X-Calibur Manual

Chapter 1 System Overview
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
1 System Overview ............................................................................. 5

1.1 System Purpose 5
1.2 Principles of Operation 7
1.3 System Structure 9
1.3.1 System Overview ............................................................................. 9
1.3.2 X-ray Generator ........................................................................... 10
1.3.3 Sample Chamber and Tray ......................................................................... 10
1.3.4 The Detector and Its Electronics................................................................. 10
1.3.5 Control Unit ........................................................................... 10
1.3.6 Computer ........................................................................... 11
1.3.7 System Software ........................................................................... 11
1.4 Operation Controls and Indicators 12
1.4.1 Front Panel indicators ........................................................................... 12
1.4.2 System Main Power Switch ........................................................................ 12
1.5 Environmental Considerations 13
1.6 Safety Information 14
1.7 Modes of Operation 15
2 Basic Operation .......................................................................... 16

2.1 System Start-Up and Shut-Down 17
2.1.1 Power On: ........................................................................... 17
2.1.2 Power Off: ........................................................................... 17
2.2 Operator Log-In and Log-Out 18
2.2.1 Log-In ........................................................................... 18
2.2.2 Log-Out ........................................................................... 22
2.3 Tube Warm-up (Tube Conditioning) 23
2.4 Loading the Sample Tray 24
2.5 User Interface 26
2.5.1 Status Buttons ........................................................................... 26
2.5.2 The Main Operator and Spectra Mode Windows ....................................... 28
2.6 Printing a File 34
2.6.1 Print Setup ........................................................................... 34
3 Data Acquisition .......................................................................... 35

3.1 Acquisition Parameters 36
3.2 Batch Run Process 39
3.2.1 Logging On to Operator Mode ................................................................... 39
3.2.2 Selecting and Running a Batch in Superuser Mode ................................... 40
3.2.3 Batch Results Display ........................................................................... 42
3.2.4 Results Table Format ........................................................................... 44
3.3 File Structure 47
3.3.1 The X-2600 Series Database ...................................................................... 47
3.3.2 Database Manipulation ........................................................................... 48
3.3.3 Spectra Files ........................................................................... 51
4 Qualitative Spectral Analysis........................................................ 52

4.1 Introduction 52
4.2 Guidelines for Acquisition Parameter Selection 53
4.3 Acquiring Spectra 54
4.4 Editing and Manipulating Spectra 55
4.4.1 Identifying Peaks ........................................................................... 55
4.4.2 Zooming Regions of Spectra ...................................................................... 56
4.4.3 Regions of Interest (ROI) ........................................................................... 57
4.4.4 KLM Markers ........................................................................... 62
4.4.5 Matching Spectra ........................................................................... 66
4.5 Analyzing Spectra - Summary 72
4.6 Spectra Mode Pull-Down Menus 74
4.6.1 Edit Menu ........................................................................... 74
4.6.2 View Menu ........................................................................... 75
4.6.3 Spectra Menu ........................................................................... 76
4.6.4 Parameters Menu ........................................................................... 79
4.6.5 Setup Menu ........................................................................... 80
4.6.6 Tools Menu ........................................................................... 80
4.6.7 Data Base Tools Menu ........................................................................... 81
4.6.8 Help Menu ........................................................................... 82
5 Quantitative Spectral Analysis.................................................... 83

5.1 Introduction 83
5.2 Sample Presentation Requirements and Reference Materials 84
5.3 Procedures 86
5.3.1 Spectra Acquisition Parameters .................................................................. 86
5.3.2 Analysis Methods ........................................................................... 88
5.4 Procedure Setup – The Procedure Wizard 95
5.4.1 Beginning the Procedure Setup Process ..................................................... 95
5.4.2 Analysis Method – None ........................................................................... 96
5.4.3 Analysis Method – Regression ................................................................... 99
5.4.4 Analysis Method – SLFP ......................................................................... 116
5.4.5 Analysis Method – AccurEx..................................................................... 118
5.4.6 Analysis Method – MultiAcq ................................................................... 119
5.4.7 Analysis Method – Sort ......................................................................... 121
5.5 The Gaussian Fit Optimizer 123
5.6 Batches 125
5.7 Modifying a Procedure 127
6 System Maintenance and Error Handling ............................ 129

6.1 Routine Maintenance 130
6.1.1 O-Ring ......................................................................... 130
6.1.2 Sample Chamber ......................................................................... 130
6.1.3 Secure the Trays ......................................................................... 130
6.1.4 Computer Operation ......................................................................... 130
6.2 Troubleshooting 131
6.2.1 Detector Related Problems ....................................................................... 132
6.2.2 Cleaning the Be Window ......................................................................... 132
6.2.3 Error Messages ......................................................................... 133
6.2.4 Measurement Problems ......................................................................... 133
6.2.5 X-Ray Generator Problems ...................................................................... 134
6.3 Communication-related problems 136
6.3.1 No Controller Answer ......................................................................... 136
6.3.2 Communication Error ......................................................................... 136
6.3.3 Transmission Failure ......................................................................... 136
6.3.4 No Bias Supply ......................................................................... 136
6.4 Operation and Error Messages 136
7 Site Requirements and System Installation .......................... 137

7.1 Site Requirements 137
7.2 Electrical Power Connection 138
7.3 Unpacking and Installing the X-2600 System 139
7.3.1 Unpacking ......................................................................... 139
7.3.2 Hardware Installation ......................................................................... 139
7.3.3 Software Installation ......................................................................... 139
7.3.4 Running nEXt ......................................................................... 139
7.3.5 Importing Old ExWIN Files ..................................................................... 140
8 System Calibration ........................................................................ 141

8.1 Introduction 141
8.2 The Setup Table 141
8.2.1 Machine Parameters ......................................................................... 142
8.2.2 Controller and Tube Parameters ............................................................... 143
8.2.3 System Configuration ......................................................................... 145
8.2.4 MCA (DPP) Parameters ......................................................................... 146
8.2.5 Calculation Parameters ......................................................................... 148
8.2.6 Detector Parameters ......................................................................... 150
8.2.7 Analytic Instrument Parameters ............................................................... 152
8.2.8 Environment Configuration ...................................................................... 153
8.2.9 Filter_Stations Parameters ........................................................................ 155
8.2.10 Gain Calibration Setup Data ..................................................................... 156
8.3 System Calibration 157
8.3.1 Energy Calibration ......................................................................... 157
8.3.2 Calibration Setup (Gain and Zero Calibration)......................................... 157
8.3.3 Gain Calibration ......................................................................... 157
8.4 Initial Operation and Test 158
Appendix A Theory ........................................................................ 159

A.1 X-Rays 159
A.2 X-Ray Fluorescence (XRF) 161
A.2.1 Introduction ......................................................................... 161
A.2.2 XRF Spectra ......................................................................... 162
A.3 Relative Line Intensities and Probability .................................................. 163
A.3.1 XRF Detection ......................................................................... 163
A.3.2 Sources of Background ......................................................................... 165
A.4 Applications of XRF ......................................................................... 166
Appendix B System Specifications ..................................................................... 168

B.1 Specifications and Facility Information 168
B.1.1 X-Ray Generation ......................................................................... 168
B.1.2 X-Ray Detection ......................................................................... 168
B.1.3 Auto-sampler ......................................................................... 168
B.1.4 Computer and Software ......................................................................... 168
B.1.5 Power & Dimensions ......................................................................... 169
Appendix C Detector Theory ........................................................................ 170

C.1 Detector 170
C.1.1 Si PIN diode detector ......................................................................... 170
C.1.2 Silicone Drift Detector (SDD) .................................................................. 170
Appendix D Energy Calibration ........................................................................ 172

D.1 Peak Position Adjustment 172
Chapter 1
System Overview
1.1 System Purpose

The X-2600 series of ED-XRF Spectrometers (Figure 1-1) is designed to detect the
elements in analyzed samples and determine their concentrations using X-Ray
Fluorescence (XRF). They are sensitive to elements from Z=9 (Fluorine) to Z=100
(Fermium). Samples can be in solid, powder or liquid form.
The analysis performed by X-2600 series systems can by divided into two
categories:
Qualitative analysis – Identification of the elements in a sample and
inspection of the acquired spectra on a comparative basis.
Quantitative analysis – Quantitative determination of the concentrations
of the elements in a sample. This is performed after carrying out
calibration procedures, using a pre-analyzed set of standards and
empirical models, or via the fundamental parameters method.
The system software (nEXt™) runs under Windows 7 or higher. All parameter
and data files are saved on hard disk in Microsoft Access format and can be read
and manipulated using Microsoft Word or Microsoft Excel.
Figure 1-1: X-Calibur

1.2 Principles of Operation

X-2600 series systems utilize the phenomenon that when a sample is irradiated
with x-ray radiation, the sample's atoms are excited. As the atoms return to
their initial stable state, they emit x-ray photons (X-ray Flouresence – XRF).
Each element has its distinct characteristic emission lines. The energies of these
lines are documented in tables and stored in the computer's memory, as shown
in the figure below. A given sample's elements are identified by comparing the
lines in the acquired spectrum to the corresponding element lines listed in the
system's database.
Figure 1-2: Elemental X-Ray Lines
The intensity (magnitude) of the element's lines in the acquired spectrum is

related to its concentration. Increasing the concentration of an element results
in a proportional increase in the intensity of the fluorescent radiation
characteristic of that element. By using empirical or theoretical physical models,
the system can provide precise qualitative and quantitative analysis.
X-Calibur or X-Cite systems are using detectors that are Peltier cooled to below
<40 °C. The Silicon PIN-diode detector (PD) or Silicon Drift Diode (SDD), For more
information, please see appendix C. X-rays emitted from the sample reach the
detector through a very thin Beryllium window that isolates the vacuum inside
the cryostat from the atmosphere in the sample chamber. (The detectors can
also be provided with super thin non-Beryllium window especially optimized for
light element detection).
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.
1.3 System Structure

Figure 1-3 shows the major system components. Operator operations will
involve using the keyboard, mouse and monitor.
Figure 1-3: X-2600 Major Components
1.3.1 System Overview

The X-2600 series hardware includes the following components:
X-ray Generator: X-ray tube and High Voltage Power Source (HVPS)
X-Ray detector
Sample Chamber and Tray
Controller Unit
nEXt Spectra Acquisition and Analysis Software Package
Built-in PC, mouse, keyboard and monitor.
1.3.2 X-ray Generator

The X-ray Generator consists of the X-ray tube and it's Power Unit. The X-ray
tube (50kV, 50W for the X-Calibur, 35kV, 9W for X-Cite) is housed in an X-ray
radiation shield. The ceramic envelope of the tube is surrounded by high voltage
insulating material. The cathode voltage is held close to the ground potential
while the anode is held at positive High Voltage, supplied by the H.V. power
supply. The filament current heats the filament, causing it to emit electrons (this
is the emission current). The electrons are accelerated towards the anode by the
electric field. Each electron acquires energy less than or equal to the anode
potential multiplied by the electric charge of the electron.
The excitation beam is collimated to form a spot, about 8mm in diameter at the
center of the sample area.
Up to six thin metal foil filters are installed. The filter is used to modify the
spectrum of the excitation beam in order to obtain optimum excitation of the
analyzed elements.
1.3.3 Sample Chamber and Tray

