JP2017015625A - Adsorption device and analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an analyzer capable of performing analysis with high accuracy in a short time.SOLUTION: An adsorption device 2 comprises: a cell 20 which includes a substrate and a sealing member joined to the substrate to form a hollow structure together with the substrate and is provided with first and second through holes through which an inside space and an outside space of the hollow structure communicate with each other; a plurality of carbon nano-tube bundles which extend from the substrate in the inside space and are located apart from each other; and a heater 23 provided on at least one of the substrate and the sealing member.SELECTED DRAWING: Figure 1

Description

  Embodiments described herein relate generally to an adsorption device and an analysis device.

  Currently, research is underway to clarify metabolic reactions and biochemical pathological mechanisms from the concentration of volatile substances contained in exhaled breath and their fluctuations.

For example, ethane, pentane and hydrogen peroxide (H ₂ O ₂ ) in exhaled breath have a high correlation with oxidative stress. When these concentrations in exhalation increase, symptoms of lipid oxidation, asthma or bronchitis appear.

Nitric oxide (NO), carbon monoxide (CO), and H ₂ O ₂ in exhaled breath have a high correlation with lung diseases. As these concentrations in expired air increase, symptoms of asthma or chronic obstructive pneumonia are seen.

Hydrogen (H ₂ ) and carbon isotopes ( ¹³ C) in exhaled breath are highly correlated with gastrointestinal diseases. Higher concentrations of these in exhaled breath can cause symptoms of dyspepsia, gastritis or duodenal ulcers.

  In addition, acetone in exhaled breath has a high correlation with metabolic abnormalities. As the acetone concentration in the exhalation increases, symptoms of diabetes are seen. On the other hand, people with lower acetone concentrations in breath compared to healthy people tend to have metabolic syndrome.

  The above-described relationship is expected to be applied to simple early bed diagnosis without pain. However, the concentration of volatile substances contained in exhaled breath ranges from ppm (parts per million) to ppb (parts per billion). Therefore, in order to quantitatively analyze the exhalation component, an analyzer having a high resolution is required.

  As one of the analytical methods, a technique using a property that a metal complex selectively adsorbs a specific molecule is known. For example, certain manganese phthalocyanines have a high adsorption capacity for acetone. When the surface of a conductive substrate made of carbon nanotubes is modified with manganese phthalocyanine, the electrical conductivity changes according to the amount of acetone adsorbed by manganese phthalocyanine. Therefore, the sensor provided with the conductive substrate surface-modified with manganese phthalocyanine can be used for measuring the acetone concentration in the breath.

  However, metal complexes show approximately equal adsorption capacity for molecules with similar chemical structures. If the surface of the conductive substrate is not flat, it is difficult to uniformly modify the surface with a metal complex. Non-uniform surface modification makes accurate measurement difficult.

  As another analysis technique, a technique using a semiconductor made of a metal oxide is known. In this technique, oxygen is adsorbed while the metal oxide is heated. When a reducing substance such as carbon monoxide or hydrocarbon is mixed in the atmosphere, a reaction occurs between oxygen adsorbed on the metal oxide and the reducing substance, and oxygen adsorbed on the surface of the metal oxide is reduced. Along with this, the specific resistance of the metal oxide is reduced. This method utilizes such a phenomenon.

  This technique has a high detection sensitivity even when the detection time is short and the reducing substance has a low concentration. However, this method requires a complicated configuration when the atmosphere contains a plurality of reducing substances.

JP 2010-107310 A Japanese Patent Laying-Open No. 2015-7625

  The problem to be solved by the present invention is to make it possible to realize an analyzer capable of performing analysis with high accuracy and in a short time.

  According to the embodiment, the substrate includes a base member and a sealing member that is bonded to the base material and forms a hollow structure together with the base material, and each communicates the internal space and the external space of the hollow structure. Provided in at least one of the cell provided with the first and second through holes, the plurality of carbon nanotube bundles extending from the base material in the internal space and positioned away from each other, and the base material and the sealing member An adsorption device including the heater is provided.

  According to another embodiment, the support that supports the adsorption device, the first flow path that guides the fluid to be measured and the purge gas to the first through-hole, and one or more substances in the gas are quantified. A measuring device, a second flow path connecting the second through hole and the measuring device or the outside, one or more first valves attached to the first flow path, and attached to the second flow path There is provided an analyzer including one or more second valves.

The figure which shows schematically the analyzer which concerns on embodiment. The graph which shows the temperature change of the heater at the time of an analysis. The top view of the adsorption | suction apparatus which the analyzer of FIG. 1 contains. Sectional drawing along the IV-IV line of the adsorption | suction apparatus of FIG. The disassembled perspective view of the adsorption | suction apparatus of FIG.3 and FIG.4. The top view of the heater contained in the adsorption | suction apparatus of FIG. 3 thru | or FIG. The perspective view which shows schematically the carbon nanotube bundle | flux which the adsorption | suction apparatus of FIG. 3 thru | or FIG. 5 contains. The top view which shows roughly an example of the relationship between arrangement | positioning of a carbon nanotube bundle | flux, and the flow of expiration. The figure which shows schematically a part of analyzer which concerns on a comparative example. The figure which shows schematically the adsorption | suction apparatus which concerns on a modification.

