JPH09318508A - Specimen bend-cutting equipment for analyzing gas in holes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas extracting equipment capable of extracting gas in holes inside a metal specimen, and a component analyzing equipment which uses the gas extracting equipment and is excellent in precision. SOLUTION: This specimen bend-cutting equipment 10 consists of the following; a vacuum chamber 11 for arranging a specimen 8 having holes 80, a punch 12 for bend-cutting which is air-tightly inserted in the vacuum chamber 12 in such a manner that advance and retreat are possible, and a leading-out pipe for leading out gas to be inspected in the holes 80 from the vacuum chamber 11. In this case, a retainer 14 for retaining the specimen 8 which is arranged facing the punch 12 for bend-cutting is installed in the vacuum chamber 11.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sample breaking device for gas analysis in holes, which is a device for accurately collecting gas in holes generated inside a metal, and an analyzer using the same.

[0002]

2. Description of the Related Art Voids, which are fine pores formed in a metal by casting, welding, plating, and other manufacturing processes, deteriorate the strength and surface quality of the obtained product. Therefore, many efforts have been made to clarify the cause of the generation of vacancies in order to prevent them. In order to elucidate the cause of the above-mentioned generation of vacancies, it is extremely important to analyze the components of foreign substances existing in the vacancies.

The foreign substance existing in the pores may be present as a gas in the pores, may be present as a solid on the inner surface, or may be present in both of them, but especially as a gas. Most often when you do. Therefore, it is extremely important to analyze the components of the gas in the holes. Various methods have been conventionally proposed as a method for analyzing the gas in the holes, but the gas sampling method is particularly characteristic.

That is, the first method is a method in which a metal sample is cut in glycerin, and the gas in the pores is sampled and analyzed according to the water replacement (Reference: Journal of Welding Society 3).
9, (1970), p. 1075). The second method is a method of forming a through hole from the outer surface of the sample to the hole by using a manual drill in a vacuum container connected to an analyzer, collecting gas in the hole, and analyzing the gas. (References:
J. Inst. Metals 84, (1955), p.
455).

The third method is a method characterized in that an electric drill is used instead of the manual drill in the second method (Reference: Iron and Steel (1982) N).
o. 7, p. 858). A fourth method is a method in which a gas in a hole is collected by heating and melting a sample in a vacuum container connected to an analyzer, and the gas is analyzed.

[0006]

[Problems to be Solved] However, there are the following problems in the above conventional gas analysis in holes. That is, in the first method, it is difficult to collect a highly pure vacant gas due to the influence of the gas or the like dissolved in glycerin from the beginning. Further, in the second and third methods, the heat generated by the drill may change the gas in the pores or may affect new gas generated from the base material of the sample. Furthermore, in the above fourth method,
It is affected by the gas generated from the entire sample during dissolution.

In other words, in the conventional method, confusion of other gas newly generated in the process of collecting the in-hole gas, etc., and part of the alteration of the in-hole gas are present in the in-hole It has a great influence on the gas composition. Therefore, it was difficult to collect high-purity vacant gas as it was.

The present invention has been made in view of such conventional problems, and a gas sampling device capable of sampling the gas in the holes inside the metal sample with high purity, and a gas sampling device using the gas sampling device. It is intended to provide an accurate component analysis device.

[0009]

According to a first aspect of the present invention, there is provided a vacuum chamber for placing a sample having holes, a breaking punch which is hermetically inserted into the vacuum chamber so as to be able to move back and forth, and the inside of the vacuum chamber. And a support pipe for supporting the sample, which is disposed facing the breaking punch in the vacuum chamber. It is a characteristic sample breaker for gas analysis in holes.

What is most noticeable in the present invention is to have the breaking punch and the support for breaking the sample in the vacuum chamber. That is, it is possible to implement a method of breaking and breaking the sample in the vacuum chamber, whereby the gas in the holes can be collected.

