JP3359983B2 - Glow discharge emission spectroscopy cathode plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cathode plate for glow discharge emission spectroscopy, and more particularly to a cathode plate for analyzing a sample having a curved surface.

[0002]

2. Description of the Related Art Glow discharge optical emission spectroscopy is a method for obtaining information on the distribution of elements from a solid surface in the depth direction, and is widely used industrially. For example, the industrial application range of this analysis method for evaluating metal plates and the like, such as the composition distribution of various elements in the steel plate in the depth direction, is extremely wide.

[0003] In the conventional glow discharge emission spectroscopy, it is usually possible to use only a flat plate material of several cm square. As shown in FIG. Is evacuated 17 by an evacuation pump (not shown). At this time, the vacuum is maintained by the O-ring 5, and the flat analysis sample 16 is mounted on the flat cathode plate 15 by a pressing mechanism (not shown), for example, an air cylinder attached to the glow discharge emission spectrometer main body. You. Thereafter, the degree of vacuum is set from 1 Torr to 20 Torr, and an argon gas 18 is introduced. When a voltage of about 1000 V is applied between the flat cathode plate (cathode) 15 and the anode (anode) 19, a glow discharge is generated, and the ionized gas sputters the flat plate-shaped analytical sample 16 of the cathode. The generated atoms emit light by excitation. The generated light passes through the window plate 20 and is measured by the spectroscope 21. By this method, usually 100
A film or a surface layer having a thickness of less than μm can be analyzed. Further, by this method, a composition of up to about 0.1 atomic% can be analyzed.

However, in the conventional glow discharge emission spectroscopy shown in FIG. 4, the shape of the sample is limited to a flat plate, and when the sample has a curvature such as a roll, a tube, a round bar, or the like. Since the discharge light emitting unit 2 cannot maintain a vacuum, it cannot be applied to a sample having a curvature.

In order to solve this problem, Japanese Utility Model 5-2
No. 8516 proposes a sample holder of a glow discharge optical emission spectrometer for a sample having a curvature as shown in FIG. 5, FIG. 6 and FIG. FIG. 6 is a sectional view showing a state where the block body 22 shown in FIG. 5 is attached to a glow discharge optical emission spectrometer, and FIG. 7 is an external perspective view thereof.
The block body 22 shown in FIG. 5 is provided with a measurement hole 24 at the center of a surface 23 in contact with the flat cathode plate 15 of the glow discharge optical emission spectrometer, and a sealing ring 25 for holding a vacuum at a position surrounding the measurement hole 24. , A sample insertion hole 26 communicating with the measurement hole 24 is provided. In this analysis method, a rod-shaped sample 27 having a curvature is inserted into the sample insertion hole 26 of the block 22 and the rod-shaped sample 2 is made of an epoxy resin.
7 and the block body 22 are sealed, and are pressed and fixed with fixing screws 28 as shown in FIG. 7 to perform measurement.

In the analysis method shown in FIG. 7, the shape of the flat cathode plate 15 for a flat test piece can be used, but the rod sample 27 needs to be bonded to the block body 22 with epoxy resin, Since the same number of blocks 22 as the sample 27 are required, there is a disadvantage that a rapid and large amount of analysis cannot be performed.

Japanese Utility Model Publication No. 5-31558 discloses a glow discharge optical emission spectrometer for analyzing a sample having a curvature as shown in FIG. The analysis sample 4 having the curvature of the flat cathode plate 15 of this analyzer.
The O-ring 5 is attached so as to surround the opening 3 of the discharge light emitting unit 2. The analysis sample 4 is fixed by the flat cathode plate 1.
A suction cup 29 fixed with screws on the outer periphery of the sample 5 is brought into close contact with the analysis sample 4, and the space 30 between the flat cathode plate 15 and the analysis sample 4 is evacuated by a vacuum pump 31. Is fixed to the flat cathode plate 15.

However, in this fixing method, the force for pressing the analysis sample 4 against the flat cathode plate 15 is weak.
In addition, since the flat surface of the flat cathode plate 15 of the analyzer in contact with the analysis sample 4 is flat, a gap is generated between the analysis sample 4 and the flat cathode plate 15 and the O-ring 5, and a glow discharge occurs. If a voltage is applied to cause the discharge, abnormal discharge occurs in the gap, and the flat cathode plate 15 is damaged.

