JP2001056305A - Fluorescent x-ray analyser and recording medium used therein - Google Patents
Fluorescent x-ray analyser and recording medium used thereinInfo
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- JP2001056305A JP2001056305A JP11233461A JP23346199A JP2001056305A JP 2001056305 A JP2001056305 A JP 2001056305A JP 11233461 A JP11233461 A JP 11233461A JP 23346199 A JP23346199 A JP 23346199A JP 2001056305 A JP2001056305 A JP 2001056305A
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- sensitivity
- fluorescent
- sample
- elements
- intensity
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、いわゆるファンダ
メンタルパラメータ法を具現化した蛍光Ｘ線分析装置お
よびこれに使用する記録媒体に関するものである。The present invention relates to an X-ray fluorescence analyzer embodying the so-called fundamental parameter method and a recording medium used for the same.
【０００２】[0002]
【従来の技術】従来より、試料に１次Ｘ線を照射して、
試料中の各元素から発生する蛍光Ｘ線の強度を測定し、
それらの測定強度に基づく強度と、試料の組成すなわち
試料中の各元素の含有率を仮定して計算した各元素の蛍
光Ｘ線の理論強度とが合致するように、前記仮定した各
元素の含有率を逐次近似的に修正計算して、試料中の各
元素の含有率を算出する蛍光Ｘ線分析方法、いわゆるフ
ァンダメンタルパラメータ法（以下、ＦＰ法）がある。
ここで、測定強度に基づく強度とは、例えば、以下のよ
うにして求める。2. Description of the Related Art Conventionally, a sample is irradiated with primary X-rays,
Measure the intensity of fluorescent X-rays generated from each element in the sample,
The assumed content of each element is such that the intensity based on the measured intensity and the theoretical composition of the fluorescent X-ray of each element calculated assuming the composition of the sample, that is, the content of each element in the sample, match. There is a so-called fundamental parameter method (hereinafter, referred to as FP method) in which an X-ray fluorescence analysis method for calculating the content of each element in a sample by successively approximating and correcting the ratio is used.
Here, the intensity based on the measured intensity is obtained, for example, as follows.
【０００３】まず、あらかじめ使用する蛍光Ｘ線分析装
置において、組成が既知の標準試料について、１次Ｘ線
を照射して発生した蛍光Ｘ線の強度Ｉm を測定する。一
方、前記既知の組成における含有率での理論強度Ｉt を
算出する。そして、前記測定強度Ｉm をその理論強度Ｉ
t で除することにより、各元素ごとに、理論強度に対す
る測定強度の比いわばその装置の装置感度Ｉm ／Ｉt を
算出しておく。そこで、組成が未知の分析対象の試料
に、１次Ｘ線を照射して発生した蛍光Ｘ線の強度ｉm を
測定し、発生した蛍光Ｘ線ごとに、前記装置感度Ｉm ／
Ｉt を用いて、測定強度ｉm に基づき理論強度スケール
に換算した強度ｉt （以下、測定強度に基づく強度とい
う）を次式のように算出する。 ｉt ＝ｉm ／（Ｉm ／Ｉt ）＝ｉm ×Ｉt ／Ｉm [0003] First, in the fluorescent X-ray analysis apparatus in advance using a composition of the known standard sample, measuring the intensity I m of the fluorescent X-ray generated by irradiating the primary X-rays. On the other hand, to calculate the theoretical intensity I t in content in the known composition. Then, the measured intensity Im is converted to the theoretical intensity I.
By dividing the t, for each element, previously calculated by an apparatus sensitivity I m / I t ratio so to speak apparatus for measuring intensity to the theoretical strength. Therefore, the sample of unknown analyte composition, for each intensity i m of the fluorescent X-ray generated by irradiating the primary X-rays is measured, generated fluorescent X-ray, the device sensitivity I m /
Using I t, measured intensity i on the basis of the m theoretical intensity scale in terms of the intensity i t (hereinafter, referred to as intensity based on the measured intensity) is calculated by the following equation. i t = i m / (I m / I t) = i m × I t / I m
【０００４】前記組成が既知の標準試料としては、特定
元素を高い含有率で含む純物質またはその酸化物にそれ
ぞれ１元素を代表させた標準試料（以下、単一成分型の
標準試料と呼ぶ）を複数用いる場合と、１個で複数の元
素を含みそれらの元素を代表する標準試料（以下、複数
元素型の標準試料と呼ぶ）を単数用いる場合とが考えら
れる。一般にＦＰ法においては、試料の組成が異なると
共存元素によるＸ線吸収の効果が異なることなどから、
分析対象試料に組成が近似する複数元素型の標準試料を
用いると、より正確な組成が求められることが知られて
いる。そこで、ＦＰ法において、分析対象試料に組成が
近似する複数元素型の標準試料を検索してその装置感度
を用いることが、例えば、以下のように行われている。[0004] As a standard sample having a known composition, a standard substance in which one element is represented by a pure substance containing a specific element at a high content or an oxide thereof (hereinafter, referred to as a single-component standard sample) May be used, and a single standard sample containing a plurality of elements and representing those elements (hereinafter, referred to as a multi-element type standard sample) may be used. In general, in the FP method, when the composition of the sample is different, the effect of X-ray absorption by the coexisting element is different.
It is known that a more accurate composition is required by using a multi-element type standard sample whose composition is similar to the sample to be analyzed. Therefore, in the FP method, a method of searching for a multi-element type standard sample whose composition is similar to the sample to be analyzed and using the device sensitivity is performed, for example, as follows.
