X-Calibur Manual
X-Calibur Manual
X-Calibur Manual
X-2600
2600 Series System
Operation Manual
Revision 3.0 November 2011
1
X-2600 Series System Operation Manual
Revision 3.0 November 2011
Contents
Chapter 1
System Overview
WARNING
The Beryllium window is extremely fragile and poisonous! Never (ever)
touch it!!!
The detector converts the X-ray photons into very small electrical pulses, which
are amplified by the preamplifier. The preamplifier output is further amplified
and shaped by a Digital Pulse Processor (Multi Channel Analyzer board), into
pulses having the highest signal-to-noise ratio. The DPP board (referred to as
MCA in the Graphical User Interface) is installed inside the spectrometer system.
The data of the accumulated spectra are stored and displayed on the computer's
monitor as spectra histogram.
A separate analog detector voltage power supply ensures proper operation of
the detector. The detector cannot operate at room temperature. If the detector
begins to warm, (temperature increases above –40 °C) its bias voltage will
automatically be turned off to prevent damage to the detector crystal.
Therefore, it is recommended that the X-Calibur not be turned off for an
extended period of time after is has been installed.
ED-XRF analysis tools enjoy the following advantages:
• Broad concentration range from ppm levels up to 100%.
• Sensitivity to all the elements in the periodic table from Fluorine to Fermium.
• Fast response: Typical analysis time is usually under a few minutes.
• Simultaneous analysis of many elements.
• Non destructive: The x-ray radiation does not leave any effects in the sample after
analysis. Rare or precious samples as well as calibration standards can be tested
unlimited number of times without losing any of their authentic properties.
• Flexibility of sample form: The sample may be in solid, powder, liquid or thin film
form; or even be a few layers of elements plated on a thick base substrate. In most
cases, samples are analyzed with minimal sample preparations.
Chapter 1 System Overview
and transmits system status reports to the computer. This report is displayed on
the computer monitor, and is updated every second.
1.3.6 Computer
X-2600 series systems have a minimum computer configuration consisting of:
Dual Core processor
Windows 7 or higher operating system
2Gb DDR3
300Gb hard disk
Monitor, pointing device and keyboard
WARNING
This equipment contains a HIGH VOLTAGE power supply.
WARNING
Overriding safety features or interlocks should not be done under any
circumstances. These features have been installed for your safety.
The equipment will not operate normally if the red warning lamp or the sample
chamber cover is faulty or missing. (Note that if the red warning lamp bulb is not
operable, the equipment will also not operate.)
In addition, the following precautions are required:
- Only authorized personnel should perform maintenance work inside the
machine.
- The equipment should not be operated if the leaded glass window in the
chamber lid or if any of the safety micro switches is broken.
- Electrical Safety Consideration
The system is intended to operate from a power source that does not exceed
250V (for both the 120V and 240Vversions) between either supply conductors or
between supply conductor and ground. A protective ground connection by way
of the grounding conductor in the power cord is essential for safe operation.
This product is grounded through the grounding conductor of the power cord. To
avoid electrical shock, plug the power cord into a properly wired receptacle
before connecting to the product input or output terminals. A protective ground
connection using the grounding conductor in the power cord is essential for safe
operation. Upon loss of the protective ground, all accessible conductive parts
(including knobs and controls that may appear to be insulated) can render an
electric shock.
Use only the power cord and connector specified for your product and valid in
the country where the machine is installed. Make sure that both are in good
condition. Do not use extension cables. To avoid fire hazard, use only a fuse of
the correct type, voltage rating and current rating as specified.
Mode Description
Operator Allows running of pre-defined batchesonly.
Superuser Allows: Procedure and batch setup and run.
Chapter 2 Basic Operation
Chapter 2
Basic Operation
This Chapter contains initial operation information that should be useful for
most operators of the X-2600 series system. It is assumed that system
installation has already been completed and that qualified personnel have
checked out the system.
In addition, the system's major software screens are introduced in this chapter.
Chapter 2 Basic Operation
i NOTE
In the present software version, you MUST log-in in either as Superuser
or as Operator.
(4) Choose the subsystems you want to initialize from the Initialization Mode
field.
If you are logging on as an “Operator”, all subsystems will be initialized
(refer to Section 2.2.1.2 for more details).
(5) Click the NEXT>> button.
You will enter the Initialization Status window (refer to Section 2.5, User
Interface).
(6) Click the NEXT>> button.
You will enter the Main Spectra Mode window (see Figure 2-10).
Chapter 2 Basic Operation
Mode Description
Operator Run predefined batches only
Superuser Create and control procedures and batches. Run manual acquisitions.
Make changes and set parameters.
If your operator mode is Operator, you must perform a Full Initialization. In this
case, the Partial Init button will not appear, and you must perform a Full
Initialization, in which all subsystems will be initialized.
If your operator mode is “System Administrator”, no initialization will be
performed.
If your mode allows you to perform a partial initialization, click the Partial Init
button or choose one of the options from the Initialization mode pull-down
field.
If you click the Full Initialization button, the window shown in Figure 2-3 will be
displayed. Using the left mouse button, select the objects to be initialized and
click OK.
Click All if you decide to initialize all options.
Click Cancel to cancel your selections and return to the Log-In window without
selecting any options.
If you may click the Partial Init button, the Partial Initialization box shown in
(Figure 2-3) will be displayed. If you choose Partial Initialization from the
Initialization mode pull-down field, you may, depending on your operator
privileges (“Superuser” only), be given the options shown in Figure 2-4.
i NOTE
If your operation mode Operator you must perform a Full Initialization.
In this case, the Partial Init button will not appear.
Chapter 2 Basic Operation
During the initialization process, the window shown in Figure 2-5 will be
displayed, showing the result of each of the initializations.
The possible results are described in Table 2-2.
Chapter 2 Basic Operation
Status Description
Failed Initialization failed – subsystem may not be connected or operational.
Error and warning messages may be seen in the Event Viewer (see section
2.5.1).
OK Initialization was successful
Not Required Initialization was not requested
2.2.2 Log-Out
To log out of the system:
(1) If you are in Spectra Mode, select Exit from the Edit pull-down menu or
press Alt + X. Alternatively, you may click the Close (×
×) button on the
upper right corner of the screen.
(2) The nEXt application will close.
Chapter 2 Basic Operation
CAUTION
Use of high voltages (especially > 30 kV) without adequate prior tube
conditioning may result in arcing, leading to premature and/or
catastrophic x-ray tube and related circuit failures.
WARNING
The Be window is extremely fragile. Avoid touching it and do not spill
sample powders and liquids on it. Make sure no sharp sample edges
come in contact with the Be window.
(1) Open the sample tray door (Figure 2-6) by pulling the handle, and place
the samples in the appropriate tray positions - Figure 2-6 and Figure 2-7).
(2) Close the Auto-sampler door, making sure it is completely closed. (If the
door is not completely closed, the interlock system will not allow x-ray
analysis to proceed.)
Chapter 2 Basic Operation
The buttons are described in Table 2-3, and the indicators are described in
Table 2-4).
Button Description
X-ray on/off: Indicates whether X-rays are on/off.
This indicates that the system is in stand by mode for initial operating
Chapter 2 Basic Operation
Indicator Description
“Controller This area contains an indication of system status.
Off”
Clicking the Error or Warning button displays the Event Viewer (see Figure 2-9),
allowing you to view the messages issued.
You may select and delete any or all of the messages from the Viewer using
either the Remove Item or the Remove All buttons.
i NOTE
Removing an entry from the Event Viewer does NOT remove it from the
Event data base.
The data included in the Event Viewer are described in Table 2-5.
Chapter 2 Basic Operation
Data Description
Date Date at which problem occurred. An indicator as to the severity of the problem is also
included.
If this indicator is the problem is
Red a system stopper
Blue an error - it is possible to continue, but not with this operation
Yellow a warning
Time Time at which the problem occurred.
Sourc Subsystem in which the problem occurred.
e
Error Problem description.
i NOTE
Both the Error and Warning buttons are activated simultaneously.
! IMPORTANT
If an error occurs which causes the system to stop, a message box
explaining the problem will be displayed.
The various parts of the Spectra Mode window are shown in Figure 2-11 and are
described in the following sub-sections.
The Spectra Mode Button Bar (Figure 2-13) is useful for selecting frequently
used functions. These functions are summarized in the following figure. In
addition, in many cases, keyboard keys are reserved for similar functions. These
"Hot-keys" are indicated in Table 2-6.
Autoscale (in both the vertical and horizontal directions) – set spectrum F9
in the active window to auto vertical and horizontal full scale.
Erase main spectrum in active window. F7
TIP
This feature s usefull for analysis by comparing corresponding spectra
for different samples.
Chapter 3
Data Acquisition
Acquiring spectra is the first and one of the most important steps performed in
both qualitative and quantitative analysis. Acquisition parameters are used in the
spectrum capture process to determine the spectrum profile and parameters.
They are generally chosen to enhance the number of counts obtained for the
elements of interest.
This chapter discusses:
1. Acquisition Parameters: Menu choices and variable descriptions
2. Guidelines for Setting Acquisition Parameters: Considerations for
optimizing spectra acquisition.
3. Methods of Spectra Acquisition: Manual and automated methods.
4. Saving and Retrieving Spectra Files: A spectrum file can be used
later for further analysis, without the need for additional
acquisition. Saving and retrieving these files allows this.
5. File Management with nEXt.
Chapter 3 Data Acquisition
Field Description
Station Number X-2600 series systems have 8 positions (stations) defined on the sample tray
(1-8) and 8 positions (9-16) on the reverse side of the tray.
Filters Six filter positions on the filter rack are available: Open (no filter), Ti, Fe, Cu, Rh
and W.
Emission Current, Sets the tube emission current. The intensity of the tube excitation beam is
µA directly proportional to this value.
Choose this parameter to get max of 35% – 40% dead time:
Set the Preset Time to zero in the Acquisition parameters dialog box.
This will allow a flexible acquisition time.
Click the MCA Status button in the button bar.
The MCA Stat information box will be displayed.
Enter a value for the Emission Current in the Acquisition parameters box.
Start acquisition by clicking the Start acquisition button in the button bar.
Field Description
the number of counts. This means that increasing the counting rate improves
the statistics when acquiring at a higher rate but with the same acquisition time
interval.
Collimator Not applicable on X-2600 series systems.