  Hereinafter, embodiments will be described in detail with reference to the drawings. In addition, the same referential mark is attached | subjected to the component which exhibits the same or similar function through all the drawings, and the overlapping description is abbreviate | omitted.

  An analysis apparatus 1 shown in FIG. 1 is an apparatus for analyzing the concentration of a specific component contained in exhaled breath, for example, a volatile organic compound. Here, the specimen is typically human exhalation, but may be exhalation of animals other than humans. The volatile organic compound is, for example, ethane, pentane or acetone.

  The analysis device 1 includes an adsorption device 2, a support 3, conduits 5 a to 5 d, a measurement device 6, first valves 7 a and 7 b, and a second valve 8.

  The adsorption device 2 includes a cell 20 having a hollow structure and a heater 23 for heating the cell 20. The cell 20 is provided with a pair of through holes that connect the internal space and the external space. A plurality of carbon nanotube bundles are accommodated in the internal space of the cell 20. These carbon nanotube bundles physically adsorb one or more substances in the breath, that is, the above components. The detailed structure of the adsorption device 2 will be described later.

  The support 3 supports the adsorption device 2 in a detachable manner. The support body 3 includes a support body 31 and a power source (not shown) built therein. The support 3 further includes a pair of electrodes 32a and 32b electrically connected to the power source. These electrodes 32 a and 32 b are electrically connected to the heater 23.

  The conduits 5a and 5c and the first valves 7a and 7b constitute a first flow path that guides the fluid to be measured and the purge gas to the first through hole. As the purge gas, for example, helium, hydrogen, or nitrogen gas can be used.

  The first valve 7a includes two inflow ports and one outflow port. Between the state in which one inflow port and the outflow port communicate with each other and the state in which the other inflow port and the outflow port communicate with each other. It is an electric valve that can be switched under electrical control. In addition, the first valve 7b includes one inflow port and one outflow port, and is electrically switched between a state in which the inflow port and the outflow port are in communication with each other and a state in which the communication is interrupted. It is an electric valve that can be operated under control.

  One end of a conduit 5a is connected to the first through hole. The outflow port of the first valve 7b is connected to the other end of the conduit 5a. One end of a conduit 5c is connected to the inlet of the first valve 7b. The outflow port of the first valve 7a is connected to the other end of the conduit 5c. One end of a conduit 5e is connected to the first inlet of the first valve 7a. A supply source 9 to be measured is connected to the other end of the conduit 5e. One end of a conduit 5f is connected to the second inlet of the first valve 7a. A purge gas source 10 is connected to the other end of the conduit 5f.

  The conduits 5b and 5d and the second valve 8 constitute a second flow path that connects the second through hole and the measuring device 6 or the outside of the measuring device 6.

  The second valve 8 includes one inflow port and two outflow ports, a state in which the inflow port is in communication with one outflow port, a state in which the inflow port is in communication with the other outflow port, and an inflow port. It is an electrically operated valve that can be switched under a state of electrical control between a state in which neither of the two outlets is in communication.

  One end of a conduit 5b is connected to the second through hole. An inflow port of the second valve 8 is connected to the other end of the conduit 5b. One end of a conduit 5 d is connected to the first outlet of the second valve 8. A measuring device 6 is connected to the other end of the conduit 5d. One end of a conduit 5 g is connected to the second outlet of the second valve 8. The other end of the conduit 5g communicates with the outside of the measuring device 6.

  The measuring device 6 quantifies the one or more substances desorbed from the carbon nanotube bundle. The measuring device 6 is, for example, a flame ionization detector, a thermal conductivity detector, a laser gas analyzer, a gas chromatograph, a gas chromatograph mass spectrometer, or a Fourier transform infrared spectrophotometer.

  The controller 11 controls the operating state of the heater 23 and the states of the first valves 7a and 7b and the second valve 8 so as to sequentially perform first to fifth operations described later. The controller 11 is connected to a power source built in the support body 31. The controller 11 further controls the supply of power to the pair of electrodes 32a and 32b.

  Hereinafter, the analysis by the analyzer 1 will be described with reference to FIGS. 1 and 2.

  FIG. 2 is a graph showing a temperature change of the heater 23 included in the adsorption device 2 of FIG. The horizontal axis indicates time, and the vertical axis indicates temperature (° C.). In the method described here, the first to fifth operations are sequentially performed. T1 to T5 in FIG. 2 represent periods in which the first to fifth operations are performed.

  In the first operation, the heater 23 is not operated, and only the fluid to be measured among the fluid to be measured and the purge gas is guided to the first through hole, and the gas in the cell 20 is measured through the second through hole. Discharging to the outside of the device 6 is included. That is, in the first valve 7a, the first inlet is connected to the supply source 9 to be measured, and the first valve 7b is opened. Thus, exhaled air is supplied from the supply source 9 to be measured to the internal space of the cell 20 through the conduit 5e, the first valve 7a, the conduit 5c, the first valve 7b, and the conduit 5a. At the same time, in the second valve 8, the second outlet is connected to the outside of the measuring device 6. Thereby, the gas in the cell 20 is discharged from the internal space of the cell 20 to the outside of the measuring device 6 through the conduit 5b, the second valve 8, and the conduit 5g.