【０００５】まず、使用する蛍光Ｘ線分析装置におい
て、単一成分型の標準試料を多種類用い、各元素から発
生する蛍光Ｘ線に対する前記装置感度を求めて、その装
置に記憶させておく。この装置感度のデータは、元素ご
とに１つの装置感度データを保有し、装置感度データを
保有していない元素の装置感度を、その元素に原子番号
が近接し装置感度データを保有する元素の装置感度デー
タから推定することにより、その装置において種々の分
析対象試料に共通に使用できる（以下、この装置感度の
データを感度推定型感度ライブラリと呼ぶ）。一方、そ
の装置において、複数元素型の標準試料を多種類用い、
各元素から発生する蛍光Ｘ線に対する前記装置感度も求
めて、その装置に記憶させておく。この装置感度のデー
タは、標準試料ごとにそれが含む複数元素の各装置感度
データを保有し、その装置において組成が近似した分析
対象試料に使用できる（以下、複数元素型の標準試料に
よる装置感度のデータを標準試料感度ライブラリと呼
ぶ）。標準試料感度ライブラリには、各標準試料の既知
の組成も含めることができる。First, in a fluorescent X-ray analyzer to be used, multiple types of single-component standard samples are used, and the device sensitivity to fluorescent X-rays generated from each element is determined and stored in the device. The device sensitivity data is one device sensitivity data for each element, and the device sensitivity of an element that does not have device sensitivity data is the device sensitivity of an element whose atomic number is close to that element and has device sensitivity data. By estimating from the sensitivity data, the device can be used in common for various samples to be analyzed (hereinafter, this device sensitivity data is referred to as a sensitivity estimation type sensitivity library). On the other hand, the device uses multiple types of multi-element type standard samples,
The apparatus sensitivity to the fluorescent X-ray generated from each element is also obtained and stored in the apparatus. This instrument sensitivity data holds instrument sensitivity data of a plurality of elements included in each standard sample, and can be used for an analysis target sample whose composition is similar in the instrument (hereinafter, instrument sensitivity by a multi-element type standard sample). Is referred to as a standard sample sensitivity library). The standard sample sensitivity library can also include the known composition of each standard sample.
【０００６】このような準備の後に、分析対象試料につ
いて、広い元素の範囲でいわゆる定性分析を行う。この
際得られた各蛍光Ｘ線の測定強度ｉm と、感度推定型感
度ライブラリ中の該当元素の装置感度ＩUm／ＩUtとか
ら、前記測定強度に基づく強度ｉt ＝ｉm ／（ＩUm／Ｉ
Ut）を求め、いわゆる半定量分析として、前述したよう
に、ＦＰ法により、分析対象試料の概略の組成が算出で
きる（添字U は、単一成分型の標準試料に基づく数値で
あることを示す）。そこで、その概略の組成に近似した
組成の標準試料を標準試料感度ライブラリから検索し、
その標準試料の装置感度Ｉm ／Ｉt と前記測定強度ｉm
とから再度前記測定強度に基づく強度ｉt＝ｉm ／（Ｉ
m ／Ｉt ）を求め、半定量分析として、ＦＰ法により、
分析対象試料のより正確な組成が算出できる。After such preparation, a so-called qualitative analysis is performed on a sample to be analyzed in a wide range of elements. And measuring the intensity i m of the time each of the obtained X-ray fluorescence, and a device sensitive I Um / I Ut of the corresponding elements in the sensitivity estimation type sensitivity library, intensity based on the measured intensity i t = i m / (I Um / I
Ut ) and the approximate composition of the sample to be analyzed can be calculated by the FP method as described above as a so-called semi-quantitative analysis (the subscript U indicates a numerical value based on a single-component standard sample). ). Therefore, a standard sample having a composition similar to the approximate composition was searched from the standard sample sensitivity library,
Device sensitivity I m / I t and the measured intensity i m of the standard sample
Based on the measured intensity again the intensity i t = i m / (I
m / I t ), and as a semi-quantitative analysis, by the FP method,
A more accurate composition of the sample to be analyzed can be calculated.
【０００７】[0007]
【発明が解決しようとする課題】しかし、感度推定型感
度ライブラリや標準試料感度ライブラリに含まれる装置
感度は、装置固有の値をもつので、分析装置ごとに装置
感度を求めてその装置に記憶させなければならない。特
に、多種多様な分析対象試料を正確に分析するには、同
様に多種多様な標準試料を用いて装置ごとに標準試料感
度ライブラリの装置感度を求める必要があり、作業に長
時間を要する。However, since the device sensitivity included in the sensitivity estimation type sensitivity library and the standard sample sensitivity library has a value unique to the device, the device sensitivity is obtained for each analyzer and stored in the device. There must be. In particular, in order to accurately analyze a wide variety of samples to be analyzed, it is necessary to similarly determine the device sensitivity of a standard sample sensitivity library for each device using a wide variety of standard samples, which requires a long time.
【０００８】本発明は前記従来の問題に鑑みてなされた
もので、ＦＰ法を具現化した蛍光Ｘ線分析装置におい
て、その装置についての多種類の標準試料中の各元素か
ら発生する蛍光Ｘ線に対する装置感度を求めておくこと
が不要で、多様な分析対象試料について簡単に正確な分
析ができる装置およびこれに使用する記録媒体を提供す
ることを目的とする。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems. In an X-ray fluorescence analyzer embodying the FP method, an X-ray fluorescence generated from each element in various kinds of standard samples for the apparatus is provided. It is an object of the present invention to provide a device which does not need to determine the sensitivity of the device to and which can easily and accurately analyze various samples to be analyzed, and a recording medium used for the device.
