80 seconds and FIG. 20 also graphically illustrates the sensitivity of the sensor made from the coating of FIG. 18.
- FIG. 21 graphically illustrates the ability of one disclosed zinc oxide sensor to detect sulfur in liquids of concentrations ranging from 10 ppm to 155 ppm and further that such a sensor may have limited effectiveness for sulfur concentrations of 183 ppm or higher.
- FIG. 22 graphically illustrates the high crystallinity of four zinc oxide coatings in the (002) plane, specifically sample numbers 65, 67, 130 and 134, which were fabricated using identical process parameters.
- FIG. 23 also graphically illustrates the high crystalline structure in the (002) plane of sample number 67 in comparison to sample numbers 23 and 106.
- FIG. 24 graphically illustrates the ability of sample 67 to detect sulfur and liquids at low concentrations (10.7 ppm to 48 ppm) and the increased sensitivity of sample 67 with the with the high crystallinity in the (002) plane versus samples 23 and 106, which have low crystallinity in the (002) plane as shown in FIGS. 22-23.
- FIG. 1 shows a cross section of a substrate 30 that is at least partially coated with a plurality of zinc oxide microstructures 31.
- the microstructures 31 may protrude outwardly from the substrate 30.
- the treatment of the substrate 30 (or electrode) may also impact the morphology of the microstructures 31.
- microstructures is used herein to describe the nature in size of the zinc oxide microstructures, one skilled in the art will understand that the actual scale of the zinc oxide protrusions 31 may approach or enter the nano- scale or alternatively, be larger than the micro-scale.
- the substrate 30 may be conductive or non-conductive.
- Non- conductive substrates 30 may be ceramic or any of a variety of non-conductive substrates that are apparent to those skilled in the art. Conductive substrates may also vary greatly and may eliminate the need for a working electrode 32
- a working electrode 32 is attached or coupled to the substrate 30 and zinc oxide protrusions 31.
- the disclosed sulfur sensor is designed based on the physical adsorption of organo-sulfur compounds onto zinc oxide.
- the inventors have surprisingly found that the rate of physical adsorption of organo-sulfur compounds onto zinc oxide may be a function of the crystallinity of the zinc oxide and, more specifically, the orientation of the crystallinity of the zinc oxide in the (002) plane, or a plane that protrudes vertically upward from the substrate 30 in FIG. 1 or a plane that protrudes horizontally to the right from the surface 33 of the substrate 30 as shown in FIG. 2.
- the rate of physical adsorption is also dependent upon the rod-like or ribbon-like morphology of the zinc oxide coating and the oxygen deficiency of the zinc oxide coating.
- the physical adsorption of organo-sulfur compounds onto zinc oxide protrusions results in a change in the resistivity of the outer layer of the zinc oxide microstructures.
- microstructures corresponds directly to the amount of sulfur in the liquid available to react with the zinc in the zinc oxide microstructures 31.
- This change in resistivity can be measured by measuring a voltage change for a known current applied across the sulfur sensor and the liquid being measured.
- applying a constant voltage across the working and reference electrodes 32, 35 will also result in a constant current flow between the electrodes 32, 35 once the zinc oxide coating becomes saturated with sulfur compounds or in equilibrium with the sulfur concentration in the liquid 34.
- sulfur concentrations can be determined by measuring the amount of time it takes for the voltage to stabilize when a constant current is applied or by measuring the amount of time it takes for the current to stabilize when a constant voltage is applied.
- a substrate 30 with a zinc oxide coating (not shown) on the surface 33 of the substrate 30 is at least partially submerged in a liquid 34.
- a reference electrode 35 is also at least partially submerged in the liquid 34.
- the working and reference electrodes 32, 35 are coupled to a potentiometer 36.
- a known current is applied through the working electrode 32 to the substrate 30 and zinc oxide coating on the surface 33.
- an equilibrium will be established based on the concentration of sulfur in the liquid being measured, as illustrated in FIG. 3.
- the X axis is the concentration of sulfur in the liquid being measured and the Y axis is the equilibrium constant for the adsorption of the sulfur onto the zinc oxide.
- FIG. 4 x-ray diffraction spectrums are graphically illustrated for seven different samples A-G.
- Crystallinity in the (002) plane is indicated by a peak at or about 34 along the X axis (2-theta scale).
- samples A and C show no or minimal crystallinity along the (002) plane
- samples B and D-G show crystallinity along the (002) plane with sample G showing the highest level of crystallinity along the (002) plane.
- FIGS. 5-10 compare the abilities of samples A, B and G from FIG. 4 to detect sulfur at concentrations of 15 ppm and 350 ppm.
