WD-XRF Manual Zsxhelp

X-RAY FLUORESCENCE SPECTROMETER
ZSX Primus Series
SOFTWARE OPERATION MANUAL
RIGAKU CORPORATION
ME0B-13 20200515
CONTENTS
CONTENTS
1. OUTLINE OF ZSX GUIDANCE SCREEN .................................................... 1

1.1 MAIN SCREEN ........................................................................................................................ 1
1.2. PROGRAM MENU ................................................................................................................... 6
1.3 SOFTWARE OPTIONS .............................................................................................................. 9
1.4 ABOUT ZMONITOR................................................................................................................ 10
1.5 SAMPLE PREPARATION ......................................................................................................... 11
2. ANALYSIS .................................................................................................. 14
2.1 USE OF SUITABLE ANALYSIS TYPE ............................................................................... 14
2.2 EZ ANALYSIS .................................................................................................................... 15
a. Configuration of Screen for EZ Analysis .......................................................................... 16
b. Procedure for Sample Setting in EZ Analysis .................................................................. 19
c. Detailed Description of Each Area ................................................................................... 22
2.3 ANALYSIS ......................................................................................................................... 64
a. Before Analysis ................................................................................................................ 64
b. EZ Scan ........................................................................................................................... 86
c. SQX Analysis (Option) ..................................................................................................... 90
d. Quantitative Analysis ....................................................................................................... 93
e. Analysis Control ............................................................................................................... 95
f. Control ID ........................................................................................................................ 103
g. Sample ID Table............................................................................................................. 106
h. Cycle Repeat Analysis ................................................................................................... 108
i. Fixed Time/Period Analysis .............................................................................................. 111
j. LIMS Analysis Command Interface (Option) ................................................................... 112
3. QUALITATIVE ANALYSIS .........................................................................116

3.1 QUALITATIVE ANALYSIS ................................................................................................ 116
3.2 CREATION OF QUALITATIVE APPLICATION................................................................. 117
a. Application File ............................................................................................................... 122
b. Selection of Qualitative Analysis Range ........................................................................ 129
c. Sample Preparation Information .................................................................................... 132
d. Setting of Analysis Parameters ...................................................................................... 140
ZSX Primus IV/IVi Software Operation Manual i-1

CONTENTS
e. Setting of Measuring Conditions .................................................................................... 146

f. Output Condition ............................................................................................................. 154
g. Printing of Application Information ................................................................................. 158
h. Output of Application Information .................................................................................. 159
3.3 QUAL RESULT ................................................................................................................ 160
3.3.1 QUALITATIVE DATA HANDLING ............................................................................ 161
a. Marker Setting ............................................................................................................... 167
b. Data Processing............................................................................................................. 171
c. Calculation ..................................................................................................................... 181
d. Scale Change ................................................................................................................ 189
e. Processing of Qualitative Analysis File .......................................................................... 195
f. Delete Qualitative Analysis Result Files ......................................................................... 200
g. Display Measuring Condition ......................................................................................... 200
h. Printing of Qualitative Chart ........................................................................................... 201
i. Transfer of Qualitative Analysis Results .......................................................................... 211
3.3.2 SQX CALCULATION (OPTION) .............................................................................. 214
a. Detailed Description of SQX Calculation ....................................................................... 218
b. Impurity Data.................................................................................................................. 233
c. Printing ........................................................................................................................... 236
d. Judge Material (Option) ................................................................................................. 238
e. Automatic Overlap Correction ........................................................................................ 239
f. Export SQX analysis result to a CSV file ........................................................................ 239
g. Registration of Matching Library From SQX Calculation Result .................................... 240
h. Collective Calculation of All Mapping Measurement Points........................................... 241
3.4 SENSITIVITY LIBRARY (OPTION) .................................................................................. 242
a. Procedure to Register Library ........................................................................................ 245
b. Measuring Condition ...................................................................................................... 246
c. Library Samples ............................................................................................................. 253
d. Library Sample Measurement........................................................................................ 267
e. Sensitivity Calibration .................................................................................................... 270
f. Drift Correction for Scattering Library ............................................................................. 275
g. Scattering Sensitivity Calibration ................................................................................... 277
3.5 OUTPUT HAZARDOUS ELEMENTS (OPTION) ......................................................................... 280
3.5.1 OUTLINE .................................................................................................................. 280
3.5.2 PREPARATION OF QUALITATIVE APPLICATIONS ................................................ 280
3.5.3 DRAWING OF HAZARDOUS ELEMENT ANALYSIS REPORT .............................. 284
a. SQX CALCULATION ..................................................................................................... 284
b. DRAWING OF REPORT ................................................................................................ 286
i-2 ZSX Primus IV/IVi Software Operation Manual

CONTENTS
3.5.4.CUSTOMIZATION OF TEMPLATE........................................................................... 289

a. LAYOUT OF REPORT ................................................................................................... 289
b. DESCRIPTION OF NAMES .......................................................................................... 290
c. LIMIT RANGE VALUE MANAGEMENT SHEET OF TEMPLATE .................................. 291
d. ANALYSIS RESULT ....................................................................................................... 292
4. QUANTITATIVE ANALYSIS ..................................................................... 293

4.1 QUANTITATIVE ANALYSIS ............................................................................................. 293
a. Empirical Calibration Method ......................................................................................... 294
b. FP Quantification Method .............................................................................................. 295
c. Various Samples Needed for Quantitative Analysis ....................................................... 297
4.2 CREATION OF QUANTITATIVE APPLICATION .............................................................. 298
a. Creation of Application File ............................................................................................ 299
b. Setting of Application Information .................................................................................. 309
c. Setting of Standard Samples ......................................................................................... 326
d. Setting of Analysis Information ...................................................................................... 336
e. Measuring Condition Setup (Optimize MC’s) ................................................................ 376
f. Measurement of Standard Samples ............................................................................... 400
g. Regression Calculation (Calibration) ............................................................................. 418
h. Setting of Control Information ........................................................................................ 463
i. Printing of Application Information .................................................................................. 475
j. Output of Application Information .................................................................................... 478
4.3 QUANTITATIVE ANALYSIS TECHNIQUES..................................................................... 479
a. Measuring Conditions .................................................................................................... 479
b. Empirical Calibration Method ......................................................................................... 490
c. FP Quantification Method .............................................................................................. 497
4.4 RESULT DISPLAY ........................................................................................................... 505
a. Result Display ................................................................................................................ 506
b. Collection of Analyzed Results ...................................................................................... 512
c. Printing of Analyzed Results .......................................................................................... 519
d. Transfer of Analyzed Results ......................................................................................... 526
e. Saving of Analyzed Results ........................................................................................... 529
f. Deletion of Analyzed Results .......................................................................................... 529
g. Start of Data Processing Program from Analyzed Result .............................................. 530
4.5 QUANTITATIVE SIMULATION ........................................................................................ 531
b. Differences in Standard Sample Setting ........................................................................ 536
c. Setting of Analysis Information....................................................................................... 537
d. Regression Calculation .................................................................................................. 540

CONTENTS
e. Unknown Sample Quantification.................................................................................... 541

f. Printing of Quantitative Application Information .............................................................. 545
4.6 AUTOMATIC QUANTITATIVE APPLICATION SETUP（ZSX PRIMUS IV/IVI） ................ 547
4.6.1 CREATION OF APPLICATION USING AUTOMATIC QUANTITATIVE APPLICATION
SETUP ............................................................................................................................... 551
b. Application Information Setup ........................................................................................ 554
c. Setting Procedure for Standard Samples ...................................................................... 560
d. SQX Measurement of Standard Samples ...................................................................... 561
e. Setup of Composition Information (Automatic Setup Item) ........................................... 562
f. Setup of Analysis Conditions (Automatic Setup Item) .................................................... 564
g. Optimize MC’s (Automatic Data Storage Item) .............................................................. 567
h. Regression Calculation (Checking of Tentative Calibration Curve) ............................... 569
4.6.2 CANCELLATION OF AUTOMATIC QUANTITATIVE APPLICATION SETUP .......... 574
5. MAPPING ANALYSIS (OPTION) ............................................................. 576

5.1 INTRODUCTION ............................................................................................................ 576
5.2 MAPPING TABLE............................................................................................................ 577
a. Coordinates for Mapping ............................................................................................... 578
b. Creation of Mapping Table ............................................................................................. 580
c. Deletion of Measuring Point ........................................................................................... 582
d. Insertion of Measuring Points ........................................................................................ 583
5.3 MICRO MAPPING MEASUREMENT .............................................................................. 585
a. Sample Loading ............................................................................................................. 586
b. Designation of Mapping Position ................................................................................... 587
c. Setting of Analysis Conditions........................................................................................ 592
d. Analysis and Sample Unloading .................................................................................... 594
5.4 MAPPING DATA PROCESSING ..................................................................................... 595
a. Display Method .............................................................................................................. 598
b. Highlighting of Displayed Data ....................................................................................... 604
c. Creating Image File ........................................................................................................ 608
d. Mapping Data Export ..................................................................................................... 611
e. Delete Mapping File ....................................................................................................... 612
f. Print ................................................................................................................................. 613
6. UTILITY AND MAINTENANCE ................................................................ 614

6.1 UTILITY............................................................................................................................ 614
a. Atomic Symbols ............................................................................................................. 615
b. Compound Table ............................................................................................................ 617
c. Sample ID Table ............................................................................................................. 627

CONTENTS
d. Universal Standard Samples ......................................................................................... 631

e. Material Standard Tables (Option) ................................................................................. 642
f. Unit Setting ..................................................................................................................... 654
g. Program Operation (Option) .......................................................................................... 655
h. System Management ..................................................................................................... 667
i. Information Transferred Using E-Mail ............................................................................. 697
j. Operation of Automatic Power Control (Option) ............................................................. 699
k. Information about External Transmission ...................................................................... 701
6.2 MAINTENANCE ............................................................................................................... 703
a. Check List ...................................................................................................................... 704
b. Self-Diagnostics ............................................................................................................. 706
C. PC Maintenance ............................................................................................................ 711
d. Error Log ........................................................................................................................ 713
e. Record for Spectrometer Status Check ......................................................................... 715
f. Record for Self Diagnostics Result ................................................................................. 717
g. Record for Check Analysis Result ................................................................................. 722
h. Record for Drift Correction Result.................................................................................. 728
i. Record for PHA Adjustment Result ................................................................................. 732
j. Record for Calibration Curve Constants ......................................................................... 737
k. Test Measurement.......................................................................................................... 739
6.3 DATA SAVING AND LOADING ........................................................................................ 754
a. Data Saving ................................................................................................................... 756
b. Data Loading.................................................................................................................. 760
6.4 CONVERSION OF SAMPLE ID ....................................................................................... 764
6.5 SETTING FOR E-MAIL .................................................................................................... 766
6.6 TRANSMISSION AND TRANSMISSION FORMATS....................................................... 768
a. Data and Transmission Types ....................................................................................... 768
b. Transmission Specification ............................................................................................ 770
c. Structure of Transmitted Text ......................................................................................... 774
d. Texts Common to All Transmission Types ..................................................................... 776
e. Transmission Type 1 ...................................................................................................... 780
f. Transmission Type 2 ....................................................................................................... 787
g. Transmission Type 3 ...................................................................................................... 791
h. Transmission Type 4 ...................................................................................................... 793
GLOSSARY.................................................................................................... 796

CONTENTS

CHAPTER 1 OUTLINE OF ZSX GUIDANCE SCREEN
1. Outline of ZSX Guidance Screen
1.1 Main screen

The main screen of the ZSX Guidance is shown below. All programs are operated from
this main screen.
Title Bar Menu Bar
Tool Bar
Work Area
Flow Bar
Status Bar Task Bar of

Windows
Area Description
Work Area Each program is displayed and operated.
Menu Bar Area A menu used in a running program is displayed.
Tool buttons of a running program and the ZSX Guidance main
Tool Bar Area
menu are displayed.
The positioning of a screen started by a qualitative or quantitative
Flow Bar
application program is displayed.
ZSX Primus IV/IVi Software Operation Manual 1

Marks and Expressions
Marks and expressions used in this manual are explained below.
Expression Meaning
OK or Cancel Means a button in a screen.
1. Click OK . Means an operating procedure.
Means a selection operation for a

Select [File] [Print].
menu.
<Vacuum> or <Air> Means a selection item.
Mark Meaning
Means a precaution.
Means a note.
ZSX Guidance Screen Operation Tool Buttons
Button Name Function

Flow bar The same as [Window] [View] [Flow bar].
switch Whether the flow bar is displayed or not is switched.
Small The same as [Window] [View] [Small menu].
menu The size of the ZSX Guidance menu is changed.
The same as [Window] [Cascade].
Cascade
Two or more screens are displayed in a cascade.
The same as [Window] [Tile].
Tile
Two or more screens are displayed in a tile.
2 ZSX Primus IV/IVi Software Operation Manual

ZSX Guidance Common Tool Buttons
Button Name Function

Point Used to select, for example, a measuring point on a
designation qualitative analysis chart
X-axis Used to designate a range along the abscissa axis of a
designation graph
Y-axis Used to designate a range along the ordinate axis of a
designation graph
Area
Used to designate a rectangular area on a graph
designation
Execute Scale change after designating an area is executed.
The display scale of a graph is returned to the default

Default scale
values.
Y-axis The full scale is changed according to the peak with the
maximization highest X-ray intensity in a qualitative analysis chart.
Clear The designated point or area is cleared.
Move to left The field of view of a graph is moved to the left.
Move to right The field of view of a graph is moved to the right.
X-axis The abscissa axis (X-axis) of a graph is expanded around

expansion the display origin.
X-axis Abscissas (X-axis) of a graph are expanded from the
reduction display origin.
Y-axis The ordinate axis (Y-axis) of a graph is expanded around
expansion the display origin.
Y-axis Ordinates (Y-axis) of a graph are expanded from the
reduction display origin.

Program Menu
The ZSX Guidance menu consists of the tool bar shown below.
The normal menu is shown above, while the small menu is shown below.
In the case of the small menu, when the mouse cursor is placed on a button, the Help
function displays its menu item name.
In a description for an operating procedure, the operation of a button on the program menu
is expressed as follows.
“Click Utility on the menu.”
Logon User Display Function
The user who has logged on to “ZSX Guidance” is displayed on the tool bar.
When this user name is clicked, a menu to log off from “ZSX Guidance” is displayed.

Flow Bar
An indicator of an operation flow that appears when creating a qualitative analysis

application or a quantitative analysis application is called a flow bar. All screens and
dialog boxes necessary for setting are called from this flow bar. This can also be regarded
as menu items that are always displayed. A screen that is an object of processing is
displayed in yellow on the flow bar. The flow for a quantitative analysis application is
shown below as an example. A downward triangle mark indicates that there is a
submenu. The flow bar is generally displayed in the closed condition at first to display
all menus. Setting can be made so that only executable menus will be displayed without
distinguishing between main menus and submenus.
Main menu Submenu No submenu

1.2. Program Menu

Clicking one of the following buttons with icons on the tool bar can start each menu.
Each menu will be explained below.
 EZ Analysis
Analysis operations can be done easily on an analysis screen on which display screens
necessary for daily routine analyses have been put together. For details, see “2.2 EZ
ANALYSIS”.
 Analysis
This menu controls analyses. All measurements including the standard sample
measurement are possible using this menu. For details, see “2.3 ANALYSIS”.
 Data Processing
This menu carries out data processing for qualitative analysis results and quantitative
analysis results. This menu has submenus of Qual Result (3.3) (including the functions
of Qualitative Data Handling (3.3.1) and SQX Calculation (3.3.2)), Result Display (4.4)
and Quantitative Simulation (4.5). See a section written in parentheses after each
submenu item.
 Qualitative Application
This menu creates qualitative analysis applications. Applications for the qualitative
analysis and SQX analysis are created from this menu. This menu starts the flow bar.
For details, see “3.2 CREATION OF QUALITATIVE APPLICATION”.

 Quantitative Application
This menu creates quantitative analysis applications. Applications for the empirical
calibration method and FP quantification method are created from this menu. This
menu starts the flow bar. For details, see “4.2 CREATION OF QUANTITATIVE
APPLICATION”.
 Utility
This menu controls information for analyses such as the compound registration and
sensitivity libraries. This menu has submenus of Atomic Symbols, Compound Table,
Sample ID Table, Universal Standard Samples, Sensitivity Library (optional), Material
Standard Tables (optional), Program Operation and System Management. See section
3.4 for Sensitivity Library and “6.1 UTILITY” for the other submenu items.
 Maintenance
This menu controls information concerning the condition of the system such as the
spectrometer check and maintenance record. This menu has submenus of Check List,
Self Diagnostics, PC Maintenance, Error Log, Record for Spectrometer Status Check,
Record for Self Diagnostics, Record for Check Analysis, Record for Drift Correction,
Record for PHA Adjustment and Test Measurement. For details, see “6.2
MAINTENANCE”.
 Startup / Shutdown
This menu starts up and shuts down the system. This menu has submenus of System
Startup, Tube/Atmosphere Change, System Shutdown and Status Display.

 Micro Mapping (Option)
This menu is used to make an analysis by specifying measurement positions while

looking at an image of a sample using the sample observation mechanism. Select this
menu to designate measurement positions while looking at an actual image of the
sample that is set in the adapter holder of the sample adapter. For details, see <5.3
MICRO MAPPING MEASUREMENT>.

1.3 Software Options

Various options are available for the ZSX Primus Series.
Options concerning the software and their functions are outlined below:
Option Name Outline of Functions
SQX Software FP method program to make qualitative analyses and
calculate semi quantitative analysis values without using
standard samples (SQX analysis).
Matching Library*1 In the SQX analysis, a matching library sample that has
composition most similar to that of an analysis sample is
automatically retrieved for more accurate analyses.
SQX Scattering Makes SQX analyses by estimating main components
FP Method*1 using scattered rays for samples whose main components
are unknown, such as industrial waste.
Material Judgment*1 Using SQX analysis results, an appropriate standard is
retrieved and output from the material standard table
that has been registered beforehand.
Quant Scattering Makes corrections for the quantitative analysis using
FP Method scattered rays. For example, theoretical matrix correction
coefficients can be calculated to create calibration curves
using ratios of fluorescent X-rays to Compton scattering
rays for the analysis of heavy elements in mineral
samples.
FP Method Theoretical An overlap correction can be made using the FP method
Overlap Correction without measuring the fluorescent X-rays of interfering
elements. This function is especially useful when
interfering lines cannot be measured in the case of thin
film samples and in similar cases.
Glass Bead Correction In the empirical method, the ignition loss correction and
dilution ratio correction can be made.
Correction Charge In molten metal analysis, the charge quantity of each
Calculation material is calculated from an analysis result and output
to adjust the concentrations of elements in the molten
metal to target values.
Program Operation Used to perform Fixed Time/Period Analysis, Automatic
Power-Off, Energy and Saving Operation corresponding to
set-up conditions.
Mapping Used to take a picture of a sample using the camera for a
mapping measurement.
Output Hazardous From an SQX calculation result, data needed for drawing
Elements*1 up a report on hazardous elements can be output.
LIMS Analysis Used to read an analysis request file created by the LIMS
Command Interface (Laboratory Information Management System) and
register sample IDs.
*1: Available only when the system has the SQX Software option
Options that the system does not have are not displayed on the screen.

1.4 About ZMonitor

When ZSX Guidance starts up, the measuring control programs and ZMonitor
automatically start. The measuring control programs are not displayed on the Windows
task bar even after they starts. When ZMonitor starts, the ZSX Guidance icon appears in
the notification area at the right end of the task bar. ZMonitor has functions such as
displaying measuring control programs in operation.
When the ZSX Guidance is terminated, the measuring control programs and ZMonitor are
also terminated automatically.
Restart ZSX Guidance
1. Double-click the icon of (ZSX Guidance) on the desktop.
ZMonitor is not started, it starts from ZMonitor.
Display Measuring Control Programs in Operation
The measuring control program unit consists of more than one program. The names of
programs in operation can be displayed using the following procedure:
 1. Select [Status] on the pop-up menu of ZMonitor.

1.5 Sample Preparation

All samples for this system are set in sample holders for analyses. Though solid samples
have no restriction for their shapes, liquid samples must be analyzed in dedicated
holders. Sample preparation for those samples will be described below. The same sample
preparation must be made for comparisons between samples and standards in
quantitative analysis.
Sample Preparation for Analysis
The X-ray fluorescence analysis is basically a surface analysis. So make sure that
sample surfaces are free from contamination.
 Metal Sample
Surface treatment is necessary to remove contamination on sample surfaces and to

make analyzed surfaces identical for all samples. In general, hard samples should be
ground using an abrasive paper belt or a grinder and soft samples should be processed
using a lathe or a milling machine. In some cases, a file is used, or cut surfaces are not
ground and are analyzed intact.
 Powder Sample
 Crushing
Samples are crushed to make sample grains small and uniform. A vibrating mill is
generally employed.
 Pressing
A fixed quantity of powder sample is pressed intact or after binder or the like for sample
forming is added, in order to form a pelletlike sample. Before pressing, sample is
generally filled into a ring or cup as a support to retain the sample.

 Glass Fusion Bead
In the case of a powder sample, especially in the case of ore and material for the ceramic
industry, X-ray intensities may not correlate with concentrations because of grain size
effects or mineral effects. In such a case, the sample is vitrified to make it uniform before
an analysis. This sample is called a glass fusion bead. Li2B4O7 (or other materials) is
generally used as flux for vitrification.
 Casting
Metal powder such as chips is re-fused to make a block of metal sample. A centrifugal
casting machine is generally employed. After re-fusing, samples are treated like solid
metal samples.
 Liquid Sample and Unpressed Powder Sample
Liquid sample and powder sample that is not pressed are usually measured in the
helium atmosphere. Sample is put in a dedicated cell and set in a sample holder.
When PP is used as the window material of a liquid sample holder for the instrument of
the high output (4 kW) type, the window material may be damaged. Avoid taking a long
time (10 minutes or more) for a measurement.
For the details of the handling of the sample holders, see the instruction manuals of the
liquid and powder sample holders.
 Film Sample
If a thin sample such as a filter or a film is analyzed in an ordinary sample holder,

scattered X-rays and fluorescent X-rays from the support plate on the opposite side of
the sample will penetrate the sample and be detected. Such a thin sample is analyzed
with the sample placed on a hollow aluminum or titanium cup.

Sample Holder
When the instrument is the ZSX Primus, sample size that can be housed in a sample
holder is up to 51 mm dia.  40 mm. Set a sample to a sample holder with the analysis
side facing down. If the sample moves during a measurement, fix it using a ring. In the
case of a film sample, put a hollow cup on it.
When the instrument is the Primus III+, sample size that can be housed in a sample
side facing up.
When the instrument is the ZSX Primus IV, sample size that can be housed in a sample
side facing up.
Sample size to be set to sample holder is 52mmDia. x 30mmH maximum in case of ZSX
Primus IVi. Set the sample surface to be analyzed downward. If it seems to move in the
holder during measurement, fix it with a ring. Put a hollow cup over the sample in case
of film shape sample
A metal sample, pressed powder sample or glass bead sample is set in the sample holder
directly. Liquid sample is poured into a dedicated cell and then loaded into the sample
holder.
When a liquid sample cell is used for the ZSX Primus/Primus IVi, cut a film so that the film
or retainer ring does not protrude from the sample holder. Otherwise, the sample holder
may be stuck in the instrument.
Selection of Sample Mask
Select a sample mask suitable for the sample diameter. Though a sample mask diameter
is generally the same as a measurement diameter, they can be different when the system
has a diaphragm. A diaphragm diameter should be the same as or smaller than the
sample mask diameter.

CHAPTER 2 ANALYSIS
2. ANALYSIS
2.1 USE OF SUITABLE ANALYSIS TYPE
The ZSX Guidance has the following two types of analyses. Use a suitable one for your
purpose.
 EZ Analysis
Analysis operations can be done easily on an analysis screen on which display screens
necessary for daily routine analyses have been put together.
 Analysis
It is possible to make analyses with complicated sequences such as the repeated
analyses.
Since EZ Analysis has been designed for daily routine analyses, the following functions
have been omitted. When any of these functions is necessary, use the “Analysis” program.
Analysis Type Kind

Duplicate reservations in the
same sample position
Analysis Repeated analysis
Control ID
Designation of measurement
point coordinates
Bias correction sample
Analysis Standard sample
Management Library sample
PHA adjustment

CHAPTER 2 ANALYSIS
2.2 EZ ANALYSIS
In EZ Analysis, operational procedures are simple and easy to understand thanks to
graphic display, and it is possible to carry out easily analyses, analysis reservations and
checking of analyzed results.

CHAPTER 2 ANALYSIS
a. Configuration of Screen for EZ Analysis
EZ Analysis consists of a reservation screen and a progress screen, and the screen can be
switched by clicking the tab for each screen. Each screen is divided into areas according
to functions.
Reservation Tab Display Screen

This screen consists of <Sample ID Table Display Area>, <ASC Display Area>,
<Sample ID Setting Area>, and <Analyzed Result Display Area>.
Sample ID Table Display Area
ASC Display Area Sample ID Setting Area
The sample ID table area is displayed only when a sample ID table to be displayed has been
registered using the [Option] setting of the EZ Scan program.

CHAPTER 2 ANALYSIS
Analyzed Result Display Area

Analyzed results and X-ray intensities are displayed only when an analyzed sample
ID has been selected.
The sizes of the areas on the screen can be changed freely by dragging each boundary line.

CHAPTER 2 ANALYSIS
Progress Tab Display Screen
Reservation and Progress Display Area Spectral Display Area
Resetting of Size of Each Screen Area
To return the sizes of display areas on the screen to the default sizes, follow the
procedure described below:
1. Select [View]  [Reset].

CHAPTER 2 ANALYSIS
b. Procedure for Sample Setting in EZ Analysis
Described below is an example of a procedure from sample setting to the completion of

an analysis in EZ Analysis.
First, set a sample position in the ASC display area.
1. Click EZ Analysis on the menu.
2. Select a sample position in the ASC display area.
When there is no reserved or analyzed sample ID on the startup of EZ Analysis, the system
makes the sample position A-1 selected.
When a sample position is selected, the sample type and application selected previously
are automatically copied.
Reservations for the successive analyses of samples using the same application can be
made only by selecting sample positions continually.
3. To change the sample position, drag and drop the image of a sample position in the
ASC display area.
4. Select an analysis type in the sample ID setting area.

CHAPTER 2 ANALYSIS
5. When EZ Scan has been selected for the analysis type, select a sample type,
measuring range, diameter and measuring time. If necessary, set detailed
information using the Advanced... button.
6. In the case of an analysis type other than EZ Scan, select an application that has
been created beforehand.
7. If necessary, enter a sample name and an operator name.
EZ Scan Quantitative/Qualitative Analysis
To carry out the sample film setting for EZ Scan, use the sample ID setting screen.

CHAPTER 2 ANALYSIS
8. To change the analysis order, right-click a sample ID and select [Priority analysis].
That sample ID is set at the top of reserved ones.
9. When samples have been set, click Start to start analyses.
10.When the analyses have been completed, check analyzed results in the analysis
result display area.
By selecting a measured sample ID in the ASC display area on the Reserve tab
screen, analyzed results can be checked.
ASC Display Area Analyzed Result Display Area
11.To check or reanalyze qualitative analysis data, check an SQX calculation or make a
calculation again, right-click a sample ID on the reservation and progress display
area or analyzed result screen or the position of an analyzed sample in the ASC
display area, and select [SQX Calculation] or [Qual Data Handling].

CHAPTER 2 ANALYSIS
c. Detailed Description of Each Area
ASC DISPLAY AREA
Sample positions for sample IDs are displayed graphically on a screen resembling the
ASC.
Sample positions can be set here.
Progress such as during an analysis or during transportation can be understood at a
glance.
The image of the position of a selected sample ID is enlarged.
A sample type icon or a sample name can be selected and displayed in the position of a
preset sample ID.
The ASC display area displays the positions of reserved sample IDs.
Before analyses, put sample holders on the ASC of the spectrometer in accordance with
reserved sample IDs.
Sample Type Display Sample Name Display
The number of samples displayed in the ASC display area varies depending on the number
of trays that the spectrometer has. Up to 12 samples can be loaded on one tray.

CHAPTER 2 ANALYSIS
Sample Type
The following sample types can be used:
Metal & Fusion Film &

Powder Polymer Filter Liquid
Alloy Bead Coating
Progress of Analysis of Sample
The progress of an analysis is displayed using colors.
Waiting for During

Reserved Loading Unloading Analyzed
Analysis Analysis
Blue Green Yellow Red Pink Gray
Sample Information
Information on a sample ID is displayed.
A calculation Program
An analysis
error has occurred operation
setting is
during an reservation
incorrect.
analysis. position.
The program operation reservation position cannot be edited.

CHAPTER 2 ANALYSIS
Display Sample Type Icons in Sample Positions
To display sample type icons in the ASC display area, make the following setting:
1. Select [View]  [Icon on sample].
Display Sample Names in Sample Positions
To display sample names in the ASC display area, make the following setting:
1. Select [View]  [Sample name on sample].
When setting has been made such that sample names are displayed on samples, a sample
name can be edited in the ASC display area by double-clicking a selected sample position.
Setting of Sample Position
Set a sample position by specifying a number for the X-direction and an alphabetic
character for the Y-direction, as shown below:
Sample Changer Range Allowed for Sample Position

ASC48(54/60) A-1 to H-6(I-6/J-6)
ASC96 (Option) A-1 to H-12
In the case of the ASC48, the range allowed for the sample position varies depending on
the number of trays (up to four). If the number of trays is one, the range is from A-1 to B-6
and up to 12 samples can be set.
In the case of the ACS96 (option), up to 96 samples can be analyzed successively.
The ASC54/60 applies only to ZSX Primus IVi.

CHAPTER 2 ANALYSIS
Change Sample Position
1. In the ASC display area, drag the image of a sample ID the position of which is to be
changed.
2. Drop it in a destination sample position.
Copying
When a sample position where a sample ID has not been set is selected in the ASC
display area in EZ Analysis, the sample ID selected previously is automatically copied.
1. Select a sample ID image to be copied or an ID line in the progress display area.
2. Select a sample position where a sample ID has not been set in the ASC display area.
Reservations for the successive analyses of samples using the same application can be
made only by selecting sample positions continually.
Copy Arbitrary ID(s)
A sample ID for which an analysis has been complete as well as an ID in the preset table
can be selected for the sample ID copy function. Thus, an analyzed ID on the progress
display tab can also be copied.
1. Select a sample ID image to be copied or a sample ID on the progress display tab.
2. Right-click the mouse and select [Copy].
3. Right-click a sample position to which to paste in the ASC display area.
4. Select [Paste].
The following procedure can also be used for copying:
1. Keep the Ctrl key of the keyboard pressed down.

2. In the ASC display area, drag the image of a sample ID the position of which is to be
changed.
3. Drop it in a destination sample position.

CHAPTER 2 ANALYSIS
Cut Specified Sample ID
1. Select a sample ID image to be cut or a sample ID on the progress display tab.
2. Right-click the mouse and select [Cut].
A sample ID that has been cut can be pasted in the same sample position or pasted in any
position by right-clicking a sample position for pasting in the ASC display area and
selecting [Paste].
The Delete key has the same function as cutting.
Clear Sample ID(s)
All sample IDs, analyzed sample IDs or specified sample ID can be cleared. Source
sample IDs remain in the preset table after the copying operation, while they do not
remain in the table after the cutting operation.
Clear All Sample IDs
1. Select [Edit] [Clear All IDs].

2. Click Yes .
Take care because cleared sample IDs cannot be restored.
Clear Analyzed Sample IDs
1. Select [Edit] [Clear Analyzed IDs].
The following procedure can also be used for clearing:
1. Click Clear Analyzed IDs in the ASC display area.

CHAPTER 2 ANALYSIS
Clear Specified Sample ID
1. Drag the image of a sample ID to be cleared in the ASC display area.
2. Drop it in an area outside the ASC panel screen.
Take care because a cleared sample ID cannot be restored.
Change Analysis Order
In EZ Analysis, the analysis order of an arbitrary sample ID can be set at the top or an
arbitrary sequence number.
Reserve
1. Right-click the image of a sample ID the analysis order of which is to be changed or a
sample ID on the progress display tab.
2. Select [Priority analysis].
Progress
1. To change the analysis order, click the up- and down-arrow buttons on the right of
the sample ID.
To change the order of analysis reservations during measurement;
<Progress screen>
1. Click the sample ID to change the order.
2. Change the order by pressing right side Up/Down button of sample ID.
3. As the Status changes to Reserved, click Analyzet to go to <Reserved>.

CHAPTER 2 ANALYSIS
To change the order of the sample placed in the inlet sample chamber during
measurement;
1. Select the priority sample by clicking its sample ID (or figure).
2. Select [Priority Analysis] by right click.
It takes some time to change the sample, as the atmosphere of the inlet sample chamber
needs to be restored to atmospheric pressure.
When Sample ID Setting Is Incorrect
When the set contents of any sample ID are incorrect, the warning mark appears on the
image of the sample and an analysis is impossible unless a correction is made.
When the mouse cursor is put in the sample position, the contents of a problem are
displayed. Make a correction according to the displayed contents.

CHAPTER 2 ANALYSIS
When Calculation Error Occurs During Analysis
When a problem arises and an analyzed result cannot be calculated after an analysis is
completed, such as when library sensitivity has not been registered, the error mark
appears.
When the mouse cursor is put in the sample position, the contents of a calculation error
are displayed. Make a correction according to the displayed contents, and make an
analysis again.
Display of Progress of Analysis
The status of a set ID line changes as shown below until it is deleted from the preset
table after an analysis is complete. This status is shown by the description and color of
the status item of a sample ID and the color of a sample position in the ASC display area.
Waiting for During

Reserved Loading Unloading Analyzed
Analysis Analysis
Blue Green Yellow Red Pink Gray

CHAPTER 2 ANALYSIS
After Analysis
By clicking or right-clicking a sample ID for which an analysis is completed, a menu can

be displayed to call up screens for analyzed results and the identification analysis. Each
menu item is described below.
After an analysis is completed, operation is possible on any of a sample image in the ASC
display area and the Progress tab on the Progress tab screen.
Display Analyzed Results
Checking of analysis results is possible on the Reserve tab screen or using Result
Display.
Checking on Reserve Tab Screen

1. Click the ID of a sample on the ASC for which an analysis is completed to display the
analyzed result in the right part of the screen.
Checking Using Result Display

1. Right-click the ID or analyzed result of a sample on the ASC for which an analysis is
completed or a measured sample ID on the Progress tab screen.
2. Select [Result Display].
Display Qualitative Data Handling Screen
1. Right-click the image or analyzed result of a sample ID for which an analysis is
2. Select [Qual Data Handling].
Display SQX Calculation Screen
1. Right-click the image or analyzed result of a sample ID for which an analysis is
2. Select [SQX Calculation].

CHAPTER 2 ANALYSIS
Sample ID Setting Area
This area is used to make setting for a sample ID selected in the ASC display area or
sample ID setting area.
Select an analysis type and an application that has been created beforehand.
In the case of EZ Scan, detailed setting can also be made here.
Like the progress display area, this area can also be used to edit memoranda such as the
sample names and operator names of sample IDs and output file names.
It is possible to choose whether or not to set a file name for EZ Scan and the qualitative
analysis using [Option] of the EZ Scan program.

CHAPTER 2 ANALYSIS
Sample ID
Information to identify each sample to be analyzed is called a sample ID.

In EZ Analysis, it is used on the Progress tab screen.
At the time of an analysis, the Progress tab screen is used to check identification
information such as an analysis type, application name and sample name and settings
such as the result output.
Selection of Analysis Type
In EZ Analysis, five analysis types, EZ Scan, qualitative analysis, quantitative analysis,

check analysis and drift correction sample, can be set. The setting procedure for each
analysis type is described below:
It is possible to set <Favorite> for EZ Analysis, in which to store five analysis types of
<EZ Scan>, <Qualitative Analysis>, <Quantitative Analysis>, <Check Analysis> and
<Drift Correction Sample> and applications. Each setting procedure is described below:
Analysis Type Description

Qualitative analysis that can be made easily without
EZ Scan
creating an application.
Analysis to know the kinds of unknown components.
Qualitative Analysis
Qualitative applications must be created beforehand.
Analysis to know the concentrations of known
Quantitative Analysis components. Calibration curves etc. must be stored
beforehand.
Analysis to judge whether or not a calibration curve
Check Analysis
operates normally
Drift Correction Sample Analysis to correct the drift of a calibration curve
It is possible to select in advance applications used
routinely and frequently for the qualitative and
Favorite
quantitative analyses, and routine setting work for
analyses becomes easy.
It is possible to set up to five applications in the Favorite.
Operation in the sample ID setting area is impossible when no sample ID has been
selected and for a sample ID for which an analysis is completed.

CHAPTER 2 ANALYSIS
Make Setting for EZ Scan
The setting procedure for EZ Scan is described below. When more than one sample needs
to be analyzed, repeat the procedure. The file name of EZ Scan becomes the same as the
sample name by default. When the same sample name as an already saved file name is
set, a subdivision number of “_1” to “_999” is automatically added to the end of the file
name.

2. Click EZ Scan in the sample ID setting area.
ZSX Primus/ Primus III+ ZSX Primus IV/ IVi
3. Select an appropriate sample type using or .

4. Select B to Cm or F to Cm for “Measuring range”.
5. Select an appropriate diameter using or .
6. Select Short , Normal or Long for “Measuring time”.
7. If necessary, click the Advanced... button and carry out detailed setting.
8. Enter a sample name if necessary.
9. Enter an operator name if necessary.
10.Enter a Sample film if necessary.
11.Change the output folder if necessary.
12.Enter a file name if necessary.
When a sample name is not entered, registration is conducted using a name that consists
of a year (four digits of the Christian era), month (two digits), day (two digits) and time (two
digits of an hour and two digits of a minute).
Due to the software specifications, the measurement range may be indicated as B-Cm or
F-Cm

CHAPTER 2 ANALYSIS
In case of ZSX Primus IV / IVi, the sample film which has the suffix (N) at the end of sample
film name is made X-ray absorption correction by the film itself and the impurity correction
in the film at a same time, therefore, the impurities setting for the film which used to be done
per measurement diameter are not needed. Refer to the instruction manual “PROCEDURE
FOR ADDITION OF SAMPLE FILM INFORMATION” regarding details of sample film. (This
is the function of ZSX Primus IV/IVi only, and applicable to the equipment shipped newly.)
As a ZSX Primus IV/IVi‘s particular function, the setting up of fixed angle measurement can
be made on the screen of EZ Scan setting. It is possible to make measurement accuracies
better for objective elements. The best suited analysis line is selected automatically during
the measurement. (This is the function of ZSX Primus IV/IVi only, and applicable to the
equipment shipped newly.)
1. Select <Fixed angle elem.> and then click … on the right side.
2. As the fixed angle measurement screen (periodic table) comes out, click the objective
elements.
3. Set a common measuring time for the objective elements. The default values is 2 seconds,
i.e. peak measuring time: 2sec., background measuring time 2sec. x 2 points
(Background subtraction is curried out by 2 points method). Click OK after setting.

CHAPTER 2 ANALYSIS
Sample Type
Sample types that can be selected for EZ Scan are described below:
Sample Type Description
Metal & Alloy Used for metal and alloy samples.
Used for powder pressed and formed into a pellet. By

entering a sample size, a quantification calculation can
Powder
be made with a film thickness taken into consideration.
Binder can also be set.
By entering a sample size, a quantification calculation
Polymer can be made with a film thickness taken into
consideration. Binder can also be set.
Flux, oxidizer and ignition loss can be set. By entering a

Fusion Bead sample size, a quantification calculation can be made
with a film thickness taken into consideration.
Used for liquid that has been instilled on filter paper

and dried. By entering a sampling quantity, a
Filter
quantification value converted into liquid can be
calculated.
Film & Used for a single-layer thin film sample or a
Coating single-layer thin film sample on a substrate.
Liquid Used for liquid sample.

CHAPTER 2 ANALYSIS
Measuring Range
Select a measuring diameter from <B-Cm> and <F-Cm>.
The measuring range <B-Cm> can be selected when the system has a crystal with which
all elements from B to Cm can be measured.

CHAPTER 2 ANALYSIS
Diameter
Selection can be made from the following measuring diameters by the diaphragm
changer.
ZSX Primus, ZSX Primus IV/IVi
Selection of measuring diameter
Auto,0.5,1,10,20,30,35mm
ZSX Primus III+

Selection of measuring diameter
10,20,30,35mm
When <Auto> is selected for the measuring diameter, the sample mask diameter is
automatically checked using X-ray measurement and measurement is carried out with the
optimum measuring diameter. However, when the liquid has been selected for the sample
type and the spectrometer has the helium flush mechanism and sealing option, the
diameter is fixed to 30mm because Helium/Vacuum is set for the atmosphere.
Measuring Time
Time Description
With this setting, analysis precision is lower but a
Short
result can be obtained more quickly.
Normal This is the default setting.
This setting takes a longer time, but trace components

Long
can be checked more precisely.
Shortest＊ Setting shorter measurement time than Short
(This is the function of ZSX Primus IV/IVi only, and applicable to the equipment shipped
newly.)
Detailed Setting for EZ Analysis
When Advanced... is clicked on the EZ Analysis screen, the setting screen for each
sample type appears and information can be set according to a sample.

CHAPTER 2 ANALYSIS
Sample Type - Metal & Alloy
1. Select a component type from <Metal> and <Oxide>.

Usually, select <Metal> in the case of a metal or alloy
sample.
2. Specify a balance. When analyzed values are to be
calculated from the measured intensities of all
elements, select <None>.
3. When an optional matching library is to be used, select
<Search> or <Specify>. When <Specify> is selected,
select matching library data registered beforehand.
4. To make the impurity correction, select <Use>,
impurity data registered beforehand and a correction
method from <Concentration> and <Intensity>.
It is possible to set the sample film correction on the sample ID setting screen.
The sample film correction is used to correct X-ray absorption by a sample film. When the
impurity correction has been set for a selected sample film, the default impurity correction is
automatically set.
If the analysis line is affected by higher order line interference, the selection of <Add MC's
to eliminate high order lines> will automatically use the optimum optical condition data with
the least interference for SQX calculation. (This is the function of ZSX Primus IV/IVi only,
and applicable to the equipment shipped newly.) Details please refer to the operation
manual “SQX Analysis Considering Influence of Hight-Order lines”.

CHAPTER 2 ANALYSIS
Sample Type - Powder or Polymer or Liquid
The set contents are the same for powder, polymer and a liquid.
1 Select a component type from <Metal> and <Oxide>.

2. Specify a balance. When a balance is to be specified, select a compound or an element
for the balance. In the case of a polyethylene sample, analyzed values are calculated
with a component that is set here, such as CH2, regarded as a balance. When
<Estimate> is selected for the balance, analyzed values are calculated after
estimating the balance of unmeasured elements.
3. When an optional matching library is to be used, select <Search> or <Specify>. When
<Specify> is selected, select matching library data registered beforehand.
4. To make the impurity correction, select <Use>, impurity data registered beforehand
and a correction method from <Concentration> and <Intensity>.
5. As for the sample size, set sample weight, diameter, area, etc. when a sample
thickness affects analyzed values. When <Estimate> has been selected for the
balance, this item must always be set.
6. When binder has been used for a pressed sample, select <Used> and a compound for
the binder and enter sample weight and binder weight.
When binder is set, analyzed values are calculated in the quantification calculation with the
effect of the binder taken into consideration. Set components in a binder compound
beforehand using the “Compound Table” program.
When the system has the scattered ray FP method option, <Estimate> for a balance can be
selected, and Rh-K Compton scattering rays and Thomson scattering rays are measured.
Set 20mm for the measuring diameter. (For ZSX Primus IV/ IVi, 20mm and 30mm can be
selected depending on the specifications.)

CHAPTER 2 ANALYSIS
Sample Type - Fusion Bead
1. Select a component type from <Oxide>. In fusion bead samples, each component is
contained as an oxide.
for the balance. The optional <Loss on ignition> can also be specified for the balance.
3. When an optional matching library is to be used, select <Search> or <Specify>. When
<Specify> is selected, select matching library data registered beforehand.
5. As for the sample size, set sample weight, diameter, area, etc. when a sample
thickness affects analyzed values.
6. Select the type of flux used to prepare a fusion bead, and enter sample weight and
flux weight.
7. When oxidizer has been used, select its type and enter oxidizer weight.
The setting items of the flux, sample weight, flux weight and oxidizer weight are added to
the sample ID setting screen. Set those sample information.
When the optional loss on ignition is selected for a balance, analyzed values are calculated
with the loss on ignition regarded as a balance. This feature is useful for a sample
containing a loss on ignition.
When fluorescent X-rays with short wavelengths, such as the Zr-K line, are measured, the
thickness of a fusion bead affects analyzed values. In such a case, set a sample size.

CHAPTER 2 ANALYSIS
Sample - Filter
This setting is used to analyze liquid with the instillation filter paper method using filter
paper such as the UltraCarry or MircoCarry.

3. Select a filter type.
4. Select a material component.
5. Enter the weight of the instillation part of a filter.
6. Enter the effective diameter of the instillation part of a filter.
7. Enter sampling volume for instillation.
8. Select an output unit in liquid for final analyzed results from <mass%> and <ppm>.
When Rigaku’s filter such as the UltraCarry, UltraCarryLight or MicroCarry is selected for
the filter type, a material, weight and effective diameter are automatically displayed. When
using the UltraCarry or UltraCarryLight, set 30mm for the measuring diameter. When using
the MicroCarry, set 20mm for the measuring diameter.

CHAPTER 2 ANALYSIS
Sample Type - Film & Coating
This setting is used to analyze a thin film sample, the thickness and composition of a
thin film on a coated plate, paper with the main component regarded as the balance and
a thin sample.

for the balance. When a balance has been specified, be sure to set a sample size.
3. In the case of a sample that has a substrate, such as a coated plate, select <Yes>,
click Setting... and set the composition of the substrate.
5. When paper or the like is to be analyzed, set sample weight and a diameter or an
area in the “Sample size” frame.
When a thin sample such as paper, which consists mainly of organic matter, is to be
analyzed, specify cellulose or the like for a balance and set sample weight, diameter, etc.
as the sample size.
Regarding substrate setting, fixed values for the base substrate and the number of layers
under the top layer for analysis can be set and the screening analysis of the top layer
becomes possible. (This is the function of ZSX Primus IV/IVi only, and applicable to the
equipment shipped newly.)

CHAPTER 2 ANALYSIS
To register, call and edit setting conditions in the EZ Scan as templates;
It is possible to set application conditions preliminary set to EZ Scan using <preset>.

(This is the function of ZSX Primus IV/IVi only, and applicable to the equipment shipped newly.)
To register EZ Scan setting conditions as a preset template;
1. Complete the setting conditions of EZ Scan preliminary.

2. Click Preset , and then select Save as… .
3. Select <Preset> folder on the Save Preset screen and enter template name, then click
OK to save.
Creating a new folder in the Preset folder makes sorting easier.
To call a template registered by EZ Scan setting;

2. Click Preset and select the objective template name.
3. Input <Sample name>, and set the output folder.

4. Set the file name if necessary.

CHAPTER 2 ANALYSIS
5. Click Analyze to start measurement.
To edit a template in the preset folder;
Delete a registered template:
1. Click Preset , and select Edit… .
2. Select the objective template to be deleted, and then click Delete .
3. Click OK to delete.
To change a template name;
1. Click Preset , then select Edit… .

2. Select the objective template name to be changed, and click Rename… .
3. Input a new template name and click OK .
To move a registered template to another folder;
1. Click Preset and select Edit… .

2. Select the objective template to be moved, and click Move… .
3. Click the destination folder on the Browse Folder screen, and then click OK .

CHAPTER 2 ANALYSIS
Make Setting for Qualitative Analysis
A qualitative analysis can be made using a created qualitative application.

2. Click Qual Analysis in the sample ID setting area.
3. Select the folder of an application for “Folder” in “Analytical condition”.

4. Select an application in “Analytical condition”.
7. Input items necessary for the selected application appear. Enter each item.
8. If necessary, click ... at the right end and change the output folder.
9. Enter a file name if necessary.

CHAPTER 2 ANALYSIS
Execute Unknown Sample Quantitative Analysis
An unknown sample quantitative analysis can be made using a created quantitative

application.

2. Click Quant Analysis in the sample ID setting area.

5. Set the number of measurements in “Analytical condition”.

CHAPTER 2 ANALYSIS
Execute Check Analysis
The check analysis is carried out to ensure that prepared calibration curves are in
normal operation. Ordinarily the same sample is analyzed for assessment. By executing
the check analysis for the same sample several times a day, X-R control charts can be
drawn to check the relationship between the average values and ranges of analyzed
values. The setting procedure for check samples is described in <4.2 h. Setting of
Analysis Control Information>.

2. Click Check analysis in the sample ID setting area.
If necessary, an output format that is a combination of a file format and a transfer method
can be designated on the “Result output” list. When an output format that has a transfer
method other than RS232C or TCP/IP is selected, enter a file name.

CHAPTER 2 ANALYSIS
Execute Drift Correction
When the number of standard samples and the number of analyzed components are
small, calibration curves can be prepared each time before analyzing unknown samples.
However, in ordinary quantitative X-ray fluorescence analysis, only the calibration of
X-ray intensities is necessary before analyzing unknown samples. This calibration of
X-ray intensities is called the drift correction. By calibrating X-ray intensities using
several samples, the same calibration curves can be used for a long period of time.
Analysis time can be shortened significantly. In the case where the drift correction is
insufficient, calibration curves must be re-created. For the setting procedure for the drift
correction, see “4.2 f. Measurement of Standard Samples”.

2. Click Drift corr. sample in the sample ID setting area.
In EZ Analysis, unlike “Analysis”, <First sample>, <Last sample> or <Intermediate> need

not be set for “Update Selection”. A calculation is automatically made.

CHAPTER 2 ANALYSIS
Application Search Function
For the easy selection of an application, a search function that narrows down objects
using the form and application name is available.
・Narrowing Down Using Form

The application names of the relevant form (application type) are displayed in the
application selection area.
・Search Box
A search can be made by entering a character string. When “*” is set for the
character string, all character strings are used for that part.

CHAPTER 2 ANALYSIS
About Reservations for Program Operation
If any of the positions of registered sample IDs overlaps with any of sample positions to
be used for analyses in Program Operation when EZ Analysis is started, the screen
shown below will appear:
If the screen is displayed, delete or move the sample ID(s) for EZ Analysis so that any
sample position does not overlap.
The position of any registered sample ID must not overlap regardless of whether its status
is reserved or analyzed.

CHAPTER 2 ANALYSIS
Operation for ID Line
The operational procedure for ID lines such as EZ Scan, qualitative analysis,

quantitative analysis, check analysis and drift correction sample is described below.
Basic operations are creation, editing, copying and deletion. For the detailed setting
procedure for each ID, see each paragraph.
Add New ID
Edit Sample ID
1. Select a sample image to be edited in the ASC display area on the Reserve tab screen,
or select an ID to be edited in the sample ID setting area.
2. Change the set contents according to editing contents in the sample ID setting area.
Setting of Sample Information
A sample name and an operator name can be set for the sample information. The sample
name is used to identify each sample and the operator name to identify an operator.
Those are treated as memoranda. They can be used for sorting or searching in Result
Display described later.
When setting has been made such that sample names are displayed on samples, a sample
name can be edited in the ASC display area by double-clicking a selected sample position.
For the display of a sample identification name such as a sample name and an operator
name, refer to the sample ID structure in “6.1 h. System Management”.
Selection of Application Folder
A folder in which applications for the SQX analysis, quantitative analysis, etc. are stored
must be selected. Ordinarily all applications are stored in the common folder. If you
create a folder other than the common folder (AnlCond), the folder in which a specific
application is stored must be selected before that application is selected.
For a user for whom a data storage folder has been specified beforehand using the User
Administration program, the specified folder or common folder is used for storage.

CHAPTER 2 ANALYSIS
Setting of File Name for Qualitative Analysis Result
A sample name automatically becomes the default file name of a qualitative analysis
result. When the same sample names are set successively, three-digit successive
numbers are automatically added to file names. If the first file name has a number at its
end, the number with the digit(s) is automatically incremented. Therefore, if you set
one-digit number, the 10th file name will return to 1.
A folder to save a result file can be specified using <Folder> in the sample ID setting
area. A subfolder can also be created and specified by pressing ... .
This sample name is specified for processing in the qualitative data handling, SQX
calculation, etc.
Setting of File Name for Quantitative Analysis Result
Using the “Data Transfer Setting” program on the “System management” menu, setting
can be made for output to a text file or an HTML file. When <Specify file name> has been
selected for “File name type”, enter a file name for the result output when setting a
sample ID.
Setting of Manual Input Data
This operation is possible in the case of an application for which setting has been made
for manual input data in the SQX analysis, quantitative analysis, etc.
Set Manual Input Data
In the case of an application for which setting has been made for manual input data, add
the following operation in the ordinary ID setting procedure:
1. Enter manual input data under “Input data”.

CHAPTER 2 ANALYSIS
Specify Folder for Saving Result Data File
Although the results of analyses specified in the sample ID setting area on the Reserve
tab screen are generally saved in the following folders, quantitative analysis results and
qualitative analysis results can be saved in subfolders that have been created:
Analysis Type Folder User

Quant. Analysis,
C:\Rigaku\SxIdv\UserData\AnlRslt
Qual. Analysis, Unrestricted
and its subfolders
EZ Scan
Quant. Analysis,
Qual. Analysis,
C:\Rigaku\SxIdv\UserData\AnlRsltU\(
EZ Scan Logon
user name)
(When the data storage User
and its subfolders
folder is specified using
User Administration)
Other Types
(Check Analysis, Drift C:\Rigaku\SxIdv\UserData\AnlRslt Unrestricted
Correction)
The procedure to specify a data storage folder is as follows:
Specify an output folder in the sample ID setting area on the Reserve tab screen.
As an example, let us assume that the logon user is “rigaku” and the data storage folder
“rigaku” has been created beforehand using User Administration.
1. Click ... of the output folder.

CHAPTER 2 ANALYSIS
2. Select the folder “Common” and click OK .
It is also possible to create a subfolder directly under the Common folder. To create a new
subfolder, select the above-mentioned Common folder and then click Create folder....
As for folder designation, specify a folder under the above-mentioned common folder
(AnlRslt) or user folder (AnlRsltU).
By creating a data management folder beforehand for each logon user using User
Administration, data management can be carried out easily.

CHAPTER 2 ANALYSIS
Display Buttons Only for Analysis Types to Be Used
To display buttons only for analysis types to be used, follow the procedure described
below:
1. Select [Tool]  [Option…].

2. Place check marks for analysis types to be used.
It is possible to change the order of analysis types using the arrow buttons.
3. Click OK .

CHAPTER 2 ANALYSIS
Select Applications to be Displayed Using Favorite Button
It is possible to register five typical applications used frequently. Applications that can
be set for Favorite are ones registered in the common folder (AnlCond) including
subfolders.
The procedure to set applications is as follows:
1. Select [Tool]  [Option…].

2. Click Add... and select applications to be set.
It is possible to change the order of display using the arrows.
3. Click OK .

CHAPTER 2 ANALYSIS
Call Contents of Sample ID Table
In EZ Analysis, it is possible to call a sample ID table that has a frequently used

measurement sequence. The following two methods can be used for calling:
・Calling of Sample ID Table

Select menu items [File]  [Load from Sample ID Table] on the EZ Analysis screen.
・Calling Using Sample ID Button

Click a sample ID button in the ID table area in the upper part of the ASC panel.
In the case of the calling using the menu item [Load from Sample ID Table], the
following two methods can be used to specify sample positions:
A: Sample positions registered in a sample ID table are used intact.

B: Sample positions registered in a sample ID table are ignored, and IDs are set from
a specified position in order.
In the case of the calling using a sample ID button in the upper part of the ASC panel,
sample positions registered in a sample ID table are used intact.
A sample ID table to be called from EZ Analysis must meet all of the following conditions:
・Only analysis jobs that can be used in EZ Analysis are contained.
・Only sample IDs using the center measurement for the mapping mode are contained.
・Only analysis conditions using the same atmosphere as the current atmosphere of the
instrument are contained.
When sample positions registered in a sample ID table are used, the following conditions
must also be met:
・Only IDs using sample positions that have not been used by EZ Analysis are contained.
(Example: When the sample position A-1 has been reserved or analyzed, it is
impossible to call a sample ID table using the sample position A-1.)
・The same sample positions are not used duplicately in a sample ID table.

CHAPTER 2 ANALYSIS
Calling Using Menu Item Load From Sample ID Table
1. Select [File]  [Load from Sample ID Table...].

2. Select a sample ID table to be loaded, select a method to specify sample positions and
then click OK .

CHAPTER 2 ANALYSIS
Setting Procedure for Sample ID Buttons to Be Displayed and Calling Procedure
・Setting Procedure for Sample ID Buttons
1. Select [Tool]  [Option...].

2. Click Add… for the sample ID table and select sample ID tables to be set (it is
possible to register up to three sample ID tables). It is possible to change the
order using the arrows.
3. Click OK . Sample ID buttons are created in the upper part of the ASC panel.
To select sample IDs on the EZ Scan screen, follow the procedure described below:
1. Click a sample ID button in the upper part of the ASC panel. The contents of
sample IDs in the sample ID table are automatically set.
In the case of the calling using a sample ID button in the upper part of the ASC panel,
sample positions registered in a sample ID table are used intact.

CHAPTER 2 ANALYSIS
Progress Tab Display Screen
The statuses of sample IDs set in the reservation table and the spectrum being
measured are displayed.

CHAPTER 2 ANALYSIS
Operation for Preset Table
The operational procedure for the preset table is described below. The maximum number
of IDs that can be set in the preset table is the maximum number of samples that can be
put on the ASC. A sample ID remains even when an analysis is completed.
Analysis types that can be set for an ID are the following five types:
Analysis Type Description

Qualitative analysis that can be made easily without
EZ Scan
creating an application.
Analysis to know the kinds of unknown components.
Qualitative applications must be created beforehand.
Analysis to know the concentrations of known
Quantitative Analysis components. Calibration curves etc. must be stored
beforehand.
Analysis to judge whether or not a calibration curve
Check Analysis
operates normally
Drift Correction Sample Analysis to correct the drift of a calibration curve
Two or more sample ID lines cannot be selected for EZ Analysis.
In EZ Analysis, only one sample ID can be set at a time in the same sample position
regardless of whether it has been reserved or analyzed.
Blank Line
A blank line is not used in EZ Analysis.

First determine a sample position in the ASC display area, and then set other items.

CHAPTER 2 ANALYSIS
Spectral Display
This screen displays a qualitative analysis chart during the qualitative analysis. The
scale for X-ray intensities can be changed.
Each measuring range is indicated sequentially in turn with tab form in the spectral display.
newly.)
Analyzed Result Display
The analyzed results and X-ray intensities of a selected analyzed sample ID are
displayed.
In the quantitative analysis etc., the display of analyzed results and X-ray intensities
can be switched by clicking the specified position of a measured sample on the ASC to
select the sample ID and clicking Analyzed result or Intensity .

CHAPTER 2 ANALYSIS
In EZ Analysis, only the result of a sample ID now on display is displayed.

The contents of a cleared sample ID for which an analysis is completed cannot be
checked on the EZ Analysis screen.
To check the contents of a cleared sample ID, use “4.4 Result Display”.
To make operation easier, EZ Analysis does not have the following analyzed result
functions.
If any of theses functions is necessary, use “4.4 Result Display”.
Analyzed Result Functions Not Included in EZ Analysis

Kind
Display of all sample IDs

Analyzed Setting for printing
Result
Function Drawing of plotting chart
Filing of result data
Operation in the sample ID setting area is impossible when no sample ID has been
selected and for a sample ID for which an analysis is completed.
An analyzed result for which the analyzed sample ID has been deleted on the EZ Analysis
screen can be displayed by selecting [Data Processing]  [Result Display] on the menu. It
is also displayed on the analyzed result screen of the “Analysis” program.

CHAPTER 2 ANALYSIS
2.3 ANALYSIS
a. Before Analysis
“Analysis” on the main menu performs qualitative analyses and quantitative analyses
and makes adjustments for those analyses. The three analysis types shown in the table
below are available for routine analysis. Special types of measurement such as the PHA
adjustment and quantitative analysis setup are called analysis control. The routine
analysis is intended for an operator and the analysis control is intended for a manager of
the system or analyses. It is recommended that a PHA adjustment be performed before
routine analyses.
Division Kind of Analysis

EZ scan
SQX analysis
Routine
Quantitative analysis
Analysis
(including intensity
measurement)
PHA adjustment
Check analysis
Drift correction sample
measurement
Bias correction sample
Analysis measurement
Control Standard sample
measurement
Library measurement
Performance diagnosis
measurement
Noise test
For the qualitative (SQX) analysis and quantitative analysis, applications must be
created beforehand. See chapters 3 and 4 for the procedures to create them.
The EZ scan performs the qualitative (SQX) analysis and creates measuring conditions
directly by dialogs. This type is recommended for beginners in the X-ray fluorescence
analysis.
Measuring conditions to control the spectrometer and information necessary for

quantification calculation are called applications.
Screens for analysis and the setting procedure for each analysis are described below.
Make a startup check and start up the system to make it ready for analyses.
1. Click Analysis on the menu.

CHAPTER 2 ANALYSIS
Configuration of Screens for Analysis
The Analysis program has the main screen <Sample ID Setting> and sub screens
<Analyzed Result>, <Qual Analysis Chart>, <ASC Status> and <Operation Status>.
The <Analyzed Result>, <Qual Chart> and <ASC Status> screens overlap each other in
the initial status, but they are displayed in the foreground when the button in the upper
right part of the <Sample ID Setting> screen is clicked. When the main screen <Sample
ID Setting> is closed, all the sub screens are closed.
Sample ID Setting
(Main Screen)
Analyzed Result Qualitative ASC Status Operation

Chart Status
Each screen will be described below.
Sample ID Setting
An area to display information about a sample to be analyzed or a control command in

one line for one sample is called the ID line. This ID line is stored in the preset table
after each setting. The Sample ID Setting screen is therefore used to edit the preset
table. This screen is also used to start analyses for the preset table and to switch its
operating condition or result display.
See the paragraph “Operation for Preset Table”.

CHAPTER 2 ANALYSIS
Analyzed Result Screen
This screen appears in the foreground when the corresponding button in the upper right
part of the Sample ID Setting screen is clicked. All results of the qualitative and
quantitative analysis are displayed on this screen. When an analysis or measurement is
complete, the newest result is automatically displayed. Old data can be displayed by
clicking an ID line in the upper part of this screen. The upper part is called the ID
selection area and the lower part called the result display area. The results of the
analysis for the ID in the light blue cursor line selected in the ID line selection area are
displayed.
In the quantitative analysis, analyzed results and X-ray intensities can be switched by
clicking Analyzed Result or Intensity in the lower part of the screen.
When Display Latest Data is clicked, the newest analyzed results are displayed. The
analyzed result display is updated each time the analysis of one sample is complete.
The “Analyzed Result” screen has the same functions as those of “Result Display”. For the
details of operations, see <4.4 RESULT DISPLAY>.

CHAPTER 2 ANALYSIS
Qualitative Chart Screen
part of the Sample ID Setting screen is clicked. This screen displays a qualitative
analysis chart during the qualitative analysis. When the qualitative analysis starts, this
screen is automatically displayed in the foreground. The scale for X-ray intensities can
be changed.
Each measuring range is indicated sequentially in turn with tab form in the spectral display.
newly.)

CHAPTER 2 ANALYSIS
ASC Status Screen
part of the Sample ID Setting screen is clicked. Sample positions designated in the
preset table are displayed. They do not necessarily correspond to sample holders really
placed on the ASC.
Screen of Setting for ASC48
Screen of Setting for ASC96 (Option)

CHAPTER 2 ANALYSIS
Operation Status Screen
This screen appears when [Window] [5:Operation Status] is selected on the menu.
The analysis or measurement status for an ID line is displayed. This screen consists of
three screens - the progress of the analysis for the ID line, spectrometer status and
mapping measurement positions. They can be switched using the button in the lower
right part of the screen. Examples of the spectrometer status and the progress of the
analysis are shown below.
Display of Screens
When the Analysis program is started, screens are arranged automatically. If any screen
size or position has been changed, the screens cannot be displayed as before using the
<Tile Windows> or <Cascade Windows> functions. In that case, they can be displayed as
shown below by selecting [Window] [Initial Position] on the menu.

CHAPTER 2 ANALYSIS
Operation for Preset Table
The operating procedure for the preset table on the Sample ID Setting screen is
described below. Up to 999 ID lines can be set in the preset table. An ID line for which an
analysis or measurement has been complete moves to the ID list on the Analyzed Result
screen. That is, an ID line in the preset table is deleted each time an analysis is complete.
Analysis or measurement types that can be set in an ID line are of the following four
types:
ID Type Description
EZ Scan Setting for a qualitative analysis
Setting for a qualitative analysis, quantitative analysis
Sample ID
and analysis control
Control ID Setting for a control ID such as atmosphere change
Cycle Repeat Analysis Setting for cycle repeat analysis
In the above figure, line numbers 1 through 7 are called the ID lines. Line numbers 8, 5
through 7 are called the blank line and selected lines, respectively.
Blank Line
The blank line to set a new ID line is always displayed in the preset list regardless of the
number of preset IDs. To add a new ID line, this blank line is selected. This blank line
cannot be copied or deleted even when it is included in selected IDs.

CHAPTER 2 ANALYSIS
Cursor Line
This is a display line to select a specific ID in the preset table. The cursor line is moved
with the up and down arrow keys or by clicking the mouse.
It is used to designate a position to insert an ID, to identify an already preset ID line to
be changed and in similar cases.
Selected Lines
Two or more ID lines can be selected by dragging the mouse.
Take special care for selected ID lines because they can be easily deleted by pressing the
Delete key.
Operation for ID Line
The operating procedure for ID lines such as the EZ scan, sample ID, control ID and
cycle repeat analysis is described below. Basic operations are creation, insertion, edition,
copying and deletion. More than one line can be selected. For the detailed setting
procedure for each ID, see each paragraph.
Add New ID
1. Select [Edit] [Add New ID].

2. Select an objective ID.
Insert New ID
1. Select an ID line for insertion.

2. Select [Edit] [Insert New ID].
3. Select an objective ID.

CHAPTER 2 ANALYSIS
Edit ID Line
1. Select an ID line to be edited.

2. Select [Edit] [Edit Content of ID].
3. Change the set contents.
Copy
The copy function can reproduce the previous ID line(s) or an ID line or lines in any
position. Each procedure is described below.
Copy of Previous ID Line(s)
To copy one preset ID line is called “Copy of ID above”. To copy two or more preset lines is
called “Batch Copy of ID above”. The processing can be carried out regardless of whether
the line next to the copied line is a blank line or another ID line. In “Copy of ID above”
and “Batch Copy of ID above”, sample positions are updated successively.
Copy Previous Line
1. Select the ID line next to the copied line.

2. Select [Edit] [Copy of ID above].
Batch Copy of ID Line
1. Select the ID line next to the copied line.

2. Select [Edit] [Batch Copy of ID above].
3. Enter the number of samples to be copied.

CHAPTER 2 ANALYSIS
Copy Arbitrary ID Line(s)
An ID line for which an analysis has been complete as well as a line in the preset table
can be selected for this copy function. Thus, an analyzed ID line from the result display
can also be copied. The procedure is the same. A copied ID line can be pasted to a blank
line or another ID line.
1. Select an ID line to be copied.

2. Select [Edit] [Copy].
3. Select an ID line to which to paste.
4. Select [Edit] [Paste].
See the procedure to select two or more lines.
Clear ID Line(s)
All ID lines or specified ID lines can be cleared. Clearing of specified ID lines means
cutting, but the most recent cleared ID lines can be pasted. Source ID lines remain in the
preset table after the copying operation, while they do not remain in the table after the
cutting operation. In the case of clearing of all IDs, the pasting operation is impossible.
Clear All IDs
1. Select [Edit] [Clear All ID Lines].
Take care because cleared ID lines cannot be restored.
Cut Specified ID Line
1. Select an ID line to be cut.

2. Select [Edit] [Cut].
An ID line that has been cut can be pasted in any position.
The Delete key has the same function as cutting.

CHAPTER 2 ANALYSIS
Select Two or More ID Lines
The procedure to select two or more ID lines for copying or cutting of ID lines is
described below. Three types of selections can be used: selection of all ID lines, selection
of successive ID lines and selection of ID lines in arbitrary positions.
Select All ID Lines
1. Select [Edit] [Select All].
Select Successive ID Lines
1. Click the first line of successive ID lines.

2. Click the last line of successive ID lines with the Shift key pressed down.
or
1. Drag successive ID lines.
Select ID Lines in Arbitrary Positions
1. Click an ID line.

2. Click ID lines in arbitrary positions with the Ctrl key pressed down.

CHAPTER 2 ANALYSIS
Display of ID Line in Analysis
For the ID line currently in analysis, the progress of the analysis is generally displayed
or the progress of a cycle repeat analysis is displayed. Each of these is described below.
Display of Progress of Analysis
The status of a set ID line changes as shown below until it is deleted from the preset
table after an analysis is complete. This status is shown by the color of the SEQ#. The
default colors are shown below.
Background Character
SEQ# Description
Color Color
001 Preset White Blue
002 Waiting for analysis Green Blue
003 During preparation (waiting for loading) Yellow Red
004 During analysis Red Yellow
005 Analyzed (waiting for unloading) Violet White
ID Line for Cycle Repeat Analysis
The cycle repeat analysis is carried out in one ID line. Therefore, in the case of a
10-times analysis, that ID line remains until measurement is repeated 10 times. When
that ID line is double-clicked, the “Progress of Cycle Repeat Analysis” screen appears.
Care must be taken to note that the ID line of an analyzed result is moved to the area of
analyzed results. The “Progress of Cycle Repeat Analysis” screen is closed automatically
when the cycle repeat analysis is complete.

CHAPTER 2 ANALYSIS
Common Operations for ID Line
As described before, items for the EZ scan, sample ID, control ID and cycle repeat
analysis can be set in ID lines. Common operations concerning IDs except the control ID
are described below.
Measuring
Common Sample Sample Manual
Point File Name
Operation Position Information Input Data
Coordinates
EZ Scan Necessary Necessary Impossible Necessary Impossible
SQX
Necessary Necessary Possible Necessary Possible
Analysis
Sample ID
Quantitative
Necessary Necessary Possible Possible Possible
Analysis
Analysis
Necessary Necessary Impossible Possible Possible
Control
Control ID None None None None None
Cycle Repeat
Necessary Necessary Possible Possible Possible
Analysis
The setting of measuring point coordinates can be selected only in the case of a system
equipped with the mapping mechanism.

CHAPTER 2 ANALYSIS
Setting of Sample Position
Set a sample position by specifying a number for the X direction and an alphabetic
character for the Y direction, as shown below:
Sample Changer Range Allowed for Sample Position

ASC48(ASC54/60) A-1 to H-6(I-6/J-6)
ASC96 (Option) A-1 to H-12
A sample position can be set from the image display of the table using Select…. In the case
of the ASC48, the range allowed for the sample position varies depending on the number of
trays. If the number of trays is one, the range is from A-1 to B-6 and up to 12 samples can
be set.
Sample Position Selection Screen for ASC48
Sample Position Selection Screen for ASC96 (Option)

CHAPTER 2 ANALYSIS
Setting of Sample Information
A sample name and an operator name can be set for the sample information. The sample
name is used to identify each sample and the operator name to identify an operator.
Those are treated as memoranda. They can be used for sorting or searching in Result
Display described later.
To enter a sample name, double-click the cell to activate the vertical cursor. An operator
name can be entered in the same way, but it can also be selected from a list that has been
registered beforehand.
Selection of Application Folder
A folder in which applications for the SQX analysis, quantitative analysis, etc. are stored
must be selected. Ordinarily all applications are stored in the common folder. If you
create a folder other than the common folder, the folder in which a specific application is
stored must be selected before that application is selected. Select an objective folder from
<Folder> below the application selection list of the analysis information.
Setting of File Name for Qualitative Analysis Result
If you want to permanently record an analyzed result, you must specify a file name. If
you do not set a file name, an analyzed result will be lost after it is completed. Care
should be taken because old data will be overwritten if the same file name is specified.
When the same IDs are set successively, three-digit successive numbers are
automatically added to file names. If the first file name has a number at its end, the
number of the digit(s) is automatically incremented. Therefore, if you set one-digit
number, the 10th file name will return to 1.
A folder to save a result file can be specified using <Folder> below the file name input
field. A subfolder can also be created and specified by pressing Browse... .
Setting of File Name for Quantitative Analysis Result
Using the “Data Transfer Setting” program on the “System management” menu, setting
can be made for output to a text file or an HTML file. When <Specify file name> has been
selected for “File name type”, enter a file name for the result output when setting a
sample ID.