The Sample Chamber is shielded with sheets of lead, and the viewing window is
made of leaded glass. The sample tray is moved by a stepper motor and
controlled from the nEXt software. An optical switch senses its precise position.
The standard sample tray contains 8 positions to hold the samples or standards
and an additional 8 position on the reverse side of the tray to hold energy
calibration samples.
1.3.4 The Detector and Its Electronics

The detectors are described above.
1.3.5 Control Unit

The control unit controls all the communications between the computer and the
system, including: operation of the X-ray generator, auto position within the
sample chamber, and safety devices on the cabinet, as well as determining other
operational parameters.
The control unit receives commands and parameters from the computer, such as
sample tray wheel motion, start and stop of X-ray generation, the high voltage
applied to the tube, emission current values, etc. The control unit also monitors
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
1.3.7 System Software

The “nEXt” system software runs under the Windows 7 Operating System.
System functions are controlled using both mouse and keyboard input.
The quantitative functions are organized into analysis Procedures. A procedure is
a complete set of parameters and instructions on how to analyze the samples. A
wizard aids in creating procedures.
The fundamental parameters algorithm, as well as empirical algorithms based on
calibration standards, are integrated in a single, complete software package.
Output utilities allow the results to be presented in graphical and numerical
formats.
The software is extremely flexible. It enables you to collect many different
spectra, each under separate excitation conditions, from the same sample,
optimize each acquisition for best sensitivity for a specific group of elements,
and combine all these procedures into one batch command.
The user interface and software operation are described in Chapter 2, Basic
Operation.
1.4 Operation Controls and Indicators

The X-2600 series has two main controls/indicators as listed below:
1.4.1 Front Panel indicators

1. The Green LED indicator shows that the main system is powered up.
2. The Red X-ray enable switch (), in its enable position (lighted), allows X-
ray generation through operator control via the software. In the switch’s
standby position (dark), X-ray generation is disabled. This switch provides
the means for manual, unconditional cessation of X-ray generation.
Normally the switch should remain in the enable position.
Figure 1-4: X-Ray Enable Switch
1.4.2 System Main Power Switch

This switch, located on the right rear panel, turns the system's power on and off.
The unit should only be turned off for servicing.
Figure 1-5: Main Power Switch

1.5 Environmental Considerations

X-2600 series systems are designed to operate in both static and mobile
environments.
Make sure the system site is maintained free from strong acoustical noise.
Strong electrical fields such as those generated by arc welding instruments,
induction furnaces, large electric power lines, etc., can interfere with signals
from the X-ray detector and decrease its resolution. Do not hesitate to consult
your Xenemetrix service agent if you suspect that such problems exist.
Keep the system and its vicinity clean and dust-free since circuit boards and
components in the system and computer could fail due to an accumulation of
conductive dust or from corrosion.
Avoid extreme temperatures or high humidity. The recommended operating
temperature range is 20° to 25°C (68° to 77°F). Constant temperature assures
the stability of system calibration.
WARNING
This equipment contains a HIGH VOLTAGE power supply.
A good system ground is essential to ensure safe operation and minimal

interference. Make sure that the ground connections at the installation
site are secure and have low resistance to ground.
It is not advisable to place a printer or other equipment that could generate

mechanical vibrations or acoustical noise on top of the system cabinet, since
these vibrations may degrade the detector's resolution.
1.6 Safety Information

X-Series equipment is intrinsically safe from radiation hazards due to a thorough
shielding design around the x-ray source and the sample chamber. Every system
is inspected and tested to ensure the level of radiation around the sample
chamber does not exceed free ambient radiation levels. The systems are
equipped with safety micro switches to ensure covers and parts are correctly
aligned to completely shield any radiation. Finally, in keeping with accepted
standards, warning stickers as well as flashing red lamp indicate the presence of
X-rays.
WARNING
Overriding safety features or interlocks should not be done under any
circumstances. These features have been installed for your safety.
In general, standard safety procedures for operating all electrical machinery

should apply to your X-Series Spectrometer. Each system should be operated
only as indicated in this manual. Refer to the following figure for general safety
points.
Figure 1-6: X-Calibur Series Spectrometer safety points

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.
1.7 Modes of Operation

X-2600 series systems may be operated at two different levels: Operator and
Superuser. These levels are described in Table 1-1.
Table 1-1: Operational Modes
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.
2.1 System Start-Up and Shut-Down

System start-up and shut-down are described below.
Note: do not turn off the system without first logging out of the Windows
operating system.
2.1.1 Power On:

(1) Turn the system Main Power switch ON. This switch is
located on the rear of the system cabinet to the left
(when viewed from the rear of the system). Refer to
Figure 2-1.
Figure 2-1: Main Power Switch Location (On Back of System)
2.1.2 Power Off:

(2) After exiting Windows 7, power off any peripherals, turn
off the Main Power switch.
2.2 Operator Log-In and Log-Out

2.2.1 Log-In
The X-Calibur and X-Cite system software restricts system operation to
authorized users. To operate the system, you must log on to the system.
To log on, perform the following steps in the Log-On window (see Figure 2-2):
(1) Enter your name in the User Name field.
Your name will appear on all results reports printed while in operator
mode.
(2) Enter password (7 for Superuser and 1 for Operator) in the Password
field.
(3) Choose your operation mode from the Mode pull-down field (refer to
Section 2.2.1.1 for more details).
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).
Figure 2-2: Log-In Window
2.2.1.1 Passwords and Operator Modes

Your system manager will assign you a password, defining your operation mode.
When you enter your password, the Title bar will change to indicate your
operator mode.
The possible operator modes are described in Table 2-1.
Table 2-1: Operator Modes
Mode Description
Operator Run predefined batches only
Superuser Create and control procedures and batches. Run manual acquisitions.
Make changes and set parameters.
2.2.1.2 Initialization Mode

Initialization Mode determines which parts of the system you want to initialize
before beginning to work. Depending on your operator mode, there are two
possibilities:
Partial Initialization
Full Initialization
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.
Figure 2-3: Partial Initialization Options I
Figure 2-4: Partial Initialization Options II
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.
Figure 2-5: Initialization Status
Table 2-2: Initialization Status
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.
2.3 Tube Warm-up (Tube Conditioning)

If the instrument is not used for more than 24 hours it is necessary to gradually
condition the x-ray tube before using very high voltage (>30 kV) acquisitions. If
the voltages will be below 30 kV, then Warm up is not necessary. Predefined
automatic conditioning routines, (Warm-up Batch) is found in the Tools menu. If
the warm-up routine is missing, please consult with your service engineer to
redefine this important automatic acquisition.
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.
Note that it is recommended not to load the auto-sampler before performing

Warm-up.
The system will activate the x-ray system, increasing the voltage in successively
higher steps, each step taking 10 seconds. After approximately 3 to 4 minutes,
Warm-up Batch is complete and you can proceed.
You may run the Warmup program at any time by selecting Run Warmup Batch
from the Tools pull-down menu.
2.4 Loading the Sample Tray

Following start-up, the next step an operator typically takes is to load the sample
tray in order to begin data acquisition. It is recommended to have samples
prepared and identified in advance to allow ease of loading and to avoid
mismatches with procedure and or batch definitions, as noted below.
Take extra care in loading samples in order to avoid contacting the Be (Beryllium)
window located under the sample cup at the x-ray position.
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).
Figure 2-6: Autosampler Door

Figure 2-7: Autosampler Door and Autosampler
(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.)
2.5 User Interface

The X-2600 series User Interface runs under the Windows 7 operating system.
You should be familiar with the mouse operations as well as with the notions of
windows, boxes, fields, etc. Refer to your Windows 7 documentation for
information on these concepts.
2.5.1 Status Buttons

The Main X-2600 series control windows contain several Status buttons and
indicators in the upper right corner (see Figure 2-8).
Figure 2-8: Status Buttons
The buttons are described in Table 2-3, and the indicators are described in
Table 2-4).
Table 2-3: Status Buttons
Button Description
X-ray on/off: Indicates whether X-rays are on/off.
Power supply for the detector (±120/180 V)
Error: This button is:

red if there are error messages in the Event Viewer,
gray if there are no error messages in the Event Viewer,
This indicates that the system is in stand by mode for initial operating
Table 2-4: Indicators
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.
Figure 2-9: Event Viewer
The data included in the Event Viewer are described in Table 2-5.
Table 2-5: Event Viewer Data
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.
The information displayed in the Event Viewer is contained in a database which

can be edited by a user having the proper authorization.
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.
2.5.2 The Main Operator and Spectra Mode Windows

When the initialization process is complete, if you are logged-in in Operator
mode, you may:
Continue to the Main Operator Mode (not presently operative) window by
clicking NEXT>> (in this window, you may only choose a batch to run
automatically),
Return to the previous window by clicking <<BACK, or
Exit the nEXt software by clicking Cancel.
If you have logged-in in Superuser mode, the Cancel button is replaced by a

Superuser button. In this case, you may click the Superuser button to enter the
main Spectra mode window (see Figure 2-10).
Figure 2-10: Main Spectra Mode Window
The various parts of the Spectra Mode window are shown in Figure 2-11 and are
described in the following sub-sections.
Figure 2-11: Main spectrum window with spectrum

2.5.2.1 Spectra Mode Button Bar

The Main Spectra Mode window (Figure 2-10) contains a Spectra screen. A
spectrum will be displayed in this screen when it is acquired or if a spectra file is
opened by clicking the Open Spectrum button (refer to Table 2-6) and selecting
the file in the Open Spectra box (Figure 2-12) which appears.
Figure 2-12: Open Spectra Box
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.
Figure 2-13: Spectra Mode Button Bar

Table 2-6: Spectra Mode Button Controls
Button Description Hot Key

Batch. Click this button to select a batch file from the data base. A batch Ctrl + O
is a collection of instructions specifying where samples are located on
the auto-sampler and allowing automatic spectra acquisition and
subsequent analysis of the acquisition results.
Construct a New Procedure (wizard). A procedure contains parameters
for collecting data (acquisition method) and a set of instructions for
converting the resulting data into a concentration result.
Open an existing Procedure. Open a procedure in the data base for P
modification.
Start Acquisition of a spectrum. F5
Stop spectrum acquisition. F8
X-Ray Controller Status. F6
Set Acquisition Parameters. Displays the Acquisition Parameters box for A

setting or changing these parameters (refer to Chapter 3 for details).
Save Spectrum. Save the currently displayed spectrum.
Open Spectrum. Open a spectrum in the data base.
Analyze Spectrum using procedure currently in memory. C
Toggle spectrum scale between normal and bipolar.
Expand spectrum. Ctrl + F1
Compress spectrum. Ctrl + F2
Scale spectrum up. Ctrl + F3
Scale spectrum down. Ctrl + F4
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
Identify peaks. Automatically identify elements associated with the

spectrum peaks.
Show Multi-Channel Analyzer status (see Figure 2-14). The information
box displayed is moveable within the window.
Show Spectra acquisition parameters. The information box displayed is
moveable within the window.
Show Region Of Interest status. The information box displayed is

moveable within the window.
Print Spectrum. Ctrl + P
You may open a spectrum as “overlap” (refer to Chapter 4 for a discussion of

overlaps).
TIP
This feature s usefull for analysis by comparing corresponding spectra
for different samples.
The following subsections describe the main screen elements:
2.5.2.2 The Title Bar

The title bar Contains the window icon for the software, the program title of the
application and the control menu buttons for maximizing or minimizing the
screen or for closing the application.
2.5.2.3 Menu Bar

