JPH0252239A - Analysis methode - Google Patents
Analysis methodeInfo
- Publication number
- JPH0252239A JPH0252239A JP20283888A JP20283888A JPH0252239A JP H0252239 A JPH0252239 A JP H0252239A JP 20283888 A JP20283888 A JP 20283888A JP 20283888 A JP20283888 A JP 20283888A JP H0252239 A JPH0252239 A JP H0252239A
- Authority
- JP
- Japan
- Prior art keywords
- calibration curve
- absorbance
- analysis
- sample
- results
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004458 analytical method Methods 0.000 title claims abstract description 74
- 238000011088 calibration curve Methods 0.000 claims abstract description 116
- 238000002835 absorbance Methods 0.000 claims abstract description 48
- 238000005259 measurement Methods 0.000 claims description 18
- 238000004020 luminiscence type Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000012488 sample solution Substances 0.000 description 35
- 239000000523 sample Substances 0.000 description 23
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000004993 emission spectroscopy Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012493 hydrazine sulfate Substances 0.000 description 1
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は鉄、非鉄金属等の金属中の成分分析又は水溶液
中の金属を分析する分析方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an analysis method for analyzing components in metals such as iron and non-ferrous metals, or for analyzing metals in aqueous solutions.
（従来の技術）
上記のごときは金属の分析方法としては、例えば、特開
昭４８−３１９８７号公報に開示されているごくと標準
試料の測定に基いて標準検量線を設定し、試料の測定結
果をもとにして該検量線からイオン量を分析している。(Prior art) In the above metal analysis method, for example, a standard calibration curve is set based on the measurement of a standard sample disclosed in JP-A-48-31987, and the sample is measured. Based on the results, the amount of ions is analyzed from the calibration curve.
（発明が解決しようとする課題）
ところが、このような分析方法においては、常時検量線
が一定であり、種々の外的要因の変化に基く検量線の変
更修正がなされず、分析値に誤差が生ずる等の欠点をと
もなうものである。(Problem to be Solved by the Invention) However, in such an analysis method, the calibration curve is always constant, and the calibration curve is not changed or corrected based on changes in various external factors, resulting in errors in the analytical values. However, it comes with disadvantages such as:
（課題を解決するための手段）
本発明は、このような欠点を解決するためなされたもの
で、イオン濃度の異なる標準試料の吸光度又は発光強度
を測定してその結果をもとに検量線を設定し、該検量線
に基き試料の成分分析を行うようにした分析方法におい
て、前記標準試料の吸光度又は発光強度を外的要因の変
化に応じ再測定し、その結果を演算器へ導いて新たな検
量線を設定して該検量線に基き以後の試料成分分析を行
うことを特徴とする分析方法と、この種の分析方法によ
る分析精度をより高めるため、さらに前記分析方法によ
り分析すると同時に前記した前後の検量線設定時刻間に
行った試料成分分析結果を前後の測定結果から推定して
設定される検量線に基き修正するようにした分析方法と
、前記分析方法により分析したうえ以後の試料成分分析
を前後の測定結果から予測して設定される予測検量線に
基き行うようにした分析方法とよりなるものである本発
明は、分析誤差について発明者等が検討した結果、春、
夏、秋、冬の気温の変化、又これら時期の１日の内、午
前と午後、昼間と夜間には気温の変化があり、更に昼間
と夜間においては電力使用量増減にともなう電圧の変化
等の外的要因の変化により吸光度、発光度等が変化し、
分析誤差になることが明らかになった。そこで、本発明
においては、例えば、分析誤差が生ずるおそれのある上
記のごとき外的要因の変化が起きる毎に検量線を設定す
る、つまり、初期検量線設定から一定時間経過後再度検
量線を設定し、その時の検量線に基き試料成分分析を行
い、外的要因の変化による分析誤差を解消するものであ
る。(Means for Solving the Problems) The present invention was made to solve these drawbacks, and it measures the absorbance or luminescence intensity of standard samples with different ion concentrations and creates a calibration curve based on the results. In this analysis method, the absorbance or luminescence intensity of the standard sample is remeasured in response to changes in external factors, and the results are led to a computer to perform a new analysis. An analysis method characterized by setting a standard calibration curve and performing subsequent sample component analysis based on the calibration curve, and in order to further improve the analysis accuracy by this type of analysis method, the analysis method An analysis method that corrects the sample component analysis results performed between the calibration curve setting times before and after the calibration curve is estimated from the measurement results before and after the calibration curve is set, and a sample that has been analyzed using the above analysis method and then The present invention consists of an analysis method in which component analysis is performed based on a predicted calibration curve that is set by predicting from the previous and subsequent measurement results.As a result of the inventors' study on analysis errors, the present invention was developed in the spring.
