Beruflich Dokumente
Kultur Dokumente
EDX Series
Measuring Hazardous Elements
SHIMADZU CORPORATION
ANALYTICAL & MEASURING
INSTRUMENTS DIVISION
Contents
Contents
About this manual
1. Sensitivity and Precision in X-Ray Fluorescence Spectrometry.....................................
1.1 Precision of X-Ray Spectrometry
......................................................
1.1.1 Standard Deviation
......................................................
1.1.2 Lower Detection Limit
......................................................
1.2 Differences in Sensitivity Due to Sample Material and Shape ...............................
1.2.1 Differences in Sensitivity Due to Sample Material ..........................................
1.2.2 Differences in Sensitivity Due to Sample Size or Thickness ...........................
1.2.3 Scattered X-ray and Fluorescent X-ray
......................................................
1.2.4 Correcting for Sample Shape and Material ......................................................
2. Analytical Conditions
......................................................
2.1 Example of Setting Parameters
......................................................
2.1.1 Example of Setting Parameters
......................................................
2.2 Key Points for Setting Parameters
......................................................
2.2.1 Overview
......................................................
2.2.2 Element Registration
......................................................
2.2.3 Element Information
......................................................
2.2.4 Measurement Conditions
......................................................
2.2.5 Process for Spectra
......................................................
2.2.6 Internal Standard Correction
......................................................
2.2.7 Result Format
......................................................
2.2.8 Standard Sample Registration
......................................................
2.2.9 Standard Sample Measurements
......................................................
2.2.10 Calibration Curve Preparation
......................................................
3. Controlling Precision
......................................................
3.1 Drift Check Analysis
......................................................
3.1.1 Analyzing Control Sample
......................................................
3.1.2 Results Outside the Control Range
......................................................
3.2 Drift Standardization
......................................................
3.2.1 What is Drift Standardization?
......................................................
3.2.2 Registration of Reference Intensities for Standardization Samples ..................
3.2.3 Drift Coefficient Renewal
......................................................
3.2.4 Drift Coefficient Criteria
......................................................
3.3 Measurement Time Reduction
......................................................
3.3.1 Measurement Time Reduction
......................................................
4. Interpreting Data and Making Determination
......................................................
4.1 The possibility of Determination Errors
......................................................
4.1.1 Determination Errors Due to Overlapping Spectra ..........................................
4.1.2 Determination Errors Due to Diffracted Lines ................................................
4.2 ExReport Function
......................................................
4.2.1 ExReport Function
......................................................
5. Hints for Configuring Conditions
......................................................
1
1
1
2
3
3
4
4
5
6
6
6
6
6
8
9
10
12
13
14
15
17
18
22
22
22
22
23
23
23
27
28
29
29
30
30
30
31
32
32
33
X-Ray Counts
In the case of x-rays per unit time (cps), the standard deviation is as follows.
Standard Deviation of X-Ray Intensity (cps)
=
X-Ray Counts
x b.
PVC
Aluminum
Copper
Tin
Lead
Cd
1.2
1.5
50
200
Pb
2.3
2.5
20
30
---------
Note that even though they are both plastics, the lower detection limit for polyethylene and polyvinyl
chloride (PVC) is quite different. This is due to x-ray fluorescence from target elements being absorbed
by the chlorine contained in polyvinyl chloride.
PVC
Aluminum
Copper
Tin
Lead
Cd
5mm
5mm
3mm
100 m
150 m
20 m
Pb
5mm
0.7mm
0.5mm
20 m
30 m
---------
2.Analytical Conditions
2. Analytical Conditions
2. Analytical Conditions
[Example]
Register Cd,Pb,Hg,Cr,Br in Periodic Table.
Also register Cl,Sb.