【０００９】[0009]
【課題を解決するための手段】前記目的を達成するため
に、請求項１の装置は、まず、試料に１次Ｘ線を照射し
て、試料中の各元素から発生する蛍光Ｘ線の強度を測定
し、それらの測定強度に基づく強度と、試料中の各元素
の含有率を仮定して計算した各元素の蛍光Ｘ線の理論強
度とが合致するように、前記仮定した各元素の含有率を
逐次近似的に修正計算して、試料中の各元素の含有率を
算出する蛍光Ｘ線分析装置である。そして、前記測定強
度に基づく強度を求めるために、当該装置についての各
元素から発生する蛍光Ｘ線に対する装置感度であって原
子番号の近接する元素の装置感度を推定できる多数元素
の装置感度（感度推定型感度ライブラリ）と、当該装置
と同型の基準となる装置についての各元素から発生する
蛍光Ｘ線に対する装置感度であって原子番号の近接する
元素の装置感度を推定できる多数元素の装置感度（感度
推定型感度ライブラリ）と、前記基準となる装置につい
ての組成が既知の多種類の標準試料中の各元素から発生
する蛍光Ｘ線に対する装置感度（標準試料感度ライブラ
リ）とを記憶する記憶手段を備える。In order to achieve the above object, an apparatus according to claim 1 first irradiates a sample with primary X-rays, and intensifies fluorescent X-rays generated from each element in the sample. Are measured, and the intensities based on the measured intensities and the theoretical intensities of the fluorescent X-rays of the respective elements calculated assuming the contents of the respective elements in the sample match, so that the content of the respective assumed elements is This is an X-ray fluorescence spectrometer that calculates the content of each element in a sample by correcting the ratio in a successive approximation. Then, in order to obtain the intensity based on the measured intensity, the device sensitivity (sensitivity) of a large number of elements, which is the device sensitivity to the fluorescent X-ray generated from each element in the device and which can estimate the device sensitivity of an element having an atomic number close to the device. Estimated type sensitivity library) and device sensitivities of a number of elements that can estimate the device sensitivities for fluorescent X-rays generated from each element in the reference device of the same type as the device and of the elements having close atomic numbers ( Storage means for storing a sensitivity estimation type sensitivity library) and an apparatus sensitivity (standard sample sensitivity library) for fluorescent X-rays generated from each element in the various kinds of standard samples whose composition of the reference apparatus is known. Prepare.
【００１０】請求項１の装置によれば、ＦＰ法を具現化
した蛍光Ｘ線分析装置において、当該装置と同型の基準
となる装置についての標準試料感度ライブラリを、当該
装置についての感度推定型感度ライブラリと前記基準と
なる装置についての感度推定型感度ライブラリとを用い
て、当該装置についての標準試料感度ライブラリに変換
して使用できるので、当該装置についての標準試料感度
ライブラリを求めておかなくても、すなわち、当該装置
についての多種類の標準試料中の各元素から発生する蛍
光Ｘ線に対する装置感度を求めておかなくても、多様な
分析対象試料について簡単に正確な分析ができる。According to the first aspect of the present invention, in the X-ray fluorescence spectrometer embodying the FP method, a standard sample sensitivity library for a reference device of the same type as the device and a sensitivity estimation type sensitivity for the device are used. Using the library and the sensitivity estimation type sensitivity library for the reference device, the standard sample sensitivity library for the device can be converted and used, so that the standard sample sensitivity library for the device need not be determined. That is, it is possible to easily and accurately analyze various samples to be analyzed without having to determine the device sensitivity to X-ray fluorescence generated from each element in various types of standard samples of the device.
【００１１】請求項２の記録媒体は、ＦＰ法を具現化し
た蛍光Ｘ線分析装置において前記測定強度に基づく強度
を求めるために使用するコンピュータ読み取り可能な記
録媒体であって、当該装置についての各元素から発生す
る蛍光Ｘ線に対する装置感度であって原子番号の近接す
る元素の装置感度を推定できる多数元素の装置感度と、
当該装置と同型の基準となる装置についての各元素から
発生する蛍光Ｘ線に対する装置感度であって原子番号の
近接する元素の装置感度を推定できる多数元素の装置感
度と、前記基準となる装置についての組成が既知の多種
類の標準試料中の各元素から発生する蛍光Ｘ線に対する
装置感度とを記録した記録媒体である。請求項２の記録
媒体を、ＦＰ法を具現化した蛍光Ｘ線分析装置に使用す
れば、請求項１の装置と同様の作用効果が得られる。A recording medium according to a second aspect is a computer-readable recording medium used for obtaining an intensity based on the measured intensity in a fluorescent X-ray analyzer embodying the FP method. Device sensitivities for a large number of elements, which are device sensitivities to fluorescent X-rays generated from the elements, and are capable of estimating the device sensitivities of elements having close atomic numbers
Regarding the device sensitivity to X-ray fluorescence generated from each element for the device of the same type as the device and the device sensitivity of a large number of elements capable of estimating the device sensitivity of the element having an atomic number close to the device, Is a recording medium that records the device sensitivity to X-ray fluorescence generated from each element in various types of standard samples whose composition is known. When the recording medium according to the second aspect is used for an X-ray fluorescence analyzer embodying the FP method, the same operation and effect as the apparatus according to the first aspect can be obtained.