Temperature changes in summer, autumn, and winter, as well as temperature changes in the morning and afternoon, daytime and nighttime during these seasons, and voltage changes during the daytime and nighttime due to increases and decreases in electricity usage, etc. Absorbance, luminescence intensity, etc. change due to changes in external factors,
It became clear that this was an analysis error. Therefore, in the present invention, for example, a calibration curve is set every time a change in external factors such as those described above that may cause analysis errors occurs, that is, a calibration curve is set again after a certain period of time has passed from the initial calibration curve setting. Then, sample component analysis is performed based on the calibration curve at that time to eliminate analysis errors caused by changes in external factors.
検量線の設定方法としては、単一標準試料に基く検量線
設定では正確な設定が困難であり、従って、イオン量の
異なる標準試料種類が多い程精度は向上するが、作業能
率等の関係から２〜４種類が好ましく、例えば溶液循環
型自動吸光分析法、原子吸光分析法、赤外線吸収分析法
の場合は吸光度を、また、高周波誘導結合プラズマ発光
分析法（Ｉ ＣＰ分析法）、スパーク発光分析法（カン
トハック分析法）、グロー放電発光分析法（ＧＤ３分析
法）の場合は発光強度を測定し、その結果を演算器へ導
き、現在時刻の検量線を設定し、これに基き試料成分の
分析を続ける。しかして、一定時間経過後、即ち、外的
要因の変動により分析誤差が生ずるおそれがきたとき、
上記のごとく吸光度又は発光強度を再度測定し、現在時
刻の新たな検量線を設定し、以後、新たな検量線に基き
試料成分の分析を続けることにより分析誤差を解消する
ものである。このようにして外的要因の変動に応じて順
次新たな検量線を設定するものである。As for how to set the calibration curve, it is difficult to set the calibration curve accurately by setting the calibration curve based on a single standard sample.Therefore, the more types of standard samples with different ion amounts are used, the higher the accuracy will be, but due to work efficiency etc. Two to four types are preferable, for example, absorbance in the case of solution circulation type automatic absorption spectrometry, atomic absorption spectrometry, infrared absorption spectrometry, high frequency inductively coupled plasma emission spectrometry (I CP analysis), spark emission spectrometry. (Canthack analysis method) and glow discharge optical emission spectrometry (GD3 analysis method), the luminescence intensity is measured, the results are sent to a calculator, a calibration curve for the current time is set, and the sample components are analyzed based on this. Continue. However, after a certain period of time has elapsed, that is, when there is a risk that analysis errors may occur due to fluctuations in external factors,
As described above, the absorbance or luminescence intensity is measured again, a new calibration curve for the current time is set, and thereafter analysis of sample components is continued based on the new calibration curve to eliminate analysis errors. In this way, new calibration curves are sequentially set in response to changes in external factors.
更に、分析精度を向上するためには、上記のごとく複数
回の検量線を設定しても検量線設定間において厳密には
外的要因の変動が生しているから、それぞれの検量線設
定値を演算器へ導き、検量線設定間の検量線を推定設定
し、この推定検量線によりその間の成分分析値を修正す
れば一層分析精度を向上することができる。Furthermore, in order to improve analysis accuracy, even if the calibration curve is set multiple times as described above, strictly speaking, fluctuations due to external factors occur between the calibration curve settings, so it is necessary to set the calibration curve setting value for each calibration curve. The analysis accuracy can be further improved by guiding the calculation unit to a calculator, estimating a calibration curve between the calibration curve settings, and correcting the component analysis values between the calibration curves using this estimated calibration curve.
このような検量線設定間に推定検量線を設定する演算式
としては、例えば、
ｆｃｘ）−ａｘ’″−’ ＋ ｂ ｘ ’−’ ＋ ｃ
ｘ ”−’−ｆ （ｘ） ：吸光度又は発光強度、
ａ、ｂＸｃ：定数、Ｘ：時間、ｎ：標準試料測定回数、
ｆ（ｙ）＝Ａｙ’″−１＋ Ｂ ｙｍ−２＋ＣｙＩＩ−
Ｊ・・・ｆ（ｙ）：吸光度又は発光強度、
Ａ、Ｂ、Ｃ：定数、ｍ：イオン水準、ｙ：イオン量、
で、検量線設定間のほぼ中間点時刻の検量線を設定し、
これに基き分析済の分析値を補正する。As an arithmetic expression for setting an estimated calibration curve between such calibration curve settings, for example, fcx)-ax'''-' + b x '-' + c
x"-'-f (x): Absorbance or emission intensity, a, bXc: constant, X: time, n: number of standard sample measurements, f(y)=Ay'"-1+B ym-2+CyII-
J...f(y): absorbance or emission intensity, A, B, C: constant, m: ion level, y: ion amount, Set a calibration curve at approximately the midpoint time between the calibration curve settings,
Based on this, the analyzed value is corrected.
更にまた、分析精度を向上するためには、上記のごとく
前後の検量線を設定後は前後の測定結果からその後の予
測検量線を予測設定し、以後の試料成分分析はこの予測
検量線に基き行うようにしてもよい。Furthermore, in order to improve analysis accuracy, after setting the previous and subsequent calibration curves as described above, a subsequent predicted calibration curve should be set based on the previous and subsequent measurement results, and subsequent sample component analysis should be based on this predicted calibration curve. You may also do so.
