JPH065627Y2 - Gas analyzer for aluminum material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an apparatus for analyzing an extremely small amount of gas in an aluminum material.

In this specification, the term "aluminum" includes aluminum alloys in addition to pure aluminum.

Prior Art and Its Problems Aluminum material contains an internal gas and a gas adsorbed on the surface thereof, and a substance such as water which reacts with aluminum to generate a gas is adsorbed on the surface thereof. These gases are mainly H ₂ gas, and other extremely small amounts of CO gas, CO ₂ gas, H ₂ O gas and the like are present. Depending on the application of the aluminum material, the above gases are extremely harmful, so it is necessary to keep these amounts in a very small amount, and the gases adsorbed on the surface and the gases generated by the reaction of the substances adsorbed on the surface with aluminum (hereinafter both are collectively referred to as The result has been improved to some extent. However, the fact is that the internal gas has not been sufficiently researched. If the internal gas amount of the aluminum material, especially the H ₂ gas amount is large, there are the following problems. That is, when an aluminum material is used for a vacuum aluminum material, for example, a particle acceleration pipe (beam line) used in an accelerator such as a synchrotron, a large amount of gas is released when a beam is run inside the pipe, There is a problem that the pressure inside the pipe becomes very high. This is the effect that the synchrotron radiation emitted from the beam is incident on the inner surface of the pipe and strikes the internal gas of the aluminum material. Moreover, when an aluminum material is used for the vapor deposition substrate, Se, a-Si is formed on the substrate surface.
The phenomenon of "blister" occurs when depositing etc.,
It is known that this is also due to the influence of the release of internal gas. Furthermore, it has been known that surface defects such as "cracking", "blisters", and "scratches" that occur during rolling are also due to the effect of the internal gas of the aluminum material. Therefore, there is a demand for the development of an aluminum material having an extremely small amount of internal gas, but in developing an aluminum material having a small amount of internal gas, it is necessary to accurately analyze the internal gas.

Conventionally, analysis of the internal gas of an aluminum material has been performed by the following two methods.

(a) A method of quantifying internal gas and surface gas by preparing a plurality of samples from the same material with different surface area-to-volume ratios and performing gas analysis of each sample.

(b) Two samples of the same shape and size are made from the same material, and one of the samples is first heated to quantify the total amount of extracted gas. Then, the other sample is heated, and the gas extracted within the first fixed time is quantified as the surface gas, and the internal gas is quantified by comparing the total gas amount with the surface gas amount.

However, each of the above methods has the following drawbacks. That is, in the method (a), it is necessary to prepare a large number of samples, and the actual surface and internal gas have nonuniformity in the samples. According to the method (b), it is difficult to accurately separate the surface gas and the internal gas, and moreover, the amount of the surface gas varies, so that an accurate quantification cannot be performed. Due to these drawbacks, there is a problem that the conventional method cannot accurately quantify an extremely small amount of internal gas, for example, 0.05 cc / 100 g Al or less.

An object of the present invention is to solve the above problems and to provide a gas analyzer for an aluminum material, which can accurately quantify only a trace amount of internal gas with a small amount of material.

Means for Solving Problems A gas analyzer for aluminum material according to the present invention comprises a discharge cleaning chamber, a vacuum exhaust device provided in the discharge cleaning chamber,
A gas analysis chamber, a vacuum evacuation device provided in the gas analysis chamber, a sample passage provided between the chambers, a closing member that can be opened and closed in the sample passage, and a discharge cleaning chamber and a gas analysis chamber, respectively. And a manipulator which is provided and delivers the sample between the two chambers through the sample passage.

Embodiment Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

In FIG. 1 showing the configuration of the device of the present invention, the device for analyzing an extremely small amount of gas is a discharge cleaning chamber (1) and a gas analysis chamber.
(2), a sample passage (3) provided between the chambers (1) and (2), a closing member (4) provided in the sample passage (3) so as to be openable and closable, and an electric discharge cleaning chamber (1 ) And a manipulator (5) (6) which is provided in the gas analysis chamber (2) and which transfers the sample (S) between the chambers (1) and (2) through the sample passage (3). .