As the above-mentioned sample to be used for analysis, those whose pore positions have been confirmed beforehand by X-ray photography or the like are used. Then, the hole position is located in the central portion of the sample, and the sample is processed into a size that can be arranged in the vacuum chamber and can be broken. Here, the breaking means breaking as described above, that is, breaking by applying bending stress.

The above-mentioned vacuum chamber is a chamber having airtightness and is constructed so as to have a reduced pressure atmosphere as described later or an atmosphere filled with a desired gas. Further, in order to maintain this airtightness, the breaking punch is also inserted airtightly.
Further, the lead-out pipe is connected to a separately provided gas analyzer, which also has airtightness like the vacuum chamber.

The breaking punch is capable of advancing and retracting as described above, and is for holding the sample between the supporting body and breaking it. Also,
It is preferable that the tip of the breaking punch, which comes into contact with the sample, is formed in a wedge shape. This makes it possible to easily break the sample at an accurate position.

The support, together with the punch for breaking, holds the sample and supports the sample at the time of breaking. It is preferable that, for example, two protruding contact portions are arranged on the support body at positions corresponding to both sides of the tip position of the breaking punch. As a result, after the sample is clamped at three points of the abutting portions at the two locations and the tip of the breaking punch, the tip of the breaking punch is set as a starting point by further advancing the punch for breaking. ， The sample can be easily broken.

Further, in this case, it is preferable that the two abutting portions of the support have a cylindrical shape. In this case, the frictional state between the sample and the contact portion at the time of breaking the sample can be optimized, and the sample can be smoothly broken.

As for the sample, it is necessary to grasp the internal hole positions in advance as described above.
It is preferable to provide a breaking notch, which is a linear groove serving as a starting point of breaking, on the surface portion corresponding to the hole position. As a result, a more accurate break position can be secured and break can be facilitated. Further, it is preferable to provide notches for alignment at the portions which are in contact with the two contact portions of the support on both sides of the breaking notch. As a result, the alignment of the sample can be performed extremely easily.

Next, the operation of the present invention will be described. When collecting the gas in the pores of the sample by using the sample breaking device for analyzing the gas in the pores of the present invention, first, the sample is placed in the vacuum chamber, and the punch for breaking and the support are provided. To pinch. At this time, the sample is arranged so that the hole position thereof is located at a position corresponding to the tip of the breaking punch.

Then, the inside of the vacuum chamber is adjusted to a desired atmosphere, for example, a vacuum atmosphere. Then, bending stress is applied to the sample by advancing the breaking punch. As a result, the sample is broken around the tip of the breaking punch.

At this time, the hole position of the sample is arranged in advance at a position corresponding to the tip of the breaking punch. As a result, the holes break due to the above-mentioned breaking, and the gas in the holes is released from the sealed state and released into the vacuum chamber. That is, the release of the gas in the holes is performed by the breaking. Therefore, unlike the conventional case, there is no possibility that the in-hole gas is altered or another gas is newly generated and mixed in the process of collecting the in-hole gas. Therefore, it is possible to collect a very pure gas in a hole as it is, and to use it for accurate component analysis.

Next, as in the invention of claim 2, the vacuum chamber is connected with a standard gas chamber for introducing a standard gas from the outside, and the standard gas chamber is cut off from communication with the outside. And a second septum for blocking communication between the first septum and the vacuum chamber, and a deaeration chamber connected to an exhaust device between the first septum and the second septum. preferable.

Here, the septum is a partition plate into which a needle of a syringe can be inserted / removed, and is usually used for partitioning the analysis system and the external environment at the inlet of a gas analyzer or the like. It is what Further, by providing the standard gas chamber having the above structure using two such septa, the accuracy of the calibration in the standard gas can be improved, which can contribute to the quantitative analysis of the vacancy gas.