  When exhaled air flows through the internal space of the cell 20, the carbon nanotube bundle adsorbs a part of the substance contained in the exhaled air. After the carbon nanotube bundle has adsorbed a sufficient amount of substance, the second operation is performed.

  In the second operation, neither the fluid to be measured nor the purge gas is supplied to the internal space of the cell 20, the communication between the second through hole and the measuring device 6 and the outside thereof is interrupted, the heater 23 is operated, It includes raising the temperature of the cell 20 to the first temperature. That is, in the first valve 7a, the second inlet and the purge gas source 10 are connected, and the first valve 7b is closed. In the second valve 8, the first outlet and the measuring device 6 are not communicated with each other, and the second outlet and the outside of the measuring device 6 are not communicated. Thereby, the supply of the exhalation to the internal space of the cell 20 and the discharge of the gas from the internal space of the cell 20 are stopped.

  Many of the components contained in exhaled breath are nitrogen, oxygen, carbon dioxide and water vapor. The concentration of the volatile organic compound to be measured is only 1% or less of the entire exhalation. When measuring, if the gas contains a large amount of a substance that is not the object of measurement, noise increases with respect to the signal obtained for the object to be detected, and high-accuracy measurement is hindered. In particular, in the analyzer 1, the influence of water on the measurement accuracy is great.

  When the temperature of the internal space of the cell 20 is raised to the first temperature, the force that binds the water molecules is weakened. As a result, water molecules are easily detached from the carbon nanotube bundle. The first temperature is 100 ° C., for example.

  In the third operation, while the heater 23 is operated and the temperature of the internal space of the cell 20 is maintained at the first temperature, only the purge gas out of the fluid to be measured and the purge gas is guided to the first through hole, and the second through hole is formed. This includes discharging the gas in the cell 20 to the outside of the measuring device 6 via. That is, in the first valve 7a, the second inlet and the purge gas source 10 are brought into communication, and the first valve 7b is opened. Accordingly, the purge gas is supplied from the purge gas source 10 to the internal space of the cell 20 through the conduit 5f, the first valve 7a, the conduit 5c, the first valve 7b, and the conduit 5a. At the same time, the second outlet 8 communicates with the outside of the measuring device 6 at the second valve 8. As a result, a gas containing a substance not to be measured is discharged from the internal space of the cell 20 to the outside of the measuring device 6 through the conduit 5b, the second valve 8, and the conduit 5g. As a result, the non-measurement substance adsorbed by the carbon nanotube bundle, particularly water, is removed from the internal space of the cell 20.

  In the fourth operation, neither the fluid to be measured nor the purge gas is supplied to the internal space of the cell 20, the communication between the second through-hole and the measuring device 6 and the outside thereof is interrupted, and the heater 23 is operated. And raising the temperature of the cell 20 from the first temperature to the second temperature. That is, in the first valve 7a, the second inlet and the purge gas source 10 are connected, and the first valve 7b is closed. Further, in the second valve 8, the first outlet and the measuring device 6 are not communicated, and the second outlet and the outside of the measuring device 6 are not communicated. Then, the temperature of the internal space of the cell 20 is raised from the first temperature to the second temperature. The second temperature is, for example, 300 ° C. Note that purge gas remains in the internal space of the cell 20. This residual gas helps heat conduction in the interior space of the cell 20.

  The carbon nanotube bundle does not chemically adsorb the above substances but only physically adsorbs them. Therefore, when the carbon nanotube bundle is heated to the second temperature, the carbon nanotube bundle desorbs almost all of the adsorbed measurement target substance. When this desorption occurs, the concentration of the measurement target substance in the gas in the internal space of the cell 20 becomes higher than the concentration of the measurement target substance in the exhalation.

  In the fifth operation, while the heater 23 is operated and the temperature of the cell 20 is kept at the second temperature, only the purge gas out of the fluid to be measured and the purge gas is guided to the first through hole, and then through the second through hole. It includes discharging the gas in the cell 20 to the measuring device 6. That is, in the first valve 7a, the second inlet and the purge gas source 10 are brought into communication, and the first valve 7b is opened. Accordingly, the purge gas is supplied from the purge gas source 10 to the internal space of the cell 20 through the conduit 5f, the first valve 7a, the conduit 5c, the first valve 7b, and the conduit 5a. At the same time, in the second valve 8, the first outlet is connected to the measuring device 6. In this way, the gas containing the substance to be measured at a high concentration is sent from the internal space of the cell 20 to the measuring device 6 through the conduit 5b, the second valve 8 and the conduit 5d. The measuring device 6 quantifies the substance contained in the gas.

  In this way, in the analyzer 1, the gas having a higher concentration of the substance is supplied to the measuring device 6. Therefore, for example, even if the analysis accuracy of the measuring device 6 is low, quantitative analysis can be performed with sufficiently high accuracy. Moreover, since the measurement apparatus 6 may have low accuracy, it is possible to use an inexpensive apparatus having a small size.

