JP2011237453A - Sample collection device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable a quick and efficient introduction of samples to be detected into a sample analysis device, and enhance detection speed to carry out a large amount of tests at a short time.SOLUTION: The sample collection device for collecting samples, to be introduced into a mass spectrometer for analyzing the samples, from a ticket 9. The sample collection device comprises a vaporization container body for vaporizing the samples attached to the ticket 9 that passes through the vaporization container body, and a sample pull-in passage 241 one end of which opens inside the vaporization container body and the other end of which is communicatively connected to the mass spectrometer side. On an inner surface of the vaporization container body, trapezoidal projections 253a are provided along a surface of a sample pull-in aperture 245 of the sample pull-in passage 241 as to separate the ticket 9 from the sample pull-in aperture 245.

Description

  The present invention relates to a sampling device.

In general, as a dangerous goods detection device that prevents dangerous goods from being brought into airports or public facilities, a technique for detecting dangerous goods by heating and vaporizing a sample collected from an inspection object is known (patent) Reference 1).
According to Patent Document 1, a sample is collected by wiping off a portion of a sample, such as a PC keyboard or a bag handle, where the explosive powder or the like is attached, with the test piece. A technique for detecting a sample heated and vaporized by introducing it into a mass spectrometer is disclosed.

By the way, a sample adhering to a ticket or the like is collected, for example, in an accommodating portion under atmospheric pressure conditions, and the collected sample is analyzed by a mass spectrometer maintained in a reduced pressure state of about 10 ⁻³ Pa, for example. . In this case, in order to connect the inside of the accommodating part under atmospheric pressure conditions with the inside of the mass spectrometer in a reduced pressure state, it is necessary to connect while maintaining the pressure difference between the inside of the accommodating part and the mass spectrometer. Therefore, the storage unit and the mass spectrometer are connected by a capillary tube having a large pressure loss. In general, in a straight channel pipe, the pressure loss is proportional to the length and inversely proportional to the fourth power of the pipe diameter.

For example, as shown in FIG. 8, an ionization chamber (illustrated) in a mass spectrometer 307 in a reduced pressure state of 10 ⁻³ Pa is applied to a sample attached to a ticket 9 accommodated in an accommodating portion 303 under atmospheric pressure conditions. For example, the inside of the housing portion 303 and the inside of the mass spectrometer 307 are connected so as to be circulated using a capillary tube 323 having an inner diameter of about 0.3 mm and a length of 10 m or more. The pressure difference between the inside and the mass spectrometer 307 is maintained.
In FIG. 8, reference numeral 311 indicates a heater, and reference numeral 327 indicates an exhaust pump.

JP 2004-301749 A

However, if a large amount of airflow including a sample under atmospheric pressure condition is introduced into the mass spectrometer 307 at a time, the ionization chamber cannot be maintained in a reduced pressure state of 10 ⁻³ Pa. Therefore, the airflow including the sample is approximately 1 sccm. It will be introduced into the ionization chamber at a flow rate. For this reason, in the conventional technique, although the pressure difference between the container 303 and the mass spectrometer 7 can be maintained, the detection signal is output from the mass spectrometer 307 after the air flow including the sample is held over the suction port of the capillary tube 323. There is an inconvenience that it takes about 5 minutes to obtain. Accordingly, there is a problem that it takes time to introduce the sample into the mass spectrometer 307 and a large amount of inspection cannot be performed in a short time.

  The present invention has been made in view of such circumstances, and a sample to be detected can be quickly and efficiently introduced into a sample analyzer, and the detection speed is improved and a large amount of inspection is performed in a short time. It is an object of the present invention to provide a sampling device that can perform the above processing.

In order to solve the above problems, the present invention employs the following means.
The invention as a reference example of the present invention is a sample introduction device for introducing a sample contained in a sample collection device into a sample analysis device equipped with an exhaust device, and one end of which can be distributed to the sample collection device. A differential exhaust pipe to be connected; a differential exhaust apparatus connected to the other end of the differential exhaust pipe for exhausting and depressurizing the differential exhaust pipe; the differential exhaust pipe and the sample analyzer; And a pressure in the differential exhaust pipe to which the connection channel is connected is 50 Pa or more and 70 kPa or less, and a conductance of the connection channel is 1 × 10 ⁻ Provided is a sample introduction device that is ¹⁰ or more and 1 × 10 ⁻⁷ m ³ / s or less.

