JP2001255320A - Method for trace component analysis in steel with high accuracy - Google Patents
Method for trace component analysis in steel with high accuracyInfo
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- JP2001255320A JP2001255320A JP2000068958A JP2000068958A JP2001255320A JP 2001255320 A JP2001255320 A JP 2001255320A JP 2000068958 A JP2000068958 A JP 2000068958A JP 2000068958 A JP2000068958 A JP 2000068958A JP 2001255320 A JP2001255320 A JP 2001255320A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は鉄鋼中微量成分の高
精度分析方法に関わり、さらに詳しくは、誘導結合プラ
ズマ質量分析において、マトリクス成分である鉄を分離
除去することによる鉄鋼中微量成分の高精度分析方法に
関わる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for high-accuracy analysis of trace components in steel, and more particularly, to high-accuracy analysis of trace components in steel by separating and removing iron as a matrix component in inductively coupled plasma mass spectrometry. Involved in accuracy analysis methods.
【０００２】[0002]
【従来の技術】鉄鋼材料に要求される特性は不純物や添
加成分の影響を受ける。特に最近の高純度材料では従来
問題とならなかったような極微量成分の管理のための分
析が必要となってきた。材料中の微量成分分析には従来
は材料を酸などで加熱溶解して水溶液とし、これを原子
吸光計や誘導結合プラズマ（以下ＩＣＰと略記する。）
発光分光計で濃度を測定する方法がとられてきた。2. Description of the Related Art The characteristics required of steel materials are affected by impurities and added components. In particular, recent high-purity materials require analysis for managing trace components, which has not been a problem in the past. Conventionally, for analysis of trace components in a material, the material is heated and dissolved with an acid or the like to form an aqueous solution, which is then analyzed by an atomic absorption spectrometer or inductively coupled plasma (hereinafter abbreviated as ICP).
A method of measuring the concentration with an emission spectrometer has been adopted.
【０００３】しかし、上記方法においては試料の分解に
時間がかかる上、最近の材料の高純度化に伴う極微量分
析への要求を満たすことができない。材料の迅速分解方
法としては特開平８−１２２３２２号公報に開示されて
いる金属試料連続電解装置などが、ＩＣＰ発光分光計に
用いる試料の溶解供給装置として公知となっている。こ
の方法を用いると試料を電解により分解し、そのままＩ
ＣＰ発光分光計に導入することにより迅速に分析を行う
ことができる。However, in the above-mentioned method, it takes a long time to decompose the sample, and it cannot meet the demand for the ultra-trace analysis accompanying the recent high purity of the material. As a method for rapidly decomposing a material, a metal sample continuous electrolysis apparatus disclosed in JP-A-8-122322 is known as a sample dissolution supply apparatus used in an ICP emission spectrometer. According to this method, the sample is decomposed by electrolysis, and
The analysis can be performed quickly by introducing it into a CP emission spectrometer.
【０００４】しかしながらマトリクス成分によるスペク
トルの妨害や、試料溶液の塩濃度が高くなるために試料
導入部での詰まりを起こすなどの問題がある。そのため
に、特に最近の高純度材料分析のための方法においては
マトリクス成分を除去することが必要となってきた。ま
た、ＩＣＰ発光分析計でも測定できないような微量の成
分を分析する必要があるときには、ＩＣＰ質量分析計を
用いることが考えられるが、ＩＣＰ質量分析計の場合に
は高感度であるため、よりマトリクス成分の影響を受け
やすく、マトリクス成分の除去は必須である。[0004] However, there are problems such as interference of the spectrum by the matrix component and clogging of the sample introduction part due to the high salt concentration of the sample solution. For this reason, it has become necessary to remove matrix components, particularly in recent methods for analyzing high-purity materials. When it is necessary to analyze a trace amount of components that cannot be measured by an ICP emission spectrometer, an ICP mass spectrometer may be used. It is susceptible to components and removal of matrix components is essential.
