JP2006266988A - Sample preparation method for glow-discharge mass spectrometry - Google Patents
Sample preparation method for glow-discharge mass spectrometry Download PDFInfo
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- JP2006266988A JP2006266988A JP2005088006A JP2005088006A JP2006266988A JP 2006266988 A JP2006266988 A JP 2006266988A JP 2005088006 A JP2005088006 A JP 2005088006A JP 2005088006 A JP2005088006 A JP 2005088006A JP 2006266988 A JP2006266988 A JP 2006266988A
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- 238000001036 glow-discharge mass spectrometry Methods 0.000 title claims abstract description 18
- 238000005464 sample preparation method Methods 0.000 title 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000005096 rolling process Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 11
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
Description
本発明は、グロー放電質量分析法に関する。 特にグロー放電質量分析法における銀のショット状試料の成形方法に関する。 The present invention relates to glow discharge mass spectrometry. In particular, the present invention relates to a method for forming a silver shot sample in glow discharge mass spectrometry.
従来、銀中の不純物分析としては、誘導結合プラズマ発光分光法、フレームレス原子吸光法、あるいは誘導結合プラズマ質量分析法といった湿式分析装置による定量がなされている。それ以外の方法はあると推測するが開示がなされていないのが現状である。 Conventionally, as an impurity analysis in silver, quantification is performed by a wet analyzer such as inductively coupled plasma emission spectroscopy, flameless atomic absorption, or inductively coupled plasma mass spectrometry. It is assumed that there are other methods, but the current situation is that no disclosure has been made.
グロー放電質量分析は、極微量の元素を多数、同時に定量できる質量分析法の一つで、アルゴンガス中で測定試料を陰極とし、放電セルを陽極として、その間でグロー放電を起こさせ、試料原子をスパッタしさらにイオン化することで分析対象となる元素のイオンを取り出し、磁場と電場により二重に収束した後、検出器によってそこに流れるイオン電流密度により各元素の定量を行ない、主成分と分析対象元素との間のイオン電流強度の比に相対感度係数（以下「RSF」という)を乗じて各元素濃度を求める。 Glow discharge mass spectrometry is one of the mass spectrometry methods that can quantitate many trace elements at the same time. In argon gas, the sample to be measured is the cathode and the discharge cell is the anode. The ions of the element to be analyzed are extracted by sputtering and further ionized, and after double focusing by the magnetic field and electric field, each element is quantified by the ion current density flowing there through the detector, and the main component and analysis The concentration of each element is obtained by multiplying the ratio of the ionic current intensity with the target element by the relative sensitivity coefficient (hereinafter referred to as “RSF”).
グロー放電の陰極となる測定試料は、ピン状あるは平板上（フラット状）で使用する。また市販のグロー放電質量分析装置におけるRSF値は、推奨値がメーカーから与えられており、それが適用されるが、経験則からその推奨RSF値はピン状試料を用いて決定したと考えられる。また必ずしもその推奨RSF値を適用できるわけではなく、その場合は標準物質によりRSF値を決定しなければならない。 A measurement sample to be a cathode for glow discharge is used in a pin shape or on a flat plate (flat shape). Moreover, the recommended value is given from the manufacturer for the RSF value in a commercially available glow discharge mass spectrometer, and it is considered that the recommended RSF value was determined using a pin-shaped sample from an empirical rule. In addition, the recommended RSF value is not necessarily applicable. In that case, the RSF value must be determined by the standard substance.
特許公報第２６３７０００号（出願人：信越化学工業株式会社）には、同じグロー放電質量分析法におけるインジウムを用いた放電用電極調整法について記載があるが、対象試料及び調整方法が異なる。
上記従来の湿式分析法では極微量元素の分析、例えば銀中のロジウム（定量下限０．０１ｐｐｍ）においては、主成分の分離操作、言うなれば微量成分の濃縮操作が必要となり、操作が煩雑で２〜３日程かかる上、操作に熟練を要する。
またグロー放電質量分析装置への試料の導入は、ピン状あるいは平板上でなければならず、ショット状の銀試料についてはこれまで検討がなされていなかった。
Japanese Patent Publication No. 2637000 (Applicant: Shin-Etsu Chemical Co., Ltd.) describes a discharge electrode adjustment method using indium in the same glow discharge mass spectrometry, but the target sample and the adjustment method are different.