CHAPTER 2 ANALYSIS
Setting of Measuring Point Coordinates
In ordinary measurement, the center of a sample in a sample holder is measured. This

measurement is called the center measurement. On the other hand, in the case of a
system equipped with the optional mapping mechanism, distribution measurement of a
sample can be carried out. This analysis is called the mapping analysis. In the mapping
analysis, a mapping table in which measuring points have been set beforehand is
designated before measurement.
Carry Out Mapping Analysis
A mapping analysis is carried out according to coordinates that are preset in a mapping
table. Include the following operation in the ID setup.
1. Select <Mapping> for the measuring point coordinates.

2. Click Select… .
3. Select a mapping table.
4. Click OK .
When carrying out a mapping analysis, be sure to use a sample holder for the mapping.

CHAPTER 2 ANALYSIS
Create Mapping File
To display a mapping analysis result using the “Mapping” program, a mapping file must
be created. Although a mapping file can be created using the “Result Display” program
after an analysis, it can be created automatically by selecting <Create mapping file>
when setting a sample ID.
 1. Select <Create mapping file> under “Mapping file”.

 2. Click Setting… .
 3. Enter a file name.
 4. Select a folder if necessary.
 5. Click OK .
A subfolder can be created and specified by pressing Browse… on the “Mapping file name”
screen.
Setting of Manual Input Data
This operation is possible in the case of an application for which setting has been made
for manual input data in the SQX analysis, quantitative analysis, etc. In the case of the
mapping analysis, manual input data must be set for each measuring point. If you want
to set the same value for all points, click Copy All points .

CHAPTER 2 ANALYSIS
Set Manual Input Data
In the case of an application for which setting has been made for manual input data, a
value must be entered for each measuring point. Include the following operation in the
ID setup.
1. Click Input data… .

2. Enter a value into each cell.
3. Click OK .
Copy All points copies the value of the coordinates where the cursor is placed.

CHAPTER 2 ANALYSIS
Specify Folder for Saving Result Data File
Although analyzed results that appear on the Analyzed Result screen after analyses or are
displayed by the Result Display program are generally saved in the following folders,
quantitative analysis results and qualitative analysis results can be saved in subfolders
that have been created:
Analysis Type Folder User

Quant. Analysis,
C:\Rigaku\SxIdv\UserData\AnlRslt
Qual. Analysis, Unrestricted
and its subfolders
EZ Scan
Quant. Analysis,
Qual. Analysis,
C:\Rigaku\SxIdv\UserData\AnlRsltU\(
EZ Scan Logon
user name)
(When the data storage User
and its subfolders
folder is specified using
User Administration)
Other Types
(Check Analysis, Drift C:\Rigaku\SxIdv\UserData\AnlRslt Unrestricted
Correction)
The procedure to specify a data storage folder is as follows:
As an example, let us assume that the logon user is “rigaku” and the data storage folder
“rigaku” has been created beforehand using User Administration.
1. Click Browse... in the “Result output” frame.

CHAPTER 2 ANALYSIS
2. Select the folder “rigaku” and click OK .
It is also possible to create a subfolder directly under the rigaku folder. To create a new
subfolder, select the above-mentioned rigaku folder and then click Create folder....
As for folder designation, specify a folder under the above-mentioned common folder
(AnlRslt) or user folder (AnlRsltU).
By creating a data management folder beforehand for each logon user using User
Administration, data management can be carried out easily.

CHAPTER 2 ANALYSIS
When a sample ID is clicked on the Sample ID Setting screen, the folder to save the data of
that sample ID is displayed in the upper part of the screen (only a subfolder).
The folder for saving that has currently been set is used for a sample ID that has been set
newly or created using <Copy of ID above>. However, the common folder (or its subfolder)
or the logon folder (or its subfolder) is used to store sample IDs that have been read from a
sample ID table.
Specify Result Folder for Analyzed Result Display
Of the above-mentioned folders to save analyzed results that appear on the Analyzed
Result screen or are displayed by the Result Display program, specify a folder for display
using these programs. The storage location is not restricted to the above-mentioned
common folder AnlRslt and its subfolders. It is also possible to display data in folders in the
user folder AnlRsltU.
 1.Click the title bar or a sample ID in the Analyzed Result window to move the focus
to the Analyzed Result window.
 2.Select [View]→[Select Folder].
Or
1. Click Browse... on the Analyzed Result screen and select a folder.

CHAPTER 2 ANALYSIS
PHA adjustment results, drift correction results and check analysis results are
unconditionally saved in the AnlRslt folder. If the folder for data displayed in the Analyzed
Result window is not the AnlRslt folder when carrying out these measurements, results will
not be displayed automatically on analyses. Therefore, it is generally advisable to specify
the AnlRslt folder.

CHAPTER 2 ANALYSIS
b. EZ Scan
EZ Scan is a program to carry out qualitative analyses without creating qualitative

applications. This is a qualitative analysis mode for operators who have no experience of
the X-ray fluorescence analysis. Measuring conditions need not be prepared.
When more detailed measuring conditions should be set, create applications as
described in the chapter “QUALITATIVE APPLICATION”.

CHAPTER 2 ANALYSIS
Setting for EZ Scan
Setting items will be described below. For the sample position and sample information,
see the paragraph <2.3 a. Before Analysis>.
For items other than the measuring time and file name, see the paragraph “2.2 EZ
Analysis - Make Setting for EZ Scan”.
Measuring Time
Time Description
Standard This is the default setting.
With this setting, analysis precision is lower but a

Short
result can be obtained more quickly.
This setting takes a longer time, but trace components
Long
can be checked more precisely.
This is the setting of the shortest measuring time which
Shortest＊
is shorter than “Short”.
“Shortest” is the function of ZSX Primus IV/IVi only, and applicable to the equipment
shipped newly.
File Name
Set a file name to store qualitative spectral data. A default file name is displayed by
searching the last sample IDs already created including analyzed sample IDs as shown
below.
Created EZ scan sample ID Default file name
No created EZ scan sample ID EZS001 is automatically set at first.
The number is automatically incremented

Last file name is EZSnnn
like EZSnnn (nnn=002-999).
The number is automatically incremented
Last file name is ABCXYZ. like ABCXYZnnn (nnn=001-999). If no
number of nnn, 001 is added.
The default file name displayed may be changed.

A folder to store the result file by the <Folder> setting displayed under the file name
input can be specified. It is possible to create a folder by clicking Browse .

CHAPTER 2 ANALYSIS
Make Setting for EZ Scan
The setting procedure for the EZ scan will be described below. When more than one
sample needs to be analyzed, repeat the procedure. Care must be taken because old data
will be overwritten if you set the same file name as one that has already been used.
1. Click EZ Scan on the Sample ID Setting screen.
ZSX Primus /Primus III+ ZSX Primus IV/ IVi
2. Select a sample position.

5. Select a type nearest to a sample to be analyzed for “Sample type”.
6. Select F to Cm or B to Cm for “Meas. Range”.
7. Select an appropriate measuring diameter using ▲ or ▼ .
8. If necessary, click the Advanced... button and carry out detailed setting.
9. Select Standard , Long or Short for “Time”.
10.Change the file name if necessary.
11.Click OK .
A component type etc. for each sample type are default settings for new registration in
the advanced setting in EZ Analysis, as shown below:

CHAPTER 2 ANALYSIS
Component
Sample Type Balance Others
Type
Metal & Alloy Metal None None
Powder Oxide None None
Polymer Metal CH2 None
Fusion Bead Oxide None Flux: Li2B4O7, dilution ratio: 10
Filter Metal ― MicroCarry, sampling: 50L
Film & Coating Metal None None
Liquid Metal H2O None
To change the measuring condition or output information, see “Edit EZ Scan Condition”
in “3.2 a. Application File”.
When detailed information is different from the above default contents, change the sample
information using the SQX calculation program, and recalculate analyzed values. For the
detailed operational procedure, see “3.3.2 SQX CALCULATION”.

CHAPTER 2 ANALYSIS
c. SQX Analysis (Option)
A Fundamental Parameters (FP) program to calculate semi-quantitative analysis values

using built-in sensitivity libraries for components detected by the qualitative analysis is
called SQX. This is a new FP program that has a function to obtain stable X-ray
intensities by adding the intensity measurement to the qualitative analysis. It also has
new software functions such as the automatic overlap correction, photoelectron FP and
material discrimination.
SQX is an abbreviation of Scan Quantitative X.
When components that comprise a sample are unknown, a qualitative analysis is

generally carried out to determine the unknown components in the sample.
Semi-quantitative values (approximate quantification values) may also be desired and
the SQX analysis can be employed for that purpose.
A qualitative analysis that carries out quantification to some extent is called the
semi-quantitative analysis.
The operation flowchart of the SQX analysis is shown below. The sample transportation,
operation control, etc. during an analysis are carried out automatically.
SQX analysis start
Qualitative analysis in specified element range
Automatic peak detection
Identification analysis for detected peaks
Overlap correction for analyzed peaks
Quantification calculation for detected components
Display of analyzed result
SQX analysis end

CHAPTER 2 ANALYSIS
Setting for SQX Analysis
Unlike the EZ scan, the SQX analysis has various functions such as setting for manual
input data and the optional mapping analysis that are applicable to specific purposes.
The standard measurement will be described first and then details will be explained.
For descriptions of setting items, see the paragraph <2.3 a. Before Analysis>.
1. Click Sample ID on the Sample ID Setting screen.

2. Click Qual .
4. Enter a sample name in the “Sample information” frame if necessary.
5. Set an operator name in the “Sample information” frame if necessary.
6. Select a folder that has an application for “Folder” in the “Analytical condition”
frame.
7. Select an application in the “Analytical condition” frame.
8. Enter a file name in the “Result output” frame.
9. When SQX Scattering FP method (Option) is put to use, enter the conditions
on the sample size by clicking Setting Sample Size.
10.Click OK .

CHAPTER 2 ANALYSIS
Setting Sample Size
It is necessary to enter the sample-size condition when the analysis is carried out by
using SQX Scattering FP method. Measure the sample size in advance before analyzing
and enter it.
 1. Click Sample ID on the Sample ID Setting screen.

 2. Click Qual
 3. Click Sample Size Setting.
 4. Enter Mass by gram unit.
 5. Enter Height by mm unit.
 6. Enter the base size by Diameter or Area or Cell.
 7. Click OK.
The base size shows the actual size of the analysis surface and has three kinds of the
setting way as follows.
Setting Setting contents

Diameter Sample diameter of a pressed briquette or a disc.
Area Base area of the samples like small pieces etc.
Cell Select a cell when sample is put into a sample cell. If a sample cell
used is cylinder whose top and bottom have same diameter,
diameter may be entered instead.
Mass per unit area is calculated with input data of mass and base size. Height is used to
correct intensity calculation against depth and the value of height requires less
precision than mass and base size.

CHAPTER 2 ANALYSIS
d. Quantitative Analysis
The analysis for process control or quality control is called quantitative analysis. To
execute quantitative analysis, applications must be prepared beforehand. Key words
such as “non-destructive”, “fast”, “high precision” and “low cost” are known as features of
the X-ray fluorescence analysis. However, it is essential that careful consideration be
given to all aspects of quantitative analysis for the method to be used correctly. For the
creation of quantitative applications, see chapter 4.
Flowchart of Routine Control Analysis
The recommended procedure of the routine control analysis is shown below. When an
operating procedure for the control analysis has been established, follow it. For the
operating procedure for the check analysis, drift correction, etc., refer to the following
paragraphs for the analysis control.
Routine control analysis
PHA adjustment
Check analysis result?

OK
NG
Drift correction
Check analysis result?

OK
NG
Second time through?

No
Yes
Calibration curves must be re-created.

Contact your system manager.
Start unknown sample analysis.

CHAPTER 2 ANALYSIS
Carry Out Quantitative Unknown Sample Analysis
When the results of the PHA adjustment and check analysis are satisfactory, you can
carry out the quantitative analysis on unknown samples. The setting procedure for it is
described below. For descriptions of setting items, see the paragraph <2.3 a. Before
Analysis>.
1. Click Sample ID on the Sample ID Setting screen.
2. Click Quant.

6. Select <Quant analysis> in the “Analytical condition” frame.
frame.
9. Set the number of repetitions for “Repeat times”.
10.Click OK

CHAPTER 2 ANALYSIS
e. Analysis Control
The analysis control means the PHA adjustment, check analysis, drift correction and so
on in the quantitative analysis. Analysis control items other than the PHA adjustment
should be executed if necessary and are classified as follows:
Analysis Control Description

Check Analysis Preparation for quantitative analysis
Drift Correction Sample Quantitative application setup and analysis preparation
Bias Correction Sample Quantitative application setup and analysis preparation
Standard Sample Quantitative application setup
Library Sample Spectrometer sensitivity setup
PHA Adjustment Preparation for qualitative/quantitative analysis
<Library sample> is only effective when the SQX software option is attached.

CHAPTER 2 ANALYSIS
Update Selection
“Update Selection” is designated for <Drift corr. sample>, <Bias corr. sample>,
Standard sample> and <Scattering drift library> of Library sample. In these types of
measurement, in parallel with a series of measurement, calculation control such as
preparation for calculation, data storage and calculation instructions must be carried
out to obtain various coefficients. By setting “Update Selection” properly, this calculation
control can operate correctly.
Update Selection Description

Flag for the first sample in a series of ID lines.
First sample
Initializes calculation information for each analysis type.
Flag for the last sample in a series of ID lines.
Last sample
Executes calculation using a series of measured results.
Intermediate Flag for an ID line other than the above.
If <Last sample> is not measured, coefficients will not be updated for Drift Correction
Sample, Bias Correction Sample, Standard Sample or Scattering drift library.
Automatic Calibration Curve Update
Calibration curve coefficients for the empirical calibration method and sensitivity
constants for the FP method are ordinarily calculated using the Regression Calculation
program in the quantitative application flow. However, they can also be automatically
calculated and saved using Update Selection for standard samples after measuring
them.
This function can be used for an application for which data has been examined using the
Regression Calculation program and calibration curve coefficients and matrix correction
coefficients for the empirical calibration method or sensitivity constants for the FP
method have been registered. This function is effective when X-ray intensities have
changed greatly after replacing the X-ray tube of the spectrometer.
In this automatic update, only calibration curve coefficients for the empirical calibration
method or sensitivity constants for the FP method are calculated. Matrix correction
coefficients for the empirical calibration method or theoretical intensities and overlap
correction coefficients for the FP method are not calculated. (Values that have been
registered are used intact.)
The standard samples from <First sample> to <Last sample> are used for calculation.
Sample selection used in the Regression Calculation program is also reflected.

CHAPTER 2 ANALYSIS
Execute PHA Adjustment
The PHA adjustment should be executed before routine unknown analyses. In the case
of 24-hour continual operation, PHA adjustment should generally be carried out once a
day. After the P-10 gas cylinder or PC window is exchanged, the energy axis should be
checked and readjusted, if necessary. The axis is ordinarily stable and does not shift. The
PHA adjustment should be carried out about 30 minutes after aging and any adjustment
of the P-10 gas flow rate. Both of the two detectors are adjusted using the built-in
samples of the instrument. The PHA adjustment can be started from the Analysis menu
or the Spectrometer Startup menu. For the procedure from the Spectrometer Startup
menu, see <1.2 b System Startup> described before.
Since the system has two detectors, the PC and SC, set IDs for both of them.
1. Select [Edit] [Add New ID] [2:Sample ID].

2. Click Control .
5. Select <PHA adjustment> in the “Analytical condition” frame.
6. Only in the case of the ZSX Primus II or ZSX Primus III+, select a sample position.
7. Select <PC> or <SC> for the code name.
8. Click OK .
In the case of an instrument for which Step 6 is unnecessary, the PHA adjustment sample
has been housed in the instrument, and the built-in sample is automatically measured to
make the PHA adjustment.

CHAPTER 2 ANALYSIS
Execute Check Analysis
The check analysis is carried out to ensure that prepared calibration curves are in
normal operation. Ordinarily the same sample is measured for assessment. By executing
the check analysis for the same sample several times a day, X-R control charts can be
drawn to check the relationship between the average values and ranges of analyzed
values. The setting procedure for check samples is described in <4.2 h. Setting of
Analysis Control Information>.

5. Set an operator name if necessary.
6. Select <Check analysis> in the “Analytical condition” frame.
frame.
8. Select a limit range name.
9. Set the number of repetitions for “Repeat times”.
10.Click OK .

CHAPTER 2 ANALYSIS
Execute Drift Correction
When the number of standard samples and the number of analyzed components are
small, calibration curves can be prepared each time before analyzing unknown samples.
However, in ordinary quantitative X-ray fluorescence analysis, only the calibration of
X-ray intensities is necessary before analyzing unknown samples. This calibration of
X-ray intensities is called the drift correction. By calibrating X-ray intensities using
several samples, the same calibration curves can be used for a long period of time.
Analysis time can be shortened significantly. In the case where the drift correction is
insufficient, calibration curves must be re-created. For the setting procedure for the drift
correction, see <4.2 f. Measurement of Standard Samples>.

6. Select <Drift corr. sample> in the “Analytical condition” frame.
frame.
9. Select an appropriate item for “Update Selection”.
10.Set the number of repetitions for “Repeat times”.
11.Click OK .
Be sure to make setting for “Update Selection”.

CHAPTER 2 ANALYSIS
Execute Bias Correction
Analyzed results of unknown samples using prepared calibration curves may have
constant biases from expected values. This is because, for example, the preparation
method for the standard samples on the market that are used to prepare the calibration
curves is different from that for the unknown samples. The operation to correct this
phenomenon is called the bias correction. For the setting procedure for the bias
correction, see <4.2 h. Setting of Analysis Control Information>.

6. Select <Bias corr. sample> in the “Analytical condition” frame.
frame.
9. Select an appropriate item for “Update Selection”.
11.Click OK .

CHAPTER 2 ANALYSIS
Execute Standard Sample Measurement
The standard sample measurement must always be carried out to prepare calibration
curves or FP sensitivity curves. Because quantitative analysis in the X-ray fluorescence
analysis employs the standard sample comparison method, standard X-ray intensities
are necessary. Samples used to create calibration curves are called standard samples
and the procedure to measure them is described below. For the setting procedure for
standard samples, see <4.2 c. Setting of Standard Samples>.
1. Select [Edit]  [Add New ID]  [2:Sample ID].

2. Click Control.
6. Select <Standard sample> in the “Analytical condition” frame.
frame.
9. Select a code name.
10.Select an appropriate item for “Update Selection”.
12.Click OK.

CHAPTER 2 ANALYSIS
Execute Library Sample Measurement
Reference X-ray intensities are necessary for the X-ray fluorescence analysis. Standard
samples are generally used to create calibration curves, but in some cases standard
samples that have concentrations similar to those of unknown samples are not available.
In those cases, the FP quantification method can be used to perform quantitative
analyses without standard samples. Spectrometer sensitivity is referenced in that FP
quantification method. A collection of spectrometer sensitivity values is called a
sensitivity library. The procedure to measure those library samples is described below.
For the sensitivity library, see <3.4 SENSITIVITY LIBRARY(OPTION)>.

2. Click Control.
6. Select <Library sample> in the “Analytical condition” frame.
7. Select a library type.
8. Select a code name.
9. Click OK.

CHAPTER 2 ANALYSIS
f. Control ID
An ID designed to control the spectrometer, not to execute an ordinary analysis or

measurement, is called a control ID. The spectrometer control includes the following
items:
Spectrometer
Description
Control
Used to stop temporarily the execution of this ID line to
Temporary stop
change a sample holder or to wait for the arrival of a sample
Atmosphere Switches the analysis chamber atmosphere to the one
change suitable for the sample.
Raises the tube voltage and current slowly to the specified
Tube aging
values.
X-rays and the power of the spectrometer can be turned off
Automatic power
automatically after analyses by specifying in Program
off (Option)
Operation

CHAPTER 2 ANALYSIS
Wait Without Terminating Measurement
This function can be used, for example, when you have set ID lines to analyze unknown
samples but want to stop a series of analyses because it takes a long time to prepare
samples. This can also be used when you want to stop measurement while a sample is
exchanged in the case of one-sample loader. To cancel a temporary stop or to terminate
measurement, follow the message.
1. Select [Edit] [Add New ID] [3:Control ID].

2. Select <Temporary stop>.
3. Click OK .
Change Analysis Chamber Atmosphere
This function is used to change the analysis chamber atmosphere according to the
application to be analyzed or measured.

2. Select <Atmosphere change>.
3. Select <Vacuum>, <Air> or <Helium/Vacuum> for the atmosphere.
4. Click OK .
When the spectrometer does not have the helium flush mechanism, <Helium/Vacuum>
cannot be selected. When the spectrometer has the helium flush mechanism, <Air> cannot
be selected.
Set Automatic Aging
Automatic aging for the X-ray tube is carried out.

2. Select <Tube aging>.
3. Click OK .

CHAPTER 2 ANALYSIS
Set Automatic Power Off
It is possible to use this function only when the program operation option is attached.
The contents of a method to select must be set beforehand using Program Operation.

2. Select <Automatic power-off>.
3. Select a method.
4. Click OK .
A sample ID cannot be set after a control ID for <Automatic power-off>.

CHAPTER 2 ANALYSIS
g. Sample ID Table
As described before, an area to place IDs in order of analysis is called the preset table.
When you must set the same sample IDs each time to this preset table, you can save
time and trouble by creating a sample ID table. For example, when the same contents
must be set every time as in the case of the PHA adjustment, a sample ID table in which
IDs have been set beforehand can be loaded to the preset table. This sample ID table is
also used for the cycle repeat analysis described later. In addition, sample IDs set in the
Analysis program can be registered in a sample ID table. For further details, see <6.1 c.
Sample ID Table>.
Load Sample ID Table
1. Move the cursor line to the line for insertion.

2. Select [File] [Load from Sample ID Table].
3. Select a table name.
4. Click OK .
After insertion, existing ID lines move and follow the inserted sample ID table.
If the number of blank lines in the preset table is smaller than the number of IDs in the
specified ID table, that table cannot be loaded.

CHAPTER 2 ANALYSIS
Save to Sample ID Table
1. Select ID lines to be saved.

2. Select [File] [Save to Sample ID Table].
3. Enter a table name.
4. Click OK .
The EZ scan ID and cycle repeat analysis ID cannot be saved in a sample ID table. And
“Secure vacuum” and “Power off” in the control IDs cannot be saved in a sample ID table.

CHAPTER 2 ANALYSIS
h. Cycle Repeat Analysis
The cycle repeat analysis can be used to check the performance of the system. The
dynamic mode and the static mode are available in the cycle repeat analysis. Before
executing a cycle repeat analysis, ID lines must be set beforehand in a sample ID table.
A sample ID table must be set even when one sample is to be used for a cycle repeat
analysis. Only one ID line is set, but an analyzed result is displayed in one ID line for
each analysis. Up to a maximum of 999 repeats can be set.
Repeat Mode Description
Carries out analyses for the designated number of

Dynamic Mode repetitions, unloading the sample holder from the analysis
chamber each time.
Carries out analyses for the designated number of

Static Mode repetitions, with the sample holder loaded in the analysis
chamber.
The output of calculated results can be selected from among the raw intensity, X-ray
intensity and concentration. The “interval” means a delay time from each completion of
measurement to the next measurement. The maximum interval is 99 hours and 59
minutes.
Output Description
X-ray intensities before the background subtraction and

Raw intensity
various corrections are output as results.
X-ray intensities after the background subtraction and

X-ray intensity
various corrections are output as results.
Concentration Concentrations or film thicknesses are output as results.

CHAPTER 2 ANALYSIS
Set Cycle Repeat Analysis
1. Select [Edit] [Add New ID] [4:Cycle Repeat Analysis].

2. Select <Dynamic> or Static> for “Mode”.
3. Select a sample ID table.
4. Set the number of repetitions for “Recycle time”.
5. Select <Raw intensity>, <X-ray intensity> or <Concentration> in the “Output”
frame.
6. Set hours and minutes for “Interval”.
7. Click OK .
Set auto drift correction (For ZSX Primus IV/IVi only);
Automatization of correction (Auto drift correction) can be made using the sample ID
table for automatic drift correction which is set the check sample setting (lower limit,
upper limit, having been set, and drift correction. Labor-saving of analysis preparation
work is realized with this function.
Auto drift correction executes the following sequence automatically.

1, Check analysis is executed with check samples.
2. Judges automatically if the analyzed value is within the range.
3. In case it is out of range, measures drift correction samples automatically and
updates correction coefficients.
4. Executes the check analysis again.

CHAPTER 2 ANALYSIS
5. Makes judgement automatically if it is in the range and repeat 4. and 5. above to see
if it is out again.
Auto drift correction is made up to two times. If it is the case that the check analysis after
second drift correction is still out of range, make calibration curves again.
1. Select [Edit] -> [Add new ID] -> [5:Auto drift correction…].
2. Auto Drift Correction screen is indicated and the sample ID table can be selected.
Select the objective sample ID table from the pull down list, then click OK .
3. Auto drift correction sequence is set in the sample ID setting screen. Set the
designated sample on the sample tray.
4. Click Analyze to start analysis. Judgment of tolerance and drift correction are
executed automatically.
Make the dedicated sample ID table for auto drift correction beforehand.

CHAPTER 2 ANALYSIS
i. Fixed Time/Period Analysis
To start specified analyses at a specified time, the fixed time analysis and the fixed
period analysis can be used. For example, with the fixed time analysis, a PHA
adjustment can be made at a specified time once a day. With the fixed period analysis, a
check analysis can be made at constant time intervals.
It is possible to use this function only when the program operation option is attached.
The fixed time analysis and fixed period analysis have priority over all analyses except
the one now in progress. So sample IDs for the SQX analysis, quantitative analysis, etc.
that have been set on the Analysis screen are carried out after the fixed time/period
analysis.
The next analysis date/time and

sample ID are displayed.
The fixed time/period analysis is not valid unless the Analysis program on the main
menu has been started. For the setting procedure, see <6.1 g. Program Operation>.

CHAPTER 2 ANALYSIS
j. LIMS Analysis Command Interface (Option)
The LIMS (Laboratory Information Management System) is an information management

system to support analysis and quality control operations through interfacing with an
analytical instrument.
This option provides functions to interface with the LIMS, reads an analysis request file
created by the LIMS and registers a sample ID based on the content of the file.
Analysis Request File
 The ZSX Guidance reads an analysis request file in “C:\EXTLIST”. Set the LIMS
beforehand such that an analysis request file is created in “C:\EXTLIST”.
 Create beforehand a quant application that will be used for an analysis. When it has
a component that requires manual input data, make setting such that input is
possible.
 After reading an analysis request file, make an analysis in the ordinary procedure
using the registered sample ID.
 Format of Analysis Request File
The analysis request file can have any file name and the extension of the file is fixed
with TXT.
The analysis request file may consist of the sample analysis request of more than one
sample. Sample analysis request for one sample is written in one line.
Line change codes are CRLF(0DH 0AH).
Analysis request 1(CRLF)
Analysis request 2(CRLF)
-
-
Analysis request n(CRLF)
 Format of Analysis Request
Sample request for each sample is written in one line and the analysis request consists
of three or more fields depending on number of manual inputs and the fields are
separated by a TAB((HT,09H).
Field 1 HT Field 2 HT --- HT Field m
Consecutive TAB characters between fields are regarded as one separator.

CHAPTER 2 ANALYSIS
 Format of Field
Field Content of field Description

Field 1 Sample position Shows a sample position on the ASC or turret.
Example: A1-A6,B1-B6 .. H1-H6, 1-12
Format: 3 characters or less
Field 2 Application name Application name of quantitative analysis.
The application must be registered in “Common
folder” of application in advance.
Example: NiOre(Bead)
Format: Maximum 16 characters
The last part in 16 characters may be set with space.
Field 3 Sample name This character string consists of sample name
information according to the structure defined in
Sample ID Structure program in ZSX software. The
sample name part can be divided into more than one
items and set one space between the items. The
number of characters of each item should match
with the setting in sample ID structure setting so
that the actual number of characters is smaller than
the number defined in sample ID structure, fill space
in the rest of part.
Example:
Sample ID structure setting:
Sample name : 16 characters, Operator: 16
characters
Sample1234SSSSSSJamesSSSSSSSSSSS
S: Space
One space before operator name is divider of items.
Field 4 Manual input data The first manual input data in numerical value
1 Example: 0.4959 for sample weight
This item is not necessary to set when the
application does not have any manual input.
Field 5 Manual input data The second manual input data in numerical value
2 Example: 9.24 for flux weight
This item is not necessary to set when the
application has less than two manual inputs.
Field Manual input data The value of the N-th manual input data is set.
3+N N

CHAPTER 2 ANALYSIS
 The intensity measurement cannot be used and only the quantitative analysis is
made.
 The measurement is only for center measurement and not for mapping measurement.
 The manual input data are set in the sample ID file following the order of quant
application. If number of manual input set in analysis request is larger than the
number of manual input registered in the quantitative analysis application, the rest
of manual input data are disregarded. If the number of manual input data set in
analysis instruction is smaller than the number of manual inputs registered in the
quantitative analysis application, the software display an error message and any
analysis request cannot be registered to the sample ID file for the file.
When there is only one sample position, set “1”.
A null field cannot be set. When a sample name need not be set (there is no input memo in
the sample ID structure), set a dummy character string such as “dummy” or “abc”.

CHAPTER 2 ANALYSIS
Read Analysis Request File
1. Select [File]  [External Analysis Request...] on the “Sample ID Setting” screen.
2. Select an analysis request file.
3. Click OK .
Sample IDs are registered on the “Sample ID Setting” screen according to the selected
analysis request file.
When sample IDs have been registered normally, the analysis request file is deleted.
If at least one of the analysis commands in the analysis request file is erroneous, no sample
ID will be registered and the analysis request file will not be deleted.
Delete Analysis Request File
1. Select [File]  [Delete External Analysis Request File...] on the “Sample ID Setting”
screen.
2. Select an analysis request file to be deleted.
3. Click OK .
4. Click Yes on the dialog to confirm the deletion.

CHAPTER 3 QUALITATIVE ANALYSIS
3. QUALITATIVE ANALYSIS
3.1 QUALITATIVE ANALYSIS
The analysis method used to determine the presence or absence of elemental

components is called qualitative analysis. In the case of the scanning-type spectrometer,
the crystal and detector are rotated in a coupled manner so as to satisfy Bragg’s formula.
This process measures fluorescent X-rays with various wavelengths generated
simultaneously from the sample. The result of such a measurement is a qualitative
analysis chart, with an abscissa axis of 2-theta angle and an ordinate axis of X-ray
intensity. Qualitative analysis is completed by identifying each spectral line on this
chart. This identification process is performed automatically after each measurement.
The Qualitative Data Handling program performs data processing, such as overlapped
display of more than one measured data.
The semiquantitative analysis, which produces quantitative analysis results for
components detected through the qualitative analysis, is called the ScanQuantX (SQX)
(option). SQX uses qualitative analysis results for element ranges of B to Cm or F to Cm.
The general flow of qualitative analysis is shown below:
Start
Creation of qualitative application
Measurement
Qualitative data handling
Carry out semiquantitative

analysis? Yes
No SQX calculation
End

3.2 CREATION OF QUALITATIVE APPLICATION
It is very useful to carry out a qualitative analysis to know what components are present
in the sample. The semiquantitative analysis program augments the qualitative
analysis, providing approximate quantities of those components. In this system, this
semiquantitative analysis program is called the SQX. To perform qualitative analysis
and semiquantitative analysis, you must create a qualitative application.
Since the application procedure for qualitative analysis is the same as an SQX
application without the setting for the SQX calculation, an example of the creation of an
SQX application is described below. The operational flow to create the application is
shown below:
Start
Use template?
No
Yes
Selection of template Creation of original application
Carry out SQX analysis?

No
Yes
Selection of category Selection of qualitative only
Setting of application name etc.
End
When Qual Application is clicked on the menu, steps are displayed on the flow bar in the
right part of the screen to show the creation procedure.
Each step displayed on the flow bar is described below:
1. To start this procedure, click Qual Application on the menu.

Example of Creation of Qualitative Application
An example of the creation of an SQX application using the template for metals and
alloys is described below. Default conditions will be accepted. When operations for an
application file are complete, it is registered. Check the set contents and change them if
necessary.
1. Click Application File on the flow bar.
2. Select <Create a new application>.

3. Click Next > .
4. Select <Use an application template>.
5. Select the <Metal & Alloy> icon under the “Metal & Alloy” tab.

7. Enter an application file name.

8. Enter a “description of application” if necessary.
9. Select <Common> for the folder.
10.Click Finished .
The folder specified by the user with User Administration in “6.1 h. System Management”
has been selected as the default.

11 When SQX Scattering FP Method (Option) is utilized, check [Estimate

non-measuring component] by clicking. The measuring condition of [Scatter] is
added.
SQX Scattering FP method (Option) has the capability of estimating the extent of influence
by non-measurable elements to measurement element using scattered X-rays.
Consequently, it makes possible to obtain the accurate analysis on elements to be
interested without measuring ultra light elements.
When SQX Scattering FP method is employed, don’t specify the elements ranging from B
to O as measurement elements because the component estimation of these ultra light
elements is done by using scattered X-rays.
12.Click Next .
13.When a sample film is used, make setting for it and then click Next .
14.Select a measuring diameter.

15.Select <No> for “Sample spin”.
16.Select <Vacuum> for “Atmosphere”.
When SQX Scattering FP method is used, only 20 mm can be set for the measuring
diameter under the condition that the sealing (option) is not in use. （Selection of
measurement size, 20mm or 30mm, can be made depending on ship date of ZSX Primus
IV/IVi.）

17.Click Next .
18.Click Next .
19.Select items to be printed in the “Print information” frame.

20.Click Next .
Since a recalculation can be made after measurement by changing calculation conditions

arbitrarily, it is recommended that the default conditions be used for initial SQX
calculations.

a. Application File
Use Another Template
There are two kinds of templates: a group to carry out the SQX calculation and a group
for qualitative analysis alone. A template for qualitative analysis is simply an
application without the SQX calculation. Templates for the SQX calculation are
classified into seven types: the metal & alloy, powder, glass fusion bead, polymer, filter,
film & coating and liquid. For those templates, only the SQX calculation conditions are
different. All other measuring conditions are the same. There is no need to prepare
many applications for SQX analysis because a recalculation can be made after
measurement by changing calculation conditions.

5. Select an objective sample type tab.
6. Select a template icon in the sample type panel.
When SQX software is not attached, only <Qualitative＞ can be used.

Creation Without Template
When creating an application without using a template, select <Create your own
application>.

4. Select <Create your own application>.
Select Existing File
This operation is used to check or change the contents of a previously created

application.

2. Select <Modify an existing application>.
4. Select a sample type folder.
5. Select an objective application file.
6. Click Finished .

Save After Changing Name
When a part of an existing application has been changed, the old contents will be
overwritten if that application is saved under the same name. For comparison with past
data, it is recommended that an application with which measurement was made at least
once be kept without changing its contents.

2. Select a file to be saved under a new name on the “Modify an Existing Application”
screen.
4. Select <Rename and save the application>.
6. Select <Application> for “File Type”.
7. Enter a new application name that is not the same as any existing file name.
Before this operation, an existing application must be loaded.

Register as Template
A created application can be registered as a template. A new application can be created

using the registered template.

2. Select <Rename and save the application>.
4. Select <Template> for “File Type”.
5. Select a sample type folder.
6. Enter a new template name that is not identical to any existing template name.
7. Click Finish .
Delete Application

2. Select <Delete an application>.
4. Double-click a sample type folder.
5. Select an application file to be deleted.

Edit EZ Scan Condition
A qualitative application used for EZ Scan can be edited.

2. Select <Modify an existing application>.
3. Click Next> .
4. Select <EZ Scan> for the sample type.
5. Select a desired EZ Scan application file.
EZ Scan applications are edited from the following nine applications when setting is
made for EZ Scan:
Application Name Element Range Measuring Time Type of Sample

F-U_Solid_E F – Cm Shortest Solid
F-U_Solid_F F – Cm Short Solid
F-U_Solid_N F – Cm Standard Solid
F-U_Solid_S F – Cm Long Solid
B-U_Solid_E B – Cm Shortest Solid
B-U_Solid_F B – Cm Short Solid
B-U_Solid_N B – Cm Standard Solid
B-U_Solid_S B – Cm Long Solid
F-U_Liquid_E F – Cm Shortest Liquid
F-U_Liquid_F F – Cm Short Liquid
F-U_Liquid_N F – Cm Standard Liquid
F-U_Liquid_S F – Cm Long Liquid
Although operational procedures for qualitative applications are the same as those for
ordinary applications, alterations become invalid to the EZ Scan settings at the time of
an analysis such as the measuring diameter, atmosphere, metal/oxide, compound table
and print option and to the contents that are set using EZ Scan in System Parameters.

Outline of template condition for EZ Scan (For ZSX Primus IV/IVi, in case of standard four
crystal composition)
Application Spectrum Filter Slit Crystal Detector Scanning angle
name (deg)
**_Solid_E Heavy Al25 S2 LiF(200) SC 5.000-90.000
**_Liquid_E Heavy(1) Ni400 S2 LiF(200) SC 13.000-19.000
Light(Ca-K) Al25 S4 LiF(200) PC 110.000-147.000
Light(Cl-Al) Be30(opt) S4 PETH/PET PC 62.000-147.000
Light(Mg-F) Be30(opt) S4 RX26 PC 35.000-77.500
**_Solid_F Heavy Al25 S2 LiF(200) SC 5.000-90.000
**_Liquid_F Heavy(1) Ni400 S2 LiF(200) SC 13.000-19.000
Light(Ca-K) Al25 S4 LiF(200) PC 110.000-147.000
Light(Cl-P) Be30(opt) S4 GeH/Ge PC 90.000-144.000
Light(Si-Al) Be30(opt) S4 PETH PC 105.500-147.000
Light(Mg-F) Be30(opt) S4 RX26 PC 35.000-77.230
**_Solid_N Heavy Al25 S2 LiF(200) SC 5.000-90.000
**_Liquid_N Heavy(1) Ni400 S2 LiF(200) SC 13.000-19.000
**_Solid_S Ca-KA Al25 S4 LiF(200) PC 110.000-116.000
**_Liquid_S K -KA Al25 S4 LiF(200) PC 133.000-140.000
Cl-KA Be30(opt) S2 GeH/Ge PC 90.000-96.000
S -KA Be30(opt) S4 GeH/Ge PC 107.000-114.000
P -KA Be30(opt) S4 GeH/Ge PC 138.000-144.000
Si-KA Be30(opt) S4 PETH/PET PC 106.010-112.010
Al-KA Be30(opt) S4 PETH/PET PC 138.990-147.990
Mg-KA Be30(opt) S4 RX26 PC 35.000-41.000
Na-KA Be30(opt) S4 RX26 PC 43.000-49.000
F -KA Be30(opt) S4 RX26 PC 70.000-77.000
The “Light” condition which straddles over numbers of light elements is the exclusive
measuring condition for ZSX Primus IV/IVi. (This is the function for ZSX Primus IV/IVi only,
and applicable to the equipment shipped newly.)
If any element from B to O cannot be measured by reason of the constitution of the

spectroscopic crystals installed in the spectrometer, applications with the element range of
B – U cannot be used.
Above-mentioned applications for EZ Scan are used for both “EZ Analysis” and “Analysis”
program. For contents to be set at the time of an analysis, such as the sample type, see
“2.2 EZ ANALYSIS” and “2.3 b. EZ Scan”.
When EZ Scan based on the film & coating model is performed, long wavelength X-rays of
heavy element (L line, M line) become detectable. (This is the function for ZSX Primus
IV/IVi only, and applicable to the equipment shipped newly.)

Creation of Application Folder
When creating an application, an application folder can be created on the screen to enter
an application name. Although the <Common> folder is ordinarily used, another folder
can be specified. An application folder is created on the “Application Name Input” screen,
which appears when creating a new application.
1. Click Browse... on the right of the “Folder” field.

2. Click a folder under which to create a new folder on the “Select Folder” screen.
3. Enter a folder name to be created.
4. Click OK .
5. Click OK .
An application folder can be created in a subfolder of Anlcond, forming multi-layer

subfolders. This folder can be used in common with quantitative applications.
An application folder is created also when a new folder is specified for an analysis condition
file in User Administration in <6.1 h. System Management>. The procedure described here
is used to create an application folder independent of users.

b. Selection of Qualitative Analysis Range
Set Qualitative Analysis Range
For a single component in the light element range, setting can be made by clicking an
element symbol.
For a component in the heavy element range in the case of the full range qualitative
analysis, setting can be made by clicking Ti-U .
Elements in the heavy element range (Ti to U) can be measured with one crystal and that
measurement is called the full range qualitative analysis. It is displayed as “Heavy” or “Hv”.
Delete Qualitative Analysis Range
1. Select a component to be deleted from the ones displayed on the left side of the
screen.
2. Right-click the mouse to display a pop-up menu.
3. Click Delete .
To delete all qualitative analysis ranges, click Delete all. In that case, the fixed angle
analysis conditions are also deleted.

Add Fixed Angle Analysis
This function is effective only when the SQX software option is attached.
When there is a component of special importance, measure it by adding a fixed angle
analysis. One can obtain better statistical data on X-ray intensities using fixed angle
measurements. Although a long measuring time can also be set in the qualitative
measurement, it is virtually impossible because the total measuring time becomes very
long. The fixed angle analysis measures three positions, a peak position and two
background positions. Because a longer measuring time for an individual element can be
set compared to the qualitative analysis, X-ray intensities with smaller statistical errors
are obtained.
1. Click Fixed angle elem. in the “Fixed angle analysis” frame on the “Select Element
Range” screen.
2. Select an element name for a fixed angle analysis on the periodic table.
3. When you selected the element name for the full range qualitative analysis (Heavy),
select an individual line name.
4. Click Next .
The fixed angle measurement cannot be set for a component for which the qualitative
analysis is not made. Setting cannot be made for Ti to U unless the full range qualitative
analysis (Heavy) is carried out.
Delete Fixed Angle Analysis
1. Click Fixed angle elem. in the “Fixed angle analysis” frame on the “Select Element
Range” screen.
2. Select a component to be deleted from the elements displayed in light blue on the
periodic table.

Add Overlap Line Detection
This function is effective only when the SQX software option is attached.
The overlap line detection is a function to make a quantitative analysis only from a
2-theta scan measurement result without making a fixed angle measurement, assuming
that a sample surely contains an element regardless of an automatic identification
result. The overlap line detection should be set when an element of interest may not be
automatically identified because of the overlap of the characteristic X-rays of another
component.
1. Click Overlapped elem. in the “Fixed angle analysis” frame on the “Select Element
Range” screen.
2. On the periodic table, select the element name of a component for which to carry out
the overlap line detection.
3. When you selected the element name for the full range qualitative analysis (Heavy),
select an individual line name.
4. Click Next .
The overlap line detection can also be added at the time of the SQX calculation. See
“Change Measured Element Line” in “3.3.2 a. Detailed Description of SQX Calculation”.
Delete Overlap Line Detection
1. Click Overlapped elem. in the “Fixed angle analysis” frame on the “Select Element
Range” screen.
2. Select a component to be deleted from the element names displayed in orange on the
periodic table.
To delete all fixed angle measurement and overlap line detection conditions, click Delete
all .

c. Sample Preparation Information
Sample information to be set varies depending on the sample type of an application.

Setting items are described below for each sample type:
Sample Type - Metal & Alloy
1. When a measurement is to be made using “Sample film”, set a sample film.
Absorption by the sample film is corrected at the time of a quantification calculation.
n case of ZSX Primus IV / IVi, the sample film which has the suffix (N) at the end of film
name is made X-ray absorption correction by the film itself and the impurity correction in the
film at a same time, therefore, the impurity setting for the film which used to be done per
measurement diameter is not needed. Refer to the instruction manual “PROCEDURE FOR
ADDITION OF SAMPLE FILM INFORMATION ” regarding details of sample film. (This is
the function of ZSX Primus IV/IVi only, and applicable to the equipment shipped newly.)
2. When Show option is clicked, detailed set contents are displayed in the lower part of
the screen.

3. Set sample preparation information.
The option information setting is used to set items that are not ordinarily used and to display
memoranda and comments on analysis results.

SampleType - Powder, Polymer
1. When binder is to be used, set information on it. Select <Used> and a binder
component and set sample weight and binder weight.
2. When a sample film is to be used, set information on it. This setting is used to correct
the absorption of X-rays by the sample film.
3. When a sample has been pulverized, set information on a container. This setting is
used to display a comment on an analyzed result.
4. When a sample thickness affects analyzed values, make setting for “Sample weight
thickness”. When <Input for each sample> is selected, a sample size is set for each
sample at the time of an analysis.
When binder is set, analyzed values are calculated with the absorption of X-rays by the
binder taken into consideration.
Make setting for “Sample weight thickness” when fluorescent X-rays with short
wavelengths are to be measured and X-ray intensities are to affect sample thicknesses.
When a weight thickness varies for each sample, select <Input for each sample>.
In case of ZSX Primus IV / IVi, the sample film which has the suffix (N) at the end of film
ADDITION OF SAMPLE FILM INFORMATION ” regarding details of sample film. (This is

Sample Type - Fusion Bead
1. Enter the kind and weight of flux and sample weight in “Sample and flux”. Analyzed
values are calculated using an obtained dilution ratio.
2. When a sample has been pulverized, set information on a container. This setting is
used to display a comment on an analyzed result.
3. Set information on oxidizer, which is added when producing a fusion bead, and make
setting for “Non-wetting”. The information on the oxidizer is used to calculate
analyzed values. “Non-wetting” is used to display a comment on an analyzed result.
4. Set a bead diameter when you want to estimate the effect of a thickness on analyzed
results.

Sample Type - Filter
1. Select a filter type. When “Other” is selected, enter a filter material, filter weight and
effective diameter.
2. Select a filter material.
3. Enter the weight of the instillation part of a filter.
4. Enter a sampling quantity for instillation.
5. Select an output unit in liquid for final analyzed results from <mass%> and <ppm>.
6. When a sample film is to be used, select <Used> and a sample film.
the filter type, a material, weight and effective diameter are automatically displayed. When
using the UltraCarry or UltraCarryLight, set 30mm for the measuring diameter. When using
the MicroCarry, set 20mm for the measuring diameter.
C6H10O5 (cellulose) is set for the filter material of the UltraCarry, UltraCarryLight and
MicroCarry. If a material is not displayed when setting the <Other> filter, enter and register
a compound name using “Special compound” in the “Compound Table” program.
The filter weight means the weight of the part of a filter where instilled liquid diffuses. In the
case of light elements, because of the ununiformity of diffusion, analyzed results can be
improved by analyzing liquid with known concentrations using the SQX analysis and
obtaining weight that leads to accurate analyzed values.
Since detection sensitivity for fluorescent X-rays is not uniform on a filter, a value slightly
different from the actual diameter of the instillation part of a filter must be used as the
effective diameter to obtain accurate analyzed values. When using the <Other> filter,
analyze liquid with known concentrations using the SQX analysis, obtain an effective
diameter that leads to accurate analyzed values, and set that diameter.
An element that is vaporized by drying after instillation cannot be analyzed.

Since filters such as the UltraCarry, UltraCarryLight and MicroCarry consist of C, O and H,
C and O cannot be analyzed.
There may be an element that is difficult to analyze depending on an impurity in a filter

material and the material of a hollow cup used as a support. It is recommended that
checking be made before making an analysis.
When setting <Other> for the filter type, obtain beforehand suitable weight and sampling
diameter using various standard liquids, and set them.
When a gel sample such as grease is to be analyzed using the SQX analysis (FP method)
after sample processing using the filter paper method, use the Film & Coating for the
sample model.

SampleType - Liquid
1. When diluent is to be used, set information on it. Select <Used> and a diluent
component and set sample weight and diluent weight.
2. When a sample film is to be used, set information on it. This setting is used to correct
the absorption of X-rays by the sample film.
3. When a sample thickness affects analyzed values, make setting for “Sample weight
thickness”. When <Input for each sample> is selected, a sample size is set for each
sample at the time of an analysis.
When diluent is set, analyzed values are calculated with the absorption of X-rays by the
diluent taken into consideration.
Make setting for “Sample weight thickness” when fluorescent X-rays with short
wavelengths are to be measured and X-ray intensities are to affect sample thicknesses.
When a weight thickness varies for each sample, select <Input for each sample>.
measurement diameter is not needed. Refer to the instruction manual “Sample Film
Information Registration” regarding details of sample film. (This is the function of ZSX
Primus IV/IVi only, and applicable to the equipment shipped newly.)

Sample Type - Film & Coating
1. When a measurement is made using a sample film, set information on it. The
correction of absorption by a sample film is made at the time of the quantitative
calculation.
Sample Type - Qualitative
1. Enter a memo if necessary.

d. Setting of Analysis Parameters
Measuring Condition
Set a measuring diameter, sample spin and atmosphere.

“Sealing (option)” can be selected only when the measuring diameter is 30mm. When the
atmosphere is <Helium/Vacuum>, the sealing is unconditionally set to “IN”. The sealing
can be selected also when the atmosphere is <Vacuum>.
Select a measuring diameter according to the sample mask diameter of a sample holder.
When the sample spin is set, a sample rotates during a measurement. In the case of a
sample that consists of a single crystal or has segregation, select <No> for the sample spin
because a sample rotates during a 2-theta scan and therefore an abnormal peak may
appear. Liquid samples should not be rotated.
When the sealing (option) is in the “IN“ position because the atmosphere is Helium/Vacuum
or when the attenuator is used, only 30mm can be set for the measuring diameter.
When SQX scattering FP method is used and the partition is not used, only 30mm and
20mm of measurement diameter is selectable. (This function is only for ZSX Primus IV/IVi
and applicable only for the equipment shipped newly.)
In the case of the helium condition, because the atmosphere absorbs X-rays, components
that have atomic numbers smaller than 9-fluorine cannot be measured.

In the <Helium/Vacuum> mode, the sample chamber is set in the helium atmosphere and
the spectroscopic chamber in a vacuum.
For the qualitative application, it is possible to set individually the selection of APC ON/OFF,
evacuation speed Slow/Fast, vacuum degree High/Intermediate/Low of inlet sample
chamber. (This function is only for ZSX Primus IV/IVi and applicable only for the equipment
shipped newly.)
Sample Information
This information cannot be set for an application of the sample type “Qualitative”.
Component Type
The metal, oxide or compound table can be used for the conversion method.
The compound table can be created using the utility menu. For details, see “6.1 b.
Compound Table”.
 Metal
As in the case of a metal sample, a quantification calculation is made in the SQX
calculation assuming that a simple substance (for example, Fe or Si) exists in a sample.
 Oxide
A quantification calculation is made in the SQX calculation assuming that a standard
oxide such as Fe2O3 or SiO2 exists in a sample. Select this conversion for a pressed
sample or a glass fusion bead sample made of oxide powder.
 Compound Table
A quantification calculation is made in the SQX calculation assuming that each element
exists in a sample in a form defined in the compound table prepared by a user.
For example, in case of sample which is mixture of components without oxygen like metal
or sulfide and oxide like SiO2, element or compound can be set in each element of
chemical compound list beforehand.

Balance
This item is not displayed when the sample type is “Filter”, “Film & Coating” or
“Qualitative”.
This item is generally set when a component with the maximum concentration is to be
defined as the balance component for the SQX calculation.
An element or a compound can be set as the balance component. However, in the case of
a compound, it must be registered beforehand as a compound.
When a check mark is placed for “Estimate non-measuring component” on “Select
Element Range”, <Estimate> is set for the balance.
1. Set an element name or a compound name for “Balance”.
The balance component is treated in the concentration calculation as the residual, which is
100% minus the total of the other components.

Film Setting
This item can be set only when the sample type is “Film & Coating”.
Set this detailed information when analyzing a coating layer on a thin film or a
substrate.
1. Click Setting .

2. Set each item.
3. When there is a substrate, select <Yes> for “Substrate”, click the Setting... button and
set the constitution of the substrate.
4. Click OK .
Regarding substrate setting, fixed values can be set for base substrate and number of
layers under the top layer for analysis, and the analysis of the top layer becomes possible.
(This is the function of ZSX Primus IV/IVi only)
The SQX result of multi layers under the analyzed layer (top layer) including substrate can
be imported. By substrate settings with fixed values for the base substrate and the layers
below the top layer for analysis, the analysis of the top layer makes possible. (This is the
function of ZSX Primus IV/IVi only, and applicable to the equipment shipped newly.)
1. Click Import… .

2. As data file selection screen is indicated, select SQX result file for under layers
of the analyzed layer and click OK to close the substrate setting screen.

Fixed/Input Components
When there is a fixed value or a component value to be entered manually at the time of
an analysis, set information in the “Fixed/Input Components” dialog that appears when
the Setting... button is clicked.
When <Fixed> is set for “Type”, set information to enter an analyzed value manually.
Calculation Setting
Selection of Use of Matching Library (Option)
When a matching library is to be used for the SQX calculation, make the following
setting:
1. Select <Search> or <Specify>.

2. When <Specify> is selected, select a registered matching library sample.
For the matching library, see “3.4 SENSITIVITY LIBRARY (OPTION)”.

Correction Setting
1. Click Setting... .

2. When the impurity correction is to be made, place a check mark.
3. Set impurity data and a correction method.
When the sample film setting has been made, the impurity data list displays the
impurity data of the sample film type.
When the sample film setting has not been made, the impurity data list displays
the impurity data of the ordinary type.
4. When the helium atmosphere correction is to be made, place a check mark.
5. Click OK .
Setting contents for the sample film in the sample preparation information dialog are
displayed for the sample film absorption correction, and a correction is made for the
absorption of fluorescent X-rays by the sample film.
ADDITION OF SAMPLE FILM INFORMATION” regarding details of sample film. (This is
To make the impurity correction, impurity data must be registered beforehand.

For the procedure to register impurity data, see “3.3.2 b. Impurity Data”.
Helium atmosphere correction is indicated when the atmosphere of <Parameters> is set to

the Helium.

e. Setting of Measuring Conditions
Change Measuring Order
Measurement is generally made in order of wavelength (from the shortest to the longest)
to carry out an automatic identification analysis and to shorten the analysis time. The
measuring order from the shortest wavelength has been set as the default. When you
want to know the qualitative analysis result of a certain component first, you can change
the measuring order in a selected measuring range.
1. Select a component on the list.

2. Click ▲ or ▼ in the “Measuring order” frame.
Because a fixed angle analysis is made immediately after the qualitative analysis of that
component, the measuring order of fixed angle analyses components cannot be changed.
To reset measurement in order of wavelength (from the shortest to the longest), click
Wavelength.
It is possible to change measuring conditions in a lump.

Tube wattage: For all measuring conditions keeping tube voltages (kV) related library
conditions unchanged, tube current (mA) is changed based on the designated wattage
(1.5kW/2.4kW/3kW).
Protection filter: Primary X-ray filters equipped are arranged for the measurement line
automatically to prioritize the protection of X-ray tube window. In case of
specifications without Be30 filter, no filter is set to lighter element range
than Cl-Ka.
Time : Continuous scan speeds are changed at the time. The change can be made
easily while checking total measuring time.
newly.)
Measuring Condition
A measuring condition used to create a library is copied and used, so a measuring

condition cannot be changed directly when executing an SQX analysis. After a new
measuring condition is created using a sensitivity library and sensitivity values are
registered, it can be selected here.
For qualitative analysis only, an original measuring condition can be created. A
measuring condition of a library can also be used.

Change Spectral Line
The measuring condition of a spectral line to be selected must have been created
beforehand using a library.

2. Click Property .
3. Select a spectral line in the “Element line” frame.
4. Click OK .
The library measuring conditions are displayed for the items that cannot be changed such
as tube voltage. When <Qualitative> is selected for application type, these condition can
be changed.
Measurement Using Different Library Condition
For example, when you want to make an SQX calculation using a special spectral line,
you can select a library. For example, when it is preferable from the viewpoint of
analysis precision that the K line be changed to the L line in the case of samples thinner
than the bulk thickness, make the selection here. However, the measuring condition of a
spectral line must have been created beforehand using a library.

3. Select a library in the “Sensitivity library” frame.
4. Click OK .

Lower X-Ray Intensities
To carry out measurement when X-ray intensities exceed the upper limit of counting
linearity, use the attenuator or reduce the current. The pre-measurement function,
which will be described later, can also be used to set the attenuator or change the
current automatically for measurement. The upper limit of X-ray intensities for the
qualitative analysis is in general 1000 kcps for both the SC and the PC.
Change Scan Method
The step scan or the continuous scan can be set for the scan method. In general, the step
scan is used for the qualitative analysis. A scan speed that is not available in the step
scan can be set in the continuous scan, which is effective especially for a high-speed
scan.
1. Select a component to change a scan method.

3. Select <Step scan> or <Continuous scan> for “Scan method” in the “2-theta scanning
condition” frame.
4. Click OK .

Change Scan Range
A scan range can be widened. Care must be taken when narrowing the range because
the SQX calculation may be affected.
1. Select a component to change a scan range.

3. Change the start angle in the “2-theta scanning condition” frame.
4. Change the end angle in the “2-theta scanning condition” frame.
5. Click OK .
A range of 5 to 118 degrees can be measured for the SC and a range of 13 to 148 degrees
for the PC.
In the application by SQX Scatter FP method (Option), the 2-theta angle of Start and End in
“2 theta scanning condition” of <Scatter> cannot be changed. (This is limited to the
specifications of which scattering sensitivity library contains LiF(220) in it.)
Change Measuring Time
In general, when changing the measuring time, the time for each step is changed.
Because the time for each step is limited, the step size itself may be changed. In that
case, special care must be taken because it may affect the SQX calculation. In the case of
the continuous scan, the speed (degrees per minute) is changed.
1. Select a component to change a measuring time.

3. Set a measuring time for each step at “Time” or “Speed” in the “2-theta scanning
condition” frame.
4. Click OK .

Change Preparatory Measurement Method
To make measurement without counting loss, sensitivity can be automatically adjusted

by making a preparatory measurement. In that case, a full-scale value can be selected.
By selecting the preparatory measurement, however, the measuring time becomes
longer.
Intensity
Adjustment Description
Method
Pre-measurement is not made, so measures against counting
No
loss are not taken.
Pre-measurement is made at the peak angle set in the 2-theta
Pre-measurement
scan condition. Whether counting loss occurs is checked at the
at peak
peak position.
Pre-measurement is made in the angle range set with the start
and end angles in the 2-theta scan condition. If there is a peak
Pre-scan
that causes counting loss in that range, the system lowers the
sensitivity and makes measurement again.
The system makes main measurement without making
pre-measurement, automatically distinguishes the range where
High speed counting loss occurred directly from the main measurement
（ZSX Primus IV) result. When that range is detected, sensibility is automatically
lowered and measurement is made again. Use this method when
the throughput in the qualitative analysis is needed.
1. Select a component to change a pre-measure method.

3. Select <No>, <by pre-measurement at peak>, <by pre-scan> or <High speed> for
“Intensity adjustment”.
4. Click OK .
To adjust the sensitivity automatically, the attenuator is used or the tube current is reduced,
depending on the system configuration.

Change Measuring Conditions for Fixed Angle Analysis
Because the fixed angle analysis uses the same optical system as the qualitative
analysis for measurement, fixed angle measurement conditions are the same as
qualitative analysis conditions. In addition, since the fixed angle analysis is made
immediately after the qualitative analysis, background positions are automatically set.
Therefore, only the peak position and measuring time can be set as measuring
conditions exclusive for the fixed angle analysis.
1. Select a fixed angle component that has a FA mark as its spectral line name.
3. Select an angle for measurement for “Peak angle”.
4. Set measuring times in the peak and background angle positions for “Time”.
5. Click OK .
A peak angle in the qualitative analysis is obtained automatically. Therefore, if spectral lines
overlap, the peak angle shifts. Taking that into consideration, in the fixed angle analysis
X-rays are counted in the designated peak position.
Background intensities are measured in each position on both sides of an objective peak.

To enhance measurement accuracy, the designated peak and BG angles of fixed angle
measuring condition can be changed. Release the check box of <auto>, then input peak
angle and BG angle. (This function is applied depending on ZSX software version.)

f. Output Condition
Set Print Information
Items to be printed just after measurement with the SQX or qualitative application are
selected. Selection can be made for the chart output, peak list, SQX calculation results
(option) and material judgment (option). All items can be printed for an SQX analysis
application. For a qualitative analysis application, selection can be made only for the
chart output and peak list.
Print
Description
Information
A qualitative analysis chart measured using the designated
Chart Output
measuring conditions is printed.
Peak List A list of detected peaks is printed.
Semi quantitative analysis values normalized so that the
SQX Result total of the concentrations of detected components will be
100% are printed.
Based on an SQX result, a material judgment result
Material
obtained from the condition set in the material standard
Judgment
table is printed.
1. Select items to be printed in the “Print information” frame.

2. Click Next .
 SQX Application
 Qualitative Application

Make Setting for Data Processing
In the qualitative data processing, setting is made for the element/oxide conversion, the
identification elements, the smoothing and the peak detection sensitivity. Those are
described below:
 Element/Oxide Conversion
Setting is made to convert a component constituting a qualitative application from an

element to an oxide and vice versa. A component type that has been set in “3.2 d.
Setting of Analysis Parameters” is used to make a quantification calculation assuming
that the specified component type exists in a sample. However, a conversion that is set
here is used to carry out the element/oxide conversion after the FP quantification
calculation for result output. When setting is not made here, results are output using
the component type used for the quantification calculation.
1. Place a check mark for the “Element/Oxide conv.” check box, and click Setting .
2. Click an element to be converted on the periodic table. The setting is switched to an
element or to an oxide each time an element is clicked.
3. Click OK .
For example, trace heavy elements in rock generally exist as oxides in a sample. To output
them as the concentrations of elements, specify the conversion of these trace heavy
elements into elements.

 Identification Elements
The setting of identification elements is used to specify whether an element is selected

for or excluded from identification.
For example, when peaks of Ka and Kb appear clearly and their intensity ratio is within
an allowable range, even an “Excepted” element is identified. Therefore, the difference
between “Selected” elements and other elements is that a “Selected” element is
identified if some peak can correspond to that element even when only a single peak
such as Ka appears.
When elements that may be identified erroneously are set to “Excepted”, the number of
identification errors can be reduced.
Setting of Identification Elements
1. Click Identification Elements.. .

2. Select <Select> or <Except> with the mouse on the periodic table. <Select> and
<Except> are switched alternately when clicked with the mouse.
3. Click OK .
The “Unanalyzable” elements cannot be selected because these elements generally

cannot be analyzed using X-rays.

 Smoothing
This is the function of smoothing processing for a qualitative spectrum. As the number of
points used for smoothing becomes greater, the chart becomes smoother. However, if the
number of points is too large, the spectrum will be deformed. Because smoothing can
also be carried out after measurement, it is recommended that the default value be used.
There must be an odd number of points used for smoothing.
 Peak Detection Sensitivity
The peak detection sensitivity is the value to determine the sharpness of peak detection
in the automatic peak search. To detect a peak, the threshold value is used to judge
whether a peak on the spectrum is a real peak or a fluctuation of X-ray intensities. The
peak detection sensitivity coefficient is the indicator to change that threshold and its
standard value is 1.0. As the value becomes larger than 1.0 (the sensitivity becomes
higher), smaller peaks can be detected. As the value becomes smaller (the sensitivity
becomes lower), only peaks with higher peak/background ratios are detected. The range
allowed for the peak detection sensitivity is 0.3 to 2.0.
1. Set the number of smoothing points using [Calculation] [Smoothing] in the
Qualitative Data Handling program.
2. Set a peak detection sensitivity coefficient using [Calculation] [Peak Search] in
the Qualitative Data Handling program.
Output of Detection Limits for Undetected Elements in Fixed Angle Measurement
Elements that were not detected in the fixed angle measurement can be added to a
group of output elements.
 1. Select <Output detection limit for undetected element (fixed angle)>.

g. Printing of Application Information
Application information and measuring conditions can be printed.

2. Select <Print application information>.
4. Select a folder on the “Select an Application to Print” screen.
5. Double-click the folder of an objective type on the tree display.
6. Select an objective application icon.
8. If necessary, select <Application information> in the “Print item” frame.
9. If necessary, select <Measuring condition> in the “Print item” frame.

h. Output of Application Information
It is possible to output application information and measuring conditions as a file in the

Excel book format.

2. Select <Output application information to Excel book>.
4. Select a folder on the “Select an Application to Output” screen.
8. Click Browse on the “File Name Input” screen and specify a folder in which to save a
file.
9. Enter a file name.
10.To open an Excel file after it is created, place a check mark at “open an output file”.
Excel is a registered trademark of Microsoft Corporation of the United States.

3.3 QUAL RESULT
The Qual Result program reprocesses qualitative analysis and SQX analysis results and
consists of the qualitative data handling process and SQX calculation.
Qualitative Data Handling Process:

The operation to attach markers (element names and X-ray line names) to a spectrum
obtained from a qualitative analysis is called the qualitative data handling. Basically,
peaks are detected and markers are attached automatically after a qualitative analysis.
To execute more detailed data processing, use this program. Using a result of this
program, semi quantitative values can be calculated using an SQX calculation.
By overlaying two or more measured data items, they can be compared. That function
can be used for comparison with a blank sample and comparison between normal parts
and abnormal parts.
SQX Calculation:
In the SQX calculation, though a calculated result is automatically displayed after
measurement, a recalculation can be made after detailed setting. For example, a
recalculation can be made after adding a new peak using the Qualitative Data Handling
program. And a calculation condition can be changed. For example, the metal conversion
can be changed to the oxide conversion. The standard unit of concentrations used here is
mass%, but this can also be changed.
When an analyzed peak overlaps with another interfering line, corrected intensities are
calculated using overlap correction coefficients that have been registered beforehand
and then analyzed values are calculated.
In the SQX calculation, a collection of spectrometer sensitivity values called a common
library is used for a quantification calculation. Though the library registered on
shipping is generally used, a calculation can also be made using a matching library. For
further details, see “3.4 SENSITIVITY LIBRARY”.
When the logon user (or the group to whom he/she belongs) does not have “Change
authority of Analysis Result”, it is impossible to save a changed result. When another user’s
analyzed result folder without “Permit changing by other users” is displayed, it is impossible
to save a changed result. In those cases, [Read Only] is displayed in the title bar.

3.3.1 QUALITATIVE DATA HANDLING
1. Click Data Processing on the menu.

2. Click [Qual Result].
Concept of Qualitative Analysis Result File
A measured result file consists of charts obtained with the measuring conditions of two
or more components. In the example shown below, a file consists of a full range
qualitative analysis result of heavy elements of Ti to U and individual qualitative
analysis results of light elements such as Ca and K.
An SQX calculation is made after qualitative data handling is complete for all measured
results.
Qualitative Analysis Result File
Heavy Ca K
2 Angle
In the measuring range of heavy elements, one crystal covers an element range of Ti to
Cm(U). That is possible because wavelengths of components are adjacent and the
resolution of the crystal is high.
In the range of light elements, unlike the range of heavy elements described above,
because wavelengths of components are dispersed and the resolution of the crystal is low,
the entire wavelength range cannot be measured at a time. The individual qualitative
analysis is therefore used.
when EZ Scan based on the film & coating model is performed, long wavelength
X-rays of heavy element (L line, M line) become detectable. (This is the function for
ZSX Primus IV/IVi only, and applicable to the equipment shipped newly.)

Procedure for Qualitative Data Handling
Select first a measured result file for an identification analysis. In the ZSX Guidance,
two or more measuring condition graphs can be displayed simultaneously. Two or more
files can be opened simultaneously and overlaid as reference data. In that case, only one
file is an object of processing and the other files are not changed. The ordinary procedure
is to terminate the data handling of one file, proceed to the next file and then finally
compare the data items by overlaying them.
Start
Selection of qualitative file
Selection of measuring condition
Identification analysis
All measuring conditions

No complete?
Yes
All qualitative files complete?

No
Yes
End
Be sure to save processed data.

Procedure for Identification Analysis
The procedure for peak identification in the qualitative data handling is shown below.
According to this procedure, all peaks on the spectral chart are identified. In general, the
results of heavy elements are identified first. Heavy elements generate X-rays with long
wavelengths from a sample as well as spectral lines ordinarily used for analyses.
Therefore, in an analysis of light elements, it is effective to make an identification
analysis using the analyzed results of the heavy elements.
Start
Identification of peaks from X-ray tube
Identification of pair peaks
Identification of highest peak
Other peaks left?

Yes
No
Other results left?

Yes
No
End
Peaks from the X-ray tube include Thomson scattering rays such as the K, L and M lines,
Compton scattering rays and their higher-order rays.
Pair peaks mean peaks in pairs such as the K and K1 lines and the L and L1 lines.

Open Qualitative Chart
A file of qualitative analysis results is opened to display a chart of each measured result.
On the displayed chart, data processing items such as the identification analysis and the
net intensity update can be executed.
Open Target File
1. Click Browse... at the right end of the target files.

2. Select a target file.
3. Click OK .
4. Select the <Spectrum> tab.
5. Select a spectrum name to be displayed.
6. Click View .
A measurement result file saved in the selected folder can also be selected on the
dropdown list on the left of Browse... .
When the program is started, the “Target File Selection” screen appears.

Open Reference File

2. Click Add in the lower part of the screen.
3. Place check marks in the check boxes of reference files to be displayed.
4. Click OK .
5. Click the “Conditions” tab.
6. Select spectral names to be displayed in the measuring condition display area.
7. Click Open .
It is possible to select up to 11 reference files simultaneously.

Delete Reference File

2. Select a file to be deleted by clicking it in the lower part of the screen.
Switch Reference File and Target File

2. Select an objective reference file by clicking it in the lower part of the screen.
3. Click Target . The target file is switched to a reference file, and the reference file is
switched to the target file.

a. Marker Setting
A combination of an element name and an X-ray line name is called a marker. A function
to attach a marker to an identified peak is called a marker setting. Basically, a marker
setting is carried out automatically after a qualitative analysis is complete. But in some
cases editing operations are necessary to identify an unknown peak, to delete an
unnecessary peak, and so on. Using this marker setting function, you can check and
modify automatically identified peaks.

Attach Marker Using Element Name
To check an attached marker or to check an element identified with the 2-theta search,
follow the procedure described below. For example, when your system has the Rh tube,
scattered rays of the characteristic X-rays of the target material always enter the
detector. In that case, designate Rh as the element name and check its marker position.
1. Select [Marker] [Element Search...].

2. Select an element on the element list.
3. When a straight line appeared in that angle position on the chart, check the peak.
4. Select a line name to be added.
5. Click Add .
6. If necessary, repeat steps 2 to 5.
7. Click Close .
X-ray lines that cannot be detected with the optical system used in the measuring condition
are eliminated from objects of searching.
When “All Lines” is selected for “Level”, minor line names are also displayed as well as
major line names.
“Relative int.” represents the relative intensities of lines in the same series. For example,
KA 150 in the K line corresponds to LA 100 in the L line.
The scale can be changed with the marker editing dialog displayed.

Attach Marker Using 2-Theta Angle
When there is a peak without a marker on the chart, you can attach a marker using the
peak angle. For example, let’s assume that there is a peak without a marker near a
2-theta angle of 57.5 degrees with the measuring condition “Heavy”. You can search for a
marker from that 2-theta angle and identify the peak.
1. Click the tool button .

2. Click a peak angle for searching in the chart.
3. Select [Marker] [2-theta Search...].
4. Click Search .
5. If a suitable candidate is not displayed, change the search level.
7. Select a candidate near the designated 2-theta angle from the elements displayed as
a search result.
8. Click Add .
9. Click Close .
When “All Lines” is selected for “Level”, minor lines are displayed as well as major lines.
When “Higher orders” is checked, the higher-order lines of the designated line are also
retrieved.
When <Identified elements> is selected, only the lines of the elements identified in this file
are displayed. This function can be used to retrieve the higher-order lines of heavy
elements and lines with long wavelengths in the light element range.
The scale can be changed with the marker editing dialog displayed.