Chapter 3 Data Acquisition
The entries in the Batch Selection screen are described in Table 3-2.
Field Description
Select batch Select a batch to run from the pull-down list.
Description Description of selected batch.
# Line number in this list.
Station Auto-sampler station position number of sample on which the Procedure operates.
Click in cell and select station number from pull-down field.
Choose 0 to take spectrum from the data base.
Choose 1 … 16 to acquire spectra from one of the auto sampler stations.
Sample/Spectru When an auto-sampler station position is indicated, enter a sample name (such as
m "Concrete", or "Unknown sample"). If zero is used, browse in a spectrum file from
explorer.
Procedure Name of procedure to be used in analysis.
Save Spectra Select Yes (check) to save acquired spectra.
Select No (un-check) to discard acquired spectra after analysis.
Save Statistics Select Yes (check) to save analysis statistics data.
Select No (un-check) to discard analysis statistics data after analysis..
NOTE
You may also view Batch results files by selecting Show Batch Results
from the Edit pull-down menu.
The entries in the Batch Run Results screen are described in Table 3-3.
Chapter 3 Data Acquisition
Field Description
# Number of sample in Batch.
Station Auto-sampler station position number of sample on which the Procedure
operates.
Spectrum Spectrum name.
Procedure Name of procedure used in analysis.
Element Element being analyzed.
Counts Total number of counts.
Intensity Calculated intensity.
Concentration Measured element concentration in either % or ppm.
The control buttons in the Batch Run Results screen are described in Table 3-4.
Field Description
Close Exit the Results screen without saving.
Save Save the Results. You will be prompted for a file name.
Print Print the Results table.
Format Format the results display table. The dialog box shown in Figure 3- will be
displayed, allowing you to select the content and format of the display.
Stat. Build a results histogram.
A window similar to that shown below will be displayed. There will be a screen
for each of the elements measured.
Field Description
Mean – red
SD – dotted black
RSD – dotted violet
The maximum and minimum values are also listed.
Click on a histogram block (cube) to view the Sample name, Concentration, and
Sample number for a particular sample.
Select Options from the View pull-down menu to choose between Standard view
and Scientific view. Scientific view uses smaller histogram segments and is useful
when there are many histogram segments.
Use the Print pull-down menu to print the Active statistic window, All statistic
windows, or just the Summary table.
Field Description
Short Report
If Show Errors in Report is checked, error bound will be added to the results as
shown below:
Chapter 3 Data Acquisition
Field Description
.
One-Line Report –
Net Intensities
Chapter 3 Data Acquisition
Match_Database.mdb is the database file for the Setup Table. The Setup Table
(stored in the Match_database.mdb file) is the configuration file of the X-2600
system. All parameters have been set at the factory and should NOT be changed
without consulting an authorized Xenemetrix service engineer.
Chapter 3 Data Acquisition
All procedures and batches created in the nEXt Superuser mode are stored in the
Semi_database.mdb file
You may export, import, or modify portions of the this database. To perform any
of these operations, you must be in the Main Superuser window:
Select the Data Base Tools pull-down menu.
You will be given the options shown in Figure 3-1.
These options are described in Table 3-6. The most useful options is Database
Utilities. All options concerned with import and export of old data from old and
obsolete ExWin software can be ignored.
In Database Utilities it is possible to remove procedures and batches that have
become irrelevant in the analytical work.
Operation Description
Data Base Select this option to modify or export part of a database. The following screen will be
Utilities displayed:
Chapter 3 Data Acquisition
Operation Description
Open Data Base: Open a database. The standard Windows Open dialog box will be
displayed from which to open files with the.mdb extension.
The name of the selected database will be displayed below this button.
File Type: Select the type of files you wish to work with:
Select Procedures to display a list of procedures within the selected database.
This is the place were selected procedures can be removed from the procedure list in
the nEXt software. Note that removing procedures from the system is an irreversible
act.
Select Spectrum to display a list of spectra stored within the database.
List Field: A list of the files of the file type selected will be displayed here.
Source Data Base: Select a database from which to import files.
The name of the selected database will be displayed below this button.
Close: Click to close the Data Base Utilities dialog box.
Remove: Click to remove all data sets connected with a selected entry in the List Field.
Export: Select an entry in the List Field and click Export to export the selection. (Click
the left mouse button with the Ctrl key depressed to select multiple entries.) A message
will be displayed stating that the selected files will be copied to a temporary directory
called Export_Data_Base.
All tables and spectra connected with the selection will be copied and given the same
names, with the date and time added. For example: set1_17_2_2000_11_27_53.mdb
Click OK to proceed.
Chapter 3 Data Acquisition
Operation Description
The copied files may be “zipped”, sent by e-mail, copied onto diskette, etc.
Import: After clicking Source Data Base to select a database from which to import data,
select the portions of the database for import. The system will check for pointer
compatibility with your presently active database.
You will be prompted as to whether you want to replace files within your database or
give it a new name (append to your database).
Click the Browser button to navigate to the procedure files you want to import.
Check the Import with spectra box to import the spectra associated with the chosen
procedure.
Then click Import to import the files.
Import Old Import Batches created with previous software versions.
Batch You will be presented with the Import batch dialog box. Which is the same as the
Import Old Procedures dialog box
Chapter 3 Data Acquisition
Operation Description
Import The standard Open dialog box will be displayed.
ExWin.ini Navigate to the file you want to import and click Open.
Parameters
Chapter 4
Qualitative Spectral
Analysis
4.1 Introduction
The objective of qualitative analysis is to identify the elemental components of
unknown substances. X-ray spectrometry is particularly suited to this type of
analysis as it is rapid, non-destructive, and measurable signals can be obtained
from a very small specimen.
The first step in qualitative analysis is spectra acquisition. Following spectra
acquisition, the spectra must be manipulated and studied to best determine
additional spectra acquisition and/or the qualitative answer desired.
This chapter covers guidelines for qualitative analysis including various spectral
manipulations.
In the following discussion, it is assumed that you have entered the Main
Spectra window.
Chapter 4 Qualitative Spectral Analysis
(16) Click the Start Acquisition button in the button bar or press the A key.
(17) If you have set the Preset Time parameter to any value other than “0”, the
acquisition will terminate automatically.
If you have set the Preset Time parameter to “0”, click the Stop Acquisition
button to stop the acquisition.
(18) You may save the spectra by clicking the Save spectra button .
For a detailed discussion of spectra acquisition, refer to Chapter 3.
Chapter 4 Qualitative Spectral Analysis
The elements that may be associated with the various peaks will be
superimposed on the spectrum (see Figure 4-3).
A Peaks Identification Report will be displayed (Figure 4-3). The report shows
the energies of the detected peaks, the number of counts in the maximum, the
peak areas, and the value of the Full Width at Half Maximum (FWHM) and
possible element identification. There is an option to print the report or save it
for later evaluation (refer to Figure 4-3).
The Peak Identification parameters are described in Table 4-1.
Chapter 4 Qualitative Spectral Analysis
Parameter Description
Energy eV Calculated energy position of the peak.
FWHM eV Full width of peak at half peak maximum. This is a measure of the resolution of the
spectrometer at the peak’s energy.
Counts in Number of counts in the energy channel of the peak maximum.
Max
Gross Area Calculated number of counts in the region under the peak.
Possible Possible element line identification.
Element(s)
Because of reasons listed earlier, automatic peak identification may not always
be correct, and it is advisable to verify the identification manually by using the
KLM markers (refer to section 4.4.4).
(3) Locate the Region of Interest bar on the bottom of the spectra window.
(4) Using the mouse, left click and sweep along the area in which you wish to
create a region of interest.
(5) Release the mouse button. The ROI will now be indicated by a different
color. Refer to Figure 4-5.
You may set multiple ROI’s in this manner.
You may also set (or reset) the ROI by clicking the right mouse button within the
Spectra window and choosing Region Of Interest from the pop-up menu that
appears.
Option Description
Set low limit Set lower limit (in eV) of ROI.
Chapter 4 Qualitative Spectral Analysis
Option Description
In the dialog box, enter the lower limit of the ROI and click OK.
Remove all ROI Remove all ROI settings. ROI regions will revert to the original spectrum
color.
Report Display an ROI report. A box containing the following data will be displayed:
ROI: Name of component ROI’s. “Main” is the name associated with the ROI
that includes the highest peak. Other ROI’s are numbered.
Low limit eV: Lower limit of ROI.
High limit eV: Upper limit of ROI.
Gross Counts: Total number of counts in the ROI.
Net Counts: Gross Counts minus the number of background counts in the
ROI.
Gross CPS: Total counts per second.
Net CPS: Total counts per second minus background counts per second.
Stat Error 2*sigma %: Statistical 2 error of peak identification.
Option Description
Set Element Set the ROI for a particular element. The dialog box shown below will be
ROI displayed.
For the chosen element, the location of the X-ray spectral lines is shown.
To select a different element, click the Element button. You will be given a
Periodic Table of Elements.
Chapter 4 Qualitative Spectral Analysis
Option Description
To save the ROI, select Region Of Interest (ROI) the select Save ROI from the
Spectra pull-down menu (see Figure 4-7).
In the dialog box that appears, enter a name of the ROI and click Save.
To retrieve the ROI, select Region Of Interest (ROI) and then Retrieve ROI from
the Spectra pull-down menu (see Figure 4-7).
In the dialog box that appears, select the name of the ROI from the pull-down
field and click OK.
Chapter 4 Qualitative Spectral Analysis
NOTE
Automatic peak identification may not always be correct due to the
close proximity of the K, L, M lines for some elements. It is therefore
advisable to verify the identification manually using the KLM Markers.
The buttons appearing in the KLM Toolbar are described in Table 4-4.
Table 4-4: KLM Toolbar Buttons
Field Description
Replace the last KLM marker set with the next lowest marker in the Table of
Elements. The corresponding element lines will appear at the energy locations on
the screen. For a positive identification, match the KLM Marker lines with the
Spectra Peaks
Replace the last KLM marker set with the marker ten positions lower in the Table
of Elements. The corresponding element lines will appear at the energy locations
on the screen. For a positive identification, match the KLM Marker lines with the
Spectra Peaks
Remove the last marker previously set in all Spectra windows.
Add a KLM marker in all Spectra windows. Clicking this button displays the Table
of Elements from which to choose the marker.