In the conventional wet analysis method described above, in the analysis of trace elements, for example, rhodium in silver (lower limit of determination 0.01 ppm), a separation operation of the main component, in other words, a concentration operation of the trace component is necessary, and the operation is complicated. It takes about 2-3 days and requires skill in operation.
In addition, the introduction of the sample into the glow discharge mass spectrometer must be in the form of a pin or a flat plate, and a shot-like silver sample has not been studied so far.
すなわち、グロー放電質量分析装置を用いて多元素を同時に迅速分析可能とすること、さらに標準試料を用いて銀中不純物の定量におけるＲＳＦ値を確立することを目的とする。 That is, an object is to enable rapid analysis of multiple elements simultaneously using a glow discharge mass spectrometer, and to establish an RSF value in the determination of impurities in silver using a standard sample.
本発明は、上記のような事情に鑑み発明されたものであって、
（１） グロー放電質量分析法において、銀のショット状試料を融解鋳造し塊状とし、圧延、切り出しにより一定の形状に成形することにより試料を作成し、該試料を用いて、試料中不純物を同時に迅速分析するグロー放電質量分析法。
（２）上記（１）記載の銀ショットの粒径が２ｍｍ以下、品位が、９９．９９mass%以上であるグロー放電質量分析法。
である。
The present invention was invented in view of the above circumstances,
(1) In glow discharge mass spectrometry, a silver shot-like sample is melt cast and formed into a lump shape, and a sample is prepared by rolling and cutting into a fixed shape, and the sample is used to simultaneously detect impurities in the sample. Glow discharge mass spectrometry for rapid analysis.
(2) A glow discharge mass spectrometry method in which the particle size of the silver shot described in (1) is 2 mm or less and the quality is 99.99 mass% or more.
It is.
以下、本発明に関して、詳細に述べる。
本発明においては、サンプリングしたショット状銀を予め、希硝酸及び超純水等により洗浄し、脱脂した（例えば、アセトンを用いる。）後、乾燥する。
これにより、付着している表面の汚染物質を除去する。
Hereinafter, the present invention will be described in detail.
In the present invention, the sampled shot silver is previously washed with dilute nitric acid and ultrapure water, degreased (for example, using acetone), and then dried.
This removes adhering surface contaminants.
サンプリングした銀を鋳型に投入し、溶解する。 この際、鋳型の材質は、高純度のカーボン等である。不純物が、混入することを未然に防止するためである。また鋳型の深さは浅いほうが望ましい。
溶解は、バーナ等を当てて、銀の溶解温度（９８０．６℃）以上とする。
The sampled silver is put into a mold and dissolved. At this time, the material of the mold is high-purity carbon or the like. This is because impurities are prevented from being mixed. It is desirable that the mold depth is shallow.
Melting is performed at a melting temperature of silver (980.6 ° C.) or higher by applying a burner or the like.
溶解、鋳造により塊状とした試料を圧延機等により、所定の形状の試料とする。
例えば、その厚さは３．５ｍｍ内、好ましくは２ｍｍ厚である。
A sample made into a lump by melting and casting is made into a sample of a predetermined shape by a rolling mill or the like.
For example, the thickness is within 3.5 mm, preferably 2 mm.
上記の所定の厚さになった試料をカッター等により、所定の大きさに成形する。
カッターは、例えばファインカッターを用いる。
所定の大きさとは、例えば幅３．５ｍｍ以内、長さ１５から２５ｍｍ、好ましくは幅２ｍｍ、長さ２０ｍｍである。
The sample having the predetermined thickness is formed into a predetermined size with a cutter or the like.