The Menu bar contains pull down menus for utilizing different aspects of the
software. All of the software included functions can be accessed from the menu
bar. Most of them can also be accessed from the Spectra mode button bar.
Figure 2-14: MCA, STR and ROI Status
2.5.2.4 Regions of Interest (ROI) Definition Bar

The Regions of Interest (ROI) Definition bar can be used to define various
regions of the spectra for further mathematical manipulation. Regions of interest
are primarily used to effect background correction, internal standards, and
inter-element corrections.
See Chapter 4 for more details.
2.5.2.5 Program Status Bar

The Program Status bar displays information of the operation currently selected.
2.6 Printing a File

2.6.1 Print Setup
You may format a print-out by choosing Print Setup… from the Edit pull-down
menu in the Main Superuser window.
Chapter 3 Data Acquisition
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.
3.1 Acquisition Parameters

The acquisition parameters determine the conditions under which spectral data
will be acquired.
Since spectra acquisition is central to both qualitative and quantitative analysis,
special attention should be give to the following points when setting up
acquisition parameters:
• Nature of the analysis: qualitative or quantitative;
• The level of precision required for the analysis;
• The desired time for the analysis (how quickly are results desired);
• The spread of elements of interest by atomic mass number.
For example, if the spread is large, it may be necessary to break the
analytical procedure into two or more groupings so elements requiring
similar excitation parameters are run together.
• The physical nature of the sample. For example:
Will it be affected if it is run in a vacuum?
Does the sample degas?
Is particle size important?
Does the sample have a crystalline form that could produce
diffraction peaks?
Spectra acquisition can be accomplished either manually or as part of an
automated routine called a Batch. In either case, the necessary parameters for
spectra acquisition are found in the Acquisition Parameters box, shown in Figure
3-1. It is accessed from the Parameters pull-down menu or by clicking the

button, or by pressing the “B” key on the keyboard
Table 3-1 contains a description of these parameters.

Figure 3-1: Acquisition Parameters Screen

All values entered become effective on the next acquisition activation.
Table 3-1: Acquisition Parameters
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.
After approximately 30 seconds, click the Stop acquisition button.

Check the Dead time value displayed in the MCA Stat box.
If the value is less than 35%, increase the Emission Current in the Acquisition
parameters box and repeat the acquisition process.
If the value is more than 45, decrease the Emission Current in the Acquisition
parameters box and repeat the acquisition process.
High Voltage, kV Sets the high voltage to the X-ray tube. This value effectively regulates the X-
ray tube output spectral distribution.
This parameter should be set to approximately 30% higher than the maximum
fluorescence peak energy of the element to be measured.
Atmosphere You can choose between Air, Vacuum or Helium.
Energy Range This parameter sets the energy range of the spectrum's acquisition. There are
two ranges: 0-10 keV and 0-40 keV.
Use the smallest energy range that includes the peak to be measured.
Note: Do not confuse the Energy Range (units keV) with the High Voltage units
kV).
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. With SDD detector the high
throughput can be used for any application without loss of resolution.
Note: Statistic precision improves in inverse proportion to the square root of
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.
3.2 Batch Run Process

3.2.1 Logging On to Operator Mode
To select a Batch to run in Operator Mode, you must start from the main X-2600
Log-In window
(Figure 3-2).
Figure 3-2: X-2600 Log-In Window
Perform the following steps to begin the run process:

(7) Enter the following information:
User Name: (obligatory)
Password: (1)
(8) Click NEXT>> when you have entered the above information.
(9) Click NEXT>> again when the initialization process is complete (see Figure
3-3). Refer to Chapter 2 for more details on the operations associated
with this window.
(10) You will be given the Batch Selection screen (Figure 3-).
(11) The Operator can select which (predefined) Batch to run.
(12) The Operator can assign name to sample.
Figure 3-3: Initialization Status window
Figure 3-4: Batch Selection window in Operator Mode
3.2.2 Selecting and Running a Batch in Superuser Mode

To run a Batch in Superuser mode: Select Batch button on button bar or select
Open Batch from
Edit Manu and get the screen shown in Figure 3-5
Figure 3-5: Batch Selection Screen in Superuser Mode
The entries in the Batch Selection screen are described in Table 3-2.
Table 3-2: Batch Selection Results
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..
(13) Select a Batch to run from the Batch pull-down field.

(14) Click the RUN button to run the selected Batch.

(15) A message similar to the one shown in Figure 3-6 will be displayed.
Figure 3-6: Batch Running Message
3.2.3 Batch Results Display

When the run is complete, the Results screen shown in Figure 3-7 will be
displayed.
Figure 3-7: Batch Run Results Screen
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.
Table 3-3: Batch Run Results
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.
Table 3-4: Results Screen Control Buttons
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.
The locations of the statistical parameters will be indicated by colored vertical

lines:
Mode – blue
Median – green
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.
3.2.4 Results Table Format

Clicking the Format button in the Batch Run Results screen (Table 3-4) displays the Report
Format box shown in Figure 3-8.
Figure 3-8: Report Format

The effects of each of the format choices are described in Table 3-5.
Table 3-5: Report Formats
Field Description
Short Report
The Counts and Intensity entries in Figure 3- are not displayed.

Long Report Formats the report as shown in Figure 3-.
One-Line Report -
Concentration
If Show Errors in Report is checked, error bound will be added to the results as
shown below:
Field Description
This applies to all the Results screen formats.

One-Line Report –
Gross Counts
.
One-Line Report –
Net Intensities
3.3 File Structure

3.3.1 The X-2600 Series Database
All data and parameter files for X-2600 series systems are stored in Microsoft
Access™ format database (see Figure 3-99).
Figure 3-9: Typical X-2600 Database
The database is composed of a number of tables containing parameter and

measurement data. A typical table within the database is shown in Figure
3-1010.
Figure 3-10: Typical Parameter Table
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.
3.3.2 Database Manipulation
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.
Figure 3-11: Data Base Tools Pull-Down Menu
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.
Table 3-6: Data Base Tools
Operation Description
Data Base Select this option to modify or export part of a database. The following screen will be
Utilities displayed:
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.
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).
Change Data Select the database to be used.

Base You will be given a standard Windows Open box from which to select a database. You
may have to navigate to the directory containing your database files (with a .mdb
extension).
Import Old Import procedures created with previous software versions.
Procedures You will be presented with an Import Old Procedures dialog box:
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
Import The standard Open dialog box will be displayed.
ExWin.ini Navigate to the file you want to import and click Open.
Parameters
New Data Save as a new database.

Base You will be given a standard Windows Save As... box. Enter a name and click the Save
button. Your file will be saved as a new Access format database (with a .mdb extension).
3.3.3 Spectra Files

Spectra files acquired with the X-2600 series systems are saved with file names of
the form * .str. You may also open spectra files of the form *.spc. The extension .spc
indicates spectra acquired with previous software (ExWin) versions.
Chapter 4 Qualitative Spectral Analysis
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.
4.2 Guidelines for Acquisition Parameter

Selection
See Chapter 3 for an introduction to spectra Acquisition Parameters.
Since the purpose of qualitative analysis is to identify the components in a
sample, acquisition parameters should be selected to optimize the identification
procedure. This is done by maximizing the spectral range covered by the
excitation-detection system, as well as by obtaining sufficient sensitivity to
identify even trace amounts of the elements present in a sample. This is
accomplished by optimizing the X-ray levels. Dead time in % in the acquisition
sequence is a good indication of this optimized level. Voltage (kV) and current
(µA) settings, combined, should allow maximum productivity.
Filters, spectral display ranges (10keV and 40keV) and the high and low
throughput ranges are also useful in optimizing spectra.
The following are guidelines to help achieve good qualitative analysis.
1. Set the µA setting to achieve satisfactory dead time values for maximum
productivity for your system or by selecting Dead time optimization from the
Tools pull-down menu.
2. You will be given the Dead time optimization box (see Figure 4-1).
Enter the desired Dead Time range and click OK. A recommended range is
from 35% to 40%.
Figure 4-1: Dead Time Optimization Box
3. Once the elements of the sample have been identified it is possible to

work within two energy regions, such as 10keV range or 40keV range.
4.3 Acquiring Spectra

Once you have set the Acquisition Parameters, you may manually acquire
spectra by performing the following steps:
(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.
4.4 Editing and Manipulating Spectra

4.4.1 Identifying Peaks
After spectra have been acquired, automatic identification of peaks can be
performed. The identification is reliable provided the system is properly energy
calibrated and the peaks are significantly higher than the background and not
severely overlapped by other peaks. The identification will improve as more
counts accumulate in the peaks.
To automatically identify the peaks, From the Spectra pull-down menu, select
Peak Identification (see Figure 4-2).
Figure 4-2: Spectra Pull-Down Menu
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.
Figure 4-3: Peaks Identification
Table 4-1: Peak Identification Parameters
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).
4.4.2 Zooming Regions of Spectra

You may place a vertical cursor line on a spectrum by placing the mouse cursor
on the point of interest and clicking the right-mouse button. The cursor line will
appear. Pointing and clicking at a new location will move the cursor.
To zoom in on certain areas of the spectrum use the Expand, Compress, Up or
Down, buttons as indicated in Table 4-2 and Figure 4-4.
Table 4-2: X-2600 Zoom Button Controls

Expand spectrum about the cursor position. Ctrl + F1
Compress spectrum about the cursor position. Ctrl + F2
Scale spectrum up in the active window. Ctrl + F3
Scale spectrum down in the active window. Ctrl + F4
Autoscale (in both the vertical and horizontal directions) F9
Figure 4-4: Scaling
4.4.3 Regions of Interest (ROI)

The Regions of Interest (ROI) Definition bar can be used to define various
regions of the spectra for further mathematical manipulation. Regions of interest
are primarily used to effect background correction, internal standards, and
inter-element corrections.
The lower and upper limits of the energy range in keV of the spectrum are
shown at the left and right ends of the bar. At the center of the bar, the Vertical
Full Scale (VFS) is displayed.
To create a Region of Interest, perform the following steps (see Figure 4-5):
(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.
Figure 4-5: Region Of Interest (ROI)
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.
Figure 4-6: Pop-Up Menu - ROI
You will be given the options described in Table 4-3.
Table 4-3: ROI Options
Option Description
Set low limit Set lower limit (in eV) of ROI.
Option Description
In the dialog box, enter the lower limit of the ROI and click OK.
Set high limit Set upper limit (in eV) of ROI.

In the dialog box, enter the upper 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.
You may Save or Print the table.

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.
Option Description
Click an element in the table to return to the previous dialog box.

The spectral line locations can then be used to set the upper and lower
limits of the ROI as described above.
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.
Figure 4-7: Spectra Pull-Down Menu - ROI
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.
4.4.4 KLM Markers

4.4.4.1 The KLM Button Bar
KLM Markers indicate the positions of K, L, and or M peaks provided by the
computer for various elements. Unknown peaks can be matched against these
markers.
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.
KLM markers may be set or removed via the KLM toolbar.

To display the KLM toolbar, select KLM toolbox from the View pull-down menu.
A third row of buttons will be displayed in the Spectra window Button Bar
(Figure 4-8).
Figure 4-8: KLM Toolbar
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.
Display a table of KLM spectral lines selected. (Not presently operational.)

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.
4.4.4.2 Setting KLM Markers

Selecting this function displays the Table of Elements (see Figure 4-9). Point at
and click the desired element in the table. The KLM marker (which appears at
the energy position for the selected element) will be superimposed on the
spectrum (see Figure 4-10). Placing the cursor on the KLM marker line causes the
X-ray lines for the selected element to be displayed (for example, Ka1 and Ka2
for Si in Figure 4-10).
Figure 4-9: Table of Elements
Figure 4-10: KLM Markers
Repeat the process to display as many KLM markers as you want.