The sample introduction apparatus according to the present invention introduces a sample collected by a sample collection apparatus into, for example, a mass spectrometer used as a sample analysis apparatus. The mass spectrometer is generally maintained at a reduced pressure of about 10 ⁻³ Pa for sample analysis.
According to the present invention, the sample analyzer is brought to a reduced pressure state of about 10 ⁻³ Pa, and the pressure in the differential exhaust pipe is set to 50 Pa or more and 70 kPa or less by the operation of the differential exhaust device. When the pressure is further reduced, the gas containing the sample contained in the sampling device is sucked into the differential exhaust pipe due to the pressure difference between the sample analyzer, the differential exhaust pipe, and the sampling device, and further, the connection flow path And is introduced into the sample analyzer.

  In this case, since the pressure difference between the differential exhaust pipe and the sample analyzer is small, it is possible to maintain the pressure difference between the differential exhaust pipe and the sample analyzer using a connection flow path with low pressure loss. it can. For example, the length of the connection channel can be shortened while maintaining the size of the conventional channel cross-sectional area. As a result, the time taken for the sample to pass through the connection channel can be shortened and introduced quickly into the sample analyzer, and the sample detection time can be shortened.

  Here, the lower limit of the pressure in the differential exhaust pipe is determined from the sensitivity of the sample analyzer. That is, it is determined from the pressure corresponding to the minimum value of the explosion signal that can be detected. For example, since 140 explosion signals are obtained when the pressure in the differential exhaust pipe is 7000 Pa, if the signal intensity is proportional to the pressure in the differential exhaust pipe, a pressure of 50 Pa or more is required to obtain one signal. Is required. Therefore, the pressure in the differential exhaust pipe needs to be at least 50 Pa or more. On the other hand, the upper limit of the pressure in the differential exhaust pipe is determined from the pressure loss of the connection flow path, specifically, the minimum diameter and length. For example, when a connection passage having an inner diameter of 0.1 mm and a length of 10 cm is employed, the pressure in the differential exhaust pipe is 73 kPa.

Further, when the length of the connection channel is shortened, the conductance increases. However, when the conductance of the connection channel is less than 1 × 10 ⁻¹⁰ m ³ / s, the flow rate of the airflow passing through the connection channel decreases, and the sample analysis This is not preferable because the efficiency of introducing the sample into the apparatus is lowered. On the other hand, if the conductance of the connection flow path exceeds 1 × 10 ⁻⁷ m ³ / s, the flow rate of the airflow passing through the connection flow path increases, and if the pressure loss of the connection flow path is not increased, the inside of the differential exhaust pipe And the pressure difference between the sample analyzer and the inside of the sample analyzer cannot be maintained.

In the said invention, it is good also as an internal diameter of the said connection flow path being 0.1 mm or more and 3.0 mm or less.
At present, the minimum diameter of a connection channel (capillary tube) that can be easily obtained is 0.1 mm. Further, if the inner diameter of the connection flow path is less than 0.1 mm, the flow rate of the airflow passing through the connection flow path is not preferable. On the other hand, the upper limit of the inner diameter of the connection channel is determined from the pressure in the differential exhaust pipe and the length of the connection channel. For example, when the pressure in the differential exhaust pipe is 50 Pa, in order to maintain the pressure difference between the differential exhaust pipe and the sample analyzer, the inner diameter is 3.0 mm in the connection flow path having a pipe length of 10 cm. Is the upper limit. If the inner diameter of the connection flow path exceeds 3.0 mm, the pressure loss of the connection flow path is reduced and the flow rate of the airflow passing through the connection flow path is increased, which is not preferable because it falls on the detection lower limit of the sample analyzer.

Moreover, in the said invention, it is good also as the length of the said connection flow path being 50 cm or less.
The upper limit of the length of the connection channel is determined from the pressure in the differential exhaust pipe and the minimum diameter of the connection channel. For example, when the pressure in the differential exhaust pipe is 70 kPa, in order to efficiently introduce the sample into the sample analyzer, the upper limit is 50 cm for the length of the connection channel having an inner diameter of 0.1 mm. If the length of the connection channel exceeds 50 cm, it is not preferable because it takes time for the sample to pass through the connection channel.

  The invention as a reference example of the present invention is a sample introduction device for introducing a sample contained in a sample collection device into a sample analysis device equipped with an exhaust device, and one end of which can be distributed to the sample collection device. A differential exhaust pipe to be connected; a differential exhaust apparatus connected to the other end of the differential exhaust pipe for exhausting and depressurizing the differential exhaust pipe; the differential exhaust pipe and the sample analyzer; A connection flow path that connects the flow path and a pipe heating section that heats the differential exhaust pipe, the connection flow path having an insertion section that is inserted into the sample analyzer. In the sample analyzer, a sample introduction device is covered with a high thermal conductivity member having a higher thermal conductivity than the connection channel, and at least a part of the high thermal conductivity member is in contact with the heating unit for piping. provide.