【０００５】従来マトリクスである鉄を除去する方法と
して４−メチル−２−ペンタノンによる溶媒抽出法がも
っとも広く用いられてきた。しかし迅速溶解法として金
属試料連続電解装置を用いて試料を分解しても、溶媒抽
出によってマトリクス成分の分離を行っていては迅速性
が損なわれてしまい、また有害な有機溶剤を用いること
や作業が煩雑であるといった問題点が残る。[0005] Conventionally, a solvent extraction method using 4-methyl-2-pentanone has been most widely used as a method for removing iron as a matrix. However, even if the sample is decomposed using a continuous electrolysis apparatus for metal samples as a rapid dissolution method, the rapidity is impaired if the matrix components are separated by solvent extraction. However, there remains a problem that the operation is complicated.
【０００６】また、鉄と共にＳｂ，Ｍｏ，Ｓｎ，Ｖなど
の元素が溶媒に抽出されてしまうため、これらの元素の
分析法としては使えないという欠点もある。この対策と
して簡便で有機溶剤を用いない方法にイオン交換樹脂を
用いる特開平７−４３３５３などに開示されている方法
がある。しかし、この方法ではフッ酸を用いる必要があ
るため、廃液の処理や器具の取り扱いなどの点で問題が
残る。In addition, since elements such as Sb, Mo, Sn, and V are extracted into a solvent together with iron, there is a drawback that they cannot be used as a method for analyzing these elements. As a countermeasure to this, there is a method disclosed in Japanese Patent Application Laid-Open No. 7-43353 which uses an ion exchange resin as a simple method using no organic solvent. However, in this method, it is necessary to use hydrofluoric acid, so that problems remain in treatment of waste liquid and handling of equipment.
【０００７】また、フッ酸以外の酸を用いる方法として
は塩酸溶液にシュウ酸を加えて鉄オキサラト錯体を形成
し、鉄は陰イオン錯体として陽イオン交換カラムに吸着
しないようにし、オキソ酸系以外の金属は陽イオンとし
て陽イオン交換カラムに吸着させる方法が公知である。
その場合三価の鉄がシュウ酸によって二価に還元される
ことを防ぐため、酸化剤として過酸化水素を加える必要
があるが、気泡が発生してＩＣＰ分析装置に導入すると
きに試料の吸い上げを阻害して定量性が低下するという
欠点があった。As a method using an acid other than hydrofluoric acid, oxalic acid is added to a hydrochloric acid solution to form an iron oxalato complex, and iron is prevented from being adsorbed on a cation exchange column as an anion complex. A method for adsorbing a metal as a cation on a cation exchange column is known.
In this case, it is necessary to add hydrogen peroxide as an oxidizing agent to prevent trivalent iron from being reduced to divalent by oxalic acid. However, when bubbles are generated and the sample is introduced into the ICP analyzer, the sample is sucked up. And there is a disadvantage that the quantitative property is lowered by inhibiting the above.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記のような
問題点を解決し、連続的に電解溶液を供給するＩＣＰ質
量分析にも対応可能な迅速なマトリックス成分除去を可
能とすることにより、鉄鋼中微量成分の高精度分析方法
を提供せんとするものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and enables rapid matrix component removal that can also be used for ICP mass spectrometry that continuously supplies an electrolytic solution. It is intended to provide a high-precision analysis method of trace components in steel.
【０００９】[0009]
【課題を解決するための手段】本発明は、連続的に電解
溶液を供給するＩＣＰ質量分析において、ＩＣＰ質量分
析に電解溶液を導く前処理として、イオン交換樹脂によ
りマトリックスである鉄を分離除去するが、特に、イオ
ン交換時の試料溶液中に酸化剤として硝酸を含有させ、
電解溶液の連続供給を阻害することなくＦｅ3+のオキサ
ラト錯体を安定に存在せしめて、分離除去することを特
徴とするもので、その要旨とするところは以下の通りで
ある。According to the present invention, in ICP mass spectrometry for continuously supplying an electrolytic solution, iron as a matrix is separated and removed by an ion exchange resin as a pretreatment for leading the electrolytic solution to the ICP mass spectrometry. However, in particular, nitric acid is contained in the sample solution during ion exchange as an oxidizing agent,
The method is characterized in that the oxalate complex of Fe 3+ is stably present without inhibiting the continuous supply of the electrolytic solution, and is separated and removed. The gist thereof is as follows.