When the KLM markers for several elements appear to be at the same position,
you may differentiate between them using the following procedure:
1. Expand the spectra about the KLM position.
2. Click the MCA Status button.
3. Click on the marker.
4. The exact location in eV of each marker will be seen in the first line
(Position) of the MCA Status box (see Figure 4-11).
Figure 4-11: KLM Marker Positions
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).
Figure 4-12: KLM Table
4.4.5 Matching Spectra

4.4.5.1 Build Pure Element Spectrum
This function displays a theoretical elemental spectrum for elements in the
periodic table. Such a spectrum can be used for reference for positive
identification of components using the Overlap function (see Section 4.4.5.2).
This function can also be selected from the Spectra pull-down menu.
To Build a Pure Element Spectrum (in one of the Spectra windows), perform the
following steps:
(19) Click the right mouse button in one of the Spectra windows.
You will be given the Select Element box (see Figure 4-13).
(20) Choose an element:
Select an element from the Element scroll box
or
Click the Element button and select an element from the Table of
Elements which appears.
Figure 4-13: Select Element Box
(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.
Figure 4-14: Gauss Parameters Box
Table 4-5: Gauss Parameters
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
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
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.
* Ref.: Jenkins, Gould, and Gedcke, Quantitative X-Ray Spectrometry, Marcel Dekker, 1981
(23) Click OK to display the pure element spectrum or Cancel to abort.

(24) The Pure Element spectrum will be displayed as an overlap to the main
spectrum in the chosen Spectrum window (Figure 4-15).
Figure 4-15: Pure Element Spectrum Overlap
4.4.5.2 Overlapping Spectra

Quick comparative analysis of spectra, such as with unknown samples against
standards of known composition, can be carried out for element identification. A
routine of overlapping spectra can be applied in quality control procedures to
ensure that intermediate and final products meet specification.
To access the Overlap commands, click the right mouse button in the spectrum
area to display the pop-up menu (see Figure 4-16). These commands are
described in Table 4-6.
The secondary menus shown in Figure 4-16 list the overlap spectra currently
chosen and may be different from those shown.
Figure 4-16: Overlap Commands

Table 4-6: Overlap Commands
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.
Figure 4-17: Main to Overlap
4.4.5.3 Mathematically Modifying Spectra

Further comparative analysis can be performed by mathematically modifying
one spectrum with respect to another, leaving the resultant spectra to show a
difference between the two samples. In addition to adding and subtracting
spectra, certain spectral features can be enhanced by multiplying the spectrum
by a constant value or by adding a constant value to the spectrum. The resulting
spectrum is displayed in a Main Spectrum window.
To multiply one of the spectra by a constant or to add a constant to a spectrum:

(1) In the Spectra pull-down menu (Figure 4-18), select Analytic tools.
(2) To multiply a spectrum by a constant, select Multiply by constant from
the sub-menu that appears.
In the Multiply constant box that appears enter the multiplication factor
and click OK.
(3) To add a constant to a spectrum, select Add constant from the sub-menu.
In the Add constant box that appears enter the constant and click OK.
Figure 4-18: Spectra Pull-Down Menu
To multiply a spectrum by a constant or add a constant to all four spectra:

(4) Select either Multiply spectra by constant or Add constant to spectra
from the Spectra pull-down menu.
(5) Enter the number to be added or multiplied by in the box that appears
and click OK.
4.5 Analyzing Spectra - Summary

This section summarizes the use of several of the spectra analysis utilities.
(1) Display a spectrum, either previously saved or newly acquired.
(2) Click one of the Scale buttons in the button bar to zoom in on certain
portions of the spectrum:
Click Expand, to expand the spectrum about the present (blue

cursor line position.
Click Compress, to compress the spectrum about the present
cursor position.
Click Scale Up, to scale the spectrum up.
Click Scale Down, to scale the spectrum down.
(3) Click the Identify Peaks button to display a table including

possible peak identifications.
(4) Display KLM markers (useful for positive peak identification):
• Select KLM Toolbar from the View pull-down menu.
• Click the Add KLM button.

• In the Periodic Table, click an element
The KLM lines for this element will be superimposed on the
spectra.
(5) Select Region of Interest (ROI) (useful for defining portions of spectra for
further analysis):
• Maximize one of the spectra by clicking in its title bar.

• In the Region of Interest bar at the bottom of the screen, use the
left mouse button to sweep across the region of interest.
• Release the mouse button.
The Region of Interest within the spectrum will be indicated by a
different color.
• Erase part or all of the Region of Interest by using the right mouse
button to sweep across the region of interest.
(6) Select an Overlap (useful for comparing spectra):
• Click the STR (Open Spectra) button.

• In the Open dialog box, check As overlap, select a spectrum file,
and click Open.
The overlap spectrum will appear as a curve.
(7) MCA Status:
• Click the MCA Status button in the button bar.

• An MCA Stat information box will appear in the upper right corner
of the spectrum screen.
• Click the left mouse button at a point in the screen.
The cursor (blue vertical line) will move to that position.
• The Position entry in the information box gives the location of the
cursor in keV.
The Counts entry gives the number of counts at that position.
4.6 Spectra Mode Pull-Down Menus

This section contains a summary of the pull-down menus available in the Spectra
window.
4.6.1 Edit Menu

Table 4-7: Edit Pull-Down Menu Entries
Entry Description Hot Key

Open Recipe Open a recipe saved in the database. Ctrl O
New Procedure Invoke a wizard to create a new procedure. P
Open Procedure Open a procedure saved in the database.
Save Spectrua Save the current spectra to disk. You will be given the standard Ctrl S
Save… box from which to choose the save location.
Open text file This entry displays the standard Windows Open dialog box for .txt
files from which to open a text file previously saved from within
the nEXt software. This obviates the need to use external
programs such as Word or Access.
Select a file to display its conternts.
Click Close to close the display.

Click Save to save the file.
Click Print to print the file.
Click Graph to build a graph from the data.
You will be given the Build graph box from which to select the
vertical and horizontal axes.
Click Build to display the graph.
Show Batch Display latest batch run results.

results
Show Analyze Display latest results obtained by clicking the Analyze button.
results
Operator Mode Enter Operator Run mode.
Change working Select default directory.
directory
Print… Print the currently displayed spectra. Ctrl P
Print Preview Preview how a spectral print-out will look (not yet operational).
Print Setup… Format a hard copy page.
Recent File Display a list of recently opened spectra files (not yet operational).
Exit Exit the nEXt program. Alt X
4.6.2 View Menu

Table 4-8: View Pull-Down Menu Entries

Toolbar If checked, the toolbar (button bar) will be displayed.
Status Bar If checked, the Status Bar at the bottom of the Superuser window
will be displayed.
KLM toolbar If this entry is checked, the KLM toolbar will be displayed.
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.
4.6.3 Spectra Menu

Most of the entries in the Spectra pull-down menu are the same as those
appearing in the pop-up menu. The only difference is that selections chosen
from the pop-up menu operate only on spectrum in which the menu is invoked
by clicking the right mouse button, while selections chosen from the pull-down
menu operate on all four spectra.
Table 4-9: Spectra Pull-Down Menu Entries
Entry Secondary Description Hot Key

Entry
Open Spectra List and set Acquisition parameters.
Save Spectra Save current spectra to disk. You will be given a

standard Save as.. box to select a destination
and file name.
Peak Display a table listing the pertinent data and I
Identification possible identification of each peak in the
spectrum.
Bipolar Mode Display all spectra in bipolar mode.
Erase Spectra Erase all spectra. F7
Analyze Apply current procedure to analyze spectra.
Multi Spectra Apply current procedure to analyze a sequence

Analyze of spectra. You will be given the standard Open
file box to choose which spectra to analyze.
Analytic tool
Digital Filter Apply a digital filter to all spectra. You will be D

prompted to enter the filter width.

Entry
Remove Escape Subtract the detector escape peak from all K

Peak spectra and display the resultant spectra as
overlaps.
Gross Display spectra with background counts
included.
Net Display spectra with background counts
excluded.
Build Pure Construct the characteristic spectrum of a
Element chosen element.
Build tube Construct the characteristic spectrum of the X-

spectra ray tube.
Select the tube number, filter number and
enter the tube voltage.
Multiply spectra Multiply all spectral values in all spectra by a

by constant constant.
Add constant to Add a constant to all spectral values in all

spectra spectra.
Logarithm Displays logarithm of spectra as overlaps.


Entry
Real time peak Continuously displays peak identification data

identification during acquisition.
Spectra Transform spectra. Not yet operational.

transformation
Region of
Interest (ROI)
Report Display an ROI report.
Remove all ROI Remove all ROI settings. ROI regions will revert
to the original spectrum color.
Save ROI Save ROI to disk.
Retrieve ROI Retrieve ROI from disk.
Set element ROI Set the ROI for a particular element.
Overlaps
Remove all Remove all overlap displays from spectra. F10

overlaps
Set main as Change main spectrum to overlap.

overlap
Swap Interchange main and overlay spectra. S
Scale
Scale Up Scale all spectra up. Ctrl F1
Scale Down Scale all spectra down Ctrl F2
Expand Expand all spectra about the cursor location. Ctrl F3
Compress Compress all spectra about the cursor location. Ctrl F4`
Autoscale Automatically maximizes the spectrum in both F9

the vertical and horizontal directions while

Entry
maintaining the aspect ratio of the spectrum.

Status
Controller Status Display X-ray controller status parameters. F6
MCA Status Display MCA Status parameters. Shift F6

The first two entries give the cursor position
and the number of counts at that position.
Spectrum Status Display Spectrum Status parameters. Alt F6
ROI Status Display ROI Status parameters. Ctrl F6
Erase all Erase all notes appearing on the spectra. Ctrl E

messages
4.6.4 Parameters Menu

Table 4-10: Parameters Pull-Down Menu Entries

Acquisition List and set Acquisition parameters. A
Parameters
4.6.5 Setup Menu

Table 4-11: Setup Pull-Down Menu Entries

Setup Table Display a tab window for setting system software parameters. Alt S
Refer to Chapter 10, Software Calibration, for more details.
Setup ADC Display a table for setting the parameters for the ADC (Analog to
Digital Converter). Refer to Chapter 9 , Software Calibration, for
more details.
4.6.6 Tools Menu

Table 4-12: Tools Pull-Down Menu Entries

X-Ray On/Off Turn X-rays on (off).
Vacuum On Not applicable to X-Calibur series systems.
Helioum On Not applicable to X-Calibur series systems.
Dead time Sets the µA setting to achieve satisfactory dead time values for
optimization maximum productivity for your system.
Auto Acq Batch Select a batch to run or modify.

You will be given the Auto acquisition batch dialog box from which
to select a batch.
You may Run the batch, Save the batch, Remove a selected row,
Insert a row (Acquisition Parameters), or Clear the entire contents.
When you are done, you may click OK (you will be prompted as to
whether or not to save the batch) or Cancel to close the box
without saving.
Reset Motors… Re-initialize all axis motors (X, Y, Z, θ).