According to the present invention, when the differential exhaust pipe is depressurized more than the pressure in the sampling device by the operation of the differential exhaust device, the air flow including the sample accommodated in the sampling device is converted into the differential exhaust pipe. The sample is sucked in and introduced into the sample analyzer through the connection channel. In this case, since the insertion portion of the connection channel is covered with the high thermal conductivity member in the sample analyzer, and a part of the high thermal conductivity member is in contact with the heating portion for piping, the high thermal conductivity member The heat of the piping heating part can be transmitted to the insertion part by the heat conduction. Therefore, it is possible to prevent the temperature of the insertion portion from being lowered and to prevent the sample from aggregating and adsorbing in the insertion portion. As a result, the airflow can easily flow through the connection flow path, and quick and highly sensitive measurement can be performed.
As the high thermal conductivity member, for example, a metal, more specifically, a copper member is preferable. In addition, stainless steel, aluminum, silver, tungsten, molybdenum, or the like may be employed.

In the said invention, it is good also as a connection flow path heating part heating the said insertion part via the said high thermal conductivity member is provided.
According to such a structure, an insertion part can be heated more reliably.

  The present invention is a sample collection device for collecting a sample to be introduced into a sample analysis device for performing sample analysis from a substrate, a vaporization container for vaporizing a sample attached to the substrate passing through the inside, and one end of the sample collection device A sample drawing channel having an opening in the vaporization vessel and the other end connected to the sample analyzer so as to be able to flow therethrough, and the inner surface of the vaporization vessel has the opening of the sample drawing channel and the base material A sampling device is provided in which a concave portion or a convex portion is provided along the opening surface.

  According to the present invention, when the substrate passes through the inside of the vaporization container, the sample adhering to the substrate is vaporized, and the vaporized sample is drawn into the sample drawing channel from the opening and moved to the sample analyzer side. Sent. In this case, the opening of the sample drawing channel can be prevented from being blocked by the base material by the concave portion or the convex portion provided along the opening surface of the inner surface of the vaporization container. Moreover, since a groove part is formed in the inner surface of a vaporization container by a recessed part or a convex part, the flow path of the airflow containing a sample is securable. Thereby, the vaporized sample can easily flow into the sample drawing channel, and the sampling efficiency of the sample can be improved.

In the said invention, it is good also as the said recessed part or convex part being formed along the moving direction of the said base material.
According to such a configuration, the air flow in the vaporization container can be effectively flowed along with the movement of the base material, and the sample collection efficiency can be further improved.

  The invention as a reference example of the present invention includes a sample analysis device including the sample introduction device, the sample collection device, and a sample analysis device that analyzes the sample collected by the sample collection device and introduced by the sample introduction device. Provide a system.

  According to the present invention, it is possible to quickly and efficiently introduce a sample to be detected into a sample analyzer, thereby improving the detection speed and performing a large amount of inspection in a short time.

1 is a schematic configuration diagram of a sample analysis system according to a first reference embodiment of the present invention. It is an enlarged view of the junction part of the capillary tube and mass spectrometer which concern on the 2nd reference embodiment of this invention. It is an enlarged view of the junction part of the capillary tube and mass spectrometer which concern on the modification of the 2nd reference embodiment of this invention. It is a schematic block diagram of the sample-collecting apparatus which concerns on one Embodiment of this invention. (A) is sectional drawing of the vaporization chamber of the sampling apparatus of FIG. 4, (b) is a figure which shows the inner wall face of the vaporization chamber. (A) is sectional drawing of the modification of the vaporization chamber of Fig.5 (a), (b) is a figure which shows the inner wall face of the vaporization chamber. (A) is sectional drawing of another modification of the vaporization chamber of Fig.5 (a), (b) is a figure which shows the inner wall face of the vaporization chamber. It is a schematic block diagram of the conventional introduction system which introduces the extract | collected sample into a mass spectrometer.

[First Reference Embodiment]
Hereinafter, a sample introduction device, a sample analysis device, and a sample analysis system according to a first reference embodiment as a reference example of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the sample analysis system 1 includes a sample collection device 3, a sample introduction device 5, and a mass analysis device (sample analysis device) 7, and a ticket (base material) is activated by the operation of the sample collection device 3. In order to collect a sample such as a dangerous substance adhering to 9, introduce the collected sample into the mass analyzer 7 by the sample introduction device 5, and analyze the structure and composition of the sample by the mass analyzer 7. belongs to.

  The sample collection device 3 includes a vaporizing heater 11 and is disposed so that the ticket 9 taken in from the outside can be heated. In addition, the sample collecting device 3 is configured to heat and vaporize the sample attached to the ticket 9 under atmospheric pressure conditions by the operation of the vaporizing heater 11 and separate the sample from the ticket 9 to collect the sample.