Element
Registration
Element
Information
Measurement
Condition
( For EDX-720 )
Voltage
Filter (*1)
DT%(*2)
Cd
50kV
100
MoNi
40
Sb
50kV
100
MoNi
40
Pb
50kV
100
Ag
40
Hg
50kV
100
Ag
40
Br
50kV
100
Ag
40
Cl
50kV
100
Ag
40
Cr
30kV
100
Al
40
Smoothing
Process for
No. of Points
Repeat
Times
Repeat Times
Calculation
Points
Cd
11
100
20
Sb
11
100
20
Pb
11
100
Hg
11
100
Br
11
100
Cl
100
Cr
11
100
Spectra
Internal Standard
Correction
BG Calculation
Curve
Result Format
Calibration
(*1) For EDX-700HS/800HS, use Mo filter instead of MoNi filter. Use Ni filter instead of
Ag filter. For EDX-900HS, use Zr filter instead of a MoNi filter. Use Ni filter instead of
Ag filter.
(*2) For EDX-700HS/800HS spectrometers, set DT% to 25. For EDX-900HS, set DT% to
10.
7
2. Analytical Conditions
2. Analytical Conditions
Proc. Calc.
Type of Quantification
Unit
Quant.
Calibration Curve
ppm
Enter settings for Pb, Hg, Cr and Br in the same way. However, in the case of Pb, also change the line to
La.
2. Analytical Conditions
50 kV
Auto
MoNi
Live Time and 100 sec
40
Fitting
22.72 23.52
10
2. Analytical Conditions
Similarly, use the following table to enter settings for the other elements. Regarding other parameters, set
Current to Auto for all of the elements, and Intensity Calculation Method to Fitting. The initial
voltage setting for Cl is 15 kV. In this case, change it to 50 kV to allow simultaneous measurement with
Pb, Hg and Br.
Voltage
Meas.Time (sec)
Analysis Range(keV)
Filter(*1)
DT%(*2)
Cd
50kV
LiveTime 100
22.72-23.52
MoNi
40
Sb
50kV
LiveTime 100
25.88-26.68
MoNi
40
Pb
50kV
LiveTime 100
10.32-10.82
Ag
40
Hg
50kV
LiveTime 100
9.74-10.24
Ag
40
Br
50kV
LiveTime 100
11.66-12.16
Ag
40
Cl
50kV
LiveTime 100
2.42-2.82
Ag
40
Cr
30kV
LiveTime 100
5.12-5.62
Al
40
(*1) For EDX-700HS/800HS, use Mo filter instead of MoNi filter. Use Ni filter instead of
Ag filter. For EDX-900HS, use Zr filter instead of a MoNi filter. Use Ni filter instead of
Ag filter.
(*2) For EDX-700HS/800HS spectrometers, set DT% to 25. For EDX-900HS, set DT% to
10.
11
2. Analytical Conditions
Number of Points :
Repeat Times :
Method:
Repeat Times :
Calculation Points :
BG Calculation
11
1
Savitzky-Golay
100
20
Similarly, use the following table to enter settings for the other elements.
Smoothing
BG Calculation
No. of Points
Repeat Times
Repeat Times
Calculation Points
Cd
11
100
20
Sb
11
100
20
Pb
11
100
Hg
11
100
Br
11
100
Cl
100
Cr
11
100
12
2. Analytical Conditions
On
CdKa_BG
Similarly, enter the internal standard settings for Pb, Hg, Br, Cr and Cl. However, do not enter internal
standard settings for Sb.
13
2. Analytical Conditions
Similarly, enter the result format settings for Pb, Hg, Br and Cr.
14
2. Analytical Conditions
Standard PE Samples
PE-1
PE-2
PE-3
PE-4
PE-5
PVC-6
PE-6
15
2. Analytical Conditions
After entering the values, close the window by clicking [OK]. Then click [Apply] in the Standard Sample
window to confirm the settings.
16
2. Analytical Conditions
Click [Apply] to register the standard samples in the Sample Schedule. Place the first standard sample in
the instrument. Then click [Start] button in the Analysis window to start measurement.
After the first sample has been measured, the sample chamber will open automatically. After exchanging
samples, click the [Start] button to resume measurement.