Field Description
Delete all KLM markers in all Spectra windows.
Replace the last KLM marker set with the marker ten positions higher in the
Table of Elements. The corresponding element lines will appear at the energy
locations on the screen. For a positive identification, match the KLM Marker lines
with the Spectra Peaks
Replace the last KLM marker set with the next higher marker in the Table of
Elements. The corresponding element lines will appear at the energy locations on
the screen. For a positive identification, match the KLM Marker lines with the
Spectra Peaks
Move the cursor in all Spectra windows one channel to the left of its present
position.*
Move the cursor in all Spectra windows ten channels to the left of its present
position.*
Move the cursor in all Spectra windows one channel to the left of its present
position.*
Move the cursor in all Spectra windows ten channels to the right of its present
position.*
* The 10kV range has 1000 channels, with each channel having a width of 10eV.
The 40kV range has 2000 channels, with each channel having a width of 20eV.
Remove KLM: Selecting this function erases the last marker previously set. This
is desirable, for example, when there is incorrect peak identification due to
serious overlap or other spectral features.
Remove All KLMs: Selecting this function erases all KLM markers previously set
in the particular Spectrum window
KLM Table: Selecting this function displays information on the KLM markers set
in the Spectrum window.
The energy of each of the KLM lines for each of the markers is listed in this
table (Figure 4-12).
Chapter 4 Qualitative Spectral Analysis
(21) If you wish to see or modify the default Gaussian fit parameters, click the
Gauss button in the Select Element box. You will be given the Gauss
Parameters box (see Figure 4-14).
When you are done, click OK to accept any changes made or Cancel to
accept the default values.
The parameters appearing in the Gauss Parameters box are described in
Table 4-5.
(22) In the Select Element box, enable the lines (K, L, M) you want to display.
Chapter 4 Qualitative Spectral Analysis
Parameter Description
FWHM at Energy resolution of the spectrometer, in eV, extrapolated to 0eV energy,
0eV
Zero Shift Energy calibration of the spectrometer maybe not exactly perfect, this term
represents displacement of zero, in eV. Should be 0 at perfect calibration.
Gain Factor As above, this term corrects for non-perfect gain calibration. Normally
shouldn’t deviate from 1.000.
Fano Factor Constant used for calculation of the spectrometer resolution versus energy.
This value should not be changed unless the detector is replaced.
Tail Term A Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*
Tail Term B Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*
Tail Term C Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*.
Tail b/a Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*
Lower Limit Coefficient used to find automatically the lower energy border of multiplet to
FIT or Peak to build. The program will take the peak with lowest energy in the
multiplet and will take for this border the energy of this peak minus FWHM of
this peak multiplied by this coefficient. This parameter is a default value used
when employing the FIT method within a procedure.
Upper Limit As above - for upper energy border (peak with highest energy and plus instead
of minus will be taken). This parameter is a default value used when employing
Chapter 4 Qualitative Spectral Analysis
Parameter Description
the FIT method within a procedure.
* Ref.: Jenkins, Gould, and Gedcke, Quantitative X-Ray Spectrometry, Marcel Dekker, 1981
Parameter Description
Remove Removes an overlap spectrum from the Spectrum window.
overlap
Set as main Interchange currently displayed spectrum and overlap display. The
spectra overlapped spectrum is generally in outline form while the main spectrum is
filled. This function can also be activated by pressing the S key..
Main + Adds the selected overlap spectrum to the main spectrum.
Overlap
Main - Overlap Subtracts the selected overlap spectrum from the main spectrum.
Main to Converts a main spectrum to an overlap spectrum (see Figure 4-17).
Overlap This function is useful for checking which parameter values are optimal for a
particular measurement task:
1. Acquire a spectrum.
2. Convert this spectrum to an overlay.
3. Acquire the spectrum a second time.
4. Compare the two spectra and note differences.
Show Negative Displays energy range containing both positive and negative
Energy energies.
Negative energy has no physical meaning, but the concept is useful
for performing zero calibration.
If this entry is checked, an energy range from some negative value
(depending on the energy range being used) to the maximum
value for the range will be displayed.
If the entry is unchecked, an energy range from zero to the opper
range limit will be displayed.
Region of
Interest (ROI)
Remove all ROI Remove all ROI settings. ROI regions will revert
to the original spectrum color.
Save ROI Save ROI to disk.
Overlaps
Scale
Compress Compress all spectra about the cursor location. Ctrl F4`
Operation Description
Data Base Remove not wanted procedures or batches
Utilities Export/Import of various types of database files.
Change Select the database to be used.
Data Base
Import Old Import procedures created with the ExWin software.
Procedures
Import Old Import a batch created with the ExWin software.
Batch
Import Import a default parameters file (*.ini) created with the ExWin software.
ExWin.ini
parameter
s
Chapter 4 Qualitative Spectral Analysis
Entry Description
Help Topics Display a list of the help topics available. (Not yet implemented.)
About Displays the nEXt software revision number.
Chapter 5 Quantitative Spectral Analysis
Chapter 5
Quantitative Spectral
Analysis
5.1 Introduction
The objective of quantitative spectral analysis is to determine how much of a
specific element is present in a sample of unknown composition. XRF is used to
compare intensity data from samples with the intensity data from reference
materials of known concentration. Once this comparison is proven reliable,
Xenemetrix X-2600 series systems can be used to rapidly check samples by
automating concentration data acquisition and analysis functions in a framework
called batches.
This chapter describes the framework for using X-2600 series systems for
concentration analysis both with and without standards.
Similarity in physical structure and concentration between reference materials
for calibration and unknown samples is of paramount importance.
This requirement is frequently simulated mathematically for solid materials using
various algorithms that model energy interactions in the sample. Reference
materials, if available, are usually used together with mathematical models to
obtain empirical correction algorithms. Reference concentrations (entered into a
data table) are then correlated to calculated concentrations (obtained from the
algorithm) using multivariate regression.
Correlation gives an estimation of how good the algorithm models the physical
process. Different algorithms are accurate under certain conditions, and when
there are significant deviations from these conditions the accuracy of the
algorithm is increasingly reduced.
Chapter 5 Quantitative Spectral Analysis
5.3 Procedures
The first step in quantitative spectral analysis is to create a Procedure. A
Procedure is a collection of functions for performing mathematical analysis of
spectral data. To run an analysis of an unknown sample, a procedure for
analyzing the data must be created and saved. In addition, it must be carefully
tested to estimate its accuracy.
Quantitative spectral analysis is divided into 2 parts: Procedure and Batch. A
procedure contains parameters for collecting data (an acquisition method) and a
processing algorithm to convert the resulting data into a concentration result to
form an empirical calibration or correlation.
A batch is a collection of instructions, allowing automatic spectra acquisition and
subsequent analysis of the sample against predefined procedures, yielding an
analytical result.
The first step in qualitative analysis is to create a Procedure. To run an analysis
of an unknown sample, a procedure for analyzing the data must be created and
saved, then tested to verify the consistency of the results and to make an
estimate of the method's accuracy. Elements of a procedure are discussed in
detail below.
The following sections describe the main procedure elements.
Field Description
Station Number X-2600 series systems have 16 positions (stations) defined on the sample tray.
Stations 1-8 are sample-cup stations.
Stations 9-16 are the mid-points between the sample-cup positions on the
reverse side of the sample tray (9 is between 1 and 2, 10 is between 2 and 3,
etc.). These stations hold element sample disks. Stations 9-15 are factory
equipped with the following disks: 9-Al, 10-Cu, 11-Mo, 12-Sn, 13-Ti, 14-Al-Cu
and 15-Ti-Sn.
These samples are used for re-calibration of the energy scale and system
testing.
Station 16 can be used for user-defined standard
Emission Current, Sets the tube emission current. The intensity of the tube excitation is directly
µA proportional to this value.
High Voltage, kV Sets the high voltage to the X-ray tube. This value effectively regulates the X-
ray tube output spectral distribution.
Preset Time, sec Sets the acquisition time (the net time the sample is exposed to x-rays).
The time chosen is in real time.
For automatic data acquisition, enter a positive value.
Enter '0' to manually run the acquisition for testing purposes. Terminate manual
data acquisition by clicking the Stop-acquisition button.
Atmosphere If Vacuum is specified, the acquisition will start only after the vacuum in the
sample chamber reaches the “Minimum level for measurement”. When Helium
is specified the acquisition will start after “Helium waiting time” (specified in
the Setup Table) When air is specified, acquisition starts immediately.
Energy Range This parameter sets the energy range of the spectrum's acquisition. There are
two ranges: 0-10 keV and 0-40 keV.
Throughput Select the optimum throughput rate: low or high. The optimum depends upon
the specific application.
In general, better separation between peaks can be achieved at Low
throughput. The advantage of using High is that the spectra can be acquired at
much higher count rates; since the processing time of each count is shorter, the
dead time is shorter. In cases where the resolution at low energies is not critical
and you want to acquire spectra faster, select High.
Note: Statistic precision improves in inverse proportion to the square root of
the number of counts. This means that increasing the counting rate improves
the statistics when acquiring at a higher rate but with the same acquisition time
interval.
The maximum counting rate is depending on peaking time set in the factory.
Consult your XENEMETRIX Service if obtained maximum count rate does not
meet your requirement.
Collimator Not applicable to X-2600 systems.
Chapter 5 Quantitative Spectral Analysis
i NOTE
The following information serves as a guideline and will be true for
most X-ray applications. It is recommended to combine these
guidelines with empirical experience to apply the most feasible
method.
Excitation voltage (kV) and current (µA) settings are determined by the elements
contained in the samples to be measured.
The kV setting must exceed the excitation potential of the analyte element by a
factor of approximately 1.6 to ensure adequate excitation of the analyte line.
5.3.2.1 None
Only spectra acquisition is desired, without the performance of analysis.
5.3.2.2 Regression
In many industries, accuracy of better than 1% in the determination of
concentration and composition is necessary. To achieve this accuracy, the
analysis method most often used is regression. Here, measured quantities are
calibrated against precise calibration standards of known concentrations,
yielding an accuracy of better than 1%.
Regression Model
The equation that relates concentration with measured intensity is:
Ci = Ki · Ii · Mi
Where:
Ci = Concentration of the analyte expressed in % or ppm.
Ii = The net peak intensity after subtraction of background counts and line
overlaps.
