JP2020197544A - Adsorber and analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize an analyzer capable of analysis with high accuracy and in a short time. An adsorption device includes a base material and a sealing member joined to the base material to form a hollow structure together with the base material, and each of an internal space and an external space of the hollow structure are provided. A cell provided with first and second through holes for communication, a plurality of carbon nanotube bundles extending from the base material in the internal space and located apart from each other, and at least one of the base material and the sealing member. It is equipped with a heater provided in. [Selection diagram] Fig. 1

Description

Embodiments of the present invention relate to an adsorption device and an analyzer.

Currently, research is underway to clarify metabolic reactions and biochemical pathological mechanisms from the concentrations 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. Higher levels of these in the exhaled breath manifest as symptoms of lipid oxidation, asthma or bronchitis.

In addition, nitric oxide (NO), carbon monoxide (CO) and H ₂ O ₂ in exhaled breath are highly correlated with lung disease. High levels of these in the exhaled breath show symptoms of asthma or chronic obstructive pneumonia.

Hydrogen (H ₂ ) and carbon isotope ( ¹³ C) in exhaled breath are highly correlated with gastrointestinal disorders. High levels of these in the exhaled breath show symptoms of dyspepsia, gastritis or duodenal ulcer.

In addition, acetone in exhaled breath has a high correlation with metabolic disorders. High levels of acetone in the exhaled breath show symptoms of diabetes. On the other hand, humans with lower exhaled acetone concentrations compared to healthy humans are more prone to metabolic syndrome.

The above-mentioned relationship is expected to be applied to a simple and painless early bed diagnosis. 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 exhaled breath component, an analyzer having high resolution is required.

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

However, metal complexes exhibit approximately equal adsorption capacity for molecules with similar chemical structures. Further, when the surface of the conductive substrate is not flat, it is difficult to uniformly modify the surface with the metal complex. Non-uniform surface modifications make accurate measurements difficult.

As another analysis method, 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 a hydrocarbon is mixed in the atmosphere, a reaction occurs between the oxygen adsorbed on the metal oxide and the reducing substance, and the oxygen adsorbed on the surface of the metal oxide is reduced. Along with this, the specific resistance of the metal oxide becomes smaller. This method utilizes such a phenomenon.

This method has a short detection time and exhibits high sensitivity even at low concentrations of reducing substances. However, this method requires a complicated configuration when a plurality of reducing substances are contained in the atmosphere.

JP-A-2010-107310 JP 2015-7625

An object 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 base material includes a base material and a sealing member bonded to the base material to form a hollow structure together with the base material, and each communicates the internal space and the external space of the hollow structure. A cell provided with first and second through holes, a plurality of carbon nanotube bundles extending from the base material in the internal space and located apart from each other, and at least one of the base material and the sealing member. A suction device including the above heater is provided.

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

The figure which shows schematic the analyzer which concerns on embodiment. The graph which shows the temperature change of a heater at the time of analysis. The plan view of the adsorption device included in the analyzer of FIG. FIG. 3 is a cross-sectional view taken along the line IV-IV of the suction device of FIG. An exploded perspective view of the suction device of FIGS. 3 and 4. The plan view of the heater included in the suction device of FIGS. 3 to 5. 3 is a perspective view schematically showing a bundle of carbon nanotubes included in the adsorption device of FIGS. 3 to 5. The plan view which shows an example of the relationship between the arrangement of carbon nanotube bundles, and the flow of exhalation. The figure which shows a part of the analyzer which concerns on a comparative example roughly. The figure which shows schematic the adsorption device which concerns on the modification.

Hereinafter, embodiments will be described in detail with reference to the drawings. Components that exhibit similar or similar functions are designated by the same reference numerals throughout the drawings, and duplicate description will be omitted.

The analyzer 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 sample is typically human breath, but may be the breath of an animal other than human. The volatile organic compound is, for example, ethane, pentane or acetone.