That is, when performing the calibration, it is necessary to supply an accurate amount of the standard gas into the vacuum chamber. However, since the amount of gas supplied is very small, the atmosphere present at the needle tip of the syringe also has a great influence. In contrast, in the present invention, first, the needle tip of the syringe can be pierced only through the first septum to sufficiently exhaust the atmosphere or the like of the needle tip in the deaeration chamber. Therefore, when the standard gas is supplied by penetrating the second septum through the needle tip, the standard gas having a very high purity can be supplied.

The support in the vacuum chamber preferably has a heater for heating the inner surface of the hole of the sample after breaking. As a result, it is possible to locally heat the substance existing on the inner surface of the hole after the gas in the hole is released. Therefore, when new gas is generated from the inner surface of the pores due to this heating, it is possible to know the composition of the reaction product or the like involved in the generation of the pores by analyzing the new gas.

The support in the vacuum chamber preferably has a fiberscope for observing the inner surface of the hole of the sample after breaking. As a result, it is possible to locally observe the inner surface of the hole after breaking, and it is possible to help clarify the cause of the hole by grasping the appearance state.

Further, the vacuum chamber may have a carrier gas inlet for feeding a carrier gas for leading out the test gas. In this case, an analyzer that uses a carrier gas, such as a gas chromatograph, can be adopted as the analyzer connected to the lead-out pipe.

Next, as an in-hole gas analyzer using the sample breaking device, it has a vacuum pump for reducing the pressure in the vacuum chamber and a mass analyzer connected to the outlet pipe. There is an in-hole gas analyzer.

In this apparatus, the inside of the vacuum chamber is sufficiently decompressed by the vacuum pump, and then the sample is broken by using the sample breaking device. As a result, the high-purity vacant gas is sent to the mass spectrometer through the vacuum chamber and the outlet pipe. for that reason,
According to this device, it is possible to accurately analyze the components of the gas in the holes.

[0028] Another sample gas analyzer using the sample breaking device having the carrier gas inlet is a carrier gas generator connected to the carrier gas inlet and the outlet pipe. There is also a device characterized in that it has a gas chromatograph connected to the. In this case, the cost of the entire apparatus can be reduced by replacing the expensive mass spectrometer with a gas chromatograph.
The gas chromatograph may be replaced with an infrared spectrophotometer.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION

First Exemplary Embodiment A void gas analyzer according to an exemplary embodiment of the present invention will be described with reference to FIGS. 1 to 5. As shown in FIGS. 1 and 2, the in-hole gas analyzer 1 of this example is an in-hole gas analyzer using a sample breaking device 10 for in-hole gas analysis.

As shown in FIGS. 1 and 2, the sample breaking device 10 is a vacuum chamber 11 for arranging a sample 8 (FIG. 3) having holes 80, and an airtight chamber that can be moved back and forth into the vacuum chamber 11. The breaking punch 12 is inserted into the vacuum chamber 11 and the lead-out pipe 13 for leading out the test gas in the holes 80 from the vacuum chamber 11. Further, in the vacuum chamber 11, there is provided a support body 14 arranged to face the punch 12 for breaking and supporting the sample 8. A mass spectrometer 3 having a vacuum pump 2 for reducing the pressure inside the vacuum chamber 11 is connected to the outlet pipe 13.

This will be described in detail below. The breaking device 10
The vacuum chamber 11 has a cylindrical shape with an inner diameter of 25 mm and is made of stainless steel. As shown in FIGS. 1 and 2, the breaking punch 12 is arranged so as to be able to advance and retract from below the central portion of the vacuum chamber 11.

As shown in FIGS. 1 and 2, the breaking punch 12 is arranged in a guide portion 16 for airtightly guiding the advance / retreat of the punch 12. The airtightness between the guide portion 16 and the breaking punch 16 is maintained by an O-ring 165 provided therebetween. In addition, as shown in FIG. 1, the breaking punch 12 has a tip 121 formed in a wedge shape. On the other hand, the rear end 122 of the breaking punch 12
As shown in FIGS. 1 and 2, it is provided with a diameter larger than that of the main body and is projected to the outside of the vacuum chamber 12 so as to abut against a hydraulic jack 17 for pressurization.