【００１２】[0012]
【発明の実施の形態】以下、本発明の一実施形態の蛍光
Ｘ線分析装置について説明する。まず、この装置の構成
について、図１にしたがって説明する。この装置は、試
料１３が載置される試料台８と、試料１３に１次Ｘ線２
を照射するＸ線管等のＸ線源１と、試料１３から発生す
る蛍光Ｘ線６の強度を測定する検出手段９とを備えてい
る。検出手段９は、試料１３から発生する２次Ｘ線４を
分光する分光素子５と、分光された蛍光Ｘ線６ごとにそ
の強度を測定する検出器７で構成される。分光素子５と
検出器７は種々の波長の蛍光Ｘ線６を測定するように、
図示しないゴニオメータ等の連動手段により連動され
る。なお、分光素子５や連動手段を用いずに、エネルギ
ー分解能の高い検出器を検出手段としてもよい。また、
この装置は、検出手段９で測定された測定強度に基づく
強度と、試料１３中の各元素の含有率を仮定して計算し
た各元素の蛍光Ｘ線６の理論強度とが合致するように、
前記仮定した各元素の含有率を逐次近似的に修正計算し
て、試料１３中の各元素の含有率を算出する算出手段１
０を備えている。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an X-ray fluorescence spectrometer according to one embodiment of the present invention will be described. First, the configuration of this device will be described with reference to FIG. This apparatus includes a sample table 8 on which a sample 13 is placed, and a primary X-ray 2
An X-ray source 1 such as an X-ray tube for irradiating the sample 13 and detection means 9 for measuring the intensity of fluorescent X-rays 6 generated from the sample 13 are provided. The detecting means 9 includes a spectroscopic element 5 for separating the secondary X-rays 4 generated from the sample 13 and a detector 7 for measuring the intensity of each of the separated fluorescent X-rays 6. The spectroscopic element 5 and the detector 7 measure fluorescent X-rays 6 of various wavelengths,
It is linked by a linking means such as a goniometer (not shown). Note that a detector having a high energy resolution may be used as the detection unit without using the spectroscopic element 5 and the interlocking unit. Also,
This apparatus is designed so that the intensity based on the measured intensity measured by the detection means 9 and the theoretical intensity of the fluorescent X-ray 6 of each element calculated on the assumption of the content of each element in the sample 13 match.
Calculation means 1 for correcting the assumed content of each element successively and approximately to calculate the content of each element in the sample 13
0 is provided.
【００１３】さらに、この装置は、前記測定強度に基づ
く強度を求めるために、当該装置についての各元素から
発生する蛍光Ｘ線６に対する装置感度であって原子番号
の近接する元素の装置感度を推定できる多数元素の装置
感度と、当該装置と同型の基準となる装置についての各
元素から発生する蛍光Ｘ線に対する装置感度であって原
子番号の近接する元素の装置感度を推定できる多数元素
の装置感度と、前記基準となる装置についての組成が既
知の多種類の標準試料中の各元素から発生する蛍光Ｘ線
に対する装置感度とを記憶する記憶手段１１を備えてい
る。なお、具体的には、算出手段１０はコンピュータ、
記憶手段１１はそのコンピュータのメモリやハードディ
スク装置で構成できる。また、同型とは、Ｘ線源や検出
手段等の仕様が共通する同一の機種を意味する。Further, in order to obtain the intensity based on the measured intensity, the apparatus estimates the apparatus sensitivity to the fluorescent X-rays 6 generated from each element in the apparatus, and the apparatus sensitivity of an element having an atomic number close thereto. The device sensitivity of a large number of elements that can be estimated and the device sensitivity of an element having the same atomic number as that of the reference device of the same type as the device with respect to the fluorescent X-rays generated from each element, which can be estimated And a storage unit 11 for storing the sensitivity of the device serving as the reference to X-ray fluorescence generated from each element in various types of standard samples whose composition is known. Note that, specifically, the calculating means 10 is a computer,
The storage means 11 can be constituted by a memory or a hard disk device of the computer. In addition, the same type means the same model having the same specifications of the X-ray source and the detection means.
【００１４】この装置の記憶手段１１には、前記の内容
を以下のようにして記憶させることができる。まず、こ
の装置において、多種類の単一成分型の標準試料３を、
順に、試料台８に載置し、Ｘ線源１から発生させた１次
Ｘ線２を照射して、発生した２次Ｘ線４を分光素子５に
入射させ、分光された主たる構成元素から発生した蛍光
Ｘ線６の強度ＩUmを検出器７で測定する。一方、前記既
知の組成における含有率での理論強度ＩUtを算出手段１
０で算出する。そして、前記測定強度ＩUmをその理論強
度ＩUtで除することにより、各元素（例えば原子番号４
〜９２）ごとに、装置感度ＩUm／ＩUtを算出手段１０で
算出し、この装置についての感度推定型感度ライブラリ
として記憶手段１１に記憶させておく。The above contents can be stored in the storage means 11 of this device as follows. First, in this apparatus, various types of single-component standard samples 3 are prepared.
The sample is placed on a sample table 8 in order, and is irradiated with primary X-rays 2 generated from an X-ray source 1, and the generated secondary X-rays 4 are made incident on a spectroscopic element 5. The intensity I Um of the generated fluorescent X-ray 6 is measured by the detector 7. On the other hand, the calculation means 1 calculates the theoretical intensity I Ut at the content in the known composition.
Calculate with 0. Then, by dividing the measured intensity I Um by the theoretical intensity I Ut , each element (for example, atomic number 4
９２92), the device sensitivity I Um / I Ut is calculated by the calculation unit 10 and stored in the storage unit 11 as a sensitivity estimation type sensitivity library for this device.