  In addition, the carbon nanotube bundle does not chemically adsorb the above substance, but only physically adsorbs it. Therefore, the adsorption device 2 can be used repeatedly. The adsorption device 2 may be replaced with a new one for each analysis.

  Furthermore, since the adsorption device 2 uses physical adsorption by a carbon nanotube bundle rather than chemical adsorption by a metal complex or the like, nonuniformity due to surface modification by a metal complex does not occur. Therefore, analysis accuracy is not affected by this non-uniformity.

  Instead of performing the fourth and fifth operations, the fourth operation described above may be changed as follows and the fifth operation may be omitted.

  Specifically, in the fourth operation, only the purge gas out of the fluid to be measured and the purge gas is guided to the first through hole, and the gas in the cell is discharged to the measuring device through the second through hole. However, the heater 23 is operated to raise the temperature of the cell 20 from the first temperature to the second temperature. That is, in the first valve 7a, the second inlet and the purge gas source 10 are brought into communication, and the first valve 7b is opened. Accordingly, the purge gas is supplied from the purge gas source 10 to the internal space of the cell 20 through the conduit 5f, the first valve 7a, the conduit 5c, the first valve 7b, and the conduit 5a. At the same time, in the second valve 8, the first outlet is connected to the measuring device 6. In this state, the heater 23 is operated to raise the temperature of the cell 20 from the first temperature to the second temperature. In this way, the gas containing the substance to be measured at a high concentration is sent from the internal space of the cell 20 to the measuring device 6 through the conduit 5b, the second valve 8 and the conduit 5d. The measuring device 6 quantifies the substance contained in the gas.

  In this modification, instead of supplying all the components adsorbed by the bundle of carbon nanotubes to the measuring device 6 at the same time, these components are sequentially supplied to the measuring device 6 according to the ease of desorption. Therefore, for example, it is possible to qualitatively and quantitatively determine individual components without using a measuring device 6 including a column. Thus, according to this modification, qualitative and quantitative analysis can be performed with a simple configuration.

  In FIG. 1, electric valves that perform control using a motor are used as the first valves 7 a and 7 b and the second valve 8, but these valves may be electromagnetic valves.

  Moreover, although the two valves of the first valves 7a and 7b are used as the first valve, the first valve may be a single valve having the functions of the first valves 7a and 7b.

  Furthermore, although the valve provided with one inflow port and two outflow ports was used as the second valve 8, the second valve may be a valve provided with one inflow port and one outflow port. Good. In this case, the outlet of the second valve is connected to the conduit 5d. Further, the second valve 8 may be two valves like the first valves 7a and 7b.

  The analyzer 1 may include a temperature sensor that measures the temperature of the internal space of the cell 20. In this case, the controller 11 can control the power supplied to the electrodes 32a and 32b based on the output of the temperature sensor.

  Next, the adsorption device 2 will be described in detail with reference to FIGS. 3 to 8.

  As shown in FIGS. 3 to 5, the adsorption device 2 includes a cell 20 including an adsorption device main body 21 and a sealing member 22, and a heater 23.

  As shown in FIG. 7, the adsorption device main body 21 includes a base material 211 and a plurality of carbon nanotube bundles 212a to 212d.

  The base material 211 has a thin plate shape, for example. The substrate 211 may be hard or flexible. As a material of the base material 211, for example, silicon, glass, magnesium oxide, sapphire, or aluminum oxide can be used. Here, as an example, the base material 211 is assumed to be a silicon substrate. In the case where a silicon substrate is used as the base material 211, for example, the technology and apparatus used in the semiconductor process can be used for manufacturing the adsorption device body 21.

  The carbon nanotube bundles 212 a to 212 d extend from one main surface of the base material 211. Here, the carbon nanotube bundles 212 a to 212 d extend in a direction substantially perpendicular to one main surface of the base material 211. Each of the carbon nanotube bundles 212a to 212d may extend straight or bend.

  Each of the carbon nanotube bundles 212a to 212d is composed of a large number of carbon nanotubes each extending in the length direction thereof. The carbon nanotube is, for example, a single wall tube. The carbon nanotube may be any of an armchair tube, a zigzag tube, and a chiral tube.

  The length of the carbon nanotube is, for example, in the range of 50 μm to 100 μm. The diameter of the carbon nanotube is, for example, in the range of 10 nm to 100 nm. In each of the carbon nanotube bundles 212a to 212d, the distance between the carbon nanotubes is in the range of 10 nm to 100 nm, for example.

  The diameter of each of the carbon nanotube bundles 212a to 212d is, for example, in the range of 1 μm to 100 μm. The height of the carbon nanotube bundles 212a to 212d is, for example, in the range of 50 μm to 100 μm.

  The carbon nanotube bundles 212a to 212d are located away from each other. The distance between the carbon nanotube bundles 212a to 212d is, for example, in the range of 1 μm to 100 μm.

  The carbon nanotube bundles 212 a to 212 d extend from a plurality of unit regions on the base material 211. Each of these unit areas is composed of a plurality of sub-areas arranged radially. Specifically, each unit region is composed of a plurality of sub-regions, and typically has rotational symmetry. Each sub-region has a shape extending outward from the rotation axis.