【００１０】（１）ブロック状鉄鋼試料を電解セル内に
配置し、該試料の表面に電解液を連続的に供給して電解
しつつ連続的に電解した溶液を誘導結合プラズマ質量分
析することにより目的の微量成分を定量する分析方法に
おいて、該電解した溶液を誘導結合プラズマ質量分析に
導く前段階で、微量成分の分析の障害となるマトリクス
成分である鉄をイオン交換樹脂によって、あらかじめ分
離除去することを特徴とする誘導結合プラズマ質量分析
による鉄鋼中微量成分の高精度分析方法。(1) A block-shaped steel sample is placed in an electrolytic cell, and an electrolytic solution is continuously supplied to the surface of the sample to conduct electrolysis, and the continuously electrolyzed solution is subjected to inductively coupled plasma mass spectrometry. In an analysis method for quantifying a target trace component, before the electrolyzed solution is led to inductively coupled plasma mass spectrometry, iron, which is a matrix component that hinders trace component analysis, is separated and removed in advance by an ion exchange resin. A high-precision analysis method for trace components in steel by inductively coupled plasma mass spectrometry.
【００１１】（２）前記イオン交換樹脂による鉄の分離
除去において、イオン交換時の前記電解した溶液中に硝
酸とシュウ酸を含有させて、鉄を陰イオンであるＦｅ3+
のオキサラト錯体とすることにより、陽イオン交換樹脂
に吸着されないようにして分離除去することを特徴とす
る前記（１）に記載の鉄鋼中微量成分の高精度分析方
法。(2) In the separation and removal of iron by the ion-exchange resin, nitric acid and oxalic acid are contained in the electrolyzed solution at the time of ion-exchange, so that iron is converted to Fe 3+ which is an anion.
(1) The method for high-precision analysis of trace components in steel according to the above (1), wherein the oxalato complex is separated and removed so as not to be adsorbed on the cation exchange resin.
【００１２】[0012]
【発明の実施の形態】本発明の詳細を図を参照しながら
説明する。図１は、本発明における試料溶解、マトリク
ス分離および分析装置を組み合わせたシステムの一例を
概略的に示すものである。金属試料２に電圧を印加する
ための電源１、電解液を供給するための装置３、電解セ
ル４などが図示されている。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described with reference to the drawings. FIG. 1 schematically shows an example of a system in which a sample dissolution, a matrix separation, and an analyzer according to the present invention are combined. A power supply 1 for applying a voltage to the metal sample 2, a device 3 for supplying an electrolytic solution, an electrolytic cell 4, and the like are illustrated.
【００１３】電解セル４の内部は金属試料２と適宜の隙
間を有するように電極が金属試料２の試料面と対向して
設置され、金属試料２が正極、対極が負極となるように
電源１と接続されている。このように構成された電解セ
ル４に電解液が供給され、定電圧が印加されることによ
り金属試料２が電気分解される。電解液はポンプ５およ
びバルブ６を通して電解セルに供給される。電源１およ
びポンプ５・バルブ６はコンピュータ７によって制御さ
れている。Electrodes are placed inside the electrolysis cell 4 so as to have an appropriate gap with the metal sample 2 so as to face the sample surface of the metal sample 2, and the power supply 1 is arranged so that the metal sample 2 is a positive electrode and the counter electrode is a negative electrode. Is connected to The electrolytic solution is supplied to the electrolytic cell 4 configured as described above, and the metal sample 2 is electrolyzed by applying a constant voltage. The electrolytic solution is supplied to the electrolytic cell through the pump 5 and the valve 6. The power supply 1 and the pump 5 and the valve 6 are controlled by a computer 7.