このような本発明方法による分析は、例えば、鉄（鋼）
中の成分（Ｐ、Ｍｎ、■、Ａ１、Ｓｉ、Ｃ，Ｓ等）、非
鉄金属中の成分、各種溶液中の成分等を分析することが
できる。Analysis by such a method of the present invention can be performed, for example, on iron (steel).
Components (P, Mn, ■, A1, Si, C, S, etc.), components in nonferrous metals, components in various solutions, etc. can be analyzed.
次に本発明を図面により説明する。Next, the present invention will be explained with reference to the drawings.
（溶液循環型自動吸光分析）
第１図において試料溶液槽（１）から標準試料溶液を反
応槽（２）へ導入し、一方、試薬槽（３ａ）、（３ｂ）
、（３ｃ）、（３ｄ）、（３ｅ）から試薬を反応槽（２
）へ導き、ヒーター（４）で加熱しつつ、ｐ ｅ ：ｌ
＋をＦｅ２＋へ還元した後、試料溶液（有色イオン）を
空気吹込管（５）からの空気吹込みによりフローセル（
６）へ循環移動させつつ該フローセル（６）に発光体（
７）から発光し、ホトマル（８）で有色イオン呈色域の
吸光度を複数回測定してその結果を演算器（９）へ導入
し平均値を演算する。次いで、試薬槽（３ａ）、（３ｂ
）、（３ｃ）、（３ｄ）、（３ｅ）から発色試薬を反応
槽（２）へ導き、発色イオンとしこれを上記同様にフロ
ーセル（６）へ循環移動させつつ発光体（７）から発光
し、ホトマル（８）で発光域の吸光度を複数回測定し、
その結果を上記演算器（９）へ導き、その平均値を演算
して前記有色イオン呈色域の測定結果と合わせる。(Solution circulation type automatic absorption analysis) In Fig. 1, the standard sample solution is introduced from the sample solution tank (1) into the reaction tank (2), while the reagent tanks (3a) and (3b)
, (3c), (3d), and (3e) into the reaction tank (2
) and while heating it with the heater (4), p e :l
After reducing + to Fe2+, the sample solution (colored ions) is transferred to the flow cell (
The luminescent material (
7), the absorbance of the colored ion color region is measured multiple times using a photomultiplier (8), and the results are introduced into a calculator (9) to calculate an average value. Next, reagent tanks (3a) and (3b
), (3c), (3d), and (3e) are led to the reaction tank (2), where they are converted into colored ions and circulated to the flow cell (6) in the same manner as described above, while being emitted from the luminescent body (7). , the absorbance of the luminescent region was measured multiple times with Photomar (8),
The results are led to the arithmetic unit (9), and the average value thereof is calculated and combined with the measurement results of the colored ion color range.
このようにして、前記標準試料のイオン濃度を変化させ
たもの数種類を同様に測定し、その結果を演算器（９）
に導いて現在時刻の検量線を設定する。この検量線に基
き、試料（被分析体）のイオン量を分析し、その結果を
プリンター００）へ表示するしかして、このような分析
を継続して外的要因により分析誤差が生ずる事態が予想
されるとき、つまり一定時間経過後に上記のごとく操作
して新たな検量線を設定し、以後この検量線に基き分析
を行い、外的要因による分析誤差を解消するものである
。In this way, several types of standard samples with different ion concentrations are measured in the same way, and the results are sent to the computer (9).
and set the calibration curve for the current time. Based on this calibration curve, the amount of ions in the sample (analyte) is analyzed and the results are displayed on the printer (00).However, if this type of analysis is continued, it is expected that analysis errors will occur due to external factors. In other words, after a certain period of time has elapsed, a new calibration curve is set by operating as described above, and subsequent analysis is performed based on this calibration curve to eliminate analysis errors caused by external factors.
更に、より一層分析精度を向上する場合は前記設定検量
線と上記新たな設定検量線から両者間の試料測定時刻に
おける検量線を測定試料毎に推定し、この検量線に基き
前記検量線設定時がら新たな検量線設定後迄に分析した
分析値を各々修正する。Furthermore, in order to further improve the analysis accuracy, estimate a calibration curve between the set calibration curve and the new set calibration curve at the sample measurement time for each measurement sample, and use this calibration curve to estimate the calibration curve at the time of setting the calibration curve. However, each analytical value analyzed up to the time of setting a new calibration curve is corrected.