The analyzer 1 includes a suction device 2, a support 3, conduits 5a to 5d, a measuring device 6, first valves 7a and 7b, and a second valve 8.

The suction 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 housed in the internal space of the cell 20. These carbon nanotube bundles physically adsorb one or more substances in the exhaled breath, that is, the above-mentioned components. The detailed structure of the adsorption device 2 will be described later.

The support 3 detachably supports the suction device 2. The support 3 includes a support main body 31 and a power supply (not shown) built therein. The support 3 further includes a pair of electrodes 32a and 32b electrically connected to this power source. These electrodes 32a and 32b are electrically connected to the heater 23.

The conduits 5a and 5c and the first valves 7a and 7b form 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 inlets and one outlet, and is between a state in which one inlet and the outlet are in contact with each other and a state in which the other inlet and the outlet are in contact with each other. It is an electric valve that can be switched under electrical control. Further, the first valve 7b is provided with one inflow port and one outflow port, and electrically switches between a state in which the inflow port and the outflow port are in contact with each other and a state in which the communication is cut off. It is an electric valve that can be operated under control.

One end of the conduit 5a is connected to the first through hole. The outlet of the first valve 7b is connected to the other end of the conduit 5a. One end of the conduit 5c is connected to the inflow port of the first valve 7b. The outlet of the first valve 7a is connected to the other end of the conduit 5c. One end of the conduit 5e is connected to the first inflow port 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 the conduit 5f is connected to the second inflow port 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 form a second flow path that connects the second through hole with the measuring device 6 or the outside of the measuring device 6.

The second valve 8 includes one inflow port and two outflow ports, and the inflow port is in a state where the inflow port and one outflow port are in contact with each other, and the inflow port and the other outflow port are in contact with each other. It is an electric valve that can switch between two outlets that are not in contact with each other under electrical control.

One end of the conduit 5b is connected to the second through hole. The inflow port of the second valve 8 is connected to the other end of the conduit 5b. One end of the conduit 5d 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 the conduit 5g is connected to the second outlet of the second valve 8. The other end of the conduit 5g leads to the outside of the measuring device 6.

The measuring device 6 quantifies the above-mentioned one or more substances desorbed from the carbon nanotube bundle. The measuring device 6 is, for example, a hydrogen 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 the first to fifth operations described later. Further, the controller 11 is connected to a power source built in the support main body 31. The controller 11 further controls the supply of electric 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 shows time and the vertical axis shows temperature (° C). In the method described here, the first to fifth operations are sequentially performed. T1 to T5 in FIG. 2 represent periods during which the first to fifth operations are performed.

In the first operation, the heater 23 is not operated, only the fluid to be measured and the purge gas to be measured are guided to the first through hole, and the gas in the cell 20 is measured through the second through hole. It includes discharging to the outside of 6. That is, in the first valve 7a, the first inflow port and the supply source 9 to be measured are communicated with each other, and the first valve 7b is opened. As a result, exhaled air is supplied from the supply source 9 to be measured to the internal space of the cell 20 via the conduit 5e, the first valve 7a, the conduit 5c, the first valve 7b, and the conduit 5a. At the same time, the second valve 8 communicates the second outlet with the outside of the measuring device 6. As a result, the gas in the cell 20 is discharged from the internal space of the cell 20 to the outside of the measuring device 6 via the conduit 5b, the second valve 8, and the conduit 5g.

When the 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 the 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 cut off, and the heater 23 is operated. It involves raising the temperature of the cell 20 to a first temperature. That is, in the first valve 7a, the second inflow port and the purge gas source 10 are made to communicate with each other, and the first valve 7b is closed. Then, 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 with each other. As a result, the supply of exhaled air to the internal space of the cell 20 and the discharge of gas from the internal space of the cell 20 are stopped.

