WO2013039189A1 - Dispositif de génération de plasma et spectrophotomètre d'émission - Google Patents

Dispositif de génération de plasma et spectrophotomètre d'émission Download PDF

Info

Publication number
WO2013039189A1
WO2013039189A1 PCT/JP2012/073585 JP2012073585W WO2013039189A1 WO 2013039189 A1 WO2013039189 A1 WO 2013039189A1 JP 2012073585 W JP2012073585 W JP 2012073585W WO 2013039189 A1 WO2013039189 A1 WO 2013039189A1
Authority
WO
WIPO (PCT)
Prior art keywords
narrow portion
channel
plasma
sectional area
cross
Prior art date
Application number
PCT/JP2012/073585
Other languages
English (en)
Japanese (ja)
Inventor
高村　禅
山本　保
Original Assignee
国立大学法人北陸先端科学技術大学院大学
株式会社マイクロエミッション
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 国立大学法人北陸先端科学技術大学院大学, 株式会社マイクロエミッション filed Critical 国立大学法人北陸先端科学技術大学院大学
Priority to JP2013533727A priority Critical patent/JP6083047B2/ja
Publication of WO2013039189A1 publication Critical patent/WO2013039189A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/48—Generating plasma using an arc
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
    • G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/0006—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature
    • H05H1/0012—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature using electromagnetic or particle radiation, e.g. interferometry
    • H05H1/0025—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature using electromagnetic or particle radiation, e.g. interferometry by using photoelectric means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/0006—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature
    • H05H1/0012—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature using electromagnetic or particle radiation, e.g. interferometry
    • H05H1/0037—Investigating plasma, e.g. measuring the degree of ionisation or the electron temperature using electromagnetic or particle radiation, e.g. interferometry by spectrometry