（原子吸光分析）
第２図において、試料溶液槽（１）から標準試料溶液を
噴霧室（１１）へ噴霧し、導入管（１２）から可燃ガス
、導入管（１２ａ）から助燃ガスを噴霧室（１１）へ混
合導入し、燃焼して炎（１３）を生成する。一方、中空
陰極ランプ（１４）から発光し、分光器（１５）を経て
ホトマル（１６）で吸光度を測定し、この値を演算器（
９）へ導入し、更にイオン濃度の異なる標準試料を上記
のごとく測定し、これに基き検量線を設定する。検量線
設定後、上記標準試料溶液を分析すべき試料溶液に変更
して、上記のごとく吸光度を測定し、その結果を演算器
（９）へ導いて検量線に基きイオン量を分析し、プリン
ター００）へ表示する。(Atomic absorption spectrometry) In Fig. 2, the standard sample solution is sprayed from the sample solution tank (1) into the spray chamber (11), the combustible gas is supplied from the introduction pipe (12), and the auxiliary combustion gas is supplied from the introduction pipe (12a) to the spray chamber. (11) and burns to produce a flame (13). On the other hand, light is emitted from a hollow cathode lamp (14), the absorbance is measured by a photomultiplier (16) through a spectrometer (15), and this value is calculated by a calculator (
9), and further measure standard samples with different ion concentrations as described above, and set a calibration curve based on this. After setting the calibration curve, change the above standard sample solution to the sample solution to be analyzed, measure the absorbance as described above, send the result to the calculator (9), analyze the ion amount based on the calibration curve, and print it to the printer. 00).
このようにして分析を継続し、外的要因により分析精度
が低下するおそれのある事態になったとき、即ち一定時
間経過後、上記のごとく操作して新たな検量線を設定し
、以後この検量線に基き分析を行うことにより外的要因
による分析誤差を解消するものである。更に、分析精度
を向上するためには、前記設定検量線と上記新たな検量
線から両者間の試料測定時刻における検量線を測定試料
毎に推定し、この検量線に基き、前記検量線設定時から
新たな検量線設定時まで分析した分析値を各々修正する
。If analysis continues in this way and a situation arises in which the analytical accuracy is likely to decrease due to external factors, that is, after a certain period of time has elapsed, a new calibration curve is set by operating as described above. By performing analysis based on lines, analysis errors caused by external factors are eliminated. Furthermore, in order to improve analysis accuracy, a calibration curve at the time of sample measurement between the set calibration curve and the new calibration curve is estimated for each measurement sample, and based on this calibration curve, the calibration curve at the time of setting the calibration curve is estimated. Correct each analysis value from the time of setting the new calibration curve.
（高周波誘導結合プラズマ発光分光分析）第３図におい
て、標準試料槽（１）から噴霧用アルゴンガス（１７）
により標準試料溶液を噴霧室（１１）へ噴霧し、プラズ
マガス（１８）、冷却ガス（１９）を誘導コイル（２０
）により形成したプラズマ炎（２１）に導入して標準試
料溶液中に含有される元素を発光させこの光を分光器（
２２）にて含有元素特有の単色光に分光して元素毎の発
光強度を演算器（９）へ導入する。このようにしてイオ
ン濃度の異なる標準試料溶液を数種類測定して、検量線
を設定する。設定後、標準試料溶液を分析すべき試料溶
液に変え上記のごとく測定し、検量線に基きイオン量を
測定することにより元素濃度を算出してプリンター００
）へ表示する。しかして外的要因等により分析精度が低
下するおそれのある事態に至ったとき、上記のごとくイ
オン濃度の異なる標準試料溶液により新たな検量線を設
定し、以後この検量線に基き上記のごとく分析を行い外
的要因による分析誤差を解消するものである。更に分析
精度を向上するためには、前記設定検量線と上記新たな
設定検量線から両者間の試料測定時刻における検量線を
測定試料毎に推定し、この検量線に基き前記検量線設定
時から新たな検量線設定時までに分析した分析値を各々
修正するとともに、以後の試料成分分析を前後の測定結
果から予測される予測検量線に基き行う。(High-frequency inductively coupled plasma emission spectroscopy) In Figure 3, the argon gas for spraying (17) flows from the standard sample tank (1).
The standard sample solution is sprayed into the spray chamber (11), and the plasma gas (18) and cooling gas (19) are sprayed into the induction coil (20).
) is introduced into the plasma flame (21) formed by the standard sample solution to emit light from the elements contained in the standard sample solution.
At step 22), the light is separated into monochromatic lights specific to the contained elements, and the emission intensity of each element is introduced into a computing unit (9). In this way, several types of standard sample solutions with different ion concentrations are measured and a calibration curve is set. After setting, change the standard sample solution to the sample solution to be analyzed, measure as above, calculate the element concentration by measuring the amount of ions based on the calibration curve, and print the printer 00.
). However, when a situation arises where the analysis accuracy may be reduced due to external factors, etc., a new calibration curve is set using standard sample solutions with different ion concentrations as described above, and subsequent analysis is performed as described above based on this calibration curve. This is to eliminate analysis errors caused by external factors. In order to further improve the analysis accuracy, a calibration curve at the sample measurement time between the above set calibration curve and the above newly set calibration curve is estimated for each measurement sample, and based on this calibration curve, the calibration curve is calculated from the time when the above calibration curve was set. Each analysis value analyzed up to the time of setting a new calibration curve is corrected, and subsequent sample component analysis is performed based on the predicted calibration curve predicted from the previous and subsequent measurement results.