In addition, Japanese Utility Model Publication No. 3-91959 discloses FIG.
1 shows a sample mounting device for glow discharge emission spectroscopy for analyzing a sample having a curvature as shown in FIG. In this analysis method, a flat plate-like cathode plate 15 is used for a conventional flat plate, but a method using a sample holder to analyze the analysis sample 4 having a curvature is used. The analysis method in this case is as follows. First, the analysis sample 4 is placed on the holding spring-type fixing jig 33 in the sample holding lower holder 32, and the O-ring 34 is inserted into the O-ring groove. The sample holder 32 and the sample storage upper holder 35 are fastened with fixing screws 36. And analysis sample 4
The flat adjustment holder 37 having the same curvature as that described above is placed on the analysis sample 4, and the O-ring 38 is inserted into the O-ring groove of the sample storage upper holder 35, and the sample storage upper and lower holders 32 and 35 are illustrated. The sample is fixed to the flat cathode plate 15 by a sample pressing device 39 which is not provided.

However, in this method, it is necessary to put the analysis sample 4 in the upper and lower holders 32 and 35 for storing the sample, and to evacuate all the upper and lower holders 32 and 35 for storing the sample. Therefore, there is a drawback that a rapid and large amount of analysis cannot be performed. Further, in order to mount the flat adjustment holder 37 on the sample storage upper holder 35, there must be a certain gap between them, but abnormal discharge is likely to occur in this gap, and it is difficult to perform stable measurement. There is a disadvantage that there is.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and makes it possible to analyze a sample having a curved analysis surface in glow discharge emission spectroscopy. An object of the present invention is to provide a cathode plate for glow discharge emission spectroscopy.

[0012]

According to the present invention, there is provided a cathode plate in a glow discharge optical emission spectrometer, comprising:
A concave portion 1a having the same curvature as the analysis sample 4 is provided in the opening 3 of the discharge light emitting portion 2 of FIG. A cathode plate 1 in a glow discharge emission spectrometer;
A concave portion having the same curvature as the analysis sample 4 is provided in the opening 3 of the discharge light emitting section 2 of the cathode plate 1, and the sample holder 7 for holding the analysis sample 4 on the cathode plate 1 and the analysis sample 4 are connected to the cathode. Plate 1
A glow discharge emission spectroscopy cathode plate, comprising: a pressing mechanism 8 for pressing against the surface of the cathode plate.

[0013]

The operation of the present invention will be described in detail with reference to the drawings. FIG. 1 shows a state in which a cathode plate 1 for glow discharge emission spectroscopy, in which an opening 3 of a discharge light emission part 2 of the present invention is provided with a concave portion 1a having the same curvature as an analysis sample 4, is mounted on a glow discharge emission spectrometer. is there. FIG.
Shows an apparatus having a pressing mechanism 8 and a sample holder 7.

An analysis sample 4 is placed on the opening side of the opening 3 of the discharge light emitting portion 2 of the cathode plate 1 for glow discharge emission spectroscopy.
A concave portion 1a having the same curvature as that of FIG. The size of the concave portion 1a is larger than the diameter of the opening 3 of the discharge light emitting portion 2, and the O-ring 5 is inserted between the concave portion and the analysis sample 4 so that the discharge light emitting portion 2 can maintain a vacuum. It is necessary to make the size such that the ring groove 6 can be provided. When the curvature of the analysis sample 4 changes, the glow discharge emission spectroscopy cathode plate 1 is brought into close contact with the concave portion on the opening side of the opening 3 of the discharge light emitting portion 2 of the cathode plate 1 so as to prevent abnormal discharge from occurring. Therefore, the curvature of the concave portion on the opening side of the opening 3 of the discharge light emitting portion 2 of the glow discharge emission spectral analysis cathode plate 1 needs to be provided with the same curvature as that of the analysis sample 4.

The O-ring 5 is mounted on the O-ring groove 6 of the cathode plate 1 for glow discharge emission spectroscopy. The O-ring used at this time is for maintaining the discharge light emitting unit 2 in a vacuum. In order to stably maintain the vacuum of the discharge light emitting unit 2, the O-ring 5 has a large elastic modulus. For example, rubber or the like is preferable. The shape may be a disk shape. Next, the analysis sample 4 is mounted. The analysis sample 4 is supported by the sample holder 7, and the analysis sample 4 is brought into close contact with the opening 3 of the discharge light emitting section 2 of the glow discharge emission spectroscopy cathode plate 1 by a pressing mechanism 8. Press.