【００１５】同様に、この装置と同型の基準となる装置
において装置感度 SＩUm／ＩUtを算出し、基準となる装
置についての感度推定型感度ライブラリとして、この装
置（本実施形態の装置）の記憶手段１１に記憶させてお
く（添字 Sは、基準となる装置についての数値であるこ
とを示す）。さらに、前記基準となる装置において、複
数元素型の標準試料を多種類用い、標準試料ごとに、各
元素から発生する蛍光Ｘ線に対する装置感度 SＩm ／Ｉ
t も求めて、基準となる装置についての標準試料感度ラ
イブラリとして、この装置（本実施形態の装置）の記憶
手段１１に記憶させておく。標準試料感度ライブラリに
は、各標準試料の既知の組成も含める。Similarly, the apparatus sensitivity S I Um / I Ut is calculated in a reference apparatus of the same type as this apparatus, and this apparatus (the apparatus of this embodiment) is used as a sensitivity estimation type sensitivity library for the reference apparatus. (The subscript S indicates that it is a numerical value for the reference device). Further, in the reference apparatus, multiple types of standard samples of a plurality of elements are used, and for each standard sample, the device sensitivity S Im / I to fluorescent X-rays generated from each element is used.
t is also obtained, and stored in the storage unit 11 of this device (the device of the present embodiment) as a standard sample sensitivity library for the reference device. The standard sensitivity library also includes the known composition of each standard.
【００１６】記憶手段１１が記憶すべきこれらの内容
は、いったん、フロッピーディスク、ＭＯディスク、Ｃ
Ｄ−ＲＯＭ、ハードディスク等のコンピュータ読み取り
可能な記録媒体に記録し、その記録媒体からこの装置
（本実施形態の装置）の記憶手段１１に取り込んで記憶
させることもできる。なお、通常は分析対象試料１３の
組成は複数元素型の標準試料の組成に近似すると考えら
れるので、標準試料感度ライブラリ作成のための標準試
料には複数元素型の標準試料を用いるが、分析対象試料
１３が単一の元素しか含まない純物質かその酸化物であ
ることも予想される場合には、単一成分型の標準試料も
用いてよい。These contents to be stored in the storage means 11 are once a floppy disk, an MO disk,
The data may be recorded on a computer-readable recording medium such as a D-ROM or a hard disk, and may be taken from the recording medium and stored in the storage unit 11 of the apparatus (the apparatus of the present embodiment). Since the composition of the sample 13 to be analyzed is generally considered to be close to the composition of the standard sample of the multiple elements type, the standard sample for the preparation of the standard sample sensitivity library uses the standard sample of the multiple elements type. If the sample 13 is expected to be a pure substance containing only a single element or its oxide, a single-component standard sample may be used.
【００１７】以上のように、同型の装置においては、あ
る１台の基準となる装置において標準試料感度ライブラ
リを作成すれば足り、従来のように各装置において作成
する必要はない。標準試料感度ライブラリを作成しなか
った装置においては、その装置についての感度推定型感
度ライブラリを作成して記憶し、同型の基準となる装置
で作成した標準試料感度ライブラリを記憶し、併せて、
前記基準となる装置についての感度推定型感度ライブラ
リを記憶すればよい。As described above, in an apparatus of the same type, it is sufficient to create a standard sample sensitivity library in a certain reference apparatus, and it is not necessary to create it in each apparatus as in the prior art. In an apparatus for which a standard sample sensitivity library was not created, a sensitivity estimation type sensitivity library for the apparatus was created and stored, and a standard sample sensitivity library created with a reference apparatus of the same type was stored.
What is necessary is just to store the sensitivity estimation type sensitivity library for the reference device.
【００１８】次に、この装置の動作について説明する。
分析対象試料１３を試料台８に載置し、Ｘ線源１から発
生させた１次Ｘ線２を照射し、試料１３中の各元素から
発生する蛍光Ｘ線６の強度ｉm を検出器７で測定する。
算出手段１０は、記憶手段１１から、この装置について
の感度推定型感度ライブラリ中の該当元素の装置感度Ｉ
Um／ＩUtを呼び出し、測定強度に基づく強度ｉt ＝ｉm
／（ＩUm／ＩUt）を算出し、ＦＰ法による定量分析とし
て、この測定強度に基づく強度ｉt と、試料１３中の各
元素の含有率を仮定して計算した各元素の蛍光Ｘ線６の
理論強度とが合致するように、前記仮定した各元素の含
有率を逐次近似的に修正計算して、試料１３中の各元素
の含有率を算出する。これにより、試料１３の概略の組
成が求まる。なお、測定強度に基づく強度ｉt の算出に
あたり、分析対象試料１３と標準試料３との分析面積の
相違等を考慮することは、従来と同様に行う。また、こ
こでのＦＰ法は、特願平７−６８７４７号等に記載され
ているように、いわゆるセミファンダメンタルパラメー
タ法（ＳＦＰ法）でもよい。Next, the operation of this device will be described.
The analysis sample 13 is placed on the sample stage 8, is irradiated with primary X-rays 2 generated from a X-ray source 1, detector intensity i m of the fluorescent X-rays 6 generated from the elements in the sample 13 Measure at 7.
The calculating means 10 stores the device sensitivity I of the corresponding element in the sensitivity estimation type sensitivity library for this device from the storage means 11.
Call the Um / I Ut, based on the measured intensity intensity i t = i m
/ Calculates the (I Um / I Ut), a quantitative analysis by FP method, the intensity i t based on the measured intensity, a fluorescent X-ray of each element that is calculated assuming the content of each element in the sample 13 The content rates of the respective elements in the sample 13 are calculated by successively approximating and correcting the assumed content rates of the respective elements so that the theoretical strengths of No. 6 match. Thus, the approximate composition of the sample 13 is obtained. Incidentally, in the calculation of the based on the measurement strength intensity i t, taking into account the differences or the like of the analysis area of the analysis sample 13 and the standard sample 3 is performed in the same manner as before. The FP method here may be a so-called semi-fundamental parameter method (SFP method) as described in Japanese Patent Application No. 7-68747.