  Here, as shown in FIG. 8, each of the unit regions 2110 is composed of a plurality of sub-regions 2110a to 2110d arranged radially. Each of the sub-regions 2110a to 2110d has a shape extending outward from the center of the unit region 2110. Specifically, the center region end of the unit region 2110 has a smaller radius of curvature than the opposite end. It has a droplet shape. The length direction Da of the sub-region 2210a is parallel to the length direction Dc of the sub-region 2110c. The length direction Db of the sub-region 2210b is parallel to the length direction Dd of the sub-region 2110d. The directions Da and Dc are perpendicular to the directions Db and Dd.

  The directions Da to Dd are inclined with respect to the straight line L when viewed from a direction perpendicular to the sub-regions 2110a to 2110d. In this case, the angle θa formed by the direction Da with respect to the straight line L is, for example, in a range greater than 0 ° and less than 90 °. In this case, the angle θb formed by the direction Db with respect to the straight line L is, for example, in a range greater than 90 ° and less than 180 °. Further, in this case, an angle θc formed by the direction Dc with respect to the straight line L is set to be, for example, in a range larger than 180 ° and smaller than 270 °. In this case, the angle θd formed by the direction Dd with respect to the straight line L is, for example, in a range greater than 270 ° and less than 360 °. Here, the angles θa, θb, θc, and θd are 45 °, 135 °, 225 °, and 315 °, respectively.

  The straight line L is a straight line passing through the center of the opening located on the inner space side of the adsorption device 2 among the openings of the through holes TH1 and TH2 shown in FIGS. The directions Da to Dd do not have to be inclined with respect to the straight line L when viewed from a direction perpendicular to the sub-regions 2110a to 2110d. Further, the sub regions 2110a to 2110d do not have to have a shape extending outward from the center of the unit region 2110.

  The carbon nanotube bundles 212a to 212d have substantially the same cross-sectional shape perpendicular to the height direction as the sub-regions 2110a to 2110d over their entire height. The unit regions 2110 shown in FIG. 8 are arranged vertically and horizontally on the base material 211. As shown in FIGS. 3 to 5, the unit structures 212 each composed of the carbon nanotube bundles 212 a to 212 d are also arranged vertically and horizontally on the base material 211 corresponding to the arrangement of the unit regions 2110.

  Here, each of the unit regions 2110 is composed of four sub-regions 2110a to 2110d, but each of the unit regions 2110 may be composed of two, three, or five or more sub-regions. Alternatively, each unit region 2110 may be one continuous region.

  A base layer 213 shown in FIG. 7 is interposed between the unit region 2110 and the unit structure 212. The underlayer 213 includes a barrier layer 213a and a catalyst layer 213b.

  The barrier layer 213a suppresses the material constituting the catalyst layer 213b from diffusing into the base material 211. The barrier layer 213a is made of, for example, alumina, silicon dioxide, tantalum pentoxide, or hafnium oxide. The barrier layer 213 a exists only between the unit region 2110 and the unit structure 212, but may be provided so as to cover the entire main surface of the base material 211. The barrier layer 213a can be omitted.

  The catalyst layer 213b serves as a seed for generating carbon nanotubes and a catalyst for promoting the growth thereof. The catalyst layer 213b exists only between the unit region 2110 and the unit structure 212. The catalyst layer 213b is made of a metal such as iron, nickel, and cobalt, for example.

  The sealing member 22 has a thin plate shape, for example. The sealing member 22 may be hard or flexible. Here, as an example, it is assumed that the sealing member 22 is a glass plate. When a glass plate is used as the sealing member 22, it is easy to form recesses and through-holes described later. Moreover, when a silicon substrate is used as the base material 211 and a glass plate is used as the sealing member 22, they can be joined without an adhesive.

  As shown in FIG. 5, the sealing member 22 has recesses RS1 to RS3 and grooves GR1 and GR2 on one main surface thereof. The recess RS3 is located between the recess RS1 and the recess RS2. The groove GR1 communicates the recess RS1 and the recess RS3. The groove GR2 connects the recess RS1 and the recess RS2.

  Here, the recesses RS1 and the recesses RS3 are connected by the two grooves GR1, but the number of the grooves GR1 that connect the recesses RS1 and the recesses RS3 may be 1 or 3 or more. . In addition, here, the recesses RS2 and RS3 are connected by the two grooves GR2, but the number of the grooves GR2 connecting the recesses RS2 and RS3 may be 1 or 3 or more. Also good.

  The sealing member 22 is joined to the base material 211 so that the bottom surface of the recess RS3 faces the unit structure 212. As shown in FIG. 4, the sealing member 22 forms a hollow structure together with the base material 211. Specifically, in this hollow structure, the recesses RS1 to RS3 shown in FIG. 5 form the chambers CH1 to CH3 shown in FIGS. 3 and 4, respectively. As shown in FIG. 3, the grooves GR1 and GR2 shown in FIG. 5 constitute a flow path FP1 that connects the chambers CH1 and CH3 and a flow path FP2 that connects the chambers CH2 and CH3, respectively. The unit structure 212 is located in the chamber CH3.

