JPH02254335A - Analyzer for gas in metallic material - Google Patents

Abstract

PURPOSE:To make it possible to determine only a minute amount of inner gas accurately with a small amount of a material by providing a sample introducing chamber, evacuating devices, surface-gas removing and gas analyzing chamber, a sample path, a closing member, a manipulator and the like. CONSTITUTION:A sample S is set in a manipulator 3 and inputted into a sample introducing chamber 1. Then, a sample path 3 is closed with a closing member 4. The inside of the chamber is evacuated with an evacuating device 6, and the inside of the sample introducing chamber 1 is made to be a high vacuum state. The inside of the surface-gas removing and gas analyzing chamber 2 is also evacuated with an evacuating device 39, and a high vacuum state is obtained. Then, the closing member 4 is opened, and the sample S is inputted into the chamber 2 with the manipulator 13. After the closing member 4 is closed, surface-gas removing treatment is performed for the sample S. Gas analysis is further performed in the chamber 2. During this period, another sample S is introduced into the sample introducing chamber 1, and the inside is made to be the high vacuum state. When the gas analysis of the first sample S is finished, the closing member 4 is opened, and another sample S is inputted into the chamber 2. After the closing member 4 is closed, the surface gas removing treatment is performed for this sample by the same way.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to an apparatus for analyzing minute amounts of gas in metal materials such as aluminum, copper, iron, magnesium, etc.

In this specification, words indicating metals such as "aluminum,""copper,""iron," and "magnesium" include each alloy as well as a pure metal.

Prior Art and Problems of the Invention For example, aluminum materials contain internal gases and gases adsorbed on their surfaces, and substances such as water that react with aluminum and generate gases are adsorbed on their surfaces. These gases are mainly H2 gas, with very small amounts of CO gas, CO2 gas, H20 gas, etc. also present. Depending on the use of aluminum material,
Since the above gases are extremely harmful, it is necessary to reduce the amount of these gases to a very small amount. There has been some success with regard to gas). However, the reality is that sufficient research has not yet been conducted on internal gases.

If the amount of internal gas in the aluminum material, especially H2 gas, is large, the following problems occur. In other words, when aluminum material is used for ultra-high vacuum or ultra-high vacuum applications, for example in particle acceleration pipes (beam lines) used in accelerators such as synchrotrons, when a beam is run inside the pipe, a large amount of The problem is that gas is released and the pressure inside the pipe becomes very high. This is the result of the synchrotron radiation emitted from the beam entering the inner surface of the pipe and knocking out the gas inside the aluminum material. In addition, when aluminum material is used for a young substrate, Se, A-8i, etc. are applied to the surface of the substrate.
A phenomenon called "blister" occurs, and it is known that this is also caused by the release of internal gas. Furthermore, it is known that surface defects such as cracks, blisters, and skin scratches that occur during rolling are due to the effects of internal gases in aluminum materials. Therefore, there is a demand for the development of an aluminum material with an extremely small amount of internal gas, but in developing an aluminum material with a very small amount of internal gas, it is necessary to accurately analyze the internal gas.

Conventionally, the analysis of internal gas in aluminum materials has been carried out using the following two methods.

(a) A method in which a plurality of samples with different surface area to volume ratios are prepared from the same material, and each sample is subjected to gas analysis to quantify internal gas and surface gas.

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

However, each of the above methods had the following drawbacks. That is, in the method (a), it is necessary to prepare many samples, and there is non-uniformity in the samples regarding the actual surface and internal gas. In method (b),
Accurate separation of surface gas and internal gas is difficult, and moreover, variations in surface gas occur, making accurate quantification impossible. Due to these drawbacks, the conventional method has a problem in that it is not possible to 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-mentioned problems and to provide a gas analyzer in a metal material that can accurately quantify only a trace amount of internal gas using a small amount of material in a short time.

Means for Solving the Problems The first gas analyzer in a metal material according to the present invention performs surface gas removal treatment on the surface of the metal material, heats the metal material to extract internal gas, and performs quantitative analysis. The apparatus includes a sample introduction chamber, a vacuum evacuation device provided in the sample introduction chamber, a surface gas removal treatment and gas analysis chamber equipped with a surface gas removal treatment device, a gas extraction device, and a gas quantitative device; A vacuum exhaust device installed in the gas removal processing and gas analysis room,
A sample passage provided between the sample introduction chamber and the surface gas removal processing/gas analysis chamber, a closing member provided in the sample passage so as to be openable and closable, and a sample passage provided between the two chambers through the sample introduction chamber and the sample passage. The device is equipped with a manipulator that transfers the sample and holds the sample during the surface gas removal process.