As the cutter, for example, a fine cutter is used.
The predetermined size is, for example, within 3.5 mm in width and 15 to 25 mm in length, preferably 2 mm in width and 20 mm in length.
また試料の形状は、その本願発明の分析結果であるＲＳＦ値については、メーカー推奨ＲＳＦ値を利用できるよう、ピン状に成形することとした。仮に平板状として信頼性の高い分析値を得るには、多くの標準試料による検量線作成が必要であると判断したためである。 Further, the shape of the sample was formed into a pin shape so that the manufacturer's recommended RSF value can be used for the RSF value which is the analysis result of the present invention. This is because, in order to obtain a highly reliable analytical value in the form of a flat plate, it was determined that it was necessary to create a calibration curve with many standard samples.
上記の所定の大きさに成形した試料は、酸洗浄及び超純水等により洗浄する。これにより、表面の不純物を予め除去しておくためである。
この後脱脂して乾燥し、試料調整とする。
The sample molded into the predetermined size is cleaned with acid cleaning, ultrapure water, or the like. This is because the impurities on the surface are removed in advance.
Thereafter, the sample is degreased and dried to prepare a sample.
この後、グロー放電質量分析装置にて、銀中の不純物、例えば極微量のロジウム等を分析する。
グロー放電質量分析の条件例を表１に示す。
Table 1 shows an example of conditions for glow discharge mass spectrometry.
（実施例１）
実試料(銀のショット状試料)を黒鉛鋳型に投入し、ガスバーナーにより溶解し、塊状に成形した。
その後、圧延機（製品名：大野ロール製 8型2段圧延機 2RM-216S）を用いて、２ｍｍ厚に成形し、ファインカッター（製品名：EB-SR-602，Refine Tec 社製)を用いて、２ｍｍ（幅）×２０ｍｍ（長さ）に成形した。
Example 1
An actual sample (silver shot sample) was put into a graphite mold, dissolved by a gas burner, and molded into a lump.
After that, using a rolling mill (product name: Ono Roll 8-type two-high rolling mill 2RM-216S), it is formed to a thickness of 2 mm, and a fine cutter (product name: EB-SR-602, manufactured by Refine Tec) is used. 2 mm (width) × 20 mm (length).
その後、図１に概略図を示すグロー放電質量分析装置（製品名：ＶＧ９０００，Ｆ．Ｉ．Ｅｌｅｍｅｎｔａｌ Ａｎａｌｙｓｉｓ社製）によりロジウムを分析測定した。
前記した従来法（鉄共沈による分離後、さらに陽イオン交換樹脂により鉄を分離し、誘導結合プラズマ質量分析する方法）による化学分析値と比較した。
その結果、表２に示すように、本法によるグロー放電質量分析により、化学分析値と良く結果が一致し、極微量のロジウムの定量分析が可能であることが確認できた。
また従来法でロジウムの測定のみに２〜３日かかっていた測定が、本法による調整法を用いてグロー放電質量分析で測定することにより、他元素と同時に２時間程度で迅速に測定することが可能となった。
The results were compared with the chemical analysis values obtained by the above-described conventional method (a method in which iron is separated by cation exchange resin after separation by iron coprecipitation and inductively coupled plasma mass spectrometry).
As a result, as shown in Table 2, it was confirmed by glow discharge mass spectrometry according to this method that the results agreed well with the chemical analysis values and that quantitative analysis of a very small amount of rhodium was possible.
In addition, the measurement that took 2-3 days only for rhodium in the conventional method should be measured quickly in about 2 hours simultaneously with other elements by measuring by glow discharge mass spectrometry using the adjustment method of this method. Became possible.
(実施例２)
銀の標準試料を実施例１と同様に試料を成形し、グロー放電質量分析装置で
測定した。測定条件は、実施例１と同様にした。
標準試料の保証値と比較した。
(Example 2)
A silver standard sample was molded in the same manner as in Example 1 and measured with a glow discharge mass spectrometer. The measurement conditions were the same as in Example 1.