- FIGS 5-10 also illustrate that variations in process parameters can affect the physical characteristics of the zinc oxide coating.
- the disclosed zinc oxide coatings are prepared using a metal-organic compound vapor deposition (MOCVD) apparatus.
- MOCVD metal-organic compound vapor deposition
- Samples A and B were prepared using a zinc acetylacetone precursor, with a chamber temperature of about 500°C, a pressure of about 2.5 torr, an oxygen flow rate of about 50 ml/min, an argon flow rate of about 50 ml/min and with the zinc acetylacetone precursor temperature of about 145°C. As shown in FIG. 6, the coating of sample A is not effective for measuring sulfur concentrations at either the 15 ppm or 350 ppm concentrations.
- sample B was prepared using a zinc acetylacetone precursor, a chamber temperature of about 550°C, a pressure of about 10 torr and an oxygen and argon flow rates of about 50 ml/min. As shown in FIG. 8, sample B is not capable of detecting sulfur levels as low as 15 ppm but is quite capable of detecting sulfur levels at 350 ppm.
- FIGS. 9-10 a SEM photograph of the coating of sample G is shown in FIG. 9 which was prepared using a diethyl zinc precursor, a chamber temperature of about 500°C, a pressure of about 2.5 torr, oxygen and argon flow rates of about 50 ml/min and a precursor temperature of only about 30°C.
- sample G is capable of quickly detecting a sulfur concentration of 350 ppm, but is not sensitive enough to detect the sulfur concentration of 15 ppm.
- FIGS. 4-10 it is apparent that zinc oxide coatings with a high crystallinity, such as those exhibited by samples B and D-G, are capable of adsorbing organo-sulfur compounds. Further, it will be noted that the diethyl zinc precursor used for sample G produced a zinc oxide coating that detected sulfur at a concentration of 350 ppm much faster than sample B, which was formed using a zinc acetylacetone precursor.
- FIGS. 5-6 establish that, without crystallinity along the (002) plane, fast adsorption of organo- sulfur compounds may not be possible, at least at the 15 ppm and 350 ppm concentrations. Thus, FIGS. 4-10 surprisingly illustrate that crystallinity in the (002) plane may be one factor that enhances adsorption of sulfur compounds on zinc oxide coatings.
- FIGS. 11-14 comparisons of different substrates and different coating densities are provided.
- a copper substrate coated with zinc oxide is shown in FIG. 12 and can detect sulfur concentrations of 1, 15 and 350 ppm as shown in FIG. 11.
- the zinc oxide coating of FIG. 12 is less dense than the zinc oxide coating of FIG. 14, which was coated onto a stainless steel substrate and is capable of detecting sulfur concentrations of 15, 350 and 3600 ppm as shown in FIG. 13.
- the higher concentration of 350 ppm was detected by the coating of FIGS.
- FIG. 15 two SEM photographs, of different magnifications, are shown of the same coating.
- the sample of FIG. 15 was prepared using a furnace temperature of 500°C and an increased manifold temperature of 300°C.
- a zinc acetylacetone precursor was utilized and the coating process was carried out for two hours at a pressure of 10 torr.
- the argon and oxygen flow rates were 50 ml/min.
- This procedure produced an oxygen deficient zinc oxide coating as shown in FIG. 15, with excellent rod- like structures that protrude upwardly from the substrate (not shown) and therefore have a high crystallinity in the (002) plane.
- the oxygen deficiency was established by measurement which revealed that the coating of FIG.
- the wt% ratio of zinc to oxygen for a fully saturated zinc oxide (ZnO) coating is 3.75, or the molecular weight of zinc (30) divided by the molecular weight of oxygen (8).
- the 4.09 ratio (73.22/17.9) of the coating of FIG. 15 is indicative of an oxygen deficient zinc oxide coating.
- FIGS. 16-17 the same parameters were used except, in FIG. 16, the manifold temperature was set at 200°C while the manifold temperature for the coating of FIG. 17 was set at 300°C.
- an increased manifold temperature produces better rod- like microstructures.
- FIGS. 18-19 the effects of variations in the reaction time were measured.
- the deposition process was carried out for two hours, which produced the rod-like structures shown in FIG. 18 having an average thickness of about 0.7 microns.
- increasing the reaction time to about 3.5 hours as shown in FIG. 19 produces rod- like structures having an average thickness of about 1 micron.
- the less dense coating of FIG. 18 may be preferable for measuring low sulfur concentrations while the more dense coating of FIG. 19 may be more preferable for measuring higher concentrations of sulfur compounds.
- FIG. 20 illustrates, graphically, the response of a sensor coated with the coating of FIG. 18 to liquids having differing amounts of sulfur, specifically 5 ppm and 386 ppm.