  The sample introduction apparatus 5 includes a differential exhaust pipe 13 having one end connected to the sample collection apparatus 3 and a differential exhaust pump (differential exhaust apparatus) 19 connected to the other end of the differential exhaust pipe 13. An adjustment valve 21 that adjusts the exhaust flow rate of the dynamic exhaust pump 19 and a capillary tube (connection channel) 23 that connects the differential exhaust pipe 13 and the mass spectrometer 7 are provided.

  The differential exhaust pipe 13 has an upstream side connected to the sampling device 3 so as to be able to flow, and a downstream side connected to the differential exhaust pump 19 so as to be able to flow. The differential exhaust pipe 13 has a flow passage cross-sectional area of a flow passage on the sample collection device 3 side (hereinafter simply referred to as “collection device side flow passage”) 15, and a flow passage on the differential exhaust pump 19 side (hereinafter referred to as “flow passage”). This is simply referred to as “pump-side flow path”), and is formed to be smaller than the cross-sectional area of the flow path of 17 so that the pressure difference between the inside of the pump-side flow path 17 and the inside of the sampling device 3 under atmospheric pressure conditions is maintained. It has become. The differential exhaust pipe 13 is used while maintaining the pressure of the pump side flow path 17 in a reduced pressure state of 50 Pa or more and 70 kPa or less. In addition, the pressure inside the pump side flow path 17 is determined based on Formula (3) mentioned later.

  In the differential exhaust pipe 13, a pipe heater 25 is provided around the pipes of the sampling-side flow path 15 and the pump-side flow path 17. The pipe heater 25 is arranged so that heat is transmitted to the inner wall of the differential exhaust pipe 13 so that the entire inner wall of the differential exhaust pipe 13 is heated. The piping heater 25 is heated at, for example, 100 ° C. or more and 200 ° C. or less during operation of the sample introduction device 5. If the heating temperature of the pipe heater 25 is less than 100 ° C., the sample sucked together with the air flow in the differential exhaust pipe 13 may be attached and stay on the inner wall, which is not preferable. Moreover, when the heating temperature of the piping heater 25 exceeds 200 ° C., it is not preferable because it may be decomposed depending on the sample.

  In addition, as the heater 25 for piping, it is good also as employ | adopting a well-known ribbon heater, for example. Since the ribbon heater is a soft ribbon and easy to handle, it can be easily wound along the outer peripheral surface of the differential exhaust pipe 13.

  The differential exhaust pipe 13 may be formed of quartz, or the inner wall of the differential exhaust pipe 13 may be covered with quartz. Thereby, it is possible to effectively prevent the sample from adhering to and staying on the inner wall of the differential exhaust pipe 13.

  The differential exhaust pump 19 includes an intake port and an exhaust port (not shown), and the intake port is connected to the end of the pump-side flow path 17 of the differential exhaust pipe 13 so as to be able to flow therethrough. In addition, the differential exhaust pump 19 exhausts the pressure in the differential exhaust pipe 13 by sucking the gas in the differential exhaust pipe 13 from the intake port and exhausting it to the outside through the exhaust port. Yes.

The regulating valve 21 is disposed in the vicinity of the intake port of the differential exhaust pump 19. The adjustment valve 21 includes a valve mechanism (not shown) so that the exhaust flow rate of the differential exhaust pump 19 is controlled by opening and closing the valve.
The capillary tube 23 is, for example, a quartz thin tube having an inner diameter of about 0.3 mm, an outer diameter of about 0.04 mm, and a length of about 10 cm. The capillary tube 23 has a differential exhaust pipe 13 side connected to the pump side flow path 17 and a side connected to the mass spectrometer 7 directly connected to an ionization chamber (not shown) in the mass analyzer 7. The pipe 13 is connected so as to be able to flow while maintaining a pressure difference between the inside of the pump-side flow path 17 of the pipe 13 and the inside of the ionization chamber of the mass spectrometer 7.

In the present embodiment, the conductance of the capillary tube 23 is in the range of 1 × 10 ^{−10 to} 1 × 10 ⁻⁷ m ³ / s. The conductance of the capillary tube 23 is determined based on the expressions (1) and (2) described later.
A pressure gauge (not shown) for measuring the pressure in the mass spectrometer 7 is provided between the capillary tube 23 and the differential exhaust pump 19.

The mass spectrometer 7 includes an ionization chamber to which the capillary tube 23 is connected, a detection unit (not shown) for detecting ions of the sample sent from the ionization chamber, and an analysis for maintaining the inside of the mass spectrometer 7 in a reduced pressure state. A device exhaust pump (exhaust device) 27 is provided.
The ionization chamber is configured to ionize a sample included in an airflow sent via the capillary tube 23 to generate ions.