The support 14 is provided in the vacuum chamber 11 at a position facing the breaking punch 12. The support 14 is provided with a contact portion 142 made of two round bars on a base 141. These two contact portions 142
Are provided in parallel so that the wedge-shaped tip 121 of the breaking punch 12 is located in the center between them.

Further, the vacuum chamber 11 is provided with the lead-out pipe 13 at one end and a viewing window 18 at the other end. The viewing window 18 has a detachable flange 119.
It is a glass window arranged in the central part of the table so that the arrangement state of the sample 8 can be observed.

The outlet pipe 13 has an inner diameter of 6 mm and an outer diameter of 8 m.
It is made of stainless steel and is connected to the mass spectrometer 3 through a ceramic chip. In addition, the derivation pipe 13
A Teflon tube having an inner diameter of 4 mm and an outer diameter of 6 mm is inserted over the entire length of the tube in order to inactivate the inner surface of the pipe and reduce the dead volume. The mass spectrometer 3 connected to the lead-out pipe 13 is a device integrally provided with the vacuum pump 2. Therefore, the derivation pipe 1
Reference numeral 3 also serves as an exhaust passage for adjusting the atmosphere in the vacuum chamber 11 and a conveying passage for the test gas.

The mass spectrometer 3 is a VGA double-focusing mass spectrometer ZAB-SE, and its measurement conditions are as follows. Ionization: Electron ionization method, 70 eV, 200 μA 1
50 ° C., ion acceleration voltage: 8 kV, mass range: m / z = 1 to 250, scan rate: 1.0 sec / decade, intertime: 0.5 sec, ion detection voltage: 2.0 kV, amplifier gain: 5 × 10 -5A,

Further, the sample 8 for analyzing the gas in the holes by the present apparatus 1 is processed into the shape shown in FIG. That is,
The position of the hole 80 is confirmed in advance by X-ray photography, and it is positioned at the center of the top, bottom, left and right, and the width is 10 m
m, length 23 mm, thickness 5 mm.

Further, the sample 8 has a vacuum chamber 11
A linear breaking notch 85 and a positioning notch 86, which are the starting points of breaking, are provided on the surface facing the support 14 when arranged inside. The breaking notch 85 is provided at a position corresponding to the position of the hole 80 inside the sample 8, and the positioning notch 86 is provided at a portion contacting the two contact portions 142 of the support body 14, respectively.

Next, using this device 1, holes 80 of the sample 8 are obtained.
In analyzing the gas in the holes inside, the sample 8 is first placed in the vacuum chamber 11 as shown in FIGS. That is, the flange 11 in the vacuum chamber 11
9 is removed, the sample 8 is inserted into the vacuum chamber 11, and is sandwiched by the support 14 and the breaking punch 12.
Next, the flange 119 is attached again, and the vacuum chamber 11 is sealed. Next, the vacuum pump 2 is operated to operate the vacuum chamber 11 via the outlet pipe 13.
The air inside is discharged and the pressure is reduced to 10 ^-7 mBar.

Next, the high voltage power source of the ion source in the mass spectrometer 3 is turned on to start the mass analysis. Then, after the ionic strength is stabilized, a load is applied to the breaking punch 12 by the hydraulic jack 17. Thereby, as shown in FIG. 4, the sample 8 is broken by the bending stress. as a result,
The gas in the holes 80 is discharged into the vacuum chamber 11 and guided to the mass spectrometer 3 through the outlet pipe 13.
In addition, the moment of breaking is judged by the breaking sound emitted at the time of breaking. Then, the scan No. of the mass spectrometer 3 at the time of breaking. Read and continue mass spectrometry for a while.

Next, an example of a mass chromatogram showing the result of mass spectrometry is shown in FIGS. In this mass chromatogram, the horizontal axis shows the scan number. The (scan number) and time are taken, and the ionic strength output is taken on the vertical axis. Then, FIG. (A) (b) each Ar ^+, Ar
⁺⁺ output, and FIG. 3C shows the output of H ₂ O ⁺ . The breaking timing of the sample 8 is indicated by the solid line B (Break) in the figure.