The second gas analyzer in a metal material according to the present invention is an apparatus for performing a surface gas removal treatment on the surface of a metal material, and then heating the metal material to extract and quantify the internal gas, An introduction chamber, a vacuum evacuation device provided in the sample introduction chamber, a surface gas removal processing chamber equipped with a surface gas removal processing device, a vacuum evacuation device provided in the surface gas removal processing chamber, a gas extraction device, and a gas extraction device provided in the surface gas removal processing chamber. A gas analysis room equipped with quantitative equipment,
A vacuum evacuation device installed in the gas analysis chamber, sample passages installed between the sample introduction chamber and the surface gas removal processing chamber, and between the surface gas removal processing chamber and the gas analysis chamber, and each sample passage. A closing member that can be opened and closed freely is used to introduce the sample into the sample introduction chamber, carry the sample into the surface gas removal treatment chamber through the sample passage, hold the sample during the surface gas removal treatment, and further perform the surface gas removal treatment. It is equipped with a manipulator that transports the sample to the gas analysis chamber.

After setting the sample on the operation manipulator and putting the sample into the sample introduction chamber, the The sample passage is closed with a closing member and evacuated using a vacuum evacuation device to bring the inside of the sample introduction chamber into a high vacuum state. −
On the other hand, the surface gas removal treatment and gas analysis chamber or the surface gas removal treatment chamber is also evacuated to a high vacuum state using a vacuum evacuation device. Next, the closing member is opened and the sample is put into the surface gas removal processing and gas analysis chamber or the surface gas removal processing chamber using the manipulator, and after the closing member is closed, the sample is subjected to the surface gas removal treatment, and then the sample is subjected to the surface gas removal processing and gas analysis chamber. Perform gas analysis in the gas analysis room or inside the gas analysis room. During this time, another sample is introduced into the sample introduction chamber, and the interior thereof is kept in a high vacuum state. When the gas analysis of the first sample is completed, open the closing member, place another sample into the surface gas removal treatment and gas analysis chamber, or the surface gas removal treatment chamber, close the closing member, and proceed in the same manner as above. This sample is subjected to surface gas removal treatment.

Example Embodiments of the invention will be described below with reference to the drawings.

The same parts and parts are denoted by the same reference numerals throughout the drawings, and their explanation will be omitted.

In FIGS. 1 and 2 showing the configuration of the first embodiment of the apparatus according to the present invention, the apparatus for analyzing a trace amount of gas in a metal material includes a sample introduction vacuum chamber (1) (sample introduction chamber). , vacuum chamber for surface gas removal treatment and gas analysis (2
) (surface gas removal processing and gas analysis room).

A sample passage (3) is provided between the two vacuum chambers (1) and (2), and a closing member (4) that can be opened and closed is provided in this sample passage (3).

There is a peephole (5) on the top wall of the sample introduction vacuum chamber (1).
) is formed. In addition, a vacuum chamber for sample introduction (
1) is equipped with a vacuum evacuation device (6) and a Payart Albert vacuum gauge (7) (hereinafter referred to as BA vacuum gauge) for measuring the degree of vacuum in the sample introduction vacuum chamber (1). The vacuum exhaust device (6) is a sample introduction vacuum chamber (1
) connected to the aluminum vacuum exhaust pipe (8)
It consists of a valve (9), a turbo-molecular pump (IO), and a rotary pump (11), which are installed in the exhaust pipe (8) in series from the vacuum chamber (1) side in the following order.

The sample introduction vacuum chamber (1) also includes a sample introduction manipulator (13) for introducing the sample (S) into the chamber through a sample inlet (12) formed on its side wall. The sample inlet (12) is closed when the manipulator (13) is taken out. A sealing device (not shown) seals between the periphery of the manipulator (13) and the sample inlet (12). The manipulator (I3) has a clamping function, an axial movement function and a rotational movement function.