Delete Marker
Markers that were attached erroneously and unnecessary markers can be deleted.
1. Select [Marker] [Delete Marker...].

2. Select a line to be deleted.
4. Click Close .
More than one line can be selected.

b. Data Processing
Procedures for data processing such as the background fitting and the peak
deconvolution are described below. Although X-ray intensity calculation has been made
automatically after a qualitative analysis, operations for an SQX calculation are carried
out here. The purpose of these procedures is basically to update net intensities.
Background Fitting
To make a quantitative analysis, background intensities must be subtracted. Though the

background subtraction is carried out automatically after a qualitative analysis, a
recalculation can be made. After background fitting, net intensities necessary for an
SQX calculation can be updated. The two modes available to subtract background
intensities are fitting of the entire measured range and using a function for a designated
range.
Calculate Background for Entire Range
This method calculates a background for the entire 2-theta angle range measured with
the measuring condition, and uses the calculated background to subtract the intensity of
the continuous X-rays.
1. Select [Processing] [Background Fitting] [Entire Fitting...].

2. Click OK .
3. Select an element to update a net intensity.
4. Click OK .
Calculated background intensities can be subtracted from the original spectrum. See the
“Subtract” menu in “Calculation”.

Calculate Background for Designated Range
Background intensities of a designated range are subtracted. The point designation and
the range designation can be used. A straight line is generally used for fitting. But when
the objective peak overlaps with another peak or when the background is oblique,
another function is used. For the selection of background processing, see “4.3
QUANTITATIVE ANALYSIS TECHNIQUES”.

Point Designation

2. Click 2 to16 points on both sides of an objective peak in the chart.
3. Select [Processing] [Background Fitting] [Function Fitting...].

4. The designated 2-theta angles are displayed. Modify them if necessary.
5. Select a fitting function.
6. Click OK .
8. Click OK .

Range Designation

2. Drag the left side of an objective peak to designate a range.
3. Drag the right side of an objective peak to designate a range.

4. Select [Processing] [Background Fitting] [Function Fitting...].
5. The designated 2-theta angle ranges are displayed. Modify them if necessary.
7. Click OK .
9. Click OK .

Entire Range Background Subtraction
After entire range background fitting, that background is subtracted. This function is
valid only just after a background calculation.
1. Execute entire range background fitting.

2. Select [Calculation] [Subtract...].
3. Click OK .
Peak Deconvolution
When an objective peak overlaps with a peak of another element, it may be necessary to
deconvolution the two peaks. The function deconvolution and the standard profile
deconvolution can be used for peak deconvolution. The function deconvolution separates
a waveform regarding it as a single shape. That is, a calculation is made regarding a
peak width and the shape of a peak foot as constant. On the other hand, the standard
profile deconvolution separates a peak using a spectrum (standard profile) without
overlap that has been extracted beforehand. The standard profile deconvolution can
therefore carry out separation more accurately taking each peak shape into
consideration.

Execute Function Deconvolution

2. Designate a range including objective overlapping peaks in the chart by dragging the
mouse.
3. Select [Processing] [Peak Deconvolution] [Function...].

4. The designated 2-theta angle range is displayed. Modify it if necessary.
5. Select a background subtraction method at “BG calculation”.

6. Click OK .
8. Click OK .

Standard Profile Deconvolution

2. Designate a range including objective overlapping peaks by dragging the mouse.
3. Select [Processing] [Peak Deconvolution] [Standard Profile...].

5. Select a background subtraction method at “BG calculation”.
6. Select Data Search .
7. Select a standard profile used for a calculation from the standard profile list.
8. Click OK .
10.Click OK .
The 2-theta adjustment function is used when peaks of light elements shift due to the
sample.

Extract Standard Profile
To execute the standard profile peak deconvolution, standard profiles must have been
determined beforehand. Using pure substances such as metals and reagents,
measurement without counting loss or overlap must be made. It is useful for calculations
that will be made later to set a wider extraction range.
1. Display a peak to extract as a standard profile.

3. Designate a range including an objective peak without overlap by dragging the
mouse.
4. Select [Processing] [Extract Standard Profile...].
6. Select <Peak> or <BG> for “Type”.
7. Enter a comment if necessary.
8. Click OK .

Check X-Ray Intensities
The peak list function is used to check net intensities and background intensities of a
processed component. A peak displayed on that list can also be deleted. The following
items are displayed:
・Peak angle (deg.)

・Net intensity (kcps)
・Background 1 angle (deg.) and Background 2 angle (deg.)
・Line type
・It is also possible to display fixed angle measurement data (FA) and overlap line
detection data (OV).
1. Make a spectrum displayed beforehand.

2. Select the <Peak List> tab.

When you want to display fixed angle measurement data (FA) and overlap line detection
data (OV), click Fixed angle and Overlapped lines .
It is possible to copy displayed data to the clipboard. Press the Ctrl+C key to copy data to
the clipboard, and press the Ctrl+V key to paste data to the spreadsheet software Excel (R)
or the like.
Background angles are not output at the time of the printing of a peak list. If necessary,
output them via the clipboard.
FA or OV information is not printed at the time of the printing of a peak list. If necessary,
output them via the clipboard.

c. Calculation
Various calculations such as smoothing and peak search are described below. Because
the peak search and the automatic identification are carried out automatically after a
qualitative analysis, they generally need not be executed.
Smoothing
Smoothing is applied to a measured spectrum when the spectrum is not smooth and
shows significant statistical errors. Take care because a spectrum can be deformed if the
number of smoothing points is too large.
1. Select [Calculation] [Smoothing...].

2. Set the number of smoothing points in a range of 5 to 49.
3. Click OK .

Peak Search
This function deletes markers attached automatically to peaks and runs a new peak
search. Since this operation is executed automatically after a qualitative analysis, use
this manual procedure to search for peaks again after changing detection sensitivity.
1. Select [Calculation] [Peak Search...].

2. Set a coefficient of 0.3 to 2.0 for “Sensitivity”.
3. Click OK .
As the sensitivity value becomes smaller, only peaks with higher peak/background ratios
are detected.
This function clears all spectral line names. Peak positions alone are checked again. Using
the automatic identification, spectral line names can be reattached.

Automatic Identification
This function performs an identification analysis automatically after a peak search with
different sensitivity. When there are special components that require special attention,
they can be selected or eliminated here from objects of identification.
1. Click [Calculation] [Identification...].

2. Select elements that need not be identified.
3. Click OK .

Obtain Peak Width
The peak width of fluorescent X-rays is determined by an element and line type. By
knowing beforehand the width of a certain peak, overlap of peaks can be checked. Using
that peak width, angular resolution is assessed.

2. Designate a range including an objective peak by dragging the mouse.
3. Select [Calculation] [Resolution Calculation...].

5. Click OK .

Change Axis of Abscissas of Chart
In general, the abscissa axis of a chart is displayed in the 2-theta angle. In that case, for
example, when one wants to compare the spectra of the same element using different
crystals, comparison by overlapping the spectra is impossible because the abscissas are
expressed in the 2-theta angle. In such a case, the abscissas can be displayed in the
wavelength () or the energy (E).
When <Add> is not selected, the measured result is overwritten.
Once the axis is changed from the 2-theta angle to the wavelength, it cannot be returned to
the 2-theta. It is recommended that <Add> be selected.
Change to Wavelength Display

3. Select [Calculation] [Wavelength Conversion...].

5. Select a conversion step.
6. To add converted data to the qualitative analysis result file, select <Add>.
7. Click OK .
To convert the entire measured angle range, click Entire range .

Change to Energy Display

3. Select [Calculation] [Energy Conversion...].

5. Select a conversion step.
6. To add converted data to the qualitative analysis result file, select <Add>.
7. Click OK .
To convert the entire measured angle range, click Entire range .

Normalization Using Reference File
Normalization can be used when at least one reference file has been designated. This
function normalizes intensities using the spectrum of the reference file. The point
designation and the area designation can be selected.
 Point Designation
Normalization is carried out using the peak intensity.

2. Click a standard point for normalization.
3. Select [Calculation] [Normalize...].
4. The designated 2-theta angle is displayed. Modify it if necessary.
5. Select standard data.
6. Click OK .
 Area Designation
Normalization is carried out using a peak profile.

6. Click OK .
The menu of [Normalize…] can be selected when only one chart window is displayed.

Reset Normalization
Normalized data can be returned to the original condition.

2. Click Reset .
Obtain Intensity Difference of Spectrum Using Reference File
This function calculates intensity differences using data in a reference file. For example,
data of filter paper before dripping is set as a blank sample in a reference file and that
data is subtracted from data of filter paper after dripping.
1. Select [Calculation] [Subtract...].

3. Click OK .

d. Scale Change
To edit markers and process the data of the displayed spectrum, the procedure described
below can be used to change the displayed area to make the process easier:
Expand Display
This function is used, for example, to expand part of a full range qualitative analysis
chart and to check background.
1. Designate an objective range using the tool bar .

2. Select [View]  [Scale Change...].
3. The designated 2-theta angles and X-ray intensities are displayed. Modify them if
necessary.
4. Click OK .
To change the scale to the one designated in the measuring condition, click Default.
Display X-Ray Intensities Using Logarithmic or Root Scale

2. Select <Log> or <root> in the Intensity frame.
3. Click OK .

Display Legend

2. Select the “Legend” tab.
3. Select <Legend>.
4. Click OK .
In the case of the overlapped drawing of two or more files, the legend is displayed by
default.
Change Scale According to Highest Intensity in Displayed Range
The full scale of a chart is adjusted according to the peak top of an objective element. A
peak higher than that of the objective element is displayed off scale. Since that peak top
cannot be checked, marker setting is impossible. In such a case, the vertical full scale
can be set according to the highest intensity in the displayed range.
1. Click .
Return Changed Scale to Default Value
An expanded or reduced scale can be returned to the initial condition.
1. Select [View] [Set Default Scale].
The initial value is called the default.
Scroll Chart Display Area
When changing the chart display area, it can be scrolled horizontally and continuously
using the procedure described below instead of using the common tool bar:
 1. Click the icon on the tool bar, and the cursor will change to a right and left
arrow.
 2. Drag the mouse right or left and hold it. The area scrolls continuously in the
direction of dragging.

Simultaneous Wide-Range Screen and Expanded Screen
In processing a full range qualitative analysis result, the measured range is so wide that
marker setting and data processing may be difficult. In such a case, the scale change
operation is useful. After an ordinary scale change, a selected part is displayed, and you
cannot see the original wide range of the measured data. For example, to edit the
markers, it may be difficult to check pair peaks. In that case, a wide-range screen and a
smaller region processing screen can be displayed simultaneously. That wide-range
screen is called the panorama. When you set a scale range to be changed on that
panorama window, the scale of the processing window is changed. The scale of the
panorama window is not changed.
1. Select [View] [Open Panorama].

2. Designate a range to be changed on the panorama window using the mouse.
3. Click Apply .
▲ , ▼ and - on the panorama window mean the expansion, reduction and

default scale in the panorama window, respectively.

Print With Expanded Display
When the full scale is adjusted to a high-intensity peak, you cannot see small peaks.
When the full scale is adjusted to a small peak, high peaks are displayed off scale. In
such a case, by displaying an expanded view of a small peak in the same window, both
can be displayed in optimum full scales. That operation is called the zoom. The
procedure shown below would print the window with the expanded view displayed:
1. Select [View] [Open Zoom].

2. Select the section of the chart that you want enlarge by dragging it into view.
3. Select the specific section of the chart to enlarge by dragging a box over it to the scale
line.
The selected area will be enlarged and displayed in the chart.
Because the display cannot be saved in a file, print a hard copy of the screen or use the
“Active Chart” printing. (See the last part in “h. Printing of Qualitative Chart”.)
When a scale change or the like is executed, the zoom setting is canceled.

Change Graph Colors
1. Select [View] [Style] [Graph...].

2. Select display colors.
3. Click OK .
Change Filling of Spectrum
Set the degree of the filling of an area below a line that indicates a spectrum when a
spectral graph is displayed.

2. Select transparency from <0> to <100>.
When <0> is selected, the area is filled with a selected color. When <100> is selected,
only the line of a spectrum is displayed. When an absorption spectrum is displayed or in
a similar case, changing the transparency makes comparison easier.
When a spectrum is printed on the printer, only the line of the spectrum is output
(transparency: 100%) regardless of this style setting.

Display Auxiliary Line With Cursor
An auxiliary line can be attached to the cursor to designate a point or area.

2. Select a necessary auxiliary line for <X axis> or <Y axis> in the “Cursor” frame.
3. Click OK .
Change Spectrum Style
This function changes styles of spectrum display such as colors and line widths.

2. Select a file to be changed.
3. Click Style .
4. Select <Dot> or <Line>.
5. Make selection for “Width”.
6. Make selection for “Color”.
7. Click OK .

e. Processing of Qualitative Analysis File
Functions to compare charts by overlapping two or more data items and to add or delete
measuring conditions are described below. Because qualitative measurement data is
generally used for the SQX calculation described later, it is recommended that measured
results necessary for the calculation that have been processed be saved.
Overlapped Drawing of Spectra
Overlapped drawing of two or more files and overlapped drawing in one file can be used.
Up to 12 measuring conditions can be overlapped. For both drawing methods,
overlapped drawing is impossible when conditions such as the number of steps and the
units of the abscissa are not identical.
Overlapped Drawing of Two or More Files
This function is used, for example, to overlap measured results of a normal sample and
of an abnormal sample. Up to 11 overlapping files can be selected. The types of
applications used can be different. However, results of reference files with measuring
conditions different from that of the target file can not be overlaid.

2. Click Browse... at the right end of the target files.
3. Select a target file.
4. Click OK .
5. Click Add in the lower part of the screen.
6. Place check marks in the check boxes of reference files to be displayed.
7. Click OK .
8. Click the “Conditions” tab.
9. Click a spectrum name to be displayed.
10.Click Open .

It is possible to select up to 11 reference files simultaneously.

Overlapped Drawing of Measuring Conditions in One File
For example, the crystals LiF and Ge can be used for the Ca-K line. Because the
2-theta angle is different for each crystal, the abscissa axis is converted beforehand to
wavelengths. By overlapping those data items, comparison can be made to determine
which profile has higher intensities or better resolution, for example.
1. Select a target file with clicking Browse... .

2. Select [View] [Unique...] on the menu bar.
3. Select a spectrum to be overlapped.
4. Click OK .

Add or Delete Qualitative Data
A measuring condition in another file can be added to a target file or a measuring

condition in a target file can be deleted. In both cases, because important measured data
is processed, it is strongly recommended that a backup copy be made before this
operation.
Delete Measuring Condition in Qualitative File
This function is used, for example, to delete components of B to O from a file in which a
qualitative analysis was made for B to U and to change that file to a qualitative file of F
to U. Care must be taken because deleted components cannot be restored.

2. Select [Edit] [Edit Target File...].
3. Select a component to be deleted from the target file.

Add Measuring Condition to Qualitative File
For example, let’s assume that you made a full range qualitative analysis and want to
measure a component again with a slightly widened measuring range. With a
conventional system, all components must be measured again with a loss of time. In
such a case, to shorten the measuring time, only a changed measuring condition can be
measured again and the result can be added to the original file. Because a measuring
condition in a reference file is copied, it is not deleted.

2. Select reference files on the “Reference Files” tab.
3. Select [Edit] [Edit Target File...].
4. Select a reference file on the “File Edit” screen.
5. Select a measuring condition to be added from the list of the reference file.
6. Click Add .
An added component is placed at the bottom of the measuring condition list of the target
file.
When <Use added spectrum for SQX analysis> is selected, the identification result of a
spectrum added to the target file can be used for an SQX analysis.

f. Delete Qualitative Analysis Result Files

Select and delete unnecessary qualitative analysis result files.
1. Select [File]  [Delete…].

2. Click a file to be deleted.
3. Click OK .
g. Display Measuring Condition
1. Select [View]  [Measuring Condition…].

2. Check the displayed measuring condition.
3. Click OK .

h. Printing of Qualitative Chart
Three methods can be used to print qualitative charts: printing of all qualitative charts,
printing of selected components and printing of charts that are selected as objects of
processing (described as “active” hereafter). In all cases, one file is processed. Printing of
all qualitative charts can be executed even when files have not been selected with the
Qualitative Data Handling program. Common setting items and individual setting
items for each printing method are shown below:
Setting Item All Spectra Selected Spectra Active Chart

Header Setting Possible Possible Possible
Landscape/ Landscape/ Landscape/
Paper Direction
Portrait Portrait Portrait
File Name
Possible Impossible Impossible
Printing
Measured Date
and Time Possible Impossible Impossible
Printing
Individual or
Scale Setting Same as display Same as display
common
Overlapping Impossible Possible Possible
No. of Graphs Landscape : 10
Fixed for file 1
in One Sheet Portrait : 9
Selected
components can be
Option  
printed on the
second sheet.
Those items are set beforehand using the print setting function, but some of them can be
changed on printing.

Set Header
Character strings set as the header are printed in the upper part of a printing sheet. The
header is divided into the left, center and right areas and an arbitrary character string
can be set for each of them. In the initial setting the common header has been set for
each chart, but individual headers can also be set.
1. Select [File] [Print Setting...].

2. Select <All Spectra>, <Selected Spectra> or <Active Chart>.
3. Enter arbitrary character strings in the input cells in the “Header” frame.
4. Click OK .
Set Paper Direction

2. Click the “Common Setting” tab.
3. Select <Portrait> or <Landscape> in the “Default orientation” frame.
4. Click OK .

Print Setting in All Spectra Mode
To print a chart in the All Spectra mode, the scales of all qualitative charts can be set.
For the individual scale setting, each spectrum is displayed in its full scale reflecting
each result measured with each measuring condition. In the case of the common scale
setting, the full scale is set according to the highest peak in the measuring conditions.
The default setting is the individual scale. Setting can also be made for the printout of
file names and measurement dates and times. Because those cannot be set on printing,
they must be set here beforehand. In the cases of Selected Spectra and Active Chart,
those printouts cannot be set.

2. Click “All Spectra” tab.
3. Select <Individual> or <Common> for “Element scan scale”.
4. Select <File name print> if necessary.
5. Select <Meas. date print> if necessary.
6. Click OK .
Number of Graphs Printed in One Sheet
 In the All Spectra mode, all measured results are printed in one sheet.
 In the Selected Spectra mode, up to 9 graphs in the case of Portrait or up to 10
graphs in the case of Landscape can be printed.
 In the Active Chart mode, one graph is printed in one sheet.
The setting procedure for each mode is described below:

Set Number of Graphs in All Spectra Mode
In the All Spectra mode, Landscape and Portrait can be set for the printing direction.
Each printing image is shown below. Basically, all charts are printed on one sheet.
Partial Qual.
Chart
Full Range
Chart
Portrait Landscape
In the Landscape printout, the full range qualitative analysis chart is located in the
lower part and partial qualitative analysis charts are located in the upper part. In the
Portrait printout, the full range qualitative analysis chart is located in the lower part
and partial qualitative analysis charts are located in the upper and middle parts. The
number of those rows cannot be set, but the number of divisions in each row can be
preset. When the number of measuring conditions is larger than that preset number of
divisions, a second page is used.

2. Click the “All Spectra” tab.
3. Make setting for <Maximum chart number> in the “Number of element scans for
each block in portrait” frame.
4. Make setting for <Minimum chart number> similarly.
5. Make setting for <Maximum chart number> in the “Number of element scans for
each block in landscape” frame.
6. Make setting for <Minimum chart number> similarly.
7. Click OK .

Set Number of Graphs in Selected Spectra Mode
Any selected measuring conditions in a qualitative analysis file can be printed.

Overlapped printing is also possible. The maximum number of graphs that can be
printed varies depending on the paper direction. Up 10 graphs in the case of Landscape
or up to 9 graphs in the case of Portrait can be printed on one sheet. Setting can be made
easily using the formatting tool in which graphs to be printed are displayed in rectangles.
In the initial setting, four (two by two) graphs are printed on one sheet. By clicking an
arbitrary position, the format can be modified.

2. Click the “Selected Spectra” tab.
3. Set the number of graphs in the “Portrait format” frame.
4. Set the number of graphs in the “Landscape format” frame.
5. Click OK .

Printing
Setting for printing in the All Spectra mode can be made when the Qualitative Data
Handling program is started. Setting for printing in the Selected Spectra and Active
Chart modes can be made when a qualitative analysis file is opened or when a chart is
displayed. Though the printout format is basically set using [Print Setting...], it can be
changed on printing. The printer, bit map file or a metafile can be used as the output
device for printing.
 Printer
The printer is ordinarily used as the output device for printing. When your system is
equipped with a color printer, a qualitative analysis chart displayed on the screen can be
printed.
 Bit Map File
A displayed image is filed and can be pasted using word processor software etc. When
the image size is changed, however, the image may be deformed. Typically the file size is
large.
 Metafile
This is an image file in which a method to create an image is recorded and can be pasted
using word processor software etc. that can read metafiles. Even when the image size is
changed, the image is not deformed. The file size is smaller than that of a bit map file.

Print Chart in All Spectra Mode
In the case of printing in the All Spectra mode, the output device, paper direction,
header setting, etc., can be changed. Only in this mode can printing be executed without
displaying a chart using the Qualitative Data Handling program. In addition, the
components that need not be printed can be selected and the method to display the scale
can be changed only through the All Spectra mode.
1. Select [File] [Print Chart] [All Spectra...].

2. Select a file to be printed in the “File selection” frame.
3. Select <Printer>, <Bitmap> or <Metafile> for “Output”.
4. In the case of <Bitmap> or <Metafile>, change the folder to output a file if necessary.
5. If necessary, select <Horizontal> or <Vertical> for “Direction”.
6. When the header must be changed, click Change Header... .
7. Click OK .

Eliminate Unnecessary Components From Printing
In the All Spectra mode, one sheet is basically used to display all measuring conditions.
Components that should not be printed on the same page can be printed on another page,
or settings can be made so as not to print them at all.
1. Click Advanced... on the “Print All Spectra” screen.

2. Select components that are not to be printed on the same page in the “Select
excepted spectra” frame.
When clicking All , all spectra are a subject for selection of excepted spectra
When clicking All clear , all spectra are not excepted.
3. Select <Separated page> or <No output> in the “Excepted spectra” frame.
4. Click OK .
Change Scale Mode
Only in the case of the All Spectra mode, the scale mode can be changed.
1. Click Advanced... on the “Print All Spectra” screen.

2. Select <Linear> or <Log> in the “Scale” frame.
3. Click OK .

Print Selected Spectra
This <Selected Spectra> mode is valid when a target file and a reference file are selected.
Overlapped charts are output in the same image as the one on the screen. The number of
graphs that can be printed simultaneously varies depending on the paper direction. The
output order can be designated. In the case of “Vertical”, graphs are laid out in the
vertical order. In the case of “Horizontal”, graphs are laid out in the horizontal order.
1. Select a file to be printed.

2. Select [File] [Print Chart] [Selected Spectra...].
3. Select measuring conditions to be printed.
5. Select <Vertical> or <Horizontal> for “Output order”.
7. In the case of <Bitmap> or <Metafile>, change the file output folder if necessary.
8. To change the header, click Change Header... .
9. If necessary, set the numbers of graphs to be printed in the “Format” frame.
10.Click OK .

Print Active Chart
When a chart/charts is/are displayed, the chart(s) in the active condition can be printed.
This function can be used, for example, to print a chart/charts after background fitting
or zooming. Needless to say, overlapped charts can be output intact.
1. Select a file to be printed.

2. Select a chart/charts to be printed.
3. Select [File]  [Print Chart]  [Active Chart...].
6. In the case of <Bitmap> or <Metafile>, enter a file name.
7. Change the file output folder if necessary.
8. To change the header, click Change Header... .
9. Click OK .

i. Transfer of Qualitative Analysis Results
Qualitative analysis results that can be transferred are qualitative element information,
an SQX analysis result, a peak list and 2-theta - X-ray intensities. The transmission
format and the spreadsheet format can be used as the text format. The disk saving and
the external transmission can be used as the transfer method. The text formats and
transfer methods that can be selected vary depending on the data type.
 Objects of Transmission
Data Type Contents
Qualitative element Detected elements and the analyzed values or
information X-ray intensities
SQX analysis result Components and analyzed results
Peak list Element lines and net intensities
2-theta - X-ray 2-theta scan angle and X-ray intensity for each
intensities spectral line
In qualitative analysis information, analyzed values are output when SQX analysis result is
obtained. When SQX analysis result is not obtained in such a case that only qualitative
analysis has been done, X-ray intensities are output.
 Data Type and Text Format

Text formats that can be used for each data type are shown below:
Transmission Spreadsheet
Data Type
format format
Qualitative element
Usable Unusable
information
SQX analysis result Usable Unusable
Peak list Usable Unusable
2-theta - X-ray
Usable Usable
intensities
More than one qualitative analysis result file can be selected for qualitative element
information and an SQX analysis result. For a peak list and 2-theta - X-ray intensities,
select one file and then select spectral lines to be transferred.
 Transfer Method and Text Format

The relationship between the transfer method and the text format is as follows.
For the external transmission, RS232C and TCP/IP can be used as the
transmission method.
Transfer Method Transmission Format Spreadsheet Format
Disk saving Usable Usable
External transmission Usable Unusable

Transfer Qualitative Analysis Result
The procedure to save an SQX analysis result into the disk is used as an example for
explanation.
1. Select [File] [Transfer Qual Data…].

2. Select a qualitative analysis result file.
3. Select <SQX result> in the “Data type” frame.
4. Select <Disk save> for “Trans. method”.
5. Select a folder to save the file.
7. Click OK .
When <Peak list> or <2-theta - intensities> is selected in the “Data type” frame, the
“Spectrum Selection” screen appears after clicking OK.
When <2-theta - intensities> is selected in the “Data type” frame, “Text format” can be
selected from <Transmission format> and <Spreadsheet format>. And the format can be
selected from <CSV> and <TAB>.
To carry out the external transmission, select <RS232C Transmission> or <TCP/IP

Transmission> for “Trans. method”.

Select Spectral Lines to Be Transferred
To transfer <Peak list> or <2-theta - intensities>, select spectral lines after the dialog on
the “Qual Data Transmission” screen.
1. Select spectral line names.

2. Click OK .
To select all spectral lines, click All.
To return to the dialog on the “Qual Data Transmission” screen, click Cancel.

3.3.2 SQX CALCULATION (OPTION)

2. Click [Qual Result].
3. Click Browse on the right of the target file field.
4. Select one target file.
5. Click OK .
6. Select the <SQX Calculation> tab.
A measurement result file saved in the selected folder can also be selected on the
dropdown list on the left of Browse... .
The unit ppm can be used for a component with a specified concentration or less in SQX
calculation results by setting system parameters in <6.1.h System Management>.

Procedure for SQX Calculation
1. Select a file to be used for a calculation.

2. Select the <SQX Calculation> tab.
3. Click Calc. Condition .
4. Change necessary calculation conditions.
5. Click OK .
6. Click Calculate .
It is recommended that calculated data be saved after an SQX calculation.

Result Output Selection
The contents of display on the screen and printing output can be set.
1. Select [File]  [Result Output Selection] on the menu.
2. In the “Result Output Selection” dialog, place check marks for items to be displayed
or printed.
Up to four items can be printed.
3. Click OK .

Component names, analyzed values and units in final results are unconditionally
displayed and printed.
The contents of each item are as follows:
Item Contents
Detection limit after taking account of the
Det. limit
background subtraction.
Analysis line type used for an analyzed value
El. line
calculation.
Intensity Net X-ray intensity.
The item “w/o normal” means an analyzed value
before normalization to 100%. The item “liquid
w/o normal/liquid conc.
conc.” means an analyzed value converted to that of
original liquid in the case of a filter sample.
Depth from a sample surface at which an analysis
line is measured. When a sample is thinner than
Analyzing depth (mm) this thickness, the sample thickness affects an
analysis value. In this case, set a sample thickness
using the sample size setting function.
Intensity ratio of analysis line to the intensity of a
sample that has an obtained constitution and an
infinite thickness. This item is valid only when a
Intensity ratio sample thickness is set. When this value is 1.0, an
intensity is the same as that of a sample with an
infinite thickness and an analyzed value is not
affected by a thickness.
Component name for a quantification calculation
Component (Org) before conversion when the element/oxide
conversion is specified.
Quantification calculation result before conversion
Result (Org)
when the element/oxide conversion is specified.

a. Detailed Description of SQX Calculation
Detailed setting items such as change of calculation conditions is described below:
Recalculation for File After Qualitative Data Handling
When a new marker was added or net intensities were updated using the Qualitative
Data Handling program, a recalculation can be made. The SQX calculation is made
using a result processed by Qualitative Data Handling.

2. Select <Qualitative analysis result> for “Calculation method”.
3. Click OK .

Change Component Type
In the SQX calculation, the metal (elemental) conversion, the oxide conversion or the
compound table is set for the component type. In general, the metal conversion is set for
metal samples, residual components in polymer, etc., and the oxide conversion is set for
powders, glass, etc. The compound table is used to make a quantification calculation
using a combination of compounds set by a user.

2. Select <Metal> or <Oxide> for “Component type”.
3. Click OK .
Make Calculation With Combination of Metal Conversion and Oxide Conversion
Two methods can be used for a calculation using a combination of metals and oxides.
One is to specify a compound table that has been created beforehand. The other is to
change component names on the “Component Condition” screen.
In the case of rock samples, for example, an SQX calculation may be made using the
oxide conversion for main components and the metal conversion for minor components.
In such a case, component names can be changed on the “Component Condition” screen.
When a compound table is to be used, select it for the component type. Specify each
component on the “SQX Calculation” screen according to the following procedure:
1. Select a component to change the conversion method.

2. Click Change .
3. Select a metal or an oxide at “Component” on the pull-down list.
4. Click OK .
Set Balance Component
For example, when analyzing polyethylene, the compound CH2, the main component, is
not measured and is treated as the balance. In a calculation, components other than
measured ones are treated as the residual (balance component). In the SQX calculation,
that balance component can also be set. When the sample model is a thin film, the
balance component must be set. Only one balance component can be set.

2. Select a component name from the dropdown list of the balance.
3. Click OK .

Set Binder for Powder Sample
If binder is used when pressing a powder sample, binder must be set because it affects
analyzed results.

2. Click Setting... for “Advanced setting”.
3. Select <Used> and select a binder compound.
4. Enter sample weight and binder weight.
5. Place a check mark for <Used> for “Sample film”, and select a sample film name.
6. Click OK .
This setting is possible when the sample type is the powder or polymer.
Set Sample Preparation Condition for Fusion Bead
To analyze a fusion bead and obtain analyzed values, a flux type and a dilution ratio
must be set because a sample is diluted with flux.

3. Select <Used> and the compound name of flux, and enter sample weight and flux
weight.

4. When oxidizer is used for fusion, select <Used> and the compound name of the
oxidizer, and enter added oxidizer weight
5. Click OK .
Set Sample Size
When the sample type is the powder, polymer or fusion bead and a sample thickness
affects analyzed values in the case of some analysis line, a quantification calculation
with the weight thickness of a sample taken into consideration becomes possible by
setting a sample size.
1. Select “Sample size” and click Setting... .

2. Enter sample weight.
3. Set a base size according to a sample shape.

Output of Detection Limits for Undetected Elements in Fixed Angle Measurement
Elements that were not detected in the fixed angle measurement can be added to a
group of output elements.
 1. Select <Output detection limit for undetected element (fixed angle)>.

 2. Select <Qualitative analysis result> for “Calculation method”.

Estimate non-measuring components (SQX Scattering FP method option)
1. Select <Estimate> for “Balance”. The option <Estimate> is displayed only for the
result file of measurements using a qualitative application created with a check
mark placed for “Estimate non-measuring component”.
2. Select a scattering ray library name to be used for the SQX scattering ray calculation
from the pull-down list. （In case of the specifications of scattering library with
LiF(200), this is done automatically.）
3. Click Setting... for “Sample size” and enter sample size information.
4. Click OK .
It is possible to operate <Estimate non-measuring component> only for the result files of
qualitative analysis measurement, of which application is to be prepared by SQX Scattering
FP method.
In case of the specifications using scattering library with LiF(200), the selection of “Estimate
non-measuring component” is possible for the analysis of measurement diameter 30mm
and 20mm qualitative analysis result file. (This is applicable to the sample model of powder,
polymer and liquid only.)

Calculate With Thin Film Model
Filters, films, coating samples, etc. are treated as thin films. A thin film sample coated
with a metal film or the like is treated as a film sample with a substrate. Solution on
dripping paper is treated as a filter sample.
Make Setting for Film
The procedure for the SQX calculation for a film sample without a substrate is used as
an example for explanation.

2. Make sure that the sample type is “Film & Coating”.
4. Make setting for “Unit of components” and “Unit of weight”.
5. Select <Fixed> or <Analyze> for “Film weight”. In the case of <Fixed>, enter a fixed
value.
6. Do not place a check mark for “Substrate”.
8. Click OK .

Coating Sample With Substrate
Set substrate information in setting for a thin film.
1. Place a check mark for “Substrate” in the “Advanced Setting” dialog, and push the
Setting... button.
2. Set a component in the “Component” field.

3. Select <Balance> or <Fixed> in the “Type” field.
4. When the type is <Fixed>, enter a value in the “Conc.” field.
5. Repeat steps 2 to 4 according to components in the substrate.
6. Click OK .

Make Setting for Filter

2. Make sure that the sample type is “Filter”.
4. Select a filter type.
5. Weight can be entered when the filter type is “MicroCarry” or “Other”.
6. A sampling diameter can be entered when the filter type is “Other”.
7. Enter a sampling volume. This item is used when converting to a liquid
concentration.
8. Select a liquid concentration unit from <mass%> and <ppm>.
10.Click OK .
the filter type, a material, weight and sampling diameter are automatically displayed.

Exclude Component From Calculation
The SQX calculation uses all components detected in a qualitative analysis. If, for
example, Cl detected in measurement of a metal sample can be judged evidently to be a
contaminant, it can be excluded from the calculation.
1. Select a component to be excluded.

Since more than one component cannot be selected, select one by one.
Change Measured Element Line
Let’s assume that Co in the heavy element region is to be measured with the full range
qualitative analysis. When the main component is Fe, the ordinary measured element
line Co-K overlaps with Fe-K1. In that case, Co-K1, which does not overlap, is
generally used as the measured element line for a calculation. Thus, when one
component has two or more measured element lines, selection can be made from them
for a calculation.
1. Click Change .

2. Select <Analyze> for “Analyzed value”.
3. Select a spectral line.
4. Select a measured element line for calculation in the “Element line” frame.
When a check mark is placed for “Display overlapped lines”, a characteristic X-ray
intensity in the overlap line detection is displayed on the list of element lines with
“(characteristic X-ray line name) (OV)”.

5. Click OK .
Add Component
Even a component the peak of which is not detected can be added when overlap line
detection data is displayed.
1. Click Add... .

2. Set a component name to be added.
3. Place a check mark for “Display overlapped lines”.
4. Select a measured element line for calculation in the “Element line” frame.
5. Click OK .
Display Spectrum Directly From SQX Calculation Result
It is possible to display the spectrum of each component directly on the SQX calculation
screen, enabling the checking of spectra used for the SQX calculation.
1. Select a component to be displayed by clicking it.

2. Click Spectrum .
3. The spectrum of the analysis line is displayed.

Because it is impossible to display the spectra of two or more components, select one
component at a time.
A chart in the Heavy range displays the range of +/-5 deg. to the angle of an analysis line.
Add Fixed Value
This function is used to set information about a component with a known concentration
as a fixed value. Two or more fixed values can be set.
1. Click Add .

2. Set a component name to be added.
3. Select <Fixed> for “Analyzed value”.
4. Enter a fixed value.
5. Click OK .
A component name other than an element name must have been set beforehand in the
compound table.

Matching Library (Option)
Unlike the common library, a library registered using standard samples for each kind of
unknown is called the matching library. When a matching library that has
concentrations similar to those of unknown samples is available, a more accurate SQX
calculation can be made. However, a matching library can be used only for the bulk
model and cannot be used for the thin film model.
For libraries, see “3.4 SENSITIVITY LIBRARY”.
Retrieve Matching Library
A matching library is automatically retrieved and a calculation is made.
1. Set “Search” for “Matching library”.

2. Click OK .
Specify Matching Library
When concentrations of unknown samples can be estimated to some extent, a matching

library can be specified for a calculation.
1. Set “Specify” for “Matching library”.

2. Select the type of a library
3. Select a library sample name.
4. Click OK .

Various Correction Methods
The impurity correction, sample film correction and helium atmosphere correction can
be used. The sample film correction is automatically made when the sample film setting
described below has been carried out:
<Helium atmosphere correction> can be selected when the atmosphere specified in the
application is Helium.
Set Impurity Correction
For example, if filter paper itself contains a certain component, that component must be
subtracted when calculating concentrations of unknown samples deposited onto the
filter. In that case, the impurity correction can be carried out by executing a qualitative
analysis of filter paper itself and registering X-ray intensities. X-ray intensities or
analyzed values can then be subtracted.

2. Click Setting... for “Correction setting”.
3. Place a check mark for “Impurity correction” and set an impurity name and a
correction method.
When a sample film has been set, impurity data items only of the sample film type
are displayed as the options.
4. Click OK .

Set Sample Film Absorption Correction
Since a sample film absorbs X-rays generated from a sample, a correction must be made.

4. Click OK .
5. Click OK again.
When the sample type is not “fusion bead”, a sample film can be set on the “Advanced
Setting” screen.
A sample protection film designated by Rigaku must be employed.
Set Helium Atmosphere Correction
When the helium atmosphere is selected, the atmosphere absorbs X-rays. That
absorption has a greater effect on lighter elements than heavier ones. By using this
correction, library samples need not be measured in the helium atmosphere. This setting
is possible only when the helium atmosphere has been selected.

2. Click Setting… for “Correction setting”.
3. Select <Helium atmosphere correction>.
4. Click OK .
The helium atmosphere correction can be selected when the atmosphere is

Helium/Vacuum(Sealing IN).
Lower Limit of Detection
The unit of a lower limit of detection is as follows:
Model Unit
Bulk and Thin Film (Except Filter) Unit preset for analysis value
Thin Film (Filter) Unit preset for liquid concentration

b. Impurity Data
The procedure to register, change and delete impurity data used for the SQX calculation
is described below:
Add Impurity Data
A result of an SQX calculation is added as impurity data. X-ray intensities or analyzed

values added here can be used as impurity data for calculations of other samples. A
component that is not used for calculations can be deleted on registration.
1. Carry out an SQX calculation.

2. Select [Impurity Data]  [Add Data].
3. Set a type. In the case of measurement data using a sample film, conduct
registration using the “Sample film” type. In the case of measurement data without a
sample film, conduct registration using the “Normal” type.
4. In the case of the “Sample film” type, set a sample film name used for “Reference”.
5. Enter an impurity data name.
6. To delete a component, select it.
7. To delete a component, click Delete .
8. To change the contents of a component, select it.
9. To change the contents of a component, click Change .
10.To change the contents of a component, change its intensity or concentration.
11.When the contents of a component have been changed, click OK .
12.Click OK .

Edit Registered Impurity Data
The registered contents of impurity data can be changed. A component that is not used
for calculations can be deleted.
1. Select [Impurity Data]  [Change Data].
2. Select impurity data to be changed.

3. Click OK.
4. To delete a component, select it.
5. To delete a component, click Delete.
6. To change the contents of a component, select it.
7. To change the contents of a component, click Change.
8. To change the contents of a component, change its intensity or concentration.
9. When the contents of a component have been changed, click OK.
10.Click OK.

Delete Registered Impurity Data
The procedure to delete registered impurity data is described below:
1. Select [Impurity Data]  [Delete Data].

2. Select impurity data to be deleted.
3. Click OK .
More than one impurity data name cannot be selected.
Print Impurity Data
The procedure to print registered impurity data is described below:
1. Select [Impurity Data]  [Print Data].

2. Select impurity data to be printed.
3. Click OK .
More than one impurity data name cannot be selected.

c. Printing
The procedure to print an SQX calculation result is described below. The procedure to
change the output order of components and their output number of digits is also
described.
Print Result
An SQX calculation result is printed out.
1. Select [File]  [Result print].
Set Output Order of Components
The mode to print in order of an atomic number (from the smallest to largest) and the
mode to print in order of an analyzed value (from the largest to smallest) can be selected.
1. Select [File]  [Print Format...].

2. Select <Atomic number> or <Analyzed value> for “Output order”.
3. Click OK .

Set Output Number of Digits
The number of digits of a printed calculation result can be set. For example, when an
analyzed result is 12.3456, it is output as shown below:
Output Digits Description Output

2 effective digits Output in 2 significant figures 12
3 effective digits Output in 3 significant figures 12.3
Fixed decimal point Output with fixed decimal point 12.3456

2. Select <2 effective digits >, <3 effective digits> or <Fixed decimal point> for “Output
digits”.
3. Click OK .
Set Trace Output
When the reliability of analyzed result is doubtful, setting can be made so that the value
will not be output. The output is called the trace output. For a component with a
concentration lower than detection limit in bulk samples, “Trace” is output instead of the
analyzed value.

2. Select <Trace output>.
3. Click OK .

d. Judge Material (Option)
It is possible to judge the material of the sample in the SQX Calculation program. To
judge material, material judgment standards registered using <Material Judgement
Standards> are retrieved. Although material can be judged on making an SQX analysis,
it can be judged again here.
 1.Select [File]→[Material Judgement…].

 2.Select <Standard> if necessary.
 3.Select <Category> if necessary.
 4.To print a result, click Print .
 5.Click X for termination.

e. Automatic Overlap Correction
In the SQX calculation, an overlap correction is made for interfering lines using
theoretical intensity overlap correction coefficients that have been stored beforehand in
this system. The correction is made when the measured element line is a K line in the
K series or an L line in the L series. Only primary rays are taken into consideration as
interfering lines.
The overlap correction is not made for measured element lines after peak deconvolution
and for ones for which intensities have been entered using the SQX Analysis program.
When a measured element line is identified together with another interfering line, an
overlap correction is made by calculating net intensities at an angle calculated
theoretically.
The automatic overlap correction is used not only in the “SQX calculation” in the data
processing but also in the data processing in the “Analysis” program.
f. Export SQX analysis result to a CSV file
It is possible to export a CSV file of SQX analysis result that can be read using spread
sheet program.
Operate as follows when calculated result is displayed in the main window of SQX
calculation.
Data such as component, result, unit, detection limit, El. Line and intensity are output
as displayed.
1. Select [File]→[Data Export…].

2. Click Browse… and select a file output folder.
4. Click OK .

g. Registration of Matching Library From SQX Calculation Result
In the case of the matching library, sensitivity values are registered using standard
samples for each kind of unknown material. In an SQX analysis calculation, a library
that has components similar to those of unknown samples is retrieved and more
accurate concentrations can be obtained.
It is also possible to register a matching library directly from the SQX calculation.
1. Click Browse... of the target file and select an SQX analysis result file to be
registered in a matching library.
2. Click the <SQX Calculation> tab to display an SQX result.
3. Select [File]  [Save Matching Library...].
4. Enter and select the following items on the Save Matching Library screen:
・Library sample name: Enter a name intelligible as a matching library.

・Standard value (Std. value): Enter the standard values of components such that
the total of the values of all the components becomes 99 to 100 mass%.
・Save: Place check marks for components for which to register sensibility values.

5. Click OK . The matching library and sensibility values are automatically registered.
When entering standard values, use the concentrations of component names in an SQX
calculation result.
h. Collective Calculation of All Mapping Measurement Points
For qualitative analysis results of the mapping measurement, it is possible to use

calculation conditions set on the SQX calculation screen for the qualitative analysis
results of all the points of the same mapping measurement and make a recalculation.
Calculation conditions to be used are items set on the [Calculation Condition] screen
except [Calculation method]. [Qualitative analysis result] is always used for the
calculation method.
1. Click the qualitative analysis result of one point in SQX mapping analysis results.
2. Click Calc Condition... and change calculation conditions if necessary.
3. Select [File]  [Lump calc]. The number of mapping measuring points and the point
number of the data being calculated are displayed on the screen during a calculation.
The recalculation result is automatically reflected in the mapping result and Result Display.

3.4 SENSITIVITY LIBRARY (OPTION)
This is a function of the SQX software option.

The results of a sensitivity calculation using the FP method by measuring samples of a
pure metal or a reagent are called the spectrometer sensitivities. A collection of those
spectrometer sensitivity values is called the sensitivity library. The common library, the
matching library (option) and the scattering library (option) are available as the
sensitivity library. Though the common library has been registered beforehand, a user’s
own libraries can also be registered.
Because a library is basically a collection of sensitivity values, it does not depend on a

measuring method. A library can therefore be used for both the SQX analysis and the
quantitative analysis. However, qualitative analysis is used for actual library
measurement.
The function called the library drift correction is available to use libraries for a long term.
Libraries depend on the spectrometer conditions, which change over long periods of time.
To correct libraries using a small number of samples without remeasuring all library
samples is called the standardization of libraries.
Common Library
The common library has been registered using standard substances such as pure metals
and reagents without using standard samples for each kind of samples. By measuring
library samples for representative elements and saving sensitivity values beforehand,
the analyzed value of an element that is not registered in the library can be calculated
by estimating its sensitivity from those of elements that have atomic numbers before
and after that of the analyzed element.
The sensitivity library that Rigaku created by measuring many standard substances is
called the master common library. That master common library reproduced with many
library samples is called the common library.
This library can be used for both the bulk sample model and the thin film sample model in
qualitative or quantitative analysis.

Matching Library (Option)
In the case of the matching library, sensitivity values are registered using standard
samples for each kind of unknown material. In an SQX analysis calculation, a library
that has components similar to those of unknown samples is retrieved and more
accurate concentrations can be obtained.
To reduce errors caused by low concentrations, when the concentration of a component in

a library sample is 0.1% or lower and the concentration of that component in an
unknown sample is over three times as high as that in the library sample, an analyzed
value is calculated using the common library.
A matching library that a user registers is called the user matching library.
This library can be used only for qualitative analysis and cannot be used for quantitative
analysis.
This library can be used only for bulk samples and cannot be used for thin films.
Library Drift Correction
Like the drift correction in the quantitative analysis, calibration of X-ray intensities to
use created sensitivity libraries for a long term is called the standardization of libraries.
That operation is called the drift correction and its purpose is to re-establish libraries
using a small number of samples. This system has samples for the library
standardization, so it is recommended that setting be made for drift correction.
Scattering Sensitivity Library
The scattering sensitivities used in SQX Scattering FP method (option) mean the
equipment sensitivities of Compton scattering X-rays (Rh-KC) and Thomson scattering
X-rays (Rh-KT), which originate from the target material (Rhodium) in X-ray tube.
The scattering sensitivity libraries are assorted on each sample type.
Scattering Library Drift Correction
It performs drift corrections for scattering sensitivity library. It is necessary to carry

out the corrections on every library.

Various Correction Functions for SQX Analysis
In the SQX analysis, quantification values are calculated using the common library and
matching libraries. In this case, the following three correction functions can be used
separately or in combination with each other:
Correction Name X-Ray Intensity Concentration

Impurity Correction Bulk sample and thin film sample Bulk sample
Sample Film Correction Bulk sample and thin film sample Not applicable
Atmosphere Correction Bulk sample and thin film sample Not applicable
 Impurity Correction
Among other uses, this function is used to eliminate components contained in filter
paper for drip samples and impurity lines from the X-ray tube.
 Sample Film Correction
To analyze liquid samples, a film is used to protect the sample. This function is used to
correct absorption of X-rays by the film.
 Atmosphere Correction
For samples like liquids that cannot be measured in the vacuum condition, the sample
chamber atmosphere is changed to the helium condition or the like. This function is used
to correct absorption of X-rays by the helium atmosphere.

a. Procedure to Register Library
The operation flow to register each type of library is shown below. The common library
uses standard substances and the matching library uses standard samples. Other than
that difference, the same procedure is used for both types of libraries.
Library drift corrections to calibrate X-ray intensities are registered using other
procedures. In the detailed descriptions below, the procedure for each purpose is
explained.
1. Click Utility on the menu.

2. Select [Sensitivity Library].
Flowchart to Create Sensitivity Library
Start
Common or matching
library? No
Yes
Create measuring condition
Prepare library samples Prepare drift correction samples
Measure library samples Measure drift correction samples
Update sensitivity Update intensities
End End

b. Measuring Condition
To register a new common or matching library, a measuring condition must be created

first. Basically, to register a sensitivity library, a qualitative analysis must be made.
Click the button shown below on the flow bar:
Because all the measuring conditions for Scattering sensitivity library (option) are fixed, the
user cannot edit them.
Library
Usually, the common sensitivity library named <Standard> has been set beforehand. In
general, because a library is spectrometer sensitivity, one measured element line has
one sensitivity value. For example, when the same component has different measured
element lines such as Cd-K and Cd-L, a library can have two or more components. To
create a new library of the same measured element line as that registered already in the
common library, an original library can be created.
A combination of those libraries can also be used.

Create New Library
The procedure to create a new original library other than the common library is
described below:
1. Select [File] [New Library].

2. Enter a library name.
3. Click OK .
4. Select an element on the periodic table.
5. To change the measured element line, click Change Line and select another measured
element line.
Select Existing Library
1. Select a library name on the “Library measuring condition” screen.
Display Measuring Condition
1. Select a measured element line.


Measuring Conditions
The measuring conditions are classified into common conditions, qualitative conditions
and quantitative conditions.
Conditions Description
Common The excitation condition, optical condition and PHA condition are
Condition set.
Qualitative
The scan method, angle range, etc. are set.
Condition
Quantitative
The background subtraction, measuring time, etc. are set.
Condition
For the setting procedure for each condition, see “3.2 e. Setting of Measuring Conditions”,
“4.2 d. Setting of Analysis Information” and “4.3 a. Measuring Condition”.
Set Common Conditions
For the detailed setting contents, see “4.3 a. Measuring Condition”.
1. Select a measured element line to set a detailed measuring condition.

2. Click Property.
3. Click the “Common condition” tab.
4. Set the excitation, optical and PHA conditions.
5. Click OK.

Add Measuring Condition
The procedure to add a new measured element line is described below:
1. Select [File] [Add New Measuring Condition].

2. Click an element to be added on the periodic table.
3. Click Change Line in the “Element line” frame.
4. Select a measured element line.
5. Click OK .
6. Click OK .
To add the full range qualitative analysis, click Heavy Elements .

A measured element line cannot be selected for the heavy element full range qualitative
analysis.

Set Qualitative Conditions
For the detailed setting contents, see “3.2 e. Setting of Measuring Conditions”.

3. Click the “Qualitative condition” tab.
4. Make setting for “2-theta scanning condition”.
5. Make setting for “Intensity control”.
6. Click OK .

Set Quantitative Conditions
For the detailed setting contents, see “4.2 d. Setting of Analysis Information”.

3. Click the “Quantitative condition” tab.
4. Make setting for “Peak & Background”.
5. Click OK .

Delete Measuring Condition
The system manager alone can delete a measuring condition.

Care must be taken because a deleted measuring condition cannot be restored.
1. Select [File] [Delete Measuring Condition].

2. Select a library to be deleted in the “Library” frame.
3. Select a measured element line to be deleted in the “Measuring” frame.
4. Click OK .
Print Library Measuring Condition
A created measuring condition can be printed.
1. Select [File] [Print].

2. Select a library to be printed in the “Library” frame.
3. Select a measured element line to be printed in the “Measuring Condition” frame.
4. Click OK .

c. Library Samples
Library samples are classified into ones for the common or matching library and drift
correction samples for intensity correction. The former require standard values to
calculate spectrometer sensitivity values. The latter do not require standard values
because they are used only for intensity correction.
Common or Matching Library Samples
For the common or matching library, samples to calculate spectrometer sensitivity

values are called library samples. Components constituting samples and their
concentrations are set first. Then X-ray intensities of those samples are measured.
Spectrometer sensitivity values are calculated from those X-ray intensities. Standard
substances are used for the common library and standard samples for each kind of
unknown are used for a matching library.
Library Drift Correction Samples
Samples to recalibrate intensities are called library drift correction samples. If standard
samples are stable for a long term, they can also be used for library drift correction
samples.

Scattering Library Samples
This is the library sample to be used for obtaining the equipment sensitivities of
Compton scattered X-rays (Rh-KC) and Thomson scattered X-rays (Rh-KT) that
originates from the element of X-ray tube material when SQX Scattering FP method
(option) is employed. The scattered X-ray intensities are collected with the measurement
of library samples after setting up components and their concentrations of library
samples.
Scattering Library Drift Correction Sample
This is a drift correction sample used for scattering sensitivity library. It is necessary to
prepare drift correction samples for each library. Either the  method to correct by one
point or the  method to correct by two points can be chosen as the drift correction
method on each library but the use of the  method is generally selected.

Create New Library Sample
The procedure to create a new library sample is described below. A library sample of an
aluminum plate using the measured element line Al-K will be used as an example.
1. Select [File] [New...].

2. Select <Common library> for “Library type”.
3. Select <Bulk> in the “Sample model” frame.
4. Enter a library sample name at “Library sample”.
5. Click OK .
6. Select <Element> in the “Type of component to add” frame.

7. Click Al .
8. Click OK .

9. Select <Standard> in the “Component type” frame.

10.Enter 100 for “Std. value” in the “Component value” frame.
11.Select <mass%> for “Unit” in the “Component value” frame.
12.Select a library name in the Library field.

13.Set a measurement line in the El. line field.
14.Click Edit... in the Measuring Condition frame, set an appropriate condition and click
OK .
By clicking Add in the Measuring Condition frame on the main screen, the common library
with a different measuring condition can be registered additionally for the same component.
Select the common library with a different measuring condition for a library in the line of an
additional measurement.

15.Click Common Conditions .

16.Select a measuring diameter.
17.Select <Yes> or <No> for “Sample spin”.
18.Select <Vacuum> or <Helium/Vacuum> for “Atmosphere”.
19.Select sealing.
20.Click OK .
“Sealing” is displayed only when the spectrometer has the helium flush mechanism and the
sealing (option). Usually select <OUT> for “Sealing”.
21.Click Output information .

22.Select items to be printed out in the “Output information” frame.
23.Set the number of smoothing points for “Smoothing” in the “Data processing” frame.
24.Select sensitivity for “Peak detection level” in the “Data processing” frame.
25.Click OK .
26.Select [File] [Save].
Though Al alone is set for measurement in the above example, two or more measured
element lines can be set such as K-K and Br-K in the case of KBr of common library
samples.
The total of the standard values of components must be within a range of 99.0 to 101.0.
The maximum number of characters of a library sample name is 16.

It is possible to add a different common library condition using Add in the Measuring
Condition frame.
Change Measuring Condition
A measuring condition can be changed if necessary. But part of the excitation and optical
conditions and the PHA condition cannot be changed in the library measurement. The
conditions concerning intensity shifts and the angle range can be set here.
1. Select a component name to change measuring conditions.

2. Click Measuring condition .
3. Change necessary items.
4. Click OK .
In the case of the ZSX Primus, ZSX Primus II or ZSX Primus IV/IVi, the attenuator can be
selected only when the measurement diameter is 30 mm and the sealing is “OUT”.
In the case of the ZSX Primus III+, the attenuator can be selected only when the
measurement diameter is 30 or 20 mm.

Set Matching Library Sample (Option)
The procedure to set a matching library sample is the same as that for a common library
sample except that bulk samples alone can be used. Two or more measured element lines
can be set.
1. Select [File] [New].

2. Select <Matching library> for “Library type”.
3. Enter a library sample name for “Library sample”.
4. Click OK .
5. For the setting procedures after this, see the paragraph for a common library
sample.
Only “Bulk” can be selected for “Sample model”.
It is also possible to register a matching library sample from the SQX calculation of the
[Qual Result] program.
It is impossible to save a library sample registered from the SQX calculation after it is
updated. The sample size, sample film correction, etc. are also stored and can be
displayed.

Create Library Drift Correction Sample
The library drift correction sample has no model such as bulk or thin film and does not
need standard values. Other than those differences, the setting procedure is the same as
that for a common library sample.

2. Select <Drift correction library> for “Library type”.
3. Enter a new library sample name for “Library sample”.
4. Click OK .
5. For the setting procedures after this, see the paragraph for a common library
sample.

Create Scattering Library Sample
This setup functions only when SQX Scattering FP method (option) is attached.
In the case of a scattering library sample, only scattered rays are set for a measurement
line.
 1. Select [File] [New] in due order.

 2. Select <Scattering library> in “Library type” frame.
 3. Select <Bulk> for ”Sample model”.
 4. Enter a new library name for “Library sample”.
 5. Click OK .
 6. Select <Element> in “Type of components to add” .

 7. Click components to add.
 8. Click OK .

When preparing the scattering library, it is possible to use the standard sample that only
consists of non-measuring elements such as carbon and hydrogen.
It is also possible to set compounds such as oxides.
Compton and Thomson, which are scattered rays for the scattered ray correction, are
displayed additionally in fields for components.
 9. Select a component to enter standard value.

 10. Select <Std. value> in “Component type”.
 11. Enter a standard value.
 12. Select a component of <Compton>.

 13. Select a library.
 14. On Component Thomson, select the same library name as that in component of
Compton.

 15. Select the line of scattered rays to be edited, click Edit... in the Measuring
Condition frame, and edit a measuring condition.
 16. Click OK .
 17. Select Common Conditions by clicking.
 18.Click OK upon the completion of entering the conditions.

 19.When all items have been set, select [File]  [Save].
In SQX Scattering FP method, it is possible to use only 20mm in diameter only when
Sealing is OUT and to select 30 mm in diameter only in case that Sealing is IN under He
atmosphere.

Create Scattering Library Drift Correction Sample
This setup functions only when SQX Scattering FP method is attached.

The scattering library drift correction sample is used only for the sensitivity of scattered
X-rays
 1. Select [File] [New].

 2. Select <Scattering drift correction library> for “Library type”.
 3. Enter a new sample name for “Library sample”.
 4. Click OK .
 5. Refer to the setting procedure on Scattering Library Sample for the following
settings:

Save Under Different Name
A library sample can be saved under a different name.
1. Select [File] [Save As...].

2. Select a library type for “Library Type”.
3. Enter a new library sample name for “Library sample”.
4. Click OK .
Delete Library Sample
A library sample can be deleted. Care must be taken because a deleted sample cannot be
restored.
1. Select [File] [Delete].

2. Select a library type for “Library type”.
3. Select a library sample to be deleted for “Library Sample”.
4. Click OK .

Print Library Sample Information
Saved information about library samples can be printed. The content of a sample or a
list of sample names can be printed. In the case of the content of a sample, measuring
conditions can also be printed.
1. Select [File] [Print...].

2. Select a library type for “Library type”.
3. Select a library sample.
4. Select <Print content of a sample>, <Print content of a sample(with measuring
conditions)> or <List sample names>.
5. Click OK .

d. Library Sample Measurement
Preset library samples are measured.
1. Click Library Sample Meas. .
2. Select a library type for measurement on the “Library Sample Meas.” screen.
3. Select sample names.
4. Set a sample position.
5. Set sample information if necessary.
6. Click OK .

7. Put samples to be measured in the preset sample positions.

8. Click Analyze .
When there are many library samples to be measured, you can easily select necessary
samples by clicking All and then clicking unwanted samples to deselect them.
Reselect Library Samples
To delete an ID or add one in the preset library samples on the ID list, reselect library
samples.
1. Select [File] [Select Condition...].

2. Reselect library sample names to be measured on the “Library Sample Meas.”
screen.
5. Click OK .

Change Contents of Sample ID
The sample information that is set on the screen where library samples are selected is
common to all IDs. To identify IDs more distinctly, change sample information
individually. Sample positions can also be changed individually.
1. Select an objective sample ID on the “Library Sample Meas.” screen.

2. Select [Edit] [Edit Content of ID...].
 3.Change library type, sample name if necessary.

 4.Change the sample position if necessary.
 5.Change the sample information if necessary.
 6.Click OK .
Add, insert, cut, copy paste sample ID
It is possible to add, insert, cut, copy and paste sample ID of library sample as done in
sample ID edit in Analysis program.
 1. Select a sample ID in on the “Library Sample Meas.” screen.

 2. Select [Edit] and select from [Cut], [Copy], [Paste], [Add New ID…] and [Insert New
ID…].

e. Sensitivity Calibration
The sensitivity calibration obtains spectrometer sensitivity by comparing measured

X-ray intensities of library samples and theoretical X-ray intensities calculated from
constituting components using the FP method. When measurement has been made for a
newly created library, sensitivity calibration must always be carried out.
1. Click Library Update on the flow bar.
Select Library
1. Select [File] [Open...].

2. Select <Common library>, <Matching library> or <Drift correction library> for
“Library type”.
3. Select a library name.
4. Click OK .

Display SFP Sensitivity List
The SFP method that takes the photoelectron enhancement effect into consideration can
be used for boron (B) to oxygen (O) in bulk samples. The SFP sensitivity list displays
only those elements. Carry out the following procedure after selecting library:
1. Select [Data] [List SFP Sensitivities].
Display Sensitivity List
Carry out the following procedure after selecting library:
1. Select [Data] [List Sensitivities].

Change Scale
This function is used to expand a part of a sensitivity graph.
1. Select [View] [Scale Change...].

2. If necessary, enter a range for abscissa in “Atomic No.”.
3. If necessary, enter a range for the ordinate axis of the sensitivity.
4. Click OK .
To return the sensitivity graph to the initial scale, click Default.
Select Sensitivity Update on Sensitivity List
1. Select [Data] [List Sensitivities].

2. Click ▼ to update data for each element.
3. Select <No>, <Yes> or <Delete>.

4. Click OK .

Select Sensitivity Update on Graph
1. Click an element (rectangular mark) with the mouse on the graph.
2. Select <Update>, <Do not update> or <Delete> in the “Sensitivity” frame.
3. Click OK .
Update Sensitivity Library
After making selection for Sensitivity Update, carry out the following procedure:
1. Select [File] [Save].
Save is displayed beside List under the title bar of the “Library Update” screen. A
sensitivity library can also be updated using this Save.
Print Library List
1. Select [File] [Print Library List].

“Library type”.
4. Click OK .

Print Graph
1. Select [File] [Graph Print].

“Library type”.
4. Click OK .
<Print Library List> and <Graph Print> can be operated regardless of the library that has
been displayed.

f. Drift Correction for Scattering Library
This setup functions only when SQX Scattering FP method is attached.

The settings of a drift correction for Scattering library are operated.
Carry out the settings after the setup of Scattering Drift Correction Sample is
completed.
Create the condition of drift correction for Scattering library
 1.Click Scattering Drift Correction on the flow bar of sensitivity library.

The window of Scattering drift correction appears.
 2.Select a library name for Library.

 3.Select a measuring line of scattered X-rays to be set up from the list and then click
Property .

 4.Select a calculation method from < Alpha method > or < Alpha-beta method >.
 5.Select the drift correction sample at High side. If <Alpha-beta method> method is
used, it is necessary to select the drift correction sample at Low side too.
 6.Click Alpha-beta reset when resetting the coefficients currently stored.
 7.Click OK .
 8.Select [File] [Save] in due order when the setting is completed.
Reference intensities are automatically stored when the first measurement of drift
correction samples is carried out.
The setup of drift corrections for scattering library is completed at the initial operation
only. The coefficients of drift correction are automatically updated at every
measurement of scattering drift correction samples.
Print Scattering Drift Correction
 1.Select [File] [Print].

g. Scattering Sensitivity Calibration
This calibration functions only when SQX Scattering FP method is attached.

The sensitivity calibration obtains spectrometer sensitivity of scattered X-rays by
comparing measured X-ray intensities of library samples and theoretical X-ray
intensities calculated from constituent using the FP method. When measurement has
been made for a newly created library, sensitivity calibration must always be carried
out.
Prepare Scattering Sensitivity
 1. Click Scattering Library Update on the flow bar of the sensitivity library.
The window of Scattering Library Update is displayed.
 2. Select a library name to be calculated.

The FP calculation of theoretical X-ray intensities starts automatically.
 3. Select the scattering line from <Compton> or <Thomson>.
 4. Select calculation formula from <Ratio>, < Linear > or<Quadratic>.
 5. Click Calculate . Upon the completion of calibrating the sensitivity, the window of
Library Calibration Graph appears.

 6. As the need arises, operate sample selections of <Selected> / <Deselected>

by clicking plots on the graph.
 7.Click Recalc. to start re-calculating new sensitivity if the condition of the sample
selection is changed.
 8.Click Save to save the sensitivity.
Print Graph
 1. Click Print .
 2. Select the output from <Printer>, <Bitmap>, <Metafile> in ”Output” .
 3. When either <Bitmap> or <Metafile> is selected, create <File output folder> and
<File name>.
 4. Click OK .

Display Result
 1. Click Result to print out the result.
Close Graph
 1. Click X at the upper right corner of the graph.

3.5 Output Hazardous Elements (Option)
3.5.1 OUTLINE
In the SQX analysis, which is a standardless analysis method, lower limits of detection
can be reduced by using the fixed angle measurement for the analyses of Cd, Pb, Hg, Cr
and Br, which are object elements of the WEEE, RoHS and ELV Directives. Reports on
these hazardous elements can also be drawn up. This section describes the method and
contents of the SQX analysis to analyze elements including hazardous ones using the
hazardous element analysis option.
Qualitative applications for the SQX analysis of the sample types of metal, powder and
polymer have been registered beforehand as templates. By using these templates, the
analyses of Cd, Pb, Hg, Br and Cr can be made with high precision.
To analyze other samples, prepare qualitative applications referring to the template of
metal, powder or polymer.
3.5.2 PREPARATION OF QUALITATIVE

APPLICATIONS
Qualitative applications are used as analysis conditions.
Since the following qualitative application templates have been registered beforehand,
qualitative applications can be prepared using these template conditions:
Template for Hazardous Element Analysis (Standard Measuring Condition)

Sample Template Name Analysis Diameter Type
Metal Metal_RoHS 20mm Metal and alloy
Oxide Powder Powder_RoHS 20mm Powder
Polymer Polymer_RoHS 20mm Film and coating
“Metal_RoHS” and “Powder_RoHS” should be used for bulk samples, whose X-ray
intensities are not affected by thicknesses. “Polymer_RoHS” should be used for thin film
samples, whose X-ray intensities are affected by thicknesses. Therefore, when making an
analysis using “Polymer_RoHS”, enter beforehand the coating weight (mg/cm2) of an
analysis sample using Input Data... in the “Sample ID Setting” window on the Analysis
screen. When analyzing a polymer sample, use a disklike or pressed sample.

The procedure to prepare a qualitative application is described below, using the analysis of Cu
alloy with an analysis diameter of 20mm as an example:
1. Click Qual Application on the main menu.

2. Click <Create a new application> on the screen for an application and click Next .
3. Select <Use an application template> and the “Metal & Alloy” tab.
4. Select the “Metal_ROHS” template and click Next .

5. Enter an application name and click Finished .

6. In the right part of the “Select Element Range” screen, fixed angle analysis conditions
have been set beforehand to analyze trace elements with sufficient precision. If any
element (for example, Br or Hg) need not be analyzed, delete a setting for Br-Kα or
Hg-Lα on the left part of the screen. For deletion, right-click a spectral line to be
deleted and select [Delete]. (The measurement time can be shortened.)
7. Click Next .
8. Set information for <Sample Preparation> and click Next .
9. On the “Parameters” screen, first select a measuring diameter.
10. Then set <No> for the sample spin.
11. Click Next .

The “Check Measuring Condition” screen appears.

12. When the measuring diameter is 10mm, make necessary changes such as
lengthening the scan measuring time.
13. Click Next . Change settings on “Output information” if necessary.
14. Select <Output detection limit for undetected element (fixed angle)>.
When a check mark is placed for <Output detection limit for undetected element (fixed
angle)>, elements that were not detected in the fixed angle measurement are also
displayed on an analysis result and their detection limits are output. When you want to draw
up a hazardous element analysis report, be sure to place a check mark.

3.5.3 DRAWING OF HAZARDOUS ELEMENT

ANALYSIS REPORT
a. SQX CALCULATION
The setting procedure for an analysis is outlined below:
1. Click Data Processing  Qual Result on the main menu.

2. Select a target data file for [Target file].When the data file has been stored in a
subfolder, click Browse... , select an appropriate folder and then select the data file.
Like Br shown above, when a check mark has been placed for <Output detection limit for
undetected element (fixed angle)> on “Calculation Condition”, a detection limit is also displayed
for an element with an analysis result of zero.
When a liquid sample has been analyzed using a filter, a detection limit for the concentration of
the original liquid sample is displayed, as shown below:

By placing a check mark for <Output detection limit for undetected element (fixed angle)> after
an analysis is completed, detection limits can also be calculated for undetected elements in the
fixed angle measurement.
4. Place a check mark for <Output detection limit for undetected element (fixed angle)>.
5. Click <Calculate from qualitative analysis result.>.
6. Click OK .
7. Click Calculate.
Since the RoHS Directive defines values in concentration, select <mass%> for the unit of
each component.

b. DRAWING OF REPORT
1. Click Data Processing on the main menu.

2. Click Qual Result and select a necessary file.
3. Click Output Hazard. Elem.
4. Select an output type and click [OK].

5. Excel automatically starts and a report is displayed. For saving in a file, execute
[Save as].
(1) (2)
(3) (4)
“2. Analysis Results” and “3. Sample Spectrum” are created automatically.
To change the full scale in “3. Sample Spectrum”, select an appropriate file by selecting
Data Processing  Qual Result in ZSX Guidance, make the spectrum of an relevant
element displayed on the “Spectrum” tab, change the full scale and carry out the procedure
of Output Hazard. Elem. again.

Enter items (1), (2) and (3) using Excel.
Item (4) is pasted in the case of a micro mapping analysis result.
6. A new work sheet is added and a report in the Excel format is drawn up
automatically. After the report is drawn up, save it with another name in a folder
such as “My Documents” by selecting [Save As] on the [File] menu.
Because the default template files in the following folder are used as master files, do not
overwrite or delete any of them:
7. To print the report, make a setting for [Print Area], check a printing image using [Print Preview]
of Excel and select [Print].

3.5.4.CUSTOMIZATION OF TEMPLATE
a. LAYOUT OF REPORT
A report with a free layout can be drawn up by changing the layout of a report template.
<Example of Report>
Report No. Report Date:
Analyzed by:
Hazardous Element Analysis Report

Analyzed Date:
1. Sample Information
Sample name
Analysis group
Part No. No Sample Image.
Sample weight
Material
2. Analysis Results
Method X-Ray Fluorescence Analysis
Preparation
Atomic name Cadmium Chromium Lead Mercury Bromine
Atomic symbol Cd Cr Pb Hg Br
Judgment
Analyzed value
LLD
Unit
3. Sample Spectrum
<<Notes>>

b. DESCRIPTION OF NAMES
A report template can be easily customized by changing the positions of names. Details are
explained below:
Constitution of Names.
Names Contents
ANL_DATE Analysis date
SAMPLE_IMG Sample image (when available)
ANL_VAL_01 ～
Analysis value
ANL_VAL_10
JUDGE_01 ～JUDGE_10 Judgement
LLD_VAL_01 ～
Lower limit of detection
LLD_VAL_10
Manually input memo in sample ID
SMID_MEMO_01 ～
(Example: 01: Sample name, 02:
SMID_MEMO_09
Analysis company name)
SPECTRUM_IMG_01 ～
Spectral chart (image)
SPECTRUM_IMG_10
UNIT_01 ～UNIT_10 Unit
A spectral chart only of the individual qualitative analysis is output. A full range
qualitative analysis chart for Ti through U is not output.
The sheet name of a report template must be “Report”. If not, a report will not be
drawn up.

c. LIMIT RANGE VALUE MANAGEMENT SHEET OF TEMPLATE
It is possible to set limit range values on the “Standards” sheet.
Limit Range Value
Although any value can be entered for the company standard, set a value equal to or
smaller than an RoHS standard value. On a report, an analysis value smaller than a
company standard value is treated as “passed”, one larger than an RoHS standard
value as “failed” and one between an RoHS standard value and a company standard
value as “warning”.

d. ANALYSIS RESULT
Analysis results are expressed and judged as follows:
Expression Condition
N.D.-: No
Analysis A data item does not exist or an analysis value is zero.
detection
Value
[Numeric value] An analysis value exceeds zero.
Lower N.D.: No detection A lower limit of detection is zero.
Limit of
[Numeric value] A lower limit of detection exceeds zero.
Detection
An analysis value is below a company standard value.
OK In the case of no detection, a lower limit of detection is
below a company standard value.
An analysis value is equal to or greater than a company
standard value and below an RoHS standard value.
Warning In the case of no detection, a lower limit of detection is
Judgement
equal to or greater than a company standard value and
below an RoHS standard value.
An analysis value is equal to or greater than an RoHS
standard value.
NG
In the case of no detection, a lower limit of detection is
equal to or greater than an RoHS standard value.
Judgement Marks and Standard Values
NG
Analysis Value
RoHS Standard Value (Upper Limit of Threshold)

Warnin
g Company Standard Value (Lower Limit of
OK Threshold)
RoHS standard and company standard values can be used as the upper and lower limits of
thresholds for judgements in screening.