As is known from FIGS. 5 (a) and 5 (b), about 1 second after the break, Ar gas, which is considered to be in-hole gas existing in the holes 80 of the sample 8, was detected. on the other hand,
As is known from FIG. 7C, it is found that the gas in the holes of the sample 8 does not contain water.

As described above, the device 1 of this example uses the breaking device 10 having the above structure. Therefore, by breaking the sample, it is possible to easily collect high-purity vacant gas as it is, and to subject it to analysis. Therefore, the apparatus 1 of the present example can analyze the components of the gas in the holes more accurately than before, and can greatly contribute to the analysis of the mechanism of the generation of holes in the metal.

Embodiment 2 In this embodiment, a standard gas chamber 4 is provided on the side surface of the vacuum chamber 11 in Embodiment 1 so that a standard gas for quantitative analysis can be injected. That is, as shown in FIG. 6, the vacuum chamber 11 is connected to the standard gas chamber 4 for introducing the standard gas from the outside. The standard gas chamber 4 has a first septum 41 that shuts off the communication with the outside and a second septum 42 that shuts off the communication with the vacuum chamber 11, and also the first septum 41 and the second septum 42.
And a deaeration chamber 45 connected to the exhaust device.

The first and second septa 41 and 42 are partition plates made of a silicone rubber material, and are generally used as injection ports when a sample is injected using a syringe. is there. The deaeration chamber 45 defined by the septa 41 and 42 is connected to an exhaust device (not shown) via an exhaust pipe 49 as shown in FIG. The exhaust device in this example is a rotary pump.

Further, the standard gas chamber 4 and the vacuum chamber 11
A stop valve 48 is provided at a connecting portion between the and, so that communication with the vacuum chamber 11 can be completely shut off when the standard gas chamber 4 is not used. Other than that, the structure other than the standard gas chamber 4 is the same as that of the first embodiment.

Next, when the test gas is quantified using the apparatus of this example, a standard gas having the same components as the gas to be quantified is calibrated among the gases detected as the test gas. ，
The correlation between the volume of the gas and the output is found, and this is compared with the output value of the test gas for quantitative determination. Therefore, the accuracy of quantification depends on how accurate the amount of standard gas to be injected can be.

On the other hand, in the apparatus of this embodiment, the standard gas chamber 4 having the above structure is used to inject the standard gas, so that the injection amount can be controlled extremely accurately. That is, as shown in FIG. 6, the standard gas is injected using the syringe 5 with a luer lock. At this time, the most problematic is the atmosphere existing in the needle tip 51 of the syringe 5, but in the present example, this influence can be eliminated.

Specifically, first, the needle tip 51 of the syringe 5 containing the standard gas is passed through the first septum 41,
It is located in the degassing chamber 45. At this position, the atmosphere in the needle tip 51 of the syringe 5 is immediately discharged by the exhaust device connected to the degassing chamber 45. Therefore, the needle tip 51 of the syringe 5 is free from foreign matter such as air.

Next, the needle tip 51 of the syringe 5 is further advanced to penetrate the second septum 42. At this time, the needle tip 51 of the syringe 5 is free of foreign matter such as the atmosphere as described above. Then, in this state, a desired amount of standard gas is injected from the needle tip 51 of the syringe 5. As a result, a highly pure standard gas that is not mixed with the atmosphere is injected into the vacuum chamber 11. Therefore, the standard gas can be accurately calibrated.

Next, an example of a mass chromatogram obtained as a result of actually measuring the standard gas using this apparatus will be described with reference to FIG. Helium was used as the standard gas, and a syringe with a luer lock for injection having a volume of 50 μl (microliter) was used. In FIG. 7, the scan number is on the horizontal axis. And the vertical axis shows the output value of the mass spectrometer. The standard gas is 10 μl 5 times (reference E1), 1 preliminary (reference C1), 5 μl 5 times (reference E2), preliminary 1
The injection was performed once (code C2) and 1 μl in the order of 9 times (code E3). Here, the spares (C1, C2) are generated in the experimental procedure and are excluded from consideration.