The detection unit separates and detects the ions generated by the ionization chamber according to the difference in mass, and analyzes the structure and composition of the sample.
The analyzer exhaust pump 27 is configured to maintain a high vacuum state of about 10 ⁻³ Pa in the mass analyzer 7, particularly in the ionization chamber. Thereby, the ion produced | generated in the ionization chamber is sent to a detection part stably and without decomposing | disassembling.
In addition, a heater (not shown) is provided around the outer periphery of the mass spectrometer 7 so that the wall surface and the ionization chamber of the mass spectrometer 7 are heated.

Operations of the sample introduction device 5, the mass spectrometer 7 and the sample analysis system 1 according to the present embodiment configured as described above will be described.
When the ticket 9 is taken into the sample collecting device 3, the sample such as a dangerous substance attached to the surface of the ticket 9 is heated and vaporized under atmospheric pressure by the operation of the vaporizing heater 11, and collected.
In the mass spectrometer 7, the inside of the ionization chamber is maintained in a high vacuum state of about 10 ⁻³ Pa by the operation of the analyzer exhaust pump 27. The pressure in the mass spectrometer 7 can be measured by a pressure gauge provided between the capillary tube 23 and the differential exhaust pump 19.

  On the other hand, in the differential exhaust pipe 13, the differential exhaust pipe 13 is evacuated by the operation of the differential exhaust pump 19, and the pressure is reduced. Sucked in. The airflow including the sample sucked into the differential exhaust pipe 13 is depressurized through the sampling-side channel 15 having a small channel cross-sectional area, and is transferred to the pump-side channel 17 having a large channel cross-sectional area on the downstream side. Led. In this case, the piping heater 25 is heated to 100 ° C. or more and 200 ° C. or less and the inside of the differential exhaust pipe 13 is heated, so that the inside of the differential exhaust pipe 13 does not stay on the inner wall. pass. Then, part of the airflow in the pump-side channel 17 is introduced into the mass spectrometer 7 through the capillary tube 23.

In this case, the pressure in the pump-side flow path 17 of the differential exhaust pipe 13 is P _D (Pa), the pressure in the ionization chamber of the mass spectrometer 7 is P _I (Pa), and the flow rate of the airflow flowing through the capillary tube 23 Is Q (Pa · m ³ / s), the conductance of the capillary tube 23 is C (m ³ / s), the inner diameter of the capillary tube 23 is d (mm), and the tube length is L (cm), the following formula (1 ) And formula (2) hold.
Formula (1) Q = C (P _D -P _I )
Formula (2) C = 1349 (d ⁴ / L) × ((P _D + P _I ) / 2)

Here, in order to detect the sample with high sensitivity by the mass spectrometer 7, it is preferable to introduce as much airflow including the sample as possible into the ionization chamber of the mass spectrometer 7, and the pump-side flow path 17 of the differential exhaust pipe 13. It is necessary to increase the pressure difference between the ionization chamber and the ionization chamber. Therefore, while the ionization chamber is maintained in a reduced pressure state of about 10 ⁻³ Pa, the pressure in the pump side flow path 17 is preferably set high. Then, the pressure P _I in the ionization chamber of the mass spectrometer 7 can be regarded as P _I ≈0 when compared with the pressure P _D in the pump-side flow path 17 of the differential exhaust pipe 13, and Equation (1) and From equation (2)
Formula (3) P _D ² = QL / (624.5d ⁴ )
It can be expressed as.

In the sample analysis system 1 according to the present embodiment, since the capillary tube 23 having an inner diameter d of 0.3 mm and a tube length L of 10 cm is adopted, the flow rate Q of the airflow flowing through the capillary tube 23 in the equation (3) is By setting 3.3 × 10 ⁻³ (Pa · m ³ / s), that is, 2 sccm, P _D = 8076 Pa is calculated.
That is, in order to maintain the pressure difference between the differential exhaust pipe 13 and the mass spectrometer 7 using the capillary tube 23, the mass of the air stream containing the sample from the pump side flow path 17 of the differential exhaust pipe 13 at a flow rate of about 2 sccm. is introduced into the ionization chamber of the analyzer 7 may be a pressure P _D of the pump-side flow passage 17 to a vacuum of approximately 1368Pa.
In general, in a straight channel pipe, the pressure loss is proportional to the length and inversely proportional to the fourth power of the inner diameter (pipe diameter).