- the voltmeter utilized for the measurements illustrated in FIG. 20 was not capable of detecting more than 15 volts and therefore the combination of the sensor and voltmeter used for FIG. 20 cannot adequately detect a concentration of 4940 ppm as shown in FIG. 20.
- FIG. 20 also illustrates that the 0.7 micron thick rod-like structures of the coating of FIG. 18 provide a sensor that is suitable for both low sulfur detection (5 ppm) and relatively high sulfur detection (386 ppm). Further, as shown in FIG. 20, the response time for the coating of FIG. 18 is substantially reduced to about 100 seconds for the 5 ppm sulfur concentration liquid and about 80 seconds for the 386 ppm sulfur concentration liquid.
- FIG. 21 illustrates, graphically, the response of the zinc oxide sensor made from sample 106, which is stainless steel, to varying concentrations of sulfur in a liquid, specifically diesel fuels, although this disclosure is directed toward the detection of organic sulfur compounds in any liquid and in any liquid fuel.
- the sensor illustrated in FIG. 21 provides less sensitivity at the lower concentrations of 10, 20 and 48 ppm but provides substantial sensitivity for the concentrations of 135 and 155 ppm.
- the sensor illustrated in FIG. 21 is not useful for higher concentrations such as 183 and 297 ppm as the sensor appears to be saturated at those concentrations.
- FIGS. 22-23 are bar graphs of the x-ray diffraction (XRD) analysis of the crystalline structures of zinc oxide coatings made with varying parameters. Specifically, the cycle time, vacuum pressure, bubbler temperature, manifold temperature set point and chamber temperature were all varied.
- XRD x-ray diffraction
- sample 67 provides the best sensitivity between the concentrations of 10.7 ppm and 48 ppm. It will also be noted that all samples became saturated or established equilibrium in relatively short time periods. Specifically, while somewhat slower than samples 23 and 106, sample 67 established equilibrium at the higher concentration of 48 ppm in about 30 seconds and established equilibrium at the lower concentrations in about 50 seconds.
- the sensors disclosed herein is particularly useful in field applications to allow operators to determine the sulfur content of a fuel before introducing the fuel into a machine that may be designed to run on fuels having specific sulfur concentrations.
- the sensor disclosed herein may be modified to be disposable, reusable, or as an on-board sensor that determines the sulfur content of the fuel in the fuel tank neck before an appreciable amount of fuel is introduced.
- FIG. 21 shows the results of exposing an exemplary ZnO sulfur sensor formed according to this disclosure to a variety of liquids having various sulfur concentrations.
- the ZnO microstructures were formed on a copper substrate using MOCVD.
- the results in FIG. 21 show how the voltage applied across the sensor and the liquid at a constant current changed over time when the sensor was exposed to liquids having 10, 20, 48, 135, 155, 183 and 297 ppm sulfur.
- the sensor of FIG. 21 shows good sensitivity for the lower sulfur concentrations (10-155 ppm) while showing poor sensitivity for higher sulfur concentrations (183-297 ppm).
- the sensor illustrated in FIG. 18 shows good sensitivity at both low (5 ppm) and higher (386 ppm) concentrations.
- the sensor of FIG. 20 reached a saturation point in about 100 seconds for the 5 ppm liquid while the sensor of FIG. 21 reached a saturation point for all concentrations in less than one minute.
- the disclosed sensors are fast enough to be used in the field with minimal inconvenience.
- an operator may monitor the amount of time necessary for saturation of a ZnO sulfur sensor, as indicated by stabilization of the voltage across the sensor while the current remains constant.
- the operator could correlate the stabilized voltage to a sulfur content using a lookup table, or the correlation could be automated using known automating techniques, such as a computer accessing a series of lookup tables, and an absolute sulfur reading could be issued to the operator.
- any suitable deposition and/or growth method known in the art may be used.
- MOCVD may be used to form ZnO deposits on a conductive or ceramic substrate.
- FIG. 22 and Table 1 show the affect of the vacuum pressure and cycle time or time of the deposition on the (002) crystallinity, while secondary factors are the manifold temperature and bubbler temperature.
- FIG. 18 shows ZnO microstructures that have been grown over about two hours, whereas FIG. 19 shows ZnO microstructures grown under the same conditions over about 3.5 hours. The thickness of the ZnO micro-structures shown in FIG.
- the density of the ZnO microstructures shown in FIG. 19 is about 1.0 microns. While this thickness in itself is acceptable, the density of the ZnO on the surface of the conductive substrate may be too high for low concentrations of sulfur as a high density inhibits interaction between the microstructures and the liquid. Such a high density forces the ZnO
- microstructures to grow in a highly compact, ordered fashion away from the substrate.