As is known from FIG. 7, the correlation between the injection amount of the standard gas and the output value clearly appears, and it can be seen that it can contribute to the quantitative analysis of the test gas. Further, in this example, in the case of injecting a standard gas of 5 to 10 μl, about 20%
The coefficient of variation was about 40% when the standard gas of 1 μl was injected. Here, the coefficient of variation is a value obtained by dividing the standard deviation of the measured value (peak height) by its average value, and the smaller this value, the higher the accuracy of quantification.

The reason why the precision is slightly lower in the case of 1 μl is considered to be because the volume of the syringe was too large and the injection amount itself varied. Therefore, if the volume of the syringe is reduced, it is possible to perform quantification with higher accuracy. From the above, it can be seen that the present apparatus can roughly quantify the test gas on the order of 1 μl.

Embodiment 3 In this embodiment, as shown in FIG. 8, a carrier gas feeding section 71 for feeding a carrier gas for leading out a test gas into the vacuum chamber 11 in the first embodiment.
And a carrier gas generator 72 was connected to the carrier gas inlet 71. Further, instead of the mass analyzer 3 and the derivation pipe 13 of the first embodiment, an analyzer 6 in which a gas chromatograph 601 and a mass analyzer 602 are combined is used.
And a dedicated outlet pipe 73 is provided.

The gas chromatograph 601 that constitutes the analyzer 6 is a HP capillary gas chromatograph HP.
The measurement conditions are as follows: -5890A. Injection part temperature: 100 ° C., injection method: splitless mode (2 minutes), column: DB-1, 0.25 mm × 30 m 0.25 μ
m, column temperature: 40 ° C, interface temperature: 40 ° C

The mass analyzer 602 which constitutes the analyzer 6 is a VGA double-focusing mass spectrometer ZAB-S.
E, and the measurement conditions are as follows. Ionization: Electron ionization method, 70 eV, 200 μA 2
70 ° C., ion acceleration voltage: 8 kV, mass range: m / z = 13 to 250, scan rate: 1.0 sec / decade, intertime: 0.5 sec, ion detection voltage: 2.0 kV, amplifier gain: 2 × 10 -5A,

Further, the carrier gas feeding portion 71 is provided in that portion instead of the flange 19 having the viewing window 18 in the first embodiment. In addition, the outlet pipe 73
Was about 2 m long. Others are the same as those in the first embodiment.

Next, in the device of this example, when analyzing the gas in the holes of the sample, first, the sample is placed in the vacuum chamber 11 as in the first embodiment. Then,
Carrier gas is fed from the carrier gas feeding unit 71 to stabilize the analysis system. Then, the sample is cut in the same manner as in Embodiment 1, and the components of the gas in the holes are analyzed.

The analysis results are shown in FIG. 9 (a) (b) and FIG.
(A) and (b). These figures show the scan N on the horizontal axis.
o. And time, the vertical axis shows the output value of the analyzer 6.
In the figure, the pressing start point (Jack
up) and the break point (Break) are also shown.

9A and 9B and FIGS. 10A and 10B.
As is known, in this example, hydrocarbons CH ₃ , C ₂ H ₃ , C ₃ H ₅ , and C ₃ H ₇ derived from vacant gas are used.
Etc. were detected. Here, it took about 60 seconds from the break point (Break) to the output fluctuation, but it is considered that this is because the length of the lead-out pipe 7 is as long as about 2 m. As described above, according to this example, it is possible to easily perform the component analysis using the carrier gas.

Embodiment 4 In this embodiment, as shown in FIG. 11, a heater for heating the inner surface of the hole of the sample after breaking is provided in the support 14 in the vacuum chamber 11 in the first embodiment. An infrared laser 144 was provided. Others are the same as those in the first embodiment.