Most 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 less than 1% of the total exhaled breath. If the gas contains a large amount of substances other than the measurement target during the measurement, the signal obtained for the detection target becomes noisy, which hinders high-precision measurement. In particular, in this analyzer 1, water has a great influence on the measurement accuracy.

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

In the third operation, the heater 23 is operated to keep the temperature of the internal space of the cell 20 at the first temperature, and only the purge gas among the fluid and the purge gas to be measured is guided to the first through hole, and the second through hole is provided. 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 inflow port and the purge gas source 10 are made to communicate with each other, and the first valve 7b is opened. As a result, the purge gas is supplied from the purge gas source 10 to the internal space of the cell 20 via the conduit 5f, the first valve 7a, the conduit 5c, the first valve 7b, and the conduit 5a. At the same time, the second valve 8 communicates the second outlet with the outside of the measuring device 6. As a result, the gas containing the 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 target substance, particularly water, to which the carbon nanotube bundle is adsorbed 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 cut off, and the heater 23 is operated. Includes raising the temperature of cell 20 from a first temperature to a second temperature. That is, in the first valve 7a, the second inflow port and the purge gas source 10 are made to communicate with each other, and the first valve 7b is closed. Further, 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 with each other. 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. 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 substance to be measured. When this desorption occurs, the concentration of the substance to be measured in the gas in the internal space of the cell 20 becomes higher than the concentration of the substance to be measured in the exhaled breath.

In the fifth operation, while the heater 23 is operated and the temperature of the cell 20 is maintained at the second temperature, only the purge gas among the fluid and the purge gas to be measured is guided to the first through hole and 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 inflow port and the purge gas source 10 are made to communicate with each other, and the first valve 7b is opened. As a result, the purge gas is supplied from the purge gas source 10 to the internal space of the cell 20 via 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 and the measuring device 6 are communicated with each other. 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 via 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, the analyzer 1 supplies the gas having an increased concentration of the substance to the measuring device 6. Therefore, for example, even if the analysis accuracy of the measuring device 6 is low, the quantitative analysis can be performed with sufficiently high accuracy. Further, since the measuring device 6 may have low accuracy, a measuring device 6 having a small size and being inexpensive can be used.

Further, 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.

Further, since the adsorption device 2 utilizes physical adsorption by the carbon nanotube bundle instead of chemical adsorption by the metal complex or the like, non-uniformity due to surface modification by the metal complex or the like does not occur. Therefore, the accuracy of analysis is not affected by this non-uniformity.

Instead of performing the fourth and fifth operations, the above-mentioned fourth operation 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 and the purge gas to be measured 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 inflow port and the purge gas source 10 are made to communicate with each other, and the first valve 7b is opened. As a result, the purge gas is supplied from the purge gas source 10 to the internal space of the cell 20 via 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 and the measuring device 6 are communicated with each other. Then, the heater 23 is operated in this state 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 via 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 simultaneously supplying all the components adsorbed by the carbon nanotube bundle to the measuring device 6, 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 quantify individual components without using a measuring device 6 including a column. As described above, according to this modification, qualitative and quantitative analysis can be performed with a simple configuration.

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

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

Further, as the second valve 8, a valve having one inlet and two outlets was used, but the second valve may use a valve having one inlet and one outlet. Good. In this case, the outlet of the second valve connects 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 suction device 2 includes a cell 20 including a suction 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 is, for example, a thin plate. The base material 211 may be rigid or flexible. As the material of the base material 211, for example, silicon, glass, magnesium oxide, sapphire, or aluminum oxide can be used. Here, as an example, it is assumed that the base material 211 is a silicon substrate. When a silicon substrate is used as the base material 211, for example, the technology and the apparatus used in the semiconductor process can be used for manufacturing the adsorption device main body 21.

The carbon nanotube bundles 212a to 212d extend from one main surface of the base material 211. Here, the carbon nanotube bundles 212a to 212d 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 be straight or bent.