17
2. Analytical Conditions
18
2. Analytical Conditions
19
2. Analytical Conditions
Select calibration curve number 1 and click [Calculate]. This will calculate a calibration curve using
standard sample Cl intensities ratio that are below 2.0. In other words, this calculates the calibration
curve for the standard PE sample.
Next, select calibration curve number 2 and click [Calculate]. This will calculate a calibration curve using
standard sample Cl intensities (ratio) that are 2.0 or higher. In other words, this calculates the
calibration curve for the standard PVC sample.
Once both calibration curves are calculated, click [Apply] to save the results.
20
2. Analytical Conditions
Settings for Pb, Hg, Br and Cr are also configured for automatic switching between calibration curves.
For Cd, the difference between coefficients for PVC and PE is not large, so the process of configuring
automatic switching between calibration curves may be skipped.
21
3. Controlling Precision
3. Controlling Precision
22
3. Controlling Precision
23
3. Controlling Precision
Once the settings have been entered, click [OK] to close Standardization window. Then save the group
condition via the File menu.
24
3. Controlling Precision
Click [Apply] to register the standardization samples in the Sample Schedule. Place the first
standardization sample in the instrument. Then click [Start] button in the Analysis window to start
measurement.
25
3. Controlling Precision
The measured intensities are automatically registered in the original group condition. The intensities can
be confirmed via Standardization Sample tab in Standardization window.
26
3. Controlling Precision
Click [Apply] to register the standardization samples in the Sample Schedule. Place the first
standardization sample in the instrument. Then click [Start] button in the Analysis window to start
measurement.
27
3. Controlling Precision
The drift coefficient is calculated automatically after the measurement is finished and displayed on
Result Display window. These results are automatically saved into the original group condition only if
the drift coefficient is within the control range.
28
3. Controlling Precision
Given relative error (CV) = std. dev. of x-ray intensity / x-ray intensity x 100, there is an approximately
99% probability that the true value for the x-ray intensity is within the range (x-ray intensity x relative
error x 3.0).
29
PbLa
Hg
BrKa
Cr
30
Note, this diffraction phenomenon only occurs when the angle between the crystal face and x-ray tube
and the angle between the crystal face and detector are the same. However, crystal faces are oriented in
multiple directions and samples are generally not single crystals, so it is not possible to accurately predict
which crystal faces will generate intense diffraction line emissions.
Diffraction lines observed with EDX series have the following properties.
a)
b)
c)
The line widths are often about the same or wider than x-ray fluorescence peaks.
The diffraction pattern may change if the sample orientation or tilt angle is changed.
d)
e)
They are rarely observed in plastic samples. Tiny diffraction lines appear in metal samples.
They become lower when you use x-ray filter.
Currently program cannot determine automatically whether detected peaks are fluorescent x-ray lines or
diffraction lines. Therefore, be aware that the program treats diffraction lines as though they were peaks
from fluorescent x-rays, so peaks could be misidentified as other elements.
In some cases, using a primary x-ray filter for measurements can reduce the diffraction lines more than
peaks from fluorescent x-rays. If in doubt regarding whether a peak is a diffraction line or not, measure
the sample using a filter and compare the results to not using the filter.
Currently, the following cases have been reported.
Fe-based samples Tiny peaks near 10 keV may appear to be Hg peaks.
Ag-based samples Tiny peaks near 5.4 keV may appear to be Cr peaks.
Sn-based samples Tiny peaks near 5.4 keV may appear to be Cr peaks.
31
32
[Method 2] Uncheck the checkbox to the left of Analyte in Change Measuring Time window of
Analysis program..
33
2. Manually input a different name in Standard Sample field. And click any other location in the
window.
34
[Method 2] Measure the sample as an Unknown sample and load the standard sample intensities by
clicking [Read Intensity from Data] in Standard Sample window. Then reenter standard
values as necessary.
35
Deciding when to use BG internal standard correction and when not to use correction
Regular calibration curve methods are recommended for samples with low scattered x-ray intensities
(metal samples). Regular calibration curves are also recommended if samples are measured using a
smaller collimator.
36