【００１４】電解後の溶液は同じくコンピュータ７によ
って制御されたポンプ８・バルブ９によって気液分離管
１０へと輸送される。気液分離管１０では電解後の溶液
と電解によって発生したガスとを分離し、ガス成分はガ
ス抜き口２９へ、溶液成分はポンプ１１・バルブ１２を
介して混合槽１３へと進む。混合槽１３の前段には超純
水供給装置１４、硝酸供給装置１５、シュウ酸供給装置
１６がそれぞれコンピュータ７によって制御されたポン
プ１７、１９、２１・バルブ１８、２０、２２を介して
接続されており、適宜各薬品を試料溶液に添加すること
ができる。The solution after electrolysis is transported to a gas-liquid separation tube 10 by a pump 8 and a valve 9 also controlled by a computer 7. The gas-liquid separation pipe 10 separates the solution after electrolysis from the gas generated by electrolysis, and the gas component goes to the gas vent 29 and the solution component goes to the mixing tank 13 via the pump 11 and the valve 12. An ultrapure water supply device 14, a nitric acid supply device 15, and an oxalic acid supply device 16 are connected to the preceding stage of the mixing tank 13 via pumps 17, 19, 21 and valves 18, 20, 22 controlled by the computer 7, respectively. Therefore, each chemical can be appropriately added to the sample solution.
【００１５】混合槽１３で混合された試料溶液および希
硝酸、シュウ酸は陽イオン交換カラム２３に導入され
る。ここでは鉄イオンはシュウ酸によってＦｅ3+からＦ
ｅ2+に還元されるのを硝酸の酸化作用で防ぎながら、鉄
をオキサラト錯体の陰イオンとして保ち、陽イオン交換
樹脂に吸着しないようにし、流出した溶液はドレイン２
４に廃棄する。The sample solution, diluted nitric acid and oxalic acid mixed in the mixing tank 13 are introduced into a cation exchange column 23. Here, iron ions are converted from Fe 3+ to F by oxalic acid.
While preventing the reduction to e.sup.2 + by the oxidizing action of nitric acid, iron is kept as an anion of the oxalato complex so as not to be adsorbed on the cation exchange resin, and the effluent solution is drain 2
Discard at 4.
【００１６】一方、他の金属イオンは陽イオンとして吸
着させることによってカラム２３に残留するので目的元
素を鉄から分離できる。陽イオン交換樹脂に吸着した金
属陽イオンは希硝酸によってカラムを洗浄し、カラムに
残留していた鉄イオンを洗い流した後、濃硝酸にて溶離
する。カラム洗浄の際、希硝酸にシュウ酸を添加するこ
とで洗浄効果が高まり、鉄の分離能が高まる。濃硝酸に
よって溶離した目的元素の溶液はバルブ２５を切り替え
て試料供給容器２８に回収され、ＩＣＰ質量分析計２６
へと導入される。なお、酸溶液中でオキソ酸を形成し、
陰イオンとなるＳｂ，Ｍｏ，Ｓｎ，Ｖなどの元素につい
てはシュウ酸の添加は行わず、イオン交換カラムの前段
の混合槽に超純水供給装置から超純水を供給して、気液
分離管から供給された試料溶液と混合して希釈すること
で酸濃度を下げることにより、鉄の陽イオンは陽イオン
交換樹脂に吸着させ、オキソ酸を形成して陰イオンにな
っている元素のみをイオン交換カラムから流出せしめ、
これをＩＣＰ質量分析計に導入して分析することができ
る。On the other hand, since other metal ions remain in the column 23 by being adsorbed as cations, the target element can be separated from iron. The metal cations adsorbed on the cation exchange resin are washed with dilute nitric acid to wash the column, and the iron ions remaining in the column are washed away, and then eluted with concentrated nitric acid. At the time of column washing, adding oxalic acid to dilute nitric acid enhances the washing effect and increases the iron separation ability. The solution of the target element eluted by the concentrated nitric acid is collected in the sample supply container 28 by switching the valve 25, and the ICP mass spectrometer 26
Introduced to. In addition, oxo acid is formed in an acid solution,
Oxalic acid is not added to elements such as Sb, Mo, Sn, and V that become anions, and ultrapure water is supplied from the ultrapure water supply device to the mixing tank at the preceding stage of the ion exchange column to perform gas-liquid separation. By lowering the acid concentration by mixing and diluting with the sample solution supplied from the tube, the iron cations are adsorbed on the cation exchange resin, and only the elements that form oxo acids and become anions are removed. Flow out of the ion exchange column,
This can be introduced into an ICP mass spectrometer for analysis.