Definitions

  • the present invention relates to a plasma generator and an emission spectroscopic analyzer. More specifically, the present invention relates to a plasma generation apparatus and an emission spectroscopic analysis apparatus for identifying and quantifying an element based on an emission spectrum from an element contained in a solution.
  • microfluids have been developed to apply semiconductor processes to create small flow channels, reaction vessels, analytical instruments, etc. on a wafer and complete a series of chemical experiments necessary for blood testing on a single chip.
  • Research fields called “ ⁇ TAS” and “Lab on a chip” are rapidly developing.
  • a method has been developed in which minute plasma is generated and a mist-like solution is introduced therein to perform elemental analysis.
  • Non-Patent Document 1 As another method of generating plasma, a method of generating plasma by inserting an electrode into a solution and passing a current directly through the solution has been reported (for example, see Non-Patent Document 1).
  • the advantage of this method is that plasma is generated in the solution, and the evaporation of the solution plays the role of gasification of the specimen, so that a nebulizer is not required.
  • the impurities contained in the solid electrode evaporate, and it is difficult to avoid contamination of the impurities.
  • a narrow portion having a cross-sectional area significantly smaller than the cross-sectional area of the flow channel is provided in the flow channel formed of an insulating material, and the flow channel and the narrow portion are electrically conductive.
  • a liquid electrode plasma (LEP: Liquid Electrode Plasma) type emission spectroscopic analyzer (hereinafter referred to as LEP: Liquid Electrode Plasma) type that applies an electric field to the narrow part so that the electric field passes through the narrow part and generates plasma in the narrow part.
  • LEP Liquid Electrode Plasma
  • a simple LEP emission analyzer, LEP device, or LEP has already been proposed (for example, Patent Document 2).
  • This LEP has an advantage that plasma can be easily generated while reducing the amount of impurities when performing an emission analysis of elements contained in a conductive liquid. In addition, this LEP achieves downsizing of the apparatus, dramatic reduction in consumption gas and power consumption, and reduction in apparatus cost while having performance equivalent to that of ICP emission analysis.
  • the conventional LEP already proposed generates plasma in a narrow portion disposed between the electrodes when a high voltage is applied between the electrodes, but lead (Pb), thallium (Tl), cadmium (cd) In some elements such as), a sufficient amount of light cannot be obtained, and there remains a problem that measurement sensitivity is low. In other words, there are elements that cannot be measured quantitatively with the proposed technique.
  • JP 2002-257785 A Japanese Patent No. 3932368
  • the present invention has been proposed in view of such conventional circumstances, and an object thereof is to provide a plasma generation apparatus and an emission spectroscopic analysis apparatus that eliminate the disadvantages of the conventional techniques. That is, an object of the present invention is to provide a plasma generation apparatus having a long plasma generation time and an emission spectroscopic analysis apparatus having a very high measurement sensitivity.
  • Another object of the present invention is to provide an emission spectroscopic analyzer capable of detecting and analyzing even a trace amount of elements by expanding the elements that can be detected as compared with conventional LEP emission analyzers.
  • the present inventors have found that for some elements, the sensitivity is particularly poor when the voltage is forcibly cut off in a short time and the plasma generation time is shortened. Furthermore, the present inventors have found out a cause of this sensitivity decrease and also found out a method for eliminating the sensitivity decrease. These are described in detail below.
  • positive pressure release is also effective in suppressing movement of a specific interface, and for this purpose, an interface that has little contribution to light emission and plasma maintenance (that is, the above-mentioned specific specification). We thought that it is effective to actively move a different interface).
  • the inventors of the present invention connected the third and fourth flow paths to a narrow portion to reduce the movement resistance in order to release the pressure positively, and simultaneously reduce the voltage. It has also been conceived that the plasma generation time in the narrow portion can be extended by increasing the movement resistance of the flow path having the role of applying, and the present invention has been completed.
  • the present inventors are also effective to make a difference appear in the fluid movement resistance in the enlarged flow channel formed at both ends of the narrowest narrow channel with the narrowest channel cross-sectional area in the narrow portion, for example, If the enlarged flow path at both ends of the narrowest flow path is formed from a conventional symmetrical structure to an asymmetrical structure, the moving speed of the interface to one electrode side can be made slower than that to the other electrode side. It has been found that the time and region where concentration occurs can be increased, and the present invention has been completed.
  • a plasma generator for generating plasma in a conductive liquid A transport channel for transporting the conductive liquid and formed of an insulating material; A narrow portion connected to the transport channel and having a cross-sectional area significantly smaller than the cross-sectional area of the transport channel; Means for applying an electric field to the narrow portion so that the electric field passes through the narrow portion; And having The plasma generating apparatus according to claim 1, wherein a movement resistance of the conductive liquid is larger in a part of the narrow part than in another part.
  • the narrow portion is formed with a throat portion having the smallest channel cross-sectional area, and enlarged channels connected to the transport channel on both sides of the throat portion, 2.
  • the plasma generating apparatus according to aspect 1, wherein the enlarged flow channel on one side has a larger movement resistance of the conductive liquid than the enlarged flow channel on the other side.
  • the plasma generating apparatus according to aspect 2 wherein the enlarged flow path is configured asymmetrically with respect to the throat.
  • the throat is disposed closer to the other end than one end of the narrow portion;
  • the enlarged channel has a channel cross-sectional area that gradually expands from the throat toward the transport channel, The maximum channel cross-sectional area of the expanded channel disposed on the one end side is larger than the maximum channel cross-sectional area of the expanded channel disposed on the other end side, 4.
  • the maximum flow path cross-sectional area of the enlarged flow path disposed on the one end side is 1.1 to 100 times the flow path cross-sectional area at the throat portion, and the flow path cross-sectional area disposed on the other end side is 5.
  • the plasma generating apparatus according to aspect 4 wherein the maximum flow path cross-sectional area of the enlarged flow path is 1.1 to 50 times the cross-sectional area of the throat. (Aspect 6) 6.
  • the plasma generating apparatus further comprising a pressure adjusting mechanism that locally increases or decreases the pressure of the conductive liquid in the narrow portion.
  • a plasma generator for generating plasma in a conductive liquid A transport channel for transporting the conductive liquid and formed of an insulating material; A narrow portion connected to the transport channel and having a cross-sectional area significantly smaller than the cross-sectional area of the transport channel; Means for applying an electric field to the narrow portion so that the electric field passes through the narrow portion; And having An outlet channel is further disposed in the narrow portion, Guiding the conductive liquid so as to flow into the narrow portion from the transport channel and out of the outlet channel via the narrow portion; A pressure adjusting mechanism for increasing or decreasing the pressure of the conductive liquid locally is provided in the outlet channel, or a sectional area of the outlet channel is made larger than the sectional area of the narrow portion.
  • the means for applying an electric field to the narrow portion includes a solution reservoir in which an electrode is inserted, and a supply pipe for supplying the conductive liquid to the solution reservoir, and The length of the supply pipe is not less than 10 times the length of the transport flow path, or the cross-sectional area of the supply pipe is 1/10 or less of the cross-sectional area of the transport flow path.
  • the plasma generator according to any one of aspects 1 to 7. (Aspect 9) 9. The plasma generator according to any one of aspects 1 to 8, wherein an alternating voltage is used to apply an electric field to the narrow portion.
  • a plasma generator for generating plasma in a conductive liquid A transport channel for transporting the conductive liquid and formed of an insulating material; A narrow portion disposed in the transport channel and having a cross-sectional area significantly smaller than the cross-sectional area of the transport channel; Means for applying an electric field to the narrow portion so that the electric field passes through the narrow portion; And having The means includes a negative electrode and a positive electrode, The narrow portion is formed with a throat portion having the smallest channel cross-sectional area and an enlarged channel that is connected to one opening of the throat portion and has different channel lengths.
  • the expanded channel having a large channel length is configured to be arranged on either the minus electrode or the plus electrode depending on the type of element that generates the plasma. Generator.