（実施例）
次に、本発明の実施例を比較例とともに上げる実施例１
（溶液循環型自動吸光分析法による鋼中Ｐの分析例）
鋼の切削試料０．１ ｇと硝酸５ｃｃ、過塩素酸（６０
％）６ｃｃを加えて加熱溶解し、白煙処理して過塩素酸
の残量をＩ ｃｃ以下にする。これに水を加え塩類を溶
解した後、全容を２５ ｃｃとして、これを標準試料溶
液（検量線設定用）とする。(Example) Next, an example of the present invention will be described together with a comparative example. Example 1 (Example of analysis of P in steel by solution circulation type automatic absorption spectrometry) 0.1 g of cut steel sample, 5 cc of nitric acid, and perchlorine Acid (60
Add 6 cc of perchloric acid, heat and dissolve, and treat with white smoke to reduce the remaining amount of perchloric acid to below I cc. After adding water and dissolving the salts, the total volume is made up to 25 cc, and this is used as a standard sample solution (for setting a calibration curve).
次に、上記標準試料溶液（イオン量＝１．０μｇ／ ２
５ ｃｃ ）を反応槽へ移し、亜硫酸水素ナトリウム溶
液（２０％）１０ｃｃを加え、Ｆｅ”をＦｅ２すへ還元
した後、ニッケル、クロム等による有色イオンの吸光度
を測定間隔１回／秒で５回測定したところ、このときの
吸光度（Ａ）は０． ＯＯ７，０゜００７．０．００６
．０．０１０．０． ＯＯ７であった次いで発色試薬と
してモリブデン酸アンモニウム（２，５％）１０ｃｃと
、硫酸ヒドラジン溶液（３％）１４ｃｃを加え呈色が完
結した後、吸光度を測定間隔１回／秒で５回測定したと
ころ、このときの吸光度（Ｂ）は０．０３４．０．０３
４．０．０３５０、０３３．０．０３６であった。Next, the above standard sample solution (ion amount = 1.0 μg/2
5 cc) was transferred to a reaction tank, 10 cc of sodium bisulfite solution (20%) was added to reduce Fe'' to Fe2, and the absorbance of colored ions such as nickel and chromium was measured 5 times at a measurement interval of 1 time/second. When measured, the absorbance (A) at this time was 0.OO7,0°007.0.006
．． 0.010.0. Next, 10 cc of ammonium molybdate (2.5%) and 14 cc of hydrazine sulfate solution (3%) were added as coloring reagents, and after color development was completed, the absorbance was measured 5 times at a measurement interval of 1 time/second. However, the absorbance (B) at this time is 0.034.0.03
They were 4.0.0350 and 033.0.036.
次に標準試料溶液のイオン濃度を変化させ、上記に準じ
て吸光度を測定したところ、
（１）イオン量：３．０μｇ ／ ２５ ｃｃの標準試
料溶液吸光度（Ａ） ０．００６ ０．００７ ０．０
０６０．０１０ ０．００８
吸光度（Ｂ ） ０．０９４ ０．０９０ ０．０９９
０．０９４．０．０９３
（２）イオン量：５．０ μｇ ／ ２５ ｃｃの標準
試料溶液吸光度（Ａ）０．００７ ０．００７ ０．０
０６０．００９ ０．００８
吸光度（Ｂ）０．１５１ ０．１５４．０．１５２０．
１５５．０．１５２
（３）イオン量ニア、０μｇ ／ ２５ ｃｃの標準試
料溶液吸光度（Ａ） ０．００７ ０．００９ ０．０
０５０．００８ ０．００７
吸光度（Ｂ ） ０．２０８．０．２０５．０．２１０
０．２０７ ．０．２０に
のようにしてイオン量の異なる標準試料の吸光度を合計
４回測定した結果を演算器へ導き、これらの値を平均化
して第４図に出すごとき、検量線Ａ（気温１８°Ｃ）を
設定した。次いで、前記標準試料溶液に変え被分析体の
試料溶液に変え同様に吸光度を測定したところ
吸光度（Ａ） ０．００６ ０．００７ ０．００６０
．００９ ０．００７
吸光度（Ｂ ） ０．０６４．０．０６２．０．０６６
０．０６５．０．０６４
これらの平均値を求め、弐Ｂ−ＡＫ （Ｋ ：液量補正
係数）で演算した値（補正吸光度）を上記検量線Ａを設
定した演算器へ導き鋼中リン含有率Ｐ＝２０．０ｐｐｍ
と決定した。Next, the ion concentration of the standard sample solution was changed and the absorbance was measured according to the above method. 0
060.010 0.008 Absorbance (B) 0.094 0.090 0.099
0.094.0.093 (2) Ion amount: 5.0 μg / 25 cc standard sample solution absorbance (A) 0.007 0.007 0.0
060.009 0.008 Absorbance (B) 0.151 0.154.0.1520.