Move stations / For Xenemetrix use only.
filters
Gain DAC For Xenemetrix use only.
optimization
Run Warmup Run a default batch to warm up the X-ray tube.
Batch This should be done if the system has not been used for 24 hours
and a high excitation voltage is to be used.
If the system has not been used for 24 hours, you will be prompted
to run the Warmup batch.
CPS vs. current For Xenemetrix use only.
test
4.6.7 Data Base Tools Menu

Refer to Chapter 2, Table 2-8 for more details.
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
New Data Save as a new data base.

Base
4.6.8 Help Menu

Table 4-14: Help Pull-Down Menu Entries
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.
5.2 Sample Presentation Requirements and

Reference Materials
Analysis of solid samples in solid, particulate and liquid forms is possible with
XRF. In general, some sample preparation may be required, depending upon the
level of results accuracy required. For example, the extent of sample preparation
required depends on sample homogeneity and the regularity of the sample
surface.
In the case of metals, a highly polished metal surface is sufficient. In the case of
geological materials, where there is a great deal of mineralization and sample
homogeneity is low, there will be a need for sample preparation. In the latter
case, milling is required to reduce sample particle size and/or facilitate blending.
In some instances, the sample matrix may even have to be destroyed by
dissolving it in a fusion bead. The resulting solid solution is then extremely
homogeneous and elements present are converted to an oxide form.
The penetration power of the exciting radiation and the energy of the fluoresced
X-ray photons will determine the amount of radiation reaching the detector. If
the element of interest is a light element (low-Z) in a matrix with a significant
proportion of heavier elements (higher-Z), then a significant proportion of the
X-radiation produced by the lighter elements will be absorbed by the heavier
elements in the sample. The further the X-ray photon of the low-Z analyte has to
travel through the sample before escaping from the surface, the more likely it is
to be absorbed. Thus, most of the radiation from low-Z elements comes from the
upper few microns of the sample, meaning surface finish is critical.
The following diagram summarizes alternatives available for sample presentation:
Figure 5-1: Summary of Sample Preparation Choices
The objective of XRF sample preparation is to produce a homogeneous,

sufficiently thick sample with particle size small enough to render side effects
that occur during the radiation process insignificant.
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.
5.3.1 Spectra Acquisition Parameters

5.3.1.1 Acquisition Parameters
The acquisition parameters determine the conditions under which spectral data
will be acquired. These parameters are shown in Figure 5-2. Error! Reference
source not found. describes these parameters.
Figure 5-2: Acquisition Parameters

Table 5-1: Acquisition Parameters
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.
5.3.1.2 Determination of Acquisition Parameters

Acquisition parameters must be optimized to give the best compromise in terms
of the elements to be analyzed. Generally, parameters for light element analysis
(Low-Z elements) are not appropriate for heavier element 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 Analysis Methods

The following analysis methods are available for qualitative analysis:
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.
Ki = An instrument constant equivalent to the reciprocal sensitivity of the

instrument for this particular analyte.
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
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
attention to the point that if net intensity method selected in the

Elements of interest page by selecting either Net, Fit or Digital Filter, the
background is removed. Therefore, the A0 term should be very close to
zero.
5. System Energy Calibration: Precise energy calibration (“Peak Position
Goodness”) is of vital importance. It can generally be said that it is
more critical if Net or Gross is used to estimate intensities of the
peaks.
5.3.2.3 SLFP (Standardless Fundamental Parameters)

The Standardless Fundamental Parameters analysis method (SLFP), as
developed by Xenemetrix, involves the theoretical spectral modeling of the
exciting X-ray beam and its subsequent use in the iterative calculation of
concentrations. This method allows one to obtain concentrations with
reasonable accuracy (semi-quantitative analysis) without preparation of any
standards and without doing a preliminary calibration. The program is intended
to deal with all kinds of exciting beams (direct, with or without filters) and is
applicable to all Xenemetrix X-Series instrumentation.
Ratios of the X-ray intensities of various elements in a given sample are
calculated.
The software consists of two modules, SLFPA and SLFPL, corresponding
respectively to the standardless analyses of metals in alloys/oxides/geological
samples and in homogeneous light matrices. This latter case is optimized for
aqueous and organic solutions (as well as plastics). The SLFPL is currently not
operational.
In the case of alloys or oxide-mixtures, when the characteristic lines of all the
main components can be seen, efficiencies of excitation and detection for each
line of interest are calculated, followed by estimates of concentrations.
Absorption and self-excitation in a sample are then calculated and the software
introduces these as corrections for the second iteration, etc.
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
(according to intensities of their lines). Corrections in absorption and self-

excitation due to these elements are then made, and the calculation continues in
an iterative fashion.
When the Standardless algorithm is utilized for alloy analysis, any set of
acquisition conditions is acceptable (as long as all the major components are
observed). However, for the analysis of trace elements in light (low average Z)
matrices, special attention must be paid to the acquisition parameters used.
Specifically, "supported" instrument configurations must be maintained so that
the standardless module will have the necessary coherent/incoherent
(Rayleigh/Compton) scatter information available.
The conditions are summarized in Table 5-2.
Table 5-2: Light Matrix SLFP Acquisition Requirements
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.
5.3.2.5 Multi Acquisition (MultiAcq)

Multi Acquisition is actually a combination of the previous regression methods,
but is applied from 2 to up to 8 different spectra of the same standard, acquired
under different conditions into one set regression equations.
In order to use this analysis method, prepare from 2 to 8 Regression procedures
based on the same set of standards, each of them measured from 2 to 8 times,
under different conditions (excitation, energy scale, throughput, etc). In these
single acquisition procedures, all the normal procedure variables (acquisition
parameters, elements, lines, intensity methods, concentrations for each
standard, counts normalization, methods, name of the procedure) should be

specified. The type of regression equation chosen for these single acquisition
procedures is not important for the final Multi Acquisition Regression procedure.
Note that spectra names defined in Multi Acquisitions are later automatically
assigned suffixes to identify them with the step number previously specified.
These suffixes are “#1”, “#2”, etc.
5.3.2.6 Sort (Find Best Match)

The Sort method compares the spectrum acquired from the unknown sample to
a list of spectra of well-characterized standards with known concentrations. Both
the samples and the standards should be acquired under the same conditions.
The concentration of the element in the unknown sample is calculated as
follows:
4. The standard most similar to the analyzed sample is automatically found.
5. The concentrations of the elements in the sample are calculated as the
ratio between the intensity of the peaks in the sample and the
corresponding peaks in the best-match standard.
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.
5.3.2.7 Determination of Regression Models, Normalization

Techniques, Background Removal Methods
Each element in a sample may contribute to the overall spectrum measured by
influencing the amount of radiation coming from another element. This
influence may be in the form of heavier elements absorbing X-radiation from
lighter elements, thus reducing the number of X-ray photons coming from the
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.
Interference phenomena in X-ray fluorescence analysis include contributions to

the analyte peak intensity which do not come from the sample or are present by
virtue of processes other than X-ray fluorescence (as induced by the primary
excitation methods). The reduction of composite spectra to net peaks of analytes
involves compensating for this interference. This usually involves removing
spectra of line overlaps and background contributions.
Line overlaps can be overcome by using Fit. Separate peaks are identified by
comparing the acquired peak with theoretical, pure element, peaks. The system
then calculates the contribution from the element-of-interest on its own. The
contribution to the gross intensity from the overlapping peak is then removed.
Another source of errors is the absorption and enhancement of analyte
intensities by other elements present in the sample.
Effective methods for compensating for these effects are:
1. Dividing the net intensity by the background intensity.
2. Calculating the primary and secondary Mass Absorption Coefficient from
the Major Element Concentrations of the samples to be measured
(Fundamental Parameter).
5.4 Procedure Setup – The Procedure Wizard

5.4.1 Beginning the Procedure Setup Process
Setting up a Procedure is performed using the Procedure Wizard. To start the
Procedure Wizard, click the New Procedure button in the Spectra window (refer
to Chapter 2, Table 2-6: X-2600 Spectra Mode Button Controls) or type P.
The Main Procedure Wizard screen shown in Figure 5-4 (shown for the “None”
analysis method) will be displayed.
The data fields in the Main Procedure Wizard screen will vary according to the
analysis method chosen. These fields will be described in the sequel for each of
the analysis methods.
The control buttons are the same for all the Procedure Wizard screens, and are
described in Table 5-3. Some of these buttons may not be operable (dimmed) in
certain of the screens.
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.
Figure 5-3: Main Procedure Wizard Screen
Table 5-3: Main Procedure Wizard Window Control Buttons
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.
5.4.2 Analysis Method – None

Choosing None for the Analysis Method causes the main Procedure wizard
screen to change to that shown in Figure 5-4.
Figure 5-4: Main Procedure Screen (Analysis Method = None)
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.
5.4.3 Analysis Method – Regression

If you have chosen Regression for your analysis method, the Main Procedure
screen will change to that shown in Figure 5-5.
In the screen shown here, the parameter Use Global Background has been
checked. If this parameter is not checked, the Show button and the Background
File and Background ROI fields will not appear.
In addition, the parameter Count Normalization has been set to To Background
ROI. Without this choice, the from and to fields and the Set button will not
appear.
Figure 5-5: Main Procedure screen - Regression
The parameter entries in this screen are described in Table 5-5.

Table 5-5: Main Procedure Wisard Window Entries - Regression
Field Description
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).
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.
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.
The data fields appearing in the table are described in Table 5-6.
Figure 5-6: Elements of Interest Screen – Regression
Table 5-6: Elements of Interest Parameters
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.
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
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.
Figure 5-7: Standards Screen
The parameters appearing in this screen are described in Table 5-7.
Table 5-7: Standards Parameters
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
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 calculatedit 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).
Figure 5-8: Calculate Coefficients Screen

The Calculate Coefficients screen contains a table of the coefficients appearing
in the regression model you have chosen. There will be a row for each of the
standard elements you selected.
You may enter the value for any of the coefficients you may have knowledge of.
The system will use these values to calculate the other coefficients.
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.
Figure 5-9: Reports Screen

Table 5-8: Reports Controls
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.
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 <Back will return you to the previous (Calculate Coefficients)

screen.
Clicking Next> will display the Gaussian Fit Optimizer screen described
in Section 0.
Details of the various reports are given in the following paragraphs.

Coefficients Report
A typical Coefficient Report is shown in Figure 5-10. The various fields are
The report includes the regression coefficients and indices, the given and
calculated concentration of each standard, and the absolute and relative
difference between the given and calculated concentrations.
The number of coefficients shown depends on the model equation you chose
previously.
You may print the report by clicking the Print button.
Save the report by clicking the Save button. You will be given the Save As box
(Figure 5-11).
Figure 5-10: Coefficient Report
Table 5-9: Coefficient Report Fields
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.
Figure 5-11: Save As

MDL Report
A typical MDL report is shown in Figure 5-12.
Figure 5-12: MDL Report

The MDL for the elements being measured is listed for each standard used.
Regression Report
A typical Regression Report for a given standard element is shown in Figure
5-13. The various fields are described in Table 5-10.
Figure 5-13: Regression Report

Table 5-10: Regression Report Fields
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 print the report by clicking the Print button.