In this case, when a foreign substance is present on the inner surface of the pores of the sample, it can be locally heated, and since it has a high boiling point, condensation or reaction products are formed on the inner wall of the pore. The solid substance present as can be gasified. Therefore, it is possible to analyze the components caused by the generation of vacancies, which cannot be obtained only by the above-mentioned breaking, and contribute to the elucidation of the cause of vacancies. In addition, the same effects as those of the first embodiment can be obtained. Although an infrared laser is used in this example, a sheath heater or the like may be used instead.

Embodiment 5 In this embodiment, instead of the infrared laser 144 as the heater in Embodiment 4, a fiberscope for observing the inner surface of the hole of the sample after breaking is provided. In this case, by combining the so-called external observation means, it is possible to clarify the cause of pore formation from a wider perspective. Other effects similar to those of the first embodiment are obtained.

[0064]

As described above, according to the present invention, a gas sampling device capable of sampling a gas in a hole inside a metal sample with high purity, and a highly accurate component analysis device using this gas sampling device. Can be provided.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing the configuration of a gas analyzer for holes in a first embodiment.

FIG. 2 is an explanatory view showing a configuration of the breaking device of the first embodiment as seen from a vertical section.

FIG. 3 is a perspective view of a sample according to the first embodiment.

FIG. 4 is an explanatory view showing a fractured state of a sample in the first embodiment.

5 (a) Ar ⁺⁺ , (b) in Embodiment 1. FIG.
_{^{Ar +, (c) H 2}} O +, explanatory view showing the measurement results, respectively.

FIG. 6 is an explanatory diagram showing a configuration of a standard gas chamber in the second embodiment.

FIG. 7 is an explanatory diagram showing a calibration mass chromatogram according to the second embodiment.

FIG. 8 is an explanatory diagram showing a configuration of a gas analyzer for holes in a third embodiment.

9 (a) CH ₃ and (b) in Embodiment 4. FIG.
Illustration showing C ₂ H _3, measurement results, respectively.

FIG. 10 (a) C ₃ H ₅ , in the fourth embodiment,
(B) C ₃ H _7, explanation diagram showing the measurement results, respectively.

FIG. 11 is an explanatory diagram showing a configuration of a breaking device according to a fifth embodiment.

[Explanation of symbols]

 1. . . In-hole gas analyzer, 10. . . Sample breaking device, 11. . . Vacuum chamber, 12. . . A punch for breaking, 13. . . Derivation pipe, 14. . . Support, 17. . . Hydraulic jack, 2. . . Vacuum pump, 3. . . Mass spectrometer,

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayuki Matsui, Masakazu Matsuku, Aichi-gun, Nagakute-cho, Aichi Prefecture 1 No. 41 Yokomichi, Toyota Central Research Institute Co., Ltd. (72) Inventor Katsumi Nonaka, Nagachite-machi, Aichi-gun, Aichi 1 in 41 Chuo Yokodori, Toyota Central Research Institute Co., Ltd. (72) Inventor Katsuji Okuda, Nagakute-cho, Aichi-gun, Aichi Pref.

Claims (2)

[Claims] 1. A vacuum chamber for arranging a sample having holes, a breaking punch which is hermetically inserted into the vacuum chamber so as to be able to advance and retreat, and a test gas in the holes from inside the vacuum chamber. And a lead-out pipe for leading out the sample, and the inside of the vacuum chamber is provided with a support arranged to face the breaking punch to support the sample. Sample breaking device. 2. The vacuum chamber according to claim 1, wherein the vacuum chamber is connected to a standard gas chamber for introducing a standard gas from the outside, and the standard gas chamber is provided with a first septum that blocks communication with the outside. A hole having a second septum that blocks communication with the vacuum chamber, and a deaeration chamber connected to an exhaust device between the first septum and the second septum. Sample breaker for medium gas analysis.