  As shown in FIG. 5, the sealing member 22 has a first through hole TH1 and a second through hole TH2 at positions corresponding to the bottoms of the recesses RS1 and RS2. The through hole TH1 communicates the chamber CH1 with the external space of the adsorption device 2. The through hole TH2 communicates the chamber CH2 with the external space of the adsorption device 2. The number of through holes TH1 may be two or more. Also, the number of through holes TH2 may be two or more.

  The sealing member 22 may not be provided with the recesses RS1 to RS3 and the grooves GR1 and GR2. That is, the surface of the sealing member 22 that faces the base material 211 may be flat. In this case, for example, the recesses RS1 to RS3 and the grooves GR1 and GR2 are provided on the surface of the substrate 211 that faces the sealing member 22. The carbon nanotube bundles 212a to 212d are arranged on the bottom surface of the recess RS3.

  The heater 23 is provided on a surface corresponding to the outer surface of the cell 20 among the main surfaces of the base material 211. The heater 23 may be provided on the surface corresponding to the inner surface of the cell 20 among the main surfaces of the substrate 211. Alternatively, the heater 23 may be provided on a surface corresponding to the inner surface or the outer surface of the cell 20 in the main surface of the sealing member 22.

  As shown in FIG. 4, the heater 23 includes a heating element 231. The heating element 231 is, for example, a resistance heating element. As the heating element 231, for example, a patterned metal layer can be used. For example, as shown in FIG. 6, the heating element 231 is formed in a pulse wave shape on the base material 211. As a material of the heating element 231, for example, a metal such as copper or an alloy can be used. The heating element 231 has one end in contact with the electrode 32a and the other end in contact with the electrode 32b.

This adsorption device 2 is manufactured by the following method, for example.
First, the heating element 231 is formed on the base material 211. The heating element 231 is formed by sputtering using a mask, for example. Alternatively, the heating element 231 is formed by sputtering and patterned. Alternatively, the heating element 231 may be formed by printing. Next, an insulating layer that protects the heating element 231 is formed as necessary. The heater 23 may be formed on the base material 211 as described above, or may be formed separately from the base material 211 and attached to the base material 211.

  Next, the barrier layer 213a and the catalyst layer 213b shown in FIG. 7 are formed in this order on the other main surface of the substrate 211. Each of the barrier layer 213a and the catalyst layer 213b is formed by, for example, a sputtering method using a mask. Next, carbon nanotubes are generated and grown, for example, by chemical vapor deposition (CVD). Due to the presence of the catalyst layer 213b, the generation and growth of carbon nanotubes occurs selectively at the position of the catalyst layer 213b. As a result, carbon nanotube bundles 212a to 212d are obtained.

  Next, the composite body of the adsorption device main body 21 and the heater 23 thus obtained and the separately prepared sealing member 22 are joined as shown in FIG. Thus, a structure including the cell 20 and the heater 23 on one main surface thereof is obtained. When the base material 211 is made of silicon and the sealing member 22 is made of glass not containing alkali ions such as sodium ions, the adsorption device main body 21 and the sealing member 22 can be joined by, for example, surface active joining. . An adhesive may be used for joining the adsorption device main body 21 and the sealing member 22, but when they are joined directly, components contained in the adhesive do not affect the measurement.

  As described above, the adsorption device 2 shown in FIGS. 3 to 5 is obtained.

  Next, the flow of exhalation and the like in the adsorption device 2 will be described.

  At the time of adsorption, exhaled air is supplied to the internal space of the cell 20 through the through hole TH1 shown in FIG.

  The exhaled air that has passed through the through hole TH1 first reaches the chamber CH1. Since the chamber CH1 and the chamber CH3 are connected by a plurality of flow paths FP1, the flow of exhalation is divided into a plurality of flows by the flow path FP1. Since exhaled air is supplied to the chamber CH3 from a plurality of locations, there is no great variation in the flow rate in the region near the chamber CH1 in the chamber CH3.

  These flows merge in the chamber CH3. In the process of exhalation passing through the chamber CH3, the carbon nanotube bundles constituting the unit structure 212 adsorb one or more substances contained in exhalation.

  Thereafter, the flow of the exhalation is divided into a plurality of flows by the flow path FP2, and merges in the chamber CH2. Since the exhaled air is discharged from a plurality of locations from the chamber CH3, there is no great variation in the flow velocity in the region near the chamber CH2 in the chamber CH3.

  Exhaled air that has reached the chamber CH2 is discharged to the outside of the cell 20 through the through hole TH2.

  At the time of detachment, the heater 23 shown in FIG. Since the carbon nanotube bundles 212a to 212d shown in FIG. 8 only physically adsorb the above-mentioned substance instead of chemical adsorption, the heater 23 shown in FIG. 1 or the like is operated to bring the carbon nanotube bundles 212a to 212d to the temperature. When heated, the carbon nanotube bundles 212a to 212d shown in FIG. 8 desorb almost all of the adsorbed substance. When this desorption occurs, the concentration of the substance in the gas in the internal space of the cell 20 shown in FIG. 1 and the like becomes higher than the concentration of the substance in the exhaled breath.