Save the report by clicking the Save button. You will be given the Save As box
(Figure 5-11).
Regression Line Graph
The horizontal axis represents the apparent intensity of the analyzed element's
peak; the vertical axis represents the concentration. The data points indicated
along the line are the various standards (identified by their line number in the
standards table) relative to the calculated model. The best "fit" of the standards
versus the model is when the data points lie on or very close to the model line.
Figure 5-14: Regression Line
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.
Figure 5-15: Set Range

Correlation Line Graph
The horizontal coordinate represents the specified concentration of the standard
as input in the standards concentration table; the vertical coordinate represents
the calculated concentration as calculated by the regression model.
Figure 5-16: Correlation Line
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.
Figure 5-17: Deviation Line

button.
When you are finished selecting the Report parameters, click Next> to continue
to the Criterion screen (Figure 5-18).
Figure 5-18: Criterion Screen
The entries in this screen are described in

Table 5-11.
Table 5-11: Criterion Parameters
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.
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.
5.4.4 Analysis Method – SLFP

If you select SLFP for the analysis method in the Main Procedure screen, the
Figure 5-19: Main Procedure Screen - SLFP
The entries in this screen are described in Table 5-12.
Table 5-12: Main Procedure Wisard Window Entries - SLFP
Field Description
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:
Field Description
Alloy / Oxide / Geologic
Low Z Matrices & Solutions (not operational)
Support type Select type of sample support from the pull-down list.
the Acquisition Parameters screen (Figure 5-2). The parameters appearing in the
Acquisition Parameters screen are described in Error! Reference source not
ound..
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
screen.
in Section 5.5.
5.4.5 Analysis Method – AccurEx

If you select AccurEX for the analysis method in the Main Procedure screen, the
Figure 5-20: Main Procedure Screen - AccurEX
The entries in this screen are the same as those for the SLFP method.
the Acquisition Parameters screen (Figure 5-2). The parameters appearing in the
Acquisition Parameters screen are described in
Table 3-1.
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.
You have now completed the Procedure setup process.
i NOTE
If you have chosen “Fit” or “Only Fit” for the Intensity Method

screen.
in Section 0.
5.4.6 Analysis Method – MultiAcq

If you select MultiAcq for the analysis method in the Main Procedure screen, the
The entries in this screen are the same as those for the Regression Analysis
Method (see Table 5-5), with the following additions:
Next to the MultiAcq selection field, there is a field for selecting the number of
Steps (Procedures) to be used in the analysis. There may be from 2 to 8 steps.
If you have checked Use Global Background, background data will be requested
for each of the Steps (Procedures). You must choose a Background File and ROI
for each of these Steps.
Figure 5-21: Main Procedure Screen - MultiAcq
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.
Figure 5-22: Acquisition Parameters – MultiAcq
5.4.7 Analysis Method – Sort

Selecting Sort for the Analysis Method in the Main Procedure screen causes the
screen to change to that shown in Figure 5-23.
The screens appearing in the Procedure creation sequence for the Sort method
are:
• Acquisition Parameters
• Elements of Interest
• Standards
• Criterion
These screens are the same as for the Regression method.
Figure 5-23: Main Procedure Screen – Sort

5.5 The Gaussian Fit Optimizer

If you have chosen “Fit” for the Intensity Method parameter in the Elements of
Interest table, one of the screens to appear in the Procedure setup wizard for
the Regression, SLFP, or AccurEx analysis Methods will be the Gaussian Fit
Optimizer screen.
The Gaussian FIT Optimizer is a useful tool for adjusting the "Fit" intensity
calculation method (refer to Elements of Interest screen, earlier in this chapter).
Using this function, Gaussian parameters (refer to Chapter 4 for definitions) can
be adjusted and the resulting intensity spectrum can be viewed to accept,
further change parameters, or reject adjustments to the default parameter
values.
Figure 5-24 shows the Gaussian FIT Optimizer screen with default values. The
parameters are described in Table 5-13.
Figure 5-24: Gaussian Fit Optimizer Screen

Table 5-13: Gaussian Fit Optimizer Parameters
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
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
Tail Term B Coefficient in function used to describe the deviation of the actual peak shape
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
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.
EOI / BckGrnd Element of Interest/Backgroundallows one or more elements to be included or

excluded from the Fit calculation. This can be seen mainly as a “visualization
tool” to evaluate how good the selected fit is.
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.
• Refer to Quantitative X-Ray Spectrometry by R. Jenkins, R. W. Gould, and D. Gedcke,

1981, Marcel Dekker, p. 358-359.
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.
Figure 5-25: Batch Screen
The fields and control buttons appearing in the Batch screen are described in
Table 5-14.
Table 5-14: Batch Screen Fields and Controls
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
5.7 Modifying a Procedure

You may modify an existing procedure by clicking the Open Procedure
button in the Superuser window. You will be presented with the Main Modify
Procedures tab box (Figure 5-26).
The screens used to modify a procedure are the same as those for creating a
new procedure, except that the screens are displayed in a tab-screen format
instead of as a wizard.
You will have to select an existing procedure file name. Enter or change the
various parameter values exactly as described for creation of a new procedure.
Figure 5-26: Modify Procedure screen

The controls appearing at the bottom of all the screens are described in Table
5-15.
Table 5-15: Modify Procedure Controls
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”.
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
This chapter contains information regarding routine maintenance and trouble

shooting for X-2600 series systems.
This chapter also deals with troubleshooting of problems that may arise by either
incorrect operation or as a result of some other software-indicated problem. In
most cases, the error message or error condition noted by the system is self-
explanatory.
In addition, the status box is an excellent source of system information that can
frequently point out an error condition.
If you have any questions regarding the following information, contact your
Xenemetrix service representative.
6.1 Routine Maintenance

Following these maintenance steps will insure normal and reliable operation of
the system. This maintenance may be performed by the operator.
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.
6.1.2 Sample Chamber

Pumping time increases if the chamber is not clean, especially if volatile
liquid or porous materials contaminate it. In a dirty chamber, there
always exists the risk that some particles or liquid will accumulate on the
surface of the thin Be window on the x-ray tube or on the detector. This
has three negative effects:
♦ It gradually reduces the efficiency of the detector and changes its
response, especially at the low energy range. The calibration of the
system for quantitative analysis is thus diminished.
♦ The materials that are accumulated on the window may contribute
their own characteristic peaks to the acquired spectra.
♦ The window is made of thin Beryllium foil. Beryllium is a very
corrosive element: water and many other liquids and particles can
interact with it and generate pinholes within a short period. The
result is loss of the vacuum in the detector cryostat.
6.1.3 Secure the Trays
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.
6.1.4 Computer Operation

Follow the maintenance instructions in the computer's manual to assure its
proper operation.
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.
An accurate description of the problem is essential for the effective assistance

from the service department. When dealing with a problem related to operation
or analysis results, the most effective initial step is to categorize the as follows:
Hardware or software
Method and/or data associated with problem
Operator/Operation
Any connection between the problem and an action preceding it or an
environmental cause may help in the identification of the problem's source. A
further aid is to define the problem nature according to the following criteria:
Is the problem always the same?
Does the problem appear at regular intervals, or does it happen at random
intervals?
X-2600 series systems constantly monitor the major signals and component
operations in the system. Their status is displayed in the MCA Status window.
Many problems, usually hardware and operation-related are detected by the
system and fault message are displayed. Operator inputs from the keyboard are
also checked for validity and safety, and appropriate messages are displayed.
6.2.1 Detector Related Problems

High counts per second (CPS) when the X-rays are off: above 150 CPS.
This problem is mainly related to noise. The source of the noise can be
environmental, e.g., mechanical vibrations or strong electrical interference
generated by electrical instruments (computer display, switching power
supplies, large induction furnaces, arc welding instruments, etc.).
Poor vacuum in the detector cryostat will also cause the detector to be
noisy.
Poor peak resolution: zero width is larger than about 110eV (only when the X-
ray is off).on the 10keV range and Low Throughput.)
This problem is mainly related to noise. The source of the noise can be
environmental, e.g., mechanical vibrations or strong electrical
interference generated by electrical instruments (computer display,
switching power supplies, large induction furnaces, arc welding
instruments, etc.).
Poor vacuum in the detector cryostat will also cause the detector to be
noisy.
High reset rate when the X-ray is off (above 2 resets per second).
This is typically related to a low nitrogen level or to poor vacuum in the
cryostat.
Dirty Beryllium window, causing loss of sensitivity for low elements or a
constant peak within all samples.
6.2.2 Cleaning the Be Window

It is highly recommended to contact your Xenemetrix agent before trying to clean any Be
window. The Be windows are extremely fragile and will very easily break. It is recommended
never to touch the Be window.
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.
6.2.3 Error Messages

Error messages appear in the Event Viewer window described in Chapter 2.
Messages regarding problems halting system operation will be displayed on the
screen.
6.2.4 Measurement Problems

6.2.4.1 Peaks Not in the Correct Position
The proper way to verify energy calibration is to acquire a spectrum of a pure
element using the acquisition parameters as described in Chapter 5. Errors of 10-
15eV are acceptable, but larger errors require correction. You are urged not to
change the calibration if you notice errors smaller than those mentioned
above.
Common reasons for peak shifts are:
• Cabinet heat-up due to dust in the filter or faulty fans.
• Poor gain calibration.
• Dead time too high (over 60%).
• Zero correction is not in the automatic correction mode.
6.2.4.2 No System Response

The system does not respond to entries from the keyboard, the soft keys do not
function, etc.:
• An attempt to print has been made with no printer, or the printer is not
ready, powered-off, out of paper, not on-line or selected, etc. Connect
and ready the printer, or reset the main computer.
• A very slow reaction (a few seconds or more) for entries from the
keyboard. The RS-232 communication cable on the computer side is not
connected or the connector is bad. A “No Controller Answer” message
will appear in the Status window in this case.
6.2.5 X-Ray Generator Problems

6.2.5.1 No X-rays
X-rays generation is off in the following situations:
• Red X-ray ON sign lamp burnt out.
• Direct command, i.e., X-ray OFF, software key in ACQ UTILITY menu, or
STOP ACQ button clicked.
• Acquisition completed.
6.2.5.2 X-ray Tube Related Problems

• High Voltage breakdowns are identified by sudden changes in the HV and
emission current readings on Status window in the software. It is possible
to hear the noise originating inside the tube envelope.
• If the tube or cables are totally defective, they will short out the power
supply; the reading of the high voltage will be zero and the emission
current maximum for a short time, as read on the Status window.
6.2.5.3 Tube Conditioning

If the instrument is not used for more than 24 hours it is necessary to gradually
condition the x-ray tube before using very high voltage (>30 kV) acquisitions. If
the voltages will be below 30 kV, then warm up is not necessary. A predefined
automatic conditioning routine, (Warmup Batch) may be found in the Batch
screen (not yet operational). If the warm-up routine is missing, please consult
with your Xenemetrix Service Engineer to redefine this important automatic
acquisition.
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.
6.3 Communication-related problems

Communication problems are always related to communications between the
main computer and the controller. In most cases, these messages appear when
the cable is not connected or is faulty or when the control unit is not powered.
6.3.1 No Controller Answer

This condition comes about if the controller does not answer the communication
messages from the main computer. Usually it occurs if the power to the
controller is off, or the communication cable is disconnected.
This condition may also occur if initialization of the controller was not complete.
6.3.2 Communication Error

Poor character parity, etc. usually caused by excessively strong electrical
interference (sparks, welding, etc.), or a bad communication cable. You can click
Reset motors to restore connection.
6.3.3 Transmission Failure

This message is issued if transmission (communication) is not possible. It usually
occurs if the communication cable is disconnected from the plug on the
computer's back panel.
6.3.4 No Bias Supply

This message is issued if the detector bias is off. The bias is turned off if the
Detector reset rate is excessively high. This occurs when there is no liquid
nitrogen (see Section C above, on detector-related problems).
6.4 Operation and Error Messages