CHAPTER 4 QUANTITATIVE ANALYSIS
4. QUANTITATIVE ANALYSIS
4.1 QUANTITATIVE ANALYSIS
Quantitative analysis is generally used for control analyses such as process control and
quality control. To perform control analyses, it is important to select the appropriate
method. Various analysis methods are described below for your information.
The empirical calibration method and the Fundamental Parameters (FP) method are
the two primary quantitative analysis methods.
Selection of Empirical Calibration Method or FP Quantification Method
The criterion to select the empirical calibration method and the FP quantification
method is shown below. The FP quantification method cannot be used with an
application template.
Sample / Standards Conditions Empirical FP

All components in a sample are analyzed.
Some of the components in a sample are analyzed.
Standard samples that have similar composition as
unknown samples are not available.
Combination of Empirical Calibration and FP Quantification Methods
In the FP quantification method, the empirical calibration method can be used to obtain
the quantification values of some components. In this case, after determining analyzed
values using the empirical calibration method, calculation proceeds for the other
components using the FP method. Reciprocally, in the empirical calibration method, the
FP method cannot be used for any component.
In Chapter 4, the following marks are attached to descriptions for items concerning the
empirical calibration method and the FP method:
Mark Description
Indicates the empirical calibration method.
Indicates the FP method.
Bulk : Indicates a bulk sample.

Thin : Indicates a thin film sample.

a. Empirical Calibration Method
The relationship between the concentrations (or thicknesses) and corresponding X-ray
intensities of a component is called the calibration curve. The method that analyzes
unknown sample values based on such a calibration curve is called the empirical
calibration method.
Empirical Calibration Method
The empirical calibration method (standard sample comparison method) uses the
relationship between measured fluorescent X-ray intensities and concentrations
obtained from standard samples similar to unknown samples and the fluorescent X-ray
intensities of unknown samples to perform quantitative analyses.
 Correction Quantification Method
When effects of coexisting elements (absorption and enhancement of X-rays and overlap
of peaks) cannot be neglected in the empirical calibration method described above, a
calibration curve that can correct for those effects with calculations is used for
quantitative analyses. This is called the correction quantification method.
 Internal Standard Method
This is another method commonly used to correct effects of coexisting elements. Samples
that have known concentrations and contain an internal standard element added in a
constant proportion are used as standard samples. Calibration curves created from the
relationship between the X-ray intensity ratios (of the analyzed element to the internal
standard element) and concentrations are used for quantitative analyses. This method is
called the internal standard method.
 Additive Method
When standard samples are not available, a certain quantity of an analyzed element or
material that contains it (that has chemical composition similar to that of measured
material) is added to the unknown sample in several concentrations. A quantification
factor is calculated for the change of the concentration and the X-ray intensity. That
method is called the additive method.
Standard samples that have concentrations similar to those of unknown samples must be
selected to reduce effects of coexisting elements and avoid error factors characteristic of
samples.

b. FP Quantification Method
When it is assumed that an element is distributed uniformly in a sample, its fluorescent

X-ray intensity can be expressed as a function of the chemical composition of the sample
and fundamental parameters such as physical constants and a spectrometer sensitivity
value. This means that a theoretical X-ray intensity can be estimated for a given
concentration. The FP method calculates by regression the appropriate concentration or
thickness values that make the theoretical X-ray intensity and the measured X-ray
intensity identical.
The FP method is an abbreviation of the Fundamental Parameter method.
The following two methods can be used to obtain spectrometer sensitivity values:
1. Use standard samples that have composition similar to that of unknown samples
2. Use standard substances such as metals and reagents (sensitivity libraries)
Bulk Samples and Thin Film Samples
Fluorescent X-ray intensities increase as a sample becomes thicker. This makes

thickness analyses possible, but the analyzable thickness is limited. That is, after the
thickness reaches a certain value, X-ray intensities do not change. The two regions of
analysis are typically called the thin film and bulk regions. Since these regions vary
depending on the type of X-rays, thickness ranges of the bulk region and the thin film
region cannot be defined unconditionally.
FP Method and SFP Method
As described above, the quantification calculation using fundamental parameters is

called the FP quantification method. Between the FP quantification method and the
empirical calibration method is the SFP (Semi-FP) quantification method. The SFP
quantification method can be defined as “the empirical calibration method using matrix
correction coefficients obtained using the FP method”. That can be used only for bulk
samples and not for thin film samples. The SQX analysis in this software adopts the SFP
method that takes the photoelectron enhancement effect into consideration for boron (B)
to oxygen (O) in bulk samples. This method is called the photoelectron FP method.
X-rays of very light elements are affected strongly by enhancement by photoelectrons as
well as secondary enhancement by fluorescent X-rays. The photoelectron FP method
corrects the enhancement effect by photoelectrons and contributes to the improvement
of quantification precision for very light elements.

Restrictions for FP Method
 All components contained in a sample are objects of calculation.
Unlike the empirical calibration method, all components constituting the sample
are used for quantification calculation. Any unmeasured components must be
defined as the fixed value, manual input value or balance component, so that the
total of the concentrations is 100%.
 Elements must be distributed uniformly in a sample.
Assuming uniform distribution, theoretical X-ray intensities are calculated using

the FP method. Therefore, for example, in the case of powder samples, different
grain sizes for each sample will cause errors. Appropriate sample preparation is
necessary.
 In the FP quantification method, only the matrix effects can be corrected.
Though the absorption or enhancement effect to X-rays by coexisting elements in a

sample can be corrected, the measured X-rays cannot be corrected. For example,
since errors caused by overlap with a coexisting element peak and background
intensities cannot be corrected, one must measure X-ray intensities using suitable
measuring conditions. In the FP quantification method, it is assumed that net
intensities after background subtraction are used.
 In the thin film FP quantification method, information about the structure of layers
is necessary.
Concentrations cannot be calculated directly from measured X-ray intensities, and

likewise the FP method cannot identify a layer from which fluorescent X-rays are
generated. By setting the structure of layers beforehand, theoretical X-ray
intensities can be calculated. By comparing those theoretical X-ray intensities and
measured intensities, film thicknesses or concentrations are calculated. Since it is
assumed that elements are distributed uniformly in each layer, the distribution of
concentrations in the depth direction, or depth profiling within a film, cannot be
analyzed.

c. Various Samples Needed for Quantitative Analysis
Samples necessary for the quantitative analysis using the empirical calibration method
or the FP quantification method are described below. Those samples are classified into
the standard samples, drift correction samples and check samples.
Standard Samples
Standard samples are used to prepare a calibration curve or a sensitivity calibration

curve. It is preferable that these samples are similar to the unknown samples. They
must also have analyzed values that cover the concentration range of quantitative
analyses. Typically, an increase in the number of standard samples generates a more
accurate calibration curve.
Drift Correction Samples
Samples to correct long-term drifts of X-ray intensities used for calibration curves or
sensitivity calibration curves are called the drift correction samples. There are no
limitations of the concentrations and shapes of those samples. They must be stable over
long periods of time. For example, metal drift correction samples can be used for the drift
correction of a calibration curve for powder samples. If the standard samples described
above are stable, some of them can be used as drift correction samples.
Check Samples
To ensure that existing calibration curves or sensitivity calibration curves can be used in
normal operation, a check sample is run. Unlike the drift correction sample, the check
sample must be similar to the unknown samples and have known concentrations. Like
the drift correction samples, however, if the standard samples are stable, some of them
can be used for check samples.

4.2 CREATION OF QUANTITATIVE APPLICATION
The operational flow to create a quantitative application is shown below. Unlike the
procedure to create a qualitative application, many steps are necessary to create a
quantitative application. Specifically, in the flowchart shown below, the measuring
condition setup and the regression calculation may have many operational parts
themselves and may become complicated depending on the purpose of analysis. Their
operational procedures are therefore described separately in detail. In general, a
quantitative application must be created through thoughtful consideration and cannot
be set in one process. Therefore, one cannot typically follow this flow diagram in one
direction. It is necessary to repeat steps such as changing preset values, and by a trial
and error method of reconsidering and checking a good quantitative application is
developed. You need not set all items. It is possible to set necessary items alone.
Start
a. Creation of Application File
b. Setting of Application Information
c. Setting of Standard Samples
d. Setting of Analysis Information
e. Measuring Condition Setup
f. Measurement of Standard Samples
g. Regression Calculation
h. Setting of Control Information
End
1. Click Quant Application on the menu.

To create a quantitative application, components to be measured must be determined.

Similar to the qualitative application, templates are available. An application can be
created quickly by referring to a template when an appropriate one can be used.
Information items such as measured components and sample preparations have been
set beforehand in templates, so you can select necessary items. Regardless of whether a
template is used or not, a sample type must be selected.
When the menu item “Quant Application” is selected, <Application File> is started
automatically.

Example of Creation of Application File
An example using the Steel template in the Metal & Alloy category is described below:


4. Select the Metal & Alloy tab.
5. Select <Iron base>.
7. Select <Iron>.
9. Set an application name.
10 Select a diameter and an atmosphere.
11.Set a memorandum if desired.
12.Select <Common> for “Folder”.
13.Click Finish .

When a template is used, the empirical calibration curve method must be used.

Other Templates
Templates have been registered only for generally established analysis methods.
Applications for which standard samples are available on the market are set
preferentially as templates.

3. Select the tab of an application type and a category.
5. Select an appropriate template icon.
Creation Without Template
To create an application without using a template, select <Create your own application>.

4. Select the tab of an application type.

Create Folder for Applications
When registering an application by entering its name, a folder for registration can be
created.

3. Select the tab of an application type and a category.
5. Select a template.
6. Enter an application name and so on.

7. Click Browse… .
8. Select a folder on the “Select Folder” window.
9. Click Create folder… .
10.Input a folder name in the “Create Folder” window.
11.Click OK .
12.Click OK .
The Anlcond folder in the “Select Folder” window is the <Common> folder.
The folder specified by the user with User Administration in <6.1 h System Management>
has been selected as the default.

Modify Existing Application
To display an application that has already been created or modify a part of it, first select
it.
1. Select <Modify an existing application> on the “Application File” screen.
2. Click Next> .

3. Select a folder.
4. Select an application.
When the mouse pointer is placed at the application name, the memo of the application is
displayed.

When a part of an existing application has been changed, the old contents will be
overwritten if that application is saved under the same name. For comparison with data
of the past, it is recommended that an application that has been used at least once be
kept without changing its contents.
1. Select <Rename and save the application> on the “Application File” screen.
3. Select <Application> for “File type”.
4. Enter a new application name that is not identical to any existing file.
5. Select a folder to save the application.
6. When drift correction coefficient have been registered for the selected application,
the “Reset drift correction coefficients and reference intensities” check box is
displayed. Place a check mark when reference intensities for the drift correction for
the new application are to be remeasured.
A folder can be created by clicking Browse... .

Register as Template
A created application can be registered as a template. Using the registered template, a

new application can be created.
1. Select <Rename and save the application> on the “Application File” screen.
3. Select <Template> for “File type”.
4. Enter a new template name that is not identical to any existing template.
Change Analysis Type or Sample Model of Application
Another application can be created by changing an analysis type or a sample model in a

created application. This procedure can be used, for example, to estimate an application
created with the empirical method and compare it to one created with the FP method.
Usable combinations of the analysis type and sample model are “Bulk - Empirical”,
“Bulk - FP” and “Thin Film - FP”. The analysis type can be changed only between “Bulk
- Empirical” and “Bulk - FP”. The sample model can be changed only between “Bulk -
FP” and “Thin Film - FP”.
1. Select <Change analysis type/sample model> on the “Application File” screen.
3. Enter a new application name that is not identical to any existing file name.
4. If necessary, select <Analysis type change> or <Sample model change of FP method>.
5. When the sample model is to be changed, select an application type.

To change the empirical method to the FP method, the analysis unit of a component must
be “mass%”, “at%”, “ppm” or mol%”.
When flux is set, change to the thin film is impossible. When the number of components is
100 or more, change to the thin film is also impossible.
Change from the thin film to the bulk is possible only in the case of a single layer. In this
case, a substrate is not counted as the layer. When the measurement line of a substrate is
used as a measurement line for a film thickness, change is impossible.

Delete Application
1. Select <Delete an application> on the “Application File” screen.

4. Select an application to be deleted.

The application information includes setting items for the component selection and the
sample preparation.
1. Click Component Selection on the flow bar.
Setting of Component Selection
When an application has been created using a template, a standard set of components
has been selected. On the “Component Selection” screen, unnecessary components can
be deleted from the list and additional ones can be added. Select a component name used
for the quantitative calculation from the periodic table and include the choice of element,
oxide or special compound. Select a unit and an analysis type. The analysis type is
<Measure[EMP]>, <Balance>, <Input> or <Fixed>.

Add Element Component
This setting performs quantification calculations after the element conversion.
1. Select <Element> for “Type of component to add” and click an objective element
symbol in the periodic table.
Add Oxide Component
This setting performs quantification calculations with the addition of a standard oxide.
1. Select <Oxide> for “Type of component to add” and click an objective element symbol
in the periodic table.
Add Special Compound
This setting performs quantification calculations with a component other than an

element or an oxide. A component and its measured element line must be registered in
the compound table.
1. Select <Special compound> for “Type of component to add”.

2. Click an objective element symbol.
3. Select <Compounds of selected elements> or <All compounds> for “Compounds to
display”.
4. Select an objective special compound and click OK .
When a special compound is set, element symbols are not distinguished by color. But an
element that is set as a measured component in two or more places such as Si and Si3N4
is displayed in light blue.

When the sample type is the fusion bead and <All compounds> is selected for the special
compound, <Ig> is displayed as the component name. <Ig> is used for the component of
ignition loss in fusion bead samples.
Since an ignition loss component in a fusion bead can be automatically added in the
sample preparation information setting, it need not be set here.
Set here only components in a sample. Flux in a fusion bead and binder for analyzing a
powder sample should be set in the sample preparation information setting.
The component <Ig> of ignition loss in fusion bead samples is selectable only when the
fusion bead correction option is attached.
Set Analysis Unit
The units displayed at the completion of the quantification calculation can be set. When
setting the units for concentration, mass proportions cannot be mixed with molecular
proportions or atomic proportions.
1. Double-click the <Unit> selection cell.

2. Select an objective unit in the pull-down list.
Set Analysis Type to Other Than Measure
A component may be treated as a balance component, a manual input value for a

concentration or film thickness or a fixed value for a concentration or film thickness. In
each of these cases, there is no measurement for this component.
1. Double-click the <Analysis> selection cell.

2. Select <Balance>, <Input> or <Fixed>.

Setting of Thin Film Samples
Filters, films and coated samples are treated as thin film samples. Unlike bulk samples,
setting for a multi-layer (the same for a single layer) is needed. The order of layers
cannot be obtained using the X-ray fluorescence analysis. The structure of layers must
be set beforehand. In the case of coated samples, their bases can be set as substrates.
Set Substrate
1. Click Add Substrate .

2. As in the case of bulk samples, set components constituting the substrate.
3. Click Next .

Add Layer
1. Click Add layer .

2. Change the layer name as the first component if necessary.
3. Select the units for the layer thickness.
4. Select an analysis type from <Measure[FP]>, <Measure[EMP]> and <Fixed> for the
layer thickness.
5. As in the case of bulk samples, set components constituting the layer.
6. Click Next .
Insert Layer Above or Below Selected Layer
1. Select a layer on the “Component Selection for Film” screen and right-click it.
2. Select <Insert layer above> or <Insert layer below> on the menu.
3. Set information on the layer in the procedure described in the paragraph “Add
Layer”.

Change Set Contents for Layer and Substrate
1. Select a layer or substrate to be changed.

2. Click Modify .
3. Change the set contents.
4. Click Next .
Delete Layer or Substrate
1. Select a layer or substrate to be deleted.


Setting of Sample Preparation Method
To make an accurate analysis, sample information suitable for a sample must be set. For
example, to make an accurate analysis for a powder sample or a fusion bead, accurate
information is necessary such as a compounding ratio (binder weight/sample weight)
when mixing powder with binder or a dilution ratio (flux weight/sample weight) when
fusing sample using flux to make a fusion bead sample. Using this software, setting
contents for such sample information can be reflected in analysis conditions and the
theoretical matrix correction coefficients calculation. When an application is created
using a template, a sample preparation method has been preset. However, this
information is an example and should be treated as merely information for guidance.
Although setting items that are treated as memoranda need not be set, it is
recommended that they be set to record a sample preparation method.
Setting items for sample preparation information vary depending on a sample type.
Sample types are shown below:
Sample Type Analysis Samples

Metal & Alloy Metal samples such as iron, steel and non-ferrous metal
Powder Powder samples of as cement, ore, etc.
Fusion Bead Fusion bead sample of powder of cement, ore, etc.
Ceramic & Glass Lump samples of glass, ceramic, etc.
Polymer Samples of organic matter such as polymer and rubber
Samples of liquid instilled and dried on filter and of
Filter
filtered liquid
Film samples of thin polymer sheet, paper, etc. and thin
Film & Coating
film samples with multi-layer coat
Liquid Liquid samples such as solution or oil

Set Sample Preparation Method
1. Click Sample Preparation on the flow bar.

2. Change items corresponding to the sample type.
4. Click Next .
 Sample Preparation Method - Metal & Alloy

2. To set an option, click Show option . An additional option display area appears in the
lower part of the screen.
To set sample preparation information, select <Prepared>.

Set a sample preparation method, abrasive material and abrasive grit. This
setting is used for the analysis diagnosis but is not reflected in analysis conditions.
When you want to proceed to the next step without setting this item, click Cancel and select
an item on the flow bar directly.

ADDITION OF SAMPLE FILM INFORMATION ” regarding details of sample film.

 Sample Preparation Method - Powder
1. When binder is used to improve the formability of a powder sample, click <Used>
under “Binder/Grinding aids” and select a binder compound. Enter sample weight
and binder weight.
3. Set information on pulverizing, pressing dies and sample weight thickness. These
items are used for the analysis diagnosis but are not reflected in analysis conditions.
4. In the case of an ignited sample analysis, select <Converts before Ignited> and set
the component name of an ignition loss. A quantitative analysis value can be
converted into a concentration before ignition during an unknown sample analysis.
Ignition loss weight is automatically set in analysis parameters as an input
component.
Items below << Hide option on the screen are displayed only when Show option is clicked.

In the case of an ignited sample analysis, set analyzed values after ignition for the standard
values of standard samples. Register beforehand the component name of ignition loss
weight using the “Compound Table” program.
When the component names of binder and ignition loss are not displayed, register them
beforehand as binder and ignition loss using the “Compound Table” program.
Binder information is used in the theoretical matrix correction coefficient calculation in the
FP and empirical methods.
ADDITION OF SAMPLE FILM INFORMATION ” regarding details of sample film.
Checking <set to each sample>, it becomes possible to change each kind of film for
standard sample setting and when analyzed by FP method. (This is the function of ZSX

 Sample Preparation Method - Fusion Bead
1. Select a flux type under “Sample and flux”, and set flux weight and sample weight
for criteria.
2. When a component that becomes an ignition loss, such as water of crystallization or
a carbonic acid radical, exists in a sample and a correction is to be made for it, select
<Corrects for LOI in sample>.
3. When the ignition loss correction is to be made, select <Balance> or <Manual input>
for the handling of an ignition loss. If <Balance> is selected, the effect of an ignition
loss can be corrected even when the ignition loss is unknown. To use the ignition loss
value of a standard sample or an unknown sample, select <Manual input>. It is
automatically set in analysis parameters as an input component. The ignition loss
component is handled as <Ig>.
4. To use oxidizer, select <Used> and set an oxidizer type. For “Weight”, enter oxidizer
weight for a criterion. An addition ratio (oxidizer residual compound weight/sample
weight) is automatically set.
5. To prepare a fusion bead using a dilution ratio that is not constant, select <Corrects
for flux ratio>. Select <Each weight> or <Flux ratio> for “Input in analysis”.
6. When <Corrects for flux ratio> is selected, <Corrects for flux evaporation> can be
selected and setting becomes possible to make a correction for flux that evaporates
during fusion. In this case, fusion bead weight and sample weight are used, and they
are defined as input items in analysis parameters. And <Corrects for oxidizer
weight> can be selected.

The ignition loss correction and flux evaporation correction can be set only when the
system has the fusion bead correction option.
When any oxidizer is not displayed, enter and register a compound name as oxidizer using
“Special Compound” in the “Compound Table” program, and set a residual oxide at the
same time.
When <Corrects for flux evaporation> is not selected, the dilution ratio means (Flux
Weight/Sample Weight). When a correction is made for evaporation, the dilution ratio
means (Bead Weight/Sample Weight - 1).
When <Corrects for flux evaporation> is selected, only <Balance> can be selected for an
ignition loss.
8. When <Each weight> was selected for an input in an analysis for the dilution ratio
correction on the previous screen, set a component name when entering weight.
When <Corrects for flux evaporation> is not selected, enter the component names of
sample weight and flux weight. When <Corrects for flux evaporation> is selected,
enter the component names of sample weight and bead weight. When <Corrects for
oxidizer weight> is selected, enter the component name of oxidizer.
9. In the case of an ignited sample analysis, select <Converts before Ignited> and set
the component name of an ignition loss. A quantitative analysis value can be
converted into a concentration before ignition during an unknown sample analysis.
Ignition loss weight is automatically set in analysis parameters as an input
component.

Settings for pulverization, bead preparation condition and fusion bead diameter are used
for the analysis diagnosis but are not reflected in analysis conditions.
When a component name to enter weight is not displayed, enter a component name and
select a corresponding component type using “External Parameter” in “Compound Table”.
 Sample Preparation Method - Filter
This is an instillation method in which liquid such as aqueous solution is dripped on a

filter, dried and measured. In the case of the empirical method, sample preparation
information need not be set because it is regarded as a memo. In the case of the FP
method, setting like that for the SQX analysis is necessary because elements in a filter
are analyzed using the thin film FP method.
For setting contents for the FP method, see “Sample Type - Filter” in “3.2 c. Sample
Preparation Information”.
When the FP method is used, the concentration of solution can be calculated from a
sampling quantity, effective diameter and filter weight.
When the FP method is used, calculate the concentrations of elements in a filter using filter
weight and set them as the concentrations of elements in standard samples.
When Show option on the screen is clicked, setting for the type of a hollow cup to support
a filter appears. This setting is used for the analysis diagnosis but is not reflected in
analysis conditions.

 Sample Preparation Method - Ceramics & Glass, Polymer
A memo alone must be set.
 Sample Preparation Method - Polymer
1. Click <Used> under “Binder/Grinding aids” and select a binder compound. Enter
sample weight and binder weight.
3. Set information on pulverizing, pressing dies and sample weight thickness. These
items are used for the analysis diagnosis but are not reflected in analysis conditions.

When the component names of binder and ignition loss are not displayed, register them
beforehand as binder and ignition loss using the “Compound Table” program.
Binder information is used in the theoretical matrix correction coefficient calculation in the
FP and empirical methods.
 Sample Preparation Method - Liquid
1. When diluent is to be used, set information on it. Select <Used> and a diluent
component and set sample weight and diluent weight.
3. Set sample weight thickness. This item is used for the analysis diagnosis but are not
reflected in analysis conditions.
When the component names of diluent are not displayed, register them beforehand as
diluent using the “Compound Table” program.

ADDITION OF SAMPLE FILM INFORMATION” regarding details of sample film.
Checking <set to each sample>, it becomes possible to change each kind of film for
standard sample setting and when analyzed by FP method. (This is the function of ZSX
By using FP method, it makes possible to correct the measurement error caused by the
effect of sample thickness change for the analysis line having high energy in liquid
samples.
Especially for the case of tube below optics it is effective for the correction of the error due
to the difference of sample amount put in the sample holder or the error caused by the
height difference of liquid due to the difference of specific weight.
The correction of geometry effect which changes ratio of detectable area and
non-detectable area becomes possible for ZSX Primus IVi only. Sample cell CH1095 are
recommended to use for liquid sample.
<In case of tube below ZSX Primus IVi >

These values are default values of
weight thickness per unit area.
Set sample diameter or sample cell
designated.
Setting for the application of thin film

model using weight thickness value
Setting for the ratio change of

detectable and non-detectable area.
Calculating sample height using
sample weight and density is easy if
precise measurement of height is
difficult directly.

In both the empirical calibration method and the FP quantification method, standard
samples must be set. In the case of the FP quantification method, the total of the
concentrations of each standard sample must be within a range of 99 to 101%. However,
it is possible to change to within 97~103% in case of bulk FP method. In the case of thin
film samples, setting must also be made for the film thickness or weight. The number of
digits can be set and the setting for a certified value or an uncertified value can be made.
In the case of bulk samples, standard values can be copied from the Universal Standard
Samples, a database of standard values, or a sensitivity library can be used without
setting standard samples in the FP quantification method.
1. Click Standard Samples on the flow bar.

Set Standard Values
The standard values of bulk samples are set here. Analyzed values obtained using
another analysis method are set as standard values for the X-ray fluorescence analysis.
Set one sample in each line. When a standard value for a component is not available, set
a blank in the appropriate cell. That component will not be measured. If you want only
to measure X-ray intensity for a check, enter a zero.
1. Double-click the “Name” cell and enter a standard sample name.
2. If desired, double-click the “Note” cell and enter a comment.
3. Double-click the cell of each component, and enter a standard value.
Preset standard values are treated as certified values.
When the balance component is not set in the component selection of bulk FP method,
the selection of total standard sample concentration is indicated at the upper right of
standard sample setting screen.

<99~101%> is set in the initial values, however, total concentrations of standard

samples can be set in the range of 97~103% when changed to <97~103%>.
When <99 – 101%> is selected, theoretical intensities are calculated by normalized total of
concentration of all standard samples to be 100%. But in case of selection of <97~103%>,
theoretical intensities are calculated without normalization, therefore, it is effective to the
case that the total concentration of standard samples are off from 100% significantly.
 Thin Film Sample
In the case of film or filter samples, make sure to enter film thicknesses or weight values
for each layer.

Set Uncertified Values
Standard values can be treated as uncertified values. That setting does not affect a
result of the regression calculation. The setting merely indicates that those standard
values are uncertified values. Those standard values are displayed in parentheses like
(1.23) to distinguish them from certified values.
1. Right-click the mouse in the cell of the standard value of a component that you want
to set as an uncertified value.
2. Select <Uncertified>.
To restore the previous setting, follow the same procedure and select <Certified>.
Set Balance Component
An arbitrary component can be set as a balance component. Only one balance component
can be set in each sample or layer.
1. Right-click the mouse in the cell of a component to be set as a balance component.
2. Select <Calculation Balance>.
Copy One Line
1. Select a line to be copied.

2. Select [Edit] [Copy].
3. Select a line to paste into.
4. Select [Edit] [Paste].
5. Double-click the cell of a name, note or component, and change its contents if
necessary.
Delete One Line
1. Select a line to be deleted.

2. Select [Edit] [Delete].
Insert One Line
1. Select a location to insert the line.

2. Select [Edit] [Insert].

Copy From Universal Standard Samples
When you have a standard sample registered in the Universal Standard Samples,
standard values can be copied from that database. Information about certified values
and uncertified values are also copied.
1. Select a line to insert into.

2. Select [Edit] [Copy from Universal Standards].
3. Select a supplier or source.

4. Select a sample type.
5. Click OK .
6. Select a standard sample in the list.
7. Click OK .
To select all standard samples, click Select all.

Save Standards Information as Universal Standard Samples
Standard sample information such as manually input standard values can be saved to
the Universal Standard Samples. Saved standard sample information can be used for
other applications. The information is saved in the “House standards” folder of the
Universal Standard Samples.
 Create New Sample Type
1. Select [File] [Save to Universal Standards].

2. Select the “Create a New Type” tab.
3. Enter a sample type name.
4. Select a standard sample name to be saved.
5. Enter sample type information if necessary.
6. Click OK .

 Save to Existing Sample Type
1. Select [File] [Save to Universal Standards].

2. Select the “Save to an Existing Type” tab.
4. Select a standard sample name to be saved.
5. Click OK .
To select all standard sample names, click Select all.
Display X-Ray Intensities
When the “Standard Samples” screen appears, X-ray intensities are not displayed. To
check X-ray intensities after measuring standard samples, follow the procedure
described below:
1. Select [View] [Intensity].
For the equipment with DMCA (ZSX Primus IV/IVi), X-ray intensities which are already
measured standard sample cannot be input directory. If necessary, select the column of
X-ray intensity and make right click, and enter the values after deleting the content by
clicking <Delete> on the popup screen. Note that the extraction of X-ray intensity by PHA
modification to create a calibration curve cannot be performed because DMCA data is
lost due to manual input of X-ray intensity.

Copy Content of Standard Samples to Excel File
The standard values, X-ray intensities and background intensities of standard samples
can be copied to Excel files or the like.
1. Select a cell area to be copied on the “Standard Samples” screen, and right-click the
mouse.
2. Select [Copy] on the menu.
3. Paste data using the software of the destination of copying, such as Excel.
Copy Content of Standard Samples From Excel File
can be copied from Excel files or the like.
1. Copy data using the software of the source of copying, such as Excel.
2. Select a start cell for pasting on the “Standard Samples” screen, and right-click the
mouse.
3. Select [Paste] on the menu.
Export Content of Standard Samples to CSV File
can be exported to CSV files, which can be read by spreadsheet software.
1. Select [File]→[Data Export…].

2. Click Browse... and select a file output folder.
4. Click OK .

Import Standard Sample Data From CSV Files
CSV files with the predetermined format can be read to set the standard values, X-ray
intensities and background intensities of standard samples.
1. Select [File]→[Data Import…].

2. Click Browse... and select a file name.
3. Click OK .
The format of CSV files that can be imported is the same as that of exported CSV files.
Export a CSV file and check the file format.
Thin film standard sample data can also be imported and exported.

Change Typical Values
When standard samples are set, typical values are automatically calculated. Typical
values are important when considering measured element lines in the case of a thin film
etc. The average values of the set standard samples are calculated as the typical values
of components. To change them, follow the procedure described below:
1. Click Composition Information on the flow bar.

2. Double-click the cell of a typical value to be changed.
3. Change the value.
4. Click Next .
When Set Average is clicked, the averages of the standard values of standard samples are
recalculated.
When the sample model is the bulk and the units of all analysis components have been set
to mass%, ppm or ppb, the total of typical values is displayed. In the case of an FP method
application, set typical values such that the total falls within the range of 90.0 to 110.0%. In
the case of an empirical method application with which the theoretical matrix correction
coefficient calculation or analysis depth estimation is to be carried out, also set typical
values such that the total falls within that range.

The setting of analysis information is classified into “Parameters” and “Special

Standards”. “Parameters” is used to change the measuring method of a component or to
change a component to a non-measurement component. In “Parameters”, measuring
conditions concerning a whole application such as the measuring diameter and
measuring atmosphere are also set. The setting for “Special Standards” is necessary
only in the case of the FP quantification method.
1. Click Parameters on the flow bar.
The operational procedure in “Parameters” is described below:
1. On the “Analysis Information” tab, the type of each component can be changed, and
an extra component can be added or deleted.
2. On the “Measuring Condition” tab, set the measuring condition etc. of each
measured component.
3. On the “Calculate Parameter” tab, set the formula and coefficients of a process
parameter, a calculated component, etc.

d.1 Set Analysis Parameters
 Setting of Component Type and Its Detailed Setting
For an individual component, the measured element line is set or setting as a

non-measurement component such as the balance calculation or manual input is made.
In the case of a measured component, the FP method or the empirical calibration method
can be selected. The empirical calibration method can be used for one or several
components if applicable in the FP method application, but the FP method cannot be
used in the empirical calibration method application.
A component measured for correction for which the quantification calculation is not
made is also set here.
The non-measurement components, including any balance component, fixed value,
manual input, flux component, etc., can also be set.
 Setting of Calculated Parameter
For example, in a quantitative application to obtain analyzed results of Cr and Ni, you
can set a process parameter when you also want to report the ratio of Cr to Ni. One can
set a process parameter regardless of analyzed components. Like a process parameter,
information such as a known component or an additive can be used for a calculation and
a component for which external data is used can also be used for a calculation. The
following four types of calculated parameters are available:
Calculated Parameter Description

Process Parameter Ordinary parameter
Known Component
Calculated parameter of components constituting a sample
Parameter
Non-Component Calculated parameter of non-components that do not
Parameter constitute a sample
External Parameter Parameter using external data for a calculation

Setting Information on Analysis Information Screen
Add Empirical Calibration Method to FP Method Application
The analysis type is automatically determined when an application is created. For

example, when an application with the FP method is created, all measured components
are defined for the FP method. Likewise, when an application with the empirical
calibration method is created, all measured components are defined for the empirical
calibration method. The empirical calibration method can be added to the FP method
application. Follow the procedure described below:
1. Select a component to be redefined for the empirical calibration method.

3. Select <Empirical> for “Type”.
4. Click OK .

Change Measured Element Lines
In general, when there is no overlap of peaks, the K or L line is used for the measured
element line. So those measured element lines have been automatically selected. The
selected element can also be changed only for a measured element line to analyze a film
thickness in thin film samples.
1. Select a component to change the measured element line.

3. In the case of a thickness component in the film thickness analysis, select an element
for “Element line” in the “Measurement” frame.
4. Select a line for “Element line” in the “Measurement” frame.
5. Click OK .
Change Units
The procedure to change the reported units of a bulk sample or a thin film sample is
described below:
1. Select a component to change the unit.

3. Select an objective unit for “Unit” in the “Component value” frame.
4. Click OK .
Units set here are used for standard samples. Units set in limit range conditions are output
as analyzed results.

Density
This setting is made only for a film thickness component in a thin film sample. To
calculate a film thickness, a film density must be set. On initial setting, the default
density is calculated from the concentration ratios of the components. When the
accurate density of the film is known, set it as a fixed value.
Calculation with Fixed Density
1. Select a layer to fix its density.

3. Select <Fixed> for “Density” in the “Component value” frame.
4. Enter a density.
5. Click OK .
The unit of density is g/cm 3.

Setting of Non-Measurement Components
Non-measurement components include the balance component and the fixed

concentration value.
Set Balance Components
The balance component is not analyzed to calculate its quantification value. Its value is
calculated as the residual of the other components.
1. Select a component to be set as a balance component.

3. Select <Balance> in the “Component type” frame.
4. Click OK .

Known Components
The fixed value, input value or calculated value can be selected as the known
component.
Set Fixed Value for Known Component
When the concentration of a component is known for all measured samples, that
concentration can be set as the fixed value. Fixed values can be set for two or more
components.
1. Select a component to be set as a fixed value.

3. Select <Fixed> for “Known” in the “Component type” frame.
4. Enter a fixed value in the “Component value” frame.
5. Click OK .
Set Known Component as Manual Input
This setting is used when the value of a known component varies for each sample. Two
or more manual input components can be set.
1. Select a component to be set as a manual input component.

3. Select <Input> for “Known” in the “Component type” frame.
4. Click OK .
Set Known Component as Calculated Value
This setting is used when a component constituting a sample is treated like a process
parameter. Two or more calculated components can be set.
1. Select a component to be set as a calculated component.

3. Select <Calculate> for “Known” in the “Component type” frame.
4. Click OK .
5. Set the formula of a calculated component on the “Calculate Parameter” tab.

Additive / Flux
The known components described above are constituents of a sample. However, flux for a
fusion bead, oxidizer, binder for a powder sample, etc. are not contained in an original
sample and this program only displays them. Set those components using the program
for the sample preparation information.
Each of those components is handled in one of the following ways:

 Fixed Value: A mixing ratio (dilution ratio) is treated as a fixed value in an
application.
 Manual Input: A mixing ratio (dilution ratio) is entered for each sample at the time
of an analysis.
 Calculate: Flux or oxidizer weight, sample weight, etc. are entered manually at the
time of an analysis, and the software calculates an addition ratio (dilution ratio)
from them.

Advanced Settings
In the advanced settings, one can set the number of standard sample preparations, enter
a memorandum and select printed items for an analysis.
The number of standard sample preparations means the number of repetitions of

measurement until the calibration curve coefficients are updated. This sets the number
of repeats of newly prepared standard samples and uses the average values to update
calibration curve coefficients.
The maximum number of the same standard sample is nine. The averages of X-ray
intensities are stored till the designated number of measurement processes are
completed. Calibration curve coefficients can also be calculated while remaining
repetitions are still being completed.
For the first sample in the first series, <First sample> should be selected for “Update
Selection” on the “Sample ID Setting” screen. To use several series of sample IDs for the
standard sample measurement collectively for the designated number of repetitions,
<First sample> for the second series and subsequent series must be changed to
<Intermediate>. When a sample ID with <First sample> is analyzed, the calculation
table is initialized and the number of measured processes is also cleared.
This setting designates the number of repetitions of measurement till coefficients are
updated and not to measure the same sample repeatedly.
In addition, if the application is set by the bulk FP method, the selection of “Normalize
application result to 100%” is displayed.

1. Click Advanced on the “Analysis Information” tab.

2. Set the necessary number of repetitions for “Std sample prep. time”.
3. Set necessary information for “Description of Application”.
4. Select <Normalize application result to 100%> in case that the application is the
bulk FP method.
5. Select necessary items in the “Print selection in analysis” frame.
6. Click OK .
In case that the application is set by the bulk FP method, the selection of <Normalize
application result to 100%> is displayed in the initial state. When this is changed to
deselect, analysis values before normalization to 100% become application analysis
values. This is effective for the analysis of sample of which total concentration is off from
100% significantly.

Addition of Extra Component
Extra components are classified into three types: a measuring condition for correction, a
process parameter and an external parameter. Although they are not analyzed directly,
they can be used for correction of analyzed components and for calculation.
Add Element Line for Correction
Besides analyzed components, a so-called X-ray intensity correction measurement line is

added, such as a measurement line for an internal standard or a correcting
measurement line for the overlap correction.
1. Click Extra components on the “Analysis Information” tab.

2. Click Add .
3. Enter a correction component name for “Name”.
4. Select <Correction> in the “Component type” frame.
5. Select a measured element for “Element line”.
6. Select a measured element line for “Element line”.
7. Click OK .

Add Process Parameter
The process parameter is used to calculate and report analyzed results such as the ratio
of two components. The calculation formula of a process parameter can be set arbitrarily
but complicated functions cannot be used.

2. Click Add .
3. Enter a process parameter name for “Name”.
4. Select <Parameter> in the “Component type” frame.
5. Select a unit.
6. Click OK .
Setting of External Parameter
The external parameter utilizes external (non-X-ray) data for calculations. For example,
in the case of a bead sample, sample weight and flux weight are set with external
parameters. Those external parameters are used to calculate a dilution ratio with the
formula for a calculated flux component. The external parameter name is registered
beforehand as a compound.

2. Click Add .
3. Enter an element name or compound name for “Name”.
4. Select <Manual input> for “External parameter” in the “Component type” frame.
6. Click OK .

Delete Existing Extra Component
1. Select the extra component to be deleted.

Insert New Extra Component
1. Select the position for insertion of an extra component.

2. Click Insert .
3. Set a name and a component type information as in the case of addition.
Edit Existing Extra Component
1. Select an extra component to be edited.

3. Change any necessary setting items.

d.2 Evaluate Analysis Condition
1. Click Evaluation on the “Analysis Information” tab.
Evaluation of Analysis Condition
From the saved sample preparation information and analysis condition, problems etc.
concerning analysis are checked and displayed. Evaluation is carried out based on the
typical composition that was set on the “Composition Information” screen. When the
sample type is Film & Coating, the measured element line for the thin film analysis can
be evaluated.
The contents of evaluation vary depending on the sample type.

 Metal & Alloy

Contamination by abrasive is checked. When an abrasive paper belt or a grinder
and, for example, alumina abrasive are used for sample preparation, slight
contamination by aluminum occurs. The concentration of aluminum in the sample
is checked and a message appears to inform you that a problem may arise.
 Powder
Contamination from the crushing container or die is checked. When the sample film
is used in the loose powder method or the like or when the atmosphere is not a
vacuum, the fluorescent X-rays of light elements may be absorbed and the analysis
may be difficult. The absorption of X-rays by the sample film or the atmosphere is
checked. When the sample size and weight have been set, whether the sample is
thick enough to generate the measured element line is examined. For example,
when measuring the Ce-K line in a sample that consists mainly of light elements,
X-ray intensities may vary depending on the sample quantity because the Ce-K
line is not absorbed so much by the sample. This phenomenon is checked.
 Glass Fusion Bead

As in the case of powder, contamination from the crushing container is checked.
Whether elements contained in flux, oxidizer or exfoliation agent are objects of
analysis is examined. Whether halogen elements volatilize at the preset fusion
temperature is examined because they may volatilize during fusion if the fusion
temperature is high. The absorption of fluorescent X-rays to be measured is checked
against the thickness of the glass fusion bead.
 Polymer
In the analysis of chlorine in polyvinyl chloride, chlorine may volatilize affected by
X-rays from the X-ray tube. This phenomenon is checked.
 Filter
Whether elements contained in the hollow cup are objects of analysis is examined.
Volatile elements such as chlorine are checked.
 Liquid
Depending on the sample film used and the atmosphere (helium or air), the
fluorescent X-rays of light elements may be absorbed and the analysis may be
difficult. The absorption of X-rays by the sample film used and the atmosphere is
checked.
 Film & Coating

When the analysis method is the FP method, whether or not analysis is possible
using each preset measured element line is examined. In the analyses of
single-layer and multi-layer thin film samples, the analysis depth varies depending
on the line type of an element to be measured, and the accuracy of measurements is
affected greatly. In this evaluation, the optimum measurement line is retrieved and
displayed, and whether analysis is possible or not is judged. If a measurement line

has an overlapping spectral line, overlap information will be displayed.
・Evaluation
Using film thicknesses and composition set with Composition Information,
analysis precision with a combination of set measurement lines is estimated,
and whether analysis is possible or not is judged. If analysis is impossible,
problems will be displayed.
・Search Best Lines

Using film thicknesses and composition set with Composition Information, a
combination of measurement lines with which the best analysis precision is
obtained is retrieved and displayed. Whether analysis is possible or not is also
judged. If analysis is impossible, problems will be displayed.
When an interfering line (overlap line) that overlaps with an analysis line
exists, that interfering line is also displayed. Interfering lines are as follows:
K-line: Ka, Kb1

L-line: La, Lb1
M-line: Ma
When the influence of overlap exists, consider adopting the overlap correction.

Evaluation of Sample Thickness
By making a theoretical intensity calculation using typical composition and an input

thickness, an evaluation can be made for whether or not a sample thickness reaches the
bulk region. If a sample thickness does not reach the bulk region, make the sample
thickness constant or make the analyzing depth shallower by changing to a
measurement line with a longer wavelength.
This program has a function to make a calculation by changing the line, for example, by
changing the K-line to the L-line.
When a sample thickness reaches the bulk region, “Int. ratio to infinite for analyzing
depth” becomes 1.0.
When a sample thickness is thicker than “Analyzing depth”, the sample thickness has
also reached the bulk region. “Analyzing depth” means a sample thickness at which an
X-ray intensity realizes the preset “Int. ratio to infinite for analyzing depth”.

2. Click Sample Thickness .
3. Enter sample information.
4. Enter “Int. ratio to infinite for analyzing depth” to calculate an analyzing depth.
6. A calculation result is displayed.
7. To refer to a calculation result for another line of the same measurement element,
select a target line using <Line>.

This function can be used when setting has been made such that the total of typical
concentrations falls within the range of 90.0 to 110.0%.
To make an analysis after changing a measurement line, setting for a measurement line in
a measuring condition must be changed.
Evaluation of Analyzing Depth
For an FP method application using the thin film model, a calculation can be made for
how much X-ray intensities change relatively when a layer thickness is changed.

2. Click Analyzing Depth .
3. Select a layer for an intensity calculation using <Layer>.
4. Select a measurement line for an intensity calculation using <Line>.
5. Enter the maximum thickness of a layer for a calculation at <Thickness (Max.)>.
If the gradient of a graph is small in the standard sample range or thickness range
assumed for unknown samples, analysis precision will worsen.

Retrieve Optimum Measured Element Line
When an application that has the sample type of <Film & Coating> has been selected,
measured element lines can be retrieved.
1. Select the “Analysis Information” tab on the “Parameters” screen.

2. Click Evaluation .
3. Click Search Best Lines… on the “Analysis Evaluation - Film & Coating” screen.
To estimate the analysis precision of thin films, values of Composition Information are used.
The average of the values of set standard samples is set as the typical value of each
element by default. Therefore, when any standard sample has been changed, click Set
Average on the Composition Information screen for updating.
When composition information differs, optimum measured element lines may change. In
this case, reset the thickness and composition of an actual analysis sample as the
composition information, and carry out Evaluation again.
When different layers contain the same element, the simultaneous analysis of the thickness
and composition of each layer is generally difficult. By measuring the different
measurement lines of the same element, analysis may become possible. We recommend
that the composition and thickness of each layer be fixed or input manually for each
sample.

Calculate X-Rays Generated From Thin Film Sample
An intensity calculated theoretically for a specified measured element line is displayed.

If the film is too thick, it may be judged that analysis is difficult with any measured
element line.
1. Select the “Analysis Information” tab on the “Parameters” screen.

2. Click Evaluation .
3. Click X-ray Generation… on the “Analysis Evaluation - Film & Coating” screen.
4. Click Select Element Line… on the “Generation of X-rays from Thin Film Sample”
screen.
5. Select an element.
6. Select a line type.
7. Click OK .

The displayed X-ray intensity is an intensity calculated theoretically, not a measured

intensity.
Intensity Calculated
Description
Theoretically
Intensity of X-rays generated in each layer. “Total
Attenuated
intensity” is the total of these.
X-ray intensity calculated assuming a single-layer
Not attenuated
thin film that consists of that layer alone
Degree of the absorption of fluorescent X-rays
Attenuation ratio
generated in each layer by upper layers
X-ray intensity ratio assuming that the thickness of
each layer is infinite.
Ratio to infinite
When this value is 1.0, the thickness cannot be
measured.

d.3 Setting of Measuring Conditions
Detailed setting is made for each measurement of a sample component set in the
analysis information.
ZSX Primus/III+ setting screen ZSX Primus IV/IVi setting screen

(Function of ZSX Primus IV/IVi only
and applicable to the system shipped
newly.)
Change Measuring Diameter
This setting is the same for the entire application that is now being created. The
measuring diameter of unknown samples and that of standard samples must be
identical. Therefore, the measuring diameter is generally set according to that of
unknown samples.
1. Select an optimum measuring diameter for “Diameter”.
When the sealing (option) is in the “IN“ position because the atmosphere is Helium/Vacuum
or when the attenuator is used, only 30mm can be set for the measuring diameter.

Set Measuring Atmosphere
In X-ray fluorescence analysis, measurement is generally made in a vacuum. In the case

of liquid sample, however, the helium condition is generally used for measurement. In
this case, select <Helium/Vacuum> for “Atmosphere”. When the helium condition cannot
be set, measurement is made in air. Care must be taken in this case because X-rays of
light elements are absorbed more strongly in air than in helium.
1. Select <Vacuum>, <Air> or <Helium/Vacuum> for “Atmosphere”.
<Air> cannot be selected for “Atmosphere” when the spectrometer has the helium flush
mechanism (option).
Change Sealing (Option) Condition
This can be selected only when the measuring diameter is 30(28)mm. When the
atmosphere is <Helium/Vacuum>, the sealing is unconditionally set to “IN”. The sealing
can be selected also when the atmosphere is <Vacuum>.
Set Sample Spinning
When sample preparation generates a non-homogeneous surface, as in the case where a

metal sample was ground using a belt, measured intensities may vary depending on the
sample direction if the sample spin is not performed. In such a case, the sample spin
should be set.
1. Click Advanced on the “Measuring Condition” tab.

2. Select <Sample spin>.
3. Click OK .

Order of Measurement
In this spectrometer, considering the arrangement of the crystals, the measuring order
is set so that measurement will begin with components at low 2-theta angles and
proceed to higher angles. This function is called the optimization of the measuring order.
Regardless of the setting order of the components, measurement is made in the
optimized order to shorten the measuring time. To make measurement in the order of
the components in the setting list, follow the procedure described below:

2. Erase the check mark for <Optimize measuring order>.
3. Click OK .
Lengthen or Shorten Measuring Time
In general, when the measuring time of each component is made longer, measurement
precision becomes better. However, it would take a long time to change the measuring
time of each component each time. This system therefore has a function to lengthen the
measuring time collectively by multiplying it by a coefficient. An example of doubling
the measuring time is described below:

2. Select 2.0 for “Measuring time multiplier”.
3. Click OK .

Setting of APC
The APC (Automatic Pressure Control) is used to keep the vacuum level constant when
making measurements in the vacuum condition. This is especially effective for X-rays of
light elements with long wavelengths. The APC can be set for each application.
When a hygroscopic sample is measured, it may take a long time to heighten the vacuum
degree of the pre-evacuation chamber or a vacuum error may occur. In such a case, carry
out a measurement with the APC turned off.
1. Click Advanced under the <Measuring Condition> tab.

2. Select <APC> in the “Vacuum setting” frame.
3. Click OK .
Change Evacuation Speed for Pre-Evacuation Chamber
In this instrument, before loading a sample in the measurement chamber, preparatory

evacuation is completed in the pre-evacuation chamber. In the case of a pressed powder
sample or the like where the sample may be damaged if the chamber is evacuated
abruptly, it must be evacuated slowly. Select an evacuation speed suitable for a sample.
The leaking speed is also changed when unloading a sample.

2. Select <Fast> or <Slow> for “Evacuation speed” in the “Vacuum setting” frame.
3. Click OK .
Change Target Vacuum Degree for Pre-Evacuation Chamber
The target vacuum degree for pre-evacuation can be selected from the three levels of the
high, middle and low. When the high vacuum is set, variations in the vacuum degree in
the measurement chamber accompanying sample loading can be decreased. On the
other hand, when the low vacuum is set, a time required for sample loading can be
shortened. Set the target vacuum degree according to a sample to be measured and
necessary analysis precision.

2. Select a target vacuum degree at “Pre-evac. target vacuum” under “Vacuum setting”.
3. Click OK .

Change the measuring condition in a lump;
Following items are functions to change the measuring condition. (This is the function of
ZSX Primus IV/IVi only, and applicable to the equipment shipped newly.)
・Tube wattage: Tube voltage (kV) and tube current (mA) of all measuring conditions
are changed to set values.
・Protection filter: Primary X-ray filters equipped with the system are automatically
arranged for measurement line to protect X-ray tube on a priority
basis. Filter OUT is set for the area lighter than Cl-Ka in case of
the specifications without Be30 filter.
・Time: All measuring time set previously are changed to 2 second thoroughly. It can be
changed easily while checking the total measuring time. Minimum setting
time is 2 second.
Set different measurement diameters for analysis sample (applicable to FP method

only);
Generally, a quantitative analysis is made with samples of which measurement diameter

is set preliminary, however, in case that the diameter of analyzing sample and ones set in
the application are different each other (diameter of measurement sample is much
smaller in general), it is possible to set diameter for each sample when measured using
the application data preset as it is unchanged. (This is the function of ZSX Primus IV/IVi
only, and applicable to the equipment shipped newly.)
1. Click Advanced in the tab <Measuring Condition>

2. Select <Set diameter to each sample>.
3. Click OK .

In the Analysis and EZ Analysis, measurement diameter for each sample can be
changed as below when sample ID is set in the application.
Setting Analysis screen Setting EZ Analysis screen
Measured intensities to different measurement diameter are made with conversion factors
stored in advance. To improve the analysis accuracy it is recommended to make the
application having same measurement diameter as analysis sample.
When the attenuator is set in the private measuring conditioning type, setting of
measurement diameter for every analysis sample cannot be made. Adequate attenuation
of X-ray intensities using tube current and primary X-ray filter are needed in advance.

Advanced Settings of Measuring Conditions
The following three types of measuring conditions are available:
Type Description
Private Used only in one application
Library Used with library measuring conditions
Common Used in two or more applications
Since the private conditions and common conditions can be changed arbitrarily, there
are basically only two types of setting, the private (common) conditions and the library
conditions.
Set Private Conditions
In a private condition, an excitation condition, optical condition, PHA condition, peak

condition, background condition, etc. can be set. Those conditions are generally
optimized after measuring real samples and checking data. See “Measuring Condition
Setup (Optimize MC’s)” described later.

Change Excitation Conditions
For the optimum excitation conditions, see “4.3 QUANTITATIVE ANALYSIS

TECHNIQUES”. The better excitation condition is selected and switched automatically
on measurement. When you use a template, the recommended excitation conditions
have been set. Change any necessary items.
1. Select a component to change.

3. Set a tube voltage.
4. Set a tube current.
5. Select a primary filter to be used for “Filter”.
Change Optical Conditions
For the optimum optical conditions, see “4.3 QUANTITATIVE ANALYSIS

TECHNIQUES”. When you use a template, the recommended optical conditions have
been set. Change any necessary items. An item for which the system does not have a
corresponding option cannot be changed.

3. To use the attenuator, select <1/10>.
4. Change the condition for the slit if necessary.
5. Change the condition for the crystal if necessary.
6. Change the condition for the detector if necessary.
In the case of the ZSX Primus, ZSX Primus II or ZSX Primus IV /IVi, <1/10> can be
selected for the attenuator only when the measurement diameter is 30 mm and the sealing
is “OUT”.
In the case of the ZSX Primus III+, the attenuator can be set only when the measurement
diameter is 30 or 20 mm.

Change PHA Conditions
For the optimum PHA condition, see “4.3 QUANTITATIVE ANALYSIS TECHNIQUES”.
When you use a template, the recommended PHA conditions have been set. Change any
necessary items.

3. Change the lower limit in the “PHA” frame if necessary.
4. Change the upper limit in the “PHA” frame if necessary.
Change Peak and Background Conditions
For the optimum peak and background conditions, see “4.3 QUANTITATIVE ANALYSIS
TECHNIQUES”. When you use a template, the recommended peak and background
conditions have been set. Change any necessary items.

3. Select the background subtraction method if desired.
Background subtraction coefficients can be set only in the case of the 1 or 2 points method.

Special Setting
The following four measuring methods can be used for the quantitative analysis:
Measuring Method Description
A peak and backgrounds are measured with a measuring
Standard
time specified for each of them.
The optimum measuring times for a peak and backgrounds
Fixed with which the specified relative precision (%) is obtained is
precision determined using pre-measurement and then main
Time measurement is carried out.
optimization A peak is measured with the specified time. To measure
Optimize backgrounds, the optimum measuring times are determined
BG time using pre-measurement and then main measurement is
carried out.
A specified angle range is measured using a step scan to
Integration obtain integral intensities. When background measurement
has been specified, backgrounds are subtracted.
In “Fixed precision measurement”, to avoid too long measuring times, the measuring time
is limited to the total of the measuring times that have been set for a peak and backgrounds.
If the total measuring time obtained from the relative precision exceeds this maximum
measuring time, the maximum measuring time will be divided using the ratio of each
measuring time.
The procedure to set <Fixed precision> is as follows:
1. Select a measuring line on the “Measuring condition” tab.

3. Click Advanced .
4. Select <Time optimization> for “Measuring method”.
5. Select <Fixed precision> for “Method” in the “Time optimization” frame.
6. Input a required relative precision(%).
Select <Input Bkgd intensity(kcps)> when, in “Fixed precision measurement”, background

measurement is not carried out and the measuring time is obtained from manually entered
intensities. If background intensities are not entered, a calculation is made with the
intensities set to zeroes.

d.4 Setting of Calculated Parameters
There is no fundamental difference in the various types of parameters except that

objective components are ones constituting a sample or additives. Therefore, the setting
procedure is the same for all four types; the process parameter, the calculated parameter
of known components, the calculated parameter of known additives and the external
calculated parameter.
The four fundamental rules of arithmetic along with square root, natural logarithm and
exponential function can be used for calculation.
The “Calculation Parameter” tab is displayed only when a calculation parameter
component is registered.
1. Click the “Calculation Parameter” tab.

2. Double-click the coefficient cell and set necessary coefficients.
3. Click Formula 1 .
4. Double-click <Component> and <Coefficient>, and click <Operator> for the formula
in order to create a formula.
5. Follow the same procedure for Formula 2 if necessary.
The calculated results of Formula 1 can be used in Formula 2 by selecting F1 as a

component name. Take care not to execute division by zero.
If a component name includes a character string identical to any of the operators, a

calculation parameter cannot be set. Set a component name so that it will not include such
a character string.

Copy Calculation Parameter
A calculation parameter can be copied from the application currently in dialog or from
another application.
1. Select a parameter to be set and right-click the mouse. The pop-up menu of [Copy]
appears.
2. Click [Copy].
3. Select a source application from <Current application> and <All applications>.
4. When <All applications> was selected, select an application.
5. Select a calculation parameter to be copied.
6. Click OK .
If any component set in the calculation parameter to be copied is not included in the
application in dialog, an error message will be displayed and the parameter cannot be
copied.

d.5 Setting of Special Standard Samples
Special standard samples can be set only when the application is created with the FP
quantification method. In the FP method, unlike the empirical calibration method,
standard samples that have composition different from that of unknown samples can be
used. For example, when the composition of the film of unknown samples is different
from that of standard samples in the analysis of thin film samples, these special
standard samples can be set. The setting procedure is the same as that of ordinary
standard samples.
1. Click Special Standards on the flow bar.

Set Special Standards of Bulk Samples
The example of setting described below uses an alloy of Ti, Cr and Cu as standard
samples when components of metal unknown samples are Fe, Cr and Ni. Cr is used as
an example of a measured component. An application with the FP method is created
without using a template.
1. Click Special Standards on the flow bar.

3. Set a sample name.

4. Enter a memorandum for “Note” if necessary.
5. Click OK .

6. Select <Element> in the “Type of component to add” frame.

7. Click Ti , Cr and Cu in the periodic table.
8. Click OK .
9. Select the line of the component Ti.

10.Click Property .
11.Select <Standard> in the “Component type” frame.
12.Set a standard value in the “Component value” frame.
13.Select a unit in the “Component value” frame.
14.Click OK .
15.Set standard values for the components Cr and Cu.
16.Click Next > .
Since the standard samples are for the FP quantification method, the total of the
concentrations must be within a range of 99 to 101%.


Set Special Standards of Thin Film Samples

For thin film samples, film thicknesses or weight values must be set in addition to the
equivalent setting items for bulk samples described before.

Change Set Contents
1. Select [File] [Open].

2. Select an existing file.
3. Click OK .
1. Select [File] [Save as...].

2. Enter a new sample name.
3. Click OK .
Delete File
1. Select [File] [Delete...].

2. Select a file to be deleted.
3. Click OK .
To select all files, click Select all .

Setting of the case that the measurement diameter of samples set with special
standard samples are different from the measurement diameter of application;
Special standard sample can be used as standard sample for different size sample from
analysis sample. Intensity measured with different measurement diameter than
application is translated into for the diameter in the application and registered. (This is
the function of ZSX Primus IV/IVi only, and applicable to the equipment shipped
newly.)
1. Click New sample , and after input sample name, click OK .
2. Click Input components and select the components/elements of the sample to be set
using the periodic table.
3. Click Property for each element/component and input standard values. The Total
concentration must be 100mass%.
4. Confirm the measurement line for the sensitivity registration element, and then click
OK .
5. Repeat the steps above for all components to complete the setting.
6. Select adequate measurement diameter from the pull down list to set measurement
diameter.

Setting for the case that the measurement diameter of special standard sample is
the same for the application but the counting loss takes place on the measured
intensity of the measurement line of the special standard sample;
If the unknown sample is a thin film and the bulk sample is used as a special
standard for creating the sensitivity curve, counting loss often occurs when
measuring the special standard.
In this case, it is possible to measure under different measuring conditions than for
the application to reduce the intensity of measurement line of a special standard
sample so that measurements are made in the suitable counting rate. For example,
setting lower tube current than the application, or applying attenuator (available only
the case of 30mm measurement diameter) for special standard can be made. The
measured intensity is converted considering the application measuring condition and
the sensitivity registration is made using that intensity. (This is the function of ZSX
1. Click New sample , and after input sample name, click OK .
2. Click Input components and select the components/elements of the sample to be set
using the periodic table.
3. Select same measurement diameter as application from the pull down list to set
measurement diameter of special standard sample setting screen.
4. Click Property for each element/component and input standard value. Total of
concentration must be 100mass%.
5. Uncheck the <Use measuring condition of application> for the measurement line of
element of which sensitivity registration is made, and then set tube current which
does not make counting loss or set attenuator (available only for 30mm
measurement diameter). Both settings at a same time are also available.
6. Follow above steps for all components repeatedly to complete the setting.

e. Measuring Condition Setup (Optimize MC’s)
The optimum measuring conditions must be determined using the 2-theta scan and PHA
scan. Since the optimum conditions vary depending on an application, an expression
such as “THIS condition is optimum, set it” is impossible. You must understand samples
well and search for the optimum conditions by trial and error. Therefore, you may have
to go through this measuring condition setup procedure only once, or may have to repeat
it several times creating calibration curves and reconsidering the measuring conditions.
The measuring condition setup procedure is described below:
The excitation conditions, optical conditions and PHA conditions are the components of
the measuring conditions. To create a calibration curve or FP sensitivity curve, it is
fundamentally important to measure X-ray intensities of a measured component only.
That is, you must check that there are no overlapping peaks using the 2-theta scan and
that there is no overlap of energy using the PHA scan. From the viewpoint of angular
resolution or energy resolution, it may be difficult to create measuring conditions free
from all those overlaps. In that case, carry out correction calculations such as the
overlap correction in the regression calculation (Calibration program) described later.
The conditions monitored by the measuring condition setup are classified into the
excitation conditions, optical conditions and PHA conditions.
When checking each condition, it is recommended that the check be made using the
samples that have the highest and lowest concentrations in the concentration or film
thickness range of the standard samples of an individual component.

Excitation Conditions
1) Check on Counting Loss
Determine an excitation condition so that the highest intensity can be measured without
counting loss. For each measured component, carry out a 2-theta scan using the sample
with the highest concentration or film thickness in the range of the concentrations or
film thicknesses of the standard samples. If an unknown sample with a concentration
out of the range of the standard samples may be measured, create an excitation
condition taking this sample’s intensity into consideration.
In the case of the ZSX Primus or ZSX Primus III+, the upper limit of intensities that do
not cause the counting loss in the quantitative analysis is approximately 1000 kcps for
the SC and 2000 kcps for the PC. In the case of the ZSX Primus IV/IVi, the upper limit of
intensities that do not cause the counting loss is approximately 1800 kcps for the SC and
3000 kcps for the PC. Therefore, when X-ray intensities approach those values, take
sufficient care. When measuring intensities exceeding 1000 kcps using the SC or PC,
precision can be improved by adopting the integral measurement for the PHA setting or
setting a wide window.
2) Use of Primary Filter
Background can be lowered by using the primary filter. The primary X-rays from the
X-ray tube give energy necessary for excitation. When the primary filter is used, the
excitation efficiency is lower. However, even if the excitation efficiency lowers a little,
lower background may lead to a better calibration curve. For example, the characteristic
X-rays of the X-ray tube target material irradiate a sample and high efficiency and high
intensities are obtained for measured components having atomic numbers near that of
the target material, but these characteristic X-rays are scattered by the sample and
result in high background. Although the excitation efficiency lowers a little, by using the
primary filter and measuring a spectrum with lower background and a better
peak/background ratio, a better calibration curve can be created.

Optical Conditions
Improper setting of the optical conditions may cause poor accuracy of a calibration curve
or sensitivity curve. Check the following items with the 2-theta scan measurement:
1) Setting of Measured Element Line
For ordinary bulk samples, use an ordinary measured element line. For thin film
samples, a measured element line with a suitable escape depth must be selected.
2) Setting of Peak Position and Measuring Time
Basically in the empirical calibration method, standard samples that have composition
similar to that of unknown samples must be used. In such a case, since the compositions
(referred to as “matrix” hereafter) are nearly identical, backgrounds have generally
similar shapes. In that case, it is not necessary to measure background positions. By
determining only a peak angle and a measuring time in that position, a calibration curve
with sufficient reliability can be created. That measuring method is called the fixed
angle measurement or fixed angle analysis.
3) Setting of Background Positions and Measuring Time
Unlike the case described above, when standard samples of a different kind are added to
standard samples of the same kind, the background shape may vary according to the
change of the matrix. In that case, background positions as well as peak positions must
be measured. In qualitative analysis, background is estimated from a qualitative
analysis chart. In the fixed angle measurement, a background shape must be
reproduced with a small number of measured positions. Especially in the FP
quantification method, be sure to set the background measurement. For functions to
estimate the background shape, see “4.3 QUANTITATIVE ANALYSIS TECHNIQUES”.
4) Check of Overlap of Another Peak
Descriptions in paragraphs 2) and 3) are for a case where a measured element line is a
single peak. In fact, the peak of another component may overlap with the measured
element line. In such a case, further caution is suggested. It is especially important to
know constituting components, so it is recommended that all components be checked
beforehand. It is important to check the peaks of all components using the qualitative
analysis. The selection of monitored samples is also important. When peak overlap
cannot be eliminated with the optical condition, it may be eliminated by executing the
overlap correction.

 Operation Flow for Measuring Condition Setup
Determine the measured angle positions and measuring times of a peak and a
background (referred to as “BG” hereafter) by executing a 2-theta scan. According to the
flowchart shown below, determine the optimum measuring condition concerning the
2-theta angle for each component. Since the PHA condition should have been adjusted so
that the peak position will be at 200, carry out a measuring condition setup procedure
with the initial lower limit set to 100 and the upper limit set to 300.
Start
Measure sample with maximum

concentration
Measure sample with minimum

concentration
Overlapping drawing of 2-theta charts
Check overlapping peaks
Same BG shape?
No
Yes
BG fitting
Determine BG position
Determine BG measuring time
Determine peak position
Determine peak measuring position
End

Search for Standard Samples and Set Conditions Collectively
When using standard samples to set up a measuring condition, samples that must be
measured can be retrieved from the standard sample table and added collectively.
1. Click Optimize MC’s on the flow bar.

2. Select a method of searching for standard samples.
4. When a standard sample search result is displayed, set the position of each sample.
5. If necessary place a check mark for “Add heavy scan to identify overlap”.
6. Click OK .
When a check mark is placed for “Add heavy scan to identify overlap”, a 2-theta scan
condition for heavy elements is added. By referring to the automatic identification result
of this 2-theta scan measurement result, fluorescent X-rays overlapping with each
measurement line, such as the overlap of the L-line of a heavy element with an element
spectral line, can be identified more accurately. (There are two types of setting screen
depends on software version as below.)

Set Conditions
Usually, prepare a sample with high X-ray intensities and one with low X-ray intensities.
Make setting for each sample as described below:
1. Click Add .

2. Click Select All .
3. Enter a sample name.
4. Set the sample position.
5. To rotate the sample, place a check beside “Sample spin”.
6. Make sure that checks have been placed beside both items in the “Mode” frame, and
click OK .
The upper area is used to select data, while the lower area is used to display results.
The sizes of the display areas can be changed using the division line.


Set Measuring Conditions
1. Select the line for an objective measured element line.

2. Click Setting .
3. Click an item to be changed, and select or enter data.
4. Click OK .
The peak angle in the scan condition must be placed between the start angle and the end
angle.
Make Measurement for Measuring Condition Setup
1. Click Start , and measurement will start.
If the atmosphere at the startup of Measuring Condition Setup is different from the one set
in the application, data display and editing will be possible but measurement will be
impossible.

Display Measurement Result
1. Select a data item to be displayed in the data display area.

2. A measurement result is displayed in the result display area.
If there is a problem with the measurement data, such as too high X-ray intensities, a
warning mark will appear in the data display area. By placing the mouse cursor on this mark,
the contents of the warning can be checked.
When a data item for which a measurement is now being made is selected, it is displayed.
A data item for which a measurement has been completed can be displayed, and various
processes for it are possible during a measurement.

Draw Overlapping 2-Theta Charts
1. Select a 2-theta scan data item for which measurement has been made.
2. Select [View] [Select Reference Data…].
3. Select another data item that has the same measured element line.
4. Click OK .
5. Check the overlapping of peaks.
Two data items for the same element and with different peak heights are displayed so that
you can see backgrounds before and after the peaks.
Smooth 2-Theta Chart
1. Select [2-theta Scan]  [Option] [Smoothing…].

2. Enter the number of smoothing points. The range allowed is 5 to 49.
3. Click OK .

Carry Out Background Fitting
 Specify Intervals

2. Designate a range by dragging the mouse on the left side of an objective peak.
3. Designate a range by dragging the mouse on the right side of the objective peak.
4. Select [2-theta Scan] [BG Fitting] [Function Fitting].
5. Check the designated 2-theta angle ranges.
7. Click OK .
8. Check updated net intensities and click OK .

 Specify Points

2. Click 2 to 16 points on both sides of an objective peak in the chart.
3. Select [2-theta Scan] [BG Fitting] [Function Fitting].
4. Check the specified 2-theta point angles.
6. Click OK .
7. Check updated net intensities and click OK .

Set Peak Angle in Measuring Condition
1. Select [2-theta Scan] [Peak Angle Setting…].

2. Check the angle and click OK .
Set 1, 2 Point Background in Measuring Condition

2. Click one or two background positions in the chart.
3. Select [2-theta Scan] [1,2 Point BG Setting…].
4. Check the background angle.
5. Click OK .

Set Overlap Correction
Elements that may overlap with the selected measurement line are retrieved from
typical concentrations that have been set using “Composition Information” and
displayed for overlap correction setting.
1. Select [2-theta Scan] [Overlap Correction Setting].

2. Select a correcting element and click OK .
When the overlap correction has been set, measure standard samples and then calculate
overlap correction coefficients using the “Calibration” program.
The overlap rate is the ratio of an interfering line intensity to a measurement line intensity
and can be used for a criterion. A larger value means the greater degree of overlap.
An overlap correction method to be set is an overlap correction using concentrations in the

case of the empirical method and one using measured intensities in the case of the FP
method.
Calculate Background Subtraction Coefficients
1. Select [2-theta Scan] [BG Fitting] [Calculate BG Coefficient…].

2. Check the background angle and click OK .
3. Check the coefficients etc. and click OK .

Carry Out Peak Deconvolution

2. Designate a range by dragging the mouse from the left to the right of an objective
peak.
3. Select [2-theta Scan] [Peak Deconvolution] [Function…].
4. Select a type of the background calculation and click OK .
5. Check the net intensities etc. and click OK .

Calculate Peak Overlap Correction Coefficients
Overlap correction coefficients can be calculated only when the peak deconvolution was
carried out and net intensities were updated.
1. Select [2-theta Scan] [Peak Deconvolution] [Calculate BG Coefficient…].

2. Select a correcting line and click OK .
3. Check the coefficients etc. and click OK .
If a sample name entered when adding a condition differs from the sample name of a
correcting line, that correcting line cannot be selected. Be sure to register a sample using
the same name.

Calculation of Optimum Measuring Time
Once the peak and backgrounds have been determined, a precision can be estimated.
Two methods are available for estimation. One is to calculate a precision after
determining a measuring time, and the other is to calculate a measuring time after
determining a precision. When the relative precision is used in precision calculation, 1.0
is used for the relative concentration in the calculation. When the absolute precision is
used, an arbitrary value can be entered as the concentration. This function is effective
when analyzing samples for which a high precision or a shorter measuring time is
needed.
Calculate Precision
1. Select [2-theta Scan] [Analytical Precision Evaluation…].

2. Select <Calculate precision> in the “Evaluation method” frame.
3. Select <Standard> or <Optimize BG time> in the “Meas. method” frame.
4. Select a type of precision. When <Absolute> was selected, enter a concentration.

Heighten Precision
1. Double-click the peak or background measuring time.

2. Enter a longer measuring time and click Calculate .
Calculate Precision for Optimized Background Measuring Time
1. Select <Optimize BG time> in the “Meas. method” frame.