  Thereafter, for example, a purge gas is supplied to the internal space of the cell 20 through the through hole TH1, thereby discharging the gas containing the substance at a high concentration to the outside of the adsorption device 2 through the through hole TH2. As in the case of adsorption, the flow rate does not vary greatly in the chamber CH3. Therefore, the gas containing the substance at a high concentration can be discharged only by circulating a relatively small amount of inert gas.

  As described above, each of the carbon nanotube bundles 212a to 212d shown in FIG. 7 includes a large number of carbon nanotubes. In each of the carbon nanotube bundles 212a to 212d, there is a gap between the carbon nanotubes. Therefore, part of the exhalation passes through any one of the carbon nanotube bundles 212a to 212d when passing through the chamber CH3. Accordingly, each of the carbon nanotube bundles 212a to 212d adsorbs one or more substances in exhaled air not only on the surface but also inside. In each of the carbon nanotube bundles 212a to 212d, desorption of the adsorbed substance is unlikely to occur compared to the surface thereof. Accordingly, each of the carbon nanotube bundles 212a to 212d exhibits high adsorption efficiency.

  The carbon nanotube bundles 212a to 212d are positioned away from each other. That is, a gap is provided between the carbon nanotube bundles 212a to 212d. Therefore, the carbon nanotube bundles 212a to 212d do not excessively block the flow of exhalation.

  In addition, as described above, the carbon nanotube bundles 212a to 212d have substantially the same cross-sectional shapes as the sub-regions 2110a to 2110d shown in FIG. The directions Da to Dd in FIG. 8 are inclined with respect to the straight line L when viewed from a direction perpendicular to the sub-regions 2110a to 2110d. The direction of the average flow of exhalation in the chamber CH3 in FIG. 3 is parallel to the straight line L in FIG. By adopting such a structure, the flow of exhalation is optimized and high adsorption efficiency can be achieved.

  As described above, the carbon nanotube bundles 212a to 212d only physically adsorb the substance, not chemical adsorption. Therefore, it is easy to desorb almost the entire amount of the substances adsorbed by them.

  Therefore, when this adsorption device 2 is used, a gas having a sufficiently high concentration of the substance can be obtained. Therefore, for example, even if the analysis accuracy of the measuring device is low, quantitative analysis can be performed with sufficiently high accuracy. In addition, since the measurement apparatus may be low in accuracy, it can be used with a small size and a low price.

  Further, when this adsorption device 2 is used, analysis in a short time is possible as will be described below.

  FIG. 9 is a diagram schematically showing a part of the analyzer 1 according to the comparative example. In this analyzer 1, the support 3, not the adsorption device 2, incorporates a heater 23. When such a structure is adopted, not only the carbon nanotube bundle but also the support body 31 itself must be heated. In addition, it is inevitable that a minute gap is generated between the adsorption device 2 and the support 3. As a result, a long time is required to raise the temperature of the carbon nanotube bundle. According to an example, it took about 3 hours to raise the temperature of the carbon nanotube bundle from 100 ° C. to 300 ° C.

  With respect to this structure, in the analyzer 1 described with reference to FIG. 1 and the like, a heater 23 is formed in the adsorption device 2 itself. Therefore, the time required for raising the temperature of the carbon nanotube bundle can be greatly shortened. According to an example, when the heater 23 was installed on the base material 211, the time required to raise the temperature of the carbon nanotube bundle from 100 ° C. to 300 ° C. was 46.4 seconds. When the heater 23 was installed on the sealing member 22, the time required to raise the temperature of the carbon nanotube bundle from 100 ° C. to 300 ° C. was 46.0 seconds.

  Thus, when the heater 23 is provided in the adsorption device 2, the time required to raise the temperature of the carbon nanotube bundle can be greatly shortened. Therefore, for example, real-time analysis becomes possible.

  The adsorption device 2 may employ the following structure.

  FIG. 10 is a diagram schematically showing an adsorption device 2 according to a modification. In this structure, a heater 23 is joined to the cell 20 described with reference to FIG. That is, the surface of the heater 23 on the heating element 231 side and the surface of the cell 20 on the base material 211 side are joined. The heater 23 includes a heating element 231 and a substrate 232.

  The adsorption device 2 of such a modification is manufactured as follows, for example.

  First, the heating element 231 is formed on the substrate 232 by the same method as described above, and the heater 23 is obtained.

  Next, the heater 23 and the base material 211 side of the separately prepared cell 20 are joined as shown in FIG. When the base material 211 is made of silicon and the substrate 232 is made of glass not containing alkali ions such as sodium ions, the adsorption device main body 21 and the heater 23 can be bonded by, for example, surface active bonding.

  When such a structure is adopted, the heating element 231 is protected by the substrate 232, so that the heater 23 is hardly deteriorated.

  Note that the heater 23 described with reference to FIG. 10 may be bonded to the sealing member 22 side of the cell 20 instead of bonding to the base material 211 side of the cell 20. When the sealing member 22 is made of glass not containing alkali ions such as sodium ions, and the substrate 232 is made of silicon, the sealing member 22 and the heater 23 can be bonded by, for example, surface active bonding.