155.0.152 (3) Ion content near, 0 μg/25 cc standard sample solution absorbance (A) 0.007 0.009 0.0
050.008 0.007 Absorbance (B) 0.208.0.205.0.210
0.207. The results of measuring the absorbance of standard samples with different ion contents four times in total as shown in Figure 4 are calculated by averaging these values and plotting them as shown in Figure 4. C) was set. Next, the absorbance was measured in the same manner using the sample solution of the analyte instead of the standard sample solution. Absorbance (A) 0.006 0.007 0.0060
．． 009 0.007 Absorbance (B) 0.064.0.062.0.066
0.065.0.064 Calculate these average values and send the value (corrected absorbance) calculated using 2B-AK (K: liquid volume correction coefficient) to the calculator where the above calibration curve A is set to determine the phosphorus content in the steel. Rate P=20.0ppm
It was decided.
次に上記検量線Ａ設定１０時間後（気温２５゛Ｃ）に同
様の標準試料溶液で、同条件で合計４回吸光度を設定し
たところ、
（１）イオン量＝１．０μｇ ／ ２５ ｃｃの標準試
料溶液吸光度（Ａ） ０．００７ ０．００９ ０．０
０８０．０１０ ０．００６
吸光度（Ｂ ） ０．０５９ ０．０６０ ０．０５７
０．０６２ ．０．０５８
（２）イオン量：３．０ μｇ ／ ２５ ｃｃの標準
試料溶液吸光度（Ａ） ０．００９．０．０１０．０．
００９０．０１１ ０．００９
吸光度（Ｂ）０．０９２ ０．０９０ ０．０９５Ｑ、
０９５ ．０．０９３
（３）イオン量；５．０ｇｇ ／ ２５ ｃｃの標準試
料溶液吸光度（Ａ）０．０１０ ０．００ｇ ０．０
０９０．００８ ０．０１０
吸光度（Ｂ）０．１２０ ０．１２１ ０．１１９’
０．１１９ ．０．１２２
（４）イオン量＝７．０ μｇ ／ ２５ ｃｃの標準
試料溶液吸光度（Ａ） ０．００Ｂ ０．０１０ ０
．０１００．００８ ０．００８
吸光度（Ｂ）０．１５０ ０．１５１ ０．１４９０．
１５０ ０．１５１
これらの値を平均化して第４図に示すごとき検量線（Ｂ
）を設定した。Next, 10 hours after setting the above calibration curve A (at a temperature of 25°C), absorbance was measured a total of 4 times under the same conditions using the same standard sample solution. (1) Ion amount = 1.0 μg / 25 cc standard Sample solution absorbance (A) 0.007 0.009 0.0
080.010 0.006 Absorbance (B) 0.059 0.060 0.057
0.062. 0.058 (2) Ion amount: 3.0 μg/25 cc standard sample solution absorbance (A) 0.009.0.010.0.
0090.011 0.009 Absorbance (B) 0.092 0.090 0.095Q,
095. 0.093 (3) Ion amount; 5.0 gg / 25 cc standard sample solution absorbance (A) 0.010 0.00 g 0.0
090.008 0.010 Absorbance (B) 0.120 0.121 0.119'
0.119. 0.122 (4) Ion amount = 7.0 μg / 25 cc standard sample solution absorbance (A) 0.00B 0.010 0
．． 0100.008 0.008 Absorbance (B) 0.150 0.151 0.1490.
150 0.151 By averaging these values, a calibration curve (B
)It was set.
次いで標準試料溶液に変え前記同様に吸光度を測定した
ところ、
吸光度（Ａ）０．００９０．００８ ０．００８０．０
１０．０．００９
吸光度（Ｂ ）０．０７５．０．０７７．０．０７６０
．０７４ ．０．０７に
れらの平均値を求め、弐Ｂ−ＡＫ（Ｋｎ液量補正係数）
で演算した値（補正吸光度）を上記検量線Ｂを設定した
演算器へ導き鋼中リン含有率Ｐ＝ １９．９ｐｐｍ と
決定した。Next, when the standard sample solution was used and the absorbance was measured in the same manner as above, the absorbance (A) was 0.0090.008 0.0080.0
10.0.009 Absorbance (B) 0.075.0.077.0.0760
．． 074. Find the average value of these to 0.07, and calculate 2B-AK (Kn liquid volume correction coefficient).
The calculated value (corrected absorbance) was led to a calculator set with the above calibration curve B, and the phosphorus content in the steel was determined to be P = 19.9 ppm.
実施例２
上記実施例１において、検量線（Ａ）と検量線（Ｂ）の
中間時刻の検量線（Ｃ）を推定設定し、この検量線（Ｃ
）に基き、検量線（Ａ）から検量線（Ｂ）の設定時刻迄
に分析した値の修正を施した。Example 2 In Example 1 above, a calibration curve (C) at an intermediate time between the calibration curve (A) and the calibration curve (B) is estimated and set, and this calibration curve (C
), the values analyzed from the calibration curve (A) to the set time of the calibration curve (B) were corrected.
比較例１
実施例１において、検量線（Ｂ）を設定することなく、
検量線（Ａ）により分析した。これらの結果を次表に示
す。Comparative Example 1 In Example 1, without setting the calibration curve (B),
Analysis was performed using a calibration curve (A). These results are shown in the table below.