2. Select a type of precision.

Calculate Measuring Time
The method to calculate a measuring time with which a precision is 0.001 mass% for a
concentration of 2.0 mass% in the ordinary analysis is described below as an example.
“Maximum measuring time” is set to 100 seconds.
1. Select <Calculate measuring time> in the “Evaluation method” frame.

2. Enter 100 for “Maximum measuring time”.
3. Select <Standard> in the “Meas. method” frame.
4. Select <Absolute> in the “Type of precision” frame.
5. Enter 2.0 for “Conc.”.
6. Enter 0.001 for “Precision”.

Saving of Determined Measuring Conditions
Even if conditions have been determined through calculations, they will not be used for
analyses unless you save them in the files. Each time a measuring condition for an
analysis element has been determined, save it in the file using “Save Measuring
Condition”.
Save Measuring Condition
1. Click Save .

2. Check the contents and click OK .
Change Angle or Measuring Time Manually
1. Click Save .

2. Click an angle position to be changed.
3. Click Change in the center of the screen.
4. Enter an angle and a measuring time.
5. Click OK .
An item for which a new condition is left blank has not been changed from the old condition.

PHA Condition
1) Differential Measurement and Integral Measurement
Overlap of spectral lines on a qualitative chart can be corrected using the optical
condition described above and with overlap correction, if necessary. However, there is
one more item to be taken into consideration. It is the energy overlap of X-rays that
enter the detector, and can be checked with a PHA scan. X-rays of all wavelengths that
satisfy the Bragg’s formula enter the detector and are counted. If X-rays other than the
measured element line overlap, the accuracy of the calibration curve may suffer. A
condition to avoid that is called the PHA condition. A method to count objective X-rays
alone by setting a lower limit to eliminate noise and setting an upper limit to eliminate
higher-order X-rays is called the differential measurement. The range between the lower
limit and the upper limit is called the window. When there is no energy overlap issue,
the integral measurement method can be used. In the integral measurement, a lower
limit alone is set without setting an upper limit.
2) Escape Peak
Argon gas is used for the detector F-PC. When X-rays with energy higher than the Ar-K
absorption edge enter the detector, they excites Ar-K fluorescent X-rays and X-ray
signal pulses corresponding to energy lower by that of Ar-K are generated. When a
differential curve is drawn using the PHA scan, a peak appears at a pulse height lower
than an ordinary peak pulse height by this energy loss. This is called an escape peak. In
the case of the SC, which uses NaI, an escape peak corresponding to I-K appears.
3) Impurity Peak From Crystal (Fluorescent X-Rays From Crystal)
Fluorescent X-rays generated from a sample are separated by the crystal and enter the
detector to be counted. Then part of X-rays with high energy may excite the crystal and
generated secondary X-rays may enter the detector to be counted. Unlike an escape peak,
pulses generated from that impurity line must be excluded from the window. For
example, when measuring Na-K, the M line of Tl that constitutes the crystal is
generated and enters the detector. In that case, by setting the lower limit to about 150,
the impurity line from the crystal can be eliminated.

 Operation Flow for Measuring Condition Setup
Carry out a PHA scan, check energy overlap and determine measuring conditions. When
many parts of the PHA condition must be changed, you may have to execute the 2-theta
scan described in the previous paragraph again.
Start
Measure sample with maximum

concentration
Measure sample with minimum

concentration
Overlapping drawing
Escape peak exists?

Yes
No
Set lower limit excluding noises Set lower limit including escape peak
Higher-order X-rays exist?

No
Yes
Integral measurement?
No
Yes
Set upper limit No upper limit
End

Draw Overlapping PHA Scan Charts
1. Select a PHA scan data item for which measurement has been made.
2. Select [View] [Select Reference Data…].
3. Select another data item that has the same measured element line.
4. Click OK .
To select a PHA scan data item, first select a sample with higher intensities.
In general, escape peaks are conspicuous with components with high intensities and
noises are conspicuous with components with low intensities. Determine upper and lower
limits taking account of noises, escape peaks, etc.

Set PHA Pulse Height in Measuring Condition
1. Select [PHA Scan] [Detector Resolution…].

2. Change PHA upper and lower limits as necessary.
3. Click OK .
4. Check the calculated result of the detector resolution.
5. Click OK .
Save Contents Determined Using Measuring Condition Setup
1. Click Save .

2. Check the contents.
3. If there is an error in the contents, click Change and correct the error.
4. Click OK .

Print 2-Theta Scan and PHA Scan Data
1. Select data to be printed from measurement lines that were measured.
2. Select [File]  [Print].
4. When an item other than <Printer> was selected for “Output”, enter a file name and
make setting for <File output folder>.
5. Click OK .
Two or more data items can be output.
Output 2-Theta Scan and PHA Scan Data to CSV File
1. Select data to be output from measurement lines that were measured.
2. Select [File]  [Output Text File].
3. Select <CSV> or <TAB> for “Spreadsheet”.
4. Click Browse... and specify a folder for file output.
6. Click OK .

f. Measurement of Standard Samples
f.1 Standard Sample Measurement
Preset standard samples are measured.
Measure Standard Samples
1. Click Run Standards on the flow bar.

2. Select standard sample names to be measured on the “Run Standards” screen.
5. Make setting for “Repeat times” if necessary.
6 Click OK .

When there are many standard samples to be measured, you can easily select the desired
samples by clicking All and then clicking unnecessary samples to deselect them.
On the “Run Standards” screen, you need not select <Intermediate>,<First sample> or
<Last sample> for the update selection information, which is necessary on the “Sample ID
Setting” screen.
Reselect Standard Samples
To delete an ID or add one in the preset standard samples on the ID list, reselect
standard samples.

2. Reselect standard sample names to be measured on the “Run Standards” screen.
6. Click OK .

The sample information and number of repetitions that are set on the screen where
standard samples are selected are common to all IDs. To identify IDs more distinctly,
change the sample information individually. Sample positions and numbers of
repetitions can also be changed individually.
 1. Select an objective sample ID on the “Run Standards” screen.

 2. Select [Edit] [Edit Content of ID...].
 3. Change the sample name if desired.

 4. Change the sample position if desired.
 5. Change the sample information if desired.
 6. Change “Repeat times” if desired.
 7. Click OK .
Add, Insert, Cut, Copy, Paste Sample ID
It is possible to add, insert, cut, copy and paste a standard sample ID like the sample ID
setting in the Analysis program.
 1. Select an objective sample ID on the “Run Standards” screen.

 2. Select [Edit] and select an item from [Cut], [Copy], [Paste], [Add New ID…] and
[Insert New ID…].

Measure only the components added after standard sample measurement;
In case that the measuring component is added after standard sample measurement,
or the measuring conditions of particular measuring component are changed, it is
possible to measure the analysis line of the added/changed measuring component
without having to remeasure all standards. Setting procedure is same as ordinary
quantitative application.
1. Click Component selection and add element/component.

 2. Click Standard samples and input standard values for added element/component.
Confirm the X-ray intensity column is blank or zero.
3. Click Composition information and set representative value.
4. Click Parameters and decide measuring line and measuring condition.
5. Click Optimize MC’s and decide details of measuring condition of measuring line
added.
6. Click Run standards and select the standard sample and click OK after checking
<Measure only unmeasured components>. Only the standard sample which is set
component not measured yet is set to the sample ID automatically. (Sample
position is kept unchanged.)
7. Click Analyze to start measurement. Only the component not measured yet is
measured.
When the remeasurement is made with different measuring condition of particular

component, the intensity data of standard sample setting must be deleted beforehand
by right-click in the intensity column and <delete> to remove X-ray intensity for the
element.

f.2 Drift Correction Samples
Set Drift Correction Samples
1. Click Drift Correction Samples on the flow bar.
Measured X-ray intensities change (drift) with time. To correct for such a change, one
implements the drift correction method. The drift correction is performed to update
prepared calibration curves for a long period. The same operation is also necessary in
the FP quantification method. Since it typically takes a very long time to prepare
calibration curves etc. before each analysis, X-ray intensities are calibrated with several
drift correction samples. The check analysis is used to check that calibration curves are
in normal operation. If an abnormality occurred in the check analysis, the drift
correction should be run.

The drift correction is classified into two steps. Initially, the drift correction samples are
measured when calibration curves are created, and the reference X-ray intensities are
registered along with the intensities of the standard samples and the calibration curves.
Subsequently, if a check analysis shows a drift in intensity, the drift correction samples
are measured before analyzing unknown samples. The drift corrections are ratios of the
reference intensities of drift correction samples measured when calibration curves were
created to the intensities of the drift correction samples measured before analyzing
unknown samples.
The preparation for drift correction to register reference intensities is explained here.
The correction method is selected from the alpha method and the alpha-beta method
that are described below:
 Alpha Method
This is also called the one-point method. Only one sample that has about half the
highest X-ray intensity in the concentration range of a calibration curve or
sensitivity curve is set.
 Alpha-Beta Method
This is also called the two-point method. Two samples that have a high intensity
and a low intensity in the concentration range are set. This method is used when a
concentration range is wide and when X-ray intensities including background
intensities are used.
Drift Correction Samples
Since the drift correction corrects X-ray intensities, information about concentrations is
unnecessary with these samples. There is no limitation of the types of samples, except
that they must be stable for a long term and have X-ray intensities appropriate for the
alpha method or alpha-beta method in the concentration range. For example, the drift
correction of pressed powder samples can be carried out using metal samples. If
standard samples used to create calibration curves satisfy the requirements for drift
correction samples, they can be used also for drift correction.

Operation Flow for Preparation for Drift Correction
The flowchart of the procedure is shown below. As described before, when using
standard samples for drift correction, they need not be measured again. When standard
samples are not used for drift correction, X-ray intensities must be measured after the
following setting:
Start
Use standard sample(s)?

No
Yes
Set alpha or alpha-beta method Set alpha or alpha-beta method
Select from standard sample table Set new sample name(s)
Detailed setting Detailed setting
Measure drift correction sample(s)
All components set?

No
Yes
End

Use Standard Samples for Drift Correction
Setting for drift correction samples can be made on the standard sample table.
Automatic setting of drift correction samples from standard samples is also possible. The
alpha method or alpha-beta method is selected and drift correction sample names are set
here.
Start Setting Screen From Standard Sample Table
The standard values and, if already measured, X-ray intensities are displayed for each
standard sample name. Optimum drift correction samples are selected from this table.
Select a sample for each component and click High or Low , and that standard sample
will be set as a drift correction sample. Drift correction samples can also be set with Auto
selection .
1. Select [File] [Set from standard table].

2. Make selection from <Std. values & intensities>, <Standard Values> and
<Intensities> for “Display”.
3. Select a sample appropriate for the component and click High .
4. If necessary, select an appropriate sample and click Low .
5. Select High or High and Low for each component.
6. Check the selected drift correction samples and click OK .

Automatic Selection of Drift Correction Samples
To select drift correction samples from standard samples, the following three selection
criteria are used:
Criterion Description
Alpha
The alpha method alone is set.
method
Method The alpha-beta method is also set if possible.
Alpha-beta
The alpha method is selected if the condition is
method
improper.
Setting is made only for components for which drift
Unsaved
correction samples have not been selected.
Component Setting is made also for components for which drift
Saved correction samples have been selected and samples are
reselected.
X-ray intensities are compared and samples are
selected.
Measured
When measured intensities exist, the initial selection
condition is set.
Data
Standard values are compared and samples are
selected.
Standard
When measured intensities do not exist, the initial
selection condition is set.
 1.Click “Auto selection”.

2.Select <Alpha method> or <Alpha-beta method> in the “Selection method” frame.
3.Select <Select only unsaved components> or <Select saved and unsaved
components> in the “Components to select” frame.
4.Select <Measured intensities> or <Standard values> in the “Data to search” frame.
5.Click OK .

6. If necessary, select a sample not selected automatically and click High or Low .
7. Click OK .

Use Samples Other Than Standard Samples for Drift Correction
When standard samples are not suitable for drift correction samples, other samples can
be registered as drift correction samples. In that case, after setting drift correction
samples, they must be measured to register reference intensities.
1. Select a component for which to set drift correction samples.

3. Select the alpha method or alpha-beta method for the correction method.
4. Enter a drift correction sample name on the “High” side.
5. When the alpha-beta method was selected, enter a drift correction sample name on
the “Low” side.
6. Click OK .

Advanced Setting for Drift Correction
In the advanced settings, selectable items for the drift correction are the fixed time
multiplier, measuring condition, short term limits, maximum effective period and
sample preparation times.
1. Select a component for advanced setting.

Set Fixed Time Multiplier
The optimum time to analyze unknown samples is set for the measuring time in an
application. Since the drift correction is designed to recertify calibration curves using a
small number of samples, a longer measuring time may be used. But if the measuring
time in the application is changed, it must be returned to the previous value before
analyzing unknown samples. Therefore, by setting the fixed time multiplier, the
measuring time for the drift correction can be adjusted without changing measuring
conditions for unknown samples.
1. Set a multiplier for “Fixed time multiplier”.

2. Click OK on the “Advanced Setting of Drift Correction” screen.
The range allowed for the fixed time multiplier is from 0.1 to 99.9.

Set Measuring Condition to Use
The following two setting methods can be used to set a measuring condition for the drift
correction:
Measuring
Description
Condition Used
Current The measuring condition of the current application is used
Application intact.
Other Common When another measuring condition can be used in common,
Measuring that condition is used.
Condition A condition for a different measured element line can be used.
The common measuring condition means a measuring condition for which <Common> is
specified as the measuring condition type. See the paragraph “Advanced Setting of
Measuring Condition” in “4.2 d. Setting of Analysis Information”.
1. Select <Use meas. condition of current application> or <Use other common
measuring condition> for “Measuring condition to use”.
2. When <Use meas. condition of current application> was selected, click OK to
terminate the “Advanced Setting of Drift Correction” screen.
3. When <Use other common measuring condition> was selected, click “Select”.
4. Select a measuring condition.

5. Click OK .

Set Short Term Limits for Correction Coefficients
After a drift correction is carried out, correction coefficients can be checked by comparing
them to the previous correction coefficients.
1. Select <Alpha ratio change> or <Beta change> for “Short term limits”.
2. Enter a preset value.
3. In order not to update coefficients values in out of limits, select <Do not update
drift coefficients when a check error occurs>.
Set Maximum Effective Period
The effective period from the previous drift correction can be set. When the preset period
has passed and unknown sample analysis is executed without executing drift correction,
a warning is given. If you do not want to use this function, select <Unlimited>.
1. Select <Unlimited> or hours up to 999 for “Max effective period”.

Set Sample Preparation Times to Update
In the case of metal samples which have their surface is ground before each
measurement, when using the averages of values measured several times for drift
correction, the number of sample preparation times is set. By using averages, the
dispersion of data due to sample preparation can be smoothed. The range allowed is up
to 10 times. Take care because this setting is different from the number of repetitions of
measurement.
1. Select the number of preparations for “Sample prep. times to update”.
When setting sample IDs in Analysis program for a component set with more than one
sample preparation times, set sample IDs by the number of sample preparation times for
the drift correction samples and set <Last sample> at the last sample ID of drift correction
sample. Note that drift correction coefficient update is not carried out when the number of
measured sample IDs of the drift correction sample is smaller than sample preparation
times.

Reset Alpha and Beta Values
1. Click Alpha-beta reset on the “Property of Drift Correction” screen.

2. Click OK on the “Property of Drift Correction” screen.
Display Drift Correction Sample List
On the drift correction sample list, you can see which components in which applications
use a registered drift correction sample for their drift corrections. If necessary, you can
enter a memorandum.
1. Select [File] [List Drift Correction Samples].

2. Select a sample name at “Drift corr. sample”.
3. Click Input Note if necessary.
4. Enter a memorandum for “Note”.
5. Click OK .
6. Click Close .

f.3 Drift Correction Sample Measurement
Measure Drift Correction Samples
When samples other than standard samples are to be used as drift correction samples,
measure them using the “Run Drift Corr. Samples” program, and register reference
intensities.
1. Click Run Drift Corr. Samples on the flow bar.
2. Select sample names to be measured on the “Run Drift Corr. Samples” screen.

6. Click OK .

When there are many samples to be measured, you can easily select the desired samples
by clicking All and then clicking unnecessary samples to deselect them.
On the “Run Drift Corr. Samples” screen, you need not select <Intermediate>,<First
sample> or <Last sample> for the update selection information, which is necessary on the
“Sample ID Setting” screen.
When the first sample is measured, measurement results that have not been used for the
drift correction coefficient calculation are reset.
Reselect Drift Correction Samples
To delete an ID or add one in the preset samples on the ID list, reselect drift correction
samples.

2. Reselect sample names to be measured on the “Run Drift Corr. Samples” screen.
6. Click OK .

The sample information and number of repetitions that are set on the screen where drift
correction samples are selected are common to all IDs. To identify IDs more distinctly,
change the sample information individually. Sample positions and numbers of
repetitions can also be changed individually.
 1.Select an objective sample ID on the “Run Drift Corr. Samples” screen.

 2.Select [Edit] [Edit Content of ID...].
 3.Change the sample name if desired.

 4.Change the sample position if desired.
 5.Change the sample information if desired.
 6.Change “Repeat times” if desired.
 7.Click OK .
Add, Insert, Cut, Copy, Paste Sample ID
It is possible to add, insert, cut, copy and paste a drift correction sample ID like the
sample ID setting in the Analysis program.
 1.Select an objective sample ID on the “Run Drift Corr. Samples” screen.

 2.Select [Edit] and select an item from [Cut], [Copy], [Paste], [Add New ID…] and
[Insert New ID…].

g. Regression Calculation (Calibration)
The Calibration program creates calibration curves or sensitivity curves in the empirical
calibration method or the FP quantification method. After measuring standard samples,
calculations are made for each component to prepare for quantitative analysis.
Calculations are made by setting various conditions such as regression formulae,
background subtraction methods and matrix correction methods. Better calibration
curves or sensitivity curves are created through trial and error. In some cases, you must
return to recheck the measuring conditions. For further details, see “When Accuracy of
Calibration Curve Is Bad” in “4.3 b. Empirical Calibration Method”.
1. Click Calibration on the flow bar.
This software features the capability to carry out two or more regression calculations
and display their results simultaneously. You can consider and then save the results. For
example, as shown below, a result with a linear formula (right) and one with a quadratic
formula (left) can be compared and the better one can be saved:

Operational Procedure for Calibration
In the Calibration program, a calculation is made for each component according to the
following procedure:
Start
Select calculation type Selection of empirical calibration

method or FP method
Select calculation formula Selection of ratio, linear, quadratic

cubic or logarithmic
Select various corrections Setting of matrix correction, overlap

correction and internal standard
correction
Select samples Setting of sample selection, weighting

and fixed point calculation
Execute calculation Setting of calibration curve division,

registration and execution
Uncalculated component left?

Yes
No
End

g.1 Selection of Calculation Type and Formula

Usually, the analysis method with which an application is created is set as the
calculation type for all components. When the analysis method of the application is the
empirical calibration method, it cannot be changed to the FP method. When the analysis
method is the FP method, it can be changed to the empirical calibration method for any
components. In that case, after calculating quantification values using the empirical
calibration method, the FP calculation is carried out using those values as the fixed
values. Options for the formula vary depending on the calculation type.
Analysis Method in Application Analysis Type (for Each Component)

Empirical calibration method Empirical calibration method only
FP method FP method or empirical calibration method
When the total of typical concentrations is within the range of 90.0 to 110.0% in the
empirical method, a sensitivity calibration curve in the FP method can be displayed.
However, sensitivity cannot be registered.
Change Calculation Type

1. Select a component to change the calculation type.
2. Select <FP Method> or <Empirical> for “Type”.
The mark on the left of a component name indicates that the component has been
registered after a regression calculation or sensitivity calibration. When calculation has
been executed at least once for a component and the result is saved, this mark is
displayed.

Formula Type
The ratio method, linear formula, quadratic formula, cubic formula and logarithmic
formula can be used for the formula in the empirical calibration method. The ratio
method, linear formula and quadratic formula can be used for the formula in the FP
quantification method. The general form of those formulae is shown below. The constant
terms of each formula are shown in the following table. When the number of samples is
small, some formulae cannot be selected.
<Use calculated> in the options is used to calculate matrix correction coefficients and is
not selected here.
W  A I 3  B  I 2  C  I  D
Logarithmic Formula I B

W  A  ln  
 C 
W represents a concentration or film thickness, and I an X-ray intensity.
Formula Description Constant

Ratio A straight line that passes the origin is A=B=D=0
Method used.
Linear A straight line is used. A=B=0
An upward convex or downward convex A=0
Quadratic
curve is used.
Cubic A curve with two inflection points is used.
Log A logarithmic formula is used.
Calculation Type Formula Meaning of Formula

Empirical Ratio, linear, quadratic,
Calibration curve
Calibration cubic, logarithmic
FP Method Ratio, linear, quadratic Sensitivity curve
Select Formula Type
 In the Case of Empirical Calibration Method
1. Select a component for calculation.

2. Select <Ratio[one point]>, <Linear[straight]>, <Quadratic[curved]>, <Cubic
[curved]> or <Log[curved]> for “Formula”.
When the calibration constant is registered in the empirical calibration method, <Used
calculated> can be selected in the formula. This can be applied to calculating correction
coefficients with the calibration constants registered as fixed.

When <Log[curved]> is selected, it is impossible to set the matrix correction or overlap

correction. It is also impossible to set the fixed point calculation, weighting calculation or
calibration curve division.
<Log[curved]> is used to measure the film thicknesses of coatings etc. Although they can
also be measured using the FP method for thin films, <Log[curved]> can be used to
measure film thicknesses that cannot be measured using the FP method, such as films
containing organic matter.
 In the Case of FP Quantification Method

2. Select <Ratio[one point]>, <Linear[straight]>, or <Quadratic[curved]> for
“Formula”.

g.2 Setting for Correction Calculation
The matrix correction, overlap correction and internal standard correction are available
for correction calculation. The matrix correction and internal standard correction can be
set only in the case of the empirical calibration method and cannot be used in the FP
quantification method. The overlap correction can be used for both the empirical
calibration method and the FP quantification method.
Correction Calculation Valid Calculation Type

Matrix Correction Empirical calibration method
Empirical calibration method and FP
Overlap Correction
quantification method
Internal Standard Correction Empirical calibration method
Call Correction Setting Screen
1. Select a component to calculate a correction coefficient.

2. Click Correction .

Matrix Correction
The matrix correction recognizes the condition that concentrations or film thicknesses
do not correlate with X-ray intensities because of coexisting components in a sample.
Matrix correction method can be selected from <Correct concentration> and <Correct
intensity>.
<Correct concentration> method normally used is expressed as a general formula shown
below including overlap correction and used for calculation.
RijFj
Wi  ( AIi 3  BIi 2  CIi  D)(1  Ki  AijFj  QijFjFk  )
1  Wi / 100
 BijFj  DijFjFk  Ci
Item Description Item Description

Absorption/enhancement correction
Aij, aij
coefficient
Wi Quantified value
Qij, qij
coefficient (secondary correction)
Ii X-ray intensity Rij, rij Enhancement correction coefficient
Ki Constant Dij, dij
coefficient
Ci Constant Bij, bij Overlap correction coefficient
Calibration curve Analyzed values or X-ray intensities of
A, B, C, D Fj, Fk
coefficients coexisting elements j and k
The correcting values of Fj and Fk in the correction terms of Aij, Qij, Rij, Dij and Bij can
be used for either concentration correction or intensity correction. When expressed in an
uppercase character, concentration correction is used. When expressed in a lowercase
character, intensity correction is used.
Two methods are used for the matrix correction model: the dj correction method using a
binary-sample reference calibration curve and the j method using a straight-line
reference calibration curve obtained from samples with 0% concentration and with 100%
concentration. The JIS model is one of the dj method, and examples of the j method are
general correction methods of the Lachance Trail model and the de Jongh model and
special correction methods of the Rasberry Heinrich model and the Claisse Quintin
model.
The JIS, Lachance Traill and de Jongh models are widely used, but the other models are
not used so widely because they are in the stage of empirical formulae. This system
employs the general formula applicable to all correction formulae.
In general, the Aij term is employed for absorption/enhancement correction and the Bij
or bij term for overlap correction. The other correction terms are called special correction
terms.
Besides, <Correct intensity> method of matrix correction is expressed as a general

formula shown below including overlap correction and used for calculation.
RijFj
Wi  CIi(1  Ki  AijFj  QijFjFk  )
1  Wi / 100
 BijFj  DijFjFk  D
The meaning of each correction term is same to <Correct concentration> method. The
basic calibration formula when <Correct intensity> method is selected is Wi = CIi+D.
The calibration graph is plotted with the corrected X-ray intensities. Moreover, as the
special correction for fusion bead sample, <Correct intensity and BG> method can be
selected. This method is effective when the optional glass bead correction is included,
and D term of calibration intercept of <Correct intensity> method is made to D (1+RF)
and D term is corrected with dilution rate RF. When oxidizer correction method is
carried out, the correction with residual oxidant/sample weight ratio is also added.
The following three methods can be used for matrix correction:
Method Description
Enter published values Published values such as ones in JIS G 1256 for iron
manually. and steel analysis are entered manually.
Obtain with Coefficients are calculated with regression calculation
calculation. using many standard samples.
Theoretical correction coefficients are calculated with
Obtain theoretically.
the FP method. This method is generally used.

Change matrix correction method;
There are three matrix correction methods available namely <Correct concentration>, <
Correct intensity > and <Correct intensity and BG>, and the default setting is <Correct
concentration>.
<Correct intensity> is able to be selected only when the calibration formula is set to
<ratio> or <linear>. <Correct intensity and BG> is available for fusion bead sample.

Enter Published Values Manually
The procedure to enter published values manually is described below. In this method,
values are entered manually for each necessary component and regression calculation is
carried out.
1. Select a component to enter matrix correction coefficients manually.

3. Click Addition .
4. Select <Absorb/Enhance> for “Method”.

5. Select <A(concentration)> for “Type”.
6. Select a correcting component in the “1st component” box.
7. Select <Fixed> in the “Coefficient” frame.
8. Enter a published correction value.
9. Click OK .
10.Repeat steps 3 to 9 for necessary correcting components.

Calculate Matrix Correction Coefficients
To obtain matrix correction coefficients with regression calculation, many standard

samples are necessary. Furthermore, those standard samples have independent
concentrations for each component. When samples that satisfy those conditions are
available, this method can be used. In most cases, this method cannot be used.
1. Select a component to calculate matrix correction coefficients.

5. Select <A(concentration)> for “Type”.
7. Select <Calculate> in the “Coefficient” frame.
8. Click OK .
9. Repeat steps 3 to 8 for necessary correcting components.
When the number of standard samples is small, do not use this method because accurate
calculation is impossible.
Set Theoretical Matrix Correction Coefficients
To obtain reliable correction coefficients using regression calculation, many standard

samples are necessary. In the theoretical matrix correction coefficient calculation using
the FP method, correction coefficients can be calculated without standard samples.
Calculated correction coefficients are used for correcting calculation for components that
use the empirical calibration method.
Uncorrected Component Description

Analyte Corrects using all components except the
(Lachance-Traill Model) analyzed component.
Base Corrects using all components except the base
(de Jongh Model) component.
Base/Analyte Corrects using all components except the
(JIS Model) analyzed component and base component.
The Lachance-Traill model or de Jongh model is
Auto automatically selected according to typical
composition.
Here it is assumed that theoretical matrix correction coefficients have been calculated
and registered. For the procedure to calculate correction coefficients, see “Calculate
Theoretical Matrix Correction Coefficients” in “4.2 g.4 Calculation”.

Correction With X-Ray Intensities
Though concentrations are ordinarily used for term A in the general formula, X-ray
intensities can also be used.

4. Select <Special correction>.
6. Select <a(intensity)> for “Type”.
Set Special Correction Formula
To use any of the special correction methods, the Rasberry Heinrich model and the
Claisse Quintin model, follow the procedure described below. Set term R for the former
and term Q for the latter.

4. Select <Special correction>.
5. Select <Enhance> for “Method”.
6. Select a correction type at “Type” from <R(concentration)>, <Q(concentration)>,
<r(intensity)> and <q(intensity)>.
8. Select a correcting component in the “2nd component” box when the correction type
is <Q> or <q>.
10.Click OK .
11.Repeat steps 3 to 10 for necessary correcting components.

Overlap Correction
When the overlap of spectral lines exists, the overlap correction can be made. Overlap
correction coefficients to be used for this overlap correction can be calculated using the
regression calculation. The overlap correction can be applied to both the empirical
calibration method and the FP quantification method. Term B or b in the general
formula for the matrix correction is the overlap correction term.
In an application with the FP method, the FP method is selected initially for the
calculation type. In that case, an overlap correction coefficient can be calculated using
measured or theoretical intensities (option) or a fixed value can be entered.

Set Overlap Correction With Calculation
The procedure to calculate overlap correction coefficients is as follows:
1. Select a component to execute overlap correction.

2. Click Correction.
3. Click Addition.
4. Select <Overlap> for “Method”.
5. Select <B(concentration)> or <b(intensity)> for “Type”.
8. Click OK.
Set Fixed Value for Overlap Correction
The procedure to enter a fixed value for an overlap correction coefficient is described
below:

2. Click Correction.
3. Click Addition.
7. Select <Fixed> in the “Coefficient” frame.
8. Enter a fixed value.
9. Click OK.

Display Possible Overlap Lines
A correcting component can be set from possible overlap lines.

6. Click List possible overlap .
7. Click OK on the “Possible Overlap Lines” screen.

10.Click OK .
If no possible overlap line is found, the “Possible Overlap Lines” screen will not appear and
a message will be displayed.

Also in the case of the FP method, a correcting component can be set from possible
overlap lines.

4. Select <Measured intensity> or <Theoretical intensity> (option) for “Method”.
5. Click List possible overlap .
6. Click OK on the “Possible Overlap Lines” screen.

7. Select a correcting component in the “Correcting line” box.
9. Click OK .
10.Click OK .
If no possible overlap line is found, the “Possible Overlap Lines” screen will not appear and
a message will be displayed.
The overlap correction by <Theoretical intensity> is usable only when Quant. theoretical
overlap correction option is attached.

The common operations concerning calculation setting of matrix correction coefficients

and overlap correction coefficients are described below:
Change Correction Coefficient
1. Select a component to change a correction coefficient.

3. Select a correction term number to change a coefficient.
4. Click Edit .
5. Change the contents.
6. Click OK .
Insert Correction Coefficient
1. Select a component to insert a correction coefficient.

3. Select a correction term number to insert a coefficient.
5. Set the contents of the correction method and so on.
6. Click OK .
Delete Correction Coefficient
1. Select a component to delete a correction coefficient.

3. Select a correction term number to delete a coefficient.
5. Click OK .
Reset All Correction Coefficients
1. Select a component to calculate a correction coefficient.

3. Click Reset coefficients .
4. Click OK .

Internal Standard Correction
The matrix correction adjusts the calibration for effects of coexisting elements, while the
internal standard correction can correct errors resulting from thicknesses of samples. In
general, a sample that contains an element that has a peak near that of the measured
element line is added to all analyzed samples, and the ratios of the X-ray intensities of
the analyzed component to those of the added component are used for analyses. That
added component is called the internal standard sample.
As an example of such an application, one can use background intensities near the
measured peak without adding standard material to the samples. That method is called
the scattered X-ray internal standard correction. The internal standard correction
cannot be used for the FP quantification method.
Set Internal Standard Correction
1. Select a component to make internal standard correction.

3. Select <Internal standard>.
4. Select a correction line used for the internal standard.
5. Click OK .
In the case of a component for which background intensities are measured, <Background>
is displayed as an option for the internal standard correction. The above screen shows a
case where background intensities are measured for Si.

Special Correction Methods in FP Method
The automatic background subtraction and the scattered X-ray internal standard
correction are described below. Those functions are valid only in the case of the FP
quantification method and cannot be used for the empirical calibration method.
These functions are usable only when Quant Scattering FP method option is attached.
Set Automatic Background Subtraction (Option)
This function measures background intensities when measuring standard samples and
estimates background intensities when measuring unknown samples. The setting
procedure is described below. For further details, see “4.3 QUANTITATIVE ANALYSIS
TECHNIQUES”.
1. Select a component to execute automatic background subtraction.

3. Click BG Subtract/Internal Standard .

4. Select <Auto BG subtraction>.
5. Select a method in the “Calculation method of BG calibration” frame.
6. Select <Calculate> or <Fixed> in the “BG sensitivity constant” frame.
7. Click OK .
The options in the “Calculation method of BG calibration” frame can be selected when the
net intensity or gross intensity of the designated line has been saved.

Set Scattered X-Ray Internal Standard Correction
To use the quant. scattering FP method (option), theoretical background X-ray

intensities can be used as the internal standard. For further details, see “4.3
QUANTITATIVE ANALYSIS TECHNIQUES”.
1. Select a component to execute scattering internal standard correction.

3. Click BG Subtract/Internal Standard .

4. Select <Scattering internal standard correction>.
5. Select a scattered line.
6. Click OK .

g.3 Sample Selection
Standard samples are measured to create a calibration curve or an FP sensitivity curve.

In the sample selection of the Calibration program, setting is made for how the program
will utilize the measured data of those standard samples. This data is used for
calculation, to execute weighting calculation or to designate a fixed point sample.
When selecting samples to be used for calculation, this software distinguishes the
analyzed values of each sample. That is, the certified values are displayed in blue and
the uncertified values in yellow, so that you can distinguish them at a glance.
The procedure to select samples for calculation is described below:

Select Samples Used for Calculation

2. Click Sample Selection .
3. Select samples necessary for calculation in the “Select samples to calculate” frame.
4. Click OK .
In the default condition, all samples have been selected.
To select all samples, click Select All.
Clicking Deselect All makes all samples non-selected state. When a few standard samples
are selected while a lot of standard samples are there, this function is effective.
Deselect Uncertified Value
By setting uncertified samples beforehand, they can be eliminated during calculation.

3. Click Deselect Uncertified .
4. Click OK .
Restore Saved Sample Selection
This operation is valid after a regression calculation is executed and the result is saved.
The sample selection condition on saving is recorded, which helps when comparing it to
other sample selections.
1. Select a component for which a calculation was made using other sample selection.
3. Click Saved Selection .
4. Click OK .

Execute Weighting Calculation
When a regression calculation is carried out for a component that has a wide range of
concentration, samples with high concentrations may come near the calibration curve
and ones with lower concentrations may go off the curve. In such a case, the weighting
calculation is useful. The designation by measuring precision or effective digits of
analyzed values can be used. In the weighting calculation, the designation by measuring
precision to calculate using measured X-ray intensities is generally employed, but the
designation by the number of digits after the decimal point can also be set.

3. Select <Precision> or <Effective digits> for “Weighting”.
4. Click OK .
In the case of the FP method, <Effective digits> cannot be selected.
Execute Fixed Point Calculation
The setting to shift a calibration curve to samples with low concentrations using the
weighting calculation is described above. The fixed point calculation is a function to
make a calibration curve to be created pass through a designated sample. This fixed
point calculation can be used simultaneously with the weighting calculation.

3. Select <Fixed point calculation>.
4. Select a sample to be designated as the fixed point.
5. Click OK .

g.4 Calculation
After selecting a calculation type, selecting a calculation formula, setting various

correction types and selecting samples as described above, a calculation is made to
create a calibration curve or FP sensitivity calibration curve. For convenience, the
expression “regression calculation” is also used for the FP sensitivity calibration
calculation. As described before, two or more calibration curves can be created and
compared. That is, the calculated result with the optimum condition can be selected
from various calculated results and saved.
Though one calibration curve covers the whole range of concentration or film thickness
in the case of the first calculation, the calibration curve can be divided into up to three
parts in the case of a recalculation. An example of calculation is shown below:

2. Select a type.
3. Select a formula type.
4. Set correction items if necessary.
5. Select samples if necessary.
7. Click Result .
Be sure to save the calculated result.

Calibration Curve Division
In most cases, one calibration curve can be used for the whole range of concentrations.
When the matrix of samples changes at a certain value or when a concentration range is
very wide, it may be impossible to cover the whole range with one calibration curve. In
such cases, quantitative analyses are possible by dividing the calibration curve and
using an individual calibration curve for each range. Up to three regions can be set and
individual divisions are displayed as Low (L when abbreviated), Middle (M when
abbreviated) and High (H when abbreviated).

2. Select a type and a formula.
3. Select or set necessary items for the correction items and sample selection.
5. Click Recalc. .
6. Select 2 or 3 for “Number of lines”.
7. Select a formula in each division.
8. Set a division range for “Calculating range”.
9. Click OK .
The calibration curve division and calibration range setting is not available in the FP
method.

Printing of Result
Various formats are used to print regression calculation results depending on whether
the calibration curve division is used, whether the number of matrix correction
coefficients is 10 or less, whether the overlap correction is used for FP sensitivity
calibration and whether matrix correction coefficients alone are to be printed.
Graphs can be output not only to the printer but also to bit map files or metafiles.
Print Result
1. Click Print on the “Empirical Calibration Graph” or “FP Calibration Graph” screen.
3. When the “Output” setting is not <Printer>, make setting for <File name> and <File
output folder>.
4. Click OK .
Selection for <File output folder> can be made easily by clicking Browse… .
When <Matrix correction coefficients> is selected, a table of matrix correction coefficients

alone is output.

Change Scale
You can designate an area using the common tool buttons and change the scale. You can
also click the “Scale Change” button on the “Empirical Calibration Graph” screen and
enter a value manually to change the scale.
1. Click (the area designation button) on the tool bar.

2. Designate an area to change the scale in the “Empirical Calibration Graph” or “FP
Calibration Graph” screen.
3. Click Scale .
4. Check the values of X and Y axes in the designated area, and change values if
necessary.
5. Click OK .
To restore the initial scale designated in the measuring condition, click Default.

Calculation of Various Data
When the “Calibration” screen is displayed, theoretical matrix correction coefficient

calculation, standard sample quantification, etc. can be carried out. The following items
can be processed:
Menu Bar Item Processing Item

Theoretical matrix correction coefficient calculation
Calculate
Standard sample quantification
Data table processing
Data Addition and change of calculation condition
Thin film initial value setting
Calculate Theoretical Matrix Correction Coefficients for All Components
By changing concentrations of a sample step by step and checking changes of theoretical

X-ray intensities, matrix correction coefficients can be calculated. That method is called
the theoretical matrix correction. This method is widely used because it can calculate
valid correction coefficients even when the number of standard samples is small. The
following four methods are available to calculate theoretical matrix correction
coefficients:
Uncorrected Component Description

Analyte Corrects using all components except the
(Lachance-Traill model) analyzed component. The linear formula is used.
Corrects using all components including the
Base
analyzed component itself except the base
(de Jongh model)
component. The linear formula is used.
Corrects using all components except the
Base/Analyte
analyzed component and base component. There
(JIS model)
is no limitation with the calibration formula.
The Lachance-Traill model or de Jongh model is
Auto automatically selected according to typical
composition.
When there is a balance component, select the de Jongh model, JIS model or “Auto”.
When the base component is designated as the uncorrected component, set the
component with the highest concentration as the base component. To calculate the
correction coefficients of the base component, set the component with the second highest
concentration as the second base component.

1. Select the “Calibration” screen.

2. Select [Calculate] [Theoretical Alpha Calculation].
3. Select <Analyte>, <Base>, <Base/Analyte> or <Auto> for the uncorrected
component.
4. Select the base component if necessary.
5. Select the second base component if necessary.

7. Select a component name.
8. Select <Standard>, <Balance> or <Flux> for “Type”.
9. Enter a standard value if necessary.
10.Select a unit.
11.Select <Calculate alphas>.
12.Select <Use ratio with scattering line> if necessary.
13.Select a scattering line if necessary.
14.Click OK .
15.Repeat steps 6 to 14 for necessary components.
16.Click OK on the “Theoretical Alpha Calculation” screen.
17.Check the calculated result on the “Theoretical Alpha Calculation” screen.
18.Click Save .
When the main component is not included in the application condition like iron in steel, click
Addition to add the component as the <Balance> component and make a calculation.
Quant Scattering FP method (option) makes it possible to calculate theoretical coefficients

of matrix correction for the calibration curve prepare with the intensity ratio of fluorescence
X-rays to scattered X-rays (scattering internal) when this application concerned selects the
parameter of scattering condition like Rh-KC (Compton scattering) and so on.

It is possible to calculate theoretical coefficients of ignition loss correction and dilution

correction by FP method for the application of fusion bead samples when the fusion bead
correction option is attached.
When flux for a fusion bead, oxidizer and binder for a powder sample are all added to a
sample, <Flux> is displayed for the component type.
It is possible to copy displayed theoretical matrix correction coefficients to the clipboard.

Press the Ctrl+C key in the tool bar to copy data to the clipboard, and paste data to the
spreadsheet software Excel or the like.
Calculate Theoretical Matrix Correction Coefficient for Each Component
1. Select a component for which to calculate a correction coefficient.

2. Select Correction .
3. Click Theoretical Alpha Calculation .
4. Select <Analyte>, <Base>, <Base/Analyte> or <Auto> for the uncorrected
component.
5. Select the base component if necessary.

6. Select the second base component if necessary.
7. Click OK .
8. Check the calculated result on the “Correction for Empirical” screen

Execute Standard Sample Quantification
To execute the standard sample quantification, sensitivity constants and calibration

curve coefficients must have been calculated for all element lines. Check all the
marks on the left of each component name.
It is possible to quantify using a standard sample as an unknown sample to verify the
calibration curve. X-ray intensities when the standard samples were measured are used
for the calculation.
1. Select “Calibration” screen.

2. Select [Calculate] [Calculate Standards].
3. Select either <Use sample selected for calculation of calibration/sensitivity

constant> or <Use following sample> regarding the selection of the standard
samples to use for accuracy calculations,.
4. <Use following sample> is selected, select standard samples from the list.
5. Click OK .
<Use sample selected for calculation of calibration/sensitivity constant> can be selected

when the application is created based on bulk FP or empirical method. The thin film FP
method does not apply.
To print a standard sample quantification result, click Print.

It is possible to copy a displayed standard sample quantification result to the clipboard.

Press the Ctrl+C key to copy data to the clipboard, and paste data to the spreadsheet
software Excel or the like.
g.5 Data Table Processing
In the data table processing, measured X-ray intensities and analyzed results are
displayed in a table. Its contents can be checked and printed, and standard values can be
corrected.
Check Measured Data
Measured X-ray intensities and analyzed results are displayed in a table. Peak
intensities and background intensities can be displayed.

2. Select [Data] [Display Data Table...].
3. Select <Fluorescence> or <Background> for “Displaying data”.
It is possible to copy a displayed data table to the clipboard. Press the Ctrl+C key to copy
data to the clipboard, and paste data to the spreadsheet software Excel or the like.

Print Data Table

2. Select [Data] [Print Data Table...].
3. In the case of the FP method, select data to be output and click OK .
Text Output of Data Table
The contents of the data table are output to a text file that can be handled by a
spreadsheet program or the like.

2. Select [Data] [Output Text File of Data Table...].
3. Select <Fluorescence> for “Displaying data”.
4. Select <CSV> or <TAB> for “Text format”.
5. Click Browse .
6. Select a folder (directory) to save a file on the “Select Directory” screen.
7. Click OK on the “Select Directory” screen.
9. Click OK .

Correct Data Table
Standard values and X-ray intensities can be corrected.

2. Select [Data] [Correct Data Table...].
3. Select a sample to be corrected.
4. Click OK .
5. Correct the standard value and/or measured intensity of each component.
6. Click OK .

Change Background Subtraction Method
This function is used to reconsider background subtraction after obtaining results using
quantification calculation.
1. Select “Calibration” screen.

2. Select [Data] [Change BG Subtraction...].
3. Click the “Subtract BG” cell of an objective element.
4. Select <Yes> or <No>.
5. Click OK .
Only components with background measurement are displayed.
When the “Subtract BG” setting is changed from <Yes> to <No> and a calculated result is
registered without background subtraction, delete background measurement from the
measuring condition of that component using “Parameters”.

Change Measured Element Line
This function is used to consider the optimum measured element line after obtaining
results using quantification calculation. To execute this function, two or more measured
element lines must have been registered beforehand as intensity correction element
lines of extra components. X-ray intensities must also have been measured.

2. Select [Data] [Switch Analytical Lines...].
3. Select a line name for “Current line to switch”.
4. Select a line name for “New line”.
5. Click OK .
Add Theoretical Intensity Overlap Correction Line (Option)
The ordinary overlap correction uses measured X-ray intensities, while this function
uses theoretical X-ray intensities for overlap correction. This function can be used for an
application with the FP method.

2. Select [Data] [Add Overlap Line for Theoretical Intensity Correction...].
3. Select an analytical line in the “Analytical line” list.
5. Make selection for “Element” and “Line”.
6. Click OK on the “Add Overlap Line for Theoretical Intensity Correction” screen.
Theoretical intensities for the overlap correction have been calculated for lines for
correction with * marks.
This feature functions only when Quant. theoretical overlap correction option is attached.

Add Standard Sample
A standard sample may be added. For example, to add a standard sample to an

application of metal, an application in the folder of the same kind (metal) is retrieved.

2. Select [Data] [Add Standards...].
3. Select an application that has a standard sample to be added.
4. Select a standard sample to be added.
5. Click OK .
Display Saved Results
Calculated results can be displayed.

2. Select [Data] [Saved Results Preview...].
3. Select components to be displayed.
4. Click OK .

Initial Value Setting for Thin Film Sample
This function is valid only in the case of thin film samples. To analyze thin film samples,
an appropriate initial value must be set. In the initial condition, the average of the
standard samples used for calculation has been set. To change this value, use this
function. When the component type is “Fixed”, the value cannot be changed.

2. Select [Data] [Initial Value Setting for Film...].
3. Double-click the initial value of an objective component.
4. Set a new initial value.
5. Click OK .

g.6 Manual Input of Constant
Various constants in calibration curves and sensitivity calibration curves calculated

with the “Calibration” program can be displayed and changed. The basic operational
procedure is almost the same as that for the “Calibration” program, but a manually
input result cannot be checked using a graph etc. In the case of the FP quantification
method, setting can be made for the automatic background subtraction.
Open Constant Input Screen
1. Select [Constant Input] on the [Data] menu.

Display and Manual Input of Calibration Curve/Sensitivity Coefficients
The calibration curve coefficients of each component can be displayed, and entered
manually if necessary. Setting can also be made for the calibration curve division.
Set Calibration Curve Division
1. Click Change Number of Lines and Boundaries .

2. Select <2 lines [L,M]> or <3 lines [L,M,H]> in the cell for the number of lines.
3. Double-click the <L upper, M lower> cell.
4. Enter a boundary value.
5. When the number of calibration curves is 3, double-click the <M upper, H lower> cell
and enter a boundary value.

Display and Manual Input of Matrix Correction
The matrix correction coefficients of each component can be displayed, and entered
manually if necessary. Matrix correction coefficients (term A and term K) and overlap
correction coefficients (term B and term C) that are ordinarily used can be displayed as a
table. When <Display each component> is selected, special setting is possible as in the
case of the “Calibration” program. For the setting procedure for the manual input of
constants etc., see “4.2 g.2 Setting for Correction Calculation”.
The “Matrix Correction” tab is displayed when there is an empirical component.

Display and Manual Input of Overlap Correction and Internal Standard Correction
The overlap correction coefficients of each component can be displayed, and entered
manually if necessary. For the setting procedure for the manual input of constants etc.,
see “4.2 g.2 Setting for Correction Calculation”.

Display and Manual Input of Automatic Background Subtraction
Background sensitivity coefficients calculated using regression calculation and a

calculation method can be checked.
The “Auto BG subtraction” tab is displayed in an FP application.
This setting can be operated only when Quant Scattering FP method option is attached.
Change Background Sensitivity Coefficients
1. Select the “Auto BG subtraction” tab.

2. Double-click a measured element line to execute automatic background subtraction.
3. If necessary, enter a coefficient in the “a(quadratic)” box in the “BG sensitivity
coefficients” frame.
4. If necessary, enter a coefficient in the “b(linear)” box in the “BG sensitivity
5. If necessary, enter a coefficient in the “c(constant)” box in the “BG sensitivity
6. Click OK .
This screen is to check information obtained with regression calculation. Therefore, when
<Auto BG subtraction> is selected, any of the background sensitivity coefficients must not
be blank.

Set PHA conditions for a quantitative application using DMCA data;

newly.)
This function used by DMCA data makes re-extraction of X-ray intensity possible from
the DMCA data which saved by standard sample measurement. It is possible to change
the setting width of the PHA using the measurement data of the measured standard
samples without re-measuring the standard samples and reduce the burden of PHA
setting before standard sample measurement..
On the calibration/sensitivity constant calculation screen of quantitative application,

parallel comparison of calibration curves with several different PHA setting widths
with the same element is possible. Calibration line graphs shown below are example of
phosphorus (P) in copper alloy with two cases of PHA setting width 150-300 and
150-250. It becomes possible to indicate a number of calibration graphs having
different PHA setting widths on the data processing screen, hence it becomes easy to
compare intercepts and accuracies of calibration line directly. Each PHA setting
conditions are shown above the calibration graphs. (Each PHA setting conditions are
shown above the calibration line graphs. (Red box off)
It is easily recognized that the narrow PHA setting makes the accuracy of calibration
line improved.
PHA：150-300 PHA：150-250
accuracy: 0.0060 mass% accuracy: 0.0024 mass%
Change PHA condition;
1. Click Calibration in the flow bar of quantification application.

2. Select component aimed (Element line), then click Calculate to indicate the
calibration line. The PHA setting width shown above the calibration line graph is set
currently. The graph (P-KA) shows PHA setting width 150-300.

3. Click Recalc . on the calibration graph, then input any value of LL and UL into the
<PHA> column in the recalculation screen and click OK .
4. The calibration line with newly input PHA setting width is indicated. Click Save and
make PHA setting conditions and intensities of standard samples in the standard
sample set renew.
PHA setting width change is also available to FP method.
The re-extraction of X-ray intensities by the newly changed PHA setting are done for the
standard intensities of drift correction using private conditions automatically.
If PHA condition width change is carried out after unknown sample measurement was done,
the re-extraction of X-ray intensities of unknown samples are not done. The PHA condition
width must be decided before unknown sample measurement.

h. Setting of Control Information
The analysis control information is comprised of three parts: the limit ranges, check
samples and bias correction samples. The detailed setting procedures for these items are
described below, primarily for bulk samples. The only significant difference in the case of
thin film samples is that layer numbers are added and similar settings must be made for
each layer.
1. Click Limit Ranges on the flow bar.

Setting of Limit Range Condition
To control quantification values of analyzed samples, upper limits and lower limits are
set. The analyzed results on unknown samples are evaluated to determine if they are
within those standard ranges. When quantitative analysis is carried out, the limit range
check is made unconditionally except when <No limit> is set for the upper and lower
limits. If an analyzed value is out of the preset upper and lower limit range, its result
will be displayed. One can choose to set an upper and lower limit or only an upper limit
or only a lower limit for any quantification value. Two or more limit range conditions can
be created if desired.
1. Click Limit Ranges on the flow bar.

2. Double-click the “Lower limit” cell and enter a limit value.
3. Double-click the “Upper limit” cell and enter a limit value.
4. Select an output digit.
The limit range name that is automatically issued first is an application name. That first limit
range cannot be deleted. Any editing such as deletion of a component is also impossible for
the first limit range.
Create New Limit Range Condition
When creating a new limit range condition, setting can be made so that a balance
component and a fixed value component that need not be set will not be displayed in the
table.

2. Enter a limit range name.
3. Select <Eliminate balance and fixed components> or <Copy all components> in the
“Copy from application” frame.
4. Click OK .
5. Make setting for the lower limit, upper limit, output digit, unit, etc.

Save Limit Range Condition under Different Name
1. Select [File] [Save as...].

2. Enter a limit range condition name.
3. Click OK .
Delete Limit Range Condition

2. Select a limit range condition name to be deleted.
3. Click OK .
Delete Component
1. Select a component name to be deleted.

2. Right-click the mouse.
3. Select <Cut>.
In the case of a limit range condition that has the same name as the application, a
component cannot be deleted.
Add Component
1. Select the “Component” cell in the position for insertion.

3. Select <Insert>.
4. Select a component to be inserted.
A component that is not analyzed cannot be added.
Set No Limit for Upper or Lower Limit
1. Right-click a “Lower limit” or “Upper limit” cell.

2. Select <No limit>.
<No limit> can also be set by entering a zero in a cell for an upper or lower limit.

Change Unit
 1.Click the <Unit> cell to be changed.

 2.Click the arrow button at the right end of the cell.
 3.Select a unit from the pull-down list of units.
The unit selected here is used for an analyzed result. If it is different from the one set in the
application, the result will be converted using the unit selected here and output. For a
conversion factor, see the factor described in “6.1 f. Unit Setting”. However, a conversion
between mol% or at% and mass% is made with mol weight taken into consideration.
Enter Note

2. Enter information for “Note”.
3. Click OK .
Normalize Analyzed Values
This function is used, for example, to fix the total of the analyzed values to a value
different from 99 mass%.

2. Select <Yes> in the “Analyzed result normalization” frame.
3. Enter a total value for normalization at “Normalized value”.
4. Click OK .

Set Bias Correction Sample Preparation Time
Set the number of sample preparation times when making a calculation for bias
correction using the averages of repeated measurement. This procedure is designed to
smooth the dispersion resulting from sample processing such as grinding.

2. Select the number of repetitions for “Bias correction sample prep. time”.
3. Click OK .
When setting a sample ID on the Analysis screen for a component for which 2 or a larger
number was specified as “Bias correction sample prep. time”, set the corresponding bias
correction sample ID in the specified number of lines and set <Last sample> for the last line.
If the number of measured samples is less than the specified number, bias correction
coefficients will not be updated.

Setting of Check Samples
Check analysis is the method used to determine whether prepared calibration curves are
still acceptable. A sample with known concentrations is analyzed and the analyzed
values are calculated using the prepared calibration curves. The X-R control analysis, in
which the same check sample is measured three to five times a day (specified times) and
judged results of averages X and range R is recorded, is generally performed. The check
sample condition is created based on limit range conditions.
Besides, it is used for judgment of tolerance at the check analysis in case of execution of
auto drift correction. (For ZSX Primus IV/IVi only)
1. Click Check Samples on the flow bar.

Set Check Sample
1. Select [File] [New Sample…].

2. Select an objective limit range condition in the “Reference Limit Ranges” box.
3. Enter a check sample name.
4. Click OK .
5. Double-click a “Lower limit” cell and enter a value.
6. Double-click an “Upper limit” cell and enter a value.
7. Double-click a “Range upper” cell and enter a value.
Delete Check Sample

2. Select a check sample to be deleted.
3. Click OK .
Delete Component

2. Select a check sample.
3. Select a component to be deleted.
4. Select [Edit] [Cut].

Add Component

2. Select a check sample.
3. Select <Component> in the position for addition.
4. Select [Edit] [Insert].
5. Select a component constituting a part of the sample.
6. Enter a lower limit, upper limit and range upper limit.
A component that is not analyzed cannot be added.
Enter Note
1. Click Advanced.

2. Enter information for “Note”.
3. Click OK.
Clear Last Analyzed Date

2. Click Clear for “Last analyzed date”.
3. Click OK .

Setting for Bias Correction Samples
For example, in the case of iron and steel samples, when the heat history in the
preparation of standard samples used to create the calibration curves is different from
that of unknown samples, a constant analysis error may appear. To correct this error of
analyzed values based on this calibration curve is called the bias correction. Usually,
samples with known analyzed values are measured after a calibration curve is prepared
and then the bias correction is set if necessary.
One can select either an intercept correction or a linear function for the bias correction to
utilize the calibration curves. The following formula is used for the bias correction.
Either correction method can be selected for each component.
W '  W   A W  B 
Item Description
W’ Quantification value after bias correction
W Application result
A, B Correction coefficients
1. Click Bias Correction Samples on the flow bar.

 Correction by Multiplication/Division of Constant Ratio
For example, let’s assume that true values are 1.1 times as large as calculated
quantification values for all samples. The method to correct that bias between true
values and quantification values is called the A method. In that case, set the
correction coefficient A to 0.1.
 Correction by Addition/Subtraction of Constant Value
For example, let’s assume that true values are calculated quantification values
plus 0.5% for all samples. The method to correct that bias between true values and
quantification values is called the B method. In that case, set the correction
coefficient B to 0.5. This procedure is called the intercept correction method.
 Correction by Function
This method is a combination of the A method and the B method, and is called the
AB method.

Set Bias Correction Samples
A bias correction condition is set for each limit range condition. Two bias correction
samples must be set for the AB method, and one sample for either the A or the B method.
1. Select [File] [Select a Limit Range Condition…].

2. Select a limit range condition.
3. Click OK .
4. Select a component for which to carry out the bias correction.
6. Select <A method>, <B method> or <AB method> for “Method”.
7. Enter (a) sample name(s).
8. Enter the true value(s) of that component for “Standard Value”.
9. Enter (a) tolerance(s).
10.Click OK .
11.Repeat steps 4 to 10 for other components for which to carry out the bias correction.
The coefficient(s) is/are calculated automatically and need not be entered. Or only (a)
coefficient(s) can be entered to carry out the bias correction without setting a sample name.

Clear Date Updated
1. Select a component to clear the latest “updated” date.

3. Click Clear for “Date updated”.
4. Click OK .

i. Printing of Application Information
In “Print Quant Application”, the following items can be printed. For items with
“Select…” buttons, detailed items can be selected.

3. Click Next> .
7. Click Next> .
8. Select necessary items in the “Print item” frame.
9. If necessary, click Select... and make selections for detailed items.

Select Analytical Constants
1. Select <Analytical constant> on the “Print Quant Application” screen.

2. Click Select... on the right of <Analytical constant>.
3. Select items to be printed.
4. Click OK .
Select Standard Samples
1. Select <Standard sample> on the “Print Quant Application” screen.

2. Click Select... on the right of <Standard sample>.
3. Select standard samples to be printed in each frame.
4. Click OK .
To select all standard samples in each frame, click Select All under each frame.

Operational procedures for the following screens that appear when Select... is pressed
are the same. Refer to “Example of Operations”.
Example of Operations
The operational procedure to select drift correction samples is used as an example.
1. Select <Sample> for “Drift correction” on the “Print Quant Application” screen.
2. Click Select... on the right of <Sample>.
3. Select drift correction samples to be printed.
4. Click OK .
To select all samples or conditions, click Select All .

j. Output of Application Information
It is possible to output application information and measuring conditions as a file in the

Excel book format.

2. Select <Output application information to Excel book>.
3. Click Next> .
4. Select a folder on the “Select an Application to Output” screen.
7. Click Next> .
8. Click Browse on the “File Name Input” screen and specify a folder in which to save a
file.
10.To open an Excel file after it is created, place a check mark at “open an output file”.

4.3 QUANTITATIVE ANALYSIS TECHNIQUES
a. Measuring Conditions
 Measured Element Line
The characteristic X-ray spectral line used for measurement in quantitative analysis
such as the empirical calibration method or FP quantification method is called the
measured element line. The selection of this measured element line may affect analysis
precision and accuracy significantly. The measured element line to be selected varies
depending on the analyzed component, sample model, etc. The two distinct sample
models are bulk samples and thin film samples.
Effective Analyzing Depths for X-Rays
When the sample thickness increases from zero, the generated X-ray intensity changes
linearly. The region where this linear correlation holds true is called the thin film region.
That relationship can be used for the film thickness analysis for thin films etc. However,
the intensity does not increase indefinitely as the thickness increases. When the
thickness exceeds a certain threshold value, the X-ray intensity does not change as a
function of thickness. That region is called the bulk region, and the region between the
thin film region and the bulk region is called the medium thickness region. It is known
that X-rays with short wavelengths have high energy and, therefore, high penetration
through materials. Since X-rays with short wavelengths can therefore exit from the
sample surface even when they are generated in deep regions, those X-rays may be used
for concentration analyses for bulk samples. On the other hand, because X-rays with
long wavelengths have low penetration through material, those X-rays are used
especially for concentration analyses for thin film samples.
Purpose Description
In concentration analysis, X-rays that are not affected by the

sample thickness must generally be used as the measured element
Concentration
line. When selection can be made from more than one measured
Analysis
element line, by using X-rays with short wavelength, information
about deep can be obtained.
In film thickness analysis, X-rays that correlate with sample

Film Thickness thicknesses must generally be used as the measured element line.
Analysis In the case of the FP method, X-rays in the medium thickness
region can also be used as the measured element line.

 Excitation Condition
The excitation condition is set to generate X-rays effectively from components in a

sample. Items concerning the generation of X-rays include conditions for the X-ray tube
used such as the kind of target, tube voltage and tube current. A primary filter may be
used if necessary. Details are described below:
Excitation
Description
Condition
Determines the kind of primary X-rays that irradiate a
Kind of Target
sample.
Tube Voltage Voltage applied to the target
Tube Current Current that flows through the filament
Primary Filter Eliminates unnecessary X-rays from the tube.
Tube Voltage
The voltage applied to the target increases overall intensity and primarily affects the
generation of the continuous X-rays. As the applied voltage is increased, the continuous
X-rays become more powerful. On the other hand, for a specific element to be detected, it
generates X-rays when it is excited with energy higher than a certain level. Even if an
element to be excited receives energy higher than the necessary level, the excitation
effect does not change. The relationship between optimum excitation voltages and
excited elements is shown below:
Element for measurement Element for measurement

Applied Voltage
of K line of L line
30kV Be - Cl
40kV K, Ca
50kV Sc - Ba Ba - U
However, if the tube voltage and current are changed for each element in the
quantitative analysis, an extra measuring time will be necessary to change the voltage
and current and X-ray intensities will be unstable. Therefore, the same tube voltage and
current are generally used.
From the viewpoint of excitation efficiency, you must also consider the penetration depth
of the excitation X-rays. In general, as the applied voltage is increased, the excitation
X-rays penetrate deeper into a sample. And as the applied voltage is increased,
background intensities become higher.

Tube Current
This is the current that flows through the X-ray tube (electrons from the heated filament
to the anode). It significantly affects the intensities of X-rays generated from a sample.
The tube current is directly proportional to X-ray intensities to a first approximation. As
the current is increased, X-ray intensities become higher. The optimum excitation
condition should be selected from the combination of the tube voltage and current.
However, the maximum load of the tube must also be taken into consideration. The
maximum load is expressed by the following formula:
Maximum Load  Tube Voltage  Tube Current
The tube voltage and current must be set so that the voltage multiplied by the current
will not exceed the maximum load.
Primary Filter
This is located between the X-ray tube and the sample and used to reduce any
interference of continuous X-rays or characteristic X-rays generated from the X-ray tube
to analyzed X-rays. This is also used to lower background. When the primary filter is
used, X-ray intensities are reduced. However, since background intensity is also lowered,
peak/background ratios become larger and lower limits of detection are improved. The
kinds and purposes of the primary filters are shown below:
Filter Description
Absorbs the Rh K-line.
Ni400
Effective for analyses using the K-lines of Ru, Rh, Pd, Ag, Cd, etc.
Ni40 Effective for trace analyses using the Pb L-line and As K-line.
Al125 Effective for trace analyses of Ti, Cr and Fe.
Absorbs the Rh L-line.
Al25
Effective for analyses of Cd-L etc. in thin samples such as films.

 Optical Condition
The optical condition is set for the spectrum analysis of generated X-rays. The optical
condition includes the slit, analysis crystal and detector. The attenuator is used if
necessary to obtain suitable X-ray intensities. Details are described below:
Item Description
Slit Determines the resolution of a detected peak.
Crystal Separates X-rays generated from a sample.
Detector Counts separated X-rays.
Attenuator Reduces the intensities of generated X-rays.
Selection of Slit
The slit creates a parallel beam of X-rays generated from a sample. This is also an
important item to determine the resolution of a peak. Though the crystal used must also
be taken into consideration, the angular resolution is generally important for heavy
elements because there are many adjacent spectra. On the other hand, for light elements,
the sensitivity is important because there are not so many adjacent spectra.
Slit Description
S2 Standard slit for the detector SC. High resolution is obtained.
S4 Standard slit for the detector PC.
S8 Resolution lowers, but high X-ray intensities are obtained.
(ZSX PrimusIV)
Resolution higher than that of the S2 is obtained.
S1
Analysis Crystal
The analysis crystal separates X-rays that have a wavelength that satisfies the Bragg’s
formula and directs them to the detector. In general, selecting a crystal that has high
reflection intensities and high resolution contributes to analysis precision and accuracy.
Since very light elements generate X-rays with long wavelengths, a synthetic
multi-layer device (RX series) is used as the crystal for light element analysis.
Crystal Description
LiF(200) Best in resolution and reflection intensities
Ge Does not reflect secondary X-rays.
Has demerits of the large coefficient of thermal
PET
expansion and fragility.
TAP Used to separate Mg, Na, F and O.
RX25 – RX85 Synthetic multi-layer series.

Detector
The detector counts separated X-rays from the various crystals. In the ZSX, the
scintillation counter (SC) and the proportional counter (PC) are employed to cover a
wide range of measurement conditions. These detection methods are listed below:
Detector Description
Detector for heavy elements to be used with the ordinary
SC receiving slit.
Generally used for wavelengths of 0.01 to 0.3nm.
Detector for light elements to be used with the ordinary
PC receiving slit.
Generally used for wavelengths of 0.3 to 20nm.
In the case of the ZSX Primus or ZSX Primus III+, a counting range in which the
counting loss does not occur is up to 1000 kcps for the SC and up to 2000 kcps for the PC.
In the case of the ZSX Primus IV, it is up to 1800 kcps for the SC and up to 3000 kcps for
the PC. However, to carry out measurement exceeding 1000 kcps with the PC, set the
integral measurement in the PHA condition or set a wide window.
Attenuator
The attenuator is a mechanism to decrease intensities without changing excitation

conditions when X-ray intensities are so high that the counting loss occurs. In the case of
the ZSX Primus or ZSX Primus IV, the attenuator can be used only when the
measurement diameter is 30 mm by reason of the mechanism. In the case of the ZSX
Primus III+, it can be used only when the measurement diameter is 30 or 20 mm. X-ray
intensities decrease to approximately 1/10 when the measurement diameter is 30 mm
and to approximately 1/5 when the measurement diameter is 20 mm. Because it is
impossible to use this mechanism when the measurement diameter is not any of the
above, decrease the tube current in that case.
Sealing
In the analyses of liquid samples, the measuring chamber is filled with helium so as to
reduce the absorption of X-rays by the atmosphere. In the case of the helium
atmosphere, a seal with a thin film is placed between the spectroscopic chamber and the
sample chamber to separate the two chambers in this spectrometer.
By using the seal, it is possible to set only the sample chamber in the helium
atmosphere keeping the spectroscopic chamber in a vacuum. And this method can
reduce the consumption of helium gas.

 PHA Condition
Fluorescent X-rays generated from a sample are separated by the crystal and counted by
the detector. When one X-ray photon enters the detector, one signal (pulse) is generated.
The number of pulses in a unit time is counted and defined as the X-ray intensity (kcps).
X-rays are separated according to the Bragg’s formula (n=2dsin), but X-rays with the
wavelength ', which is 1/n times the wavelength  ('=n), also enter the detector. The
relationship between the wavelength  (nm) and the energy E (keV) is as follows:
1.24
E

So, when the energy of the wavelength  and that of the wavelength ’ are E and E’
respectively, the relationship E’=nE exists and the X-rays signals can be separated by
energy. Pulses with different heights therefore enter the detector successively, and they
are treated as time dependent data. A graph that has pulse height as the abscissa and
the number of pulses as the ordinate is called a PHA scan (see the figure below):
Number of Pulses (kcps)
0 200 Pulse Height
The wavelength ’ is treated as higher-order X-rays of the measured wavelength . The

wavelength  for n=1 is also expressed as the primary X-rays, and the wavelength ’ for
n=2 the secondary X-rays. When E is assumed to be 200 (arbitrary units) for convenience,
E’ for the secondary X-rays becomes 400. By setting a range of 100 to 300 as the PHA
condition, for example, only the primary X-rays will be counted. If the primary X-rays
are always set at 200, a similar PHA condition can be set regardless of a component.
Thus, the unit to separate X-rays using differences of energy is called the PHA. The
energy range to be measured is called the PHA condition. When low and high limits are
set, the measurement is generally called a differential measurement.

Pulses counted by the PHA are shown below. Since these pulses may all be generated
simultaneously, the PHA condition must be set to count pulses only of an objective
component.
Kind of Pulse Description
Electric noises Appear at 0 to 30.
X-ray pulses with the wavelength that satisfies the Bragg’s

Measured X-ray pulses
formula with n=1
X-ray pulses with wavelengths that satisfy the Bragg’s

Higher-order pulses
formula with n>1
For example, an energy loss peak is observed when Ar,

Signal pulses of escape
which is a component in detector gas used for the PC, is
peak
excited. This usually appears at 80 to 150.
Signal pulses of For example, pulses generated when the W-M line of the
fluorescent X-rays from crystal RX26 (RX25) used to measure the Na-K line enter
crystal the detector.
Integral Measurement
As explained in the paragraph “PHA Condition”, differential measurement, in which

energy only of a necessary component is selected and counted, is generally used. The
measurement condition when a lower limit of PHA condition is set but not an upper limit
is called the integral measurement. This is generally used when there is no overlap of
energy. Since the integral measurement uses a PHA condition with no limit for energy,
stable measurement is possible for main components that have high intensities.
Noises
No upper limit
Pulse Height

 Peak and Background Conditions
The fluorescent X-ray spectrum is expressed by a chart shown below. The abscissa
represents the 2-theta angle, which is the rotation angle of the detector. The standard
comparison method, in which the intensities of an unknown sample are compared to a
calibration curve prepared from a correlation between standard samples concentrations
and their corresponding X-ray intensities and the concentrations of the unknown
samples are calculated, is called quantitative analysis. In quantitative analysis, X-ray
intensities, which become the ordinate axis of a calibration curve, are measured with the
fixed-time counting method. The fixed-time counting method means collecting X-ray
intensities during a specified time while fixing the crystal and detector at a certain angle.
This angle is typically determined by a 2-theta scan prior to quantitative analysis. In
general, the characteristic X-ray intensity of a measured component is counted at its
peak position with fixed-time counting and a calibration curve is created.
100
90
80
Count Rate [ - ]
70
60
50
40
30
20
10
0
10 20 30 40 50 60 70 80 90
2-theta [deg.]
When background intensities are sufficiently low compared to peak intensities (the
peak/background ratio is large), a good calibration curve may be obtained by measuring
only a peak position. However, if background intensities are higher than variations due
to differences in concentrations (the peak/background ratio is small), a calibration curve
with poor analysis precision will be created. Generally in such a case, background
positions are measured in addition to the peak to create a calibration curve using net
intensities after subtracting background intensities. Thus, the peak and background
condition obtains net intensities to prepare a calibration curve. The methods to subtract
background intensities are shown below:
Background
Description
Subtraction
One or two background positions are designated.
1/2-Point Method
Only the linear method can be selected.
Up to 16 background positions are designated.
Multi-Point
Selection can be made from the linear, quadratic, cubic, hyperbolic
Method
and Lorentz functions.

To Carry Out Background Measurement
To calculate net intensities and create a calibration curve, background intensities are
measured. The criterion to select a background subtraction method is shown below.
When deciding whether to measure backgrounds, sufficient consideration is necessary
because the measuring time is extended as the number of measuring positions becomes
larger.
1-Point Method
As shown on the left side figure below, when the background intensities on both sides of
a peak are identical, the net intensity can be calculated by measuring only one
background position. In the case of the 1-point method, setting the background position
on the high angle side is recommended for the angular resolution.
Net Net
Intensity Intensity
Background Background
Intensity Intensity
= =
2 2
2-Point Method
As shown on the right side figure above, when the background intensities on both sides
of a peak are not identical but the background intensity can be fit with a straight line,
the net intensity can be calculated by measuring two background positions.
Background Subtraction Coefficient
The background subtraction coefficient is calculated with the 2-point method described
above. But, in real measurement, only one background position is measured and
background intensities are calculated. That background measuring position must be a
background position used for the calculation.