  Therefore, the valve mechanism of the regulating valve 21 is adjusted to control the exhaust flow rate of the differential exhaust pump 19, for example, the air flow including the sample is sucked into the differential exhaust pipe 13 at a flow rate of about 100 sccm, and the differential exhaust pipe The pressure in the 13 pump side flow paths 17 is maintained in a reduced pressure state of 50 Pa or more and 70 kPa or less. Then, by the operation of the differential exhaust pump 19, the air flow guided to the pump-side flow path 17 of the differential exhaust pipe 13 is discharged to the outside from the exhaust port at a flow rate of about 98 sccm, and is approximately about via the capillary tube 23. It is introduced into the mass spectrometer 7 at a flow rate of 2 sccm.

By doing so, the pressure difference between the ionization chamber of the mass spectrometer 7 maintained at about 10 ⁻³ Pa and the pump-side flow path 17 of the differential exhaust pipe 13 is reduced. Compared to the flow path in the case where the pressure difference between the inside of the lower sampling device 3 and the mass spectrometer 7 is maintained, the pressure difference between the inside of the ionization chamber and the pump side flow path 17 is less than the pressure loss. Can be kept.

  That is, the pressure difference between the differential exhaust pipe 13 and the mass spectrometer 7 can be maintained using the capillary tube 23 having an inner diameter d of 0.3 mm and a tube length L of 10 cm. As a result, the time taken to pass through the capillary tube 23 can be greatly reduced, and the sample collected in the sample collection device 3 can be introduced into the mass spectrometer 7 in a short time. Specifically, after the sample collected in the sample collection device 3 is sucked into the sample collection side flow path 15 of the differential exhaust pipe 13, an ion detection signal can be obtained in the mass spectrometer 7 about 1 second later. it can.

Further, according to the equations (1) and (2), the conductance C of the capillary tube 23 can be set to 1 × 10 ⁻¹⁰ or more and 1 × 10 ⁻⁷ m ³ / s or less. Here, if the length of the capillary tube 23 is shortened, the conductance increases. However, if the conductance of the capillary tube 23 is less than 1 × 10 ⁻⁷ m ³ / s, the flow rate of the airflow passing through the capillary tube 23 decreases, and the mass This is not preferable because the efficiency of introducing the sample into the analyzer 7 is lowered. On the other hand, when the conductance of the capillary tube 23 exceeds 1 × 10 ⁻¹⁰ m ³ / s, the flow rate of the airflow passing through the capillary tube 23 increases, so that the differential exhaust pipe 13 does not increase the pressure loss of the capillary tube 23. This is not preferable because the pressure difference between the inside and the mass spectrometer 7 cannot be maintained.

  As described above, according to the sample introduction device 5, the mass spectrometer 7 and the sample analysis system 1 according to the present embodiment, a sample can be quickly and efficiently introduced into the mass spectrometer 7, and dangerous substances, etc. It is possible to improve the detection speed of the sample and perform a large amount of inspection in a short time.

[Second Reference Embodiment]
Next, with respect to the sample introduction device 5, the mass spectrometer 7 and the sample analysis system 101 according to the second reference embodiment as a reference example of the present invention, the joint portion of the capillary tube 123 and the mass spectrometer 7 is shown enlarged. This will be described with reference to FIG.
In the sample analysis system 101 according to the present embodiment, the length of the capillary tube 123 of the sample introduction device 5 is about 10 cm, and the capillary tube 23 is covered with a heat conduction tube (high thermal conductivity member) 129 in the mass spectrometer 7. This is different from the first embodiment.
In the following, portions having the same configuration as those of the sample introduction device 5, the mass spectrometer 7, and the sample analysis system 1 according to the first reference embodiment are denoted by the same reference numerals and description thereof is omitted.

The capillary tube 123 is formed such that a portion (hereinafter referred to as “insertion portion”) 131 inserted into the ionization chamber of the mass spectrometer 7 has a length of about 10 cm to 20 cm.
The heat conduction tube 129 is a conduit such as copper having a high heat conductivity or a stainless steel tube, and is formed to have a length that covers the entire insertion portion 131 of the capillary tube 123. The heat conduction tube 29 is provided so that one end thereof is in contact with the pipe heater 25 provided on the outer periphery of the differential exhaust pipe 13, and one side of the inner wall of the heat conduction tube 129 contacts the insertion portion 131 of the capillary tube 123. Are arranged to be.

  According to the sample analysis system 101 configured as described above, when the sample introduction device 5 operates and the piping heater 25 is heated, the heat of the piping heater 25 is transferred to the capillary tube 123 via the heat conduction tube 129. It is transmitted to the insertion part 131. Therefore, it is possible to prevent the temperature of the tip portion from decreasing in the ionization chamber even in the fused quartz capillary tube 123 having a low thermal conductivity. Thereby, aggregation and adsorption of the sample in the insertion part 131 can be prevented, and the airflow can easily flow in the capillary tube 123. As a result, the sample can be smoothly introduced into the mass spectrometer 7 and the measurement efficiency of the sample can be improved.