【００１９】続いて、算出手段１０は、その概略の組成
に近似した組成の標準試料を記憶手段１１中の標準試料
感度ライブラリから検索する。所定範囲内で近似した組
成の標準試料があれば、算出手段１０は、その標準試料
について、以下のように、基準となる装置についての標
準試料感度ライブラリ中の装置感度 SＩm ／Ｉt を、元
素ごとに、この装置についての感度推定型感度ライブラ
リ中の装置感度ＩUm／ＩUtと基準となる装置についての
感度推定型感度ライブラリ中の装置感度 SＩUm／ＩUtと
を用いて、この装置についての標準試料感度ライブラリ
としての装置感度Ｉm ／Ｉt に変換する。これらの必要
な装置感度は、記憶手段１１から呼び出す。 Ｉm ／Ｉt ＝（ SＩm ／Ｉt ）×（ＩUm／ＩUt）／（ S
ＩUm／ＩUt）Subsequently, the calculating means 10 searches the standard sample sensitivity library in the storage means 11 for a standard sample having a composition similar to the approximate composition. If there is a standard sample of a composition similar within the predetermined range, calculating means 10, for the standard sample, as described below, the device sensitivity S I m / I t in the standard sample sensitivity library for serving as a reference device For each element, using the device sensitivity I Um / I Ut in the sensitivity estimation type sensitivity library for this device and the device sensitivity S I Um / I Ut in the sensitivity estimation type sensitivity library for the reference device, converting the device sensitivity I m / I t of the standard sample sensitivity library for this device. These required device sensitivities are retrieved from the storage means 11. I m / I t = ( S I m / I t ) × (I Um / I Ut ) / ( S
I Um / I Ut )
【００２０】算出手段１０は、この変換した装置感度Ｉ
m ／Ｉt から再度測定強度に基づく強度ｉt ＝ｉm ／
（Ｉm ／Ｉt ）を算出し、ＦＰ法による定量分析とし
て、この測定強度に基づく強度ｉt と、試料１３中の各
元素の含有率を仮定して計算した各元素の蛍光Ｘ線６の
理論強度とが合致するように、前記仮定した各元素の含
有率を逐次近似的に修正計算して、試料１３中の各元素
の含有率を算出し、結果として図示しないＣＲＴ等の出
力手段から出力する。これにより、試料１３のより正確
な組成が求まる。なお、記憶手段１１中の標準試料感度
ライブラリに、概略の組成に所定範囲内で近似した組成
の標準試料がない場合は、感度推定型感度ライブラリを
用いて得られた概略の組成を結果として出力する。The calculating means 10 calculates the converted device sensitivity I
strength based on the measured intensity again m / I t i t = i m /
Calculating the (I m / I t), as a quantitative analysis by FP method, the intensity i t based on the measured intensity, a fluorescent X-ray of each element that is calculated assuming the content of each element in the sample 13 6 The calculated content of each element in the sample 13 is calculated by successively approximating and correcting the content of each element so that the theoretical intensity of the sample coincides with the theoretical strength of the sample 13. As a result, an output means such as a CRT (not shown) Output from Thereby, a more accurate composition of the sample 13 is obtained. If the standard sample sensitivity library in the storage means 11 does not include a standard sample having a composition similar to the approximate composition within a predetermined range, the approximate composition obtained using the sensitivity estimation type sensitivity library is output as a result. I do.
【００２１】記憶手段１１が記憶する装置感度として
は、特願平６−２６８２８５にも示されているように、
前述した標準試料についての測定強度を理論強度で除し
た値（ＩUm／ＩUt， SＩUm／ＩUt， SＩm ／Ｉt ）以外
に、以下のＩUm×ＩUtp ／ＩUt等が採用できる。この装
置についての感度推定型感度ライブラリの装置感度を例
にとると、まず、この装置において、多種類の単一成分
型の標準試料３について、前述したのと同様に、主たる
構成元素から発生した蛍光Ｘ線６の強度ＩUmを検出器７
で測定する。一方、標準試料３の既知の組成における含
有率での理論強度ＩUtと含有率１００％における理論強
度ＩUtp とを算出し、その比ＩUtp ／ＩUtを求める（添
字p は、含有率１００％における理論強度であることを
示す）。As shown in Japanese Patent Application No. 6-268285, the device sensitivity stored in the storage means 11 is as follows.
Aforementioned value obtained by dividing the measured intensity of the standard sample with the theoretical intensity (I Um / I Ut, S I Um / I Ut, S I m / I t) in addition to, the following I Um × I Utp / I Ut like Can be adopted. Taking the sensitivity of the sensitivity estimation type sensitivity library of this device as an example, first, in this device, many kinds of single component type standard samples 3 were generated from the main constituent elements in the same manner as described above. Detector 7 detects intensity I Um of fluorescent X-ray 6
Measure with On the other hand, the theoretical strength I Ut at the content of the known composition of the standard sample 3 and the theoretical strength I Utp at the content of 100% are calculated, and the ratio I Utp / I Ut is obtained (the subscript p indicates the content 100%). %).