  As described above, the analysis device 1 and the adsorption device 2 have been described as being used for analysis of exhalation. However, the analysis device 1 and the adsorption device 2 can also be used for analysis of gases other than exhalation. For example, the analysis device 1 and the adsorption device 2 can also be used for analysis of exhaust gas from a combustion device.

  The analysis device 1 and the adsorption device 2 can also be used for liquid analysis. It can also be used for analysis of water such as clean water and sewage.

  The adsorption device 2 can also be used for purposes other than analysis. For example, the adsorption device 2 can be used for an air purifier to adsorb dirt having a size of 100 μm or less such as PM2.5 or floating mold existing in the air.

  Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of components disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments may be appropriately combined.

  DESCRIPTION OF SYMBOLS 1 ... Analytical apparatus, 2 ... Adsorption apparatus, 3 ... Support body, 5a ... Conduit, 5b ... Conduit, 5c ... Conduit, 5d ... Conduit, 5f ... Conduit, 5g ... Conduit, 6 ... Measuring device, 7a ... 1st valve, 7b ... 1st valve, 8 ... 2nd valve, 9 ... Supply source of measurement object, 10 ... Purge gas source, 11 ... Controller, 20 ... Cell, 21 ... Adsorption device body, 22 ... Sealing member, 23 ... heater, 31 ... support body, 32a ... electrode, 32b ... electrode, 211 ... base material, 212 ... unit structure, 212a ... carbon nanotube bundle, 212b ... carbon nanotube bundle, 212c ... carbon nanotube bundle, 212d ... carbon nanotube bundle 213 ... Underlayer, 213a ... barrier layer, 213b ... catalyst layer, 231 ... heating element, 232 ... substrate, 2110 ... unit region, 2110a ... subregion, 2110b ... Sub-region, 2110c ... sub-region, 2110d ... sub-region, CH1 ... chamber, CH2 ... chamber, CH3 ... chamber, Da ... length direction, Db ... length direction, Dc ... length direction, Dd ... length direction, FP1 ... flow path, FP2 ... flow path, GR1 ... groove, GR2 ... groove, L ... straight line, RS1 ... concave, RS2 ... concave, RS3 ... concave, TH1 ... through hole, TH2 ... through hole, θa ... angle, θb ... angle , Θc: angle, θd: angle.

Claims (5)

First and second penetrations each including a base material and a sealing member bonded to the base material and forming a hollow structure together with the base material, each communicating an internal space and an external space of the hollow structure A cell with holes,
A plurality of carbon nanotube bundles extending from the substrate in the internal space and positioned away from each other;
An adsorption device comprising a heater provided on at least one of the base material and the sealing member.   The adsorption device according to claim 1, wherein the heater is a patterned metal layer. A support for supporting the adsorption device according to claim 1 or 2,
A first flow path for guiding the fluid to be measured and the purge gas to the first through hole;
A measuring device for quantifying one or more substances in the gas;
A second flow path connecting the second through hole and the measuring device or the outside;
One or more first valves attached to the first flow path;
An analyzer comprising one or more second valves attached to the second flow path. A controller for controlling the operating state of the heater and the states of the one or more first valves and the one or more second valves so as to sequentially perform the first to fifth operations;
In the first operation, the heater is not operated, and only the fluid out of the fluid and the purge gas is guided to the first through hole, and the gas in the cell is discharged to the outside through the second through hole. Including
In the second operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole, the measuring device, and the outside is interrupted, the heater is operated, and the cell is operated. Raising the temperature to the first temperature,
In the third operation, only the purge gas out of the fluid and the purge gas is guided to the first through hole while the heater is operated to keep the temperature of the cell at the first temperature, and the second through hole is provided. Exhausting the gas in the cell to the outside via
In the fourth operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole, the measuring device, and the outside is interrupted, the heater is operated, Raising the temperature of the cell from the first temperature to the second temperature,
In the fifth operation, while the heater is operated and the temperature of the cell is maintained at the second temperature, only the purge gas out of the fluid and the purge gas is guided to the first through hole, and the second through hole is formed. The analyzer according to claim 3, wherein the gas in the cell is discharged to the measuring device via a gas. A controller for controlling the operating state of the heater and the states of the one or more first valves and the one or more second valves so as to sequentially perform the first to fourth operations;
In the first operation, the heater is not operated, and only the fluid out of the fluid and the purge gas is guided to the first through hole, and the gas in the cell is discharged to the outside through the second through hole. Including
In the second operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole, the measuring device, and the outside is interrupted, the heater is operated, and the cell is operated. Raising the temperature to the first temperature,
In the third operation, the heater is operated and the temperature of the cell is maintained at the first temperature, and only the purge gas out of the fluid and the purge gas is guided to the first through hole, and the second through hole is formed. Exhausting the gas in the cell to the outside via
In the fourth operation, only the purge gas out of the fluid and the purge gas is guided to the first through hole, and the gas in the cell is discharged to the measuring device through the second through hole, and the heater 4. The analyzer according to claim 3, further comprising raising the temperature of the cell from the first temperature to the second temperature.