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

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 apart 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 212a to 212d extend from a plurality of unit regions on the substrate 211. Each of these unit regions consists of a plurality of radially arranged sub-regions. Specifically, each of the unit regions consists of a plurality of sub-regions and typically has rotational symmetry. Each sub-region has a shape extending outward from the axis of rotation.

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 central 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 subregions 2110a to 2110d, respectively. In this case, the angle θa formed by the direction Da with respect to the straight line L is, for example, within a range larger than 0 ° and less than 90 °. Further, in this case, the angle θb formed by the direction Db with respect to the straight line L is, for example, within a range larger than 90 ° and less than 180 °. Further, in this case, the angle θc formed by the direction Dc with respect to the straight line L is, for example, within a range larger than 180 ° and less than 270 °. In this case, the angle θd formed by the direction Dd with respect to the straight line L is, for example, within a range larger 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 openings located on the internal space side of the suction device 2 among the openings of the through holes TH1 and TH2 shown in FIGS. 3 to 5. The directions Da to Dd do not have to be tilted with respect to the straight line L when viewed from a direction perpendicular to the subregions 2110a to 2110d, respectively. 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 a cross-sectional shape perpendicular to the height direction over the entire height thereof, which is substantially the same as the shape of the sub-regions 2110a to 2110d, respectively. 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 structure 212 each consisting of the carbon nanotube bundles 212a to 212d is also arranged vertically and horizontally on the base material 211 corresponding to the arrangement of the unit region 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 of the unit regions 2110 may be one continuous region.

The base layer 213 shown in FIG. 7 is interposed between the unit region 2110 and the unit structure 212. The base layer 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. Although the barrier layer 213a exists only between the unit region 2110 and the unit structure 212, it 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 carbon nanotube production and a catalyst for promoting its growth. The catalyst layer 213b exists only between the unit region 2110 and the unit structure 212. The catalyst layer 213b is made of, for example, a metal such as iron, nickel and cobalt.

The sealing member 22 is, for example, a thin plate. The sealing member 22 may be rigid 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, which will be described later. Further, 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 of the main surfaces thereof. The recess RS3 is located between the recess RS1 and the recess RS2. The groove GR1 connects the recess RS1 and the recess RS3. The groove GR2 connects the recess RS1 and the recess RS2.

Here, the recess RS1 and the recess RS3 are connected by two grooves GR1, but the number of grooves GR1 connecting the recess RS1 and the recess RS3 may be 1 or 3 or more. .. Further, here, the recess RS2 and the recess RS3 are connected by the two grooves GR2, but the number of the grooves GR2 connecting the recess RS2 and the recess RS3 may be 1, or 3 or more. May be 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 chambers CH1 to CH3 shown in FIGS. 3 and 4, respectively. The grooves GR1 and GR2 shown in FIG. 5 constitute a flow path FP1 connecting the chambers CH1 and CH3 and a flow path FP2 connecting the chambers CH2 and CH3, respectively, as shown in FIG. 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 suction device 2. The through hole TH2 communicates the chamber CH2 with the external space of the suction device 2. The number of through holes TH1 may be 2 or more. Further, the number of through holes TH2 may be 2 or more.

The sealing member 22 does not have to be provided with the recesses RS1 to RS3 and the grooves GR1 and GR2. That is, the surface of the sealing member 22 facing the base material 211 may be flat. In this case, for example, recesses RS1 to RS3 and grooves GR1 and GR2 are provided on the surface of the base material 211 facing 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 the main surface of the base material 211, which corresponds to the outer surface of the cell 20. The heater 23 may be provided on the main surface of the base material 211, which corresponds to the inner surface of the cell 20. Alternatively, the heater 23 may be provided on the main surface of the sealing member 22 that corresponds to the inner surface or the outer surface of the cell 20.