An ion gun (■5) for ion beam etching is installed on the top wall of the vacuum chamber (2) for surface gas removal processing and gas analysis.
, an analysis device (1B) that analyzes the surface state of the sample (S) after ion beam etching by Auger electron spectroscopy.
, and a peephole (17) are provided, and a BA vacuum gauge (18) is provided at the top of the side wall of this vacuum chamber (2).
, and a four-electrode mass filter (19) for analyzing gas extracted from the sample (S). Ion gun (
The casing (21) of 15) is equipped with a vacuum exhaust device (22).
) and an inert gas supply device (23). The evacuation device (22) includes an aluminum evacuation exhaust pipe (24) connected to the casing (21), and valves installed in the exhaust pipe (24) in series from the casing (21) side in the following order. (25), turbomolecular pump (
26) and a rotary pump (27). The inert gas supply device (23) is an aluminum supply pipe (2B
) and an inert gas cylinder (29) connected to the casing (21) via a gas cylinder (29) and a supply pipe (28) that has a temperature higher than the boiling point of the substance in the inert gas cylinder (29) and as much as possible. A trap (3o) containing a liquid of a substance such as liquid nitrogen having a melting point close to the boiling point of the substance in the cylinder (29) to remove impurities contained in the inert gas, and a casing (2) in the supply pipe (28).
1) and a variable leak valve (31) provided between the trap (30) and the trap (30). Also, ion gun (15)
A throttle nozzle (32) is interposed between the casing (21) and the vacuum chamber (2).

The inert gas introduced into the ion gun (I5), ionized, and accelerated passes through the throttle nozzle (32) and enters the vacuum chamber (2), and enters the sample holding manipulator (33), which will be described later. ) (34) so as to collide with the sample (S) held by the sample (S).

The vacuum chamber (2) for surface gas removal processing and gas analysis is
A pair of sample holding manipulators (33) (34) for holding the sample (S) during ion beam etching are installed at the height position corresponding to the sample passageway (3), in front and behind it (upper and lower in FIG. 2). It is equipped with Manipulator (33
) (34) and the wall of the vacuum chamber (2) are sealed by a sealing device (not shown). The manipulators (33) and (34) have a clamping function, an axial movement function and a rotational movement function. In addition, the sample gripping parts (33a) (34) of the manipulators (33) (34)
At least the part of a) that comes into contact with the sample (S) is
B.N.

It is made of ceramics such as TiN, TiC, and CrH. Among these ceramics, it is preferable to use BN. Sample gripping part (33a) (34a
), if at least the part that contacts the sample (S) is made of ceramics, the surface of the sample (S) may be subjected to ion beam etching to make the surface active. and sample (S) cannot be the host rock.

A rotatable sample melting table (35) is installed at the bottom of the vacuum chamber (2) for surface gas removal processing and gas analysis, and a plurality of BN samples are placed on this table (35). A melting crucible (36) is placed thereon. The sample melting crucible (36) is heated by a heat source (37). Since the BN sample melting crucible (36) is a material that contains few impurities and releases little gas, even if it is heated in a high vacuum state, the rate of gas release is small and the accuracy of gas analysis can be improved. By rotating the mounting table (35), all crucibles (36) can be sequentially moved to predetermined sample heating and melting positions. Vacuum chamber for surface gas removal treatment and gas analysis (2
), the height position between the manipulators (33) (34) and the crucible (3G) is such that it tapers downward and the lower end opening is located directly above the crucible (3G) at the sample heating and melting position. A funnel-shaped guide (38) is provided. The funnel-shaped guide (38) allows the manipulator (33
) (34) to ensure that the sample (S) falls into the crucible (36) at the sample heating and melting position. The funnel-shaped guide (38) is preferably made of a material with low outgassing, such as stainless steel, aluminum, or ceramics. Below the funnel-shaped guide (38), a vacuum exhaust device (39) is provided at the bottom of the vacuum chamber (2) for surface gas removal and gas analysis. This evacuation device (39) includes an evacuation pipe (4) connected to the vacuum chamber (2) via an orifice (41).
2) and the vacuum chamber (2) to the exhaust pipe (42) in the following order.
) A valve (43), a turbo molecular pump (44), and a rotary pump (45) are provided in series from the side. Also, a BA vacuum gauge (4
B) and analyzing the gas extracted from the sample (S) 4
An electrode mass filter (47) is provided.

Next, a method of analyzing a trace amount of gas in an aluminum material using the apparatus shown in FIGS. 1 and 2 will be described.