Inside the discharge cleaning chamber (1) is connected to the current introducing terminal (7) provided on the peripheral wall of the chamber (1) and contacts the sample (S) during the discharge cleaning to use the sample (S) as a cathode. An internal conductor (8) is provided. Also, a vacuum exhaust device is provided outside the discharge cleaning chamber (1).
(9), helium gas supply device for discharge cleaning (10), Bayard-Alpert vacuum gauge (11) for measuring the degree of vacuum in the high vacuum chamber (1) before and after discharge cleaning, helium during discharge cleaning
Pirani vacuum gauge (12) for measuring gas amount and current introduction terminal (7)
An external conducting wire (13) connected to is provided. The vacuum exhaust device (9) has an exhaust pipe (14) connected to the discharge cleaning chamber (1),
The exhaust pipe (14) comprises an L valve (15), a turbo molecular pump (16), and a rotary pump (17) which are installed in series in the following order from the chamber (1) side. The helium gas supply device (10) for electric discharge cleaning is installed on the way to the helium gas cylinder (19) connected to the electric discharge cleaning chamber (1) via the supply pipe (18) and the supply pipe (18). It is installed between the discharge cleaning chamber (1) and the trap (20) in the supply pipe (18) and the trap (20) which is filled with liquid nitrogen and removes impurities contained in the helium gas. Adjustable leak valve (2
It consists of 1).

Inside the gas analysis chamber (2), a crucible (23) made of alumina for sample melting placed on the mounting table (22) and a heater (24) wound around the crucible (23) were provided. Has been. Heater (2
Both ends of 4) are connected to terminals (25) provided on the bottom wall of the gas analysis chamber (2). Further, outside the gas analysis room (2), a vacuum exhaust device (26), a quadrupole mass filter (27) for analyzing the gas extracted from the sample (S), a Bayard ・
An external conductor (29) connected to the Alpert gauge (28) and the terminal (25) is provided. The vacuum exhaust device (26) is an exhaust pipe connected to the gas analysis chamber (2) through an orifice (30).
(31), and an L valve (32), a turbo molecular pump (33) and a rotary pump (34) which are provided in the exhaust pipe (31) in series in the following order from the chamber (2) side. And the exhaust pipe (31)
A Bayard-Alpert vacuum gauge (35) is provided on the valve (32) side of the orifice (30). Then, the total amount of gas extracted from the sample (S) is quantified by the two Bayard-Alpert vacuum gauges (28) and (35).

Both manipulators (5) and (6) are adapted to grasp and separate the sample (S) by applying the principle of the mechanical pencil, and each is movable in its axial direction. The manipulator (5) provided in the discharge cleaning chamber (1)
It can be freely taken in and out of the discharge cleaning chamber (1), and after holding the sample (S) outside the discharge cleaning chamber (1), enter the discharge cleaning chamber (1) and put the sample (S) into the internal conductor (8). Can be contacted with.
Also, the sample (S) can be
Is held so that the tip of the manipulator (5) and the sample (S) are electrically insulated. Further, a seal member is interposed between the outer periphery of the manipulator (5) and the peripheral wall of the chamber (1) to keep the airtight state of this portion. The manipulator (6) of the gas analysis room (2) always has the sample gripping part at the tip of the manipulator (6).
It is plugged into the gas analysis chamber (2) as it exists inside. A space between the manipulator (6) and the peripheral wall of the chamber (2) is also kept airtight by a seal member.