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

The adsorption device 2 is manufactured by, for example, the following method.
First, a heating element 231 is formed on the base material 211. The heating element 231 is formed, for example, by a sputtering method using a mask. Alternatively, the heating element 231 is formed by a sputtering method and is formed by patterning the heating element 231. Alternatively, the heating element 231 may be formed by printing. Then, if necessary, an insulating layer that protects the heating element 231 is formed. The heater 23 may be formed on the base material 211 in this way, 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 on the other main surface of the base material 211 in this order. Each of the barrier layer 213a and the catalyst layer 213b is formed by, for example, a sputtering method using a mask. The carbon nanotubes are then produced and grown, for example, by chemical vapor deposition (CVD). Due to the presence of the catalyst layer 213b, the formation and growth of carbon nanotubes occurs selectively at the location of the catalyst layer 213b. As a result, carbon nanotube bundles 212a to 212d can be obtained.

Next, the composite of the suction device main body 21 and the heater 23 thus obtained and the separately prepared sealing member 22 are joined as shown in FIG. As a result, a structure including the cell 20 and the heater 23 on one of the main surfaces thereof is obtained. When the base material 211 is made of silicon and the sealing member 22 is made of glass that does not contain alkaline ions such as sodium ions, the adsorption device main body 21 and the sealing member 22 can be bonded by, for example, surface active bonding. .. An adhesive can be used for joining the suction device main body 21 and the sealing member 22, but when they are directly joined, the 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 exhaled air in the adsorption device 2 and the like 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 exhaled air flow is divided into a plurality of flows by the flow path FP1. Since the exhaled air is supplied to the chamber CH3 from a plurality of locations, the flow velocity does not vary greatly in the region of the chamber CH3 near the chamber CH1.

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

After that, this expiratory flow 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 the chamber CH3 from a plurality of places, the flow velocity does not vary greatly in the region of the chamber CH3 near the chamber CH2.

The 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 attachment / detachment, the heater 23 shown in FIG. 1 or the like is operated. Since the carbon nanotube bundles 212a to 212d shown in FIG. 8 merely physically adsorb the above substances, not chemically adsorbing them, the heater 23 shown in FIG. 1 or the like is operated to bring the carbon nanotube bundles 212a to 212d to a 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.

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

As described above, each of the carbon nanotube bundles 212a to 212d shown in FIG. 7 is composed of 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 exhaled air passes through any of the carbon nanotube bundles 212a to 212d as it passes through the chamber CH3. Therefore, each of the carbon nanotube bundles 212a to 212d adsorbs one or more substances in the exhaled breath not only on the surface but also inside. Then, inside each of the carbon nanotube bundles 212a to 212d, desorption of the adsorbed substance is less likely to occur as compared with the surface thereof. Therefore, each of the carbon nanotube bundles 212a to 212d exhibits high adsorption efficiency.

Further, the carbon nanotube bundles 212a to 212d are positioned apart 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 impede the flow of exhaled breath.

Further, as described above, the carbon nanotube bundles 212a to 212d have substantially the same cross-sectional shape perpendicular to the height direction as the shapes of the sub-regions 2110a to 2110d shown in FIG. 8, respectively. 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 subregions 2110a to 2110d, respectively. The direction of the average flow of exhaled air in the chamber CH3 of FIG. 3 is parallel to the straight line L of FIG. By adopting such a structure, the exhaled air flow is optimized and high adsorption efficiency can be achieved.

As described above, the carbon nanotube bundles 212a to 212d only physically adsorb the above substances, not chemically adsorb them. Therefore, it is easy to desorb almost all of the above substances they are adsorbing.

Therefore, by using this adsorption device 2, it is possible to obtain a gas having a sufficiently high concentration of the substance. Therefore, for example, even if the analysis accuracy of the measuring device is low, the quantitative analysis can be performed with sufficiently high accuracy. Further, since the measuring device may have low accuracy, a measuring device having a small size and an inexpensive one can be used.