First, insert the sample (S) into the sample introduction manipulator (13).
is set, and this sample (S) is introduced into the sample introduction vacuum chamber (1) through the sample inlet (12). Then,
After closing the sample passage (3) with the closing member (4), the vacuum evacuation device (6) evacuates the sample introduction vacuum chamber (1) to a high vacuum state (10-8 to 10-9 Torr).
order). - side, vacuum exhaust device (39), (
22), the inside of the vacuum chamber (2) for surface gas removal processing and gas analysis and the inside of the ion gun (15) are brought into a high vacuum state (on the order of 10-8 to 10-' Torr). Vacuum chamber for surface gas removal treatment and gas analysis (2
) is always kept in a high vacuum state. In addition, the inner surface of the vacuum chamber (2) for surface gas removal processing and gas analysis, the crucible mounting table for sample melting (35), and the crucible for sample melting (3B)
The funnel-shaped guide (38) is previously subjected to heating and degassing treatment. Then, open the closing member (4), advance the sample introduction manipulator (13) to the left, and insert the sample (S).
is transferred from this manipulator (13) to one manipulator (33) of the vacuum chamber (2) for surface gas removal processing and gas analysis. Manipulator for sample introduction (
13) is moved to the right to close the sample passageway (3) with the closing member (4). In this state, N is inside the ion gun (15).
An inert gas such as e, Ar, etc. is introduced and ionized. The ionized inert gas is drawn out, accelerated by an electrode and an accelerating electrode, and passed through a throttle nozzle (32) to elastically collide with the sample (S).

In this way, the sample (S) is subjected to ion beam etching to remove surface gas. At this time, the pressure inside the ion gun (15) increases by introducing inert gas, but
Due to the action of the throttle nozzle (32), the degree of pressure increase in the vacuum chamber (1) becomes smaller than the degree of pressure increase in the ion gun (15), which naturally reduces the amount of impurities in the vacuum chamber (2). is less, about 1/3
It will be about 00. Therefore, the amount of impurities adsorbed on the surface of the sample (S) after ion beam etching can be reduced. Then, move the sample (S) to the other manipulator (34).
The surface gas is removed by ion beam etching in the same manner as above. After confirming that the surface gas has been removed from the sample (S) by the analyzer (1B), the sample (S) is removed from the manipulator (34) and passed through the funnel-shaped guide (38) to the crucible (36). The sample (S) is melted by heating the crucible (36) with a heat source (37), the internal gas is extracted, and the amount of gas is quantified using a four-electrode mass filter (15). While performing ion beam etching and gas analysis in the vacuum chamber (2) for surface gas removal processing and gas analysis,
A new sample (S) is placed in the sample introduction vacuum chamber (1).
is introduced and the inside is kept in a high vacuum state. and,
After the gas analysis of the first sample (S) is completed, a new sample (S) is placed in the vacuum chamber for surface gas removal treatment and gas analysis (
2) Insert the gas into the chamber and perform gas analysis. 1 crucible (36)
When the crucible becomes full, the mounting table (35) is rotated and the other crucible (35) is moved to the sample heating and melting position. In this way, a large number of samples (S) can be obtained using all crucibles (3B).
Continuously perform gas analysis on

FIG. 3 shows a second embodiment of the device according to the invention. Third
In the figure, an apparatus for analyzing a trace amount of gas in a metal material includes a vacuum chamber for sample introduction (1), a vacuum chamber for surface gas removal treatment (50), and a vacuum chamber for gas analysis (51). ing. Vacuum chamber for sample introduction (
1) and the vacuum chamber for surface gas removal processing (50), and between the vacuum chamber for surface gas removal processing (50) and the vacuum chamber for gas analysis (51), there are sample passages (3) (52), respectively. ), and each sample passage (
3052) are provided with closing members (4) and (53) that can be opened and closed.

An ion gun (15) for ion beam etching and an analyzer (16L) for analyzing the surface state of the sample (S) after ion beam etching by Auger electron spectroscopy are installed on the top wall of the vacuum chamber (50) for surface gas removal processing. and a peephole (17), and this vacuum chamber (5
A BA vacuum gauge (54) is provided at the top of the side wall of 0). The vacuum chamber (50) also includes a sample passageway (3).
) (52), before and after that,
A pair of sample holding manipulators (33) and (34) are provided to hold the sample (S) during ion beam etching. A vacuum exhaust device (57) is provided at the bottom of the surface gas removal processing vacuum chamber (50). This evacuation device (57) is provided in series from the vacuum chamber (50) side with an evacuation pipe (58) connected to the vacuum chamber (50) and the exhaust pipe (58) in the following order. It consists of a valve (59), a turbomolecular pump (60) and a rotary pump (61). At the top of the side wall of the gas analysis vacuum chamber (51), a BA vacuum gauge (18),
A four-positive electrode mass filter (19) for analyzing the gas extracted from the sample (S) is provided, and a rotatable sample melting crucible mounting table (35) and a funnel-shaped guide (38) are provided inside the filter. It is being In addition, a vacuum exhaust device (3) is installed at the bottom of the gas analysis vacuum chamber (51).
9) is provided. Further, the gas analysis vacuum chamber (51) receives the sample (S) that has been subjected to ion beam etching in the vacuum chamber (50) from the manipulator (34), and passes the sample (S) through the sample passage (52) to the gas analysis vacuum chamber (51). A manipulator (5) for transporting into the chamber (51)
6). Around the manipulator (56),
A sealing device (not shown) is used to seal between the vacuum chamber (51) and the manipulator insertion port (55) formed in the wall of the vacuum chamber (51). The manipulator (56) has a clamping function, an axial movement function and a rotational movement function.