The sample holder 7 serves to horizontally support the analysis sample 4 on the opening side of the cathode plate 1 and also determines the analysis position of the analysis sample 4. It is desirable that the sample holder 7 has conductivity, for example, a metal plate or the like. The sample holder 7 is connected to the glow discharge emission spectroscopy cathode plate 1 by screwing, welding, bonding, or the like so that the deviation from a right angle is 5/1000 mm or less.

The pressing mechanism 8 presses the analysis sample 4 so that no gap is formed in the opening 3 of the discharge light emitting section 2 of the cathode plate 1 for glow discharge emission spectroscopic analysis. The pressing mechanism 8 is fixed to the connecting rod 9 with a connecting rod 9 connected to the cathode plate 1 by screws, a pressing plate 10 for pressing the analysis sample, a fastening nut 11 for pressing the pressing plate 10 against the analysis sample 4, and a positioning nut 12. The pressing plate fixing plate 13 and the pressing nut 10 for fixing the pressing plate 10 to the pressing plate fixing plate 13 are provided. It is desirable that the surface of the pressing plate 10 in contact with the analysis sample has a shape having the same curvature as the analysis sample 4. Tightening nut 1
By rotating the sample 1, the analysis sample 4 is pressed against the opening 3 of the discharge light emitting section 2 of the cathode plate 1 for glow discharge emission spectroscopy.

By making the connecting rod 9 longer than the diameter of the analysis sample 4, cutting of the analysis sample 4 or the like becomes unnecessary, and a large amount of sample can be analyzed in a short time. Here, as the pressing mechanism 8, a method in which a screw is tightened is taken as an example. However, the analysis sample 4 is placed so that no gap is formed in the opening 3 of the discharge light emitting unit 2 of the cathode plate 1 for glow discharge emission spectral analysis. It is not limited to this as long as it is a pressing mechanism. For example, the pressing plate 10 as shown in FIG.
A mechanism for pressing the analysis sample 4 using the 1-1 or the air cylinder 11-2 may be used.

[0019]

EXAMPLE An example using the cathode plate for glow discharge emission spectroscopy of the present invention will be described. First, an embodiment in which the glow discharge emission spectroscopy cathode plate 1 does not have the sample holder 7 and the pressing mechanism 8 will be described. As the analysis sample 4, a hot rolling experiment was performed, and a rolling roll having a diameter of 80 mm and a thickness of 10 mm on which an oxide film was formed was used. Since the analysis sample 4 has a curvature, the discharge light emitting section 2 cannot be kept in a vacuum in the conventional flat plate glow discharge emission spectrometer as shown in FIG. The analysis sample 4 is cut out from the circumference to a thickness of 2 mm in the radial direction, and the opening 3 of the discharge light emitting portion of the present invention is attached to the cathode plate 1 for glow discharge emission spectroscopy having the same curvature as the analysis sample 4, and the discharge is performed. When the light emitting part 2 was exhausted,
A degree of vacuum of rr or less could be obtained. Then, while introducing and evacuating Ar gas so that the degree of vacuum of the discharge light emitting unit 2 becomes 10 Torr, a voltage of 600 V was applied to the analysis sample 4 as a cathode to discharge and emit light. At this time, as shown in FIG.
The relationship between the emission intensity of e and O and the emission time was obtained. From this result, it can be seen that even in a sample having a curvature, the element in the depth direction can be analyzed.

Next, an embodiment in which the glow discharge emission spectroscopy cathode plate 1 has a sample holder 7 and a pressing mechanism 8 will be described. As the analysis sample 4, a hot rolling experiment was performed, and a rolling roll having a diameter of 80 mm and a thickness of 10 mm on which an oxide film was formed was used. As the pressing mechanism 8, a mechanism made of a metal plate and a rod is used. The tightening nut 11 is rotated, and the analysis sample 4 is pressed against the opening 3 of the discharge light emitting unit 2 by the pressing plate 10. The analysis sample 4 was supported by the sample holder 7 and pressed against the opening 3 of the discharge light emitting section 2 of the glow discharge emission spectroscopy cathode plate 1 by the pressing mechanism 8. Thereafter, the discharge light emitting section 2 is evacuated to 1 Torr or less, and then Ar is adjusted to 10 Torr.
While introducing and exhausting a gas, a voltage of 600 V was applied to the analysis sample 4 as a cathode to discharge and emit light. As a result, discharge light emission occurred, and the same relationship between the light emission intensity of Fe and O and the light emission time as shown in FIG. 3 was obtained. The use of the sample holder 7 and the pressing mechanism 8 eliminates the need to cut the analysis sample 4 and allows a large amount of sample to be analyzed in a short time.

