X-ray Fluorescence Quantitative Analysis Geometry Effect Correction

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Solution Overview

Problem

Existing X-ray fluorescence analysis methods face challenges in accurately quantifying components due to the geometry effect, where high-energy fluorescent X-rays from samples with light elements are not detected, leading to analysis errors, especially when considering the influence of the optical system and sample depth.

Innovation Solution

A quantitative analysis method that calculates a matrix correction coefficient by simulating the geometry effect using a fundamental parameter method, allowing for accurate detection intensity calculations and subsequent content analysis in X-ray fluorescence spectrometry.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Length of stationary object

If high-energy fluorescent X-rays are measured from samples with light elements, then detection depth increases, but geometry effect causes non-detection regions and reduces measurement precision

Engineering Contradiction:
Improvedetection depthVSAvoidmeasurement precision
Core Design Contradiction:
Length of stationary objectVSMeasurement precision

Solution Approach 1:

The patent changes the parameter of detection intensity calculation by introducing a geometry effect correction term that accounts for the spatial distribution of X-ray generation and detection. The correction term modifies the detection intensity calculation to include geometric factors (angles, distances) that vary with depth, transforming the calculation from a simple intensity measurement to a depth-corrected value that compensates for the geometry effect.

Inventive Principle:
Principle #35Parameter changes

2Measurement precision

If fundamental parameter method is used to calculate theoretical intensities, then matrix correction can be performed, but geometry effect is not considered leading to analysis errors

Engineering Contradiction:
Improvequantitative analysis accuracyVSAvoidgeometry effect information
Core Design Contradiction:
Measurement precisionVSLoss of information

Solution Approach 1:

The patent applies preliminary action by pre-calculating the geometry effect correction term based on the optical system parameters and sample characteristics before performing the quantitative analysis. The correction term is derived in advance using the fundamental parameter method, incorporating geometric factors that would otherwise be lost, and then applies this pre-computed correction to the detection intensity calculation.

Inventive Principle:
Principle #10Preliminary action

3Productivity

If matrix correction coefficient is calculated using conventional methods, then calibration can be performed, but geometry effect causes detection intensity errors

Engineering Contradiction:
Improveanalysis efficiencyVSAvoiddetection intensity accuracy
Core Design Contradiction:
ProductivityVSMeasurement precision

Solution Approach 1:

The patent introduces an intermediary element - the geometry effect correction term - that acts as a mediator between the raw detection intensity and the corrected intensity used for quantitative analysis. This correction term incorporates both the optical system parameters and the depth-dependent geometric factors, serving as an intermediary calculation that bridges the gap between conventional matrix correction and the actual detected signal.

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach enables highly accurate quantitative analysis by accounting for the geometry effect, reducing errors in detecting fluorescent X-rays from deep within samples, particularly those with light elements, thereby improving the precision of component content determination.

Implementation Method 1

There is an X-ray fluorescence analysis method of irradiating a sample with primary X-rays to quantitatively analyze contents of components (elements and compounds) contained in the sample based on detected X-ray intensities of secondary X-rays emitted from the sample. The secondary X-rays include: fluorescent X-rays generated from each component in the sample irradiated with the primary X-rays

Methodology Applied
Scientific EffectX-ray fluorescence: Fluorescence

Implementation Method 2

There is a phenomenon that fluorescent X-rays generated from a certain component in a sample are absorbed by a coexisting component present around the component before the fluorescent X-rays exit through the path to a front analyzing surface of the sample

Methodology Applied
Scientific EffectAbsorption: Absorption (EM radiation)

Implementation Method 3

There is also a phenomenon (secondary excitation) that an element of the component is secondarily excited by the fluorescent X-rays generated from the coexisting component to generate fluorescent X-rays

Methodology Applied
Scientific EffectSecondary excitation: Fluorescence

Data Source

PatentEP4105649B1Quantitative analysis method, quantitative analysis program, and fluorescence x-ray analysis device
Publication Date: 2024.09.25 RIGAKU CORP
  • EP4105649B1 patent drawingFigure 1
  • EP4105649B1 patent drawingFigure 2
  • EP4105649B1 patent drawingFigure 3

AI summary

Provided are a quantitative analysis method, a quantitative analysis program, and an X-ray fluorescence spectrometer which are capable of performing a highly accurate quantitative analysis in consideration of an influence of a geometry effect. The quantitative analysis method includes: a step of acquiring a representative composition set to represent contents of analysis components; a step of acquiring a plurality of comparative compositions, in each of which the content of one of the analysis components of the representative composition is changed by a predetermined content; a detection intensity calculation step of calculating a detection intensity indicating an intensity of fluorescent X-rays detected under the influence of the geometry effect through use of an FP method with respect to a virtual sample having a thickness set in advance and being indicated by each of the representative composition and the comparative compositions; and a step of calculating a matrix correction coefficient for each of the analysis components based on the detection intensity. In the quantitative analysis method, αj is calculated through use of a calibration curve equation including: a detection intensity Ii of a component "i"; Wi representing a mass fraction of the component "i"; Wj representing a mass fraction of a coexisting component "j"; constants "a", "b", and "c"; and αj representing the matrix correction coeffieint for the component "i" with respect to the coexisting component "j".