In the apparatus shown in FIG. 3, gas analysis in the sample (S) is performed by surface gas removal treatment by ion beam etching,
The gas analysis is performed in substantially the same manner as in the apparatus shown in FIGS. 1 and 2, except that the gas analysis and analysis are performed in separate vacuum chambers (50) and (51).

In the above embodiments, the surface gas removal process is performed by ion beam etching, but the present invention is not limited to this.

Effects of the Invention According to the gas analyzer in a metal material of the present invention, only the internal gas can be analyzed after removing the surface gas of the metal material as described above, so that the internal gas can be accurately analyzed from a small number of samples. . In addition, by keeping the closing member of the sample passage closed, it is possible to introduce another sample into the sample introduction chamber while performing gas analysis in the surface gas removal treatment and gas analysis chamber or the gas analysis chamber. , it is possible to keep the inside of the chamber in a high vacuum state, and the surface gas removal treatment and gas analysis chamber, or the gas analysis chamber, can be kept in a high vacuum state at all times, so each time a gas analysis of one sample is performed. There is no need to release the vacuum state in each chamber, but only for the time necessary to bring the surface gas removal processing and gas analysis chamber, or the surface gas removal processing chamber and gas analysis chamber, to a high vacuum state.
The time required for analysis can be shortened.

[Brief explanation of drawings]

1 and 2 show the configuration of a first embodiment of the device according to the present invention, FIG. 1 is a front view, FIG. 2 is a plan view, and FIG. 3 is a second embodiment of the device according to the invention. FIG. (1)...Vacuum chamber for sample introduction (sample introduction chamber) (
2)... Vacuum chamber for surface gas removal processing and gas analysis (surface gas removal processing and gas analysis chamber), (3)... Sample passage, (4)... Simplicity member, (6)...・Vacuum exhaust device, (13) ... Manipulator for sample introduction, (1
5)...Ion gun (surface gas removal treatment device), (19
) (47)... 4-electrode mass filter (gas quantitative device), (33) (34)... sample holding manipulator, (35)... crucible, (37)... heating source, (3
9)...Evacuation device, (50)...Vacuum chamber for surface gas removal processing (surface gas removal processing chamber), (51
)...Vacuum chamber for gas analysis (gas analysis room), (
S)...Sample. Patent applicant: Showa Aluminum Co., Ltd. No. 90

Claims (1)

[Claims] 1. An apparatus for performing surface gas removal treatment on the surface of a metal material, then heating the metal material to extract and quantify internal gas, comprising: a sample introduction chamber; and a sample introduction chamber. A vacuum evacuation device installed in the surface gas removal processing and gas analysis room equipped with a surface gas removal processing device, a gas extraction device, and a gas quantitative device, and a vacuum evacuation device installed in the surface gas removal processing and gas analysis room. a sample passage provided between the sample introduction chamber and the surface gas removal processing and gas analysis chamber; a closing member provided in the sample passage so as to be openable and closable; A gas analyzer in a metal material, which includes a manipulator that transfers a sample between chambers and holds the sample during surface gas removal treatment. 2. A device that performs surface gas removal treatment on the surface of a metal material, then heats the metal material to extract and quantify the internal gas, which includes a sample introduction chamber and a vacuum exhaust system installed in the sample introduction chamber. equipment, a surface gas removal processing chamber equipped with a surface gas removal processing device, a vacuum evacuation device installed in the surface gas removal processing chamber, a gas analysis room equipped with a gas extraction device and a gas quantitative device, and a gas analysis room. A vacuum exhaust device installed in
A sample passage provided between the sample introduction chamber and the surface gas removal processing chamber and between the surface gas removal processing chamber and the gas analysis chamber, a closing member provided in each sample passage so that it can be opened and closed, and a sample introduction A manipulator that introduces the sample into the chamber, carries the sample into the surface gas removal treatment chamber through the sample passage, holds the sample during the surface gas removal treatment, and further conveys the sample subjected to the surface gas removal treatment to the gas analysis chamber. A device for analyzing gases in metal materials.