  • a plasma generator for generating plasma in a conductive liquid A transport channel for transporting the conductive liquid and formed of an insulating material; A narrow portion connected to the transport channel and having a cross-sectional area significantly smaller than the cross-sectional area of the transport channel; An electrode for applying an electric field to the narrow portion so that the electric field passes through the narrow portion; And having An outlet channel is further disposed in the narrow portion, Guiding the conductive liquid so as to flow into the narrow portion from the transport channel and out of the outlet channel via the narrow portion; The plasma generator according to claim 1, wherein the electric field is applied so that a supply speed of the liquid to the narrow portion and an evaporation speed of the liquid in the narrow portion are balanced.
  • An emission spectroscopic analysis apparatus comprising the plasma generator according to any one of embodiments 1 to 11.
  • the narrow portion refers to a channel provided in the transport channel and having a significantly smaller channel cross-sectional area than the transport channel.
  • the narrow portion preferably includes a throat portion having the smallest channel cross-sectional area, and an enlarged channel provided on both sides of the throat portion and connecting the throat portion and the transport channel.
  • the cross-sectional area of the enlarged channel is more preferably a divergent channel that gradually expands from the throat toward the transport channel.
  • the enlarged flow path has an asymmetric flow path structure with the throat as a starting point.
  • the end cross-sectional area of one enlarged flow path is about 1.1 to 100 times, and the end cross-sectional area of the other enlarged flow path is about 1.1 to 50 times. It is preferable to constitute an asymmetric narrow portion such as
  • the insulating material examples include olefinic resins such as glass, polyethylene, and polypropylene, silicones such as polydimethylsiloxane, fluororesins, and ceramics, but the present invention is not limited to such examples.
  • the flow path (transport flow path or flow path in the narrow portion) can be formed on a plate-shaped chip or plate made of an insulating material using a lithography technique, for example.
  • the narrow portion for example, a molded body having a shape that can be detachably disposed in the transport channel (can be manufactured by an injection molding method capable of mass production) may be prepared. It can be replaced with a new narrow part as appropriate and used as a cartridge.
  • the liquid sample to be analyzed is used as the conductive liquid that fills the channel and the narrow part.
  • the electrolyte used for the conductive liquid include nitric acid, acetic acid, hydrochloric acid, and the like. Among these, nitric acid having characteristics that do not easily cause an obstacle to analysis is preferable.
  • As the sample various materials can be measured, but an electrolyte made of an element such as nitric acid that does not interfere with analysis is preferable.
  • an electric field is applied to the narrow portion by a method such as applying an electric field along the narrow portion so that the electric field passes through the narrow portion.
  • a method such as applying an electric field along the narrow portion so that the electric field passes through the narrow portion.
  • the emission intensity is about 4 to 10 times that of the conventional apparatus proposed in Patent Document 2, so that elemental analysis with extremely high sensitivity is possible. It becomes.
  • an elemental analysis was performed using an asymmetric flow path of a predetermined size as a narrow portion and a 0.1 M nitric acid aqueous solution mixed with 100 ppm of lead (Pb) as a conductive liquid, the same conditions were obtained at an emission wavelength of 406 nm.
  • the emission intensity was about 10 times that of the conventional device (about 800 (arbitrary unit) for the conventional device and about 8000 (arbitrary unit) for the device of the present invention).
  • Example 1 It is a figure explaining the principal part of the plasma generator of this invention.
  • Example 1 It is a figure explaining the suitable structure of a narrow part.
  • Example 1 It is a figure explaining the structure of the emission-spectral-analysis apparatus of this invention.
  • FIG. 4 is a graph showing light emission intensity measured using the apparatus of Example 2.
  • FIG. 4 is a graph showing light emission intensity measured using the apparatus of Example 2.
  • FIG. 4 is a graph showing light emission intensity measured using the apparatus of Example 2.
  • FIG. 4 is a graph showing light emission intensity measured using the apparatus of Example 2. It is the figure which showed the relationship between an element and emitted light intensity. It is the figure which showed the introduction process of the element to the plasma in a conventional apparatus (ICP apparatus).
  • ICP apparatus ICP apparatus
  • FIG. It is the figure which showed the emitted light intensity measured using the apparatus of Example 6.
  • FIG. It is the simulation result which showed the relationship between the integration pulse number and the interface concentration rate, and the relationship between the integration pulse number and the element introduction rate to the plasma. It is a figure explaining movement resistance of a certain liquid in a certain channel.
  • Example 1 An example (Example 1) of the plasma generator of the present invention is shown in FIG.
  • the plasma generator 1 of Example 1 includes two solution reservoirs 102 as shown in FIG.
  • Each solution reservoir 102, 102 is provided with an opening, and an electrode 104 (specifically, 104a, 104b) is inserted into the solution reservoir 102, 102 from this opening.
  • the two solution reservoirs 102, 102 are connected to each other via transport channels 101, 101 separated by a narrow portion 103.
  • the narrow portion 103 is preferably detachably disposed on the plasma generator 1.
  • the wall surfaces of the transport channels 101 and 101, the narrow portion 103, and the solution reservoirs 102 and 102 are formed of an insulating material.
  • the conveyance channels 101 and 101 and the narrow portion 103 confine the conductive liquid 105 when the two solution reservoirs 102 and 102 are filled with the conductive liquid 105 (hereinafter, also simply referred to as liquid or solution), and the electrode 104a. , 104b, an electric field is generated in the vicinity of the narrow portion 103 by applying a voltage.
  • the narrow portion 103 connected to the transport channels 101, 101 on both sides has a channel cross-sectional area smaller than the channel cross-sectional area of other parts (the transport channels 101, 101 and the solution reservoirs 102, 102). Therefore, in this narrow portion 103 (particularly the throat portion 108), current and electric field are concentrated, the temperature becomes higher than the other portions 101 and 102, and boiling and plasma 106 are likely to occur.
  • the conductive liquid 105 needs to contain an element to be measured and have conductivity.
  • an electrolyte supporting salt
  • electrolytes nitric acid is suitable because its constituent elements are contained in the air and in water, and it has a property of dissolving metals well.
  • the liquid temperature of the conductive liquid 105 is not particularly limited, but is usually 15 to 40 ° C., preferably about 20 to 25 ° C.
  • the material used for the electrode 104 is preferably a noble metal such as platinum or carbon that is unlikely to be corroded by passing an electric current.
  • a voltage between the pair of electrodes 104a and 104b current and electric field are concentrated in the narrow portion 103, so that bubbles are generated, and plasma 106 is generated in the generated bubbles.
  • elemental analysis of the conductive liquid 105 can be easily performed.
  • the throat portion 108 is formed in the narrow portion 103, but the throat portion 108 is disposed closer to the other end 109b than the one end 109a of the narrow portion 103, and the throat portion On both sides 108, asymmetric enlarged flow passages 107a and 107b having different flow passage volumes and flow passage sectional areas (and enlargement ratios) are formed.
  • the mass of the conductive liquid 105 confined in one enlarged flow path 107a is larger than the mass of the conductive liquid 105 confined in the other enlarged flow path 107b.
  • the evaporation (and thus the plasma 106) region generated from the throat 108 propagates and propagates in both directions.
  • the conductivity is increased.
  • the movement resistance of the liquid 105 is increased. Therefore, the plasma generation time of the conductive liquid 105 in the enlarged flow path 107a is longer than that in the other enlarged flow paths 107b.
  • the interface concentration effect in the one enlarged flow path 107a is enhanced, and the amount of vaporization of the analysis target element existing there is also increased, so that the measurement sensitivity of the element can be improved.
  • FIG. 2 illustrates a preferred configuration within the narrow portion 103.
  • 2A is a cross-sectional view of the narrow portion 103 fractured in the horizontal direction (perpendicular to the paper surface in FIG. 1)
  • FIG. 2B is the vertical direction (the direction parallel to the paper surface in FIG. 1). It is sectional drawing of the narrow part 103 fractured
  • the narrow portion 103 has a length L of 1800 ⁇ m and a constant width W of 220 ⁇ m in the horizontal direction.
  • the vertical width that is, the channel height
  • the vertical width changes in the length direction, and is 400 ⁇ m (channel height H a ) at one end 109a and 100 ⁇ m (channel height H b ) at the other end 109b.
  • the position of the throat 108 is not the center of the narrow portion 103 (900 ⁇ m from either end) as in the prior art, but is a position biased toward either end (in the example of FIG. 2, from one end 109 a to 1500 ⁇ m). Note that (distance L a ), 300 ⁇ m (distance L b ) away from the other end 109b).
  • the channel cross-sectional area at the end 109b is set to about 1.1 to 50 times the channel cross-sectional area at the throat 108, and the channel cross-sectional area at the end 109a is set to about 1.1 to 50 times. It is preferable to set to about 1.1 times to 100 times.
  • FIG. 3 shows an example (Example 2) of an emission spectroscopic analyzer 2 in which the plasma generator 1 of the present invention is used.
  • the apparatus 2 shown in FIG. 3 is an emission spectroscopic analysis apparatus that detects plasma emission using a photosensor and controls power supply.
  • a sheet-like chip 202 made of an insulating material such as polydimethylsiloxane (hereinafter referred to as PDMS) and patterned with a narrow portion 103 is placed on the quartz glass 201.