Information regarding error messages displayed on the screen may be seen in
the Err_database.mdb database file. You will need Microsoft Access to view
this file. Consult your XENEMETRIX representative for more information.
Chapter 7 Site Requirements and System Installation
Chapter
7
Site Requirements and

System Installation
This chapter contains information regarding hardware and software installation

of X-2600 series systems.
7.1 Site Requirements

In many cases, you will find your Xenemetrix EDXRF Spectrometer already
installed and ready to run. Should you need to unpack, install, or relocate your
system, consult first with your authorized Xenemetrix service service agent.
You should make sure the system site is maintained free from excessive
mechanical vibrations and strong acoustical noise. Strong electrical fields such
as those generated by arc welding instruments, induction furnaces, large electric
power lines, etc., can interfere with signals from the X-ray detector and decrease
its resolution. Do not hesitate to consult your Xenemetrix Service Engineer if you
suspect that such problems exist.
Keep the system and its vicinity clean and dust-free since circuit boards and
components in the system and computer could fail due to an accumulation of
conductive dust or from corrosion.
Avoid extreme temperatures or high humidity. The recommended operating
temperature range is 20° to 25°C (68° to 77°F). Constant temperature assures
the stability of system calibration.
7.2 Electrical Power Connection

The AC voltage selector of the system has been set to your local line voltage. The
system's power requirement is ~180W. Do not hesitate to call your Xenemetrix
Service Engineer in case of any questions about electrical connectors or electrical
load.
The wire color code of the main power cable is:
- Live (Line): Brown or Black,
- Neutral: Blue or White,
- Ground (Earth): Yellow or Green.
WARNING
This equipment contains a HIGH VOLTAGE power supply.
A good system ground is essential to ensure safe operation and minimal

interference. Make sure that the ground connections at the installation
site are secure and have low resistance to ground.
It is not advisable to place a printer or other equipment that could generate

mechanical vibrations or acoustical noise on top of the system cabinet, since
these vibrations may degrade the detector's resolution.
7.3 Unpacking and Installing the X-2600 System

7.3.1 Unpacking
(6) Visibly check the package for any external damage and verify that the
Shock Indicator is intact.
(7) Carefully open the system crate. Note: Xenemetrix is currently improving
the system packing. Therefore make sure to inspect both inside the
system crate, as well as inside the system cabinet, to remove any
additional shipment supports, which may not be described below.
(8) Take the machine out of its crate. Check that there are no loose screws,
missing parts, or other damage to the equipment. In case of any loss or
damage found, report to the shipping company and Xenemetrix.
(9) The system was shipped with a retainer to prevent the chamber lid from
opening during transit. This must be removed before operation.
(10) The system’s power supply is universal and accepts 110 or 220 V without
any special settings. Ensure that the Main power source is stable, and
there is a good ground connection.
7.3.2 Hardware Installation

The X-Calibur system comes ready for operation.
(11) Place the system in its chosen operating location.
(12) Rotate the monitor to its vertical position.
(13) Plug the system into the electrical supply mains.
(14) Turn on the system.
All electronic components (including the PC, monitor, mouse and keyboard) are
factory-installed. In case of any question, do not hesitate to contact your
Xenemetrix representative.
7.3.3 Software Installation

Your system comes with Windows 7 and nEXt already installed. No software
installation is required.
7.3.4 Running nEXt

(15) Turn on the X-2600. This will also turn on the computer.
(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.
Figure 7-1: nEXt Log-In Window
7.3.5 Importing Old ExWIN Files

You may import ExWIN procedures and parameters for use in nEXt as follows:
To import ExWIN procedures, select Import Old Procedures from the Data Base
tools pull-down menu in the main Spectra window.
To import ExWIN parameters, select Import ExWIN.ini parameters from the
Data Base tools pull-down menu in the main Spectra window.
Refer to Chapter 3 for more details.
Chapter 8 System Calibration
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.
8.2 The Setup Table

The Setup Table contains the parameters necessary for system operation and
spectrum analysis. These parameters are grouped in the following tab screens
within the Setup Table
Machine Parameters
Controller and Tube Parameters
System Configuration
MCA’s Parameters
Calculate Parameters
Detector Parameters
Analytic Instrument
Environment Configuration
Filters_Stations
Gain Calibration Setup Data
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.
Figure 8-1: Setup Table Tabs

To access the Setup Table, choose Setup Table from the Setup pull-down menu
(or type Alt + S) in the Spectra window. This will display the screen shown in
Figure 8-2.
To access a particular parameter group screen, click on its tab.
Each of the parameter screens have four control buttons, described in Table 8-1.
Table 8-1: Parameter Screens Control Buttons
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.
8.2.1 Machine Parameters

These parameters are intended only for inclusion in the machine database. The
“Set logo” parameters group has no effect on system operation.
The Machine Parameters screen is shown in Figure 8-2 and its contents are
Figure 8-2: Machine Parameters Screen
Table 8-2: Machine Parameters
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.
8.2.2 Controller and Tube Parameters

For the x-ray generating system to function properly, the parameters in the
Controller and Tube Parameters screen must be set.
The Controller and Tube Parameters screen is shown in Figure 8-3 and its
contents are described in Table 8-3.
Figure 8-3: Controller and Tube Parameters Screen
Table 8-3: Controller and Tube Parameters
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.
8.2.3 System Configuration

System Configuration parameters deal with the vacuum, detector, liquid
Nitrogen and focus offset settings.
The System Configuration screen is shown in Figure 8-4 and its contents are
Figure 8-4: System Configuration Parameters Screen
i NOTE
The Max tube temperature is factory set to 50°C.
Table 8-4: System Configuration Parameters
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.
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.)
8.2.4 MCA (DPP) Parameters

In the MCA Parameters screen, you will set the parameters controlling the
operation of the multi-channel analyzer (MCA).
The MCA Parameters screen is shown in Figure 8-5 and its contents are
Figure 8-5: MCA Parameters Screen

Table 8-5: MCA Parameters
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).
The entries are similar to those in the MCA Parameters screen.
! IMPORTANT
Only experienced users and/or service engineers should use this utility.
Figure 8-6: MCA Dialog
8.2.5 Calculation Parameters

In the Calculation Parameters screen, you will set the various geometric and
statistical parameters that are used in the fundamental parameter procedure.
The Calculation Parameters screen is shown in Figure 8-7 and its contents are
Figure 8-7: Calculation Parameters Screen
! IMPORTANT
These variables are intended for advanced users only and in most cases
should not be changed.
Table 8-6: Calculation Parameters
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.
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.
8.2.6 Detector Parameters

The Detector Parameters screen allows you to enter or modify parameters
associated with the detector unit.
The Detector Parameters screen is shown in Figure 8-8 and its contents are
Figure 8-8: Detector Parameters Screen

Table 8-7: Detector Parameters
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
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
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
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.
8.2.7 Analytic Instrument Parameters

The Analytic Instrument screen allows you to enter or modify parameters
associated with X-ray analysis.
The Analytic Instrument screen is shown in Figure 8-9 and its contents are
described in Table 8-8. This screen is not yet operational.
Figure 8-9: Analytic Instrument Parameters
Table 8-8: Analytic Instrument Parameters
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
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.
8.2.8 Environment Configuration

In the Environment Configuration Parameters screen, you will set the
parameters that control the colors, fonts, and grids to be used on the system
monitor display.
The Environment Configuration Parameters screen is shown in Figure 8-10 and
its contents are described in Table 8-9.
Figure 8-10: Environment Configuration Parameters

Table 8-9: Environment Configuration (Display)Parameters
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:
List of fonts List of fonts: List of possible font situations.

Defaults: Accept default font scheme.
Font: Select font. You will be given the following display:
Grid Show vertical lines: Display vertical grid lines on spectra.

Show horizontal lines: Display horizontal grid lines on spectra.
Delta horizontal: Distance between horizontal grid lines.
Delta vertical: Distance between vertical grid lines.
8.2.9 Filter_Stations Parameters

In the Filter Stations Parameters screen, you will define stations and their
coordinates relative to a standard location such as the stage.
The Filter Stations Parameters screen is shown in Figure 8-11 and its contents
are described in Table 8-10.
Figure 8-11: Filters_Stations Parameters

Table 8-10: Filter Stations Parameters
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.
8.2.10 Gain Calibration Setup Data

The Gain Calibration Setup Data screen allows you to fine-tune the MCA gain
and zero coefficients. These parameters are used to properly position XRF peaks
in the displayed spectra.
The Gain Calibration Setup Data screen is shown in Figure 8-12 and its contents
are described in Table 8-11.
Figure 8-12: Maintenance Schedule Screen
Table 8-11: Gain Calibration Setup Data
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).
8.3 System Calibration

8.3.1 Energy Calibration
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.
Re-calibration is justified when the error in the energy scale is larger than +1
channel (i.e +10 eV in the 10keV range or +20eV in the 40keV range).
Energy calibration is described in Appendix D.
8.3.2 Calibration Setup (Gain and Zero Calibration)

In automatic zero correction mode, the system calculates any shifts in the zero
point from the offset value and sends a correction number to the Zero DAC,
which causes the spectrum to shift to the correct position.
In non-automatic correction you can enter correction numbers to the Set Zero
DAC window (shown in the figure above) from the keyboard, but this is not
recommended for typical operation/service. The Zero DAC values should be in
the range of 0 to 255. The Zero Shift should be less than approximately +6eV.
8.3.3 Gain Calibration

The gain calibration is performed by setting the correct value in the Set Gain DAC
window and it involves finding the correct value for the 10keV (Low/High) and
the 40keV (Low/High) settings.
Unlike Zero Calibration, Gain calibration is performed once and should stay
stable for the long term. In a properly functioning system, gain calibration
should NOT be changed frequently; it is definitely not a good practice to re-
calibrate it every day.
The gain calibration is conducted at the high end of the energy scale. The
calibration is performed by adjusting the conversion gain of the ADC, the
conversion gain is controlled by the Gain DAC. The number in the Gain DAC is
displayed in the Acq Status screen; it is saved also in the system parameters file.
As mentioned previously, gain calibration is conducted in the two energy ranges
separately and in each throughput range.
To Calibrate:
(18) Select the desired energy range and throughput.
(19) Write a number to the Gain DAC in the Set Gain DAC window or leave the
previous value in the box.
(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:
Energy Range 0-10keV 0-40keV
Station No 12 (Cu) 14 (Sn)
High Voltage 20 kV 37 kV
Filter Rh (1) Rh (1)
Emission-Current Adjust to obtain dead time of 25-35%.
(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).
8.4 Initial Operation and Test

The simplest way to verify the proper system operation is to acquire spectra
from the standards. Five pure element standards are factory-installed beneath
the sample positions on the bottom of the sample tray. They are identified as
station positions number 9 through 12 and contain elements Al (9), Cu (10), Mo
(11) and Sn (12), Ti (13), Al-Cu (14) and Ti-Sn (15) respectively.
You may use the same acquisition parameters as those used in the energy
calibration procedure.
Appendix A Theory
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.
Figure 0-1: Schematic Diagram of X-Ray Tube
Figure 0-2: Characteristic Peaks (Cu)

Appendix A Theory
A.2 X-Ray Fluorescence (XRF)