- two or more sensors may be employed for fuels of different sulfur concentrations.
- the microstructures may have incidental amounts of other elements, likely drawn from the substrate during the deposition and growth process.
- the conductive substrate is a stainless steel
- the microstructures may have between about 1.0-5.0 wt % C, between about 14.0-24.0 wt % O, between about 0.5-1.5 wt % Cr, and between about 2.5-7.0 wt % Fe, the balance being Zn.
- analysis showed that ZnO microstructures grown on a stainless steel substrate had the following composition, by weight percent: C— 3.31; O--17.90; Cr-1.04; Fe-4.53; and Zn-73.22.
Abstract
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CN201380005853.8A CN104067114A (en) | 2012-01-20 | 2013-01-16 | Zinc oxide sulfur sensors and methods of manufacture thereof |
JP2014553358A JP2015504172A (en) | 2012-01-20 | 2013-01-16 | Zinc oxide sulfur sensor and manufacturing method thereof |
DE112013000635.9T DE112013000635T5 (en) | 2012-01-20 | 2013-01-16 | Zinc oxide sulfur sensors and process for their preparation |
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US13/354,766 US8653839B2 (en) | 2009-07-17 | 2012-01-20 | Zinc oxide sulfur sensors and method of using said sensors |
US13/354,766 | 2012-01-20 |
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CN (1) | CN104067114A (en) |
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CN114994140A (en) * | 2022-05-24 | 2022-09-02 | 哈尔滨工业大学 | Zinc oxide-titanium dioxide sensor for detecting sulfur content and preparation method and application thereof |
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US20030217922A1 (en) * | 2002-05-27 | 2003-11-27 | Shinko Electric Industries Co., Ltd. | Sensor and device for detecting sulfur |
US6914279B2 (en) * | 2002-06-06 | 2005-07-05 | Rutgers, The State University Of New Jersey | Multifunctional biosensor based on ZnO nanostructures |
US7309621B2 (en) * | 2005-04-26 | 2007-12-18 | Sharp Laboratories Of America, Inc. | Method to fabricate a nanowire CHEMFET sensor device using selective nanowire deposition |
US20090286351A1 (en) * | 2006-06-02 | 2009-11-19 | Kochi Industrial Promotion Center | Manufacturing method of semiconductor device including active layer of zinc oxide with controlled crystal lattice spacing |
US20110012625A1 (en) * | 2009-07-17 | 2011-01-20 | Caterpillar Inc. | Zinc oxide sulfur sensor |
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CN1445821A (en) * | 2002-03-15 | 2003-10-01 | 三洋电机株式会社 | Forming method of ZnO film and ZnO semiconductor layer, semiconductor element and manufacturing method thereof |
US7172813B2 (en) * | 2003-05-20 | 2007-02-06 | Burgener Ii Robert H | Zinc oxide crystal growth substrate |
JP5432501B2 (en) * | 2008-05-13 | 2014-03-05 | 日東電工株式会社 | Transparent conductive film and method for producing the same |
CN102312191B (en) * | 2010-06-30 | 2015-08-19 | 中国科学院上海硅酸盐研究所 | Magnetically controlled DC sputtering is utilized to prepare the method for high resistance transparent ZnO film |
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- 2013-01-16 DE DE112013000635.9T patent/DE112013000635T5/en not_active Withdrawn
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030217922A1 (en) * | 2002-05-27 | 2003-11-27 | Shinko Electric Industries Co., Ltd. | Sensor and device for detecting sulfur |
US6914279B2 (en) * | 2002-06-06 | 2005-07-05 | Rutgers, The State University Of New Jersey | Multifunctional biosensor based on ZnO nanostructures |
US7309621B2 (en) * | 2005-04-26 | 2007-12-18 | Sharp Laboratories Of America, Inc. | Method to fabricate a nanowire CHEMFET sensor device using selective nanowire deposition |
US20090286351A1 (en) * | 2006-06-02 | 2009-11-19 | Kochi Industrial Promotion Center | Manufacturing method of semiconductor device including active layer of zinc oxide with controlled crystal lattice spacing |
US20110012625A1 (en) * | 2009-07-17 | 2011-01-20 | Caterpillar Inc. | Zinc oxide sulfur sensor |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114994140A (en) * | 2022-05-24 | 2022-09-02 | 哈尔滨工业大学 | Zinc oxide-titanium dioxide sensor for detecting sulfur content and preparation method and application thereof |
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JP2015504172A (en) | 2015-02-05 |
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