  • the chip 202 is manufactured by taking a flow path pattern of a resist material by photolithography. By placing the chip 202 on the quartz glass 201, the chip 202 naturally adheres to form a microchannel.
  • a solution reservoir 102 is formed by opening a hole in a portion corresponding to the end of the transport channel 101 by using a narrow hole device such as a punch.
  • Examples of the conductive liquid 105 include a liquid obtained by diluting a physiological condition phosphate buffer to 1/20 (volume ratio).
  • Examples of the electrodes 104 and 104 include platinum wires having a diameter of 0.5 mm. In order to pass an electric field through the narrow portion 103 and apply an electric field to the narrow portion 103, electrodes 104 and 104 connected to the power source 301 are inserted into the solution reservoirs 102 and 102. The wire-like electrodes 104 and 104 are generally inserted into the solution reservoirs 102 and 102 through a pipe (not shown) that supplies the conductive liquid 105.
  • a plasma 106 is generated in the narrow portion 103.
  • the light from the plasma 106 is introduced into the optical fiber 204, the spectrum is measured with a spectroscope 304 (for example, USB2000 manufactured by Ocean Optics), and the measured data is collected and analyzed by a computer 305 to perform emission spectroscopic analysis. It can be carried out.
  • a spectroscope 304 for example, USB2000 manufactured by Ocean Optics
  • the light generated by the plasma 106 is captured by a photosensor (not shown) built in the photosensor unit 302 disposed below the chip 202.
  • the photo sensor unit 302 controls the connection and disconnection of the electric field by the switch 303 based on the light emission intensity captured by the photo sensor, and stops the application of the electric field after a specified time from the generation of the plasma 106, whereby the light emission intensity, The light emission time and the number of times of light emission can be controlled.
  • the emission intensity of the metal element contained in the conductive liquid 105 was measured using the emission spectroscopic analyzer 2 having the above-described configuration (hereinafter referred to as a first evaluation test).
  • a first evaluation test As a measurement object, the narrow portion 103 of the present invention having the asymmetric enlarged flow passages 107a and 107b with the throat portion 108 as a base point, and the conventional narrow portion with a symmetrical flow passage with the throat portion 108 as a base point (comparative example).
  • Quartz was used as the material of the chip 202 surrounding the narrow portion 103 and the solution reservoir 102.
  • a platinum wire having a diameter of 0.5 mm was used as the plus side electrode 104b and the minus side electrode 104a, and a voltage of about 700 V to 950 V was intermittently applied between these electrodes 104a and 104b (specifically, voltage on (Pulse application was repeated 10 times with a period of 3 ms (milliseconds) and a voltage off time of 2 ms).
  • the narrow portion 103 constitutes an asymmetric channel.
  • the conductive liquid 105 includes a transition metal element to be measured (lead 100 mg / L (that is, 100 ppm Pb) or thallium 10 mg / L (that is, 10 ppm Tl)) or an alkali metal element (potassium 100 mg / L (that is, 100 ppm K) or sodium 5 mg / L (ie 5 ppm Na)).
  • a transition metal element to be measured lead 100 mg / L (that is, 100 ppm Pb) or thallium 10 mg / L (that is, 10 ppm Tl)
  • an alkali metal element potassium 100 mg / L (that is, 100 ppm K) or sodium 5 mg / L (ie 5 ppm Na)
  • An aqueous solution of 0.1 M nitric acid (HNO 3 ) was used as the solvent.
  • FIG. 4 shows the change in the emission intensity (arbitrary unit) of lead (Pb, 406 nm) corresponding to the value of the applied voltage.
  • FIG. 4A shows a change in light emission amount (which is an arbitrary unit and is also referred to as light emission intensity in the specification) when the comparative example in which the enlarged flow paths 107 and 107 in the narrow portion 103 are symmetrical is used.
  • 4B and 4C show the amount of light emitted when the present Example 2 in which the enlarged flow paths 107 and 107 in the narrow portion 103 are asymmetric is used.
  • Example 4C shows that the end 109b having a smaller flow path height Hb is directed to the positive electrode side 104b, and the end 109a having a larger flow path height H a is a negative electrode. It is a measurement result of the structure (henceforth "Example 1C") which installed the narrow part 103 so that it may face 104a side.
  • FIGS. 5, 6, and 7 in FIGS. 5, 6, and 7 to be described later, only the kind of the provided conductive liquid 105 is different, and the flow path configuration and arrangement of the narrow portion 103 are shown in FIG. (A), (B), and (C) are the same, and the flow path configuration and arrangement conditions of the narrow portion 103 shown in (A), (B), and (C) of each figure correspond to each other. Yes. Therefore, the re-explanation about these is omitted.
  • Each graph of FIG. 5 shows the change in the emission intensity of thallium (Tl, 535 nm) according to the value of the applied voltage.
  • the emission intensity increases as the voltage increases.
  • the increase rate of the emission intensity is slightly lower even when the applied voltage is increased compared to the case of Comparative Example 1 in FIG.
  • the rate of increase in emission intensity is significantly higher than that in FIG.
  • the same tendency as that shown in the case of Example 1C and Example 1B in FIG. 4 appears. I understand that.
  • the reason for obtaining the above result is that the conductive liquid 105 mixed with the transition metal element easily evaporates on the negative electrode 104a side, and the narrow portion 103 used in FIGS. distance L a and channel height H a from part 108 to the flow path end 109a of the negative electrode 104a side may be mentioned that is longer. That is, in the configuration of the narrow portion 103 used in FIGS. 4C and 5C, the local movement resistance of the conductive liquid 105 is increased, so that the generation of the plasma 106 is likely to continue for a long time. It is considered that the interface concentration effect on the above side is enhanced, and as a result, the measurement sensitivity of the element existing in the vicinity of the side is increased.
  • FIG. 6 shows changes in the emission intensity of potassium (K, 766 nm) according to the value of the applied voltage.
  • FIG. 7 shows a change in the emission intensity of sodium (Na, 589 nm) according to the value of the applied voltage.
  • the light emission intensity increases as the applied voltage increases in any flow path configuration.
  • the increase in emission intensity of Example 1B and Example 1C is higher than that of the corresponding Comparative Example 1 in any case.
  • Example 1B in FIGS. 6 and 7 a very high emission intensity was obtained, but the variation in the measurement results was also large.
  • the element to be measured shown in FIG. 6 and FIG. 7 is an element that easily emits light, as will be described later, and does not significantly reflect only the influence of the asymmetric channel structure on light emission. It is done.
  • the asymmetric structure in the narrow portion 103 of this embodiment can be said to be a means for producing a difference in the interface concentration effect in the enlarged flow passages 107a and 107b on both sides of the throat portion.
  • the element belonging to the first group is an element that emits light as much as the conventional ICP device even when the conventional LEP device is used.
  • sodium (Na), potassium (K), lithium (Li), silver ( Ag) and the like.
  • An element belonging to the second group is an element whose emission intensity becomes extremely lower than that when using a conventional ICP device when the element is caused to emit light using a conventional LEP device.
  • Heavy metals such as Pb), Tl (thallium), and cadmium (Cd).
  • the element belonging to the third group is an element that has not been atomized, and is an element that hardly emits light even when a voltage is applied for a long time with a conventional LEP device.
  • Al aluminum
  • Zr zirconium
  • FIG. 8 shows the change over time in the emission intensity when a constant voltage (700 V) is applied to each element representing each group using a conventional LEP device.
  • An example of the first group was 2 ppm sodium (Na)
  • an example of the second group was 40 ppm lead (Pb)
  • an example of the third group was 100 ppm zirconium (Zr).
  • sodium (Na) shines even if the application time is short.
  • lead (Pb) shines if the application time is lengthened.
  • Zirconium (Zr) hardly emits light regardless of the application time.
  • the conventional LEP device differs from the conventional ICP device in that the difference in sensitivity as described above appears depending on the element to be applied. In the ICP device and the LEP device, the process of entering the plasma is decisively different. The present inventors have considered.
  • the solution 11 containing the measurement element (symbol M in FIG. 9) is sprayed to the upstream side of the tube 14a by the sprayer 13 together with the carrier gas 12 such as argon. .
  • the carrier gas 12 such as argon.
  • Moisture 15 is also introduced into the tubes 14b, 14c from the other inlets 16,17.
  • the tubes 14a, 14b, and 14c are nested, and the flows in the tubes merge on the downstream side of the tubes 14a, 14b, and 14c.
  • the measurement element M and the moisture 15 are heated on the downstream side of the tube 14c by the coil 18 wound around the outer periphery of the tube 14c, and then the measurement element M is introduced into the plasma 106 (that is, vaporized). Become. That is, as shown in FIG. 9B, the measurement element M is included in the water droplet W, but since the surrounding water droplets W gradually evaporate, any measurement element M is finally introduced into the plasma 106 without fail. Will be.
  • the plasma 106 is changed to an arrow in FIG.
  • the plasma 106 collides with the interface of the solution 105 (hereinafter also referred to as the sputtering action of the plasma 106).
  • the measurement element M enters the plasma 106 (that is, vaporizes) and emits light. That is, the element M belonging to the second group that is difficult to enter the plasma 106 tends to remain in the solution 105. Therefore, the present inventors considered that it is effective to use the interface concentration effect to cause the element M belonging to the second group to emit light in the same manner as the element M belonging to the first group.