Mi = The matrix correction term and involves taking into account the net effect of
all of the absorption and enhancement the analyte radiation is subject to
during the analysis. These terms may be calculated from first principles as is
done in Fundamental Parameter analysis or they may be estimated using
multivariate regression techniques. This term is commonly known as an
influence coefficient or an Alpha factor.
The following regression models all use this general model. In some of the
models, terms are eliminated due to certain compensating factors.
1. Simple Linear Relation: C = A0 + A1 Ii
A simple linear relation between the intensity (Ii) of element I and the sample
concentration (Ci) of this element. This model is applicable when the
concentration of the analyzed elements is expected to vary over a relatively
small range, and the influence of other elements on the analyzed element may
be negligible. This method can be used when reference materials are available
that are of the same composition as the samples to be analyzed. This is known as
“in-type” analysis. A good example is a trace analysis of heavy elements in
organic samples. This model requires only two different standards to enable the
program to determine the free regression coefficients A1and A0, but more than 3
or 4 are actually needed for reasonable accuracy and higher confidence in the
analysis results.
2. Ii= A0 + Σ (Aj Cj) where j = 1 …. N elements
N is the total number of interfering elements. This model accounts for inter-
element influence or peak overlap. The model includes N + 1 free regression
coefficients A0 and Aj (which are determined by the program). A minimum of N
+ 1 independent standards are required for the determination of A0 and Aj, but
as many as (N + 1) * (N + 1) are actually recommended for better confidence.
This model requires that the concentrations for all elements that vary
significantly be known.
3. Ci = A0 +Σ
Σ (Aj Ij)
This model is almost equivalent to model 2. There is no significant advantage,
but the concentration of interfering elements need not be known. The influence
coefficients calculated in this manner are only valid for the type of samples that
were used as standards to calculate the coefficients.
4. Modified Lachance-Traill Model:
Ii = A0 + Ai Ii + Σ (Aj Cj) i ≠ j
This popular model provides high accuracy over a range of concentrations about
0 - 10% of the element of interest and compensates for inter element influence
Chapter 5 Quantitative Spectral Analysis
by the Aj coefficients. It requires that the concentrations of all elements that vary
significantly be known.
5. Modified Lucas-Tooth and Price Model:
Ci = A0 + Ai Ii + Ii Σ (Aj Ij) i ≠ j
This model has the advantage that only the concentration of the analyzed
element appears in the equation. This means that the rest of the concentrations
in the standards do not have to be known or specified.
6. Parabolic (Quadratic) Model: Ci = A0 + A1 Ii + A2 Ii2
This model may be useful when the concentration range for the various
elements is relatively wide and inter-element effects are minimal.
Considerations for Regression Model and Calibration Standards Selection
1. Linear independence: The regression coefficients (Ai, A0, and Aj) are
determined by the program. These are actually the solution of a
system of N+ 1 linear equations; in order to obtain a correct solution
for this equation system, a minimum of N+1 independent standards
are required.
"Independence" refers to standards that are not linear combinations
of other standards. For instance, the result of mixing two or more
standards in a specific proportion is not considered an independent
new standard.
N+1 standards is the minimum needed to obtain a solution, but more
standards are required in order to gain some confidence in these
determinations. As a rule of thumb, something like (N+1) * (N+1)
standards are considered to be sufficient.
There is no objection to acquiring spectra of the same standard
several times and using them in a regression analysis. Since these
spectra are not independent, they do not eliminate the basic
requirement for sampling N+1 independent standards.
2. A reliable determination of regression coefficients requires that the
standards used for analysis cover the full range of composition
expected in the sample.
3. The program uses the areas of the analyzed element peaks. If the
peaks are either too small or they are masked by much larger peaks
and their magnitude cannot be determined precisely, any regression
analysis based on these data cannot be considered accurate. It is
therefore essential that the acquisition parameters be set for best
detection of all peaks appearing in the regression analysis.
4. The free parameter A0 in the regression model is the point where the
regression line intercepts the vertical axis of the regression plot. It may
be interpreted as the background level of either the intensity or the
concentration, depending upon the regression model. You must pay
Chapter 5 Quantitative Spectral Analysis
In the case of a light matrix, the lines of components with low Z (Z< 9) cannot be
seen. Fortunately, it is possible to estimate the average Z of a sample according
to the relative intensities of observed Compton and Rayleigh scatter peaks from
the sample. In the case of direct excitation, the scatter peaks result from the
characteristic anode material of the X-ray tube; similarly, in the case of
secondary target excitation, the scatter peaks will change according the target
selected.
From the estimation of "average Z," it is then possible to calculate the matrix
absorption in the sample and the concentration of the elements of interest
Chapter 5 Quantitative Spectral Analysis
Parameter Description
Excitation Direct irradiation with Rh (K-lines), Mo (K-lines), or W (L-lines) anode X-ray tubes is
acceptable.
Tube Voltage Sufficient voltage (and current) must be used to guarantee reasonable counting
statistics for the indicated characteristic tube lines and their incoherent
components.
Energy Range The 40 keV range is universally acceptable.
5.3.2.4 AccurEx
The AccurEx method is a modification of SLFP in which some standards are used
to improve accuracy.
In addition to standards, it is possible to treat the elements that do not have
analytical peaks in the spectrum – for example, very light elements.
The approach used is to correct the excitation, absorption, and detection
efficiencies calculated by SLFP to improve the accuracy of the results.
If good standards are available, with compositions close to that of the unknown,
the Sort method can be very effective and can yield excellent results. The results
of the analysis may be verified by simply re-measuring the standard itself.
Select excitation and acquisition parameters to generate significant peaks. The
peaks should contain sufficient net counts for good precision. Otherwise,
comparison between standards and unknown samples will be based on
background counts and not on counts from the element peak. Such incorrect
comparisons may generate results that look good, but are totally false and
misleading.
The Sort method allows the use of weighing factors for the elements in the
Elements-of-Interest Table. This allows a larger statistical weight to be placed on
minor peaks as compared to major peaks. In many applications it is desirable to
sort samples according to the concentrations of the minor elements, when the
major constitute is not of primary interest. For instance, in low alloy steels, the
concentration of iron is not as relevant as the concentration, for example, of
silicon.
excitation of the light element. Heavier elements are in turn excited to produce
more X-ray photons, which enhance the number of X-ray photons that are
produced from the heavier elements by the primary X-ray producing mechanism.
Both effects have the net result of altering the direct intensity-to-concentration
correlation and can lead to erroneous concentration estimates of the elements
in a sample.
Summarizing:
1. One of the regression models (discussed previously) may be chosen for
correlation of concentrations of layers on a sample. Each regression
equation has specific limitations as explained below.
2. If analysis of several different types of samples using the same elements
is required, a separate procedure with its unique calibration curves
should be set up for each sample type.
3. It may be necessary to analyze using both light and heavy elements in
the same sample. The excitation requirements of these two types of
elements may be conflicting. In this case, two separate procedures
should be developed for the same set of samples.
NOTE
Which screens appear following the Main Procedure screen as well as
their contents may depend on the analysis Method you choose. These
screens will be described for each of the analysis methods.
Chapter 5 Quantitative Spectral Analysis
Field Description
AutoAdd If this parameter is not enabled, the system will prompt you as to whether to add
the information generated in the present screen to the database or to replace
previous information.
If this parameter is enabled, you will not be prompted, and new data will be
automatically added.
The default setting is “enabled”.
F(x) Calculate the element concentration.
Spectra Load spectra from disk for analysis (not operative in this screen).
Calc. coef Calculate the regression coefficients (not operative in this screen).
<Back Return to previous wizard screen (not operative in this screen).
Next> Proceed to next wizard screen.
Cancel Exit the Procedure Wizard and discard all entries.
Help Display on-line help.
i NOTE
In the first Procedure Wizard screen, the <Back button will not be
available.
In the final screen of the of the Procedure Wizard sequence, the Next>
button will be replaced by Save, which will allow you to save the
procedure to disk.
Select an analysis Method. The main Procedure screen may change according to
your selection. The following sections describe the Procedure wizard screen
sequences for each of the Analysis Methods.
Table 5-4: Main Procedure Wizard Window Data Fields (Method = None)
Field Description
Name of the Select a procedure name from the pull-down list or enter a new name.
procedure
Name of the Enter a name for the procedure parameters file. The default name is the same as
procedure’s the procedure name.
parameters
Method Choose one of the analysis methods (None in this case).
Select an Analysis Method (None in this case) and click Next> to continue.
If you have chosen None for your analysis method, there will be one more
screen in the procedure setup sequence – Acquisition Parameters (Figure 5-2.
The entries in the Acquisition Parameters screen are described in Chapter 3.
Select the desired parameter values and click Next>. The Acquisition Parameters
screen will be displayed again, with the <Back and Next> buttons replaced by a
Save button.
Click Save to save your procedure and exit the Procedure wizard.
Chapter 5 Quantitative Spectral Analysis
Chapter 5 Quantitative Spectral Analysis
Field Description
Name of the Select a procedure name from the pull-down list or enter a new name.
procedure
Name of the Enter a name for the procedure parameters file. The default name is the same as the
procedure’s procedure name.
parameters
Method Choose one of the analysis methods described in the previous section (Regression in
this case).
Chapter 5 Quantitative Spectral Analysis
Field Description
Remove Subtracts the Escape Peak appearing as a result of the SiK radiation escaping from the
Escape Peak Si(Li) detector.
Subtraction is performed channel by channel, for the whole spectrum, from the Zero
CutOff energy to the (Energy Range - SiKabs) energy, according to the following
formula:
NewSpc(E) = OldSpc(E) - A * exp(-B*E) * OldSpc(E+1.74).
The default values for A and B are 0.0175 & 0.336. They were chosen for the standard
XENEMETRIX Si(Li)-detector, with the 4 mm collimator. These values can be changed –
consult your XENEMETRIX Service Engineer for more information.
Background The number of channels on either side of a peak used to approximate the background
Points profile.
Use Delta The Delta Coefficient is a mathematical method used to improve the precision and
coefficients accuracy of the analysis where the standard and the unknown have similar
composition.
The idea is to use the linear approximation method of the regression model in the
vicinity of the closest standard to the unknown sample. In this method, the regression
formula (depending on the selected model 1 through 6) is expanded in a Taylor series
around the standard with the closest composition. Only the first terms (i.e., first
derivatives) in the expansion are used to obtain a linear relation between the
concentration and the intensity in the vicinity of the standard. The system finds the
most comparable standard automatically.