Quadratic and Cubic Formulae for Multi-Point Method
As shown on the left side figure below, in the case of the quadratic or cubic formula for
the multi-point method, background is expressed using a function. A quadratic or cubic
curve is used instead of a straight line. Three or more background positions must be
measured in the case of the quadratic formula, and four or more background positions
must be measured in the case of the cubic formula.
Net Net
Intensity Intensity
Background Background
Intensity Intensity
2 2
Hyperbolic and Lorentz Formulae for Multi-Point Method
So far background calculations for gentle background shapes such as continuous X-rays
have been described. As shown on the right side figure above, estimating the background
of a small peak on the shoulder of a giant peak by employing the Lorentz function or
hyperbolic function to approximate the large peak better is useful. Four or more
background positions must be measured in the case of the hyperbolic function, and five
or more background positions must be measured in the case of the Lorentz function.

Intensity Integration Measurement
In the ordinary quantitative analysis, an analysis element is measured with the

fixed-time counting method, in which measurement is made at a fixed peak angle (and
at a background angle if necessary) for a specified time. In the intensity integration
measurement, a step scan is carried out over a specified angle range like qualitative
analysis and the average of the intensities at each angle is used for analysis.
Backgrounds can also be designated in this method. This method is effective in special
cases such as when the peak of an analysis line shifts depending on the combination
form of its element in a sample and when a peak width changes.
2 2
Average Intensity Measurement
As described before, the X-ray fluorescence quantitative analysis is a standard

comparison method using calibration curves and the FP quantification method. For
example, when measuring standard samples for the empirical calibration method, stable
X-ray intensities must be measured. To prepare a calibration curve using a small
number of standard samples and estimate quantification values of unknown samples,
X-ray intensities (the ordinate axis of a calibration curve) must be measured with
especially high precision.
So, in the fixed-time counting method to count X-rays in a peak position and a
background position during a fixed time, each measurement is repeated and average
values are used as X-ray intensities. This method is called the average intensity method.
In real analyses, the number of repetitions is designated before measurement.

b. Empirical Calibration Method
When Optimized Element Line Cannot Be Determined
If you cannot determine which measured element line is optimal for a calibration curve
or a sensitivity calibration curve, set several element lines and perform a measurement.
In the regression calculation described later, a measured element line can be changed
when a component has two or more element lines. In that case, you can set two or more
element lines as <correction lines>.
For example, to analyze tin (Sn) in the analysis of polymer samples, you can set the
Sn-L line as correction lines in addition to the Sn-K line, which is generally used as
the measured element line. In the regression calculation, if the accuracy of the
calibration curve using the Sn-K line deteriorates because of thickness, you can change
the measured element line to the Sn-L line and carry out a regression calculation.
When Accuracy of Calibration Curve Is Bad
If a calibration curve is not satisfactory as shown below, troubleshoot according to the

flowchart shown below:
X-Ray Intensity [kcps]
×
×
×
×
Concentration/
Film Thickness

Accuracy is bad
a.Right standard
Enter right values
values? No
Yes
b.Same result after

Sample preparation
remeasurement? No
Yes
c.Right measuring
Set right conditions
conditions? No
Yes
d.Peak overlap
Overlap correction
effects? Yes
No
e.Matrix correction
 Did you set right standard values?
Make sure that the correct standard values have been entered.
 What is the result after the same samples are remeasured?
Remeasure the same samples and make sure the

same result is obtained.
 When the same result is obtained, the ×
spectrometer is stable.
×
○ ○
Then, in the case of powder samples, for example,
prepare samples again and remeasure them.
 When the same result is obtained, the ○
×
samples do not segregate. ○
×
If the result is not the same, the samples
segregate. Consider changing the sample × : 1st ○ : 2nd
preparation method.

 Is the measuring condition right?
Do peaks overlap? Is there any overlap of energy? Make checks again using the
2-theta scan and the PHA scan respectively. In such a case, to solve the problem
sooner, it is important to check a sample that was not monitored in the measuring
condition setup described before. Carry out a 2-theta scan and a PHA scan
specifically for a sample off the calibration curve. If it seems to be impossible from
a 2-theta scan result to eliminate overlap of spectral lines, it is recommended that
the overlap correction described later be made.
 Is peak overlap corrected?
When the optimum measuring condition for

overlap of spectral lines cannot be set, carry out
○
overlap correction. ×
×
Set overlap correction using the term B or b in the
matrix correction formula.
×
×
 If the accuracy of the calibration curve does not improve, carry out matrix
corrections.
If the accuracy of a calibration curve does not improve even after measurement is
optimized using the measuring condition and overlap correction, coexisting
elements affect the measured component. Basically all samples are affected more
or less by coexisting elements. Although in most cases using standard samples
with the same composition as unknown samples can solve the problem, matrix
corrections are used to correct any residual effects. The following three methods
are available, but in general the method to calculate theoretical correction
coefficients using the FP method is employed:
Matrix Correction
Description
Method
For example, in the case of iron and steel samples,
Use published
matrix correction coefficients published by JIS are
correction coefficients
available.
Coefficients are calculated using many standard
Calculate using the
samples that have concentrations that do not
regression calculation
correlate with each other.
Calculate using the FP Theoretical matrix correction coefficients are
method calculated using the FP method.

Matrix Correction
X-ray intensities of all components in a sample are affected by the other components to a
greater or lesser degree. In general, fluorescent X-rays generated from a certain
component are absorbed by all the components in the sample, including itself. In some
cases, secondary enhancement occurs by fluorescent X-rays generated within the sample.
The phenomenon that X-ray intensities do not correlate with a calibration curve due to
these issues is called the matrix effect. Correcting this phenomenon caused by the
matrix effect using a regression calculation is called the matrix correction.
Matrix correction can be selected from [Correct concentration] and [Correct intensity].
[Correct concentration] normally used is expressed as the linear equation below
including overlapping correction and used for calculation.
RijFj
1  Wi / 100

Aij, aij
coefficient
Wi Quantified value
Qij, qij
coefficient
Calibration
Analyzed values or X-ray intensities of
A, B, C, D curve Fj, Fk
coexisting elements j and k
coefficients
be used for either concentration correction or intensity correction. When expressed in an
uppercase character, concentration corrections are used. When expressed in a lowercase
character, intensity corrections are used.
or bij term for overlap correction.
[Correct intensity] is different at the intercept D of calibration line compared with
[Correct concentration], but as it is based on the same point of view, it is expressed as
below and used for calculation.
RijFj
1  Wi / 100

To carry out matrix corrections in the empirical calibration method, the following three
methods can be used: a) use published correction coefficients, b) calculate
experimentally using the regression calculation and c) calculate theoretically using the
FP method. These methods are described below in detail:
 Use published correction coefficients
Matrix correction coefficients for iron and steel are published. They are described
in JIS G 1256 and are available for Fe base and Ni base systems. Those correction
coefficients can be set as fixed values in the regression calculation. They basically
correct absorption/enhancement terms.
 Calculate experimentally using the regression calculation
Matrix correction coefficients are calculated using the regression calculation. In

that case, there are specific requirements described below. Taking these
requirements into consideration, this method is rarely employed. For example, the
published correction coefficients for iron and steel described in the previous
paragraph were determined using this method.
1) Variations in concentration must not correlate with each other among the
standard samples.
For example, let’s consider samples that have Fe as their main component and
contain Al and Si. Let’s assume that concentrations of components correlate with
each other. For example, when Al concentrations increase, the Si concentrations
increase, and when Al concentrations decrease, Si concentrations decrease. Such
samples cannot be used to calculate matrix correction coefficients. When
calculating correction coefficients, concentrations of components must not
correlate with each other.
2) Many standard samples must be prepared.
Twenty to thirty standard samples described above must be prepared. Basically,

since matrix correction coefficients are calculated with the regression calculation,
the appropriate number of degrees of freedom for a calculation cannot be obtained
if the number of standard samples is small.
 Calculate theoretically using the FP method
When components in a sample and their concentrations are given, theoretical

X-ray intensities can be calculated. This is called the FP method. Applying this
principle, matrix correction coefficients are calculated from variations in X-ray
intensity according to variations in concentration. To use this method, as in the
case of the FP quantification method, average concentrations of all components
are necessary.

Overlap Correction
The peak of a measured component may overlap with the peak of another component. In
general, a measured element line that does not overlap with another peak is selected.
However, if a spectral line with low relative intensity is selected, the accuracy of a
calibration curve may deteriorate. In such a case, overlap correction is made. The degree
of effect varies depending on the concentration of an overlapping element, so that effect
is corrected. Up to five components can be used as correcting components. For the
overlap correction, the above-mentioned matrix correction method or the X-ray intensity
method described below can be used. The method using X-ray intensities can be used for
both empirical method and FP method.
I ia  I ib  B j I j
Item Description
Iia X-ray intensity after correction
Iib X-ray intensity before correction
Ij X-ray intensity of correcting element j
Bj Overlap correction coefficient
This correction is used for the application in which a constant amount of material is
added to an unknown sample for correction. A component that generates X-rays with a
wavelength near that of a measured component is added. Generated fluorescent X-rays
are affected by other components in a sample and their intensities change. Since the
X-ray wavelength of the added component is near that of the measured component, the
degree of effect from other components is regarded as almost identical. This method can
therefore correct the effects of the matrix.
Ii
Ia 
Ij
Item Description
Ia X-ray intensity after correction
Ii X-ray intensity of corrected component
Ij X-ray intensity of correcting component
In the FP quantification method, the internal standard correction cannot be used.

Background Ratio Method
In the background ratio method, ratios of net X-ray intensities to background X-ray
intensities are used for the ordinate axis of the calibration curve. Generated fluorescent
X-rays are affected by other components in a sample and their intensities change. Since
the background X-ray wavelength can be regarded as similar to the peak X-ray
wavelength, the degree of effect from other components is regarded as almost identical.
This method can therefore correct the effects of the matrix. This method is especially
effective in analyzing minor heavy elements in samples that have light elements as their
main components.
I n et
Ic 
I BG
Item Description
Ic X-ray intensity after correction
Inet Net X-ray intensity before standardization
IBG Background X-ray intensity
The background ratio method cannot be used in the FP quantification method.
Calibration Curve Division
When the concentration range of a component is wide and a single regression calculation
cannot cover the entire range, a calibration curve can be divided. This method is called
the calibration curve division, and a calibration curve can be divided into one, two or
three regions. The calibration curve formula can be different in each region. For example,
a linear formula can be used in the low concentration region and a quadratic formula can
be used in the other wide concentration regions. The three divisions are called Low,
Middle and High divisions respectively and the Low division is used for a calibration
curve when there is no division.
The calibration curve division cannot be used in the FP quantification method.

c. FP Quantification Method
Selection of FP Quantification Method From Standard Samples
The applicable type of the FP quantification method judged from prepared standard
samples is described using the flowchart shown below. The accuracy of <I.Calculate like
empirical calibration method> is the best with regard to indeterminate factors.
Start
Standard samples are

prepared the same as
Yes
unknown samples?
No I. Calculate like empirical
calibration method
Standard samples with
partly different components Yes
prepared?
No II. Use libraries too
Pure substance prepared?

Yes
No III. Sensitivity calibration

using pure substances
IV. Use libraries for all components
In the empirical calibration method, standard samples that have the same
concentrations as unknown samples are necessary. But, in the FP quantification method,
even when such standard samples cannot be prepared, quantitative analyses are
possible. There is no requirement for standard samples when calculating theoretical
intensities. This is the case not only with bulk samples but also with thin film samples.

Thin Film FP Quantification Method
Seriously consider the following in the quantitative analysis of thin film samples using
the FP method:
 Set the model of thin film samples.
In the case of a single-layer thin film, setting the constituent components is sufficient. In
the case of a multi-layer thin film, the order of layers must also be set. Since theoretical
X-ray intensities can be calculated only when the order of layers is known, it must
always be set. Conversely, the order of layers cannot be obtained using the FP method.
 To calculate a film thickness, set a density.
In the thin film analysis, information about a thickness is calculated as weight. The
density is therefore necessary to analyze a thickness. A density may be calculated from
components constituting the layer from the quantitative analysis. However, to generate
a more accurate analysis, when the density of a layer is known, set it as a fixed value.
When executing the weight conversion, a density is unnecessary.
 Select a measured element line according to a purpose.
As described before, X-rays with shorter wavelengths penetrate deeper in a sample.

Therefore, in general, X-rays with short wavelengths are used to analyze thickness and
X-rays with long wavelengths are used to analyze concentrations. However, when
analyzing concentrations for a layer deeper within the sample, select X-rays that do not
attenuate in the sample.

Thin Film Sample Model
Let’s consider a sample of an Al plate with Ni and P coated on Ni+P

it. The simultaneous analysis of the thickness and
concentrations of the Ni+P layer is desired. The sample model Al
is shown on the right.
The following models can be used as a measuring method:
1) The thickness is analyzed using Ni-K, the concentration of P is analyzed using

P-K and the residual is regarded as Ni.
This is the most ordinary method.
2) The thickness is analyzed using Ni-K, the concentration of Ni is analyzed

using Ni-L and the residual is regarded as P.
This method is effective when a non-measurement component such as Li exists

instead of P.
3) The thickness is analyzed using Al-K, the concentration of P is analyzed using

P-K and the residual is regarded as Ni.
When the Ni+P layer is so thin that Al-K can penetrate it, this setting can be
used. That is, the degree of absorption of Al-K is used for a calculation.
In the above example, all components can be measured. But when a sample model is
complicated and usable X-rays are limited, the method like Item 3) can be used. Thus, by
considering a sample model and extracting analyzable X-rays, the thin film FP
quantification method can be applied to a complicated system.

When Standard Samples for Thin Film Samples Are Not Available
In the thin film FP quantification method, when standard samples that have the same
layer structure as thin film samples are not available, set standard samples as shown
below. Let’s consider the sample of an Al plate with Ni and P coated on it. Let’s assume
that only bulk samples of P and Ni are available as standard samples.
Ni+P P (No Ni) Ni (No P)
Al No substrate No substrate
Sample Model P Sample Ni Sample
The layer structure is set for each standard substance like the sample model. For
example, in the case of the P sample, Al is designated for the substrate but its thickness
is set to zero, and Ni is designated for the composition but its concentration is set to zero.
In the case of the Ni sample, by using the same setting, it can be regarded as the same
structure as that of unknown samples and can be processed as a standard sample.

Quant Scattering FP Method (Option)
In addition to fluorescent X-rays generated from a sample, characteristic X-rays and

continuous X-rays from the tube that are scattered on the sample surface also enter the
detector. Those scattered X-rays include information about a sample and therefore can
be used for analyses using the FP method. As an example of this application,
background intensities can also be calculated theoretically and eliminated.
But intensities of scattered X-rays with long wavelengths are affected by the condition of
a sample or physical phenomena such as interactions with photoelectrons, and are likely
to include errors in theoretical calculations.
The setting procedure in the scattered X-ray FP method is almost the same as that for
ordinary X-rays.
Types and Handling of Scattered X-Rays
The types of usable scattered X-rays and their symbols are as follows:
 Thomson Scattering X-rays of Primary Characteristic X-Rays
These are the Thomson scattering X-rays of the characteristic X-rays of the target
element. Since the Thomson scattering X-rays are scattered without losing energy,
they appear in the diffraction position of the target element.
“T” is attached after ordinary spectral names like Rh-KT and Rh-K1T in the
case of the Rh target, for example.
 Compton Scattering X-rays of Primary Characteristic X-Rays
These are the Compton scattering X-rays of the characteristic X-rays of the target
element. Since the Compton scattering X-rays are scattered with some loss of
energy, they appear at an angle higher than the diffraction position of the target
element by about one degree.
“C” is attached after ordinary spectral names like Rh-KC and Rh-K1C in the
case of the Rh target, for example.
 Scattered X-rays of Primary Continuous X-Rays
These are the scattered X-rays of the continuous X-rays and are the so-called
background.
For example, background around Rh is expressed as Rh-BG.

Theoretical Intensity Calculation in Scattered X-Ray FP Method
Like the theoretical intensity calculation for fluorescent X-rays, theoretical intensities
are calculated for the scattered X-rays from the composition of a sample and physical
constants. Using the atomic scattering factor for the Thomson scattering X-rays and
using the Compton scattering cross section for the Compton scattering X-rays,
theoretical intensities are calculated taking absorption by a sample into consideration.
Theoretical background intensities are calculated as the sum of Thomson scattering
X-ray intensities and Compton scattering X-ray intensities.
Quantitative Analysis Using Scattered X-Ray FP Method
Scattered X-rays can be assigned as a non-measurement component to make analyses

using its measured results. That method can be applied to either bulk samples or thin
film samples. In the thin film model, it can be applied to both the single layer films and
multi-layer films.
Let’s assume that trace components in polypropylene are to be analyzed. Polypropylene

is treated as the balance component and trace components alone are to be analyzed. In
the ordinary FP quantification method analysis, polypropylene cannot be treated as a
bulk sample. It is therefore set as a thin film sample and a sample thickness must be
input manually for each analysis. In such a case, the sample thickness can be analyzed
by measuring scattered X-rays.
For example, the Thomson scattering X-rays of primary X-rays are set as the measured
element line, and the thickness is analyzed by comparing calculated theoretical X-ray
intensities with measured X-ray intensities. In that case, standard samples can be set by
assigning that measured element line to the component for thickness measurement. The
setting procedure is the same as the ordinary one except that scattered X-rays are set as
the measured element line.
Automatic Background Subtraction
Although measurement is made at a background angle for a specified time when

measuring standard samples, background need not be measured for unknown samples.
That is called the background subtraction measurement. When standard samples are
measured, background is measured and spectrometer sensitivity constants for
background are obtained. When measuring an unknown sample, the background
intensity is estimated from the composition and subtracted automatically. By using this
function, measuring time can be shortened. This function should only be used for heavy
elements, however, because scattered X-rays with long wavelengths are apt to be
affected by a sample.
Set the background measurement in an ordinary measuring condition. Make detailed

setting on the “Auto BG subtraction” tab on the “Constants Input” screen of the
Calibration program.

Calculation of Theoretical Matrix Correction Coefficients Using Scattered X-Ray

Ratio
Let’s assume that iron in iron ore powder or copper in copper concentrate powder is to be
analyzed using the empirical calibration method. You can use the method to carry out
matrix correction with a calibration curve whose ordinate axis is the ratio of Fe-K or
Cu-K X-ray intensities to scattered X-ray intensities of the characteristic X-rays of the
X-ray tube target. Since the calibration curve is created using intensity ratios to
scattered X-rays, this method is called the scattered X-ray ratio method. That is used to
reduce the mineral effect or grain size effect characteristic of powders.
For example, in the case of the Rh target, Rh Compton scattering X-rays are set as the
measured element line for correction. When selecting the measured element line of Fe,
set Rh-KC as the internal standard. Thus, ratios to Compton scattering X-rays are
used for the ordinate axis. To calculate the theoretical matrix correction coefficients,
select the scattered X-ray ratio method in a calculation condition for Fe. After that,
make the appropriate setting corrections in the same way as the ordinary calculation of
matrix correction coefficients.

Geometry effect
In case of the measurement of liquid sample put in the sample cell, the detectable area of
fluorescence X-ray excited in the sample varies according to the height of the liquid sample.
This area is defined by the position of optics of incident side (X-ray tube side) and receiving
side (analyzing crystal・detector side) (Geometry effect).
<Correction model of geometry effect> <Conventional model>

non detection detection area
area non detection detection area
area
height of liquid
level
high high
non detection
area
low low
incident emission
incident
Application example of correction of geometry effect (For ZSX Primus IVi only)
Following is the FP sensitivity curve of Cd-Ka in case of use of 5g and 10g oil multi
element samples. In case of conventional model, sample weight is taken into account but it
is obvious that FP sensitivity curve divides into two lines caused by the difference of sample
weight, 5g or 10g, which makes difference of sample height. This is caused by that the
difference of sample height gives the difference of detection area (geometry effect). On the
other side, in case of geometry effect correction model, same sensitivity curve for both 5g
and 10g are obtained. This fact proves successful correction of error due to difference of
sample height.
<Correction model of geometry effect> <Conventional model>

4.4 RESULT DISPLAY
The Result Display program manages all sample IDs, which include the history of
measurement such as quantitative analysis results. As for data, this program collects
mainly quantitative analysis and qualitative analysis results. Since qualitative analysis
results have different data processing methods, they are treated separately with the
Qual Result menu, but recalculation results are reflected in this Result Display data.
This program also handles, on the maintenance record menu, data to monitor the
stability of the quantitative analysis such as check analysis results and drift correction
analysis results, and spectrometer control data such as PHA adjustment records.
Functions of this program are as follows:
1) All quantitative analysis and qualitative analysis results are recorded and can be
displayed freely by selecting sample IDs.
2) By copying a measured sample ID to the “Sample ID Setting” screen, the same
measurement can be made again.
3) Quantitative analysis results can be collected and a plotting chart can be drawn.
4) Result data can be saved by designating a file format.
5) Collected data can be transferred to an external device.
6) Collected data can be printed.
When the Analysis program has been started, this program becomes the “Analyzed
Result” screen.

2. Select “Result Display”.
The upper part is called the data selection area and the lower part the result display area.
The size of the display area can be changed using the dividing line.

a. Result Display
Since a sample ID entered in the Analysis program is recorded intact, its analyzed result
can be displayed by designating that sample ID. Though the main purpose is to display
quantitative analysis results, qualitative analysis results can also be displayed.
However, since this function cannot process qualitative analysis results, by processing
data using the Qual Result menu, its results can be reflected. In some cases,
remeasurement becomes necessary after checking a measured result. In that case, that
sample ID can be copied and used in the Analysis program. Display functions and
retrieval functions will mainly be described below:
Display Measured Result
By selecting a sample ID line left in the data selection area, an analyzed result can be
displayed. Since there is no blank line like the sample ID preset table in the Analysis
program, a result is always displayed.
1. Select a sample ID in the data selection area.
Switch Display
In the default condition of the quantitative analysis result display, quantification values
such as concentrations and film thicknesses are displayed. X-ray intensities can also be
checked here.
1. Click Analyzed Result or Intensity according to your purpose.

Change Display Direction
The direction to display analyzed results can be designated.
1. Select [View] [Setting].

2. Select <Horizontal direction> or <Vertical direction> in the “Display form” frame.
3. Click OK .
Change Intensity Type
The intensity type of displayed data when <Intensity> is selected or data for transfer
can be selected.
 1.Select [View]  [Setting…].

 2.Select from <Net intensity before drift correction>, < Net intensity after drift
correction> and <Internal std and overlap correction> in the “Intensities” frame.
 3.Click OK .
Display Multiple Data Items
Two or more selected data items can be displayed simultaneously.
1. Select two or more sample IDs in the data selection area.
2. Select [View] [Multi data Draw].

Sort by Item
This operation selects an objective analyzed result from a list of data. For example, when
sorting by the analysis type is selected, measured data can be sorted for each analysis
type regardless of analysis dates and times or sequence numbers. Data items are
arranged by default in the order of the analysis date and time.
1. Click title items such as Type , Application and Sample name in the data selection
area.
To restore the ordinary display order, click Analysis Date.
Copy Displayed Data to Excel File
Displayed analyzed results or X-ray intensities can be copied to an Excel file or the like
thorough the clipboard.
1. Select a sample ID for copying.

2. Select [Edit]  [Copy].
3. Paste data using the destination software.
The copying and pasting operations are possible even when two or more sample IDs are
selected and two or more data items are displayed.

Data Retrieval
When the number of measured samples becomes large and the analyzed result data
quantity increases, retrieval using the data sorting function alone may be difficult. In
addition, to draw a plotting chart described later, only samples of the same application
must be selected. In such cases, specific desired data alone can be retrieved and
extracted to the selection area. Retrieval items can be selected from the analysis date
and time, type, application and input memo. That procedure is described below:
There is a filter function with the dropdown button in the column header.
1. In the data selection area, click the dropdown button of an item for which to carry
out data extraction. A list of options is displayed according to the item. A list of
analysis types is shown below:
2. From the list, select candidates to be displayed.

3. Click OK. The selected data items are displayed.
In a column for which a filter has been set, the filter icon is displayed instead of the
dropdown button.

Recalculation Procedure
Described below is the procedure to make a quantitative calculation again when a

calibration curve has been updated after a quantitative analysis:
1. Click a sample ID for which to make a recalculation.

2. Click Analyzed Result .
3. Click Recalc . The analyzed result is updated.
To restore the original analyzed result, click Restore.

Change Folder of Displayed Data
Data to be displayed by the Result Display program can be specified using a folder for
saving on analyses and can be saved in another folder using the Result Display program.
A folder for display using the Result Display program is specified with the following
procedure:
The folder for display is always displayed in the upper part of the Analyzed Result
screen.
 1.Click Browse… to select a folder.

 2.Select a folder for display.
 3.Click OK .
Folders to save quantitative analysis results on analyses are the folders AnlRslt and
AnlRsltU and their subfolders.
The specified folder for display is saved. If it is different from the one for saving on analyses,
results are not displayed automatically on analyses, In this case, change the folder and
then reselect the one for general use.

b. Collection of Analyzed Results
Collection processes such as statistics calculations and plotting charts are performed on
stored quantitative analysis data. Basically, in the quantitative analysis, management
of analyzed results is necessary. Collected statistics calculation results can be printed
and transmitted. The procedure to draw plotting charts is described below. However,
plotting charts for X-ray intensities cannot be drawn.
For the operational procedure for the X-R control analysis to obtain statistics of results
of check analyses, see “6.2 g. Record for Check Analysis Result” in the Maintenance
menu.
Plotting Chart
A chart to check the trend of analyzed results for each component is called the plotting
chart. Statistics calculation results such as averages, maximum values, minimum
values, ranges, standard deviations and coefficients of variation are displayed. A
histogram can also be drawn.
The operation flow for the collection of analyzed results is shown below:
Start
Retrieve data for processing
Select component for processing
Draw histogram?
No
Yes
Plotting chart + histogram
Detailed histogram + statistics Plotting chart + statistics
End
Statistical processing for different application types is impossible.

The ordinary procedure to draw a plotting chart is described below. The following
procedure displays a plotting chart and statistics. To set other necessary processes,
make setting changes by referring to procedures described later before clicking OK .
1. Retrieve objective measured results with the application name or the like.
2. Select measured results for processing in the data selection area.
3. Select [View] [Plotting].
4. Select a component for processing.
5. Click OK .
After the above operation, a time-series plotting chart is displayed on the left and
statistics are displayed on the right, as shown below:
Though two or more components can be displayed simultaneously, it is recommended that

a single component be processed first.

Change Vertical Scale
On the initial drawing, the vertical scale is automatically determined from analyzed
results. That vertical scale can be set arbitrarily. An absolute setting or a relative setting
can be used. In the absolute setting, enter an integer or a real number. In the relative
setting, enter a percentage.
1. Designate objective data for a plotting chart.

3. Click the “Spindle” tab.
4. Select <Absolute> or <Relative>.
5. Enter an absolute value or a percentage for the vertical scale.
6. Click OK .
Horizontal Scale
To set the horizontal scale, a time format or a data points format can be used. In the time
format, start and end dates are designated and a time-series plotting chart is drawn. In
that case, data intervals are time intervals and therefore may not be consistent. On the
other hand, in the data points format, a plotting chart with a constant interval is drawn.
Compare those formats and draw a plotting chart suitable for your purpose.

Draw Plotting Chart with Time Format

3. Click the “Horizontal” tab.
4. Select <Time> in the “Horizontal axis” frame.
5. Set a start date in the “Horizontal scale” frame.
6. Set a start time in the “Horizontal scale” frame.
7. Set an end date in the “Horizontal scale” frame.
8. Set an end time in the “Horizontal scale” frame.
9. Click OK .
To set a date, the standard date setting function of Windows can be used.
Draw Plotting Chart with Data Points Format

3. Click the “Horizontal” tab.
4. Select <Data points> in the “Horizontal axis” frame.
5. Set a start data point in the “Horizontal scale” frame.
6. Set an end data point in the “Horizontal scale” frame.
7. Click OK .

Display Reference Lines
To check the variation condition of results drawn on a plotting chart, reference lines can
be displayed. For the reference lines, one, two or three times the standard deviation ()
or the limit range values set in the application can be selected.

3. Click the “Reference” tab.
4. Select <1*SD>, <2*SD>, <3*SD> or <Limit range>.
5. Click OK .

Display Histogram
A step-function graph that has the horizontal axis of a quantified physical parameter
characterizing an event and the vertical axis of the number of its observations is called
the histogram. This program displays a histogram rotated clockwise by 90 degrees to the
right of a plotting chart. The number of divisions for the horizontal axis is set to 7 to 13
and the right and left parts from the center are divided into three to six divisions
respectively, in order to indicate the degree of shifts from the average.
Histogram Expression in This Program

3. Click the “Histogram” tab.
4. Select <Yes>.
5. Select a value from 7 to 13 for “Division”.
6. Click OK .

Display Histogram and Statistics
When a histogram is not displayed, statistics are displayed to the right of the plotting
chart. When a histogram is displayed, statistics are not displayed. If desired, a detailed
histogram and a statistics graph can be drawn.
1. Draw a plotting chart with a histogram.
2. Double-click the histogram on the right side of the display area.
A detailed histogram is drawn from a plotting chart. Therefore, when the plotting chart is
closed the detailed histogram is also closed.

c. Printing of Analyzed Results

To print analyzed results, a fixed format is used according to a data type or an edited
format is specified on printing.
In using an edited printing format, the single result print method to print analyzed
results one by one or the multi-result print method to print continual change can be used.
The multi-result print method is used to print results that were analyzed continually
with the same conditions. That method is used for a check of change with time, quality
control, spectrometer stability test, distribution measurement in a plane (mapping
measurement) and so on.
 Output Data in Using Edited Format

Output data for each job is shown below:
Single Result Multi-Result

Job Result Format Code
Print Print
Limit range,
Intensity
Quantitative mapping
Analysis Analyzed Limit range,
value mapping
Intensity Application,
Intensity
Measurement mapping
Intensity Check sample
Check
Analysis Analyzed
Check sample
value
Drift correction
Intensity
Drift sample
Correction Updated Can be printed Can be printed
result elsewhere elsewhere
Standard
Intensity Standard sample
Sample
Bias correction
Intensity
sample
Bias Analyzed Bias correction
Correction value sample
Updated Can be printed Can be printed
result elsewhere elsewhere
Updated results of drift correction can be printed using Record for Drift Correction Result.
PHA adjustment results can be printed using Record for PHA Adjustment Result.

 Output Data With Fixed Format

It prints directly when operated to print.
Job Analysis Type Content of Print

Qualitative SQX analysis SQX analysis result
analysis Qual. only Identification result
PHA adjustment SC, PC Result and differential curve
The result of a library sample cannot be printed in the “Result Display” program. Print the
data using the “Library Sample” or “Qual. Data Handling” program.

 Print Setting
Set Single Result Print Format
1. Select the “Result Display” screen.

3. Select the “Single Result Print” tab.
4. Select <Analyzed result> or <Intensity> for “Print Format”.
5. Click Add .

6. Enter a format name for Single Result Print for “Format”.
7. Enter a title in the “Title” frame.
8. Click Setting in the “Header” frame.
9. Select an item to be output as header information under “Type” for each item.
10.Enter a heading under “Heading” for each item.
11.Select <Left>, <Centered> or <Right> under “Align Text”.
12.Click OK .
13.When <Analyzed result> was selected for “Print Format”, select <Final result> or
<Application result> in the “Data” frame.
14.Select data to be output in the “Data” frame.
15.Select <Unit> if necessary.
16.When <Analyzed result> was selected for “Print Format”, select <Color output for
out of range> if necessary.
17.If necessary, select <Reporting date> and enter its format.
18.Select <Logo output> if necessary.
When <Input memo> was set for the type of item, its contents can be entered in the printing
dialog. It can be used to print an operator name or the like.
An example is shown below in which the paper direction is <Portrait> and all header items
are aligned to the left under a title:
Entered Title
Heading Item 1 Heading Item 4


An example is shown below in which the paper direction is <Landscape> and header items
are aligned to the left, center and right under a title:
Entered Title
Heading Item 1 Heading Item 3 Heading Item 5

Heading Item 2 Heading Item 4 Heading Item 6
Set Multi-Result Print Format

3. Select the “Multi-result Print” tab.
4. Click Add .
5. Enter a format name for Multi-Result Print for “Format”.
6. Select <Portrait> or <Landscape> for “Direction”.
7. Enter a title in the “Title” frame.
8. Click Setting in the “Header” frame.
9. Select an item to be output as header information under “Type” for each item.
10.Enter a heading under “Heading” for each item.
11.Select <Left>, <Centered> or <Right> under “Align Text”.

12.Click OK .
13.Select data to be output in the “Data” frame.
14.Select <Unit> if necessary.
15.Select <Color output for out of range> if necessary.
16.Select a sample name width if necessary.
17.Select <Output statistics> in the “Statistics” frame.
18.Select output items in the “Statistics” frame.
19 Select <Reporting date> and enter its format.
20.Select <Logo output> if necessary.
21.Click OK .
For the sample name width, specify the number of printing units required for the sample
name. When the sample name width is 1, approximately 10 characters can be used. When
the sample name is long, increase the sample name width.

Print Analyzed Result

2. Select (a) sample ID(s) to be output.
3. Select [File] [Print...].
4. Check a mark in the “Print method” frame for <Single result> or <Multi-result>.
5. Select <Analyzed result> or <Intensity> in the “Print data” frame.
6. Select a format in the “Print format” frame.
7. When setting has been made for “Input memo”, enter the memo(s).
8. Click OK .
When two or more sample IDs to be output have been selected, <Multi-result> is selected
on the “Print” screen.

d. Transfer of Analyzed Results
Quantitative analysis results can be transferred by designating their sample IDs. As for
the text format, the transmission format, spreadsheet format, HTML format and output
hazardous elements format (option) are available. As for the transfer method, the disk
saving, e-mail and external transmission are available. The text format and transfer
method that can be used vary depending on the data type.
 Objects of Transfer
Analysis Type Item
Intensity
Quantitative Analysis
Analyzed result
Intensity Measurement Intensity
Intensity
Check Analysis
Analyzed result
Drift Correction Sample Intensity
Standard Sample Intensity
Intensity
Bias Correction Sample
Analyzed result
Intensity
Analyzed result
In the case of analysis types that have analyzed results, selection can be made from the
transfer of analyzed results only and that of both analyzed results and intensities.
To output intensities, select the type of intensities from <Net intensity before drift
correction>, <Net intensity after drift correction> and <Internal std and overlap correction>.
When the output hazardous elements format (option) is selected, data to draw up a report
on hazardous elements can be output.
 Selection Method and Text Format

Output
Transmission Spreadsheet HTML Hazardous
Selection Method
Format Format Format Elements
(Option)
Selection of
Valid Valid Valid Valid
one sample ID
Selection of sample IDs
Valid Valid Valid Invalid
of same code
Selection of sample IDs
Valid Invalid Valid Invalid
of different codes

In the case of mapping measurement data, more than one sample ID can be selected in the
spreadsheet format. In other cases, only one sample ID can be selected.
 Transfer Method and Text Format

Output
Transmission Spreadsheet HTML Hazardous
Transfer Method
Format Format Format Elements
(Option)
Disk Saving Valid Valid Valid Valid
E-Mail Valid Valid Valid Invalid
External
Valid Invalid Invalid Invalid
Transmission
Transfer Analyzed Results
The procedure to transfer quantitative analysis results using the CSV format in the
spreadsheet format is used as an example for explanation.

2. Select a sample ID of the quantitative analysis.
3. Select [File]  [Transfer Quant Data].
4. Select <Send result and X-ray intensity>.

5. Select <Spreadsheet format> and <CSV> for “Text format”.
6. Select <Disk save> or <E-mail> for “Trans. method”.

7. Enter a folder to save a file.

9. Select <Yes> or <No> for “Unit name” in the “Spreadsheet output options”.
10.Select <Yes> or <No> for “Analyzed date” in the “Spreadsheet output options”.
11.Select <Yes> or <No> for “Mapping position” in the “Spreadsheet output options”.
12.Click OK .
To use e-mail for transfer, its destination must be set beforehand using [Utility]  [System
Management]  [Data Transfer Setting].
To use the external transmission, its transmission condition must be set beforehand using
[Utility]  [System Management]  [System Parameters].
Only when <Transmission format> was selected for “Text format”, <RS232C
Transmission> or <TCP/IP Transmission> can be selected for “Trans. method”.
When <Output hazard. elem.> (option) is selected for “Text format” and data transfer is
carried out, XX.csv and XX_data.csv (XX: specified file name) are created in the specified
folder.
Find Folder to Save File
1. Click Browse… at “Folder”.

2. Double-click <My Computer> or <Network Neighborhood>.
3. Select an objective disk or host name.

4. Select an objective folder.
5. Click OK .

e. Saving of Analyzed Results
A quantitative analysis result can be saved in a specified folder by selecting a sample ID.
1. Select a sample ID to be saved.

2. Select [File]  [Save...].
3. Select a drive name and a folder.
4. Select OK .
By specifying a folder for data display with Result Display, saved data can be displayed.
f. Deletion of Analyzed Results
An analyzed result can be deleted by selecting a sample ID.
1. Select a sample ID to be deleted.

2. Select [File]  [Delete].
3. Select Yes .

g. Start of Data Processing Program from Analyzed Result
By selecting a sample ID, the “Qual Data Handling”, “SQX Calculation” or “Mapping”
program can be started directly according to a data type.
Job Started Program Requirements for Selection

Qual Data
The creation of a qualitative
Handling
analysis result file is specified.
Qualitative SQX Calculation
Analysis The creation of a mapping file is
Mapping specified in the mapping
measurement.
Quantitative
The creation of a mapping file is
Analysis
Mapping specified in the mapping
Intensity
measurement.
Measurement
Even when a qualitative analysis result or a mapping file is specified, a data processing
program cannot be started if that file does not exist in the specified folder.
When a mapping file is specified in the qualitative analysis, “Qual Data Handling” and “SQX
Calculation” cannot be selected.
1. Select a sample ID.

2. Select [View] and then select [Qual Data Handling], [SQX Calculation] or [Mapping].
The program is started.
Since a result file is automatically selected on a startup, file selection is unnecessary.

4.5 QUANTITATIVE SIMULATION
The Quantitative Simulation means “recalculation of measured results after

reconsidering and modifying a calibration curve” or “consideration of a quantitative
analysis without measurement”. Conditions or other components of the analysis
modified here do not change contents of an actual application file. Contents considered
and changed here are valid only in this program.
Since already measured X-ray intensities are used, there is no item concerning X-ray
intensity measurement. Since check samples are unnecessary, there is no item
concerning setting for them. Consideration on a quantitative analysis is possible without
measurement. For example, consideration is possible on the effective depth of the X-rays
of a certain component.
The operational procedure is basically almost the same as that for the quantitative
application. For details, see “4.2 CREATION OF QUANTITATIVE APPLICATION”.
Only items concerning the simulation are described below.
The operational flow for the Quantitative Simulation is shown below:
Start
a. Creation of Application
e. Regression Calculation
f. Unknown Sample Quantification
End

2. Select [Quant Simulation].

For an application to be used in the Quantitative Simulation, an application file created

for a quantitative application can be used intact or an application dedicated for the
simulation can be created. When one uses an existing quantitative application file, the
setting procedures are identical to those for a quantitative application from “Copy an
existing quant application” to “Constant input”. Items concerning an application
dedicated for the simulation and different from those for the quantitative application are
described below:
For <Rename and save the application> and <Delete an application>, the operational
procedures are the same as in the case of the quantitative application. See “4.2 a. Creation
of Application File”.
In the case of <Quant application>, selection items on the right do not appear. After
pressing Next>, the “Select an existing quant application” screen appears.

Procedure to Create Application File
1. Select <Simulation>.

3. Click Next> .
4. Select an objective tab.

6. Click Next>.
8. Select an objective template icon.
9. Click Next>.
10.Enter an application name.
11.Enter a memo if necessary.
13.Click Finish.
When a template is used, only the empirical calibration method can be selected.

Create Application with FP Method
To create an application with the FP method, select <Create your own application>.
1. Select <Simulation> on the “Application File” screen.

3. Click Next>.
4. Select an objective folder on the objective tab.
5. Click Next>.
7. Click Next>.
8. Enter an application name.
9. Select <Fundamental parameter method> for “Type of analysis”.
10.Enter a memo if necessary.
12.Click Finish.
Copy Existing Quantitative Application

2. Select <Copy an existing quant application>.
3. Click Next>.
6. Click Next>.
7. Change the application name if necessary.
8. Change the memo if necessary.
9. Click Finish.
The rule for copying a component type is shown below:

Definition for quantitative application
Bal- Em- Manual Param- Input Correc- Exter-
FP Fixed Flux
ance pirical input eter flux tion nal
         
Bal- Em- Param- Correc-
FP Fixed Fixed Flux Flux Delete
ance pirical eter tion
Definition for simulation

Select Existing Simulation File

2. Select <Modify an existing simulation application>.
3. Click Next> .
For the operational procedure for “Application Information” (“Component Selection” and
“Sample Preparation”), see “4.2 b. Setting of Application Information”.

b. Differences in Standard Sample Setting
Most operations are the same as those for standard sample setting for the quantitative
application. As for copying from other applications, a function to copy an application
dedicated for the simulation can be used.
Copy from another Application

2. Click Copy application standards .
3. Select <Quant application> or <Simulation> on the right of the folder.

5. Select an objective sample type.
6. Select an objective application.
7. Click OK .
8. Select necessary standard samples on the standard sample list.
9. Click OK .

c. Setting of Analysis Information
The operational procedure for analysis conditions (analysis parameters and special
standard samples) is also almost the same as that for the quantitative application.
Differences in the case of the simulation are described below. As in the case of the
quantitative application, special standard samples are set only in the case of the FP
quantification method.
Differences in Analysis Parameter Setting
 Property of Analysis Information
Differences in options for the component type on the “Property of Sample Component”
screen for each component are shown below:
Component Type Quantitative Application Quantitative Simulation

FP method FP method
Analyze
Empirical Empirical
Calculate as Balance Balance Balance
Known Fixed, Input, Calculate Fixed
Additive/Flux Fixed, Input, Calculate Fixed
Setting for the output number of digits is added.
 Advanced Setting of Analysis Information
Differences in setting items on the “Advanced” screen are shown below:
Setting Item Quantitative Application Quantitative Simulation

Std. sample
Selection from 1 to 9 None
prep. time
Description of
Entered Entered
Application
Repeated intensity 
Peak/BG intensity 
Net intensity before drift correction 
Print selection Net intensity after drift correction 
in Internal std/overlap corrected Internal std/overlap corrected
analysis
Uncorrected/unnormalized
Uncorrected/unnormalized result
result
Application result Application result
Final result 

 Extra Components in Analysis Information
The item of “External parameter” does not appear on the “Property for an Extra
Component” screen. The other operational procedures are the same as those for the
quantitative application.
 Measuring Condition Panel
The measuring diameter and atmosphere need not be set. The Advanced button does not
appear. The angle and time are not displayed. The incident angle is added as a setting
item.
 Property of Measuring Condition
The following items are displayed in the case of the quantitative simulation:
Item Description
Element line(El. line) The same as the quantitative application
A target element and an X-ray tube type are
Target
selected.
Tube voltage(kV) The same as the quantitative application
Take off angle A takeoff angle is entered.
A filter element is selected.
Filter
A filter thickness is entered.
For the target, selection can be made from the following three types. The initial setting is
the target of the X-ray tube used.
Target Expression Example

Target element + E + Be window thickness(m) RhE030
Target element + Side CrSide
Target element 1 + (Target element 2) Rh(W_)
For the operational procedure for the calculated parameter, see “Add Process Parameter”
and “Setting of Calculated Parameter” in “4.2 d. Setting of Analysis Information”.

Differences in Setting of Special Standard Samples
Special standard samples can be set only when the application has been created with the
FP quantification method. In the FP method, unlike the empirical calibration method,
standard samples that have different composition from that of unknown samples can be
used.
In the case of the Quantitative Simulation, the item of the background intensity does not
appear in the “Measurement” frame on the “Property for Component” screen. The other
items are the same as those for the quantitative application.

d. Regression Calculation
In the regression calculation for the Quantitative Simulation, all items concerning
background in a quantitative application do not appear. Other differences are also
described below:
Differences in Calibration Curve/Sensitivity Curve Calculation
 Setting of Correction for FP Method
The BG Subtract/Internal Standard button changes to the Internal Standard button on the
“Correction for FP Method” screen that appears when the Correction button is clicked,
and <Scattering internal standard correction> alone is set.
 Sample Selection
Differences are shown below concerning <Weighting> on the “Sample Selection” screen
that appears when the Sample Selection button is clicked:
Options for Weighting

Type
Quantitative Application Quantitative Simulation
<Normal>, <Precision>, <Normal>,
Empirical
<Effective digits> <Effective digits>
FP <Normal>, <Precision> No selection for weighting
 Others
 [Data] [Change BG Subtraction...] in the menu items cannot be operated.

 [Data] [Add Standard...] in the menu items are valid when a quantitative
application is processed.
 <Background> cannot be selected on the “Display Data Table” screen and the “Print
Data Table” screen.
Differences in Manual Input of Constants
In the case of the Quantitative Simulation, the “Auto BG subtraction” tab cannot be
used.

e. Unknown Sample Quantification
Recalculation of Unknown Sample Quantification
When unknown samples have been measured using a quantitative application created
beforehand, one can recalculate the results for the sample after changing contents of the
application. It does not mean that measuring conditions are really changed requiring
measurement of the standard samples again. For example, in an application for which
background measurement was carried out, a recalculation can be made by creating a
calibration curve using gross intensities without subtracting background intensities.
Those changed contents are not reflected in the original application and are valid only in
this Quantitative Simulation program.
1. Click Unknown Calculation on the flow bar.
2. Set a sample name in the “Sample name” box.

3. Enter the X-ray intensities of components.
4. Repeat steps 2 to 3 as necessary.
5. Select [Calculate]  [Start Calculation].
6. Click Print on the “Result of Unknown Calculation” screen as necessary.
Up to 100 samples can be calculated at a time.

Read Result File of Quantitative Application
When <Quant application> is selected on the “Application File” screen, a result file can
be read. Based on quantitative analysis results using the quantitative analysis and
intensity measurement, recalculation and unknown sample quantification can be
carried out.

2. Select [File]  [Read Result File…].
3. Select a folder where data is stored.
4. Select <Quant analysis> or <Intensity measurement> for “Data type”.
5. Select a result file to be read for “Application”.
6. Click OK .
Two or more result files can be selected. Select necessary ones referring to sample names,
measuring coordinates and analyzed dates/times.
When sample data has already been set, selected result data is added after that. However,
if the number of samples exceeds 100, data will not be added any more. When result data
for which a sample name has not been set is read, “no name” is set as its sample name.
Change Processing Method for Intensities in Result File Reading

2. Select [File]  [Read Result File…].
3. Select a folder where data is stored.
4. Click Advanced… .
5. Select <Use net intensity stored> or <Calculate from BG subtraction> for
“Processing of intensity”.
6. Select <Reapply drift correction> if necessary.
7. Click OK .
8. Select <Quant analysis> or <Intensity measurement> for “Data type”.
9. Select a result file to be read for “Application”.
10.Click OK .

Insert Sample Data
1. Click a line number for insertion.

2. Select [Edit]  [Insert].
3. Set a sample name in the sample name field of the inserted blank line.
4. Enter an X-ray intensity or fixed value in the field of each component of the inserted
blank line.
Move Sample Data
1. Click a sample data line to be moved.

2. Select [Edit]  [Cut].
3. Click a blank line.
4. Select [Edit]  [Paste].
<Cut >, <Copy>, <Paste > and <Insert> can also be performed by right-clicking at an
objective line number or sample name.
Change Component Type
When <Measure (EMP)> or <Measure (FP)> has been set for a component type, it can be
changed to <Fixed>.
1. Select [Component Type]  [Change Component Type].

2. Click the field of the type of an objective measured component.
3. Select <Measure()> or <Fixed> in the pull-down list.
4. Click OK .
Delete All Sample Data
1. Select [Edit]  [Clear All].

Copy Contents of Unknown Sample to Excel File
X-ray intensities etc. for “Unknown Calculation” can be copied to an Excel file or the like.
 1. Select and right-click a cell range to be copied on the “Unknown Calculation”

screen.
 2. Select [Copy] on the menu.
 3. Paste data using the software of the destination of copying, such as Excel.
Copy Contents of Unknown Sample from Excel File
X-ray intensities etc. for “Unknown Calculation” can be copied from an Excel file or the
like.
 1. Copy data using the software of the source of copying, such as Excel.
 2. Select and right-click a cell from which to start pasting on the “Unknown
Calculation” screen.
 3. Select [Paste] on the menu.
Write a text file of quantitative analysis result
It is possible to write a text file readable by spreadsheet program of quantitative

analysis result from the result of unknown calculation window.
 1. Select [File]  [Text Output of Analyzed Result].

 2. Select Text format from <CSV> and <TAB>.
 3. Click Browse… to specify a File output folder.
 4. Enter a File name to output.
 5. Click OK .

f. Printing of Quantitative Application Information
In “Print Quant Application”, the following items can be printed. For items with
“Select…” buttons, detailed items can be selected.

3. Click Next> .
7. Click Next> .
8. Select necessary items in the “Print item” frame.
9. If necessary, click Select... and make selections for detailed items.

Select Analytical Constants
1. Select <Analytical constant> on the “Print Quant Application” screen.

2. Click Select... on the right of <Analytical constant>.
3. Select items to be printed.
4. Click OK .
Select Standard Samples
1. Select <Standard sample> on the “Print Quant Application” screen.

2. Click Select... on the right of <Standard sample>.
3. Select standard samples to be printed in each frame.
4. Click OK .
To select all standard samples in each frame, click Select All under each frame.

4.6 AUTOMATIC QUANTITATIVE APPLICATION

SETUP（ZSX Primus IV/IVi）
Outline
Many steps are necessary to create a quantitative application in the ordinary procedure.
Many operations are required for various settings such as the setup of measuring
conditions (peak angle, background angle and PHA setting width) for an element line
and the proper settings of the coexisting element correction and overlap correction for a
calibration curve. This function automatically carries out those settings from sample
information and the data of the SQX analysis. Its purpose is to enable even an operator
who is not much experienced in the X-ray analysis to create suitable analysis conditions.
The automatic quantitative application setup function automatically sets the following
items based on the SQX data (qualitative analysis charts and SQX analysis values) of
standard samples:
・Element Line and Optical Measuring Conditions
Element line with little effect of overlap
Optical conditions with little effect of higher order lines
Optical conditions with a good SN ratio and lower limit of detection (They vary
depending on the concentration range of standard samples.)
・Peak Angle and Background Angle
The effects of nearby spectra are considered and the background measurement
angle(s) is/are determined using the 1-point method or 2-point method.
・Coexisting Element Correction
Information on elements other than a quantification component that are detected
in the SQX analysis is considered, and when it is judged that the effect of a
coexisting element exists, the coexisting element correction is automatically set.
・Overlap Correction
When it is judged that overlap affects a quantification component, the overlap
correction using the concentration of an interfering component is automatically
set.
・ Component Other Than Quantification Components That Is Detected in SQX
Analysis
When a component other than components to be quantified affects any
quantification component through a matrix or overlap, it is added to the
measurement components and regarded as a quantification component using the
sensibility library.
・Automatic Creation of Tentative Calibration Curve of Quantification Component
A tentative calibration curve is automatically created using X-ray intensities of an
element line in qualitative analysis data, and the preliminary checking of the
calibration curve is possible.
After the above automatic settings are made, determine the measuring times of the peak
and background while considering required precision, make the standard sample
measurement to create a final calibration curve, and check and register the final
calibration curve.

Ordinary Procedure for Quantitative Automatic Quantitative

Application Creation Application Setup Function
散
Setting Items
Qualitative Spectrum
Component Input
Measurement and Composition
Analysis of Standard Samples
Sample Information
Input
Sample Form &
Standard Values
・ Automatic Search for

Measuring Conditions: Element Line
Element Lines ・ Automatic Search for
Flow of Setup
Optical Conditions Optical Condition

Measurement Times
・Automatic Setup of Peak

Measuring Condition Angles
Setup:
Peak Angles ・Automatic Setup of
Background Angles Background Angles
Standard Sample
Measurement ・Automatic Theoretical
Matrix Correction
Calibration Curve
Coefficient Calculation
Creation:
・Automatic Overlap
Matrix Correction
Overlap Correction Correction Setup
Conventional Method and Automatic Quantitative Application Setup Function for

Creation of Quantitative Application
This function applies only the empirical method to quantification components.
Theoretical matrix correction coefficients are used for the matrix correction. The
concentration correction is employed for the overlap correction.

Samples and Quantification Ranges to Be Used for Automatic Quantitative

Application Setup
Shown below are sample types, quantification element ranges and component forms to
be used for the automatic quantitative application setup:
Fundamental
Quantification Balance
Sample Type Component
Element Range Component Setting
Form
Metal & Alloy Mg - U Metal Auto/Manual
Powder F-U Oxide Auto/Manual
Na - U
Fusion Bead Oxide Auto/Manual
(Excluding Tc - Cd)
Ceramics &
F-U Oxide Auto/Manual
Glass
Auto (Carbon)
Polymer F-U Metal
/Manual
Balance Component Setting

When the balance component is specified in the component selection, it is set as the
balance component for the SQX calculation using that component and for the calculation of
theoretical matrix correction coefficients.
When the balance is known, by setting it as the balance component, the automatic setup is
carried out more accurately.
Balance Component of Sample Type Polymer

If the balance component is not specified in the component selection, carbon “C” will be set
as the balance component. When the balance is known, set it as CH2 or the like.
Concentration and Measuring Diameter of Quantification Component
Since settings are automatically made using the qualitative analysis data of standard
samples, this function cannot automatically create optimum analysis conditions. In any
of the following cases, create an application using the ordinary quantitative application
setting procedure:
 In the case of a trace element that is difficult to detect using the ordinary
qualitative analysis.
 When a sample has a small diameter and detection is difficult even for
components that are not trace elements.
 When a sample is formless and smaller than the measuring diameter.
 When the ununiformity effect of a sample is large.

Quantitative Correction Method
Although the internal standard method and addition method are known as correction
methods for the quantitative analysis, it is impossible to use any of those special
corrections.
Optical Conditions
Measuring conditions are set with the standard common library conditions using the
standard crystals (LiF(200), PET(H), Ge(H) and RX26 (RX25)) and the slits S2 and S4.
Therefore, it is impossible to use other crystals, PHA conditions, slits or the output
conditions of the X-ray tube.
Component Setting and Unit of Quantification Component
To set a component, use an element, standard oxide or registered compound.

Only mass% can be used as the unit.

4.6.1 CREATION OF APPLICATION USING

AUTOMATIC QUANTITATIVE APPLICATION
SETUP
The automatic quantitative application setup program automatically processes the
items d through h in the following creation flowchart. When “Run Standards SQX” of the
item d is completed, settings are automatically made until the creation of tentative
calibration curves in the item h.
Start
b. Application Information Setup
c. Setting Procedure for Standard Samples
d. SQX Measurement of Standard Samples
e. Setup of Composition Information (Automatic Setup)

Automatic
Setup Process
f. Setup of Analysis Conditions (Automatic Setup)
g. Measuring Condition Setup (Automatic Data Storage)
h. Regression Calculation (Checking of Tentative Calibration Curve)
i. Standard Sample Measurement
j. Regression Calculation (Calibration Curve Registration)
k. Setup of Analysis Control Information
End
Set measuring times separately according to required precision.

1. Click Quant Application from the menu.

2. Select <Create a new application> on “Application File”.
4. Select <Set the analytical conditions in automatic>.

5. Select a sample type according to an analysis sample.
The procedure for the metal is described below as an example:
Only <Metal & Alloy>, <Powder>, <Fusion Bead>, <Ceramics & Glass> and <Polymer>
can be used as the sample type.

6. Set an application name.

7. Select <30 mm> for “Diameter” and <Vacuum> for “Atmosphere”.
8. If necessary, set a memo (“Description of application”).
9. Select <Common> for “Folder”.

b. Application Information Setup
The application information setup consists of setting items of the component selection
and sample preparation information.
1. Click Component Selection on the flow bar.

2. Select a measurement component from the periodic table.
3. Click Next .
Only the empirical method can be used as the analysis method for a measurement
component.
Only mass%, which is a unit of concentration, can be set as the unit.
When a special compound exists in a powder sample or the like, carry out the compound
registration beforehand.
When a balance component is known, set it using the component selection.

For example, when a sample is stainless steel, set Fe as the balance component.

Shown below is a screen on which Fe has been set as the balance component:
The automatic setup function may judge that components other than quantification
components affect the quantification components and automatically set them additionally.
The FP method is defined for added components (manual addition is impossible).
Shown below is the “Component Selection” screen after only Cr is set as a quantification
component and the automatic setup is carried out. Mn, Fe, Ni and Mo have
automatically been added as FP method components. It is impossible to delete
automatically added components.
Automatically Added
Components

Setup of Sample Preparation Information
For the automatic setup of analysis conditions, it is necessary to set sample information
correctly. As shown below, the setting contents of the sample preparation information
vary depending on a sample type. Sample types are shown below:
Sample Type Analysis Sample

Metal sample such as iron, steel or nonferrous
Metal & Alloy
metal
Powder sample such as cement or glass.
Powder Use this when using binder, grinding aids or sample
film.
Fusion Bead Glass bead sample of powder such as cement or ore
Ceramics & Glass Massive oxide sample such as glass
Sample that consists of organic matter such as a
Polymer
polymer or rubber
Setting Procedure for Sample Preparation Information
1. Click Sample Preparation on the flow bar.

2. Change setting contents according to the sample type.
3. If necessary, enter a memo.
4. Click Next .

 Sample Preparation - Metal & Alloy
1. When a sample film is used for an analysis sample, set information on the sample
film. Information on the sample film setting is used at the time of calculations in the
standard sample SQX analysis.
 Sample Preparation - Powder
1. When binder is used, click <Used> for “Binder/Grinding aids” and select the
compound of the binder. Enter the weight values of a sample and binder.
2. When a sample film is used, set information on it. Information on the settings of
“Binder/Grinding aids” and “Sample film” is used at the time of calculations in the
standard sample SQX analysis.

 Sample Preparation - Fusion Bead
1. Select a flux type in the “Sample and flux” frame, and set flux weight and sample
weight to be used as standards.
2. When it is necessary to set other items such as the loss on ignition and oxidizer, set
them. Information on the above setting items is used at the time of calculations in
the standard sample SQX analysis.
When the effect of the loss on ignition exists, select <Corrects for LOI in sample> in the
“Loss on ignition (LOI)” frame. It is possible to correct the effect of the loss on ignition.
 Sample Preparation - Ceramics & Glass
1. Enter only a memo. There is no other setting item.

 Sample Preparation - Polymer
1. When a sample film is used, set information on it.

2. Click Show option >> .
3. Select <Setting> in the “Sample weight thickness” frame.
4. Enter total sample weight at "Total weight" and a diameter at "Diameter".
In organic matter such as a polymer, the intensities of characteristic X-rays with high
energy may be affected by a sample thickness. By setting a sample thickness, it becomes
possible to obtain the SQX analysis values of standard samples after the effect of a
thickness is corrected.
Use the same sample preparation process for both standard samples and unknown
samples. It is important that they have the same sample thickness.

c. Setting Procedure for Standard Samples
The standard values of standard samples are entered.
Setting Procedure for Standard Values
Set analysis values obtained using another analysis method as standard values for the
X-ray fluorescence analysis. Set the data of one sample in one line. When a standard
value is not available, leave its cell blank.
1. Double-click the “Name” cell and enter a standard sample name.
2. If necessary, enter a comment in the “Note” cell.
3. Double-click the cell of each component and enter its standard value.
4. Click Next .
The automatic setup function may judge that components other than quantification
components affect the quantification components and automatically set the other
components and standard intensities additionally. The values of the standard sample SQX
are used for the standard values of added components.

d. SQX Measurement of Standard Samples
Select <Set the analytical conditions in automatic> on the “Create a New Application”
screen, and Run Standards SQX will be displayed additionally on the flow bar.
The SQX analysis of the standard samples set using “Standard Samples” is made.
1. Click Run Standards SQX on the flow bar.
2. On the “Run Standards SQX” screen, select the names of standard samples to be
measured.
3. Set the position of the first standard sample.
4. Click OK .

5. Set the samples to be measured in the displayed sample positions.

6. Click Analyze . The SQX measurement of the standard samples starts.
When all the samples have been measured, the “Composition Information” screen
automatically appears.
Since the qualitative analysis of all elements is made, the measuring time for one sample is
12 to 15 minutes or so. As the number of quantification components becomes larger, the
measuring time becomes longer.
e. Setup of Composition Information (Automatic Setup Item)
Based on the standard values and SQX analysis result values of standard samples,
components and their typical values are automatically set. These typical values are used
at the time of the theoretical matrix correction calculation.
In the component setting in “Composition Information”, components other than

quantification components may be automatically added. For example, since ordinarily
there is no standard value of Fe, which is the main component, in the case of a steel
sample, Fe is automatically added as a component in such a case. When a component
other than quantification components that exists in standard samples affects
quantification components, that component is automatically added. Therefore, displayed
contents can be checked here and component information other than quantification
components in standard samples can be checked.

 Example of Composition Information When Analysis Sample Is Stainless Steel and Si to

Nb Have Been Set As Quantification Components
Fe, which is the main component, has automatically been set as the balance
component.
 Example of Composition Information When Analysis Sample Is Stainless Steel and Only
Cr Has Been Set As Quantification Component
Mn, Fe, Nb and Mo are automatically added as components to be measured
because they are regarded as components that affect the quantification component
Cr.
Components to Be
Measured (Automatically
Added)
1. After checking the displayed contents, click Next .

f. Setup of Analysis Conditions (Automatic Setup Item)
The automatic quantitative application setup function automatically sets analysis

conditions (element lines, combinations of crystals and detectors and backgrounds)
except for measuring times.
1. Click Parameters on the flow bar.
Described below is the procedure to check automatically set contents on “Parameters”.
1. Click the <Analysis Information> tab and check the automatically set element lines.
Suitable element lines are automatically set based on qualitative analysis results and SQX
analysis results of standard samples.
Measurement components other than quantification components may be added as FP

method components. They are automatically added as element lines when the coexisting
element correction or overlap correction is necessary for quantification components.

 Example in Which Components Other Than Cr Are Set As FP Method Components in

Quantitative Analysis Only of Cr in Stainless Steel
2. Click the <Measuring Condition> tab. Optical conditions have automatically been
set for each element line. Check them.
When components other than quantification components are added as FP method

components, <Library> is used as the setting type. These components are quantified
using the spectrometer sensibility library at the time of the quantitative analysis.
Components to Be
Measured (Automatically
Added)

Peak and background angles of element lines of the library are also automatically set.
3. Select an element line, click Property and check the detailed contents of the settings
of each element line.
Items displayed using dimmed characters, such as the excitation conditions, optical
conditions and PHA conditions, have automatically been set and cannot be changed. The
peak and background angles have automatically been set as well and cannot be changed.
Only the peak and background measuring times can be changed. Set them while
considering required precision.

g. Optimize MC’s (Automatic Data Storage Item)
“Optimize MC’s” is a program to set various measuring conditions based on the 2-theta
scan data and PHA data of each element line.
In “Run Standards SQX”, PHA data for each element line candidate is obtained besides
qualitative analysis spectra, and a spectrum and PHA data extracted for each element
line to determine measuring conditions are automatically stored. The data of two or
more line types may be stored depending on an element. Stored line types are K (Ka) line
and L (La, Lb1) line or L (La, Lb1) line and M (Ma) line included in the measuring range
of the 2-theta scan.
If necessary, it is possible to check peak and background measurement angles,
interfering lines and PHA setting conditions.
The 2-theta scan data and PHA data of samples with the maximum and minimum
concentrations have been stored for each quantification component.
 Example of 2-Theta Scan Data

It is possible to check automatically set background information.
Overwritten
Figure
Enlarged
Figure
No line type marker is displayed with 2-theta scan data.
It is impossible to change a peak or background angle. When you want to change an angle,
turn off the automatic setup mode. For the procedure to turn off the automatic setup mode,
refer to <4.6.2 CANCELLATION OF AUTOMATIC QUANTITATIVE APPLICATION
SETUP>.

 Example of PHA Data

Only the checking of the PHA data of each element line can be carried out. It is
impossible to change a PHA condition.
When you want to change a PHA condition, turn off the automatic setup mode. For the
procedure to turn off the automatic setup mode, refer to <4.6.2 CANCELLATION OF
AUTOMATIC QUANTITATIVE APPLICATION SETUP>.

h. Regression Calculation (Checking of Tentative Calibration Curve)

This program automatically creates a tentative calibration curve for an automatically
selected element line using X-ray intensities obtained from qualitative analysis data
obtained from the SQX measurement of standard samples.
By using tentative calibration curve data, it becomes possible to assess beforehand the
accuracy of a calibration curve to be obtained. Since X-ray intensities obtained from
qualitative analysis data are used and the dispersion of intensities due to statistical
fluctuation is large, it is impossible to register a calibration curve using these
intensities.
Check Tentative Calibration Curve

1. Click Calibration on the flow bar.
2. Select a component for a calculation.
A regression calculation result graph (calibration curve) is displayed. Theoretical

matrix correction coefficients are used for the matrix correction coefficients in the
correction settings. For the overlap correction, correction coefficients are
calculated using the concentrations of overlap elements that have automatically
been set beforehand.
Check the calculated tentative calibration curve. Since the linear calibration curve
model is used for the theoretical matrix correction coefficient calculation, only a linear
expression can be used for a regression formula.

Check Details of Calibration Curve
1. Click Result on “Empirical Calibration Result”. The result of a calibration curve
calculation is displayed. It is possible to check calibration curve coefficients, accuracy,
correlation factor and matrix overlap corrections.
When at least one coexisting element affects a quantification component greatly, the matrix
correction is made for the quantification component using set measurement components.
(The base component or analysis component may not be used for the correction depending
on a matrix correction model.)
When it is judged that overlap affects the element line of a quantification component, the
overlap correction using concentrations is automatically set.

Check Tentative Intensities
It is possible to check tentative intensities used for a tentative calibration curve. “Run
Standards SQX” data is used for these tentative intensities.
1. Click the Recalc. button on the regression calculation result graph.
2. The “Recalculation of Empirical Calibration” screen is displayed. The “#” marks in
the X-ray intensity fields mean tentative intensities.

Change Element Line
Described below is the procedure to change an element line selected by the automatic
setup. Element lines that can be changed are only those of optical conditions displayed
in <g. Measuring Condition Setup (Optimize MC’s)>. When an element line is changed
and there are two or more optical conditions for it, the optimum optical condition is
automatically selected. After the automatic selection, the intensities of the element line
are reextracted from the qualitative analysis data of standard samples, and various
corrections are automatically registered.
The procedure to change the element line of Pb from La to Lb1 is described below as
an example:
1. Click Parameters .
2. Select a component to be changed and click Property .
3. Change the line type from La to Lb1 at <Element line>, and click OK . X-ray
intensities and various corrections are automatically set for the specified line type
from the qualitative analysis data of standard samples, and a tentative calibration
curve can be checked.

The automatic setup items have now been set.
As for the operational procedure after this, carry out the measurement of standard
samples, regression calculation and setup of analysis control information in that order
using set measuring conditions. For these items, refer to <4.2 f. Measurement of
Standard Samples> in <CHAPTER 4 QUANTITATIVE ANALYSIS> and sections after
that.

4.6.2 CANCELLATION OF AUTOMATIC

QUANTITATIVE APPLICATION SETUP
When you want to change measuring conditions created by the automatic quantitative
application setup function, cancel the automatic setup. By canceling, it becomes possible
to change each optical condition to set a more suitable condition manually. However,
once the automatic setup is canceled, it cannot be restored.
A quantitative application for which the automatic quantitative application setup is

canceled is defined as an empirical method application or an FP method application
when a library component has been set.
Cancel Automatic Setup
Select a quantitative application file for which you want to cancel the automatic
setup.
1. Click Quant Application , select <Modify an existing application> and click Next > .
2. The “Modify an Existing Application” screen appears. Select a relevant application
and click Finish .

3. Click Application File on the flow bar, select <Change analysis type /sample model>
and click Next > .
4. Make sure that <Change the analytical condition setting method> has been selected,
enter a new application name for “Application name”, specify a folder for saving and
click Finish .

CHAPTER 5 MAPPING ANALYSIS (OPTION)
5. MAPPING ANALYSIS (OPTION)

5.1 INTRODUCTION
This system has the mapping analysis, which drives the sample stage to make the
distribution analysis of a sample, as an optional function. The mapping analysis can
carry out the qualitative analysis and quantitative analysis like the ordinary
small-diameter analysis. Since measurement is made by moving a sample, angle
resolutions and X-ray intensities do not change depending on the analysis position and
stable distribution analysis is possible.
The mapping table to specify measuring positions beforehand is generally used for the
mapping analysis. Using a CCD camera, you can carry out the micro mapping analysis,
in which you can photograph the surface of the sample that has been set in a sample
holder and determine a measuring position seeing the picture.
Described in this chapter are the procedure to create mapping tables, the procedure to
make setting for the micro mapping analysis, and the mapping data processing.
The mapping analysis can be used for the end-window spectrometer. Necessary options
are shown below. The mapping analysis option is not available for the side-window
spectrometer.
The mapping analysis and micro mapping analysis can be used when the spectrometer
has the sample observation mechanism (option).

5.2 MAPPING TABLE

When the system has the sample observation mechanism, the mapping analysis of a
sample is possible. For that mapping analysis, measuring positions in a sample must
have been set previously. The mapping table means the table to record those positions
and the program to create that table.
In this program, measuring positions can be designated with the r-theta method or X-Y
method. That mapping table can be used in the SQX analysis or quantitative analysis.

2. Select [Mapping Tables].
If two or more measuring positions are set at the same coordinates, it will measure at the
same one by that number of positions.

a. Coordinates for Mapping
Measuring coordinates on a sample are so defined that the angle of the markers of a
sample holder for mapping is 180 deg., as shown below:
Dedicated sample holder for mapping

(For ZSX Primus IV only)
Y X-ray marker
Optical marker
.
. X
Y Sample mask for

Dedicated sample mask both X-ray marker
.
for mapping and optical marker
(For ZSX Primus IVi (For ZSX Primus
only) IVi only)

The optical marker is used to determine the direction of a holder from an image obtained
with the camera in the sample observation position in the spectrometer. The X-ray
marker is used to determine the direction of a holder in the measuring position by
measuring the neighborhood of the marker.
The center of a sample is the center of coordinates.
In the case of the r-theta coordinates, the start point of theta is the opposite side of the
markers and theta increases in the counterclockwise direction.

b. Creation of Mapping Table
By designating measuring positions with the r-theta method, A mapping table is created.
The method to designate measuring points with crossing points and the method to add
measuring points on the graphic screen can be used. In both methods, when a measuring
point is designated on the graphic screen, its coordinates are displayed in the list in
order of designation.
Create Mapping Table
1. Select [File]  [New].

2. Enter “MAP001” for “Table name”.
3. Select <r-theta> for “Coordinate”.
4. Click OK .
5. Select <Display> for “Grid Line”.
6. If desired, change the r value at “Step” in the “Grid Line” frame.
7. If desired, change the theta value at “Step” in the “Grid Line” frame.
8. Click Add crossed points .
9. If desired, click on the graphic screen to add a measuring point.
10. Select [File]  [Save].

Change Coordinates
After designating measuring positions using the r-theta coordinates or the X-Y
coordinates, the coordinates can be transformed to the other one. In the measuring point
coordinates list, the displayed measuring point coordinates are converted.
1. Select [Option]  [Setting].

2. Select <r-theta> or <X-Y> for “Coordinates”.
3. Click OK .
Designate Measuring Point Using Numerals
When a measuring point is designated on the graphic screen, the coordinates of the
measuring point are displayed in the list. The value in a cell of r(mm), theta(deg), X(mm)
or Y(mm) can be transformed. The bottom line of the measuring point list is blank. By
entering a value in that line, the measuring point can be added.
1. Double-click an objective “r(mm)” or “X(mm)” cell in the measuring point list.
2. Enter an r or X value.
3. Double-click an objective “theta(deg)” or “Y(mm)” cell in the measuring point list.
4. Enter a theta or Y value.
When one of coordinate value is entered in the bottom line of the measuring point list, the
value of the previous line is copied for the other of coordinate value.
When the Enter key alone is pressed in the bottom line of the measuring point list with both
cells left blank, the input cursor moves to the top cell.

c. Deletion of Measuring Point
All measuring points or designated measuring points can be deleted. In the case of the
deletion of designated measuring points, the measuring point designated last can be
pasted. In other words, it means temporary cutting. In the case of the deletion of all
measuring points, pasting is impossible.
Delete All Measuring Points
All measuring points are deleted from the coordinate list and the graphic screen.
1. Select [Edit]  [Clear All Points].
Or you can designate all measuring points and then delete them.
1. Select [Edit]  [Select All].
Delete Designated Measuring Points
Measuring points can be deleted from the measuring point coordinates list.
1. Hold down the Ctrl key of the keyboard.