  • FIG. 10B shows a simplified model of the plasma 106 generated in the narrow portion 103 and a part of the solution 105 in contact therewith.
  • this model assumes a simple model in which the solution 105 has no flow (that is, the flow rate is zero).
  • the concentration of the element M in the solution 105 is denoted as C o.
  • the element concentration in the portion of the solution 105 in the vicinity of the interface that defines the boundary between the plasma 106 and the solution 105 is denoted as Cb.
  • a symbol V and an arrow in FIG. 10B indicate the moving speed and moving direction of the interface due to evaporation of the solvent.
  • balance balance of concentration of the element M in this area A BD can be expressed by the following equation.
  • K in the equation is a plasma introduction coefficient representing the ease of introduction of the element M into the plasma 106.
  • Time variation of the concentration C b of the element M in the vicinity of the interface, the concentration C from o the moving speed of the area A BD of (VC o), introduction rate of the element M is introduced from the interface into the plasma 106 per unit time (C
  • C This equation means that b K) is subtracted.
  • Figure 11 shows the time course of the introduction rate of C b K of aging and elemental concentration C b in the vicinity of the interface.
  • the left vertical axis represents the concentration C b in the vicinity of the interface
  • the right vertical axis indicates the element introduction rate C b K.
  • the concentration C b of the interface that is, the region A BD near the interface
  • the introduction rate C b K of the element M into the plasma 106 is also constant regardless of the plasma introduction coefficient K if the interface concentration sufficiently progresses with time as shown in the lower curve in FIG. It can be seen that the value gradually approaches the value of (ie, VC o shown on the right axis).
  • asymmetric channel structure for the narrow portion 103 as described above. More preferably, a structure in which the enlarged flow path 107a on the negative electrode side 104a is longer than the enlarged flow path 107b on the positive electrode side 104b is adopted.
  • the reason for adopting such a flow channel structure is that when a voltage is applied, bubbles and plasma 106 are generated in the narrowest throat 108. Our experience has shown that the sputtering action of the plasma 106 described above occurs on the negative electrode side 104a.
  • the introduction of the element M into the plasma 106 is mainly due to the sputtering action, it is considered that the element M is introduced into the plasma 106 from the negative electrode side 104a. If this idea is correct, it is possible to cause interfacial concentration at a longer distance and for a longer time by making the enlarged flow path 107a on the negative electrode side 104a longer.
  • the narrow portion 103 for evaluation As the narrow portion 103 for evaluation, the symmetrical channel A, the asymmetric channel B in which the channel on the positive electrode 104b side is longer than the channel on the negative electrode 104a side, and the channel on the negative electrode 104a side are longer than the channel on the positive electrode 104b side.
  • the asymmetric flow path C was prepared. And the narrow part 103 was mounted in the plasma generator 1, the density
  • the symmetric flow path A, the asymmetric flow path B, and the asymmetric flow path C are the same as the flow path structures described in Comparative Example 1, Example 1B, and Example 1C used in the first evaluation test, respectively.
  • lead (Pb) was used as the measurement element, and an aqueous solution of 0.1 M nitric acid (HNO 3 ) was used as the solvent.
  • a lead (Pb) standard solution is diluted with the above-mentioned solvent, and sample solutions of predetermined concentrations (0 mg / L, 10 mg / L, 20 mg / L, 40 mg / L, 60 mg / L, 80 mg / L, 100 mg / L) 105 was adjusted. Note that 40 L of sample solution 105 was injected into each of the solution reservoirs 102 and 102.
  • An applied voltage intermittently applied between the electrodes 104a and 104b was set to 900 V, and a pulsed voltage composed of a voltage on time of 5 ms and a voltage off time of 60 ms was repeatedly applied 40 times.
  • the strong emission peak wavelength of lead (Pb) was 405.782 nm.
  • the asymmetric flow path A may be better when the measurement object is selected as another element (for example, an element belonging to the first group). This is because in the configuration in which the longer enlarged flow path 107a is arranged on the positive electrode 104b side, interface concentration and thus light emission characteristics may be promoted in the flow path 107a.
  • the asymmetric structure based on the throat 108 is used as a means for producing a difference in the interface concentration effect on both sides of the throat 108 in the narrow portion 103, but the present invention is not limited to this.
  • the following examples are also conceivable.
  • FIG. 13 shows a schematic view of another example (Example 3) of the plasma generator 1.
  • the pressure adjusting mechanism 110 is further provided, and the throat portion 108 in the narrow portion 103 is formed at the center of the flow path length L.
  • the basic features and structure are the same as those of the plasma generator 1 shown in FIG. 1 except that the enlarged flow path 107 (that is, 107a and 107b) connected to the throat 108 is formed symmetrically with respect to the base point. It is the same.
  • the pressure adjustment mechanism 110 includes at least an adjustment pipe 111 and an adjustment container 112 connected to one of the enlarged flow paths 107 a and 107 b (for example, 107 b).
  • the adjustment container 112 is preferably made of a material having flexibility and elasticity that easily deforms when the conductive liquid 105 flows into the inside and returns to the state before deformation when the conductive liquid 105 flows out.
  • the pressure inside or near the adjustment container 112 can be set to a pressure P 1 lower than the pressure P 0 of the conductive liquid 105 at the throat 108.
  • a compressible gas air
  • the gas is compressed by the high-pressure conductive liquid 105 when the plasma 106 is generated, and the pressure in or near the adjustment vessel 112 is set to a pressure P 1 lower than the pressure P 0 at the plasma 106 generation position.
  • Bubbles generated in the throat 108 in the narrow portion 103 due to voltage application are conducted in the energization path (enlarged flow channels 107, 107, transport channels 101, 101, solution reservoirs 102, 102) connected to the throat 108. and Grow evaporated range while forces the solution interface at a uniform pressure P 0 toward a solution reservoir 102, 102 containing the sex liquid 105 electrodes 104a, of 104b.
  • the narrow portion 103 has the throat portion 108 disposed in the center and the enlarged flow passages 107a and 107b are symmetrical as described above. Therefore, the evaporation speed is the same in both of the enlarged flow passages 107a and 107b. Try to become.
  • the plasma 106 tends to be generated on the negative electrode side 104a. Therefore, it is preferable to connect the pressure adjustment mechanism 110 to the energization path on the positive electrode 104b side.
  • FIG. 14 shows a schematic diagram of another example (Example 4) of the plasma generator 1.
  • an outlet channel 120 and an outlet port 121 are connected to the narrow portion 103 of the plasma generator 1 shown in FIG.
  • a supply pipe 130 (specifically, 130a and 130b) is connected to both of the solution reservoirs 102 and 102 into which the electrodes 104a and 104b are inserted.
  • a supply port 131 for supplying the conductive liquid 105 is connected to the supply pipe 130.
  • both supply pipes 130a and 130b are branched from one supply port 131.
  • the present invention is not limited to this, and the supply pipes 130a and 130b are connected to each other.
  • a separate supply port 131 may be prepared.
  • the throat 108 where the plasma 106 is generated includes two enlarged flow paths 107a and 107b into which the conductive liquid 105 flows from the solution reservoirs 102 and 102 into which the electrodes 104a and 104b are inserted, and the conductive liquid. 105 is connected to an outlet channel 120 that flows out toward the outlet port 121 (hereinafter, the channel to which the outlet port 121 is added is also referred to as a T-type channel).
  • Bubbles generated in the vicinity of the throat portion 108 of the narrow portion 103 push the conductive liquid 105 at a pressure P 0 toward the two enlarged flow passages 107 a and 107 b connected to the narrow portion 103 and the outlet flow passage 120. Try to spread while doing. However, since the outlet channel 120 has a larger channel cross-sectional area than the enlarged channels 107a and 107b on both sides of the throat portion 108 as shown in the figure, the movement resistance of the liquid 105 in the outlet channel 120 is reduced.
  • the supply pipe 130 is preferably configured to be significantly thinner or longer than the transport channels 101 and 101 and the enlarged channels 107a and 107b. More preferably, the supply pipe 130 has a channel cross-sectional area of 1/10 or less, or 10 times or more the length of the transport channels 101 and 101 and the enlarged channels 107a and 107b. Configured.
  • the electrical resistance in the conductive liquid 105 is proportional to the length of the conductive path and inversely proportional to the cross-sectional area of the flow path, the current supply path that can be formed by the supply pipe 130 even when a voltage is applied to the electrodes 104a and 104b. Since the electric resistance is remarkably increased, it is possible to flow electricity only to the path toward the narrow portion 103 without flowing electricity through the path via the supply pipe 130.
  • the voltage applied to the electrodes 104a and 104b may be an AC voltage. This is because if the voltage is changed to an alternating current, it can be expected that a plurality of merits in the following measurement can be enjoyed.
  • a dielectric that is, a substance that behaves as an insulator that does not conduct electricity with respect to a DC voltage
  • a voltage can be applied capacitively. For this reason, it is not necessary to bring the electrodes 104a and 104b into contact with the liquid 105, the structure of the apparatus 1 can be simplified, liquid leakage can be prevented, and contamination of impurities can be prevented. Measurement is possible.