The Delta method improves accuracy, provided the analyzed sample has composition
close to one of the calibration standards. This algorithm is popular with gold alloy
analysis.
Use Stoich. If the total concentration of the analyzed elements is known to add up to a specific
Correction amount (100% or less), this value may be entered here. An example is the analysis of
steel alloys, where the total concentration of all the elements is 100%, minus the
concentration of the carbon, which is assumed to be known (but is not detected by X-
ray). It is not reasonable to try to normalize the concentrations to a fixed number and
also normalize the spectrum's background ROI.
Use Global Remove the background by taking some "background" spectrum (from a blank matrix,
Background for example) as a reference, and subtract it from the given spectrum usingo the
formula:
NewSpc(E) = OldSpc(E) - [RefSpc(E)*ROIofOldSpc1)ROIofRefSpc]
If this feature is checked, the following additional fields and buttons will be displayed
(Figure 5-5):
Background File: Name of spectral file to be used as background.
Browse: Click to obtain the standard Browse box. Use this to navigate to desired
background spectrum file.
Background ROI: Enter the energy range to be used when subtracting the background.
Set: Click this button to enter the energy range using the mouse in the ROI bar.
Show: Display the spectrum with background subtracted as an overlap.
Chapter 5 Quantitative Spectral Analysis
Field Description
Count If To Live Time is selected all the counts in the peaks are divided by the acquisition
normalizatio time (Live Time). The intensity of each peak is expressed in counts/sec.
n If the counts are normalized to the total counts in the Regions Of Interest, the
magnitude of the peaks are expressed as the ratio of the ROI of the peak to the total
counts in all ROI.
If To Background ROI Is selected, the magnitude of the peaks are expressed as the
ratio between the counts in the ROI of the peak to the ROI of the background. In this
case, a range of energies will have to be input either by noting the ROI on the
appropriate spectrum or by entering the numeric values.
In some instances, normalization to background ROI is very useful if the ROI is defined
over the Compton and Rayleigh scattering area; normalization to background ROI is
mainly used in analysis of light matrix and organic samples as well as thin samples.
If this option is selected, , the following additional fields and buttons will be displayed
(Figure 5-5):
from: lower limit of Background ROI.
to: upper limit of Background ROI.
Set: Click this button to enter the energy range using the mouse in the ROI bar.
If you choose To Intensity of Line of Interest is selected, you can choose the line of
interest to use in the Elements of interest screen by checking the box Ref. line of
interest for the element you wish to use for normalization. The reference element
selected will not appear in the results report.
Typically, this method is useful if you want to normalize to an external or internal
standard element.
Regression Equation to be used in regression analysis. Six regression equations are available and
method are described in section 5.3.2.2 above.
Select the desired parameter values and click Next> to continue to the
Acquisition Parameters screen (see Figure 5-2).
The entries in the Acquisition Parameters screen are described in Error!
Reference source not found..
Select the desired Acquisition parameter values and click Next> to continue to
the Elements of interest screen (Figure 5-6).
This screen displays a Periodic Table together with a table of elements to be
analyzed by this procedure. This table is in Microsoft Excel™ format. To add an
element to the table, click on the element’s symbol in the Periodic Table.
To modify the data in the table, use the standard Excel data entry and
modification procedures.
You may remove an element from the data table by selecting the appropriate
row (click the number of the row appearing to the left of the element data) and
clicking the Remove button.
You may also hide the Periodic Table and enlarge the data table by clicking the
Hide table of elements button.
Chapter 5 Quantitative Spectral Analysis
The data fields appearing in the table are described in Table 5-6.
Field Description
Elm Element symbol
KLM line Information regarding the position of the characteristic lines for the element
selected is automatically indicated in the lower and upper energy limits.
Double clicking this field gives a pull-down menu from which to choose a line.
eV Low Energy for the lower end of the peak. It is recommended to check if the limits are
symmetric around the peak and do not enter inter neighboring peaks
eV High Energy for the higher end of the peak. It is recommended to check if the limits are
symmetric around the peak and do not enter inter neighboring peaks.
Chapter 5 Quantitative Spectral Analysis
Field Description
Intens Method This parameter indicates how the peak area is calculated. Choices are: Gross, Net,
Ignore, D. Filter, Fit, and Only Fit. Double clicking this field gives a pull-down menu
from which to choose a line.
Gross is gross counts between ‘eV Low’ and ‘eV High’. The ROI is set automatically
by the program, although you can modify its limits manually, by entering some
other value instead of the default value that appears in the Elements Table. This
option may be a good estimation of the peak area when the peak is well-resolved
and much higher than the background.
Note: In the empirical models, the first term in the regression equation (A0)
represents the estimated background (it is the y intercept value).
Net is the gross count minus the background, as estimated by a simple linear
interpolation between the low and high limits of the ROI.
Ignore: Do not calculate this element's intensity. This choice allows only the
concentration to be specified. (This is appropriate for elements that are not of
primary interest and/or that spectra cannot be well defined--C, for example--but a
concentration is known, yielding better overall quantitative analysis of the
remaining elements of interest.)
D. Filter (Digital Filter) is the default method. It subtracts the background from the
spectrum.
Fit is used where serious a peak overlap exists. This function is designed to break
down a complicate spectrum into its basic components; each component is a
spectrum of pure element.
The Ki factors are the ratio of the spectrum amplitude in the constructed spectrum
to the pure element spectrum. The pure element spectrum can either be generated
by the computer or by a previously acquired real spectrum of a pure element
standard, under identical acquisition conditions as those that used for acquiring the
standards and the unknown samples.
If you enter the name of a pure element spectrum file, then this spectrum is used in
the fitting process; if the entry of the pure element file name is left empty, a
spectrum is generated synthetically using Gaussian line shape.
The calculated Ki factors are used in both the Regression and Fundamental
Parameters Models to calculate intensities. The correct fit must be verified
visually.
Only Fit is used for a given element only for deconvolution calculations. The
element is excluded from further regressions and reports.
b/a Ratio The ratio of the Kβ peak of an analyte to its Kα peak. The default value is 0.2. This
value is used to determine whether line overlap of the analytical peak has taken
place in cases where FIT is used the line overlap algorithm is used to resolve the
overlapping peak intensities.
Oxide Label This label appears on the report and thus one can place any label in this box to
customize the report output.
Known conc It is possible to include elements measured by other techniques in the analysis and
to use them in the overall calculations of results. For example, the analysis of steel
may call for the analysis of Carbon. Traditionally these analyses are carried out by a
method other than X-ray.
Selecting this field gives an Enable/Disable choice box. By switching this box to Yes
the results for the element (for example, Carbon) will be requested after each
Chapter 5 Quantitative Spectral Analysis
Field Description
analysis and then used in calculating the final result depending on the data
reduction algorithm that was chosen. This feature is currently not operational.
Meas Units Allows the specification of the measurement unit per element such % or ppm.
Pure element Used for FIT calculation only.
file name Clicking this field gives the Open file box.
The default is Gaussian parameters, unless a previously prepared file is specified
and browsed in here.
Ref line of Select the reference line to be used if you chose To intensity Line of Interest for
interest Count Normalization.
Step # Step number if MultiAcq is used.
Bkg ROI Low: Low limit of ROI for the particular element when normalizing with respect to
the background radiation.
High: High limit of ROI for the particular element when normalizing with respect to
the background radiation.
This column does not appear if you did not choose to normalize with respect to the
background ROI in the first Procedure screen.
Enter the desired parameter values and click Next> to continue to the Standards
screen (Figure 5-7).
The Standards screen is used for entering standards information to allow
correlation calculations to the elements of interest. The accuracy of the analysis
cannot exceed the accuracy of the standards. Well-characterized standards are
essential to attain accurate results. In order to proceed, you must have prepared
spectra files as well as some concentration information regarding standards.
The set of standards should include materials with a broad distribution of
concentrations. In general, it is necessary to cover the full range of
concentrations suspected to be in the unknown samples.
The spectrum files must be acquired and saved prior to the calculation of the
regression coefficients. Figure 5-7 shows the Standards screen, set for
Concentrations.
To add a standard, double click in the Standard field of the table. You will be
given the Open file box from which to choose a spectrum file.
The elements appearing in the table are the ones you selected in the previous
Elements of interest screen.
Chapter 5 Quantitative Spectral Analysis
Field Description
Name of the Name given to the procedure in the first Procedure wizard screen.
procedure
Name of the set of Select or enter a file name for the calculation coefficients.
calc coefficients
Concentrations Set up concentrations for each element or compound analyzed. The
concentration of each element in each standard is entered here.
Weight The relative importance of each elements concentration data in the regression
analysis. The concentration of some elements in certain standards might by
known with high confidence while others may not be trusted. Entering a weight
value of zero to such elements caused their concentration not be included in
correlation calculations. Entering high weight factors represents a high
confidence in the listed concentration of that element in that standard. Usually,
a value of 1 is used here.
Counts Gross counts in peak.
Calculated Calculated concentrations from regression analysis.
Concentrations
Intensities This function calculates the intensities (magnitudes) of the peaks which appear
Chapter 5 Quantitative Spectral Analysis
Field Description
in the element list of standards. The calculations are based on details specified
by Elements-Of-Interest table.
After calculating the intensities, additional information is requested concerning
the expected influence of one element on the others. A matrix of asterisks (*) is
displayed; at this point you can replace some asterisks by numerical values.
The system of linear equations to determine the regression coefficients is then
solved. Wherever a numerical value replaces a previous asterisk (*) this
coefficient isn't calculatedit is considered as a limitation dictated by the
operator. A special case is when zero is entered, which means that the influence
of one element on the other is zero (i.e., α-correction is deactivated).
The Standards Deviation, RSD, and Correlation coefficients are also calculated
and displayed in a separate table.
Remove Remove a standard. Select a row click Remove.
Select the desired parameter values and settings and click Next> to continue to
the Calculate Coefficients screen (Figure 5-8).
The default value for the coefficient A0 is 0.000. This indicates an intensity of
zero and thus a concentration of zero. This setting may be used to analyze the
background radiation. In this case, a blank standard should be used; i.e., a
standard which yields no peaks.
Enter any known parameter values and click Next> to continue to the Reports
screen (Figure 5-9).