2 and 3 show specific examples of the discharge cleaning chamber (1) and the gas analysis chamber (2). The discharge cleaning chamber (1) and the gas analysis chamber (2) are each a vacuum consisting of a cylindrical body (36) and a top lid (37) and a bottom lid (38) that close the upper and lower ends of the cylindrical body (36). It consists of a tank. The top lid (37) is provided with a viewing window (39). Further, the discharge cleaning chamber (1) and the gas analysis chamber (2) are connected by a pipe (40) at the upper part.
The inside of 0) is the sample passage (3). The pipe (40) is provided with a closing member (4) composed of a sluice valve. Discharge cleaning chamber at the same height as the pipe (40)
Manipulator insertion ports (41) and (42) are provided on the right side surface of (1) and the left side surface of the gas analysis chamber (2), respectively. Also,
The discharge port (43) is located at the bottom of the right side of the discharge cleaning chamber (1), the current introduction terminal mounting port (44) is located at the upper part of the front side, and the Pirani vacuum gauge mounting port (45) is located at the bottom of the same. A discharge cleaning helium gas supply port (46) is provided at the upper part, and a Bayard-Alpert vacuum gauge mounting port (47) is provided at the lower part. Each of these ports (43) to (47) consists of a short cylindrical protrusion provided on the cylindrical body (36) and a flange provided at the tip of the protrusion, and these flanges are used. Current introduction terminal (7), Bayard-Alpert vacuum gauge (11) and Hipirani vacuum gauge (12) are attached to the respective mounting ports (44) (47) (45), and the exhaust pipe (14) and discharge cleaning The helium gas supply pipe (18) is connected to the respective connection ports (43) (46). In addition, a quadrupole mass filter attachment port (48) is provided on the upper side of the front side of the gas analysis chamber (2), a Bayard-Alpert vacuum gauge attachment port (49) is provided on the lower side of the rear side, and an exhaust port ( 50) is provided with two heater wire terminal mounting openings (not shown) on the lower surface. Each mouth (48)-(50) is a cylindrical body
It consists of a short cylindrical protrusion provided on (36) and a flange provided on the tip of the protrusion, and these flanges are used to make a quadrupole mass filter (27) and a Bayard-Alpert vacuum gauge (28 ) And the heater wire terminal (25) are attached to the respective mounting ports (48) and (49), and the exhaust pipe (31) is connected to the exhaust port (50).
It is designed to be connected to. An orifice forming plate (52) is interposed between the flange (50a) at the tip of the exhaust port (50) and the flange (31a) at the tip of the exhaust pipe (31).
An orifice (30) is formed at (52). Also the exhaust pipe
A Bayard-Alpert vacuum gauge mounting port (53) is provided in the part from the end in (31), where the Bayard-
An Alpert vacuum gauge (35) can be attached. This mounting port (35) also comprises a short cylindrical protrusion and a flange at the tip of the protrusion.

Next, a method of analyzing a trace amount of gas in an aluminum material using the device according to the present invention will be described.

First, after closing the sample passage (3) with the closing member (4), the inside of the gas analysis chamber (2) is evacuated by the vacuum exhaust device (26) to a high vacuum state (10 ⁻⁸ to 10 ⁻⁹ Torr). Order). The inside of the gas analysis chamber (2), the crucible (23) and the heater are
(24) is degassed. And the gas analysis room
The inside of (2) should always be kept in a high vacuum state. Then, while the gas analysis chamber (2) is being evacuated, the sample (S) is subjected to electric discharge cleaning in the electric discharge cleaning chamber (1). That is, after setting the sample (S) in the manipulator (5) of the discharge cleaning chamber (1), insert the tip of the manipulator (5) into the chamber (1) and insert the sample (S) into the internal conductor.
Contact (8). The inside of the discharge cleaning chamber (1) and the helium gas supply pipe (18) are previously subjected to a heating degassing process. In this state, the inside of the discharge cleaning chamber (1) is evacuated by the vacuum exhaust device (9) to a high vacuum state (on the order of 10 ⁻⁸ to 10 ⁻⁹ Torr), and then helium gas is replaced with helium gas. From the cylinder (19) through the trap (20) into the discharge cleaning chamber (1) 1 Tor
Introduce up to about r. Then, the sample (S) was used as a cathode, the discharge cleaning chamber (1) was used as an anode, and the sample (S) was subjected to discharge cleaning.
The surface gas of (S) is removed. Immediately after the discharge cleaning, the vacuum cleaning device (9) evacuates the interior of the discharge cleaning chamber (1) to a high vacuum state equivalent to the gas analysis chamber (2). Then the closure member
Open (4) and move the manipulator (5) in the discharge cleaning chamber (1) from the left, and the manipulator (6) in the gas analysis chamber (2) to the right to clean the discharge in the passage (3). Manipulator (5) from chamber (1) to manipulator (6) in gas analysis chamber (2)
The sample (S) is delivered to the manipulator in the gas analysis room (2).
(6) is moved to the left and the manipulator (5) of the discharge cleaning chamber (1) is moved to the right, and then the passage (3) is closed by the closing member (4). The delivery is not necessarily performed in the passage (3) and may be performed in either of the chambers (1) and (2). Furthermore, the crucible (2) that separates the sample (S) from the manipulator (6)
3) Drop inside. Finally, the crucible (23) is heated by the heater (24) to melt the sample (S) to extract the internal gas, and the amount of the gas is quantified by the quadrupole mass filter (27). In this way, the internal gas in the sample (S) is quantified.

The following is a description of an embodiment performed using the device according to the present invention.