  • FIG. 15 shows a schematic view of another example (Example 5) of the plasma generator 1.
  • the plasma generator 1 shown in FIG. 15 is substantially the same as the fourth embodiment except that the pressure adjusting mechanism 110 is provided in the outlet channel 120.
  • the outlet channel 120 of Example 5 does not need to have a larger channel cross-sectional area than the enlarged channels 107a and 107b on both sides of the throat portion 108 as in the case of Example 4.
  • the outlet channel 120 is provided with the pressure adjusting mechanism 110 as described in the fourth embodiment.
  • the pressure adjustment mechanism 110 includes at least an adjustment pipe 111 and an adjustment container 112 connected to the outlet channel 120.
  • the adjustment container 112 of the present embodiment also contains a gas that is deformed or compressible when the high-pressure conductive liquid 105 flows into and out of the adjustment container 112 as in the previous embodiment.
  • the inside or the periphery of the adjustment vessel 112 can be set to a pressure P 1 lower than the pressure P 0 at the location where the plasma 106 is generated.
  • Pressure adjusting mechanism 110 is provided as described above, it is set to a predetermined pressure P 1 at the time of evaporation, the outlet channel 120 (a portion of the mass) conductive liquid 105 in the vicinity of the pressure adjusting mechanism 110 It will be forcibly sucked. By this forced suction, the moving speed of the conductive liquid 105 remaining in the outlet channel 120 can be adjusted (that is, increased), and evaporation generated in the throat 108 is forced toward the outlet port 121.
  • the progress of evaporation is slowed down in the enlarged flow paths 107a and 107b on the both electrodes 104a and 104b side, and as a result, the plasma 106 in these enlarged flow paths 107a and 107b can be generated for a longer time.
  • FIG. 16A shows a flow path pattern of a T-shaped flow path
  • FIG. 16B shows an enlarged view of a part thereof (that is, a flow path near a narrow portion).
  • the T-type channel is partitioned from a first layer (made of quartz) 201 and a second layer (made of PDMS) 202 laminated on the first layer 201 (see FIG. 17).
  • the first layer 201 can be manufactured by etching.
  • the electrodes 104 a and 104 b can be produced by sputtering platinum and chromium (Pt / Cr) on the surface portion of the first layer 201 corresponding to the bottom surface of the solution reservoir 102.
  • the electrodes 104 and 104 and the second layer 202 can be formed on the bottom surface portion of the solution reservoir 102 by using the SU-8 molding method.
  • the height (depth) of the flow path produced as described above is 100 ⁇ m, and is constant from the supply port 131 to the outlet port 121 of the flow path.
  • the length of the narrow portion 103 is 500 ⁇ m, and the width and length of the solution reservoirs 102 and 102 are 1.5 mm and 3 mm, respectively.
  • the thickness of the electrodes 104 and 104 embedded in the solution reservoirs 102 and 102 is 0.3 ⁇ m.
  • the wire-like electrode 104 is inserted into a tube (not shown) through which the conductive liquid 105 circulates.
  • 105 pressure was easy to escape.
  • the electrodes 104 and 104 are embedded in the bottom surface of the solution reservoir 102, and it is difficult for the conductive liquid 105 to pass through the reservoirs 102 and 102. Therefore, the conductive liquid 105 can flow into the narrow portion 103 while maintaining a desired pressure.
  • the apparatus shown in FIG. 17 includes personal computers 401 and 402, a CCD detector 403, a spectrometer 404, an optical fiber 204, and a high-speed camera 415 as its optical system.
  • the T-type chip including the first layer 201 and the second layer 202 is fixed on the stage 405.
  • the personal computers 401 and 402 and the platinum electrode 407 are connected to a DC power source 407.
  • the sample solution 105 is filled in the syringe 408 and is pushed out by the pump 409 to the fluororesin tube 410 and passes through the T-shaped channel. Thereafter, the sample solution 105 passes through the fluororesin tube 411 and is collected in the collection container 412 as a waste liquid 413.
  • a solution adjusted to a concentration of 0.5 mg / L using an element of lead (Pb), sodium (Na), hydrogen (H wavelength 656 nm), or hydrogen (H wavelength 486 nm) is used. It was. 0.1M nitric acid (HNO 3 ) was used as the solvent.
  • the applied voltage was a pulse voltage of 600 V, the pulse on time was 0.5 ms, and the off time was 9.5 ms.
  • the flow rate for supplying the solution was set to 5 ⁇ L / min.
  • the measurement frequency N of the light emission intensity of each element was 10 times, and the average value was used as the measurement result.
  • FIGS. 18A to 18D show the behavior of the plasma 106 and bubbles observed in the narrow portion 103 of the sixth embodiment.
  • FIGS. 18A and 18B show a state of a pulse having a certain condition at an on time and a state at an off time
  • FIGS. 18C and 18D show an on time of a pulse having another condition. The state at and the state at off time are shown.
  • 18 (A) and 18 (B) it was observed that the gas-liquid interface (BD in the figure) hardly moved even when the on time was switched to the off time (arrow in FIG. 18 (B)). See).
  • FIGS. 18C and 18D when the on-time is switched to the off-time, the gas-liquid interface BD has penetrated into the outlet channel 120, and the movement amount is large. Observed.
  • the condition for applying the pulse voltage affects the interface concentration of elements and the light emission characteristics.
  • the pulse voltage is set so that the water evaporation rate in the narrow portion 103 and the supply speed of the solution 105 to the narrow portion 103 are balanced. It was found that it was necessary to apply.
  • FIG. 19A shows the light emission intensity measured using the flow channel of Example 6.
  • the horizontal axis represents the number obtained by integrating the number of pulses, and the vertical axis represents the integrated emission intensity (arbitrary unit).
  • the number of integrated pulses is small, an increase in emission intensity can be observed as the number of integrated pulses increases. However, if the number of integrated pulses increases, the emission intensity increases even if the number of integrated pulses increases. There is no increase.
  • FIG. 19B is a graph showing the result (also referred to as normalized emission intensity) obtained by dividing each data of FIG. 19A by the data of hydrogen (H wavelength 656 nm) of FIG. 19A.
  • the normalized emission intensity increases in the range of the integrated pulse number from 0 to about 50, and the peak (about 1. 5 times).
  • the solid line shown in the figure is a line showing the tendency of the measurement results of sodium (Na) and lead (Pb) in a range where the number of pulses is small. It is observed that when the cumulative number of pulses exceeds 50, it gradually decreases, and when it exceeds 200, the normalized emission intensity becomes a constant value (about 1). From this result, it can be said that the apparatus of Example 6 was able to realize the interface concentration about 1.5 times with respect to the above elements.
  • Example 6 In order to obtain a higher concentration effect, it is considered effective not only to keep the gas-liquid interface BD for a longer period of time, but also to suppress the generation of vibration at the interface BD as much as possible, as will be described later.
  • the narrow portion 103 of Example 6 is made of soft PDMS, it is assumed that vibration at the interface BD occurred and the concentration rate was not improved so much.
  • FIG. 20A shows a simulation result calculated using the narrow portion 103 made of PDMS in consideration of the influence of vibration at the interface BD.
  • the concentration of the measurement object in the liquid 105 on the inlet side is C o
  • the concentration of the measurement object in the target volume is C b
  • the introduction coefficient of the element M to the plasma 106 at the interface BD is K.
  • solvent evaporates the 0.04NL
  • measurement of the amount obtained by multiplying the C b and K and 0.04NL is introduced into the plasma 106.
  • a solvent 0.04nL at the inlet side the measurement of the amount obtained by multiplying the C o and 0.04nL come into attention volume.
  • the increase in the interface concentration rate can be calculated sequentially for each pulse (see FIG. 20A).
  • the interface concentration ratio becomes 1.5 times the initial value at about 50 pulses, as shown in FIG. 19 (B).
  • the movement due to diffusion is considered to be much smaller than the stirring effect due to vibration, and is ignored.
  • the concentration rate when there is no stirring by vibration can be estimated by simulation (see FIG. 20B). In this case, diffusion due to vibration cannot be ignored. Considering the evaporation rate per pulse using the physical property value of water as the diffusion coefficient, the same calculation as in the above simulation can be performed with the region near the interface BD having approximately 0.005 nL as the target volume ( (See FIG. 20B).
  • the plasma generator of the present invention and the emission spectroscopic analyzer equipped with the plasma generator can be suitably used in fields called microfluid dynamics, ⁇ TAS (micro total analysis systems), and Lab on a chip. According to the present invention, part of particularly necessary functions and structures can be integrated on one plate-like chip.
  • the plasma generation apparatus of the present invention and the emission spectroscopic analysis apparatus equipped with the plasma generation apparatus of the present invention may require a small amount of a specimen (for example, an inorganic component (metal, etc.) in a liquid sample), and are portable, instant, easy to maintain, inexpensive, etc. It has the characteristics of.
  • the apparatus of the present invention can measure a plurality of various inorganic components (such as metal elements) simultaneously. Therefore, the application fields of the present invention include soil inspection and water quality inspection, quality control of manufacturing processes, food inspection (measuring minerals in beverages), confirmation of industrial waste (rare metal, toxic substances), medical blood and urine Applicable to inspection. Due to such applications and advantages, the present invention has very high industrial applicability.