2. Select measuring point coordinates lines to be deleted in the measuring point list.
3. Release the Ctrl key.
Or you can designate a range of coordinates lines and then delete it.
1. Select the first coordinates line of measuring points to be deleted in the measuring
point list.
2. Select the last coordinates line of measuring points to be deleted with the Shift key
pressed down.
When you select one measuring point, you need not press the Ctrl or Shift key.
To deselect measuring points, select an arbitrary coordinates line with the Ctrl and Shift key
released.

d. Insertion of Measuring Points
Two or more measuring points or one measuring point can be inserted. To insert one
measuring point, the previous coordinates are inserted preliminarily in the insertion
position, so change those values. To insert two or more points, measuring points must be
kept in a memory using the deletion or copy operation. The copy operation is as follows.
1. Select two or more measuring points.

To select two or more points, select [Edit]  [Select All], make arbitrary selection using the
Ctrl key, or select a range using the Shift key. See the paragraph “Deletion of Measuring
Point”.
Insert One Measuring Point
1. Select the coordinate line for insertion in the measuring point list.
3. Double-click an “r(mm)” or “X(mm)” cell in the line for insertion.
4. Enter the r or X value.
5. Double-click a “theta(deg)” or “Y(mm)” cell in the line for insertion.
6. Enter the theta or Y value.
Insert Two or More Measuring Points
This operation is possible when two or more deleted or copied measuring points have
been kept in a memory.
1. Select the coordinate line for insertion in the measuring point list.

Check Measuring Area
The diaphragm determines the effective area for a measurement. You can see the
effective measurement area by a circle with the diameter of the diaphragm drawn
around the measuring point.
1. Select [Option]  [Point display].

2. Select <Meas. area(Reference)> for “Point display”.
3. Select the diaphragm diameter for measurement in the list.
4. Click OK .
Delete Mapping Table
An unnecessary mapping table can be deleted.
1. Select [File]  [Delete].

2. Select a mapping table to be deleted in the “Table name” list.
3. Click OK .

5.3 MICRO MAPPING MEASUREMENT

Using a combination of the camera and the sample stage, a qualitative or quantitative
analysis can be carried out by specifying a position or area on a sample. A sample set in a
dedicated holder is transported to the measuring position and an image is taken.
The micro mapping has the measuring modes of the point analysis, line analysis and
plane analysis. In the point analysis, to specify a position makes an analysis limited. In
the line and plane analyses, mapping data can be obtained by measuring specified
positions. The maximum number of data points for each measuring mode is shown
below.
Unit to Specify Position Point Analysis Line Analysis Plane Analysis

Maximum Number of 10 lines 10 planes
1 ID
Sample IDs (10 IDs) (10 IDs)
Maximum Number of
999 999/line 999/plane
Data Points
This program guides you using the flow bar in a series of operations from loading a
sample to unloading it. Carry out an analysis according to the procedure shown below.
Sample Loading
Take CCD image
No
Magnified picture?
Yes
Take magnified picture
Specify measuring position
Select application
Analysis
Yes
Repeat analysis?
No
Sample Unloading

Before Executing Micro Mapping Measurement
In micro mapping measurement, you must specify a qualitative or quantitative

application. Before starting micro mapping, prepare a qualitative or quantitative
application for measurement.
Determine analysis conditions etc. by starting each application.
Be sure to set the measuring diameter in the analysis parameters. Select <No> for the
sample spin.
a. Sample Loading
In the micro mapping analysis, a sample holder dedicated to mapping analysis is used.
Prepare a sample that can be set in that holder. When a sample is very small, take
measures such as embedding it in resin.
When a holder for mapping is loaded, it is moved to the photographing position and an
image of a sample is obtained automatically using the camera. The sample holder is then
moved to the measuring position and, after detecting the direction of the sample holder
using its X-ray marker, a specified position is measured.
1. Set a sample in a sample holder for the micro mapping.

2. Click Micro Mapping on the menu.
3. Click Sample Load on the flow bar.
5. Click OK .
A sample table can be displayed by clicking Select on the “Sample Load” window. Thus,
you can set a sample position visually using the sample table display.
In the “Loading sample” window, the image by the camera is displayed from loading a
sample till placing it in the photographing position of the camera.

b. Designation of Mapping Position
When a sample has been loaded and images have been taken, the whole image is
displayed. The whole image is displayed on the left, and a position or area is specified on
the right. A magnified image can be taken to observe some area in detail. In that case,
the whole image is displayed on the left and the magnified image on the right.
 Whole Image
 Magnified Image

When a position or area is specified on a magnified image, the whole image is not saved.
When the whole image is necessary, make a screen copy and save it in a bit map file or the
like.
In the case of a permeable sample, its image may be dark. Make an adjustment by
inserting aluminum foil or the like beneath the sample.
Whole Image Taken
Magnified image?
No
Yes
Display magnified image
Select position designation mode
Specify measured position or area
Position Designation Completed
Select the point designation, line designation or plane designation with a button on the
whole image display or magnified image display. Then specify a measuring position or area
using the mouse.
Display Magnified Image
1. Click on the upper right of the image on the right.

2. Move the mouse cursor to a measuring position in the whole image on the left side. A
rectangle is displayed.
3. Click the mouse. A magnified image is displayed on the right side.
A magnified image is obtained by expanding a part of the whole image. Therefore, the
definition of the image decreases a little.

Carry Out Point Designation
1. Click above the image on the right.

2. Move the mouse cursor to a measuring position in the whole image or magnified
image.
3. Click the mouse to display a point mark.
4. Click OK .
Carry Out Line Designation

2. Hold down the mouse button in a measuring position in the whole image or
magnified image.
3. Drag the mouse to display a locus of the dragging.
4. Click OK .
Carry Out Plane Designation

2. Hold down the mouse button in a measuring position in the whole image or
magnified image.
3. Drag the mouse to display a rectangle.
4. Click OK .
To change the setting, click before clicking OK and then change the setting, or click
All Clear and then make setting again.
Carry out circle designation;

2. Input diameter and step.
3. Click OK .
Applicable only to the case of full screen mapping used with full screen.

Display Grid on Image
When is clicked, it toggles to display the grid on the right side of the image.
Change Color
1. Click [Option]  [Color] on the tool bar.

2. Specify a color for the measuring area or the cross cursor.
3. Click OK .

Change Brightness of Sample Image
It may be difficult to recognize each part of a sample image depending on the light and
shade of the sample. In this case, it may become easier to recognize when the brightness
of the sample image is adjusted.
The brightness of a sample image is set with the sample image displayed on the
Mapping Position Setting screen. The procedure after the Mapping Position Setting
screen is displayed is described below:
1. Click [Setting]  [Camera...] in the tool bar.
2. Enter a number for the item Brightness. A larger number (up to 255) makes an
image brighter.
3. Click OK .
4. Click Sample Load in the flow bar again, check the position of the loaded sample and
click OK . A sample image is obtained again with the set brightness and redisplayed
on the Mapping Position Setting screen.

c. Setting of Analysis Conditions
After specifying a measuring position or area, set an application for measurement as in

the case of the ordinary analysis operation. But the EZ scan and the repeated
measurement cannot be carried out in the micro mapping analysis. A qualitative or
quantitative analysis application must be created beforehand. If the sample is not
unloaded, another flow bar can be started to create a new application or to change the
contents of an existing application. For the procedure to set an application, see <3.
QUALITATIVE ANALYSIS> or <4. QUANTITATIVE ANALYSIS> in the instruction
manual.
To carry out measurement for the same measuring position or area using another
application, click Setting Sample ID on the flow bar again without unloading the sample
after an analysis using the first application is complete.
Line Analysis Plane Analysis

In the case of the line analysis and the plane analysis, set a value to partition the
specified area. For example, when the number of partitions is 5 in the line analysis, the
number of measuring points is 6. Likewise, when the numbers of partitions for X and Y
are 3 and 4 respectively in the plane analysis, the number of data is 20 (=(3+1)(4+1)).
In the case of the point analysis, only one sample ID line is displayed. In the case of the
line analysis and the plane analysis, up to 10 sample ID lines are displayed according to
the specified number of areas. In that case, the number of partitions and an application
cannot be set individually for each sample ID line.
In the case of the point analysis, up to 999 points can be specified. In the case of the line
analysis and the plane analysis, up to 10 areas (999 points for each area) can be specified.
Set Analysis Sample ID
The procedure to set a sample ID for the qualitative analysis is described below as an
example. For the sample ID, see <2.3 a. Before Analysis> in the instruction manual. See
also procedures in <2.3 c. SQX Analysis> and <2.3 d. Quantitative Analysis> for your
information.
1. Enter a sample name in the “Sample information” frame if desired.

2. Set an operator name in the “Sample information” frame if desired.
frame.
5. Enter a file name in the “Result output” frame if desired.
6. In the case of the line analysis or the plane analysis, enter the number(s) of
partitions in the “Mapping” frame.
7. Click OK .
In the window of sample ID setting, sample unloading after completion of measurement can
be preset.

d. Analysis and Sample Unloading
Carry Out Analysis
1. Set necessary conditions on the “Sample ID Setting” screen.

2. Click OK .
3. Check the sample ID on the screen for analysis and click .
4. After the analysis is complete, click Stop .
Unload Sample
1. Click Sample Unload on the flow bar.
Measure Same Sample Again
1. Click Mapping Position Setting or Sample ID Setting on the flow bar.

5.4 MAPPING DATA PROCESSING

The program to display data measured with the micro mapping using the camera and
data measured with the mapping table will be described below. When processing micro
mapping data, an image is displayed in the upper left part. The 2-dimensional display or
the 3-dimensional display can be selected and, in the case of the 3-dimensional display,
the bird’s-eye view or the bar graph can be selected. A mapping file for mapping data
must be created using the Result Display program. A flowchart to select a display
function is shown below.
Start
Select mapping data file
2-dimensional display? Yes
No 2-dimensional display
Bird’s-eye view?
Yes
No
Bar graph (3-D) display Bird’s-eye view (3-D) display
When point or line designation is done in Micro mapping, only bar graph can be displayed.

Create Mapping File
A mapping file can be created automatically by specifying the creation of a mapping file
in the sample ID setting of the Analysis or Micro Mapping program. It can also be
created from an analyzed result using the Result Display program.
 Specify Creation of File in Sample ID Setting
1. Click <Create mapping file> in the “Sample ID Setting” window.

2. Click Setting… .
5. Click OK .

 Create Folder for Saving Mapping File
When a mapping file is created, its folder can be created.
1. Click Browse... for the result output on the Sample ID Setting screen.
2. Click a root folder in the “Select Folder” window.
3. Click Create folder… .
4. Enter a file name to create.
5. Click OK .
6. Click OK .
A mapping file is in a subfolder of the common folder (AnlRslt) or the user folder (AnlRsltU).
 Create Mapping File Using Result Display Program

2. Select [Result Display].
3. Select a series of sample IDs or one sample ID with which mapping measurement
was made.
4. Select [Edit]  [Create Mapping File…].
6. Click OK .
The following two files are created for each mapping data item:
Mapping Data File MPDT_(Specified File Name).ho
Image File MPDT_(Specified File Name).bmp
When an image file does not exist, only a mapping data file is created.

Open Mapping Data File

2. Select [Mapping].
3. Select [File]  [Open…].
4. Select a file name.
5. Click OK .
a. Display Method
The 2-dimensional display and the 3-dimensional display are available in the mapping
data display. In the case of the 3-dimesnional display, the bird’s-eye view and the bar
graph are available. In the case of the 2-dimensional display, analyzed results or X-ray
intensities are displayed. In the case of the bird’s-eye view, the Z-axis is added to display
ups and downs. Even areas that were not actually measured are displayed in a graph
through data processing. On the other hand, in the case of the bar graph display, it
displays the analyzed results or X-ray intensities only for area that was measured.
Carry Out 2-Dimensional Display
1. Select [Mapping Display]  [2-Dimentional Mapping…].

Carry Out 3-Dimensional Display
In the 3-dimensional display, the bird’s-eye view and the bar graph are available.
1. Select [Mapping Display]  [3-Dimentional Mapping…].

2. Select the <3-Dimentional Mapping> tab or the <Bar graph> tab.
 3-Dimentional Mapping
 Bar Graph

Switch Displayed Data
Displayed data can be switched to analyzed results such as concentrations and film
thickness or to X-ray intensities.
1. Click the unselected item from <Analyzed result> and <Intensity> in the “Displaying
data” frame.

Switch Scale
The scale for displayed data can be switched to the linear display or to the logarithmic
display.
1. Click the unselected item of <Linear> and <Log> in the “Scale” frame.
Switch Component
When two or more components were measured, the displayed component can be
changed.
1. Select a component name at <Data name> in the “Basic setting” frame.
Display Two or More Data in 2-Dimensional Display
When mapping data has more than one measured component, up to nine components
can be displayed simultaneously. But this function can be used only in the case of the
2-dimensional display.
1. Click Data in the “Basic setting” frame.

2. Set the number of displayed data items.
3. When to display different components, select a component for each display number.
4. Click OK .

Change Scale in 2-Dimensional Display
When more than one data are displayed, displaying methods can be switched between
using common scale for all data and using different scale for each data.
1. Select [Mapping Display] [2-Dimensional Common Scale] in the menu.
When a check mark is displayed at the left in the menu of [2-Dimensional Common
Scale], common scale is used. Common scale is useful to compare the amount among
elements. Different scaling among elements is useful to see the distribution of each
element.
Scale change can be done by changing the values in <Minimum> and <Maximum>.
When different scaling among elements is selected, the values are effective to the
element selected in <Data name> of <Basic setting>.

Display Measured Area on Sample Image
When a sample was measured in Micro Mapping program and sample image is
displayed in mapping window, measured area can be displayed on the sample image.
Displaying measured area for each measuring position designation method is shown
below.
Point designation : Display marks at measured positions

Line designation : Display a line specified
Plane designation : Display a rectangular specified
To display or erase the measured area , operate as follows.
1. Select [Mapping Display] [Measured Area] in the menu.
When a check mark is displayed at the left in the menu of [Measured Area], the
measured area is displayed.
Display Measuring Number on Sample Image
When measuring positions are specified by point designation, the number of order in
measurements can be displayed on the sample image.
To display or erase the measuring numbers , operate as follows.
1. Select [Mapping Display] [Measuring Number] in the menu.
When a check mark is displayed at the left in the menu of [Measuring Number], the
measuring numbers are displayed.

b. Highlighting of Displayed Data
Explanation will be given using data with a Maximum 100%

slope shown right as an example. In mapping
data display, ratios of analyzed results or X-ray
intensities are displayed relatively using shades Minimum 0%
of color or the like with the maximum value
along the vertical axis defined as 100%. The
number of steps means the value to divide the
range between the maximum and the minimum
at a constant interval. For example, when the
number of steps is 4, the range is divided equally
into 4 parts and displayed with shades of color.
When the minimum is 0% and the maximum is
100%, data is displayed as shown right.
When the number of steps and the minimum are

fixed and the maximum is set to 50% and to 200%, data is displayed as shown below.
100%
Maximum 200%
Maximum 50%
100%
Steps :4
Minimum : 0%
Maximum : 50%
Steps :4
Minimum : 0%
Maximum : 100%

Change Display Colors
Shades of a single color or strata of two or more colors can be used as display colors.
Even when more than one data item is displayed simultaneously, the same colors are
used for all graphs. In the case of the 3-dimensional display, the single color display
alone can be used.
1. Select a color from the seven colors at <Color:> in the “Basic setting” frame.
Display Data Using Shades of Color in 2-Dimensional Display
1. Select the <Contour Line Setting> tab.

2. Make setting for <Steps>.
3. Click the <Color Setting> tab.
4. Select <Shades> in the “Color” frame.
5. Select a color.
Display Data Using Strata of Colors in 2-Dimensional Display
For example, when the scale of displayed data is divided into 10 parts, an arbitrary
display color can be set for each step by adjusting sliders for red, blue and green. This
setting is always used when the 2-dimensional display is selected, not for each mapping
data item.

1. Select the <Contour Line Setting> tab.

2. Make setting for <Steps>.
3. Click the <Color Setting> tab.
4. Select <Color Strata> in the “Color” frame.
5. Select a color number.
6. Specify a color for each color number by adjusting the sliders for red, blue and green.
Default is clicked, default color set is applied.
The color scale under the 2-dimensional mapping image is displayed when only one data
is selected as shown above.

Display Sectional View in 2-Dimensional Display
A sectional view can be displayed by dragging in a 2-dimensional image or sample

image.
1. Select the 2-dimensional display.

2. Place the mouse cursor in the white frame of the displayed image.
3. Drag the mouse across an area to be seen to another place in the white frame.
When more than one image are displayed, sectional views of all the images can be
displayed by dragging across the sample image.

c. Creating Image File
An image file of 3-dimentional mapping, bar graph, 2-dimentional mapping or sample

image can be created. The image files created here can be used in making report using
commercial software such as work processor software.
To create an image file, select a menu of [Transfer Image File] or specify a image by
using the mouse.
Create an image file from menu
Specify an image when the image is displayed on the screen by the next operation.
1. Select [File] [Transfer Image File] in the menu.

2. Select a <File to transfer>.
3. Select from <Clipboard> and <Folder> for <Transfer to>.
4. When <Folder> is selected, set <File output folder>.
5. When <Folder> is selected, enter a file name.
6. Click OK .
When <Folder> is selected, it is possible to specify a folder in another computer connected

through network by clicking Browse… in <File output folder>..
In the field of <file name>, a default file name is displayed by the name combining mapping
file name, type of image and component name (line name) to be able to distinguished.

Select an image file using the mouse
It is possible to specify an image using the mouse to create an image file.
1. Move the mouse pointer on a position of an image to create an image file.
2. Click the right button of the mouse.
3. Click the [Transfer Image File] of the pop-up menu.
4. Set the dialog of [Transfer Image File] and click OK .
In the dialog of [Transfer Image File], the image specified by the mouse is selected when
the dialog appeared. The operation in the dialog is the same as that in [Create an image file
from menu] described above.

Check Correspondence Between Sample Image and Measurement Data
It is possible to check correspondence between measuring points displayed on a sample

image and data display area in the lower part of the screen. When a bar graph has been
displayed using the mapping display function, it is possible to check measuring points on
the bar graph.
1. Select [Mapping Display]  [Measuring Points] to display measuring points on the
sample image.
2. Click one measuring point on the sample image or in the measurement data area in
the lower part of the screen.
The selected measuring point is displayed in yellow on the sample image or in the
selection color in the measurement data area. When the mapping data has been
displayed using a bar graph, the frame of that measuring point is highlighted.
Up to 12 measuring points can be selected by holding down the Ctrl key while selecting.
The same operation is possible also from the measurement data of the analyzed result
grid.

d. Mapping Data Export
It is possible to export various items of mapping data, such as images, graphs, analysis
values and X-ray intensities, to individual sheets in an Excel file. It is also possible to
export analysis values and X-ray intensities to a CSV file.
1. [File]  [Data Export…].

2. Set a folder in which to store a file.
3. Set a file name.
4. Select <Excel Book> or <CSV> as the file type.
5. If necessary, place a check mark for <open an output file>.
The Excel program opens the file after the export.
6. Click OK .
No sheet is created when there is no data item to be exported. For example, for the result of
a measurement using a mapping table from the Analysis screen, no image sheet is created
because there is no image.
Measuring coordinates are always output in the X-Y coordinates as in the case of
displaying an image. When an expanded image was used in the micro mapping, the center
of the image area becomes the origin.

e. Delete Mapping File

It is possible to delete mapping files.
1. Select [File]  [Delete…] on the menu.

3. Select mapping files to be deleted.
4. Click OK .
When a mapping file is deleted, both a selected mapping data file and its image file are
deleted.

f. Print
The images displayed can be printed with a fixed format.

The title and note can be input for the printout.
Change title and memo
1. Select [File] [Print Title] in the menu.

2. Enter <Title> and <Note>.
3. Click OK .
Maximum number of characters for the title and memo is 32.
Print
1. Select [File] [Print] in the menu.

2. Select <Landscape> in the dialog of [Printer setting].
3. Click OK .

CHAPTER 6 UTILITY AND MAINTENANCE
6. UTILITY AND MAINTENANCE

6.1 UTILITY
Programs controlling data necessary for analysis and measurement using this system
are collected in the Utility menu. This menu consists of Atomic Symbols, Compound
Table, Sample ID Tables, Mapping Tables (optional), Unit Setting, Universal Standard
Samples, Sensitivity Library (optional), Material Standard Tables (optional), Program
Operation (optional and partly standard) and System Management. Descriptions are
given in “3. QUALITATIVE ANALYSIS” for Sensitivity Library. All other items on the
Utility menu are described in this chapter.
The operational procedure for the sensitivity library is explained in “3.4 SENSITIVITY
LIBRARY”. In this chapter, “e. Material Standard Tables” follows “d. Universal Standard
Samples”.

a. Atomic Symbols
This program provides various kinds of element information for the X-ray fluorescence
analysis. You can see general information such as atomic numbers, element names,
atomic weights and densities, and individual analysis information such as main
measured element lines, their wavelengths, absorption edge energy values, crystals
used and 2-theta angles.
1. Click Utility .

2. Select [Atomic Symbols].

Display Element Information
You can see the elemental information and optical data for the lines normally used as
measured element lines for the wavelength dispersive X-ray fluorescence spectrometer.
For the elements from calcium (Ca) through uranium (U), one of the two lines such as
the K line and the L line can be selected as the measured element line and information of
each of them is displayed.
1. Place the mouse pointer on an objective element.

2. Keep the pointer stationary for one or two seconds.
Item in Element
Description
Information
KA and LA represent K and L respectively.
Line name
For example, KA of aluminum represents Al-K.
Wavelength Displays the wavelength of the measured element line.
Edge energy When a tube voltage higher than this value is applied to
(Absorption edge energy) the target, fluorescent X-rays can be generated.
Single crystal to analyze that measured element line.
Crystal
The RX series represents the artificial multi-layers.
Displays the detector angle for each crystal.
2-theta This corresponds to the abscissa of a qualitative
analysis chart.

b. Compound Table
Compounds and external parameters are registered here.

This program registers a component other than the elemental symbols or standard
oxides registered as defaults for calculations in SQX analysis and quantitative analysis.
A new compound must be registered before either an SQX calculation or creating a
quantitative application. By registering a density in addition to a compound name and
composition, that compound can be used for thin film analysis in the FP quantification
method. To register a compound as a component to be measured, the measured
components must be set.
To use two or more compounds as components of a new named compound, mixed
compound setting can be used. To distinguish a mixed compound from ordinary
compounds, a mark is attached to it.
To distinguish kinds of compounds, a compound type can be set. For example, by
registering the type of a certain compound as flux, it can be easily retrieved by selecting
flux from elements or compounds.
By entering an external parameter at the time of an analysis, a correction can be made
using the external parameter. For example, weight of some kind can be entered as an
external parameter to calculate a dilution ratio for the bead correction.
Presettable Items
Item Name Contents

Set of oxides to be used for the quantitative analysis and SQX
calculation. Setting cannot be changed for compounds that
have been registered beforehand.
Standard oxide
Compound numbers correspond to atomic numbers. When the
oxide is selected for the component type in the SQX analysis, a
compound that is set here is used.
This item is used when the compound list is selected for the
component type only in the SQX analysis. Setting can be
made corresponding to an element such that an element and
an oxide coexist when components to be analyzed consist of an
Compound list element and an oxide like a sulfide mineral. Presettable
compounds are selected from ones registered as standard
oxides and special compounds. Like standard oxides, setting
is made such that compound numbers correspond to atomic
numbers.
Compounds other than standard oxides are registered.
Compounds for special purposes, such as flux and binder, are
Special compound
also registered here.
It is possible to register up to 200 compounds.
External parameters are registered. This is used when a
External name must be registered by reason of the software for an item
parameter that is not an actual compound, such as sample weight. It is
possible to register up to 100 compounds.

Check Setting Contents for Standard Oxides and Special Compounds

2. Select [Compound Table].
3. Click [Standard oxide] or [Special compound] on the list in the left part of the
“Compound Table” screen.
Up to 10 elements can be set.

Terms in Compound Table
Term Description
Any name can be set as a compound name. Uppercase
Compound
characters and lowercase characters are distinguished. In the
Name
case of a mixed compound, a MIX mark is attached.
This item must be set to register a compound for measurement
Analyte
for the quantitative calculation or the like.
This item must be set in the case of a component for which to
analyze a thickness using the quantitative film FP method.
Density
When a calculation is to be made as weight, this item need not
be set.
The type is used for the sample preparation information and
the setting for the SQX calculation. Compounds for which
“Flux” is set are listed when setting flux.
Types that can be selected are as follows:
Normal
Flux
Type Binder
Oxidizer: Presettable only for special compound
Non-wetting
Diluent
LOI (Flux)
Compounds other than “Normal” and “Binder” are used in the
fusion bead method.
Standard oxides, flux, etc. that have been registered beforehand cannot be changed
because they are already used for library samples etc.
A registered compound cannot be deleted. But its contents can be corrected.
Set “LOI (Flux)” as a loss on ignition component when the loss on ignition (LOI) correction
is to be made in the evaporation correction for flux in an analysis using the fusion bead
method. Set the same constituting elements as those in flux to be used.

Set Special Compound
For example, the procedure to set SiO2 under a compound name “TEST” at compound
number 33 is described below. Si is set for the analyte and 2.650 for the density, but the
compound is not registered here.
1. Click [Special compound] from the list in the left part of the screen.
2. Double-click the compound name cell at number 33.
3. Enter “TEST”.
4. Set “Si” in the “Analyte” cell.
5. Set a density in the “Density” cell.
6. Select <Normal> in the “Type” cell.
7. Set “Si” in the “Symbol” cell of “Element1”.
8. Enter the number of atoms “1” in the “Number” cell of “Element1”.
9. Set “O” in the “Symbol” cell of “Element2”.
10.Enter the number of atoms “2” in the “Number” cell of “Element2”.
To register the compound, select [File]  [Save] after the procedure described above.
Check Preset Contents
A registered compound can be checked. In addition to the preset number of atoms of each
element, density, etc., the calculated concentration ratio and molecular weight are
displayed.
1. Click an arbitrary cell in the line of a registered compound.

2. Right-click the mouse to display the menu.
3. Select <Information Display>.
You can click any cell in a compound line. Because double-clicking in a cell is used to
change the preset contents, use single-clicking to select a compound line.

Insert Element
The procedure to add an element to a preset compound is described below. In fact,

because a calculation is made regardless of element order, insertion is unnecessary.
1. Click a cell to insert an element.

2. Select [Edit]  [Element Insert].
3. Set an element in the “Symbol” cell of the inserted element.
4. Set the number of atoms in the “Number” cell of the inserted element.
Delete Element
The procedure to delete an element from a preset compound is described below:
1. Click a cell to delete an element.

2. Select [Edit]  [Element Delete].
Set Mixed Compound
A mixed compound can be created by combining already registered compounds. For

example, the procedure to register a powder consisting of Al2O3 powder and SiO2
powder mixed in the ratio 1 : 1 as a mixed compound is described below. Al2O3 and SiO2
have been registered as standard compounds at numbers 13 and 14 in the compound
table of the standard oxide list. The mixed powder will be registered at number 34 as a
mixed compound to be used for the SQX calculation. The mixed compound will be
tentatively named “TEST2”.
1. Click [Special compound] on the list in the left part of the screen.
2. Click an arbitrary cell in the compound number 34 line.
3. Select [Edit]  [Mixed Compound...].
4. Enter “TEST2” for “Compound name”.
5. Enter “34” for “Special Comp. No. ”.
6. Set “Si” for “Analyte”.
7. Select <Normal> for “Type”.
8. Enter “SiO2” for “Compound 1”.
9. Enter “1” for “Weight ratio1”.
10.Enter “Al2O3” for “Compound 2”.
11.Enter “2” for “Weight ratio 2”.
12.Click OK .

A mixed compound is used when mixed flux of Li2B4O7 and LiBO2 is used or in a similar
case.
Each mixed compound will have a “MIX” mark attached to the side of its compound name.
Set Residual Compound of Oxidizer
1. Select and right-click a compound registered as oxidizer for a special compound.
Execute “Residual Compound” on the menu that appears.
2. Set a residual compound and a residual ratio. A calculated value can also be used for
the residual ratio.
For the residual compound, set a compound that is left in a fusion bead when oxidizer is
specified for the sample type of a fusion bead in a quantitative application. For the residual
ratio, set the ratio of the weight of a residual compound in a fusion bead to original oxidizer
weight. Use a residual compound for the quantification calculation component, and use the
ratio of residual compound weight to a sample weight for the addition ratio.
If no residual compound is left after a fusion bead is created, select [None] for “Residual
compound”.

Register Compound List
1. Select and right-click [Compound list] on the list in the left part of the “Compound
Table” screen. Execute “New Table” on the menu that appears.
2. Set a component type, list name and memo. The specified component type becomes
the default setting.
Delete Compound List
1. Select and right-click a compound list to be deleted on the list in the left part of the
“Compound Table” screen. Execute “Delete” on the menu that appears.
Copy Compound List
1. Select and right-click a compound list to be copied on the list in the left part of the
“Compound Table” screen. Execute “Copy” on the menu that appears.
2. Select and right-click the place of a compound list on the list in the left part of the
“Compound Table” screen. Execute “Paste” on the menu that appears.
3. Set a list name and a memo.

Register External Parameter
1. Select [External parameter] on the list in the left part of the “Compound Table”
screen. Set a parameter name and a type on the table.
Term Description
The type is used for a component name corresponding to the

weight in the sample preparation information.
Normal parameter
Sample weight
Flux weight
Bead weight
Oxidizer weight
Type Loss on ignition
The items from the sample weight to the oxidizer weight are
used for a correction by setting each weight value at the time of
an analysis and calculating a dilution ratio.
The loss on ignition is used to convert analyzed values to ones
before ignition using the concentration of an ignition loss
entered at the time of an analysis when analyzing a powder
sample after ignition.

Printing
To print the contents of the compound table, compound name list printing, compound
structure printing including calculated concentration ratios etc. and parameter name
list printing for external parameters can be used. The compound structure printing has
two modes: the printing of the whole table and the printing of selected compounds.
Print List of All Compound Names in Table
All compound names in a selected table are printed out.
1. Select [Standard oxide], [Special compound] or [External parameter] from the list in
the left part of the screen.
3. Select <Compound name list>.
4. Click OK .

Print Structure Information of Selected Compounds
1. Select [Standard oxide] or [Special compound] from the list in the left part of the
screen.
3. Select <Compound structure>.
4. Click OK .
5. Select <Compound Selection>.
6. Select compound names.
7. Click OK .
Print Parameter Name List of Whole Table
1. Select [External parameter] from the list in the left part of the screen.
3. Select <Parameter name list>.
4. Click OK .
Print Detailed Information
Detailed contents such as components constituting a compound, their ratio and

molecular weight can be printed for individual compounds.
1. Select [Standard oxide] or [Special compound] from the list in the left part of the
screen.
2. Click the compound name cell of a compound to print detailed information.
4. Select <Information Print>.

c. Sample ID Table
To measure samples with the Analysis program, you must set ID lines. When you want
to measure two or more samples, you must set an ID line for each sample. For routine
analysis that will analyze a series of samples many times a week, ID lines can be
registered in a table and they can be loaded when necessary for an analysis. This process
creates sample ID tables.
By loading a sample ID table for an analysis, ID setting becomes easy. For example, it is
recommended that routine analyses such as PHA adjustment and check analysis be
preset in tables.
Sample ID tables must be registered for cycle repeat analysis and for program operation.
The measurement sequence carrying out auto drift correction is also set up as sample ID
table for auto drift correction. (Dedicated for ZSX Primus IV/IVi)

2. Select [Sample ID Table].

Create Sample ID Table
The operational procedure is basically the same as that for the preset table in the
Analysis program. EZ Scan and cycle repeat analysis cannot be selected when creating
or adding an ID line. For example, the procedure to create a sample ID table for a PHA
adjustment for the SC and PC is described below:
1. Select [File]  [New...].

2. Enter “PHA” for the table name.
5. Select <PHA adjustment> in the “Analytical condition” frame.

6. Only in the case of the ZSX Primus II or ZSX Primus III+, select a sample position.
7. Select <SC> for “Code name”.
8. Click OK .
10.Select <PC> for “Code name” in the “Analytical condition” frame.
11.Click OK .
12.Select [File]  [Save].
Now the sample ID table for a PHA adjustment for the SC and PC has been created.
Subsequent PHA adjustment can be performed easily by loading that sample ID table.
There is not setting for sample position since PHA adjustment sample is built in the
equipment. In regular analysis such as quantitative analysis, there is setting for sample
position.

Restrictions on Sample ID Table
Unlike the preset table in the Analysis program, some restrictions are imposed on a
sample ID table. One concerns EZ Scan and another the secure operation in the control
IDs. EZ Scan need not be registered in a sample ID table and therefore is excluded. Since
a sample ID table may be loaded by the program operation, the secure and power on/off
functions cannot be set in control IDs.
Create sample ID table for auto drift correction;
Dedicated sample ID table for auto drift correction is made. The order of the sample ID
setting is check samples and Drift Correction samples.
1. Select [File] and[New] in turn.

2. Input table name and click OK ..
3. Check <Auto drift correction>.
4. Select [Edit], [Add new ID][4:Auto drift correction…] in turn.
5. As the auto drift correction screen is indicated, select the created limit ranges
file set to the quantitative application, and select sample positions of check
samples and drift correction samples, then click OK .

6. In case of single position of drift correction sample in the sample ID table setting
screen, select <Last sample> in the update selection. In case of two, select < First
sample> and <Last sample>, and in case of three or more, set up <First sample>
and <Intermediate>, and <Last sample> for the last sample.
7. Select [File] and [Save] in turn.
It is necessary to set up preliminary check sample name for check sample setting of aimed
quantitative application, tolerance of low limit and high limit of measuring component, and
drift correction samples which is set the reference intensities.

d. Universal Standard Samples
Quantitative analysis using fluorescent X-rays is the standard sample comparison

method, in which analyses are made using the relationship between concentrations of
standard samples and corresponding X-ray intensities. Standard samples must be set
for quantitative analyses. The database to help enter this data is called the Universal
Standard Samples.
When you have a sample in this database, you can copy the standard values etc. from
this database when setting standard samples for an application. Furthermore, by
registering your standard sample in this database, you can handle it as a universal
standard sample. By managing all information concerning standard samples using this
database, information such as the same standard values can be set easily when two or
more applications use the same standard samples.
Since standard values have information about their effective digits, accurate values can
be set. For example, in the weighting of significance of standards, 10 and 10.0 are
handled differently. When an accurate analyzed value is not available, the standard
value of that component can be treated as an uncertified value.

2. Select [Universal Standard Samples].

Concept of Universal Standard Samples
The structure of the Universal Standard Samples is shown below. It has supplier folders
such as NIST (National Institute of Standards and Technology) and JSS (Japanese Steel
Standard), and each of them has sample type folders. The information on each standard
sample is registered in the appropriate sample type folder. A user’s standard sample is
registered in the “House standards” folder.
NIST
Type 1 Type 2 Type 3 Type 4 More…

….
JSS
Type 1 Type 2 Type 3 Type 4

More…
….
House standards
Type 1 Type 2 Type 3 Type 4

More…
….
More…
 Existing Data
Standard sample information such as NIST and JSS has been preregistered You can see
this information. You can also change its contents, but take care because the original
data cannot be restored if it is changed.

Display Registered Data
1. Select [File]  [Open...].

2. Select a supplier at “Supplier”.
3. Select a sample type at “Sample type”.
4. Click OK .
To display detailed sample type information, click Components .

Display Supplier Information
1. Select [View]  [Supplier Information...].
Display Sample Type Information
1. Select [View]  [Sample Type Information].

Additional Registration of Standard Samples
Your own samples can be treated as universal standard samples. By registering your
own standard sample, the same sample can be used easily for two or more applications.
Although “House standards” has been prepared as a supplier, you can create a new
supplier. Folders for various sample types will be created within those folders.
Addition of Standard Sample
To add a new standard sample, follow the flowchart shown below. As described in
“Concept of Universal Standard Samples”, a sample type folder is created in a supplier
folder. Since all the standard sample data is registered in that sample type folder, a new
folder must be created if there is not an appropriate folder.
Start
Add to existing supplier

folder? No
Yes
Create new supplier folder
Add to existing sample type

folder? No
Yes
Create new sample type folder
Set standard sample
End

Create New Supplier Folder
When creating a new supplier folder, a new sample type folder is also created.
1. Select [File]  [New]  [Create Supplier...].
2. Enter a new folder name for “Supplier”.
3. If desired, enter a vendor name for “Vendor”.
4. Enter contact information for “Contact”.
5. Click OK .
6. Enter an arbitrary sample type name for “Sample type”.
7. If desired, enter a memorandum for “Information”.
8. Set all components constituting the standard sample in the “Components” frame.
9. Set the units of the preset components in the “Unit” cells in the “Components” frame.
10.Click OK .
Create Sample Type Folder in Existing Supplier Folder
To create a new sample type folder in an existing supplier folder, follow the procedure
described below:
1. Open an existing supplier folder.
2. Select [File]  [New]  [Create Sample Type...].
3. Enter an arbitrary sample type name for “Sample type”.
5. Set all components constituting the standard sample in the “Components” frame.
6. Set the units of the preset components in the “Unit” cells in the “Components” frame.
7. Click OK .

Set Standard Sample
A standard sample is set in an existing or new folder. All standard values set in the
following procedure will be treated as certified values. To set them as uncertified values,
see “Change Standard Values to Uncertified Values”.
1. Double-click the “Name” cell.

2. Enter a standard sample name.
3. If desired, enter a memorandum for “Note”.
4. Enter a standard value in the cell of each element.
5. Repeat steps 1 to 4 if necessary.
When a standard value is not available, leave that cell blank.
Change Standard Value
A standard value of an existing standard sample is changed.
1. Open data to be changed.

2. Double-click the element cell of a standard sample to be changed.
3. Change the standard value.
To “open data” hereafter means select [File]  [Open] and select a supplier and a sample
type to load standard sample data to be changed.
Change Standard Values to Uncertified Values
A standard value that was set as a certified value can be changed to an uncertified value.

2. Click the element cell of a standard sample to be changed.
4. Select [Uncertified].

Set Standard Value as Balance Component

2. Click the element cell of a standard sample to be changed.
4. Select [Balance].
Only one balance component can be set for one sample. To cancel the balance setting and
set a standard value, first delete the balance component.
Delete Standard Value of Component
The standard value of a component in existing data is deleted.

2. Click the element cell of a standard sample to be deleted.
4. Select [Delete].
Delete Standard Sample
A registered standard sample itself is deleted.

2. Click the cell of the name of a standard sample to be deleted.

Insert Standard Sample
A new standard sample is inserted in a series of registered standard samples.

2. Click the cell of the standard sample name in the insertion position.
4. Enter a standard sample name, memorandum and standard values of components.
Copy Standard Sample
Registered standard sample data is copied.
1. Open data to be copied.

2. Click the cell of the name of the standard sample to be copied.
4. Click the cell of the name in the destination position.
If there is a duplicate standard sample name, the sample type cannot be saved. Be sure to
change its name. However, the same name can be used for a different application.
Change Supplier Folder Information
Registered information about a supplier is changed.
1. Select [View]  [Supplier Information...].

2. Change the set contents at “Vendor”.
3. Change the set contents at “Contact”.
4. Click OK .

Add Component to Sample Type Folder
The Universal Standard Samples employs a spreadsheet database. Even components

contained only in some samples must be set in the sample type. To add a standard
sample that contains a component that is not contained in the existing samples, that
new component must be added to that sample type folder.
1. Select [View]  [Sample Type Information...].

2. Set a component to be added newly in the “Components” frame.
3. Select a unit for that component.
4. Click OK .
Delete Folder
When a sample type folder is deleted, all standard samples in that folder are also deleted.
When a supplier folder is deleted, all sample type folders and standard samples in that
folder are also deleted. Take care because deleted folders cannot be restored.

Delete Sample Type Folder
1. Select [File]  [Delete...].

2. Select a supplier that has a sample type folder to be deleted.
3. Select a sample type folder to be deleted.
4. Click OK .
To delete all sample type folders, select the check box <All>.
Delete Supplier Folder
A selected supplier folder is deleted. But the <House standards> folder cannot be
deleted.

2. Select a supplier folder to be deleted.
3. Select <Delete>.
4. Click OK .
Print Standard Sample Information
1. Select [File]  [Print…].

2. Select a supplier.
4. Select a standard sample name.
5. Click OK .
To print all standard samples belonging to a selected sample type, click All.

e. Material Standard Tables (Option)
When analyzed values are calculated using the SQX analysis, material standards such
as ones for stainless steel and an aluminum alloy can be displayed (option). The
database of material standards used for that judgment is registered using the Material
Standard Tables program. Though a material standard is generally set with upper limits
and lower limits, setting with no upper limit or no lower limit is also possible. The sum of
the analyzed values of two elements can also be set as an upper or lower limit.
Although general material standards have already been set, a user’s standards can also
be set.

2. Select [Material Judgement Standards].

Existing Data
Material standards such as ASTM and JIS have been preregistered. You can see that
information. You can also change its contents, but take care because the original data
cannot be restored if it is changed.
Display Registered Data
1. Select [File]  [Open...].

2. Select a material standard at “Standard”.
3. Select a category at “Category”.
4. Click OK .

Display Standard Information
1. Select [View]  [Standard Information...].
Display Category Information
1. Select [View]  [Category Information...].

Additional Registration of Material Standards
By registering your own material standard, material judgments can be made after an
SQX calculation. A new standard folder is created and folders for various categories will
be created in that folder.
Addition of Material Standards
To add a new material standard, follow the flowchart shown below. A category folder is
created in a standard folder. Since each material standard data is registered in that
category folder, a new folder must be created if there is not an appropriate folder.
Start
Add to existing standard

folder? No
Yes
Create new standard folder
Add to existing category folder?

No
Yes
Create new category folder
Set material standard
End

Create New Standard Folder
A new standard folder is created and a new category folder is also created.
1. Select [File]  [New]  [Standard...].

2. Enter a new folder name for “Standard”.
4. Click OK .
5. Enter a category name at “Category”.
7. Set all components constituting the material standard to be registered in
the “Components” frame.
8. Set the units of the preset components in the “Components” frame.
9. Click OK .
Create Category Folder in Existing Standard Folder
A new category folder is added to an existing standard folder.
1. Open an existing standard folder.

2. Select [File]  [New]  [Category...].
3. Enter an arbitrary category name for “Category”.
5. Set all components constituting the material standard to be registered in
the “Components” frame.
6. Set the units of the preset components in the “Components” frame.
7. Click OK .

Set Material Standard
A material standard is set in an existing or new folder.
1. Double-click the cell of a material standard.

2. Enter a material standard name.
3. If desired, enter a memorandum for “Note”.
4. Enter a lower limit value in a cell of each element.
5. Enter an upper limit value in a cell of each element.
6. Repeat steps 1 to 5 if desired.
When there is not a lower limit, leave the lower limit cell blank.
When there is not an upper limit, leave the upper limit cell blank.
Both upper and lower limit cells can be left blank. When a value is entered in one of them,
“No limit” is automatically set to the other cell.

Change Upper or Lower Limit
A registered upper or lower limit value is changed.

2. Double-click the upper or lower limit cell of a material standard to be changed.
3. Change the value.
Set Upper and Lower Limits as Balance Component
Registered upper and lower limit values can be set as the balance component. The
balance setting is made for one component.

2. Click the upper or lower limit cell of a material standard to be changed.
4. Select [Balance].
Only one balance component can be set for one sample.

Delete Upper and Lower Limits
Registered upper and lower limits can be deleted. The deletion operation is done for each
component.

2. Click the upper or lower limit cell of a material standard to be deleted.
4. Select [Delete].
Insert Material Standard
A new material standard is inserted in a series of registered material standards.

2. Click the cell of the material standard in the insertion position.
4. Enter a material standard name, memorandum and upper and lower limits
of components.
Copy Material Standard
Registered material standard data is copied.
1. Open data to be copied.

2. Click the cell of the material standard to be copied.
4. Click the cell of the material standard in the destination position.
If there is a duplicate material standard name, the standard cannot be saved. Be sure to
change its name.

Delete Material Standard
A registered material standard itself is deleted.

2. Click the cell of a material standard to be deleted.
Change Standard Folder Information
Information about a standard is changed.
1. Select [View]  [Standard Information...].

2. Change the set contents at “Information”.
3. Click OK .
Add Component to Category Folder
The material standard table employs a spreadsheet database. Even components

contained only in some material standards must be set in the category. When adding a
material standard that contains a component that is not contained in the existing
material standards, that new component must be added to that category folder. Be sure
to save the file before this operation.

2. Set a component to be added newly in the “Components” frame.
3. Select a unit for that component.
4. Click OK .
5. When a confirming message appeared, click Yes .

Set Total of Two Elements as Standard
For example, in the case of the nickel alloy, the total of the analyzed values of Ni and Co
may be set as its lower limit. In that case, enter the total value in the cells of both
elements and set the standard using the “Summation” function.
1. Enter total values in the upper and lower limit cells of both components to
use total values as their standard.
3. Click Summation .
4. Select <Apply summation>.
5. Select components to be added.
6. Click OK .
There is no mark to indicate the summation setting on the material standard table after the
summation setting. When judging analyzed results, the total value of the components set
for the summation is used.

Deletion of Folder
When a category folder is deleted, all material standards in that folder are also deleted.
When a standard folder is deleted, all category folders and material standards in that
folder are also deleted. Take care because deleted folders cannot be restored.
Delete Category Folder

2. Select a standard that has a folder to be deleted.
3. Select a category folder to be deleted.
4. Click OK .
To delete all category folders, select <All>.
Delete Standard Folder

2. Select a standard folder to be deleted.
4. Click OK .

Print Standard Sample Information

2. Select a standard name.
3. Select a category.
4. Select a material standard name.
5. Click OK .
To print all material standards belonging to a selected category, click All.

f. Unit Setting
A unit to be used for the quantitative analysis can be added. A unit added here can be
used for both an empirical method application and a limit range condition but can be
used only for a limit range condition in the case of an FP method application. When a
quantitative application and a unit are changed in a limit range condition, an analyzed
value is output after a conversion using a factor that is set in the unit.
Add Unit
1. Click Utility on the menu,

2. Select [Unit Setting].
3. Click Add... .
4. Enter and select a unit name, type and factor. For the factor, set a conversion
coefficient to an existing unit of the same type. For example, as for units of
concentrations, the factor of mass% is 1.0.
Units that have been registered beforehand are displayed in gray in their display fields and
cannot be changed.
Units that can be used for calculations in the FP method and theoretical matrix correction
coefficient calculation are mass%, ppm, at% and mol% for concentrations, Angstrom, nm
and um for thicknesses and g/m2, mg/m2, mg/cm2 and ug/cm2 for weight thicknesses.
When another unit including an added unit is used, use any of the above units in a
quantitative application also in the empirical method, and set another unit in a limit range
condition.

g. Program Operation (Option)
This program performs the fixed time or periodic analysis and controls the automatic
startup and shutdown of the system. The following functions are available in Program
Operation:
Function Item Description

Setting is made for the fixed time analysis to make an
Time Preset Analysis analysis at a specified time and for the periodic analysis to
make analyses at specified intervals.
Tube Aging
The target values for the aging of the X-ray tube are set.
(standard)
Auto Power Off Setting is made to shut down the system automatically.
Setting is made for the standby condition when the system
Energy Saver
has not been used for some period.

2. Select [Program Operation].
Three functions except Tube Aging in Program Operation are optional. Only the Tube
Aging (standard) is displayed when the option is not attached.
The setting items for Auto Power Off are displayed as selection items in <Power off
method> on the “Control ID Setting” screen of the Analysis program and in <Method> for
the automatic power off on the “Spectrometer Shutdown” screen.

Fixed time analysis and periodic analysis may include <Auto start Spectrometer Startup>
and <Auto start analysist>. (This is the function for ZSX Primus IV/IVi only, and applicable
for the equipment shipped newly.)
Auto start Spectrometer Startup:

Keep the spectrometer main power switch and ZSX Guidance on.
In case of X-ray off, initialization ,change atmosphere to vacuum , turn
X-ray on, aging and PHA adjustment are executed automatically in turn.
Analysis auto start:

Even if any measurement screen is active on the screen, it is terminated
then analysis starts automatically.

Time Preset Analysis
In Time Preset Analysis, setting is made to automatically start analyses using a sample
ID table at a specified time or at specified intervals. That setting is valid when the EZ
Analysis or Analysis program on the main menu is activated. An analysis or
measurement need not be running at the time. However, when the fixed time or the end
of the specified period is approaching, the time preset analyses are performed
preferentially before other analyses that have been set. A fixed time or a period is set
and a sample ID table is selected here.

Set Fixed Time Analysis
1. Select the “Time Preset Analysis” tab.

2. Click Add .
3. Select <Fixed time analysis> for “Type”.
4. Select a sample ID table for the fixed time analysis at “Sample ID table”.
5. Set an analysis start time for “Time(hh:mm)”.
6. Click OK .
A date cannot be specified.
Setting of every day/every week/every month can be made as schedule function. (This is
the function for ZSX Primus IV/IVi only, and applicable for the equipment shipped
newly.)
<Example of setting for “8:30 a.m. every Monday”>

Setting of sample ID table for auto drift correction (For ZSX Primus IV/IVi only)
Start time/schedule of auto drift correction is set using the sample ID table preliminary
made for the auto drift correction. (This is the function for ZSX Primus IV/IVi only, and
applicable for the equipment shipped newly.)
1. Select <Time Preset Analysis>.

2. Click Add .
3. Select <Fixed time analysis> in the pull-down lists.
4. Check <Auto drift correction>. The sample ID table names set for the auto drift
correction are indicated in the sample ID table screen. And select the aimed table
name.
5. Set start time/schedule (every day, every week, every month).
6. Click OK , then close Time Preset Analysis Setting screen.
Set Periodic Analysis
1. Select the “Time Preset Analysis” tab.

2. Click Add .
3. Select <Periodic analysis> for “Type”.
4. Select a sample ID table for the periodic analysis at “Sample ID table”.

5. Set an interval for “Period”.

6. Click OK .
The measurement of the time interval starts when the EZ Analysis or Analysis program is
started on the main menu.
Change Preset Contents for Time Preset Analysis
1. Select a time preset analysis item to be changed.

2. Click Edit .
3. Change the preset contents.
4. Click OK .
Delete Time Preset Analysis Item
1. Select a time preset analysis item to be deleted.


Set Tube Aging
When turning on the X-rays after they have been turned off for a long time, the X-ray
tube voltage and current must be raised slowly to the specified load step by step. Raising
the tube voltage and current slowly is called aging. If the period when the X-rays have
been turned off is longer, a longer time should be taken to raise the tube voltage and
current. Only the target values for aging are set here and actual operation is started in
the Analysis program or on a system startup.
1. Click the “Tube Aging” tab.

2. Set the tube voltage for ordinary use at “Voltage(kV)”.
3. Set the tube current for ordinary use at “Current(mA)”.
Some combinations of tube voltage and current values cannot be selected because of
restrictions on the X-ray tube output or filament current.
When the tube voltage is selected, only those tube current values that can be combined
with it are available for selection.

Setting for Auto Power Off
Two methods can be used for Auto Power Off. One is the method to keep the X-rays and
the system turned on and the other is the method to turn off the X-rays. When the
X-rays are to be turned off, selection can be made from the method to keep the system
turned on and the method to turn it off. The methods of turning off set here become the
selection items in the Analysis program or on a system shutdown.
The setting items for Auto Power Off are displayed as selection items in <Power off
method> on the “Control ID Setting” screen of the Analysis program and in <Method> for
the automatic power off on the “Spectrometer Shutdown” screen.

Keep System and X-Rays Turned On
Setting is made to keep the system and the X-rays turned on with the X-ray output at
the lowest setting of 20kV-2mA. Because two or more control methods can be created,
they are given names to distinguish them and then saved.
1. Select the “Auto Power Off” tab.

2. Click Add .
3. Enter a name to identify a control method for “Off method”.
4. Select <Turn down the X-ray to 20kV-2mA> in the “Off condition” frame.
5. Click OK .

Turn X-Rays Off and Leave System Turned On

2. Click Add .
4. Select <Turn off the X-ray> in the “Off condition” frame.
5. Deselect <Set vacuum to Secure condition> in the “Off condition” frame.
6. Deselect <Turn off the power of spectrometer> in the “Off condition” frame.
7. Click OK .
Turn Off X-Rays and System
The software can be set to turn off the X-rays and the system.

2. Click Add .
4. Select <Turn off the X-ray> in the “Off condition” frame.
5. Select <Set vacuum to Secure condition> in the “Off condition” frame.
6. Select <Turn off the power of spectrometer> in the “Off condition” frame.
7. Click OK .

Change Preset Contents for Auto Power Off
1. Select a method to be changed on the auto power off list.

2. Click Edit .
3. Change the preset contents.
4. Click OK .
Delete Preset Contents for Auto Power Off
1. Select a method to be deleted on the auto power off list.


Set Energy-Saving Operation Condition
When the system is not used, the load of the X-rays can be automatically reduced to save
electric power. Following setting is available.
 The X-ray tube voltage and current are reduced.
1. Click the “Energy Saver” tab.

2. Select <Use Energy saving operation>.
3. Set the monitoring time for the unused system at “Standby timer”.
4. When <Cut down kV and mA> was selected, Set the target output of the X-ray tube.
5. Click OK .

h. System Management
Items to be set in System Management are conditions that should be determined before
operating the ZSX and information to add or change according to the operating condition
of the ZSX. These include the classification of users, the function assignment to users
and the management method for analyzed results. This program has the following five
functions:
 User Administration
 System Parameters
 Sample ID Structure
 Data Transfer Setting
 Record Voice
 User Administration
User Administration sets users who operate the instrument and places them in groups
in order to assign functions and set locations to which files are saved.
The following are registered at the time of shipment as the initial conditions. Only users
who belong to the Administrators group can utilize these functions.
Group User Password

Administrators Administrator No setting
Users rigaku No setting
The users of this software are unrelated to those of Windows. Register users using this
software in addition to those of Windows.
User Administration sets access rights concerning folders, files and functions of the data
processing system.
The administrator(s) of a group basically impose(s) limitations for each group on
functions of the data processing system. A user can belong to only one group.
Access rights are set for an individual folder for each group, and it is possible to give
authority for updating files of analysis conditions and analyzed results to other groups.

Add Group
It is called the addition of a group to add a group of access right settings concerning
folders, files and functions of the data processing system.
1. Select [System Management]  [User Administration].

2. Select the “Group” tab.
3. Click Add .
4. Enter a group name.
5. Enter a memo if desired.
6. For a user of the group to be set, choose whether each item is displayed or not on the
main menu. Only the chosen menu items are displayed. On an example of the main
menu screen shown below, only four menus items have been chosen:

7. Select analysis types that can be set in the Analysis program.
The selection of analysis types is applied to both <EZ Analysis> and <Analysis> programs.
8. Set data change authority for the six items including analysis conditions.
When the instrument does not have the mapping option, the check box [Change authority
of Mapping Tables] is not displayed.
When the instrument does not have the Program Operation option, the check box [Change
authority of Program Operation] is not displayed.
9. Click the “Data storage folders” tab.

10.When analyzed results are to be stored in an individual folder according to a group,
select <Use subfolder for the user>.
11.When analyzed results are to be stored in an individual folder according to a group,
select <Permit changing by other users.>.
12.Also for each analysis condition, when an individual folder is to be used according to
a group, select <Use subfolder for the user>.
13.When analysis conditions are to be stored in an individual folder according to a
group, select <Permit running Drift Corr. by other users.> and <Permit changing by
other users.>.

When the usage of individual folders for each user is set for analyzed results and analysis
conditions, subfolders that have the set user name are automatically created directly under
\AnlRsltU for analyzed results and \AnlCondU for analysis conditions.
When individual folders for each user are not used for analyzed results or analysis
conditions, the common folder is used.
14.Click OK .
Add User
It is called the addition of a user to add a user to a group that has access right settings
concerning folders, files and functions of the data processing system. It is possible to set
two or more users in one group.
1. Select [System Management]  [User Administration].

2. Select the “User” tab.
3. Click Add .
4. Enter a user name and select an already created group to which the user will belong.
5. Enter a password for <New password> and enter the same password for <New
password (re-enter)> for confirmation.
6. Click OK .
It is also possible to leave the password field blank.
Because even yourself cannot read the registered password, be sure to write it down.
A subfolder is created under the folder below:

Analysis Condition Folder Name

Common Folder Rigaku\SXIDV\UserData\AnlCond
Folder for Each User Rigaku\SXIDV\UserData\AnlCondU\(user name)
Analysis Condition Folder Name

Common Folder Rigaku\SXIDV\UserData\AnlRslt
Folder for Each User Rigaku\SXIDV\UserData\AnlRsltU\(user name)
Analysis result files are used for quantitative analysis results, qualitative analysis results
and mapping files.
The set subfolders described above become default folders. It is also possible to create a
subfolder for analysis conditions or analyzed results when an application file is created or
when a sample ID is created at the time of an analysis, respectively.
Delete User
1. Select the “User” tab.

2. Select a user to be deleted.
3. Click Remove .
Data storage folders that have been created remain intact.
Delete Group
1. Select the “Group” tab.

2. Select a group to be deleted.
3. Click Remove .
When at least one user who belongs to a group exists, it is impossible to delete that group.

 System Parameters
The system parameters are conditions and values to control data concerning the
analysis system. The parameters are divided into data processing, printing,
measurement setting, transmission condition, EZ Scan, initialization and others. When
the system has an ASC, the tab for an automatic sample loader is added.
Parameter Setting Item
Storage period for result display, matrix iteration times, negative

calibration slope, abnormal calculation mark print, upper and
Data Process lower limits for drift correction coefficient check, effective period
of analysis control
Threshold value for conversion of SQX analysis value to ppm
Date and time format, printed items in analysis, paper direction,
Print
statistics, logo print, printer setting
Measurement
(ZSX Primus, Evacuation (target vacuum degree, evacuation speed, use of APC
ZSX Primus II, (Automatic Pressure Control), pre-evacuation target
ZSX Primus vacuum ),coordinates for sample stage (r- or X-Y)
IV/IVi)
Evacuation (evacuation speed, pre-evacuation target vacuum)

Measurement
Stage coordination system・sample tray setting
Communication parameters (port, baud rate, parity, data bits,

stop bits, flow control, code type).
Transmission
Communication control (error detection, text delay time, link
control, text structure).
EZ Scan Print
Whether the instrument is initialized or not when the measuring
Initialization
control program is started
Selection of display of submenu on flow bar, time for data saving
Others
notification

Set Storage Period for Result Display
1. Select [System Management]  [System Parameters].

2. Select the “Data Process” tab.
3. Double-click the period of an objective data type.
4. Enter a period in days.
5. Click OK .
<No Limit> is set in the initial condition. To change setting of some period to <No Limit>,
right-click an objective period and select <No Limit>.

Select Date and Time Format

2. Select the “Print” tab.
3. Select a format at “Date & Time format”.
4. Click OK .
It is possible to output to printer as a PDF file using Microsoft Print to PDF to the printer.
Click Setting… on the Printer and set as follow.
1. Select <Use the following printer>, and select <Microsoft Print to PDF> from the
pull-down list.
2. Select <Print to file>.
3. Click Browse… for saving place of file to make folder.
4. Input “PDF” on the extension screen.
5. <Open the file after output> is normally not necessary to be selected.

Default setting is shown as below when shipped from factory.
Setting example using Microsoft Print to PDF
Use [Microsoft Print to PDF] without fail. No guarantee of other pdf printers working.
Set Form Feed for Each Sample

2. Select the “Print” tab.
3. Select <Paper out for each sample> in the “Printing in analysis” frame.
4. Click OK .

Change Target Vacuum Degree

2. Select the “Measurement” tab.
3. Select <High>, <Middle> or <Low> for the target vacuum degree.
4. Select <High>, <Middle> or <Low> for “Pre-evac. target vacuum” in the “Vacuum
setting” frame.
5. Click OK .

Setting of dedicated tary for helium atmosphere（ZSX Primus IV/IVi）
It is possible to designate any tray to be able to set only helium atmosphere application
as a dedicated tray for helium atmosphere.Designated sample tray and sample position
are indicated with blue.
1. Select [System management] and [System parameters] in turn.

2. Select <Measurement>.
3. Set for aimed trays.

Evacuation ASC position setting in the event of a two-stage sample holders stack
error (For ZSX Primus IVi only)
It is a function to automatically discharge the stacked sample holder to predetermined

ASC positions. When the stack error takes place, the measurement can be still
continued without break by using this function. It is possible to set up two positions for
evacuation ASC positions. If the evacuation positions have been occupied with other
sample holders, ASC moves to the ASC initialization position with the sample holder
still in its chuck. In this case, remove the holder manually, and initialize the whole
system. The sample position as evacuation can not be set analysis ID setting.
1. Select [System management] and[System parameters] in turn.

2. Select <Measurement>.
3. Set the evacuation sample position on the ASC.

Set Output for External Transmission
Select the standard to be used for transmission from RS232C and TCP/IP.

2. Select the “Transmission” tab.
3. Select <RS232C> or <TCP/IP> for “Output”.

Set Transmission Protocol
The procedure to change the number of retry actions and waiting time for the ENQ
response will be used as an example.

3. Select <Link control> in the “Communication control” frame.
4. Click Setting.. .
5. Set the number of retry actions for “Calling ENQ” in the “Retry times” frame.
6. Set the number of retry actions for “Demanding ENQ” in the “Retry times” frame.
7. Set a time in seconds for “For calling ENQ” in the “Response waiting time” frame.
8. Set a time in seconds for “For demanding ENQ” in the “Response waiting time”
frame.
9. Click OK .
10.Click OK on the “System Parameters” screen.

Set Text Start Code for Transmission

3. Click Text Structure Setting… .
4. Select <Text start code> in the “Text control code” frame.
5. Enter a text start code in 1 or 2 bytes in hexadecimal.
6. Click OK .

Set EZ Scan

2. Select the “EZ Scan” tab.
3. Select print option for each item in EZ Scan.
4. Select Sample absorption correction in EZ scan under helium atmosphere.
5. Click OK .
Sample types of metal and oxide can be selected in EZ scan. In the analysis of liquid, a
balance component should be specified. Accordingly, recalculate specifying the balance in
SQX calculation program after EZ scan analysis. Or create a qual application for the liquid
and analyze using the qual application.
When SQX software is not attached, there is no setting of <SQX result> and <Material
judgement> in “Print” frame and <Sample film absorption> in “Helium atmosphere
Correction”.

Make Setting for Initialization

2. Select the “Initialization” tab.
3. Usually, select the radio button <Initialize the spectrometer only if necessary> in the
“Initialize the spectrometer when ZSX Guidance starts up” frame.
4. Click OK .
When the radio button <Initialize the spectrometer only if necessary> is selected, the
spectrometer will be initialized only if it has not been initialized when the ZSX Guidance
icon on the Desktop is double-clicked to start the ZSX Guidance program. Usually, <Do
not initialize the spectrometer> is not used.

Set Others
Following setting can be made.
・Indication of submenu to the flow bar

・Change of notification of data saving
・Show file name input field of the qualitative analysis results

2. Select the “Others” tab.
3. Make selection for “Use submenu in flow bar”.
4. Make setting from 1 to 90 for “Days of notification after last data saving” under
“Notification of data saving”.
5. Click OK .
Uncheck the check box of <Show file name input field of the qual. Analysis result> if it is
not necessary to indicate it. Sample name becomes file name.

The setting of “Use submenu in flow bar” works as follows:
Use submenu Do not use submenu

 Sample ID Structure
The sample ID consists of the following items. The outline of each item is shown below:
Multiple Content
Option Meaning of Item
Settings Setting
Analysis type (quantitative analysis,
Transmit,
Type intensity measurement, check analysis, Impossible
text
drift correction, … , PHA adjustment)
Number to indicate a position on the turret
Position Impossible Transmit
or ASC
Application Analysis condition name Impossible Transmit
Mapping Mapping measurement type Impossible None
Times Number of repetitions Impossible None
Update selection (first, last,
Flag Impossible Text
intermediate sample)
Displays the contents of the memo in the
Memo Impossible None
application etc.
Indicates whether data has been input or
Input data Impossible Text
not. The value is not displayed.
File name Qualitative analysis file name Impossible None
Memo Memo entered on ID setting.
(See on Possible Transmit
the next page.)
Incremental setting is possible.
Selections Options are registered on a table and
(See on Possible Transmit
the next page.)
selected on ID setting.

When setting is made on the sample ID structure screen, the caution message shown
below appears. Convert measurement result data according to the message. For the
conversion, see “6.4 CONVERSION OF SAMPLE ID”.
Set Sample ID Item
1. Select [System Management]  [Sample ID Structure].

2. Select an item in order for each item number.
3. Enter any text to be displayed under “Header”.
4. In the case an item to set its contents, click Setting .
5. Adjust the setting for transmission designation, displayed text, transmitted text or
the like.
6. Click OK on the setting screen.
7. Click OK on the “Sample ID Structure Setting” screen.
The item at the left end of the sample ID is item number 1. Items after that follow to the right
in numerical order.
The maximum number of characters to be output as the sample name is 40. The
transmission sample ID is used only in the transmission format and there is no limitation on
its number of characters.
When <Output this item in sample name> is selected for <Memo> or <Selections>, set the
number of characters by actually printing data because the printing space is limited.

Add Option to Selection Item
1. Click Setting for “Selections”.

2. Click Add .
3. Enter a selection name.
4. Enter a text to be selected under “Selection”.
5. Click OK .
6. Set the number of characters on the “Selection Item Setting” screen.
7. Click OK .
Set Analysis Type Display Text and Text to Transmit
1. Click Setting for “Type”.

2. Select an analysis type and double-click its “Text to transmit” cell.
3. Enter a text for transmission.
4. Select <Transmit this item> in the “Select to transmit” frame.
5. Enter the number of characters in the “Select to transmit” frame.
6. Click OK .
The maximum number of characters to transmit is 16.

Delete ID Item
1. Select [System Management]  [Sample ID Structure].

2. Right-click the number of an item to be deleted.
4. Click OK .
The option <Space> has the same function as <Cut> on the right-click menu.

 Data Transfer Setting
To make or alter the settings for data transfer, you must have the administrative rights
for it. Preset contents are administered for each group. Obtain network information
beforehand from an administrator of the network.
Disk saving, FTP transfer and e-mail are available as the transfer method. Up to 20
destinations can be registered for one group.
Add Destination
1. Select [System Management]  [Data Transfer Setting].

2. Select the “Destination” tab.
3. Click Add .
4. Enter a destination.
5. Select a transfer method.
6. Enter information according to the transfer method.
7. Click OK .
Settings to send e-mail directly using the ZSX Guidance are made from the SMTP Info.
button on the <Destination> tab. See “6.5 SETTING FOR E-MAIL” for details.
A network drive cannot be used as a folder to save.

Set a path described using a server name and a shared folder name.
Example: \\Server name\Shared folder name

Assign Transfer Type to Destination
1. Select the “Type” tab.

2. Select a transfer type.
3. Select a destination.
Output Selection for Each Analysis Type
1. Click the “Data” tab.

2. Select an analysis type in the “Data selection” frame.
3. Select <Yes>, <No> or <Dialog> for each selectable item in the “Output selection”
frame.
When <Dialog> is selected, a dialog to determine whether to transfer data or not appears in
the sample ID setting on an analysis.

Select Print Format Output Data
1. Select the “Data” tab.

2. Click Print format output data.. .
3. Select quantitative analysis data items to be output with the print format.
4. Click OK .
Set Date and Time Format for File Name

2. Click File name specification… .
3. Select <Date & time format> for “File name type”.
4. Select a format at “Date & time format”.
5. Click OK .
Make Input File Name Valid
An output file name is created from a file name entered in setting an ID.

2. Click File name specification… .
3. Select <Specify file name> for “File name type”.
4. Enter extensions for “Print format” and “Trans. format” in the “Extension” frame.
5. Click OK .

Select Error Information Output
1. Select the “Error” tab.

2. Select an error type.
3. Select <Yes> or <No> for “Voice”, “e-mail” and “Error display”.

Transfer Analysis Progress
1. Select the “Progress” tab.

2. Select <Analysis progress> or <Completion of all samples> for “Analysis progress
type”.
3. Select <Yes> or <No> for “Voice” and “e-mail”.
4. Enter a sample ID interval in the “Analysis progress” frame.
Make E-Mail Transfer Valid
All output settings for e-mail on the panels are validated. To stop e-mail transfer,
deselect this.

2. Select <Send e-mail>.
Make Voice Output Valid
The voice output setting for the error information and analysis progress is validated.

2. Select <Output voice>.

 Record Voice
This function administers sound files used when an instrument error occurs during an
analysis and in similar cases. Sound output is determined according to a type of a
phenomenon (an analysis error, analysis progress, instrument error, etc.).
WAV files and files that multimedia supports can be handled.
Record WAV File Processing
Yes Data is updated.

No
No Error
A wav file is overwritten and then data is updated.

Yes
Data is written to a wav file with another name and
Yes then data is updated.
Data is written to a wav file with an entered name
No
and then data is updated.
Record Analysis Error Voice to New File
Connect your microphone to the personal computer and restart it.
1. Select [System Management]  [Record Voice].

2. Select <Analysis Error> for the type.
3. Select an item in the list.

4. Click Customize .

5. Set the number of repetitions.
6. Enter a new file name, or designate an existing file name.
7. Click Recording & Play .
8. Click Record .
9. Record a message through the microphone.
10.After pronouncing the message to be recorded, click Stop .
11.Click OK on the “Recording & Play” screen.
12.Click OK on the “Edit Voice” screen.
13.Click Save on the “Voice Recording” screen.
14.Select [File]  [Close Voice Recording].
When an existing file name is designated, the following procedure is added on the “Edit
Voice” screen:
1. Click Cancel for “Are you sure to overwrite?”

2. Enter a new file name.
3. Click Save .
To overwrite an existing file with the recorded data, click OK.

i. Information Transferred Using E-Mail
To use e-mail, you must contract a provider.

Make setting necessary for transmission using the e-mail software. See “6.5 SETTING
FOR E-MAIL” for setting details.
To send e-mail using the telephone line, you must prepare a modem and make setting for
dial-up connection.
Transfer Quantitative Analysis Results
 An analyzed result can be transferred on each analysis.
Data is transferred as an attached file. Two or more destinations can be designated.

The file format can be selected from the print format, transfer format and HTML format.
Setting for transfer is made using “Data Transfer Setting” in “System Management”.
See “Data Transfer Setting” in “6.1 h. System Management”.
 Analyzed results can be transferred using the Result Display program after analyses.
Data is transferred as an attached file.

The file format can be selected from the transfer format, spreadsheet format and HTML
format.
Designate the e-mail as the transmission method in “Quant. Data Transmission” in the
Result Display program. Then specify one destination.
See “4.4 d. Transfer of Analyzed Results”.
If <Send e-mail> is not selected on the “Destination” tab on the “Data Transfer Setting”
screen, data will not be transmitted even when a destination is designated.

Transfer Errors and Progress of Analysis
Errors such as hardware errors of the instrument and progress of analysis can be
transferred.
Setting for transfer is made using “Data Transfer Setting” in “System Management”.
Two or more destinations can be designated.
To designate two or more destinations, add e-mail addresses according to “Add

Destination” in “Data Transfer Setting” in “6.1 h System Management”. After the addition,
you can place check marks for destinations of e-mail on the “Type” tab.
If <Send e-mail> is not selected on the “Destination” tab on the “Data Transfer Setting”
screen, data will not be transmitted even when a destination is designated.

j. Operation of Automatic Power Control (Option)
Operation of <Turn down the X-ray to 20kV-2mA> in Auto Power Off
 The tube voltage and current are set to 20kV-2mA.