  In the present embodiment, the heat conduction tube 129 has been described by exemplifying a conduit such as copper or a stainless steel tube. However, any metal having higher heat conductivity than the capillary tube 123 may be used. Alternatively, tungsten, molybdenum, or the like may be employed.

Further, the sample introduction device 5, the mass spectrometer 7 and the sample analysis system 101 according to the present embodiment can be modified as follows.
For example, as shown in FIG. 3, an insertion portion heater (connection channel heating portion) 133 such as a sheath heater is further attached to the outer periphery of a heat conduction tube 129 covering the insertion portion 131 of the capillary tube 123, and the insertion portion heater In 133, the insertion portion 131 of the capillary tube 123 may be directly heated via the heat conducting tube 129. The insertion portion heater 133 is desirably heated to, for example, 100 ° C. or more and 200 ° C. or less.
By doing in this way, the insertion part 131 can be heated more reliably.
In this modified example, the sample attached to the wall surface of the capillary tube 123 may be vaporized and removed by heating the insertion unit 131 of the capillary tube 123 to a higher temperature by the operation of the heater 133 for the insertion unit. Good.

Next, the sample introduction device 5, the mass spectrometer 7 and the sample analysis system 201 according to an embodiment of the present invention will be described with reference to FIGS. 4 to 7 (a) and 7 (b).
The sample analysis system 201 according to the present embodiment is different from the sample collection device 3 of the first embodiment and the second embodiment in the configuration of the sample collection device 203.
In the following description, the same reference numerals are assigned to the same components as those of the sample introduction device 5, the mass analysis device 7, and the sample analysis system 1 according to the first reference embodiment and the second reference embodiment, and the description thereof is omitted. .

  The sampling device 203 includes a vaporization container main body 235 formed in a square cylinder shape, an inlet roller 237 provided on an inlet side end surface of the vaporization container main body 235, an outlet roller 239 provided on an outlet side end surface, and a vaporization container. A sample drawing flow path 241 that connects the inside of the main body 235 and the differential exhaust pipe 13 so as to be able to flow is provided. The sample adhering to the ticket 9 is vaporized inside the vaporizing container main body 235 and the vaporized sample is drawn into the sample. The sample attached to the ticket 9 is collected by suction from the sample inlet (opening) 245 of the channel 241.

  The vaporization container main body 235 is disposed so that a pair of wall surfaces (hereinafter referred to as “wall surface of the upper wall 247” and “wall surface of the lower wall 249”) are opposed to each other with a slight gap slightly wider than the thickness of the ticket 9, The other wall surfaces are arranged at a certain interval wider than the width of the ticket 9 so as to connect the end portions of the upper wall 247 and the lower wall 249. That is, the vaporization container main body 235 has a slit-shaped vaporization chamber 251 that extends in a planar shape that is narrow enough to pass the ticket 9.

The vaporization container body 235 includes a vaporization heater (not shown), and heats and vaporizes the sample attached to the ticket 9 when the ticket 9 passes through the vaporization chamber 251. The heater is desirably heated to, for example, 100 ° C. or more and 200 ° C. or less.
Further, as shown in FIGS. 5A and 5B, the inner surface of the vaporization container main body 235, that is, the inner wall of the vaporization chamber 251 is formed in a trapezoidal shape having convex portions of about 1 mm to 5 mm. A plurality of trapezoidal convex portions 253a are provided along the surface of the sample drawing port 245. In addition, each trapezoid convex part 253a does not obstruct the air flow in the vaporization chamber 251, and each recessed part 255 formed between each trapezoidal convex part 253a is the moving direction of the ticket 9, ie, the vaporization container main body 235. It is desirable that they are arranged so as to be positioned substantially linearly in the direction of the central axis 243.

The inlet roller 237 and the outlet roller 239 are a pair of rollers that are attached so as to extend in the longitudinal direction on the upper wall 247 end surface and the lower wall 249 end surface of the vaporization container main body 235, respectively. The inlet roller 237 is configured such that both rollers rotate toward the inside of the vaporizing container main body 235, while the outlet roller 239 is configured such that both rollers rotate toward the outside of the vaporizing container main body 235. As a result, the entrance roller 237 and the exit roller 239 are configured to send out the ticket by sandwiching both planes of the ticket 9 between the pair of rollers.
The sample drawing channel 241 is connected to the vicinity of the center of each of the upper wall 247 and the lower wall 249 so as to open from the upper wall 247 side and the lower wall 249 side to the vaporization chamber 251 of the vaporization container body 235.