【００１７】なお、試料溶液や洗浄液にシュウ酸を添加
する際、別の陽イオン交換樹脂カラム２７を通すことに
より、シュウ酸中の金属不純物を除去することができ、
添加剤による分析試料の汚染を防止できる。また、希硝
酸にシュウ酸を添加した液は分析の前段階におけるカラ
ムの洗浄液としても機能する。試料の分解に先だって、
超純水供給装置および硝酸供給装置からそれぞれ超純水
と硝酸を供給することにより、電解セルや試料管、イオ
ン交換カラム、気液分離管、混合槽などを適宜超純水で
希釈した硝酸で洗浄することができる。そのためのバル
ブおよびポンプの操作はコンピュータによって制御でき
る。In addition, when oxalic acid is added to a sample solution or a washing solution, the metal impurities in oxalic acid can be removed by passing through another cation exchange resin column 27,
Contamination of the analysis sample by the additive can be prevented. The solution obtained by adding oxalic acid to dilute nitric acid also functions as a column washing solution in a stage prior to analysis. Prior to the decomposition of the sample,
By supplying ultrapure water and nitric acid from the ultrapure water supply device and nitric acid supply device, respectively, the electrolytic cell, sample tube, ion exchange column, gas-liquid separation tube, mixing tank, etc. are appropriately diluted with nitric acid by ultrapure water. Can be washed. The operation of the valves and pumps for that can be controlled by a computer.
【００１８】[0018]
【実施例】本発明を用いて実際にＣｕの量が表１に示す
ような濃度で既知であるブロック状鋼材ａ，ｂを、電解
液として硝酸水溶液（硝酸と水の混合率が例えば１：
１）を用いて硝酸の水溶液の流速０．５ｍｌ／ｍｉｎ
で、鉄の溶解速度が例えば５０ｍｇ／ｍｉｎになるよう
に定電位電解法で分解し、電解後の溶液を気液分離管で
ガス成分を除いた後、バルブを介して混合槽に導入し、
同時に超純水供給装置から超純水を２．５ｍｌ／ｍｉｎ
の速度で、シュウ酸供給装置からシュウ酸１０％の水溶
液をイオン交換カラムに通して不純物を除去したもの
を、混合槽に２．５ｍｌ／ｍｉｎの流速で導入し、最終
的に混合槽における混合比率が、鉄：６０％濃硝酸：
水：シュウ酸＝１ｇ：５ｍｌ：９５ｍｌ：５ｇとなるよ
うにした。DETAILED DESCRIPTION OF THE INVENTION Using the present invention, a block-like steel material a, b whose Cu amount is actually known at a concentration as shown in Table 1 is used as an electrolytic solution in a nitric acid aqueous solution (mixing ratio of nitric acid and water is, for example, 1: 1).
Using 1), the flow rate of the aqueous solution of nitric acid is 0.5 ml / min.
Then, the iron is dissolved by a constant potential electrolysis method so that the dissolution rate of iron becomes, for example, 50 mg / min, and the solution after the electrolysis is removed from a gas component by a gas-liquid separation tube, and then introduced into a mixing tank via a valve.