Comparison with the guaranteed value of the standard sample.
その結果本法による調整法、及びRSF値を用いて、グロー放電質量分析により行った本発明例では、融解、圧延、切り出しに因る汚染あるいは濃度の減少などが懸念されたが、メーカー推奨RSF値を用いた各元素の定量値が、表３、図２に示す如く、保証値と良く一致していることが分かった。
図１は、本発明に用いたグロー放電質量分析装置の概略図である。
図２は、実施例１に示したデータの測定結果を示すグラフである。
FIG. 1 is a schematic diagram of a glow discharge mass spectrometer used in the present invention.
FIG. 2 is a graph showing the measurement results of the data shown in Example 1.
Claims (2)
A glow discharge mass spectrometry method, wherein the silver shot according to claim 1 has a particle size of 2 mm or less and a quality of 99.99 mass% or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103884772A (en) * | 2012-12-21 | 2014-06-25 | 北京有色金属研究总院 | Determination of trace impurity elements in high purity indium through glow discharge mass spectrometry method |
| JP2015232167A (en) * | 2014-06-10 | 2015-12-24 | Jx日鉱日石金属株式会社 | Separation method and analytic method for trace noble metal |
| CN106198712A (en) * | 2016-06-24 | 2016-12-07 | 锦州市国家光伏材料质量监督检验中心 | The method of trace impurity content in a kind of glow discharge spectrometry detection metal |
| CN111351833A (en) * | 2020-03-11 | 2020-06-30 | 新疆烯金石墨烯科技有限公司 | Method for detecting impurity elements and content thereof in graphene oxide |
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| JPH0968516A (en) * | 1995-09-01 | 1997-03-11 | Daido Steel Co Ltd | Glow discharge mass-spectrometry |
| JPH09145566A (en) * | 1995-11-20 | 1997-06-06 | Hitachi Cable Ltd | Pretreatment system for metal analytical sample |
| JP2001041890A (en) * | 1999-08-03 | 2001-02-16 | Nippon Light Metal Co Ltd | Analyzing method in depth direction by utilizing glow discharge |
| JP2004354132A (en) * | 2003-05-28 | 2004-12-16 | Japan Nuclear Cycle Development Inst States Of Projects | Method for analyzing impurities in metal sodium |
-
2005
- 2005-03-25 JP JP2005088006A patent/JP4756498B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0968516A (en) * | 1995-09-01 | 1997-03-11 | Daido Steel Co Ltd | Glow discharge mass-spectrometry |
| JPH09145566A (en) * | 1995-11-20 | 1997-06-06 | Hitachi Cable Ltd | Pretreatment system for metal analytical sample |
| JP2001041890A (en) * | 1999-08-03 | 2001-02-16 | Nippon Light Metal Co Ltd | Analyzing method in depth direction by utilizing glow discharge |
| JP2004354132A (en) * | 2003-05-28 | 2004-12-16 | Japan Nuclear Cycle Development Inst States Of Projects | Method for analyzing impurities in metal sodium |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103884772A (en) * | 2012-12-21 | 2014-06-25 | 北京有色金属研究总院 | Determination of trace impurity elements in high purity indium through glow discharge mass spectrometry method |
| JP2015232167A (en) * | 2014-06-10 | 2015-12-24 | Jx日鉱日石金属株式会社 | Separation method and analytic method for trace noble metal |
| CN106198712A (en) * | 2016-06-24 | 2016-12-07 | 锦州市国家光伏材料质量监督检验中心 | The method of trace impurity content in a kind of glow discharge spectrometry detection metal |
| CN111351833A (en) * | 2020-03-11 | 2020-06-30 | 新疆烯金石墨烯科技有限公司 | Method for detecting impurity elements and content thereof in graphene oxide |
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| Publication number | Publication date |
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| JP4756498B2 (en) | 2011-08-24 |
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