The Reports screen allows you to generate displays and reports based on the
calculation of the regression model and reflecting the standards and elements-
of-interest information previously specified.
The controls appearing in this screen are described in Table 5-8.
Field Description
Element Element for which the report is to be displayed.
Show Coefficients Display a detailed numeric report of the analysis
Show MDL Display a Measurement Detection Limit report.
The MDL is the minimum concentration that can be measured using a particular
standard. It is used to determine the errors in the various calculations.
Show Report Display a regression analysis report that details the real concentrations for each
element in each standard against the calculated concentration using one of the
regression models. The differences between the real and calculated
concentrations are expressed as the absolute and relative deviations. An
indication of goodness of fit and linear correlation is also given.
Show Lines Display regression line graph.
Show Correlations Display correlation graph.
Chapter 5 Quantitative Spectral Analysis
Field Description
Show Deviations Display deviation graph.
Close all Close all graphics boxes.
Number of Number of decimal places of results values.
decimals
You may enter comments or a description of the procedure in the large field in
the center of the Reports screen.
i NOTE
If you have chosen “Fit” or “Only Fit” for the Intensity Method
parameter in the Elements of Interest table, the Save entry in the above
table will be replaced by the two entries <Back and Next>.
Clicking Next> will display the Gaussian Fit Optimizer screen described
in Section 0.
Field Description
Element Standard element.
Units Coefficient units.
A0 Value of the coefficient A0.
A1 Value of the coefficient A1.
… (not shown in Values of other coefficients, if any, appearing in your regression model.
Figure 5-10)
Std. Dev. Standard deviation of result.
RSD Relative standard deviation – standard deviation relative to the average of
results.
Correlation Correlation coefficient.
Chapter 5 Quantitative Spectral Analysis
Field Description
Standard Standard used.
Intensity Calculated peak intensity.
Given Co… Given (known) concentration of standard.
Calc. Co… Calculated concentration of standard.
Abs. Dev. Absolute difference between given and calculated concentrations.
Rel. Dev. Relative difference between given and calculated concentrations.
You may choose the data range to be displayed by clicking the Set Range button
(see Figure 5-15). Return to the original data range by clicking the Autorange
button.
Print the graph by clicking the Print button.
You may choose the data range to be displayed by clicking the Set Range button
(see Figure 5-15). Return to the original data range by clicking the Autorange
button.
Print the graph by clicking the Print button.
Deviation Line Graph
The horizontal axis represents the given concentration of the standards; the
vertical axis represents the difference between the calculated and the given
concentrations.
When you are finished selecting the Report parameters, click Next> to continue
to the Criterion screen (Figure 5-18).
Field Description
Name of the Name given to the procedure in the first Procedure wizard screen.
procedure
Name of the set of Select or enter a file name for the calculation coefficients.
criterion
Remove Select a criterion (row) in the table and click Remove to remove the criterion
from the table.
Chapter 5 Quantitative Spectral Analysis
Field Description
Table Entries Name: Criterion name.
Ni from-: Lower limit for measurement acceptance (in % or concentration units)
using the element Ni as a standard.
Ni to-: Upper limit for measurement acceptance (in % or concentration units)
using the element Ni as a standard.
Cr from-: Lower limit for measurement acceptance (in % or concentration units)
using the element Cr as a standard.
Cr to-: Upper limit for measurement acceptance (in % or concentration units)
using the element Cr as a standard.
In general, two columns will appear for every element of interest chosen in the
previous screen.
When you have completed entering Criterion parameters, chick Next>. The
Criterion screen will be displayed again, with the Next> and <Back buttons
replaced by Save. Click Save to save the procedure.
Chapter 5 Quantitative Spectral Analysis
Field Description
Name of the Select a procedure name from the pull-down list or enter a new name.
procedure
Name of the The default name (can not be changed by the user) is the same as the procedure
procedure’s name.
parameters
Method Choose one of the analysis methods described in the previous section (SLFP in this
case).
Remove Escape Peak appearing as a result of the Si radiation escaping from the Silicon
Escape Peak detector, will be removed by enabling this selection.
Background The number of channels on either side of a peak used to approximate the background
Points profile.
Sample type Select the sample type from the pull-down list. The options are:
Chapter 5 Quantitative Spectral Analysis
Field Description
Alloy / Oxide / Geologic
Low Z Matrices & Solutions (not operational)
Support type Select type of sample support from the pull-down list.
Select the desired parameter values and settings and click Next> to continue to
the Acquisition Parameters screen (Figure 5-2). The parameters appearing in the
Acquisition Parameters screen are described in Error! Reference source not
ound..
Select the desired parameter values and settings and click Next> to continue to
the Elements of Interest screen (Figure 5-6). The parameters appearing in the
Elements of Interest screen are described in Table 5-6.
Select the desired parameter values and settings and click Next> to continue
to the Criterion screen (Figure 5-18). The parameters appearing in the
Criterion screen are described in
Table 5-11.
Select the desired parameter values and settings and click Next>.
You will be given the Criterion screen again with the <Back and Next> buttons
replace by a Save button. Click Save to save the procedure to disk and exit the
Procedure wizard.
NOTE
i If you have chosen “Fit” or “Only Fit” for the Intensity Method
parameter in the Elements of Interest table, the Save entry in the above
table will be replaced by the two entries <Back and Next>.
Clicking <Back will return you to the previous (Calculate Coefficients)
screen.
Clicking Next> will display the Gaussian Fit Optimizer screen described
in Section 5.5.
Chapter 5 Quantitative Spectral Analysis
The entries in this screen are the same as those for the SLFP method.
Select the desired parameter values and settings and click Next> to continue to
the Acquisition Parameters screen (Figure 5-2). The parameters appearing in the
Acquisition Parameters screen are described in
Table 3-1.
Select the desired parameter values and settings and click Next> to continue to
the Elements of Interest screen (Figure 5-6). The parameters appearing in the
Elements of Interest screen are described in Table 5-6.
Select the desired parameter values and settings and click Next> to continue
to the Criterion screen (Figure 5-18). The entries in the Criterion screen are
described in
Table 5-11.
Select the desired parameter values and settings and click Save to save the
procedure to disk.
Chapter 5 Quantitative Spectral Analysis
i NOTE
If you have chosen “Fit” or “Only Fit” for the Intensity Method
parameter in the Elements of Interest table, the Save entry in the above
table will be replaced by the two entries <Back and Next>.
Clicking Next> will display the Gaussian Fit Optimizer screen described
in Section 0.
Select the desired parameter values and settings and click Next> to continue to
the Acquisition Parameters screen (Figure 5-22). The parameters appearing in
the Acquisition Parameters screen are the same as those described in Error!
eference source not found. with the following addition:
You must select each of the steps in the Number of Step in Multi Acquisition list
in turn and enter the Acquisition Parameters for that step.
When you have entered the parameters for all the steps, click Next>. The
Acquisition Parameters screen will be displayed again, with the <Back and Next>
buttons replaced by a Save button.
Click Save to save the procedure and exit the Procedure wizard.
Chapter 5 Quantitative Spectral Analysis
Parameter Description
FWHM at 0eV Energy resolution of the spectrometer, in eV, extrapolated to 0eV energy,
Zero Shift Energy calibration of the spectrometer maybe not exactly perfect, this term
represents displacement of zero, in eV. Should be 0 at perfect calibration.
Gain Factor As above, this term corrects for non-perfect gain calibration. Normally shouldn’t
deviate from 1.000.
Fano Factor Constant used for calculation of the spectrometer resolution versus energy. This
value should not be changed unless the detector is replaced.
Chapter 5 Quantitative Spectral Analysis
Parameter Description
Tail Term A Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*
Tail Term B Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*
Tail Term C Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*.
Tail b/a Coefficient in function used to describe the deviation of the actual peak shape
from ideal Gaussian.*
Lower Limit Coefficient used to find automatically the lower energy border of multiplet to FIT
or Peak to build. The program will take the peak with lowest energy in the
multiplet and will take for this border the energy of this peak minus FWHM of
this peak multiplied by this coefficient. This parameter is a default value used
when employing the FIT method within a procedure.
Upper Limit As above - for upper energy border (peak with highest energy and plus instead of
minus will be taken). This parameter is a default value used when employing the
FIT method within a procedure.
FIT Start: Start of first FIT range. It is possible to use only one FIT range, however it is
highly recommended to set the Fit region separately for each element where the
Fit intensity method has been selected. You can define the lower and upper eV
limits as shown in the Start and Stop parameters to the left. These can either be
keyed directly into the value windows or the ROI can be defined on the spectrum
of interest by clicking the Set button.
Stop: Stop of first FIT range. It is possible to use only one FIT range. See above.
Set: Click the Set button to define the Start and Stop values on the spectrum of
interest by sweeping the mouse on the ROI Definition Bar. The Start and Stop
values will be entered in their proper positions in the screen.
Background Select propriate representation of the background. Note that it is also possible to
browse in a background file.
Build FIT Perform Fit calculation using the displayed parameters. The calculated Fit will
appear superimposed on the spectrum as an overlap. This can be seen mainly as
a “visualization tool” to evaluate how good the selected fit is.
The Fit Error (Figur of Merit) is a measure of how well the fit is. The smaller value
the better fit.
5.6 Batches
After a Procedure (and all of its elements) has been created, tested, and saved, it
can be used for quantitative analysis of unknown samples. A Batch is created to
run one or more procedures. A Batch (also called Job) is a collection of
procedures, specifying where samples are located on the auto-sampler and
allowing automatic spectra acquisition and subsequent analysis of the sample
against predefined calibrations, yielding analytical results.
The Batch run process is described in detail in Chapter 3. Here, we describe all
the fields in the Batch screen.
In order to define a new Batch or retrieve a previously stored Batch, click the
Batch button in the Spectra window button bar or choose Open Batch from the
Edit pull-down menu. The screen shown in Figure 5-25 will be displayed.
The table entries appearing in the Batch Selection screen table are described in
Chapter 3.
The fields and control buttons appearing in the Batch screen are described in
Table 5-14.
Chapter 5 Quantitative Spectral Analysis
Field Description
Batch Select a batch from the pull-down list or enter a new batch name.
Auto Change If checked, each succeeding row added to the batch table will have its station number
Station incremented by 1.
If unchecked, all succeeding rows added to the batch table will have the same station
number.