A.2.1 Introduction
The X-Calibur series system X-ray Fluorescence (XRF) utilizes the phenomenon in
which a sample is irradiated with X-rays, causing the sample's atoms to become
excited. As the atoms return to their initial stable state, they emit X-ray photons.
When an X-ray from a primary source such as an X-ray tube strikes a substance,
it can either be absorbed by an atom or scattered through the material.
The process in which an X-ray is absorbed by an atom by transferring all of its
energy to an innermost electron is called the photoelectric effect. During this
process, if the primary X-ray has sufficient energy, electrons will be ejected from
the inner shells, creating vacancies (Figure 0-3a). These vacancies present an
unstable condition for the atom.
Electrons will drop from outer shells to fill these vacancies (Figure 0-3b). The
energy transition releases X-ray photons of energy hν, where V is the frequency
and h is Planck’s constant. These energies range from 50eV to 100keV. These
fluorescence X-rays, when captured by a detector, allow elemental analysis of
elements from Fluorine (F) to Fermium (Fm).
(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
A.2.2 XRF Spectra

A typical x-ray spectrum from an irradiated sample will display multiple peaks of
different intensities. The characteristic x-rays are labeled as K, L, M, or N to
denote the shells they originated from.
A second designation, alpha α), beta β) or gamma γ), is made to denote the
X-rays that originated from the transitions of electrons from higher shells.
Hence, a KαX-ray is produced from a transition of an electron from the L to the
K shell, and a Kβx-ray is produced from a transition of an electron from the M
to a K shell, etc. Since, within the shells, there may be multiple orbits of higher
and lower binding energy electrons, a further designation is made as α1 ,α2 or
β1 , β2 , etc. to denote transitions of electrons from these orbits into the same
lower shell.
Figure 0-4: Energy Transitions
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
Figure 0-5: Table of Elements

The intensity (magnitude) of the element's lines in the acquired spectrum is
related to its concentration and the sample thickness. Increasing the
concentration of an element will result in a proportional increase in the intensity
of the fluorescent radiation characteristic of that element, while increasing the
sample thickness will result in a proportional decrease in the intensity. By using
empirical or theoretical physical models, the system can provide quantitative,
quantitative, and layer thickness analysis.
A.3 Relative Line Intensities and Probability

• K→L3 (Kα1) is twice as likely as K→L2 (Kα2).
• α1 lines are four times as intense as β1 lines.
•
• Intensities of other K lines (K→Mn) vary with the atomic number, Z.
• Intensities of L lines within the L series vary greatly with Z.
• Many transitions can be neglected due to statistical insignificance.
• Some lines are unresolved due to nearly equal energies.
• Thickness/qualitative analysis should be performed using measurements of
the characteristic lines that have the highest intensity: KαorLα.
A.3.1 XRF Detection

EXPLAIN THE SDD AND PIN DIODE
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).
Figure 0-6: Spectrum Display
The detection process proceeds as follows (Figure 0-7):

Appendix A Theory
• Fluorescence radiation enters the detector via a beryllium window.

• The incoming fluorescence disturbs a nominal current in the detector,
generating a pulse/current proportional to the energy of the fluorescence.
•
• Pulses are sent to the electronics where they are segregated into an energy-
versus-intensity plot (spectrum) via an MCA (Multi-Channel Analyser) card.
• MCA cards have from 1024 to 2048 channels that can be used to segregate
the fluorescence radiation by energy (Energy Dispersive – ED).
• The spectral peaks are approximately Gaussian distributions.
Figure 0-7: Detector Schematic
A.3.2 Sources of Background

Unwanted radiation sources may affect acquired XRF spectra:
Scatter: Some of the source x-rays strike the wafer and are scattered back at the
detector. This is commonly called “backscatter noise".
Raleigh Scatter: The collision of source x-rays with inner shell electron is an
elastic collision. E1 = E2 in Figure 0-8. This shows up as a source peak in the
spectra.
Compton Scatter: Collision of source x-rays with inner shell electron is an in-
elastic collision. E1 > E2 in Figure 0-8. This shows up as a peak having slightly less
energy than the source peak.
Bremsstrahlung (Continuum) Radiation: German for “braking radiation,” this is
noise that appears in spectra due to kinetic energy/deceleration of electrons as
they strike the anode of the x-ray tube.
Escape Peaks: Incoming fluorescence energy is lost in interactions with the
detector. The detector used in the X-2600 series is composed of Si, and therefore
Appendix A Theory
fluorescence is recognised by the detector as X - 1.74 keV. (1.74 keV is the Ka

energy of Si.)
Sum Peaks: When two fluorescent x-rays of the same energy (X) strike the
detector at the same time, they are recognised as a single incidence of
fluorescence of twice the energy (2X).
Figure 0-8: X-Ray Scatter
A.4 Applications of XRF

1. Peak locations within an XRF spectrum may be used to identify
elements within the sample material (Figure 0-9).
This is accomplished by comparing spectral peak locatios with data
stored in the system.
Figure 0-9: Element Identification
2. Determine element concentrations within a sample.

Appendix A Theory
By comparing measurement results with measurements made on samples

having known elemental concentrations, the corresponding quantities in an
unknown sample can be determined with the aid of linear (or, in some cases,
quadratic) regression methods (Figure 0-10).
Figure 0-10: Quantitative Analysis

Appendix B System Specifications
Appendix B
System Specifications
B.1 Specifications and Facility Information

The following is specification and facility information for the X-2600 series
system. Note that due to continuous improvement in Xenemetrix’s products, the
following specifications are subject to change without notification.
B.1.1 X-Ray Generation

X-Calibur: 50 Watt, 50 kV forced- air cooled end window, front anode X-ray tube.
Software selectable solid-state power supply applies voltage from 3-50 kV in 1 kV
increments (10 to 4000 A in 1 A steps). Beryllium exit window and Rh anode
standard.
X-Cite uses a 9W, 35kV X-ray tube.
B.1.2 X-Ray Detection

Silicon PIN Diode detector (FWHM: 160eV±10eV resolution at 5.9keV) or Silicon
drift diode detector (FWHM: 135eV±10eV resolution at 5.9keV) equipped with a
Be entrance window or a special light element optimized thin window. Integral
4096 channel MCA and digital pulse processor.
B.1.3 Auto-sampler
Computer controlled eight sample position tray accommodating 42 mm high
samples.
B.1.4 Computer and Software

Industrial PC-compatible computer Windows 7™ operation system. nEXt™
software for quantitative and qualitative analysis.
Appendix B System Specifications
B.1.5 Power & Dimensions
X-2600 System Power

110/220VAC
50/60 Hz
Maximum 300W
Power cable (EU or US) will be supplied with the system
Dimensions:
Unpacked: 55x55x32 LxWxH in cm
Packed: 80x80x65 LxWxH in cm
Weight: 90 kg (gross) 50kg (net)

Appendix C Theory
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.
C.1.1 Si PIN diode detector

A PIN diode is a diode with a wide, lightly doped 'near' intrinsic semiconductor
region between a p-type semiconductor and an n-type semiconductor region. The p-
type and n-type regions are typically heavily doped because they are used for ohmic
contacts. The intrinsic region presents a larger volume in which photons can produce
electron-hole pairs and so the thickness of this region can be adapted to increase
quantum efficiency.
The bulk region of Si PIN detectors is ideally composed of very high resistivity
intrinsic silicon.
C.1.2 Silicone Drift Detector (SDD)

Silicone drift detectors are offering higher performance than conventional planar
detectors. An SDD has less electronic noise than a comparable planar detector,
Appendix C Theory
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.
An SDD is a special type of photodiode, functionally similar to a planar photodiode

but with a unique electrode structure. It has much lower capacitance than a planar
diode of the same area, and since electronic noise at short shaping times is
proportional to capacitance, the SDD yields much lower noise at short shaping times.
This gives better energy resolution and high count rates. Figure C-3 is a sketch of an
SDD, showing the electrode structure: a series of drift rings which produce a radial
field, guiding the electrons to a very small, low capacitance anode. X-rays are
incident through the planar front contact, a very thin p+ junction with minimal dead
layer. Electrons produced throughout the active volume drift to the signal anode,
which is connected to a discrete JFET where the signal current is collected.
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
D.1 Peak Position Adjustment
In order to adjust the peak position, two features in the "Setup MCA" in the setup
menu have to be adjusted.
It is recommended to adjust all energy ranges and throughput's [10: low

ow & high, 40:
low&high]
Operation and adjustment
Enter the nEXt software from Superuser mode.
Click on the nEXt button and confirm that the controller and the MCA boards are
initialized
Fast peak energy calibration
For fast gain calibration click on the mouse right button and choose "Fast Gain
Calibration"
Move the peak up or down in energy, by using the arrows in the Fast Gain calibration
dialog box.
Choosing samples for calibration
It is recommended to choose calibration sample which includes two different

elements.
One element should be at the low energy and the second should be at high energy.
For example- for 10KeV Range use Al and Zn.
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.
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.

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Chapter 1 System Overview

1 System Overview ............................................................................. 5

2 Basic Operation .......................................................................... 16

3 Data Acquisition .......................................................................... 35

4 Qualitative Spectral Analysis........................................................ 52

5 Quantitative Spectral Analysis.................................................... 83

6 System Maintenance and Error Handling ............................ 129

7 Site Requirements and System Installation .......................... 137

8 System Calibration ........................................................................ 141

Appendix A Theory ........................................................................ 159

Appendix B System Specifications ..................................................................... 168

Appendix C Detector Theory ........................................................................ 170

Appendix D Energy Calibration ........................................................................ 172

1.1 System Purpose

Figure 1-1: X-Calibur

1.2 Principles of Operation

Figure 1-2: Elemental X-Ray Lines

The intensity (magnitude) of the element's lines in the acquired spectrum is

1.3 System Structure

Figure 1-3: X-2600 Major Components

1.3.1 System Overview

1.3.2 X-ray Generator

1.3.3 Sample Chamber and Tray

1.3.4 The Detector and Its Electronics

1.3.5 Control Unit

1.3.7 System Software

1.4 Operation Controls and Indicators

1.4.1 Front Panel indicators

Figure 1-4: X-Ray Enable Switch

1.4.2 System Main Power Switch

Figure 1-5: Main Power Switch

1.5 Environmental Considerations

A good system ground is essential to ensure safe operation and minimal

It is not advisable to place a printer or other equipment that could generate

1.6 Safety Information

In general, standard safety procedures for operating all electrical machinery

Figure 1-6: X-Calibur Series Spectrometer safety points

1.7 Modes of Operation

Table 1-1: Operational Modes

2.1 System Start-Up and Shut-Down

2.1.1 Power On:

Figure 2-1: Main Power Switch Location (On Back of System)

2.1.2 Power Off:

2.2 Operator Log-In and Log-Out

Figure 2-2: Log-In Window

2.2.1.1 Passwords and Operator Modes

Table 2-1: Operator Modes

2.2.1.2 Initialization Mode

Figure 2-3: Partial Initialization Options I

Figure 2-4: Partial Initialization Options II

Figure 2-5: Initialization Status

Table 2-2: Initialization Status

2.3 Tube Warm-up (Tube Conditioning)

Note that it is recommended not to load the auto-sampler before performing

2.4 Loading the Sample Tray

Figure 2-6: Autosampler Door

Figure 2-7: Autosampler Door and Autosampler

2.5 User Interface

2.5.1 Status Buttons

Figure 2-8: Status Buttons

Table 2-3: Status Buttons

Power supply for the detector (±120/180 V)

Error: This button is:

Table 2-4: Indicators