【００２２】そして、前記測定強度ＩUmにその比を乗ず
ることにより、各元素（例えば原子番号４〜９２）ごと
に、標準試料３におけるその元素の含有率が１００％で
あるとした場合の強度すなわち装置感度ＩUm×ＩUtp ／
ＩUtを算出手段１０で算出し、この装置についての感度
推定型感度ライブラリとして記憶手段１１に記憶させて
おく。この場合には、分析対象試料１３の測定強度に基
づく強度ｉr は、前記ｉt に代えて、 ｉr ＝ｉm ／（ＩUm×ＩUtp ／ＩUt）＝ｉm ×ＩUt／Ｉ
Um×ＩUtp となり、試料１３から発生した蛍光Ｘ線６の相対強度ｉ
r ともいえる。同様に、前述の装置感度 SＩUm／ＩUt，
SＩm ／Ｉt に代えて、装置感度 SＩUm×ＩUtp／
ＩUt， SＩm ×Ｉtp／Ｉt を用いることができる。また
記憶手段１１に装置感度を記憶させるかわりに、
SＩm ，Ｉt ，ＩUm，ＩUt， SＩUmの測定強度と理論強
度を別々に記憶させて、ＦＰ法演算時に、分析対象試料
１３の装置感度Ｉm ／Ｉt を計算してもよい。Then, by multiplying the measured intensity I Um by the ratio, the intensity when the content of the element in the standard sample 3 is 100% for each element (for example, atomic numbers 4 to 92) That is, the device sensitivity I Um × I Utp /
I Ut is calculated by the calculation means 10 and stored in the storage means 11 as a sensitivity estimation type sensitivity library for this apparatus. In this case, the intensity i r based on the measured intensity of the analysis sample 13, in place of the i t, i r = i m / (I Um × I Utp / I Ut) = i m × I Ut / I
Um × I Utp , and the relative intensity i of the fluorescent X-ray 6 generated from the sample 13
It can be called r . Similarly, the device sensitivity S I Um / I Ut ,
Instead of the S I m / I t, device sensitivity S I Um × I Utp /
I Ut, can be used S I m × I tp / I t. Instead of storing the device sensitivity in the storage means 11,
S I m, I t, I Um, I Ut, by separately storing the measured intensity and the theoretical intensity of the S I Um, when the FP method calculation, the device sensitivity I m / I t of the analysis sample 13 was calculated Is also good.
【００２３】なお、従来のようにこの装置において多種
類の標準試料３中の各元素から発生する蛍光Ｘ線６に対
する装置感度を直接求めて記憶手段１１に記憶させるこ
とは不要であるが、そうしてはいけないということでは
なく、この装置についての標準試料感度ライブラリをも
有し、同型の基準となる装置についての標準試料感度ラ
イブラリと合わせた全体の中から、分析対象試料１３の
概略の組成に近似する組成の標準試料を検索し、その装
置感度を用いてＦＰ法を実行するというように利用して
もよい。また、以上においては、試料の組成のみを求め
る場合について説明したが、組成と試料の厚さを求める
場合にも、本発明は適用できる。なお、以上に述べた測
定強度ｉm ， SＩm ，ＩUm， SＩUmは、定性分析の際に
得られる強度を用いてもよいし、定時計数法により得ら
れる強度を用いてもよい。It is unnecessary to directly determine the sensitivity of the apparatus to the fluorescent X-rays 6 generated from various elements in the standard sample 3 and store it in the storage means 11 as in the prior art. It does not mean that it should not be done, but it also has a standard sample sensitivity library for this device, and from the whole combined with the standard sample sensitivity library for the reference device of the same type, A standard sample having a composition similar to the above may be searched, and the FP method may be performed using the sensitivity of the apparatus. Although the case where only the composition of the sample is determined has been described above, the present invention can be applied to the case where the composition and the thickness of the sample are determined. The above-mentioned measured intensity i m, S I m, I Um, S I Um may be using the intensity obtained in the qualitative analysis, it may be used intensity obtained by ordinary counting .
【００２４】[0024]
【発明の効果】以上詳細に説明したように、本発明によ
れば、ＦＰ法を具現化した蛍光Ｘ線分析装置において、
当該装置と同型の基準となる装置についての標準試料感
度ライブラリと、当該装置についての感度推定型感度ラ
イブラリおよび前記基準となる装置についての感度推定
型感度ライブラリとを用いて、検索して得られた標準試
料の当該装置についての装置感度を推定して使用できる
ので、当該装置についての標準試料感度ライブラリを求
めておかなくても、すなわち、当該装置についての多種
類の標準試料中の各元素から発生する蛍光Ｘ線に対する
装置感度を求めておかなくても、多様な分析対象試料に
ついて簡単に正確な分析ができる。As described above in detail, according to the present invention, in an X-ray fluorescence analyzer embodying the FP method,
Using a standard sample sensitivity library for a reference device of the same type as the device and a sensitivity estimation type sensitivity library for the device and a sensitivity estimation type sensitivity library for the reference device, a search was obtained. Since the sensitivity of the standard sample for the device can be estimated and used, there is no need to obtain a standard sample sensitivity library for the device, i.e., generated from each element in various types of standard samples for the device. Even if it is not necessary to determine the sensitivity of the apparatus to fluorescent X-rays, it is possible to easily and accurately analyze various samples to be analyzed.
【図１】本発明の一実施形態の蛍光Ｘ線分析装置を示す
図である。FIG. 1 is a diagram showing a fluorescent X-ray analyzer according to one embodiment of the present invention.
２…１次Ｘ線、３…標準試料、６…蛍光Ｘ線、１１…記
憶手段、１３…分析対象試料。2 ... primary X-ray, 3 ... standard sample, 6 ... fluorescent X-ray, 11 ... storage means, 13 ... sample to be analyzed.