Description Description of selected batch. Type a description of the batch here.
Save results in Select a directory to save results files.
directory
Browse Click to navigate to directory in which to save results files.
Add Click in a row then click Add to add a new row (procedure) to the table.
Remove Click in a row, then click Remove to remove that row from the table.
Print Print the Batch table.
All stations to 0 Set all entries in Station column to zero.
This will take all spectra from already acquired and saved spectra in the data base
without acquiring any new data.
This is useful for checking or changing procedures without performing new
acquisitions.
Save Save the batch.
Clear Clear all entries from the table.
RUN Run the batch.
OK Accept any changes, save the batch, and exit the Batch screen.
Cancel Exit the batch screen without saving any changes.
Save data for If this feature is enabled, you may select a ROI from the pull-down list
ROI
Start batch When the batch is run, ignore all entries previous to this line. Otherwise all
from line # measurements will be run.
Save to ASCII Save results file in ASCII format.
format
Chapter 5 Quantitative Spectral Analysis
Parameter Description
AutoAdd If this parameter is not enabled, the system will prompt you as to whether to add
the information generated in the present screen to the database or to replace
previous information.
Chapter 5 Quantitative Spectral Analysis
Parameter Description
If this parameter is enabled, you will not be prompted, and new data will be
automatically added.
The default setting is “enabled”.
OK Accept the values entered in the screen
Cancel Exit the Modify Procedure sequence.
F(x) Calculate the spectral composition.
Spectra Display the Open file box and choose spectra from disk for analysis.
Calc. Coef. Calculate the regression coefficients.
Save Save the Procedure to disk.
Print Print the active tab screen.
i NOTE
If you have not chosen “Fit” or “Only Fit” for the Intensity Method
parameter in the Elements of Interest table of you chosen procedure,
the box shown below will be displayed, and you will NOT be allowed to
enter the Gaussian Fit Optimizer screen.
Chapter 6 System Maintenance and Error Handling
Chapter 6
System Maintenance
and Error Handling
6.1.1 O-Ring
When the sample chamber cover is closed, it seals the chamber by pressing down
an O-ring. This type of seal is very reliable provided it is kept free from dirt and
hair. The O-ring should therefore be kept clean and covered with a thin film of
vacuum-grade grease.
A loose tray may cause positioning errors; make sure that the samples tray is
properly tightened. Do not tighten it with tools; hand tightening is sufficient.
6.2 Troubleshooting
This section offers assistance in correctly diagnosing and possibly correcting
common problems. Emphasis is placed on problems arising from incorrect
operation or settings, or other difficulties that can easily be corrected by simple
means. In general, only trained service personnel must solve hardware
problems.
CAUTION
Do not attempt to repair the system on your own. Consult your service
agent before trying to repair any hardware failures.
WARNING
This is an extremely hazardous and potentially poisonous operation. Be
very careful not to exert pressure on the thin window. NEVER USE A
SWAB TO CLEAN THE Be WINDOW.
WARNING
Accidental damage (or damage due to neglect or abuse) to the Be window
is not covered under the standard warranty of the system.
Chapter 6 System Maintenance and Error Handling
WARNING
Use of high voltages (especially > 30 kV) without adequate prior tube
conditioning may result in arcing, leading to premature and/or
catastrophic x-ray tube and related circuit failures.
Chapter 6 System Maintenance and Error Handling
Chapter 6 System Maintenance and Error Handling
Chapter
7
WARNING
This equipment contains a HIGH VOLTAGE power supply.
(16) Click the nEXt icon to activate nEXt. (If you do not have an icon, click the
Start bar, then Programs, and click on nEXt there.)
(17) The nEXt log-in window (Figure 7-1) should appear.
Chapter 8
System Calibration
8.1 Introduction
A properly functioning system will be stable for months or even for years. Re-
calibration is typically required following system installation or after replacing
electronic components or after a long period during which the system was not in
use and the detector was warmed up to room temperature.
In a newly installed system, re-calibration might be necessary during the first
week or two of operation.
The Setup Table consists of a tab window. The tabs are used to choose screens
corresponding to the above parameter groups and are shown in Figure 8-1.
Field Description
Print Print the active tab screen.
OK Click OK to accept your entries and exit the Setup Table.
Cancel Exit the Setup Table without saving changes not previously saved by clicking
the Apply button.
Apply Save the changes in the current screen without exiting the Setup Table.
Help Display on-line help.
Field Description
XRF system type Indicate your system type: X-Calibur.
Set logo Name of model: Enter your system model (X-Calibur).
Serial number: Enter your system Serial Number.
Name of company: Enter the name of your company.
Revision Hardware revision. Defines changes made to system hardware according to
which software algorithms different from the original algorithms may be
used.
Field Description
Controller Port: Com1, Com2, Com3, Com4, Com5, Com6: Port to which X-ray
Parameters controller is assigned.
Acquisition delay: Time from x-ray enable to measurement.
Emission current tolerance: Allowable deviation in emission current.
High voltage tolerance: Allowable deviation in high voltage.
Filament current tolerance: Allowable deviation in filament current.
Filament current reference: Nominal filament current.
Tube parameters Min high voltage: Minimum high X-ray tube voltage value (minimum
acceleration voltage between filament and anode).
Max high voltage: Maximum high X-ray tube voltage value (maximum
acceleration voltage between filament and anode).
Min current: Minimum X-ray tube filament current.
Max current: Maximum X-ray tube filament current.
Max power: Maximum permitted X-ray tube dissipation power.
Tube: Type of tube (anode element). Select the tube type from the pull-
down field.
Power supply Voltage limit: Maximum output voltage.
Current limit: Maximum output current.
Note: These limits will always be greater than or equal to the corresponding
maximum X-ray tube values.
Chapter 8 System Calibration
i NOTE
The Max tube temperature is factory set to 50°C.
Field Description
Vacuum Maximum high voltage (kV): Maximum high voltage for the vacuum
Parameters controller.
Minimum level for measurement: Vacuum level needed to begin
measurements.
Chapter 8 System Calibration
Field Description
Maximum waiting time (sec): Maximum time allowed attaining the
minimum vacuum level for measurement. If this time is exceeded, an error
message will be displayed.
(
Linearization coefficients ( log Vacuum ) = a × Voltage + b ):
Coefficients for converting Vacuum level to a dimensional value. Not yet
implemented.
Maximum normal If the dead time is greater than this value, a warning message will be
dead time displayed.
He waiting time When a Helium atmosphere is used (by helium purge), this is the time the
system waits for Helium to fill the volume at and around the measuring
position in the chamber before starting an acquisition.
If several consecutive measurements in a Batch use Helium, the system will
wait for the Helium to fill the x-ray path volume for the first measurement
only. (After the first measurement, this volume will already be full.)
Field Description
Zero DAC DAC coefficients defining the zero peak position for Low and High
throughput for the 10 keV and 40 keV energy ranges. These values depend
on the DAC system electronics.
The Zero DAC values should be in the range of 0 to 255.
Fast Peak detection threshold values used to discriminate between signal and
noise for Low and High throughput for the 10 keV and 40 keV energy ranges.
Zero factor Low Zero energy calibration coefficient for low throughput. This coefficient
determines the iteration step used in moving the zero-energy peak to the
zero position (zero calibration).
Zero factor High Zero energy calibration coefficient for high throughput.
Zero factor Super Zero energy calibration coefficient for super high throughput.
High
I/O address MCA I/O address defined by jumpers on MCA card.
Memory address MCA memory address defined by jumpers on the MCA card.
Init MCA Enable to Initialize the particular MCA. If this parameter is disabled, the
particular MCA will not be used during data acquisition.
Inihw file name Enter an MCA initialization file name. Clicking Browse displays the standard
Open window from which to select a .txt file.
Zero region Region erased from the spectrum so that the tail of the zero energy peak
will not be displayed.
Timeout Time-out for zero energy calibration. If the time needed to perform a zero
peak measurement is greater than this, an error message will be displayed.
Zero convergence Window for zero peak values. During Zero Peak Calibration, the convergence
region should be to within ± this value.
It is recommended that a value ≥ 3eV be used so as not to cause a time-out.
Autocalibration Enable/disable zero calibration measurement.
The zero width will be measured and displayed, but the system database will
not be updated
The default is to enable.
Recalibration Enable/disable zero calibration.
The zero width will be measured and displayed, and the system database
will be updated
The default is to enable. To use this option, Autocalibration must also be
enabled.
Fast Pile-Up time This parameter is used for theoretical calculations, and must be set to 6µsec.
The system software also includes a utility that allows setting of parameters to
define automatic calibrations. To access this utility, select Setup MCA from the
Setup pull-down menu in the Superuser window (see Figure 8-6).
Chapter 8 System Calibration
! IMPORTANT
Only experienced users and/or service engineers should use this utility.
! IMPORTANT
These variables are intended for advanced users only and in most cases
should not be changed.
Field Description
System configuration Incidence angle: Angle between the central ray of the primary X-ray
beam and the sample plane.
Emergence angle: Angle between the sample surface and the beam
entering the detector.
Tube take off angle: Angle between the central ray of the X-ray beam
emerging from the tube and the tube anode surface.
Tube Be window: Thickness of Be window of X-ray tube.
Detector Be thickness: Thickness of Be detector window.
Detector Si thickness: Detector crystal thickness.
Tube-Sample distance: Distance between the X-ray tube and the sample.
This parameter is important only when working with S/W fundamental
parameters. The value used depends on your system model.
Sample-detector distance: Distance between detector and sample.
Chapter 8 System Calibration
Field Description
Sec. Target-Sample distance: Distance between the secondary target
and the sample. This parameter is applicable only for the EX-6600
systems.
System fundamental Thickness in microns of various supports (holders) which may be used to
parameters contain powder or liquid samples when the X-ray beam impinges on the
sample from below.
Support1 None:
Support2 Mylar:
Support3 Polyprop:
Support4 Prolene:
Support5 Polycarb:
Support6 Kapton:
Minimum element to Number of minimum element to identification:
peak identification Minimum atomic number of element to be identified. This parameter is
may be set as low as 9 for X-2600 series systems.
Parameter Description
FWHM at 0eV Energy resolution of the spectrometer, in eV, extrapolated to the energy 0
eV for Low and High throughput. This parameter is used for theoretical peak
building.