That is, gas analysis was performed under the following conditions.

Specimen: Severe 99.99% high-purity aluminum Vacuum degree in the discharge cleaning chamber before discharge cleaning: 1 × 10 ^-8 Torr He amount introduced into the discharge cleaning chamber: 1 Torr discharge cleaning: 500 V × 1 hour Dose amount ... 1 × 10 ¹⁹ ions / cm ² As a result, the internal gas was H ₂ = 0.005 cc / 100 g Al and CO = 0.0001 cc / 100 g Al. The amount of surface gas such as H ₂ and CO is 10 ¹³ mol
This is a negligible amount of about ec / cm ² , and it can be seen that the surface gas of the sample (S) was sufficiently removed by the discharge cleaning in the discharge cleaning chamber (1).

Although helium gas is used as the discharge cleaning gas in the above embodiment, the discharge cleaning gas is not limited to this, and the discharge cleaning gas is inert to aluminum and exists in the aluminum material. It can be used as long as it does not exist. In this case, it is preferable to use a gas having a large mass number in order to shorten the time required to remove the surface gas. Further, in the above embodiment, the liquid nitrogen is contained in the trap, but the present invention is not limited to this, and any liquid having a higher melting point than the discharge cleaning gas can be used. By the way, the melting point of helium is -272.2 ° C (26 atm), and the boiling point is -268.9.
The melting point of nitrogen is -210.6 ° C (94 mm),
-209.9 ° C (1 atm), -208.8 ° C (55.4)
6 atm) and the boiling point is -195.8 ° C. The melting point of nitrogen is higher than that of helium.

Further, in the above embodiment, the extraction of the gas from the aluminum material is performed by the vacuum melting extraction method,
The extraction of the above-mentioned gas may be carried out by other known extraction methods, such as an argon blowing extraction method and a solid phase extraction method.
Further, in the above embodiment, the quantification of the internal gas of the aluminum material is performed by the quadrupole mass filter method, but this quantification may be performed by the gas chromatograph method, the palladium tube permeation method or the like.

Effect of the Invention Since the gas analyzer for aluminum material of the present invention is configured as described above, it is possible to analyze only the internal gas in the gas analysis chamber after performing the discharge cleaning in the discharge cleaning chamber to remove the surface gas. . Therefore, the internal gas can be accurately analyzed from a small number of samples. Further, by closing the sample passage with the closing member, the gas analysis chamber can be evacuated to a high vacuum state by the vacuum exhaust device during the discharge cleaning process of the sample in the discharge cleaning chamber. Moreover, after the discharge cleaning is completed, the evacuation device sets the discharge cleaning chamber to a high vacuum state equal to the gas analysis chamber and then the blocking member is opened, and the sample is transferred from the discharge cleaning chamber to the gas analysis chamber using the manipulator. It is possible to prevent the vacuum degree of the gas analysis chamber from being lowered when the sample is transferred. Therefore, the time required for analysis can be shortened by the time required to bring the gas analysis chamber into a high vacuum state. A crucible, a heater, etc. for extracting the gas in the sample are arranged in the gas analysis chamber, and it takes a long time to degas the gas adsorbed by the crucible, the heater, etc. Once the vacuum state is released, it takes a considerably long time to return to the vacuum state.

[Brief description of drawings]

FIG. 1 is a view for explaining the principle of the device of the present invention, FIG. 2 is a front view specifically showing the device of the present invention, and FIG. 3 is a plan view thereof. (1) ... Discharge cleaning chamber, (2) ... Gas analysis chamber, (3) ... Sample passage,
(4) ... Closing member, (5) (6) ... Manipulator, (9) ... Vacuum exhaust device, (26) ... Vacuum exhaust device, (S) ... Sample.

Claims (1)

[Scope of utility model registration request] 1. A discharge cleaning chamber (1), a vacuum exhaust device (9) provided in the discharge cleaning chamber (1), a gas analysis chamber (2), and a gas analysis chamber.
A vacuum exhaust device (26) provided in (2), a sample passage (3) provided between both chambers (1) and (2), and a closing member provided in the sample passage (3) so as to be openable and closable. (4) and the manipulator (5) which is provided in the discharge cleaning chamber (1) and the gas analysis chamber (2) and which transfers the sample (S) between the chambers (1) and (2) through the sample passage (3). (6)
And a gas analyzer for aluminum material.