標準値 ２０．０ｐｐｍ
実施例３
（高周波誘導結合プラズマ発光分光分析を用いた鋼中Ｓ
ｉ、Ｍｎの分析例）
鋼の切削試料１．０ｇに６Ｎ塩酸１５ｃｃ及び硝酸５
ｃｃを加えて加熱溶解し、これに水を加え全容を１００
ｃｃとして標準試料溶液（検量線設定用）とする。Standard value 20.0 ppm Example 3 (S in steel using high frequency inductively coupled plasma emission spectroscopy
i, Mn analysis example) 15 cc of 6N hydrochloric acid and 5 cc of nitric acid to 1.0 g of cut steel sample
Add cc and heat to dissolve, add water and bring the total volume to 100
Use the standard sample solution (for setting the calibration curve) as cc.
次に、標準試料溶液（イオン量：１ｍｇ／１０Ｑｃｃ）
を噴霧室へ移しプラズマ炎に導入し、標準試料溶液に含
有されている元素（Ｓ ｉ、Ｍｎ）を発光させ、この発
光強度を測定した。更にイオン量３ｍｇ／ １００ｃｃ
、 ５ｍｇ／ １００ｃｃ、７ｍｇ／ １００ ｃｃの
合計４種類の標準試料溶液を上記のごとく発光強度を測
定し、これに基き、第４図に示すごとき検量線（Ａ）（
気温１８°Ｃ）を設定した。次いで、標準試料溶液をＣ
： ０．１２％、Ｓｉ： ０．２５％、Ｍｎ：０．３５
％、Ｐ ： ０．００１％、Ｓ ： ０．００１％、Ａ
Ｉ ： ０．００３％を含有する鋼を上記標準試料溶
液と同様の処理を施して調製した分析用試料溶液に変え
同様に発光強度を測定し、設定検量線に基き鋼中含有率
５ｉ＝０．２５１％Ｍｎ＝０．３５２％と決定した。Next, standard sample solution (ion amount: 1mg/10Qcc)
was transferred to a spray chamber and introduced into a plasma flame to cause the elements (Si, Mn) contained in the standard sample solution to emit light, and the intensity of this emitted light was measured. Furthermore, the amount of ions is 3mg/100cc
, 5 mg/100 cc, 7 mg/100 cc of total four types of standard sample solutions were measured for luminescence intensity as described above, and based on this, a calibration curve (A) as shown in Figure 4 was calculated.
The temperature was set at 18°C. Then, the standard sample solution was
: 0.12%, Si: 0.25%, Mn: 0.35
%, P: 0.001%, S: 0.001%, A
I: Change the steel containing 0.003% to an analysis sample solution prepared by performing the same treatment as the standard sample solution above, measure the luminescence intensity in the same way, and based on the set calibration curve, the content in steel 5i = 0 It was determined that .251%Mn=0.352%.
次に、上記検量線（Ａ）設定１０時間後（気温２５°Ｃ
）に同様の標準試料溶液で、同条件により合計４回の発
光強度を測定し、第４図に示すごとき検量線（Ｂ）を設
定し、分析用試料溶液に変えて、同様に発光強度を測定
し、検量線（Ｂ）に基き鋼中含有率５ｉ＝０．２５１％
、Ｍｎ＝０．３５１％と決定した。Next, 10 hours after setting the above calibration curve (A) (temperature 25°C
), the luminescence intensity was measured a total of four times under the same conditions using the same standard sample solution, and a calibration curve (B) as shown in Figure 4 was set. Measured and based on the calibration curve (B) content in steel 5i = 0.251%
, Mn=0.351%.
実施例４
上記実施例３において、検量線（Ａ）と検量線（Ｂ）か
ら第５図及び第６図に示すごとき検量線（Ｃ）を推定設
定し、この検量線（Ｃ）に基き検量線（Ａ）から検量線
（Ｂ）の設定時刻迄に分析した値の修正を施した。Example 4 In Example 3 above, a calibration curve (C) as shown in Figures 5 and 6 is estimated from the calibration curve (A) and the calibration curve (B), and the calibration is performed based on this calibration curve (C). The values analyzed from the curve (A) to the set time of the calibration curve (B) were corrected.
比較例２
実施例３において検量線（Ｂ）を設定することなく検量
線（Ａ）により分析した。Comparative Example 2 In Example 3, analysis was performed using the calibration curve (A) without setting the calibration curve (B).
これらの結果を下表に示す。These results are shown in the table below.
第１図、第２図及び第３図は本発明方法の説明図、第４
図、第５図及び第６図は本発明の実施例による設定検量
線を示す説明図表である。Figures 1, 2, and 3 are explanatory diagrams of the method of the present invention;
5 and 6 are explanatory charts showing set calibration curves according to embodiments of the present invention.
（発明の効果）
本発明によれば、気温等の外的要因による分析精度の低
下を防止し、正確な分析ができるので、品質を向上する
ことができ、また、−旦分析した値を修正し正確な分析
値が得られる等の優れた効果が得られる。(Effects of the Invention) According to the present invention, it is possible to prevent a decrease in analysis accuracy due to external factors such as temperature and perform accurate analysis, thereby improving quality. Excellent effects such as accurate analytical values can be obtained.