フロントページの続き (72)発明者 片岡 由行 大阪府高槻市赤大路町14番８号 理学電機 工業株式会社内 Ｆターム(参考） 2G001 AA01 BA04 CA01 EA01 FA01 FA06 FA29 FA30 GA01 KA01Continued on the front page (72) Inventor Yoshiyuki Kataoka 14-8, Akaoji-cho, Takatsuki-shi, Osaka Rigaku Electric Industrial Co., Ltd. F-term (reference) 2G001 AA01 BA04 CA01 EA01 FA01 FA06 FA29 FA30 GA01 KA01
Claims (2)
元素から発生する蛍光Ｘ線の強度を測定し、それらの測
定強度に基づく強度と、試料中の各元素の含有率を仮定
して計算した各元素の蛍光Ｘ線の理論強度とが合致する
ように、前記仮定した各元素の含有率を逐次近似的に修
正計算して、試料中の各元素の含有率を算出する蛍光Ｘ
線分析装置において、 前記測定強度に基づく強度を求めるために、当該装置に
ついての各元素から発生する蛍光Ｘ線に対する装置感度
であって原子番号の近接する元素の装置感度を推定でき
る多数元素の装置感度と、当該装置と同型の基準となる
装置についての各元素から発生する蛍光Ｘ線に対する装
置感度であって原子番号の近接する元素の装置感度を推
定できる多数元素の装置感度と、前記基準となる装置に
ついての組成が既知の多種類の標準試料中の各元素から
発生する蛍光Ｘ線に対する装置感度とを記憶する記憶手
段を備えたことを特徴とする蛍光Ｘ線分析装置。1. A sample is irradiated with primary X-rays, the intensity of fluorescent X-rays generated from each element in the sample is measured, and the intensity based on the measured intensity and the content of each element in the sample are measured. The content rates of the respective elements in the sample are calculated by successively and approximately correcting and calculating the content rates of the respective assumed elements so that the theoretical intensities of the fluorescent X-rays of the respective elements are calculated assuming that: Fluorescent X
In the X-ray analysis apparatus, in order to obtain an intensity based on the measured intensity, a multi-element apparatus capable of estimating the apparatus sensitivity to the fluorescent X-ray generated from each element in the apparatus and estimating the apparatus sensitivity of an element having an atomic number close thereto. Sensitivity, the device sensitivity of a large number of elements that can estimate the device sensitivity to the fluorescent X-rays generated from each element for the device of the same type as the device and the device sensitivity of the element having an atomic number close to the device, An X-ray fluorescence analyzer comprising: a storage unit for storing the sensitivity of the device to X-ray fluorescence generated from each element in various types of standard samples whose composition is known.
元素から発生する蛍光Ｘ線の強度を測定し、それらの測
定強度に基づく強度と、試料中の各元素の含有率を仮定
して計算した各元素の蛍光Ｘ線の理論強度とが合致する
ように、前記仮定した各元素の含有率を逐次近似的に修
正計算して、試料中の各元素の含有率を算出する蛍光Ｘ
線分析装置に、前記測定強度に基づく強度を求めるため
に使用するコンピュータ読み取り可能な記録媒体であっ
て、 当該装置についての各元素から発生する蛍光Ｘ線に対す
る装置感度であって原子番号の近接する元素の装置感度
を推定できる多数元素の装置感度と、当該装置と同型の
基準となる装置についての各元素から発生する蛍光Ｘ線
に対する装置感度であって原子番号の近接する元素の装
置感度を推定できる多数元素の装置感度と、前記基準と
なる装置についての組成が既知の多種類の標準試料中の
各元素から発生する蛍光Ｘ線に対する装置感度とを記録
した記録媒体。2. A sample is irradiated with primary X-rays, the intensity of fluorescent X-rays generated from each element in the sample is measured, and the intensity based on the measured intensity and the content of each element in the sample are measured. The content rates of the respective elements in the sample are calculated by successively and approximately correcting and calculating the content rates of the respective assumed elements so that the theoretical intensities of the fluorescent X-rays of the respective elements are calculated assuming that: Fluorescent X
A computer-readable recording medium used for obtaining an intensity based on the measured intensity in a X-ray analysis apparatus, the apparatus sensitivity to X-ray fluorescence generated from each element of the apparatus, which is close to an atomic number. Estimates the device sensitivities of multiple elements that can estimate the device sensitivities of the elements, and the device sensitivities for the fluorescent X-rays generated from each element in the reference device of the same type as the device, and the devices with similar atomic numbers. A recording medium which records device sensitivities of a large number of elements and device sensitivities to fluorescent X-rays generated from each element in various types of standard samples whose compositions of the reference device are known.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23346199A JP3389161B2 (en) | 1999-08-20 | 1999-08-20 | X-ray fluorescence analyzer and recording medium used therein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23346199A JP3389161B2 (en) | 1999-08-20 | 1999-08-20 | X-ray fluorescence analyzer and recording medium used therein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001056305A true JP2001056305A (en) | 2001-02-27 |
| JP3389161B2 JP3389161B2 (en) | 2003-03-24 |
Family
ID=16955405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23346199A Expired - Fee Related JP3389161B2 (en) | 1999-08-20 | 1999-08-20 | X-ray fluorescence analyzer and recording medium used therein |
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| Country | Link |
|---|---|
| JP (1) | JP3389161B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006317371A (en) * | 2005-05-16 | 2006-11-24 | Shimadzu Corp | Emission spectroscopic analyzing method and emission spectroscopic analyzer |
| JP2007333501A (en) * | 2006-06-14 | 2007-12-27 | Shimadzu Corp | Emission spectrophotometer |
-
1999
- 1999-08-20 JP JP23346199A patent/JP3389161B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006317371A (en) * | 2005-05-16 | 2006-11-24 | Shimadzu Corp | Emission spectroscopic analyzing method and emission spectroscopic analyzer |
| JP4506554B2 (en) * | 2005-05-16 | 2010-07-21 | 株式会社島津製作所 | Emission spectroscopy analysis method and emission spectroscopy analyzer |
| JP2007333501A (en) * | 2006-06-14 | 2007-12-27 | Shimadzu Corp | Emission spectrophotometer |
| JP4626572B2 (en) * | 2006-06-14 | 2011-02-09 | 株式会社島津製作所 | Optical emission spectrometer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3389161B2 (en) | 2003-03-24 |
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