[0021]

By using the cathode plate for glow discharge emission spectroscopy of the present invention, it becomes possible to perform surface analysis by glow discharge emission spectroscopy on a sample having a curved surface, which was impossible in the conventional analysis. Was. As a result, there is no limitation on the surface shape of the sample for surface analysis, the versatility of the glow discharge optical emission spectrometer is greatly expanded, and the effect in evaluating the material surface is great.

[Brief description of the drawings]

FIG. 1 shows an embodiment of a cathode plate for glow discharge emission spectroscopy according to the present invention, wherein (a) is a top view,
(B) is a side view. 1 shows a state in which an analysis sample having a curvature is attached to a cathode plate for glow discharge emission spectroscopy of the present invention using a sample holder and a pressing mechanism.

FIGS. 2A and 2B are top views of another embodiment of the cathode plate for glow discharge emission spectroscopy of the present invention, wherein FIG. 2A shows an example having a pressing mechanism provided with a pressing plate and a spring, and FIG. The example which has the press mechanism provided with the air cylinder is shown.

FIG. 3 is a diagram showing the relationship between the luminescence intensity of Fe and O and the luminescence time by glow discharge emission spectroscopy analysis of an oxide film on the surface of a roll obtained by using an analyzer equipped with the cathode plate of the present invention.

FIG. 4 is a diagram showing a state in which a flat sample is attached to a conventional glow discharge optical emission spectrometer.

FIG. 5 is a diagram showing a block body used when analyzing a sample having a curvature in the related art.

6 is a diagram showing a state where the block body shown in FIG. 5 is attached to a glow discharge optical emission spectrometer.

7 is a diagram showing an external perspective view of FIG. 6;

FIG. 8 is a view showing a state in which a sample having a curvature is attached to a glow discharge optical emission spectrometer in a conventional technique.

FIG. 9 is a diagram showing a state in which a sample having a curvature is attached to a glow discharge optical emission spectrometer in a conventional technique.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 Glow discharge emission spectroscopy cathode plate 1 a Depressed portion of cathode plate 2 Discharge light emitting portion 3 Opening 4 Analysis sample 5 O-ring 6 O-ring groove 7 Analysis sample holder 8 Pressing mechanism 9 Connecting rod 10 Pressing plate 11 Fastening nut DESCRIPTION OF SYMBOLS 12 Positioning nut 13 Pressing plate fixing plate 14 Holding nut 15 Flat cathode plate 16 Flat sample 17 Vacuum exhaust port 18 Argon gas inlet 19 Anode 20 Window plate 21 Spectrometer 22 Block body 23 Surface in contact with cathode plate 24 Measurement hole 25 Sealing Stop ring 26 Sample insertion hole 27 Sample 28 Fixing screw 29 Suction cup 30 Space 31 Vacuum pump 32 Sample holding lower holder 33 Sample holding spring type fixing jig 34 O-ring 35 Sample holding upper holder 36 Sample holding holder fastening screw 37 Flat tone Use holder 38 O-ring 39 sample pressing device

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsuyoshi Inoue 20-1 Shintomi, Futtsu City, Chiba Prefecture Nippon Steel Corporation Technology Development Division (72) Inventor Shigeru Suzuki 20-1 Shintomi, Futtsu City, Chiba Prefecture New Japan Tetsuo Uemura, Inventor 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (72) Inventor Tomio Ariyoshi 20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel Corporation Technology Development Division (56) References JP-A-6-229924 (JP, A) JP-A-7-146239 (JP, A) JP-A 63-188550 (JP, U) Opened 63-97847 (JP, U) Opened 3-9-1959 (JP, U) (58) Fields investigated (Int. Cl. ⁷ , DB name) G01N 21/62-21/74 JICST file (JOIS)

Claims (2)

(57) [Claims] 1. A glow discharge optical emission spectrometer, which is a cathode plate in a glow discharge optical emission spectrometer, wherein a concave portion having the same curvature as an analysis sample is provided in an opening of a discharge light emitting portion of the cathode plate. Cathode plate. 2. A cathode plate in a glow discharge optical emission spectrometer, wherein a concave portion having the same curvature as an analysis sample is provided in an opening of a discharge emission section of the cathode plate, and the analysis sample is held on the cathode plate. 1. A cathode plate for glow discharge emission spectroscopy, comprising: a sample holder to be analyzed; and a pressing mechanism for pressing the analysis sample against the cathode plate.