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Electromagnetism (AREA)
  • Toxicology (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)

Abstract

Le problème décrit par la présente invention consiste à fournir un dispositif de génération de plasma offrant une longue durée de génération de plasma ainsi qu'un spectrophotomètre d'émission disposant d'une sensibilité de mesure extrêmement élevée. La solution apportée par la présente invention est celle d'un dispositif de génération de plasma (1) visant à générer un plasma (106) dans un liquide électroconducteur (105) dans lequel un canal de transport a été installé, celui-ci étant formé d'un matériau isolant, pour le transport du liquide électroconducteur (105). Une partie étroite (103) possédant une section transversale considérablement plus petite que celle du canal de transport est installée dans le canal de transport. Un moyen destiné à appliquer un champ électrique à la partie étroite (103) est placé de sorte que le champ électrique passe à travers la partie étroite (103). La présente invention est caractérisée en ce que la résistance du mouvement du liquide électroconducteur (105) est plus importante sur une partie de la partie étroite (103) que sur d'autres parties.
PCT/JP2012/073585 2011-09-16 2012-09-14 Dispositif de génération de plasma et spectrophotomètre d'émission WO2013039189A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2013533727A JP6083047B2 (ja) 2011-09-16 2012-09-14 プラズマ発生装置及び発光分光分析装置