The operation of the sample introduction device 5, the mass spectrometer 7 and the sample analysis system 201 according to this embodiment configured as described above will be described.
When the sample collection device 203 is activated, the vaporization heater of the vaporization container body 235 is heated, and the inlet roller 237 and the outlet roller 239 rotate at a constant speed. Then, when the differential exhaust pipe 13 is exhausted by the operation of the differential exhaust pump 19, the air flow generated in the vaporization container main body 235 is drawn into the differential exhaust pipe 13 via the sample drawing channel 241.

  In this situation, when the ticket 9 is taken in from the entrance roller 237, the ticket 9 is fed into the vaporizing chamber 251 of the vaporizing container body 235, and the sample attached to the ticket 9 is heated and vaporized by the heat of the vaporizing heater. Then, the air flow including the vaporized sample is drawn into the sample drawing channel 241 and sucked into the differential exhaust pipe 13. In this case, the ticket 9 can be separated from the sample drawing port 245 of the sample drawing channel 241 by the plurality of trapezoidal convex portions 253 a provided on the inner wall of the vaporizing chamber 251. Therefore, the sample inlet 245 can be prevented from being blocked by the ticket 9, and the airflow can be continuously sucked into the differential exhaust pipe 13.

Moreover, the flow path of the airflow containing a sample is securable by the recessed part 255 between each trapezoid-shaped convex part 253a. Further, by arranging the trapezoidal convex portions 253a so that the concave portions 255 are positioned substantially linearly in the moving direction of the ticket 9, the air flow in the vaporization container main body 235 is effectively transferred along with the movement of the ticket 9. It can be poured into the sample drawing channel 241.
Moreover, the residence time of the airflow containing a sample can be shortened by narrowing the vaporization chamber 251 of the vaporization container main body 235 as much as possible.

  As described above, according to the sample introduction device 5, the material analysis device 7, and the sample analysis system 201 according to the present embodiment, in the sample collection device 203, the residence time of the air flow including the sample is shortened and the sample drawing flow is reduced. The prevention of blockage of the sample inlet 245 of the path 241 and the flow path of the airflow are ensured, and the sample collection efficiency can be further improved.

  In the present embodiment, the trapezoidal convex portion 253a is provided on the inner wall of the vaporization chamber 251 of the vaporization container body 235. However, instead of this, FIG. 6 (a) and FIG. ) And a pyramid-shaped convex portion 253b formed in a pyramid shape as shown in FIG. 7 and a sample drawing port 245 in the sample drawing channel 241 shown in FIGS. 7 (a) and 7 (b). It is good also as providing the radial convex part 253c and the hemispherical convex part (illustration omitted) formed hemispherical. Note that it is only necessary that the ticket 9 can be separated from the sample drawing port 245 of the sample drawing channel 241. For example, the ticket 9 may be separated from the sample drawing port 245 by providing a mesh on the inner wall. Furthermore, it is good also as providing a recessed part in an inner wall instead of providing a convex part in the inner wall of the vaporization chamber 251. FIG.

Although one embodiment and a reference embodiment of the present invention have been described in detail above with reference to the drawings, the specific configuration is not limited to this embodiment.
For example, in the first reference embodiment, the director of the capillary tube has been described as about 10 cm. However, it is sufficient that the pressure difference between the differential exhaust pipe 13 and the mass spectrometer 7 can be maintained. It may be about 13 cm or 8 cm.
Further, for example, in each of the above-described embodiments, the differential exhaust pipe 13 is illustrated in which the channel cross-sectional area of the upstream sampling-side channel 15 is smaller than the channel cross-sectional area of the downstream pump-side channel 17. As described above, it is sufficient that the differential exhaust pipe 13 is exhausted by the operation of the differential exhaust pump 19 to be in a predetermined pressure-reduced state. As a whole, the differential exhaust pipe having a uniform cross-sectional area is adopted. Also good.

3 Sample collection device 5 Sample introduction device 7 Mass spectrometer (sample analyzer)
13 Differential exhaust piping 19 Differential exhaust pump (Differential exhaust system)
23 Capillary tube (connection channel)
27 Exhaust pump for analyzer (exhaust device)

Claims (2)

A sample collection device for collecting a sample for introduction into a sample analysis device for performing sample analysis from a base material,
A vaporization container for vaporizing the sample attached to the base material passing through the inside;
One end is opened in the vaporization container, and the other end is provided with a sample drawing channel connected to be flowable to the sample analyzer side,
A sample collection device in which a concave portion or a convex portion for separating the opening of the sample drawing channel from the base material is provided on the inner surface of the vaporization container along the opening surface.   The sampling device according to claim 1, wherein the concave portion or the convex portion is formed along a moving direction of the base material.

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