At the same time, ultrapure water is supplied from the ultrapure water supply device at 2.5 ml / min.
At a rate of 10%, an aqueous solution of 10% oxalic acid from an oxalic acid supply device was passed through an ion exchange column to remove impurities, and introduced into the mixing tank at a flow rate of 2.5 ml / min, and finally mixed in the mixing tank. The ratio is iron: 60% concentrated nitric acid:
Water: oxalic acid = 1 g: 5 ml: 95 ml: 5 g.
【００１９】鉄とシュウ酸との比率は鉄がシュウ酸と錯
体〔Ｆｅ（III ）（Ｃ2 Ｏ4 ）3 〕 3-を形成するために
重量比で１：４．７以上でなければならない。混合槽で
混合された試料溶液は陽イオン交換樹脂を充填したイオ
ン交換カラムに導入される。ただし、イオン交換カラム
はあらかじめ超純水供給装置と硝酸供給装置から供給さ
れ、混合槽で６０％濃硝酸：水＝１：１の混合比で混合
された洗浄液で洗浄して不純物を取り除いたのち、超純
水供給装置と硝酸供給装置とシュウ酸供給装置から供給
され、混合槽中で、６０％濃硝酸：水：シュウ酸＝５ｍ
ｌ：９５ｍｌ：５ｇの比率で混合されたコンディショニ
ング液でコンディショニングを行ってある。The ratio of iron to oxalic acid is such that iron is complexed with oxalic acid.
Body [Fe (III) (CTwoOFour)Three] 3-To form
Must be at least 1: 4.7 by weight. In the mixing tank
The mixed sample solution is ion-exchanged with cation exchange resin.
Introduced to the exchange column. However, ion exchange columns
Is supplied from the ultrapure water supply unit and the nitric acid supply unit in advance.
Mixed in a mixing tank at a mixing ratio of 60% concentrated nitric acid: water = 1: 1
After removing impurities by washing with
Supply from water supply unit, nitric acid supply unit and oxalic acid supply unit
In a mixing tank, 60% concentrated nitric acid: water: oxalic acid = 5 m
Conditioner mixed at a ratio of 1: 95ml: 5g
Conditioning with a cleaning solution.
【００２０】イオン交換カラムでは分析目的のＣｕ陽イ
オンが吸着され、鉄は〔Ｆｅ（III）（Ｃ2 Ｏ4 ）3 〕
3-となっているため吸着されない。このときの鉄を含む
溶出液をバルブの切り替えによりドレインに廃棄し、次
に前出のコンディショニング液を２０ｍｌカラムに通
し、カラムに残留している鉄をさらにドレインに廃棄す
る。In the ion exchange column, a Cu cation for analysis is adsorbed, and iron is [Fe (III) (C 2 O 4 ) 3 ].
It is not adsorbed because it is 3- . At this time, the eluate containing iron is discarded to the drain by switching the valve, and then the conditioning solution is passed through a 20 ml column, and the iron remaining in the column is further discarded to the drain.
【００２１】次に、超純水供給装置と硝酸供給装置から
超純水と６０％濃硝酸を混合槽に１：１の混合比率とな
るように供給し（これを溶離液とする）、イオン交換カ
ラムに導入する。ここでＣｕは溶離液によって溶離され
るので、この溶液をバルブを切り替えて、ＩＣＰ質量分
析計試料容器に供給する。試料溶液をイオン交換カラム
に供給する流速と時間の積と溶離液の流速とこれをイオ
ン交換カラムに供給する時間との積を任意に変えること
により、分析目的元素であるＣｕの濃縮率を任意に変え
ることができる。さらに超純水供給装置によりＩＣＰ質
量分析計試料容器に超純水を供給することにより酸濃度
とＣｕの濃縮率を任意に変えることができる。Next, ultrapure water and 60% concentrated nitric acid are supplied to the mixing tank at a mixing ratio of 1: 1 from the ultrapure water supply device and the nitric acid supply device (this is used as an eluent), Introduce to the exchange column. Here, since Cu is eluted by the eluent, this solution is supplied to an ICP mass spectrometer sample container by switching a valve. By arbitrarily changing the product of the flow rate and the time for supplying the sample solution to the ion exchange column, the product of the flow rate of the eluent, and the time for supplying the same to the ion exchange column, the concentration ratio of Cu, which is the element to be analyzed, can be arbitrarily determined. Can be changed to Further, by supplying ultrapure water to the ICP mass spectrometer sample container by the ultrapure water supply device, the acid concentration and the Cu concentration rate can be arbitrarily changed.