Tail Term A Correction term used to describe the deviation of the peak shape from ideal
Gaussian for Low and High throughput. This parameter is used for
theoretical peak building.
Tail Term B Correction term used to describe the deviation of the peak shape from ideal
Gaussian for Low and High throughput. This parameter is used for
theoretical peak building.
Tail Term C Correction term used to describe the deviation of the peak shape from ideal
Gaussian for Low, High and Super High throughput. This parameter is used
for theoretical peak building.
Tail b/a Allows introduction of different tail corrections for β and α lines for Low and
High throughput. Normally set to 1.000. This parameter is used for
theoretical peak building.
Dw/Cps coefficient For Low and High throughput. Not yet operational.
Zero Shift Energy calibration of the spectrometer may not be exactly perfect, this term
represents displacement of zero, in eV. Should be 0 at perfect calibration.
This parameter is used for theoretical peak building.
Gain Factor As above, this term corrects for non-perfect gain calibration. Normally
shouldn’t deviate from 1.000. This parameter is used for theoretical peak
building.
Fano Factor Constant used for calculation of the spectrometer resolution versus energy.
This value should not be changed unless the detector is replaced with totally
different type. This parameter is used for theoretical peak building.
Lower Limit Coefficient used to find automatically the lower energy border of multiplet
to FIT or Peak to build. The program will take the peak with lowest energy
in the multiplet and will take for this border the energy of this peak minus
FWHM of this peak multiplied by this coefficient. This parameter is a default
value used when employing the FIT method within a procedure.
Upper Limit As above - for upper energy border (peak with highest energy and plus
instead of minus will be taken). This parameter is a default value used when
employing the FIT method within a procedure.
FIT Start Select a definite starting (lower) point for the FIT method.
Note: The FIT method builds a theoretical spectrum between the upper and
lower energy limits.
FIT Stop Select a definite stopping (upper) point for the FIT method.
FWHM factor Not yet operational.
Detector type Type of detector installed.
Chapter 8 System Calibration
Parameter Description
Pulse processing Each of these parameters is set for Low and High throughput.
PILE-UP window (Hex): The time interval after a pulse is received that
successive pulses will be rejected. This prevents pulses from piling up and
distorting a previously received pulse.
Peak detection (Hex): Time at which an amplitude measurement is made
after the system determines that a peak has arrived.
Noise inhibit (Hex): Time interval after a pulse is detected during which the
system does not make noise measurements
Processing time (Dec): Empirical parameter used to calculate the Dead Time
parameter.
Motor steps per Sets speed of sample and filter motors.
second
Chapter 8 System Calibration
Parameter Description
Station GAP Distance between sample stations.
First station offset Position of first sample station with respect to a reference pin on the station
wheel.
Filter GAP Distance between filters.
First filter offset Position of first filter with respect to a reference pin on the filter wheel.
Filter – target GAP Not applicable to X-2600 series systems.
Number of Stations Number of sample stations.
Field Description
List of colors List of colors: List of possible color combinations.
Defaults: Accept default color scheme.
Color: Select color. You will be given the following display:
Field Description
Number of Filters Number of filters to be used. Up to 6 filters may be installed for X-2600
series systems: None (no filter), Ti, Fe, Cu, Rh, and W.
Filter The filters installed on X-2600 series systems are: None (no filter), Ti, Fe, Cu,
Rh, and W.
Number of Select number between 1 and 8. This number depends on your system.
calibration stations
Calibration stations List: List of calibration stations.
Names: Enter name of calibration station selected from above list.
Chapter 8 System Calibration
Parameter Description
Periodic Table Select an element whose peak position is to be calibrated by clicking on its
icon.
KLM Lines KLM line to be used in the calibration for the selected element. The default
is average value for the Kα line.
Data Table – Acq Acquisition parameters to be used for the calibration for each measurement
Parameters range. X-Calibur systems have only 10keV and 40keV energy ranges.
I: Emission current.
V: X-ray tube voltage.
T: Acquisition time.
Station: Station to be used for acquisition.
Elements and KLM lines selected are listed for each energy range up to a
maximum of 5).
Chapter 8 System Calibration
(20) Make sure the Auto Calibration box is checked in the Setup Table/ADC
Parameters screen.
(21) Acquire a spectrum from a pure element standard. Specify a set of
acquisition parameters in order to acquire a spectrum with a large, well-
resolved peak at the higher end of the energy scale. A good estimate is:
High Voltage 20 kV 37 kV
(22) Acquire a spectrum and verify the proper position of the peak. The peak's
height should be larger than 4,000 counts in order to assure a meaningful
result. Each time you alter the Gain DAC you begin with a new
acquisition by selecting the Start button.
(23) The best way to determine the precise peak's location may be by
comparing it to a computer-generated peak of the corresponding
element, using the BUILD PURE function in the Spectra pull down menu.
(You may save the generated pure spectrum or move it to the overlap or
use the KLM markers).
Appendix A
Theory
A.1 X-Rays
X-rays are high-energy short wavelength electromagnetic waves whose
wavelengths range from about 0.1×10-10m to 100×10-10 m. They are generated
as a result of bombardment of atoms with high-energy particles or radiation of
high energy.
Some of the bombarding particles (usually electrons) are decelerated by the
atoms, giving rise to a continuous energy spectrum. The bombardment also
results in the dislodging of inner-shell electrons, leading to the formation of ions.
Electrons that orbit further out from the nucleus then undergo transitions to fill
the inner orbital vacancy. The transition from one energy level to another results
in the formation of an X-ray photon with a definite characteristic energy. The
energy value of each transition is discrete and, apart from statistical processes
that lead to line broadening, the detection of this photon can allow the process
to be recorded as a discrete line of a given energy. The radiation generated in
this process is called X-ray Fluorescence (XRF).
Figure 0-1 shows schematically a simple X-ray tube. A very high voltage is placed
across the electrodes in the two ends of the tube and the tube is evacuated to a
low pressure, about 10-6mm of mercury. The current flows between the two
electrodes and the electrons carrying this strike the metal target. This causes the
emission of X-rays.
For a metal target such as copper or molybdenum, if you plot the intensity vs.
wavelength, you will observe very sharp peaks appearing above a smooth
background radiation (see Figure 0-2).
These peaks are called characteristic lines and the X-radiation is called
characteristic radiation. They are caused by electrons being knocked out of the K
Appendix A Theory
shell of an atom and then the electrons from the L shell cascading down into the
vacancies in this K shell. The energy emitted in this process corresponds to the
so-called K alpha line. A similar process, in which electrons cascade from the M
shell to the K shell, gives rise to the K beta line. If several metals are present in
the target, each will emit its characteristic radiation independently. This property
can be used to determine qualitatively which elements are present in an alloy by
making it the target in an X-ray tube and then scanning all wavelengths emitted
by the target.
(a) (b)
Figure 0-3: XRF Creation
As the atom returns to its stable condition, electrons from the outer shells are
transferred to the inner shells and in the process giving off a characteristic X-ray
whose energy is the difference between the two binding energies of the
corresponding shells (see Figure 0-4). The emitted X-rays produced from this
process constitute X-ray Fluorescence (XRF). In most cases, the innermost (K, L
and M) shells are involved in XRF production.
Appendix A Theory
Usually, the innermost (K, L and M) shells are involved in XRF detection.
Each element has its distinct characteristic set of emission lines. The energies of
these lines are documented in tables and stored in the computer's memory, as
shown in Figure 0-5 below.
To identify the elements in a given sample, excite the sample and measure the
wavelengths of the characteristic X-rays emitted. The lines in the acquired
spectrum can then be compared to the corresponding element lines listed in the
system's database.
Appendix A Theory
The X-2600 series employs a Pin Diode detector to detect x-rays emitted from
the sample. These detectors are capable of acquiring a spectrum containing
many lines from many elements simultaneously. The detector converts the x-ray
photons to proportional electric pulses. These signals are amplified and
converted into a digital form by the Analog-to-Digital Converter (ADC). The data
of the accumulated spectra are stored and displayed on the computer's monitor
as a spectrum histogram (Figure 0-6).
Appendix B
System Specifications
B.1.3 Auto-sampler
Computer controlled eight sample position tray accommodating 42 mm high
samples.
Dimensions:
Appendix C
Detector
Theory
C.1 Detector
There are two kinds of detectors used in the X-2600 series: Si PIN diode detector or
Silicone drift detector.
particularly at short peaking times. This gives the SDD better energy resolution at
moderate count rates and much better energy resolution at high count rates. The
difference is most significant at low energies.
Figure C- 1: Sketch illustrating the design and operation of a Silicon Drift Detector
(SDD).
The SDD uses a planar cathode but the anode is very small and surrounded by a
series of electrodes. The SDD is cylindrically symmetric, so the anode is a small circle
and the drift electrodes are annular. These electrodes are biased so as to create an
electric field which guides the electrons through the detector, where they are
collected at the anode. The rest of the signal processing electronics is nearly identical
to that used with the Si-PIN diode.
The small area of the anode keeps the capacitance very small. Since the active
volume of the diode is enlarged by adding more electrodes with the same anode
area, the input capacitance is independent of detector area. This is important
because the dominant noise source in silicon X-ray spectroscopy is voltage noise,
which is proportional to the total input capacitance and increases at short shaping
times. The SDD, with its low capacitance, has lower noise, particularly at very short
shaping times.
Appendix D Energy Calibration
Appendix D
Energy
Calibration
In order to adjust the peak position, two features in the "Setup MCA" in the setup
menu have to be adjusted.
Appendix D Energy Calibration
Click on the nEXt button and confirm that the controller and the MCA boards are
initialized
For fast gain calibration click on the mouse right button and choose "Fast Gain
Calibration"
Appendix D Energy Calibration
Move the peak up or down in energy, by using the arrows in the Fast Gain calibration
dialog box.
Calibration of peak position of elements at low energy, use the “Zero offset“(Setup
MCA”).
The “Zero offset“ will move all elements in the spectra linearly.
Change of Gain DAC number, will move peaks at high energy more than peaks at
low energy.
Several iterations will be required to correct all peaks positions.
For 40KeV Range, also use low and high elements, for example - Cu and Sn.
Use the same method, in order to do tune for the 40KeV range.
Appendix D Energy Calibration
It is useful to use the KLM markers, for the spectra energy calibration
After completion of the peak energy calibration, continue working as usual and
check that your applications are working fine.