Claims (1)
を測定してその結果をもとに検量線を設定し、該検量線
に基き試料の成分分析を行うようにした分析方法におい
て、前記標準試料の吸光度又は発光強度を外的要因の変
化に応じ再測定し、その結果を演算器へ導いて新たな検
量線を設定して該検量線に基き以後の試料成分分析を行
うことを特徴とする分析方法。 ２、イオン濃度の異なる標準試料の吸光度又は発光強度
を測定してその結果をもとに検量線を設定し、該検量線
に基き試料の成分分析を行うようにした分析方法におい
て、前記標準試料の吸光度又は発光強度を外的要因の変
化に応じ再測定し、その結果を演算器へ導いて新たな検
量線を設定して該検量線に基き以後の試料成分分析を行
い、且つ、前記した前後の検量線設定時刻間に行った試
料成分分析結果を前後の測定結果から推定して設定され
る推定検量線に基き修正することを特徴とする分析方法
。 ３、イオン濃度の異なる標準試料の吸光度又は発光強度
を測定してその結果をもとに検量線を設定し、該検量線
に基き試料の成分分析を行うようにした分析方法におい
て、前記標準試料の吸光度又は発光強度を外的要因の変
化に応じ再測定し、その結果を演算器へ導いて新たな検
量線を設定して該検量線に基き試料成分分析を行い、且
つ、前記した前後の検量線設定時刻間に行った試料成分
分析結果を前後の測定結果から推定して設定される推定
検量線に基き修正するとともに、以後の試料成分分析を
前後の測定結果から予測して設定される予測検量線に基
き行うことを特徴とする分析方法。[Claims] 1. Analysis in which the absorbance or luminescence intensity of standard samples with different ion concentrations is measured, a calibration curve is set based on the results, and the component analysis of the sample is performed based on the calibration curve. In this method, the absorbance or luminescence intensity of the standard sample is remeasured according to changes in external factors, the results are led to a computer, a new calibration curve is set, and subsequent sample component analysis is performed based on the calibration curve. An analysis method characterized by: 2. In an analysis method in which the absorbance or luminescence intensity of standard samples with different ion concentrations is measured, a calibration curve is set based on the results, and component analysis of the sample is performed based on the calibration curve. The absorbance or luminescence intensity of the sample is remeasured in accordance with changes in external factors, the results are led to a computer, a new calibration curve is set, and subsequent sample component analysis is performed based on the calibration curve. An analysis method characterized by correcting the sample component analysis results performed between the previous and subsequent calibration curve setting times based on an estimated calibration curve that is set by estimating the sample component analysis results from the previous and subsequent measurement results. 3. In an analysis method in which the absorbance or luminescence intensity of standard samples with different ion concentrations is measured, a calibration curve is set based on the results, and component analysis of the sample is performed based on the calibration curve, the standard sample The absorbance or luminescence intensity of The calibration curve is set based on the estimated calibration curve, which is set by estimating the sample component analysis results performed during the time period from the previous and subsequent measurement results, and is set by predicting the subsequent sample component analysis from the previous and subsequent measurement results. An analysis method characterized by being performed based on a predicted calibration curve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20283888A JPH0252239A (en) | 1988-08-15 | 1988-08-15 | Analysis methode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20283888A JPH0252239A (en) | 1988-08-15 | 1988-08-15 | Analysis methode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0252239A true JPH0252239A (en) | 1990-02-21 |
Family
ID=16464026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20283888A Pending JPH0252239A (en) | 1988-08-15 | 1988-08-15 | Analysis methode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0252239A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04127058A (en) * | 1990-09-19 | 1992-04-28 | Nippon Steel Corp | Method and apparatus for automatically analyzing acid value and saponification value of oil |
| JP2004294205A (en) * | 2003-03-26 | 2004-10-21 | Kurabo Ind Ltd | Measuring method and measuring device of metal content in acid solution |
| JP2017106747A (en) * | 2015-12-07 | 2017-06-15 | 東亜ディーケーケー株式会社 | Analysis device, method of evaluating drift of the same, and program |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5920665U (en) * | 1982-07-30 | 1984-02-08 | 富士通テン株式会社 | Printed board |
-
1988
- 1988-08-15 JP JP20283888A patent/JPH0252239A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5920665U (en) * | 1982-07-30 | 1984-02-08 | 富士通テン株式会社 | Printed board |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04127058A (en) * | 1990-09-19 | 1992-04-28 | Nippon Steel Corp | Method and apparatus for automatically analyzing acid value and saponification value of oil |
| JP2004294205A (en) * | 2003-03-26 | 2004-10-21 | Kurabo Ind Ltd | Measuring method and measuring device of metal content in acid solution |
| JP2017106747A (en) * | 2015-12-07 | 2017-06-15 | 東亜ディーケーケー株式会社 | Analysis device, method of evaluating drift of the same, and program |
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