【００２２】試料の電解を５分間行い、上記の流速と混
合比で鉄とＣｕと硝酸と超純水とシュウを含む溶液をイ
オン交換カラムに供給し、上記のコンディショニング液
を流した後、溶離液を溶離液の供給速度を５ｍｌ／ｍｉ
ｎとして１分間供給して溶離液をＩＣＰ質量分析計で分
析したところ、表１に示すような濃度が計測された。表
１にはこの濃度を鉄鋼中の濃度に換算した値も併記して
ある。鉄鋼中の濃度に換算した値が認証値に一致してお
り、本発明により鉄鋼中微量成分の高精度分析を迅速に
行うことができる。Electrolysis of the sample is performed for 5 minutes, and a solution containing iron, Cu, nitric acid, ultrapure water, and shu is supplied to the ion exchange column at the above flow rate and mixing ratio, and the above conditioning liquid is flowed. The eluent was supplied at a rate of 5 ml / mi.
When the eluate was supplied for 1 minute as n and analyzed by an ICP mass spectrometer, the concentrations shown in Table 1 were measured. Table 1 also shows a value obtained by converting this concentration into a concentration in steel. The value converted to the concentration in the steel is consistent with the certified value, and the present invention can quickly perform a high-accuracy analysis of a trace component in the steel.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明によれば、ブロック状鉄鋼試料の
分解と、目的成分の分析に妨害となるマトリクス成分の
分離除去を迅速に行い、目的成分をＩＣＰ質量分析計に
供給できるので、迅速かつ高精度な鉄鋼中微量成分の分
析を行うことができる。According to the present invention, the decomposition of the block-like steel sample and the separation and removal of the matrix component which hinders the analysis of the target component can be rapidly performed, and the target component can be supplied to the ICP mass spectrometer. In addition, highly accurate analysis of trace components in steel can be performed.
【図１】本発明における試料溶解、マトリクス分解およ
び分析装置を組合わせたシステムの概略図を示す。FIG. 1 shows a schematic diagram of a system in which a sample dissolution, matrix decomposition, and analysis device are combined in the present invention.
１…電源 ２…金属試料 ３…電解液供給装置 ４…電解セル ５…ポンプ ６…バルブ ７…コンピュータ ８…ポンプ ９…バルブ １０…気液分離管 １１…ポンプ １２…バルブ １３…ポンプ １４…バルブ １５…硝酸供給装置 １６…シュウ酸供給装置 １７…ポンプ １８…バルブ １９…ポンプ ２０…バルブ ２１…ポンプ ２２…バルブ ２３…陽イオン交換カラム ２４…ドレイン ２５…バルブ ２６…ＩＣＰ質量分析計 ２７…陽イオン交換樹脂カラム ２８…試料供給容器 ２９…ガス抜き口 DESCRIPTION OF SYMBOLS 1 ... Power supply 2 ... Metal sample 3 ... Electrolyte supply device 4 ... Electrolysis cell 5 ... Pump 6 ... Valve 7 ... Computer 8 ... Pump 9 ... Valve 10 ... Gas-liquid separation tube 11 ... Pump 12 ... Valve 13 ... Pump 14 ... Valve 15 ... nitric acid supply device 16 ... oxalic acid supply device 17 ... pump 18 ... valve 19 ... pump 20 ... valve 21 ... pump 22 ... valve 23 ... cation exchange column 24 ... drain 25 ... valve 26 ... ICP mass spectrometer 27 ... positive Ion exchange resin column 28 ... sample supply container 29 ... gas vent
Claims (2)
し、該試料の表面に電解液を連続的に供給して電解しつ
つ連続的に電解した溶液を誘導結合プラズマ質量分析す
ることにより目的の微量成分を定量する分析方法におい
て、 該電解した溶液を誘導結合プラズマ質量分析に導く前段
階で、微量成分の分析の障害となるマトリクス成分であ
る鉄をイオン交換樹脂によって、あらかじめ分離除去す
ることを特徴とする誘導結合プラズマ質量分析による鉄