Further, by using this adsorption device 2, analysis can be performed in a short time as 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 has a built-in heater 23 instead of the suction device 2. 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 will be created between the suction 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 one example, it took about 3 hours to heat 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, the heater 23 is formed in the adsorption device 2 itself. Therefore, the time required to raise the temperature of the carbon nanotube bundle can be significantly reduced. According to one 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.

When the heater 23 is provided in the adsorption device 2 in this way, the time required for raising the temperature of the carbon nanotube bundle can be significantly shortened. Therefore, for example, real-time analysis becomes possible.

The following structure may be adopted for the adsorption device 2.

FIG. 10 is a diagram schematically showing the suction device 2 according to the modified example. In this structure, the heater 23 is joined to the cell 20 described with reference to FIG. 1 and the like. 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 modified example is manufactured as follows, for example.

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

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 base material 232 is made of glass that does not contain alkaline ions such as sodium ions, the adsorption device main body 21 and the heater 23 can be joined 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 less likely to deteriorate.

The heater 23 described with reference to FIG. 10 may be bonded to the sealing member 22 side of the cell 20 instead of being bonded to the base material 211 side of the cell 20. When the sealing member 22 is made of glass containing no alkaline ions such as sodium ions and the substrate 232 is made of silicon, the sealing member 22 and the heater 23 can be joined by, for example, surface active bonding.

Although the analyzer 1 and the adsorption device 2 have been described above for the analysis of exhaled breath, the analyzer 1 and the adsorption device 2 can also be used for the analysis of gases other than exhaled breath. For example, the analyzer 1 and the adsorption device 2 can also be used for analyzing the exhaust gas of the combustion device.

Further, the analyzer 1 and the adsorption device 2 can also be used for analyzing liquids. 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 in an air purifier to adsorb dirt such as PM2.5 or floating mold existing in the air having a size of 100 μm or less.

The present invention is not limited to the above embodiment as it is, and at the implementation stage, the components can be modified and embodied within a range that does not deviate from the gist thereof. In addition, various inventions can be formed by an appropriate combination of the plurality of components disclosed in the above-described embodiment. For example, some components may be removed from all the components shown in the embodiments. Further, components over different embodiments may be combined as appropriate.

1 ... Analyzer, 2 ... Adsorption device, 3 ... Support, 5a ... Conduit, 5b ... Conduit, 5c ... Conduit, 5d ... Conduit, 5e ... Conduit, 5f ... Conduit, 5g ... Conduit, 6 ... Measuring device, 7a ... 1st valve, 7b ... 1st valve, 8 ... 2nd valve, 9 ... Supply source to be measured, 10 ... Purge gas source, 11 ... Controller, 20 ... Cell, 21 ... Suction device main 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 layer, 213a ... Barrier layer, 213b ... Catalyst layer, 231 ... Heat generator, 232 ... Substrate, 2110 ... Unit region, 2110a ... Sub region, 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.

According to the embodiment, a plurality a substrate made of silicon, is bonded to the substrate, and a sealing member that forms a hollow structure with the base material, which extends from the front Kimoto material, positioned away from each other a carbon nanotube bundles of the catalyst layer positioned between the plurality of carbon nanotube bundles and the substrate; and a barrier layer positioned between the catalyst layer and the substrate, the barrier layer Provided is an adsorption device that suppresses the material constituting the catalyst layer from diffusing into the base material .

According to another embodiment, it said suction device, the suction device analysis apparatus comprising a support for supporting is provided.