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-203595 2011-09-16
JP2011203595 2011-09-16

Publications (1)

Publication Number Publication Date
WO2013039189A1 true WO2013039189A1 (fr) 2013-03-21

Family

ID=47883405

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/073585 WO2013039189A1 (fr) 2011-09-16 2012-09-14 Dispositif de génération de plasma et spectrophotomètre d'émission

Country Status (2)

Country Link
JP (1) JP6083047B2 (fr)
WO (1) WO2013039189A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015172571A (ja) * 2014-02-21 2015-10-01 アークレイ株式会社 プラズマ分光分析方法
JP2015179079A (ja) * 2014-02-28 2015-10-08 アークレイ株式会社 プラズマ発生用チップ、プラズマ発生装置およびプラズマ分光分析方法
WO2017158671A1 (fr) * 2016-03-14 2017-09-21 富士機械製造株式会社 Générateur de plasma

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005093394A1 (fr) * 2004-03-25 2005-10-06 Japan Advanced Institute Of Science And Technology Equipement de generation de plasma
JP2011041914A (ja) * 2009-08-21 2011-03-03 Yaskawa Electric Corp 水処理装置
JP2011180045A (ja) * 2010-03-02 2011-09-15 Japan Advanced Institute Of Science & Technology Hokuriku プラズマ発生手段、プラズマ発生装置及び元素分析方法
JP2012142150A (ja) * 2010-12-28 2012-07-26 Shibaura Mechatronics Corp 液中プラズマ発生装置、液中プラズマ処理装置、液中プラズマ発生方法、および液中プラズマ処理方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005093394A1 (fr) * 2004-03-25 2005-10-06 Japan Advanced Institute Of Science And Technology Equipement de generation de plasma
JP2011041914A (ja) * 2009-08-21 2011-03-03 Yaskawa Electric Corp 水処理装置
JP2011180045A (ja) * 2010-03-02 2011-09-15 Japan Advanced Institute Of Science & Technology Hokuriku プラズマ発生手段、プラズマ発生装置及び元素分析方法
JP2012142150A (ja) * 2010-12-28 2012-07-26 Shibaura Mechatronics Corp 液中プラズマ発生装置、液中プラズマ処理装置、液中プラズマ発生方法、および液中プラズマ処理方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015172571A (ja) * 2014-02-21 2015-10-01 アークレイ株式会社 プラズマ分光分析方法
JP2015179079A (ja) * 2014-02-28 2015-10-08 アークレイ株式会社 プラズマ発生用チップ、プラズマ発生装置およびプラズマ分光分析方法
EP2921845A3 (fr) * 2014-02-28 2015-12-02 ARKRAY, Inc. Puce pour génération de plasma, générateur de plasma, et procédé de spectrométrie de plasma
US9623511B2 (en) 2014-02-28 2017-04-18 Arkray, Inc. Chip for plasma generation, plasma generator, and plasma spectrometry method
WO2017158671A1 (fr) * 2016-03-14 2017-09-21 富士機械製造株式会社 Générateur de plasma
CN108781499A (zh) * 2016-03-14 2018-11-09 株式会社富士 等离子发生装置
JPWO2017158671A1 (ja) * 2016-03-14 2019-01-17 株式会社Ｆｕｊｉ プラズマ発生装置
EP3432691A4 (fr) * 2016-03-14 2019-04-03 Fuji Corporation Générateur de plasma
CN108781499B (zh) * 2016-03-14 2020-09-29 株式会社富士 等离子发生装置

Also Published As

Publication number Publication date
JPWO2013039189A1 (ja) 2015-03-26
JP6083047B2 (ja) 2017-02-22

Similar Documents

Publication Publication Date Title
JP3932368B2 (ja) プラズマ発生装置
US7713849B2 (en) Metallic nanowire arrays and methods for making and using same
CN104237178B (zh) 直流放电汽化辅助激光诱导击穿光谱检测水体中痕量金属元素的方法和装置
US20150004684A1 (en) Device and methods of detection of airborne agents
JP6083047B2 (ja) プラズマ発生装置及び発光分光分析装置
Tombrink et al. Liquid analysis dielectric capillary barrier discharge
US7394065B2 (en) Chemical probe using field-induced droplet ionization mass spectrometry
JP2006058031A (ja) 化学分析装置
CN101636652A (zh) 总有机碳测定装置
US20140283627A1 (en) Apparatus and method for liquid sample introduction
JP4811247B2 (ja) マイクロチップ及びそれを用いた分析デバイス
WO2014168043A1 (fr) Dispositif de mesure et procédé de mesure
Meneses-Nava et al. Stability evaluation of water droplets levitated by a TinyLev acoustic levitator for laser induced breakdown spectroscopy
CN114660152A (zh) 在固体元件之间具有开口的电化学传感器
EP4070360B1 (fr) Système et procédé de détection d'analytes dissous dans des liquides par spectrométrie de masse à ionisation de plasma
Priest et al. Structure-induced spreading of liquid in micropillar arrays
KR100824575B1 (ko) 플라즈마 발생 장치
US20160138908A1 (en) Micromechanical photothermal analyser of microfluidic samples
US11826754B2 (en) Fluidic carbon nanotube device
Macioszczyk et al. Design and fabrication of ceramic microsystem utilizing glow discharge for analysis of liquid mixtures
JP6480211B2 (ja) プラズマ発生用チップ、プラズマ発生装置およびプラズマ分光分析方法
RU2411510C1 (ru) Способ формирования термолинзы для термолинзовой спектроскопии
JP2005091006A (ja) 気液２相試料分析装置
CN103649742A (zh) 电化学检测器及其制造方法
Monwar et al. Confining Eutectic Gallium Indium (eGaIn) in Expired Artificial Kidneys to Unveil Nanoporous Conductive Wires

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12831841

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013533727

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12831841

Country of ref document: EP

Kind code of ref document: A1