鋼中微量成分の高精度分析方法。An object of the present invention is to dispose a block-like steel sample in an electrolytic cell and continuously supply an electrolytic solution to the surface of the sample to perform electrolysis while performing inductively coupled plasma mass spectrometry on the continuously electrolyzed solution. In an analysis method for quantifying trace components of iron, iron which is a matrix component that hinders the analysis of the trace components is separated and removed in advance by an ion exchange resin before the electrolyzed solution is led to inductively coupled plasma mass spectrometry. High-precision analysis of trace components in steel by inductively coupled plasma mass spectrometry.
において、 イオン交換時の前記電解した溶液中に硝酸とシュウ酸を
含有させて、鉄を陰イオンであるＦｅ3+のオキサラト錯
体とすることにより、陽イオン交換樹脂に吸着されない
ようにして分離除去することを特徴とする請求項１に記
載の鉄鋼中微量成分の高精度分析方法。2. In the separation and removal of iron by the ion exchange resin, nitric acid and oxalic acid are contained in the electrolyzed solution at the time of ion exchange so that iron is converted to an oxalate complex of Fe 3+ which is an anion. 2. The method for analyzing trace components in steel according to claim 1, wherein the components are separated and removed so as not to be adsorbed on the cation exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000068958A JP2001255320A (en) | 2000-03-13 | 2000-03-13 | Method for trace component analysis in steel with high accuracy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000068958A JP2001255320A (en) | 2000-03-13 | 2000-03-13 | Method for trace component analysis in steel with high accuracy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001255320A true JP2001255320A (en) | 2001-09-21 |
Family
ID=18587930
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000068958A Withdrawn JP2001255320A (en) | 2000-03-13 | 2000-03-13 | Method for trace component analysis in steel with high accuracy |
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| Country | Link |
|---|---|
| JP (1) | JP2001255320A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110426345A (en) * | 2019-08-02 | 2019-11-08 | 淮北市君意达金属科技有限责任公司 | It is a kind of for direct-reading spectrometer laser station for sample clamping and fixing device |
| CN111307784A (en) * | 2018-12-11 | 2020-06-19 | 中核北方核燃料元件有限公司 | Method for determining content of impurity elements in uranium boride solid sample |
| CN112213299A (en) * | 2019-07-12 | 2021-01-12 | 张家港市国泰华荣化工新材料有限公司 | Method for measuring TMSB in lithium battery electrolyte |
-
2000
- 2000-03-13 JP JP2000068958A patent/JP2001255320A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111307784A (en) * | 2018-12-11 | 2020-06-19 | 中核北方核燃料元件有限公司 | Method for determining content of impurity elements in uranium boride solid sample |
| CN112213299A (en) * | 2019-07-12 | 2021-01-12 | 张家港市国泰华荣化工新材料有限公司 | Method for measuring TMSB in lithium battery electrolyte |
| CN110426345A (en) * | 2019-08-02 | 2019-11-08 | 淮北市君意达金属科技有限责任公司 | It is a kind of for direct-reading spectrometer laser station for sample clamping and fixing device |
| CN110426345B (en) * | 2019-08-02 | 2024-01-30 | 安徽中色研达科技有限公司 | Sample clamping and fixing device for direct-reading spectrometer laser table |
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