The present invention is not limited to the above embodiment as it is, and at the implementation stage, the components can be modified and embodied within a range that does not deviate from the gist thereof. In addition, various inventions can be formed by an appropriate combination of the plurality of components disclosed in the above-described embodiment. For example, some components may be removed from all the components shown in the embodiments. Further, components over different embodiments may be combined as appropriate.
The inventions described in the original claims are added below.
[1]
A first and second penetration that includes a base material and a sealing member that is joined to the base material and forms a hollow structure together with the base material, and each communicates an internal space and an external space of the hollow structure. A cell with a hole and
A plurality of carbon nanotube bundles extending from the base material in the internal space and located apart from each other.
With a heater provided on at least one of the base material and the sealing member
A suction device equipped with.
[2]
The suction device according to [1], wherein the heater is a patterned metal layer.
[3]
A support that supports the adsorption device according to [1] or [2], and
A first flow path that guides the fluid to be measured and the purge gas to the first through hole, and
A measuring device that quantifies one or more substances in a gas,
A second flow path that connects the second through hole with the measuring device or the outside,
With one or more first valves attached to the first flow path,
With one or more second valves attached to the second flow path
An analyzer equipped with.
[4]
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 is further provided so that the first to fifth operations are sequentially performed.
In the first operation, the heater is not operated, 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 doing
In the second operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole and the measuring device and the outside is cut off, the heater is operated, and the cell is operated. Including 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 keeping the temperature of the cell at the first temperature by operating the heater, and the second through hole is performed. Including discharging the gas in the cell to the outside through
In the fourth operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole and the measuring device and the outside is cut off, and the heater is operated to operate the heater. Including raising the temperature of the cell from the first temperature to the second temperature.
In the fifth operation, only the purge gas among the fluid and the purge gas is guided to the first through hole while the temperature of the cell is maintained at the second temperature by operating the heater, and the second through hole is introduced. The analyzer according to [3], which comprises discharging the gas in the cell to the measuring device via.
[5]
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 is further provided so that the first to fourth operations are sequentially performed.
In the first operation, the heater is not operated, 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 doing
In the second operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole and the measuring device and the outside is cut off, the heater is operated, and the cell is operated. Including 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 keeping the temperature of the cell at the first temperature by operating the heater, and the second through hole is performed. Including discharging the gas in the cell to the outside through
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, while the heater is used. The analyzer according to [3], which comprises operating the cell to raise the temperature of the cell from the first temperature to the second temperature.

Claims (5)

A first and second penetration that includes a base material and a sealing member that is joined to the base material and forms a hollow structure together with the base material, and each communicates an internal space and an external space of the hollow structure. A cell with a hole and
A plurality of carbon nanotube bundles extending from the base material in the internal space and located apart from each other.
An adsorption device including a heater provided on at least one of the base material and the sealing member. The suction device according to claim 1, wherein the heater is a patterned metal layer. A support that supports the suction device according to claim 1 or 2,
A first flow path that guides the fluid to be measured and the purge gas to the first through hole, and
A measuring device that quantifies one or more substances in a gas,
A second flow path that connects the second through hole with the measuring device or the outside,
With 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 is further provided so that the first to fifth operations are sequentially performed.
In the first operation, the heater is not operated, 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 doing
In the second operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole and the measuring device and the outside is cut off, the heater is operated, and the cell is operated. Including 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 keeping the temperature of the cell at the first temperature by operating the heater, and the second through hole is performed. Including discharging the gas in the cell to the outside through
In the fourth operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole and the measuring device and the outside is cut off, and the heater is operated to operate the heater. Including raising the temperature of the cell from the first temperature to the second temperature.
In the fifth operation, only the purge gas among the fluid and the purge gas is guided to the first through hole while the temperature of the cell is maintained at the second temperature by operating the heater, and the second through hole is introduced. The analyzer according to claim 3, wherein the gas in the cell is discharged to the measuring device via the device. 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 is further provided.
In the first operation, the heater is not operated, 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 doing
In the second operation, neither the fluid nor the purge gas is supplied to the internal space, the communication between the second through hole and the measuring device and the outside is cut off, the heater is operated, and the cell is operated. Including 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 keeping the temperature of the cell at the first temperature by operating the heater, and the second through hole is performed. Including discharging the gas in the cell to the outside through
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, while the heater is used. The analyzer according to claim 3, wherein the temperature of the cell is raised from the first temperature to the second temperature by operating the cell.