 The evacuation system is set to the “Secure” condition (when <Set vacuum to
Secure condition> has been selected).
To restart the system, select <Initialize spectrometer> and <Age X-ray tube> with the
“Spectrometer Startup” program.
Operation of <Turn off the X-ray>, <Set vacuum to Secure condition> and <Turn off
the power of spectrometer> in Auto Power Off
 After the start of auto power off

 The tube voltage and current are set to 20kV-2mA and then the X-rays are
turned off.
 The evacuation system is set to the “Secure” condition (when <Set vacuum to
Secure condition> has been selected).
 5 minutes later (when <Turn off the power of spectrometer> has been selected)
 The X-ray generator and the heat exchanger are turned off.
 The spectrometer is turned off.
The personal computer and the printer are not turned off.
To restart the system, terminate the ZSX Guidance, turn on the spectrometer and restart
the ZSX Guidance.

Energy-Saving Operation
The energy-saving operation sets the specified standby condition when no measurement
has been made during the wait time to switch to the energy-saving mode. The wait time
starts when an analysis is completed or suspended. This function is valid when <Use
Energy saving operation> has been selected on the “Program Operation” screen.
 1 minute before time is up

 The message “ZSX will shift to standby mode” appears.
 A countdown starts.
When Cancel is clicked here, the countdown stops and the timer is reset.
 When time is up
 The message “ZSX is shifting to standby mode” appears.
 The system starts to switch to the standby mode.
 When the standby mode has been set

 The message “ZSX is in standby mode” appears.
Recover From Standby Mode
1. Click Cancel on the “ZSX is in standby mode” screen.

2. Check the message “ZSX will return to normal mode”.
3. Click OK .
When an analysis is started using the Analysis program in the standby mode, recovery is
made automatically.

k. Information about External Transmission
Described in this section is information necessary to transmit data to an external

communication device through an RS232C or TCP/IP line. For specific contents and
operational procedures, see an appropriate section mentioned below:
Preset Information Necessary for Transmission
To transmit quantitative and/or qualitative analysis results through an RS232C or

TCP/IP line, conditions for transmission must be set beforehand. For the structure and
formats of transmitted texts, see “6.6 TRANSMISSION AND TRANSMISSION
FORMATS”.
Preset Information Menu Operated Item

Communication [Utility]  [System Management]
“Transmission” tab
parameters  [System Parameters]
Communication [Utility]  [System Management]
“Transmission” tab
control  [System Parameters]
Text Structure [Utility]  [System Management] Text Structure Setting…
Setting…  [System Parameters] on “Transmission” tab
“Select to transmit” [Utility]  [System Management]
Setting in each ID item
in sample ID  [Sample ID Structure]
Data selection
(only for [Utility]  [System Management]
“Data” tab
quantitative  [Data Transfer Setting]
analysis results)
The upper four items in the above table should be set according to the requirements of
the external communication device. For the lowest one, selection for the RS232C or
TCP/IP transmission should be made from <No>, <Yes> and <Dialog> for each analysis
type in the quantitative analysis.
<Drift corr. update> or <Bias corr. update> can be selected in the “Data selection” frame. By
using these options, update results such as coefficients can be transmitted.
For the setting procedure, see “■ System Parameters”, “■ Sample ID Structure” or “■

Data Transfer Setting” in “6.1 h. System Management”.
When you have changed any setting for the transmission or the sample ID structure, you
must restart the ZSX Guidance to activate the changed contents.

Transfer of Quantitative Analysis Results
 Transfer Analyzed Results Just After Analysis
When selection for the RS232C or TCP/IP transmission is made from <No>, <Yes> and
<Dialog> for each analysis type, options on the “Sample ID Setting” screen and
transmission processing just after an analysis are as follows:
Setting for Transmission

Options for “Result output”
External Processing Just After
on “Sample ID Setting”
Transmission Analysis
Option not displayed for external
<No> Not transmitted
transmission
Option not displayed for external
<Yes> Transmitted
transmission
Option displayed for Unselected Not transmitted
<Dialog>
external transmission Selected Transmitted
 Transfer Using Result Display Program After Analysis
After selecting an ID to be transferred, select <Transmission format> for “Text format”

and <RS232C Transmission> or <TCP/IP Transmission> for “Trans. method” on the
“Transfer Quant Data…” screen in the Result Display program.
See “4.4 d. Transfer of Analyzed Results”.
Transfer of Qualitative Analysis Results
Since qualitative analysis results must be transmitted after checking and editing them,
a function to transmit them just after an analysis is not available.
 Transfer Using Qual Data Handling Program After Analysis
Select <Transmission format> for “Text format” and <RS232C Transmission> or

<TCP/IP Transmission> for “Trans. method” on the “Qual Data Transmission” screen in
the Qual Data Handling program.
See “3.3.1 i. Transfer of Qualitative Analysis Results”.

6.2 MAINTENANCE
Programs to manage the mechanical condition of this system are collected on the
Maintenance menu. This section describes Spectrometer Test, Maintenance Records
and Test Measurement. The Maintenance menu consists of the following:
Maintenance
Sub-Item Description
Item
Displays a list of items that an operator
Check List
should check daily.
Carries out a status check, tests of
Self-Diagnostics driving units, vacuum test,
reproducibility test, etc.
Carries out assistant driving to replace
Spectrometer
PC Maintenance the PC window and executes PC wire
Test
cleaning.
The analysis chamber is returned to the
air mode, and the lift of the sample
Sample Chamber
chamber is lowered, as automatic
Maintenance
preparation to pull out the sample
chamber.
Record of spectrometer errors and
Error Log
communication errors
Record of spectrometer status
information obtained using the
Spectrometer Check
spectrometer check in the
self-diagnostics
Record of results of various checks and
Self-Diagnostics
tests obtained using the self-diagnostics
Record of X-R values of check analysis
Maintenance Check Analysis
results
Records
Record of alpha and beta values of drift
Drift Correction
correction results
Record of variations of PHA adjustment
PHA Adjustment values and resolutions of PHA
adjustment results
Record of calibration curve constants
Calibration Curve that were changed using the regression
Constants calculation and automatic calibration
update function
Test Executes the fixed angle measurement,

Measurement 2-theta scan and PHA scan.

a. Check List
Check List displays everyday check items for the spectrometer so that the spectrometer
supervisor can inspect the contents of work on the screen. Check List includes periodical
check items such as ones shown below. For each of those items, you can see the contents
of work and carry out an inspection.
Especially when maintaining the spectrometer abroad, by using this function, a user can
see an inspection procedure at a glance and carry out the displayed procedure easily.
Inspection work is very important to maintain the reliability of the spectrometer for a
long period.
The contents of inspections by this function are recorded and displayed as marks on a
graph in Record for PHA Adjustment Result, Record for Drift Correction Result, and
Record for Check Analysis Result, etc.
Display Everyday Spectrometer Check Items for Operator
1. Click Maintenance on the menu.

2. Select [Spectrometer Test]  [Check List].
3. Make selection for “Check period”.

Make Setting for Inspection Record
1. Make selection for “Check period”.

2. Click Edit .
3. Select <Add>.
4. Make setting for “Maintained date” and click OK .
Delete Maintained Records
1. Select [File]  [Delete All Maintained Dates].

2. Click Yes .

b. Self-Diagnostics
Self-Diagnostics includes three functions of “Status”, “Driving time” and “Vacuum test”.
 Status
 Driving time
 Vacuum test

2. Select [Spectrometer Test]  [Self Diagnostics].

 Status
The spectrometer status is checked, and the spectrometer I/O status is received and
displayed. Those results are recorded and can be redisplayed.
Display Present Spectrometer Status
1. Select the “Status” tab.

2. Select <Spectrometer status>.
3. Click Start .
4. Click OK .
The integrated time when the X-rays have been turned on is displayed at “X-ray tube hour
integrator”.

Check I/O Status
1. Select the “Status” tab.

2. Select <Driving part status>.
3. Click Start .
4. Click OK .
The spectrometer status and driving part status can be obtained even if a hardware error
has occurred.

 Driving Time
This function obtains a driving time by operating a mechanical driving unit individually
by the specified number of repetitions. Units to be tested are the sample
loading/unloading mechanism, the optical system such as the filter and slit, and other
mechanisms. Continuous operation is not carried out.
Obtain Sample Loading/Unloading Operation Time
1. Select the “Driving time” tab.

2. Select <Sample transfer> in the “Item” frame.
3. Click Position Setting… .
4. Select the number of samples.
6. Click OK .
7. Make selection for “Repeat times”.
8. Click Start .

 Vacuum Test
A sample holder alone is loaded, and the attained vacuum degree and the stability of the
vacuum degree are displayed.
1. Select the “Vacuum test” tab.

2. Place a holder.
3. Set the position of the placed holder in the “Condition” frame.
4. Make selection for “Evacuation speed”.
5. Select a pre-evacuation target vacuum degree.
6. Make selection for “Use APC”.
7. Make selection for “Target vacuum”.
8. Make selection for “Evacuation time”.
9. Click Start .
10.Click Graph Display… .
11.Click OK .

c. PC Maintenance
This program has functions concerning the maintenance of the PC, which is the detector
for light elements. Center wire cleaning and the replacement of the PC window are
carried out here.

2. Select [Spectrometer Test]  [PC Maintenance].
Carry Out Center Wire Cleaning
Methane gas, which is added to prevent subsequent discharges, absorbs electrons,

ionizes and sticks to the center wire, resulting in poor energy resolution. In such a case,
by executing center wire cleaning, the original condition can be restored. This procedure
can be carried out from the personal computer without removing the proportional
counter from the spectrometer.
1. Select <Center wire cleaning>.

2. Click OK .
3. Click OK for the confirming message.
4. When the completion message screen appeared, click OK .

Replace PC Window
A very thin macromolecule film with thin metal evaporated on it is used for the PC
window. This window is a consumable that is damaged when it has been used for a long
period of time. You can make a preparation to replace this window through dialogs on
the screen.
1) Turn off the X-rays.

2) Set the air mode for the spectrometer chamber.
3) Rotate the goniometer to a position where the PC can be removed easily.
When replacing the PC window, it is recommended that P-10 gas be kept flowing. By
keeping P-10 gas flowing, the detector inner wall can be kept out of contact with air.
Therefore, after the window is replaced, a stable condition can be restored sooner.
For the procedure for replacement, see “Procedure to Replace PC Window” in the
maintenance manual.

d. Error Log
Errors that occur in the spectrometer and in communications with the spectrometer are
automatically recorded. Errors are classified into spectrometer errors, X-ray generator
errors, spectrometer response errors, X-ray generator response errors, data processing
errors, communication errors and other errors. They are classified into three levels: an
error, a warning and a failure. A warning means an error with which an analysis can
continue and changes to a failure when the analysis cannot be continued. Using the
Error Log program, errors that have been recorded automatically in a time sequence can
be displayed and printed in detail.
Up to 200 errors can be recorded in the error log. If the number of errors exceeds 200, the
oldest data will be overwritten.

2. Select [Maintenance Records]  [Error Log].
Delete All Errors
All recorded errors are deleted. Take care because deleted data cannot be restored.
1. Click All Clear .

Display Details of Error
The contents of an error are displayed in simplified form on the “Error Log” screen.
Detailed information of an error (the contents and factors of an error, maintenance
information, etc.) can be displayed and printed.
1. Select an error item to display detailed contents on the error log list.
2. Click Information .
3. Click Print if desired.
4. Click Close .

e. Record for Spectrometer Status Check
Spectrometer status information obtained with <Spectrometer Status Check> in Self

Diagnostics is recorded automatically. This program can load and display that
information.

2. Select [Maintenance Records]  [Spectrometer Check].
Display Spectrometer Status Check Result
1. Select a date and time checked.

Delete Check Result Record

2. Select the date and time of a check result record to be deleted.
3. Click OK .
To delete all records, click Select all and then OK.
Print Check Result Record

2. Select the date and time of a check result record to be printed.
3. Click OK .

f. Record for Self Diagnostics Result
Of the diagnostics and test items in Self Diagnostics, results of <Spectrometer Status
Check> can be displayed using “Spectrometer Status Check Record”. The records of the
other items can be displayed using this “Self-Diagnostics Record”. The relationship
between the self-diagnostics items and display functions is shown below:
Maintenance Maintenance Records

Spectrometer Status
Self-Diagnostics Self-Diagnostics Record
Check Record
Spectrometer
— List of check items
“Status” status
tab Driving part
Driving part status —
status
Self-diagno
“Driving time” tab Drive time —

stics items
“Vacuum test” tab Vacuum test —
Start Self Diagnostics Record

2. Select [Maintenance Records]  [Self Diagnostics].
Self-diagnostic record consists of five categories, namely, “Drive part status”,
“Drive time”, “Vacuum test”, “Performance” and “Noise test”. Sorting/filtering
each category and date of examination can be made and it is easy to extract the
requisite information.
The data displayed on the screen can be copied to clip board by pressing the Ctrl+C key. It
is easy to paste it to spreadsheet like Excel®.

Reference Data
When a diagnosis has been carried out, reference data for comparison is necessary to
judge a diagnosis result. When our service technician has made an adjustment, he or she
leaves reference data with '*' attached to the diagnosis date and time. Judge a diagnosis
result by comparison to this reference data.
Users cannot change or delete this reference data.
Display Records of Drive Time
1. Select <Self diagnostics record> in the “Kinds of files” frame.

2. Select a date and time in the “diagnostic date” box.
3. Select <Drive time> in the “Self-diagnostics items” frame.

Display Records of Vacuum Test
1. Select <Vacuum test> in the self diagnostic record.

2. Check necessary item by sorting/filtering for each item.
3. Select each examination date and time by clicking, and when make right-click
<Graph>, the graph of the change in time and degree of vacuum is displayed.

Refer the record of driving part status
1. Select <Driving part status> in the self diagnostic record.

2. Make sorting/filtering for each record and confirm them.
Refer the record of performance and noise test
1. Select <Performance> or <Noise test> in the self-diagnostic record.

2. Make sorting/filtering for each record and confirm them.
Performance makes it easy to compare the profile of each measurement result with the
shipping data.
1. Select aimed date and time.
2. Right-click, then click spectrum . The designated date and related shipping date file as
reference are selected.
3. Click Spetrum to display the spectrum.

Print Recorded Data

2. Select <Self diagnostics record> or <Driving part status> in the “Kinds of files” frame
on the “Print” screen.
3. Select a date and time to be printed in the “Diagnostic date” box.
4. Click OK .
Delete Recorded Data

2. Select <Self diagnostics record> or <Driving part status> in the “Kinds of files” frame
on the “Delete” screen.
3. Select one or more dates and times to be deleted in the “Diagnostic date” box.
4. Click OK .
Because the reference data set cannot be deleted, it does not appear in the “Diagnostic
date” list.

g. Record for Check Analysis Result
The check analysis is generally made several times a day and its results are recorded.
Monitoring the trends of those averages (X) and ranges (R) is called X-R control. Check
analysis results are recorded automatically and you can carry out the X-R control easily
using this program.

2. Select [Maintenance Records]  [Check Analysis].
Create X-R Control Chart
The specified number of check analyses are made each day, their statistics are calculated
and an X-R control chart is drawn. For a selected component, graphs of averages and
ranges are displayed in the upper and lower parts of the screen. Statistics are displayed
superimposed on the graph. Data of one day is displayed with one point. The cursor line
in the list interlocks with the cursor bar in the graph. An analyzed result out of its limit
range is displayed in red in the list.
1. Select an objective sample type at “Check sample”.

2. Select a component to be displayed at “Component”.
By dragging the dividing line, the sizes of the graph areas can be changed. To display two
graphs evenly, double-click the dividing line.

Display for Designated Period
By designating a period, data to be displayed can be limited. The following designating

methods can be used:
Method Description
All dates All data items of the designated sample type are displayed.
The start and end dates are designated. The standard
Date from
calendar function of Windows is used.
For the last x Data items of the last months from the present date are
months displayed.
For the last x Data items of the last days from the present date are
days displayed.
1. Select [View]  [Graph Setting...].

2. Click the “Period” tab.
3. Select <All dates>, <Date from>, <For the last x months> or <For the last x days>.
4. When <Date from> was selected, set the start date and the end date.
5. When <For the last x months > was selected, set the number of months.
6. When <For the last x days > was selected, set the number of days.
7. Click OK .

Set Reference Lines
For reference grid lines for the ordinate axis, the limit range values preset for the check
analysis or the standard deviation can be used. Upper and lower limits are set for
average values and an upper limit is set for ranges. In the case of the standard deviation,
+/-1 to +/-3 can be set.

2. Click the “Reference line” tab.
3. Select <Limit range>, <Standard deviation> or <None> in the “Reference lines”
frame.
4. When <Standard deviation> was selected, select <1xSD>, <2xSD> or <3xSD>.
5. Click OK .
Set Grid Lines for Period
For reference grid lines for the abscissa axis, grid lines can be drawn at intervals of the
specified number of days.

2. Click the “Reference lines” tab.
3. Select <Yes> in the “Grid in period” frame.
4. Enter the number of days for “Interval”.
5. Click OK .

In the initial condition, <Auto scaling> has been set for the vertical scales of both the X
graph and the R graph. Other options cannot be selected when <limit range> is selected
for the reference grid lines. If you want to select <Absolute> or <Relative> for the X
(average) graph or <Absolute> for the R (range) graph, change the setting for the
reference lines described before.
Reference
X Value Graph R Value Graph
Grid Lines
Standard
Auto scaling only Auto scaling only
Values
Standard
Auto scaling/Absolute/Relative Auto scaling/Absolute
Deviation
None Auto scaling/Absolute/Relative Auto scaling/Absolute
In the case of <Absolute>, specify an absolute value in the unit used, for example, in
mass%. In the case of <Relative>, specify a value relative to the average in percentages.

2. Click the “Spindle scale” tab.
3. Select <Auto scaling>, <Absolute> or <Relative> in the “Trend graph of X
value” frame.
4. In the case of <Absolute> or <Relative>, set an appropriate value.
5. Select <Auto scaling> or <Absolute> in the “Trend graph of R value” frame.
6. In the case of <Absolute>, set an appropriate value.
7. Click OK .

Data Information
The specified number of check analyses are generally made each day. Up to five data
items can be used for the average (X) calculation. On the “Data information” page, the
number of data items to be used for the average (X) calculation and the handling of data
out of its limit range are set.
When the specified number of data items is less than the number of actual analyses, the
older data items are used. If the number of analyses in one day is larger than the
specified number, excessive analyses (data items exceeding “Number of data for
averaging”) will not be used for a calculation. Even if there is an out-of-range data item
in the specified number of data items and <Not included> has been set for “Out of range”,
averages will be calculated using the specified number of data items.
Change Number of Data for Averaging for X-R Control

2. Click the “Data Information” tab.
3. Select the number of analysis times for averages at “Number of data for averaging”.
4. Click OK .
Change Handling of Out-of-Range Data for X-R Control

2. Click the “Data Information” tab.
3. Select <Not included> or <Included> in the “Out of range” frame.
4. Click OK .

Print Recorded Data
Components used for the X-R control can be printed out. The procedure to print a
component of a check sample that is not displayed now is described below as an example:
1. Select a sample type to be printed at “Check sample”.

2. Select a component to be printed at “Component”.
4. Select <All>, <List only> or <Graph only>.
Whole data of designated items can be output as Excel file in a lump by clicking [File]
[Output to Excel file].

h. Record for Drift Correction Result
To continue to use a calibration curve or a sensitivity calibration curve for a long period
of time, the same intensities as those at the time of the creation of the calibration curve
or sensitivity calibration curve are required. Because X-ray intensities change with time,
the drift correction is used to correct their changes. Because drift correction coefficients
 and  are recorded automatically, the history of their corrections can be checked.

2. Select [Maintenance Records]  [Drift Correction].
Display Drift Correction Record
The alpha method and the alpha-beta method can be used for the drift correction. One
drift correction sample is used in the alpha method, and two drift correction samples are
used in the alpha-beta method. In the case of the alpha method, a graph of beta values is
not displayed. The cursor line in the list correlates with the cursor bar in the graph. An
analyzed result out of its limit range is displayed in red in the list.
1. Select <Private> or <Common> for “Meas. condition”.

2. Select the folder of an application to be displayed.
3. Select an objective sample type at “Application”.
4. Select a measured element line to be displayed at “Element line”.


Method Description
Date from
months displayed.
days displayed.

7. Click OK .

Set Reference Lines
For the abscissa axis, reference grid lines can be drawn at intervals of the specified
number of days.

3. Select <Yes> in the “Reference line of X axis” frame.
5. Click OK .
The vertical scale can be changed to the automatic scale, absolute value or relative
value.

3. Select <Auto scaling>, <Absolute> or <Relative> in the “Trend graph of Alpha”
frame.
4. In the case of <Absolute> or <Relative>, set an arbitrary value.
5. Select <Auto scaling>, <Absolute> or <Relative> in the “Trend graph of Beta” frame.
7. Click OK .

Display Maintenance Markers
Maintenance markers are used to indicate when the maintenance of the SC or PC was
done or a detection circuit board was replaced. Colored arrows and characters for
identification are displayed on a list and a graph.
1. Select [View]  [Maintenance Marker].
Print Recorded Data
Measured element lines used for the drift correction record can be printed out. The
procedure to print a measured element line of a drift correction sample that is not
displayed now is described below as an example:
1. Select an objective sample type at “Application”.

2. Select a measured element line to be printed at “Element line”.
Whole data of designated items can be output as Excel file in a lump by clicking [File]
[Output to Excel file ]

i. Record for PHA Adjustment Result
In the PHA adjustment, which is one of the everyday control analyses, the results are
recorded automatically for each execution. In this program, variations in the energy
resolutions of the detectors can be checked. Furthermore, in the case of the PC, you can
check dates and times when maintenance operations such as the replacement of the PC
window and the wire cleaning were carried out.

2. Select [Maintenance Records]  [PHA Adjustment].
is easy to paste it to spreadsheet like Excel®..
Display PHA Adjustment Results
From PHA adjustment results of each detector, you can check PHA adjustment values
and resolution values, which indicate the performance of a detector. This system has the
SC and PC as the detectors, and data of each of them is displayed separately.
1. Click PC or SC .
The cursor line in the list correlates with the cursor bar in the graph.


Method Description
Date from
months displayed.
days displayed.

7. Click OK .

Set Reference Lines
For the abscissa axis, reference grid lines can be drawn at intervals of the specified
number of days.

3. Select <Yes> in the “Reference lines of X axis” frame.
5. Click OK .
The vertical scale can be changed to the automatic scaling, absolute value or relative
value.

3. Select <Auto scaling>, <Absolute> or <Relative> in the “Trend graph of PHA
adjustment value (Pv)” frame.
5. Select <Auto scaling>, <Absolute> or <Relative> in the “Trend graph of resolution”
frame.
7. Click OK .

Display Maintenance Markers
Maintenance markers are used to indicate when the maintenance of the SC or PC was
done and a detection circuit board was replaced. Colored arrows and characters for
identification are displayed on a list and a graph.
1. Select [View]  [Maintenance Marker].
Display PHA Curve
A PHA curve, which is a result of the PHA scan, can be displayed from an adjustment
result of each detector.
1. Select [View]  [PHA curve].

Printing
Recorded data and a specified PHA curve can be printed.
Print Recorded Data
1. Select a detector by clicking PC or SC .

Print PHA Curve
1. Select a detector by clicking PC or SC .

2. Select a PHA adjustment result with an adjustment date and time.
3. Select [File]  [PHA curve Print].
Whole data of designated items can be output as Excel file in a lump by clicking [File]
[Output to Excel file]

j. Record for Calibration Curve Constants
The record for calibration curve constants that were changed using the regression
calculation and automatic calibration update function can be displayed.

2. Select [Maintenance Records]  [Calibration Constant Record].
3. Select a folder in which a quantitative application is saved from the “Folder” list box.
4. Select a quantitative application for which to display the record for calibration curve
constants from the “Application” list box.
Detailed Result
1. Select a line for which to display a detailed result.

2. Click Detail display .

Although up to three calibration curves can be stored for one component using the
calibration division function, in the record for calibration curve constants only the first curve
is displayed. By displaying a detailed result using the “Detail display” button, the constants
and graph of each calibration curve can be displayed and printed.
The record for calibration curve constants does not have a function to delete any saved
record.

k. Test Measurement
By creating measuring conditions freely, you can execute the fixed angle measurement,
2-theta scan and PHA scan.
Mode Description
Measurement is made at a fixed angle to check X-ray
Fixed Angle
intensities. This mode is used to adjust and check the
Measurement
spectrometer.
A qualitative analysis chart is generated using the 2-theta scan
measurement. This mode is used to determine whether there
2-theta Scan
are interfering spectral lines and to check peak and
background angles.
Energy distribution of X-rays that enter a detector is measured
at a fixed angle. This mode is used to check overlap of
PHA Scan
higher-order lines, escape peaks, fluorescent X-rays from a
crystal and the resolution of a detector.

2. Select [Test Measurement].
Measured element lines, measuring conditions, etc. are set from the common menu.

Operation Flow of Test Measurement
The measuring mode can be switched using the fixed angle measurement,
2-theta scan measurement and PHA scan measurement buttons.

The flowchart common to all modes is shown below. But the fixed angle measurement
does not have calculation processing.
Start
Select measuring mode
Select element line
Set measuring conditions
Measurement
Calculation processing
End?
No
Yes
End
In the fixed angle measurement, measurement is continued till you click Stop. In the
2-theta scan and PHA scan, measurement automatically stops after measuring a specified
range.

Select Measuring Mode
1. Click , or in the middle right part of the screen.
Select Measured Element Line
When a measured element and an element line are selected, the default measuring
conditions are set automatically.
1. Select [Meas. Cond]  [Spectrum...].

2. Select an element name at “Element name”.
3. Select a measured element line in the list on the right of the element name.
4. Click OK .
Measured element lines, measuring conditions, etc. can be set also using a pop-up menu
that appears when the mouse is right-clicked.
Measuring Conditions
The measuring conditions are classified into “Common conditions”, “Sample” and
conditions for each measuring mode. Those are described in the table below. For details,
see “4.3 QUANTITATIVE ANALYSIS TECHNIQUES”.
Division Description
Classified into the excitation condition, optical condition and PHA
Common
condition. The PHA condition cannot be set in the PHA scan mode.
The sample position in the sample changer is specified. In the case of a
Sample system equipped with the mapping function, the measuring position can
also be designated.
Conditions In the fixed angle measurement, the measuring time and full scale are set.
for Each In the 2-theta scan, the scan mode, start and end angles, etc. are set.
Mode In the PHA scan, the number of steps, start and end positions, etc. are set.

Change Excitation Condition
1. Select [Meas. Cond]  [Setting...].

3. Select a target at “Target”.
4. Select a filter at “Filter”.
5. Set a tube voltage value at “Tube voltage(kV)”.
6. Set a tube current value at “Tube current(mA)”.
7. Click OK .
The tube voltage can be set at intervals of 1kV. The tube current can be set at intervals of
1mA.
Some combinations of tube voltage and current values cannot be selected because of
restrictions by the X-ray tube maximum load or filament current.

Change Optical Condition

3. Select a diaphragm at “Diaphragm”.
4. Make setting for “Sealing”.
5. Select a slit at “Slit”.
6. Select <1/1> or <1/10> at “Attenuator”.
7. Select a crystal at “Crystal”.
8. Select a detector at “Detector”.
9. Enter a 2-theta angle at “2-theta”.
10.Click OK .
Because the 2-theta angle set here is only used to determine the full scale, it need not be
set.
The sealing can be set to <IN> only when the diaphragm is set to 30(28)mm and the
attenuator to <1/1>. It may be impossible to change the sealing, depending on the current
atmosphere.
In the case of the ZSX Primus, ZSX Primus II or ZSX Primus IV/IVi, <1/10> can be selected
for the attenuator only when the diaphragm is 30 mm.
In the case of the ZSX Primus III+, <IN> can be selected for the attenuator only when the
diaphragm is 30 or 20 mm.
Change PHA Condition


3. Enter a lower level at “PHA L.L.”

4. Enter an upper level at “PHA U.L.”
5. Click OK .
In the case of the PHA scan, the PHA condition cannot be set.
To perform an integral measurement, set zero for the upper limit.
Specify Measured Sample
Specify a sample placed in the sample changer. Because the specified sample is loaded
automatically but is not unloaded, do an unloading operation if necessary.
In the case of a system equipped with the mapping function, an arbitrary measuring
position on a sample can be specified.

2. Click the “Sample” tab.
3. Set the position where a sample is to be set.
4. Select <Yes> or <No> for “Sample spin”.
5. In the case of a system equipped with the mapping function, enter “r” and “Theta”
values at “Measuring position”.
6. Click OK .

Setting for Each Measuring Mode
Condition setting for each of the fixed angle measurement, 2-theta scan and PHA scan is
described below:
Set Fixed Angle Measurement Condition
For the fixed angle measurement, the goniometer angle and the measuring time at that
angle are necessary. Because the 2-theta angle is set in the optical condition on the
“Common condition” tab, the measuring time and full scale are set here.

2. Click the “Fixed angle measurement condition” tab.
3. Enter a measuring time at “Time”.
4. At “Full scale”, enter a value with which the highest intensity to be measured can be
displayed.
5. Click OK .

Set 2-theta Scan Condition
In the 2-theta scan mode, setting is made for the scan method, number of steps, scan
range, measuring time, number of repetitions, speed and smoothing. When the scan
method is the step scan, the measuring time is set. When the scan method is the
continuous scan, the speed is set.

2. Click the “2 theta scanning condition” tab.
3. Select <Step Scan> or <Continuous scan> for “Scan method”.
4. Select the number of steps for “Step”.
5. Enter a start angle for “Start”.
6. Enter an end angle for “End”.
7. When <Step Scan> was selected, enter a measuring time for “Time/step”.
8. When <Continuous scan> was selected, enter a speed at “Speed”.
9. Enter the number of repetitions for “Repeat”.
10.Set the number of smoothing points for “Smoothing”.
11.Click OK .

Set PHA Scan Condition (ZSX Primus, ZSX Primus II, ZSX Primus III+)
In the PHA scan mode, setting is made for the scan range, measuring time and number
of steps.

2. Click the “PHA Scanning condition” tab.
3. Enter a start pulse height value for “Start”.
4. Enter an end pulse height value for “End”.
5. Enter a measuring time for each step for “Time/step”.
6. Set a value of 1 to 10 for “Step”.
7. Click OK .

Display Format
Three functions of the data selection, scale change and graph setting are available as
auxiliary display functions for measured results.
Change Scale for Fixed Angle Measurement
1. Select [View]  [Scale...].

2. Set the maximum value.
3. Click OK .
The procedure described here is to change the scale after measurement. To change the
scale during measurement, use <Fixed angle measurement condition>.

Change Scale for 2-theta Scan

2. Enter the minimum value of the 2-theta angle.
3. Enter the maximum value of the 2-theta angle.
4. Enter the minimum value of the X-ray intensity.
5. Enter the maximum value of the X-ray intensity.
6. Click OK .
Change Scale for PHA Scan

2. Enter the minimum value of the PHA.
3. Enter the maximum value of the PHA.
4. Enter the minimum value of the X-ray intensity.
5. Enter the maximum value of the X-ray intensity.
6. Click OK .

Change Type of Graph
A bar graph or a plot graph can be used to display the data.

2. Select <Bar graph> or <Plot Graph> in the “Fixed angle condition” frame.
3. Click OK .
Change Colors

2. Select the display color for each detector in the “Color” frame.
3. Click OK .

Calculation Items
The angular resolution can be calculated in the 2-theta scan mode, and the energy
resolution in the PHA scan mode.
Calculate Angular Resolution
The angular resolution can be calculated from a qualitative analysis chart obtained from
a 2-theta scan. The angular resolution is assessed with a half width (FWHM) and a 10%
width.
1. Carry out a 2-theta scan.

3. Designate a range including an objective peak.
4. Select [Calculate]  [Calculate FWHM].
5. Change the upper limit and/or lower limit of the 2-theta angle, if necessary.
6. Click OK .

Calculate Energy Resolution
The energy resolution can be calculated from a differential curve obtained from a PHA
scan. The energy resolution is assessed for the half width (FWHM). The total intensity
in the specified range divided by the total intensity in the PHA scanning range is called
the transmittance.
1. Carry out a PHA scan.

3. Designate a range including an objective peak.
4. Select [Calculate]  [Resolution].
5. Change the upper limit and/or lower limit of the PHA range, if necessary.
6. Click OK .
Printing
In Test Measurement, printing is possible.
Print Data While Doing Fixed Angle Measurement
 1.Select the fixed angle measurement mode.

 2.Select [File] [Print] [Intensity Print].
After the above procedure, a check mark is added before [Intensity Print] to indicate
that data is printed during measurement.
By repeating the same procedure, the check mark is displayed or erased to indicate that
the condition is switched.

Print Result of Fixed Angle Measurement
 1.Select the fixed angle measurement mode.

 2.Select [File]  [Print].
Print Result of 2-theta Scan and PHA Scan Measurement
 1. Select 2-theta scan or PHA scan mode.

 2.Measure a sample.
 3. Select [File]  [Print]  [Chart Print…].
 4. Select <Printer> for “Output” and click OK .
It is possible to select <Bitmap> or <Metafile> for output. When the output is selected, set
File name and File output folder.

6.3 DATA SAVING AND LOADING

All data such as analysis results and application set up information can be saved in USB
memory or hard disk. Saved data is able to be restored and utilized again. Periodic data
saving is recommended to prepare for the hard disk trouble.
Data items to be saved are classified into six types of reusable conditions and results and
communication log information for maintenance.
Data Item Description of Saved Data

User Setting
Spectrometer parameters and various preset data are saved.
Data
Qual. Condition
Qualitative analysis applications are saved.
Analysis
Conditions Quant. Condition
Quantitative analysis applications including standard
samples are saved.
Qual. Data
Qualitative analysis chart data for the Qualitative Data
Handling program is saved.
Quant. Data
Besides quantitative analysis results, result data items
displayed using the Result Display program such as check
Analyzed analysis results, drift correction results and PHA
Results adjustment results are saved.
Mapping Data
Mapping data prepared using a mapping analysis, a micro
mapping analysis or the Result Display program is saved.
Saving is possible only when the system has the optional
sample observation mechanism.
The log (text file) of communications between the spectrometer

Communication
and this software is saved. This data item is for maintenance
Log
and cannot be loaded.
When User Setting Data, Analysis Conditions (Qual. Condition and Quant. Condition) are
saved at a time, the date and time of saving are automatically recorded on the check item
list.

Three startup procedures are available for the “Data Save Load” program.
It is possible to start the program from the data saving notification bar or menu bar
when ZSX Guidance is in operation or from the shortcut in the program list that the
Windows OS manages.
Usable functions are limited as follows depending on the startup procedure:
Startup Startup From

Startup From Startup From
Function Procedure Data Saving
Menu Bar Shortcut
& Operation Notification Bar
Data Saving
Data Loading
Execution When ZSX

Guidance Is in
Operation.
Logon Operation to Logon operation

Needless Needless
ZSX Guidance is required.
User Without Access

Authority for Data
Save Load
The user without access authority for the “Data Save Load” program is a user who belongs
to a group for which the User Administration program has not set access authority for the
“Data Save Load” program.
For the details of the access authority for a program, refer to <User Administration - Add
Group> in <6.1 h. System Management>.
Save Data from Data Saving Notification
Data saving (backup of analysis conditions etc.) must be carried out periodically. This
system has a function to indicate on the main screen of this software that data saving
has not been carried out for a specific period and carry out data saving from the main
screen.
When data saving notification is displayed, carry out data saving according to the
following procedure:
1. Click Data Save on the data saving notification bar.
For the procedure to change the time that has passed from the last data saving, see “6.1.
h. System Management”.

a. Data Saving
When saving data, select (a) data item(s) to be saved.

As a device for saving, you can designate a specific folder on the hard disk or the like. A
file capacity necessary for data saving varies depending on the data item(s) to be saved
and the operating condition of the instrument.
Device for Saving Description

Data is compressed and saved in a designated folder in a
memory such as the hard disk or a USB memory or on a
Specify a folder to
network.
save
Before saving data to a CD-R, the data must be saved to the
hard disk.
Described below is the procedure to carry out data saving when ZSX Guidance is in
operation:

2. Select [Data Save / Load].

Designate Device for Saving
1. Select <Save data>.

3. Select <Specify a folder to save>
5. Select a folder (directory) name for saving.
6. Click OK .
When <Specify a folder to save> was selected, be sure to designate a drive name or a
folder name.
To designate a new directory as a device for saving, click Make New Folder and enter a
new directory name.

8. Select (a) data item(s) to be saved.

10.Check the displayed contents to be saved and click OK .
Data saving starts.
11.When the saving is completed, click OK .
The displayed “Data size (Reference)” indicates the real size of the selected data. Thanks
to compression, the size of saved data is smaller than this value.
When <analysis condition to save> is indicated, select <all> and execute Dsave.

Save Data to CD-R/DVD-R
When saved data is saved to disk media such as CD-R/DVD-R, the data has to be saved
to a hard disk temporary.
The procedure to save data has been described before in the paragraph “Designate
Device for Saving”.
1. Save data to the hard disk.

2. Starting up CD/DVD writing software and store the data to a CD-R/DVD-R.
For a procedure for saving to a CD-R/DVD, see the instruction manual supplied with the
writing software.

b. Data Loading
To load data, ZSX Guidance must be terminated.
Described below is the procedure to start up the program from the shortcut in the
program list that the Windows OS manages:
1. Select [Data Save Load] under [Rigaku ZSX Guidance] from “All Programs”.
2. On the Logon screen, enter a user name and a password registered for ZSX
Guidance.
3. When an item for a language is displayed, select a language for display.
4. Click OK .
A user who belongs to a group for which the User Administration program has not set
access authority for the “Data Save Load” program cannot log on.
For the details of the access authority for a program, refer to <User Administration - Add
Group> in <6.1 h. System Management>.

The procedure to call the function called “All Programs” to display a list of programs varies
depending on the version of Windows. For the detailed procedure to call it, see <All
Programs> in “INSTRUCTION MANUAL OF WINDOWS FUNCTIONS”.
While this function of the data saving and loading program is in operation, the ZSX
Guidance cannot be started.
Designate Device for Loading
1. Select <Load data>.

3. Select <Specify a folder to load>.

5. Select a folder (directory) name for saving.
6. Click OK .
8. Select (a) data item(s) to be loaded.
10.Check the displayed contents to be loaded and click OK .
Data loading starts.
11.When the loading is completed, click OK .
When <Specify a folder to load> is selected, be sure to specify a drive name or a folder
name.

Specify CD-R/DVD-R as Device for Loading
Insert a CD-R/DVD-R in which data has been saved into the CD/DVD-R drive and
specify the CD/DVD-R drive as the device for loading in the procedure described below.
The procedure to load the saved data has been described before in the paragraph
“Designate Device for Loading”.
1. Select <Load data>.

3. Select <Specify a folder to load>.
4. Click Browse... .
5. Select the drive in which the CD-R/DVD-R has been inserted.
6. When the data has been saved in a folder in the CD-R/DVD-R, select that folder.
It is possible to load with the same steps as above in case of saving to USB.

Details of Saved Data
Data files to be saved when each data item is selected are as follows:
Data Item Saved Folders Saved Files Archive File

\Rigaku\SXIDV\UserData\usercom *.ho USERCOM.ZIP
\Rigaku\SXIDV\UserData\param *.ho PARAM.ZIP
\Rigaku\SXIDV\UserData\ezscan *.ho EZSCAN.ZIP
User Setting \Rigaku\SXIDV\UserData\template *.ho TEMPLATE.ZIP

Data \Rigaku\SXIDV\UserData\simcond *.ho SIMCOND.ZIP
\Rigaku\SXIDV\UserData\uvoice *.* UVOICE.ZIP
\Rigaku\SXIDV\SpecData *.ho SPECDATA.ZIP
\Rigaku\SXIDV\Work *.ho WORK.ZIP
QLAP_*.ho
Analysis QNAP_*.ho
Conditions STDS_*.ho
\Rigaku\SXIDV\UserData\anlcond ANLCOND.ZIP
USER_*.ho
\Rigaku\SXIDV\UserData\anlcondU ANLCONDU.ZIP
(Qual.) QLDT_*.ho
(Quant.) QLAS_*.ho
QLDS_*.ho
*.emf
QLDT_*.ho
SMDR_*.ho
Analyzed SMDR_*.bmp
Results
\Rigaku\SXIDV\UserData\AnlRslt QNDT_*.ho ANLRSLT.ZIP
(Qual. Data) \Rigaku\SXIDV\UserData\AnlRsltU SMDR_*.ho ANLRSLTU.ZIP
(Quant. Data) SMDR_*.bmp
(Mapping Data)
MPDT*.ho
MPDT*.bmp
Communication
Log (for \Rigaku\SXIDV\Log *.* LOG.ZIP
Maintenance)

6.4 CONVERSION OF SAMPLE ID

When the sample ID structure is changed, measurement result data must be converted
using the sample ID utility program.
To change the sample ID structure, ZSX Guidance must be terminated.
Before the conversion, save data referring to “6.3 DATA SAVING AND LOADING”.
Convert Sample ID
1. Open the “\Rigaku\SX\Tools” folder on Explorer and double-click “SMIDConv”.
Do not start another program in the “Rigaku” folder. If another program is started, data may
be destroyed.
2. Select [File]  [Convert Sample ID].

3. Select a folder in which measurement result data is stored on the “Select Folder”
screen and click OK .

When the folder for saving measurement results has not been changed, select the
“\Rigaku\SXIDV\UserData” folder.
4. Click OK on the confirmation screen.
5. Check the displayed conversion results and click OK .

6.5 SETTING FOR E-MAIL

The ZSX Guidance has a function to report analysis results and errors that have
occurred using e-mail.
For information required for settings, refer to the network administrator.
Set information required to send e-mail according to the procedure described below:
1. Start up the ZSX Guidance.

3. Select [System Management]  [Data Transfer Setting].
4. Click SMTP Info. on the “Data Transfer Setting” screen.
5. Enter the sender’s name at “User name”.
6. Enter the sender’s e-mail address at “E-mail address”.
7. Enter the name of the outgoing mail server to be used for sending e-mail at
“Outgoing mail server (SMTP)”.
8. At “Port number (SMTP)”, enter the port number of the outgoing mail server to be
used for sending e-mail.

When the e-mail server does not require authentication, setting has been completed now.
Save the information that has been set according to “Save E-Mail Setting”.
When the e-mail server requires authentication, follow the steps described below:
9. When the outgoing mail server requires authentication when sending e-mail, place a
check mark for “Outgoing server (SMTP) requires authentication”.
10.Select <Following account and password are used at log on mail server (SMTP).> or
<Log on to incoming mail server (POP3) before sending mail.> according to the
setting of the e-mail server.
 When <Following account and password are used at log on mail server (SMTP).>
is selected
11.Enter an account name necessary for authentication at “Account name (SMTP)”.

12. Enter a password necessary for authentication at “Password (SMTP)”.
 When <Log on to incoming mail server (POP3) before sending mail.> is selected
11.Enter the name of the incoming mail server at “Incoming mail server (POP3)”.
12.Enter the port number of the incoming mail server at “Port number (POP3)”.
13.Enter an account name to log on to the incoming mail server at “Account name
(POP3)”.
14.Enter a password to log on to the incoming mail server at “Password (POP3)”.
Save E-Mai Setting
When information has been set, save it according to the procedure described below:
1. Click OK on the “SMTP Information” screen.

2. Click OK .
3. Click OK after checking the contents of the alarm dialog.
4. Restart the ZSX Guidance to save the information.

6.6 TRANSMISSION AND TRANSMISSION FORMATS

Analyzed results, X-ray intensities and various analysis information items can be
transmitted to another communication device through an RS232C or TCP/IP line.
Described in this section are information necessary for RS232C or TCP/IP connection
and the formats of transmitted texts (transmission formats). The transmission format
can be used to output text files using <Disk save> and <E-mail> as well as using
<RS232C Transmission> or <TCP/IP Transmission>.
a. Data and Transmission Types
Transmitted texts are classified into various types according to their purposes. The data
type determines the combination of transmitted texts and the transmission type.
 Transmission Type
The transmission type is defined for a combination of texts or for similar information
items. The transmission formats are described later for each transmission type.
Transmission
Transmitted Data
Type
Quantitative analysis results, qualitative element information
1
and SQX analysis results
2 Drift correction coefficients, bias correction coefficients, etc.
3 Spectra, peak angles, X-ray intensities, etc.
Measuring conditions, 2-theta values of all measuring points and
4
X-ray intensities
The type is the code to classify data and is specified in the first transmitted text. The
receiver processes the succeeding texts according to this code.
Transmission
Type Data Result Type
Type
_1 1 Qualitative element information Qualitative
_2 1 Quantitative analysis results Quantitative
_3 1 SQX analysis results Qualitative
_4 3 Peak list Qualitative
_5 4 2-theta-intensity data Qualitative
_6 2 Drift correction results Coefficient update
_7 2 Bias correction results Coefficient update
_ : Space code

 Quantitative Analysis Results
These results are output after each quantitative analysis or using the Result Display
program.
Output Data
Transmission
Analysis Job Analyzed X-Ray
Type
Results Intensities
Quantitative Analysis 1 Output Output
Intensity Measurement 1 Not output Output
Check Analysis 1 Output Output
Drift Correction Analysis 1 Not output Output
Bias Correction Analysis 1 Output Output
Standard Sample 1 Not output Output
In the case of an analysis job that has analyzed results, X-ray intensities can also be
output. By selecting <Output intensities for result> on the “Text Structure Setting”
screen on the “Transmission” tab in the System Parameter program in System
Management, both data items can be output. For X-ray intensities to be output, selection
can be made from net intensities before drift correction, net intensities after drift
correction and intensities after internal standard/overlap correction.
 Drift Correction and Bias Correction Update Results
Transmis-
Analysis Job Output Data
sion Type
Drift Correction Sample 2 Drift correction update results
Bias Correction Sample 2 Bias correction update results
 Qualitative Analysis Results
These results are output using the Qualitative Data Handling program.
Transmis-
Analysis Job Output Data
sion Type
1 Qualitative element information
1 SQX analysis results
3 Peak list
4 2-theta-intensity

b. Transmission Specification
Interface Specification
RS232C
Type RS232C-compliant serial interface
Communication
Data transmission from this system (PC) to external terminal
Method
Communication Selectable from 300, 600, 1200, 2400, 4800, 9600, 19200 and
Speed 38400 BPS
Start bit 1
Data bits Selectable from <7> and <8>
Data Constitution
Stop bits Selectable from <1> and <2>
Parity bits Selectable from <None>, <Even> and <Odd>
Flow Control Selectable from <RS/CS>, <Xon/Xoff> and <None>
Code Type Selectable from <JIS> and <ASCII>
Transmission
<Link control> can be selected or deselected.
Protocol
Error Detection Selectable from <None> and <BCC>
Ethernet
Communication
IEEE802.3
Method
Transmission
TCP/IP
Protocol
Connection 10BASE-T

Connector and Signal Arrangement
This System Ext. Terminal

Signal (DTE 25 pins)
(DTE 9 pins) (DTE 9 pins)
Signal Name Pin No. Connection Pin No. Signal Name Pin No.
CD 1 (N.C.) 1 CD 8
RD(RXD) 2 2 RD(RXD) 3
SD(TXD) 3 3 SD(TXD) 2
ER(DTR) 4 4 ER(DTR) 20
SG 5 5 SG 7
DR(DSR) 6 6 DR(DSR) 6
RS(RTS) 7 7 RS(RTS) 4
CS(CTS) 8 8 CS(CTS) 5
CI 9 (N.C.) 9 CI 22
After the power is turned on, the ER (DTR) signal of this system is always turned on. When
the receiver is a computer terminal or a similar device, connect the DR signal (pin No.6) of
the receiver and the ER signal (pin No.4) of this system
When the link control is not used or in the case of the RS/CS control, the RD (RXD) signal
of this system and the SD (TXD) signal of the external terminal need not be connected.

Text Delay Time
A delay time from one text to the following text can be set in a range of 0 msec to 30 sec.
(30000 msec). This time is called the text delay time. This means the minimum interval
between texts when they are transmitted consecutively without the transmission
protocol. Set this delay time according to the processing speed of the receiver.
Transmission Protocol
When the transmission protocol is used, texts and control codes are transmitted as
shown below:
Example without Text 4 Example with Text 4
Data Processing External Data Processing External
System Terminal System Terminal
ENQ ENQ
ACK ACK
Text 1 Text 1
ACK ACK
Text 2 Text 2
ACK ACK
Text 3-a Text 3-a
ACK ACK
Text 3-b Text 4-1
NAK ACK
Text 3-b Text 4-2
ACK ACK
Text 5 Text 4-n
ACK ACK
EOT Text 3-b
ACK
Text 4-1
ENQ ACK
ACK Text 4-2
Text 1 ACK
ACK Text 4-m
Text 2 ACK
:
ACK :
:
Text 3-a : :
: : Text 5 ACK
:
EOT

Line Matrix
The rule to exchange control codes and texts when the transmission protocol is used is
shown below using a line matrix for the data processing system:
Response A B C D
Status ACK NAK Invalid Response Time-Out
W To X after Terminated To W after sending Same as
Waiting for sending text after sending retry ENQ. C-W
response after EOT To A-Y on retry over.
sending
calling ENQ
X To X after To X after To Z after sending Same as
Waiting for sending next resending. demanding ENQ C-X
response after text. To A-Y on
sending text To Y after retry over.
sending last
text.
Y Terminated To Y after To Z after sending Same as
Waiting for after resending. demanding ENQ C-Y
response after sending EOT To A-Y on
sending last retry over.
text
Z Same as Same as B-W To Z after sending Same as
Waiting for A-W retry ENQ. C-Z
response after To A-Y on retry over.
sending
demanding
ENQ

c. Structure of Transmitted Text
 Basic Format of Text
A text generally consists of the following three parts:
S E
Contents of Text
S : Text start code

E : Text end code
 Text Start Code and Text End Code
For the text start code and text end code, preset values in the transmission condition
are used in the case of the RS232C or TCP/IP transmission, while fixed values are used
in the case of the file output.
Code RS232C or TCP/IP Transmission File Output

Preset value in transmission condition in
Text Start Code system parameters None
Default : 0A (Hex)
Preset value in transmission condition in
Text End Code system parameters 0D0A (Hex)
Default : 0D (Hex)
Up to two bytes can be set for the text start code or text end code for the RS232C or TCP/IP
transmission.
 Kinds of Texts
Kind Contents Remark

Data type and number of Indicates the start of
Text 1
characters for code transmission.
The text length varies
Text 2 Sample ID
depending on setting.
Data or measuring condition of Varies depending on the
Text 3
analysis, correction or peak transmission type.
Statistical data of mapping or Varies depending on the
Text 4
Qualitative data transmission type.
Indicates the end of
Text 5 Fixed character string “00”
transmission.
Texts 1, 2 and 5 have common formats regardless of the transmission type.

 Order of Transmission of Texts
The order of transmission of texts varies depending on the transmission type. In the case
of transmission just after an analysis, the start text and end text can be omitted.
Start
Text 1 Start text
Varies depending on the

Texts 2, 3 and 4
transmission type.
Text 5 End text
End
To omit the start text and end text in the case of transmission just after an analysis, deselect
<Output start and end texts> in the transmission condition in System Parameters.

d. Texts Common to All Transmission Types
Texts 1, 2 and 5 have formats common to all transmission types. “_” (an underline) will
represent a space code hereafter.
 Text 1
Text 1 indicates the start of transmission. In the case of transmission just after an
analysis, Text 1 and Text 5 can be omitted by making appropriate setting using the
“System Parameters” program.
1 2 3 4 5 6 7 8
S 1 _ T T NN E
Type No. of Code Characters
 Type
The data type is represented by two characters. “_” represents a space code.
Type Data Result Type

_1 Qualitative element information Qualitative
_2 Quantitative analysis results Quantitative
_3 SQX analysis results Qualitative
_4 Peak list Qualitative
_5 2-theta-intensity data Qualitative
_6 Drift correction results Coefficient update
_7 Bias correction results Coefficient update
_8 Qualitative result data Qualitative
 No. of Code Characters

This means the number of characters for application names etc. <Sample ID> in
Text 2 includes <Application Name>.
<No. of Code Characters> can be checked in the following procedure:
1. Select [Utility]  [System Management]  [Sample ID Structure].

2. Click Setting of a line in which <Application> is displayed in the “Item” cell.
3. Check <Number of characters> on the “Analytical Code Setting” screen.
The text start code is represented by one character hereafter for convenience.

 Text 2
Text 2 identifies a sample.

1 2 3 4 19
S 2 _ zzzzzzzzzzzzzzzz IDIDIDIDIDIDIDID YYYY-MM-DD_hh:mm ee C E

Analysis type Sample ID Analysis date and time
No. of components
 Analysis Type
This item is edited when setting has been made in “Text to transmit” and “Select to
transmit” for the item <Type> on the “Sample ID Structure Setting” screen. Up to
16 characters can be transmitted.
This item is used for compatibility with old type analyzers.
 Sample ID
This consists of the following four items and setting for transmission is made for
each item. A space code is added between items to be transmitted. When the
number of characters of “Text to transmit” for each item is larger than “Number of
characters”, the length of the text is limited to “Number of characters”. When
“Number of characters” is larger than the number of characters of “Text to
transmit”, the rest is padded with space codes.
 Application
This item is edited when setting for transmission has been made in “Select to
transmit” for the item <Application> on the “Sample ID Structure Setting”
screen. Up to 16 characters can be transmitted and this number of characters
is used for <No. of Code Characters> in Text 1.
 Sample Name
This is edited from each of <Memo> and <Selections> on the “Sample ID
Structure Setting” screen when setting to output it has been made. A space
code is added between the items. Up to 40 characters can be transmitted for
each item.
 Measuring Coordinates
This item is edited when the system has the mapping measurement function
and setting for transmission has been made in “Select to transmit” for the
item <Mapping> on the “Sample ID Structure Setting” screen. The output
format is “-99.9,-99.9”.

 Sample Position
This item is edited when setting for transmission has been made in “Select to
transmit” for the item <Position> on the “Sample ID Structure Setting” screen.
Up to four characters can be transmitted. When “Number of characters” is 3,
the sample position becomes, for example, “A-8” in the case of the X-Y type
automatic sample changer and “_12” (squeezed to the right) in the case of the
continual type automatic sample changer.
In the case of drift correction update results and bias correction update results, <Sample
ID> are padded with spaces.
 Analysis Date and Time

This item is edited using the date and time format that was set using Text Structure
Setting… on the “Transmission” tab on the “System Parameters” screen. When the
contents of the date and time format are deleted, this item will not be edited.
“YYYY-MM-DD_hh:mm” is selected in the initial condition.
 No. of Components (ee or eee)

This item indicates the number of components that will be output using Text 3.
The output size of the number of components can be set to two or three bytes
(digits) using Text Structure Setting… on the “Transmission” tab on the “System
Parameters” screen. For example, when “2” is set for the output size and the
number of components is 100, “99” is output.
 Data Type (C)
For Statistical Values of Quantitative

C Data Type C
Mapping Data
Analyzed values, or analyzed
1
values and X-ray intensities
2 X-ray intensities
3 Peak list 3 Statistical results of analyzed values
4 2-theta-X-ray intensity 4 Statistical results of X-ray intensities
5 Drift correction update results
6 Bias correction update results
Care should be taken because character positions in a text are different from values that
were preset using “Sample ID Structure Setting”.

 Text 5
Text 5 indicates the end of transmission. In the case of transmission just after an
analysis, Text 1 and Text 5 can be omitted by making appropriate setting using the
“System Parameters” program.
1 2 3 4 5 6
S 5 _ 0 0 E
The fixed character string “00” is used for compatibility with old type analyzers.

e. Transmission Type 1
Described below are the formats and contents of texts for quantitative analysis results,
SQX analysis results and qualitative element information:
 Order to Transmit Texts
When mapping measurement has been made in a quantitative analysis, a different

constitution of texts is used to send statistical results of mapping data. The transmission
order in the case other than the quantitative mapping measurement is shown below.
Start
Start text
Text 1
Text 2 Sample ID
Component names (measured

Text 3 element line names) and analyzed
values (X-ray intensities)
N All components
completed?
Y
N All data types When both analyzed values and X-ray

completed? intensities are transmitted in
quantitative analysis results
Y
N All samples
completed?
Y
Text 5 End text
End

The transmission order in the case of the quantitative mapping measurement is shown
below.
Start
Text 1 Start text
Text 2 Sample ID
Component names (measured

Text 3 element line names) and analyzed
values (X-ray intensities)
N All components
completed?
Y
When both analyzed values and X-ray
N All data types intensities are transmitted in
completed? quantitative analysis results
Y
N All measuring
points completed?
Y
Text 2 Sample ID
Text 4 Statistical results
N All components
completed?
Y
N When both analyzed values and X-ray
All data types intensities are transmitted in
completed? quantitative analysis results
Y
Text 5 End text
End

 Setting of Lengths of Items
Text 3 in the transmission type 1 has two items with variable lengths and one item for
which the output size can be selected in a fixed range. For these items, representative
names of “Name of comp.”, “Unit” and “Result” are used on the program screen to set
their output sizes. The procedure to set the output size of each item is described below:
1. Select [Utility]  [System Management]  [System Parameters].

3. Click Text Structure Setting… in the “Communication control” frame.
4. Set the output size of each item in bytes.
 Comp. name (0 - 8 bytes)

This item corresponds to <Component name>, <Line name>, <Element symbol
and Space> or <Element symbol, Line name and Space> that follows the text
number “3” and a space for separation. The default value is eight bytes. The length
of this item affects the text length.
 Unit (0 - 8 bytes)
This item follows <Component name>, <Line name>, <Element symbol and
Space> or <Element symbol, Line name and Space>. The default value is eight
bytes. The length of this item affects the text length.
 Result (6 - 7 bytes)
This item is handled differently depending on the data type.
No. of
Data Item Name
Digits
Analyzed result or
Quantitative Analysis Result 6 or 7
X-ray intensity
SQX Analysis Result Analyzed result 6
Qualitative With SQX Analysis Result Analyzed result 7
Element
Information Without SQX Analysis Result X-ray intensity 7
Though selection can be made from 6 and 7 digits, the text length is not affected
because the length in the text is fixed to 7 digits. When the length is set to 6 bytes, the
first digit is padded with a space. This is a selectable function for compatibility with old
type analyzers.
Values are edited in the floating point format and squeezed to the right. However, only
quantitative analysis results conform to formats specified for each component under
<Digit> in the limit range condition.
Asterisks (**…*) are outputs for all digits for a large value that cannot be expressed.

 Text 3 for Quantitative Analysis Result
1 2 3 4 11 12 13 19 20 21 22 23 28 29 30
S 3 _ C C C C C C C C U U U U U U U U L _ 9 9 9 9 9 9 9 _ E
Component name or Unit Analyzed result
line name (0 - 8 characters) or X-ray intensity
(0 - 8 characters)
Judgment result
 Component name or line name

A component name is edited in the case of an analyzed result, and a measured
element line name in the case of an X-ray intensity.
 Unit
A specified unit is edited in the case of an analyzed result, and “kcps” in the case of
an X-ray intensity.
 Judgment result (L)

This item is edited only when the analysis job is Quantitative Analysis, Check
Analysis or Bias Correction Sample. One of the following characters is selected
according to a judgment result. A space code is padded in the case of the other
analysis jobs.
Character Judgment Result

_ (space) Passed
H Over upper limit
L Below lower limit
 Analyzed result or X-ray intensity

An edition range is fixed to seven digits. When the output size is six bytes, the first
character becomes a space code. In the case of an analyzed result, the number of
digits after a decimal point conforms to the format specified for each component
under <Digit> in the limit range condition. In the case of an X-ray intensity, the
floating point format is used.
If an error occurs after measuring X-ray intensities and before calculating
analyzed results, “Error” is output in place of a component name and “1” is output
for <No. of components> in Text 2.
The character positions shown above are examples and vary depending on the output
sizes. However, the preset numbers of characters are common to quantitative analysis
results, SQX analysis results and qualitative element information.

 Text 3 for SQX Analysis Result
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
S 3 _ C C C C C C C C U U U U U U U U 9 9 9 9 9 9 9 9 9 _ E
Component name Unit Comp. Analyzed result
(0 - 8 characters) (0 - 8 characters) No. (6 characters)
 Component No.
The contents of a component are expressed as follows:
Component Value Meaning

Element 1 - 100 Atomic No.
Compound No. +
Compound 101 - 400
100
Layer Thickness
0 Layer thickness
for Thin Film
 Analyzed result
The floating point format with six digits is used.

 Text 3 for Qualitative Element Information
The format varies depending on whether an SQX analysis result is included or not.
When SQX Analysis Result Is Included
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
S 3 _ E E - _ _ _ _ _ U U U U U U U U _ _ _ 9 9 9 9 9 9 9 E
Unit Analyzed result
(0 - 8 characters) (7 characters)
Element symbol
 Element Symbol
The symbol of a detected element is output.
The format shown above is an example in the case where the output size of <Comp.
name> is eight bytes. It includes the following six bytes of “- _ _ _ _ _”.
 Analyzed result
The floating point format with seven digits is used.
When SQX Analysis Result Is Not Included
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
S 3 _ E E - S S S _ _ k c p s _ _ _ _ _ _ _ 9 9 9 9 9 9 9 E
Line Unit X-ray intensity
name (0 - 8 characters) (7 characters)
Element symbol
 Line name (EE-SSS)

An identified measured element line is output in an element symbol and a line
name.
The format shown above is an example in the case where the output size of <Comp.
name> is eight bytes. It includes the following two bytes of “_ _”.
 X-ray intensity
The floating point format with seven digits is used.

 Text 4 for Quantitative Mapping Statistical Results
1 2 3 4 1 11 1 1 2 2 3 3 3 3 4 4
0 7 8 4 5 1 2 8 9 5 6
S 4 _ AAAAAAA HHHHHHH L L L L L L RRRRRRRS S S S S S SVVVVVVV E
L Standard Variation
Average Maximum Range deviation coefficient
Minimum
 Each statistical value

The output size of each item is fixed to seven digits. Like an analyzed result in Text
3, when the output size of <Analyzed result> is six bytes, the first character
becomes a space code.
 No. of digits after decimal point
Statistical Data for Statistical Calculation

Value Analyzed Value X-ray Intensity
Average Same as analyzed value Floating point format
Maximum Same as analyzed value No. of digits of average
Minimum Same as analyzed value No. of digits of average
Range Same as analyzed value No. of digits of average
Standard
No. of digits of average + 1 No. of digits of average + 1
Deviation
Variation
Fixed to 2 digits Fixed to 2 digits
Coefficient
The number of digits after a decimal point for an analyzed result conforms to the format
specified for each component under <Digit> in the limit range condition.

f. Transmission Type 2
Described below are the formats and contents of texts for drift correction coefficient
update results and bias correction coefficient update results:
The constitution of texts and the transmission order are shown below:
Start
Text 1 Start text
Text 2 Sample ID
Text 3 Update result of each component
N All components
completed?
Y
Text 5 End text
End

 Text 3 for Drift Correction

1 2 3 4 11 12 13 14 29 30 39 40 41 42 51
S 3 _ E E–S S S S S T M AAAAAAAAAAAAAAAA 9 9 9 9 .9 9 9 99 S L 9 9 9 9 .99 9 99

Line name
(Fixed to 8 Application name or the Coefficient  Coefficient 
characters) like
52 53 54 69 70 85 86 95 96 105
S L HHHHHHHHHHHHHHHH LLLLLLLLLLLLLLLL 9 9 9 9 .9 9 99 9 9 9 9 9 .99 9 99

“High” “High”
“High” side sample name “Low” side sample name sample sample
ref. int. meas. int.
106 115 116 125 126
9 9 9 9 .9 9 99 9 9 9 9 9 .99 9 99 E
“Low” “Low”
sample sample
ref. int. meas. int.
The character positions shown above are examples and vary depending on the number of
code characters. However, the text length is the same for the drift correction and bias
correction.
 1 digit code
Symbol Contents Character : Meaning (“_” : Space)

T Condition type 0 : Individual 1 : Common
M Drift correction method 0 :  method 1 :  method
Short-term judgment S : Short-term judgment
S _ : Normal
result error
Long-term judgment L : Long-term judgment
L _ : Normal
result error
“S” and “L” have the same meaning for both coefficient  and coefficient . Both short-term
and long-term judgment errors can occur simultaneously.
 Application name or the like

An application name is output in the case of the individual condition and a
common measuring condition name in the case of the common measuring
condition. <No. of code characters> in Text 1 is used for the number of characters.

 Coefficient  and Coefficient 

The format of “9999.99999” is used. When the drift correction method is the alpha
method, a coefficient  becomes space codes.
 “High” side sample name and “Low” side sample name

These items are edited using <No. of code characters> in Text 1. When the drift
correction method is the alpha method, a “Low” side sample name becomes space
codes.
 Reference intensity and measured intensity

The format of “9999.99999” is used for each of the “High” side sample and “Low”
side sample. When the drift correction method is the alpha method, the reference
intensity and measured intensity of a “Low” side sample become space codes.
 Text 3 for Bias Correction

1 2 3 4 11 12 13 14 29 30 39 40 41 42 51
S 3 _ CCCCCCCC _ M AAAAAAAAAAAAAAAA 9 9 9 9 .9 9 9 99 _ J 9 9 9 9 .99 9 99

Comp. name
(Fixed to 8 Limit range name Coefficient A Coefficient B
characters)
52 53 54 69 70 85 86 95 96 105
_ J HHHHHHHHHHHHHHHH LLLLLLLLLLLLLLLL 9 9 9 99 .9 99 9 9 9 9 99 .9 9 99
“High” “High”
“High” side sample name “Low” side sample name sample sample
std. value anal. value
106 115 116 125 126
9 9 9 99 .9 99 9 9 9 9 99 .9 9 99 E
“Low” “Low”
sample sample
std. value anal. value
The character positions shown above are examples and vary depending on the number of
code characters. However, the text length is the same for the drift correction and bias
correction.

 1 digit code
Symbol Contents Character : Meaning (“_” : Space)

M Bias correction method 0 : A method 1 : B method 2 : AB method
H : Over upper L : Below
J Tolerance check result _ : Normal
limit lower limit
“Over upper limit” means that a coefficient is larger than a standard value plus a
tolerance. “Below lower limit” means that a coefficient is smaller than a standard
value minus a tolerance.
“J” has the same meaning for both coefficient A and coefficient B.
 Limit range name

This item is edited using <No. of code characters> in Text 1.
 Coefficient A and Coefficient B

The format of “9999.99999” is used. When the bias correction method is the B
method, a coefficient A becomes space codes. When the bias correction method is
the A method, a coefficient B becomes space codes.
 “High” side sample name and “Low” side sample name

This item is edited using <No. of code characters> in Text 1. When the bias
correction method is the B method, a “High” side sample name becomes space
codes. When the bias correction method is the A method, a “Low” side sample name
becomes space codes.
 Standard value and analyzed value

The format of “9999.99999” is used for each of the “High” side sample and “Low”
side sample.
When the bias correction method is the B method, the standard value and
analyzed value of a “High” side sample become space codes.
When the bias correction method is the A method, the standard value and
analyzed value of a “Low” side sample become space codes.

g. Transmission Type 3
Described below are the formats and contents of texts for peak lists. Peak list data of
qualitative analysis results is transferred from the Qualitative Data Handling program.
Start
Text 1 Start text
Text 2 Sample ID
Text 3 Peak information (measured

element line names and intensity)
N All spectra
completed?
Y
Text 5 End text
End

 Text 3 for Peak List
1 2 3 4 9 10 18 19 27 28 44
S 3 _ S S - S S S PPPPPPPPP 9 9 9 9 9 9 9 9 9 EE-SSSSS-OOOOOOOO
Spectrum X-ray
name Peak angle intensity Line name 1
(6 char.)
45 61 62 78 79
EE-SSSSS-OOOOOOOO EE-SSSSS-OOOOOOOO E
Line name 2 Line name 3
“_” represents a space code.
 Peak angle/Energy/Wavelength
The types of the abscissa axis and formats are shown below:
Abscissa Axis Unit Format

2-theta 2-theta angle 99999.999
Energy keV 999.99999
Wavelength nm 99.999999
 X-ray intensity
The length is fixed to nine digits and the floating point format with up to four
digits after a decimal point is used.
 Line name (EE-SSSSS-OOOOOOOO)

The line name consists of the following items:
Symbol Item
EE Element symbol
SSSSS Line type
OOOOOOOO Order
Up to three line names can be output. When the number of line names is two or
less, vacant areas are padded with space codes. When the order is 1, the area after
“_” is padded with space codes.
Example : Rh-KB1_ _ -Compton_, Ni-KA_ _ _ _ _ _ _ _ _ _ _ _

h. Transmission Type 4
Described below are the formats and contents of texts for 2-theta-X-ray intensity data.
This data of qualitative analysis results is transferred from the Qualitative Data
Handling program.
Start
Text 1 Start text
Text 2 Sample ID
Text 3 Measuring condition
Text 4 2-theta-X-ray intensity
N All data items

completed?
Y
N All spectra
completed?
Y
Text 5 End text
End

 Text 3 for 2-Theta-X-Ray Intensity
1 2 3 4 11 12 13 14 19 20 23 24 27 28 31 32 40 41 46 47 51
S 3 _ EL-SSSSS E E KK-MMM F F F F MMMM A A A A CCCCCCCCC SSSSSS DDDDD

Meas.
Spectrum Ele- kV-mA Filter diam- Atten- Crystal Slit Detec-
name ment name eter uator name tor
name
52 59 60 67 68 76 77 85 86 92 93 101 102 106 107 108
999-9999 999-9999 S S S S S S S S S EEEEEEEEE TTTTTTT FFFFFFFFF DDDDD A E

Start angle End angle Full No. of
PHA 1 PHA 2 or the like or the like Step scale data
items
Measuring condition items for 2-theta-X-ray intensity data are output in the following
numbers of digits:
No. of
Item Name Remark
Digits
Spectrum Name 8 Symbol : EL-SSSSS
X-Ray Tube Target Element 2 Symbol : EE
2 digits for tube voltage and 3 digits for
kV-mA 6
tube current
Filter Name 4
Diaphragm Name 4 This means a measuring diameter.
Attenuator Name 4
Crystal Name 9
Slit Name 6
Detector Name 5
Preset Values of PHA 1 8
Used only in the case of PC+SC
Preset Values of PHA 2 8
measurement
Start The format varies depending on the
9
angle/energy/wavelength abscissa axis.
End The format varies depending on the
9
angle/energy/wavelength abscissa axis.
Step 7 “9.99999” format
Full Scale 9 “99999.999” format
No. of Data Items 5 “99999” format
“1”: 2-theta, “2”: Energy,“3”:
Type of Abscissa Axis 1
Wavelength

Type of Abscissa Axis Abscissa Axis Unit Format

“1” 2-theta 2-theta angle 99999.999
“2” Energy keV 999.99999
“3” Wavelength nm 99.999999
 Text 4 for 2-Theta-X-Ray Intensity
1 2 3 4 12 13 14 21 22
S 4 _ AAAAAAAAA _ 99999999 E
X-ray
2-theta intensity
“_” represents a space code.
 2-theta angle/energy/wavelength
The types of the abscissa axis and formats are shown below:
Abscissa Axis Unit Format

2-theta 2-theta angle 99999.999
Energy keV 999.99999
Wavelength nm 99.999999
 X-ray intensity
The length is fixed to eight digits and the floating point format with up to four
digits after a decimal point is used.

GLOSSARY
GLOSSARY
Absorption Edge
This is the minimum energy necessary to generate fluorescent X-rays by exciting an

element in a sample. The relationship between the absorption edge wavelength abs (nm)
and the minimum excitation voltage V0 (keV) is expressed by the following formula.
1.24
V0 
a b s
For example, to generate K series X-rays (such as K and K1) of Ti, energy higher than
the K absorption edge must be absorbed by a sample. In that case, voltage of about 5kV
must be applied.
Accuracy
This is the error between standard values and X-ray analysis values in the empirical
calibration method. This value is calculated as the root mean square of errors from a
calibration curve including errors caused by a sample. This is usually expressed as d.
(Ci  Wi) 2
d 
nm
Item Description
Ci Chemical analysis value
Wi X-ray analysis value
n Number of samples
m=2 for linear formula, m=3 for quadratic formula
m
The number of matrix correction coefficients is also added.
 Reproducibility
Aging
To turn on the X-rays after they have been turned off for a long time, the X-ray tube
voltage and current must be elevated slowly to the specified load step by step. Raising
the tube voltage and current slowly is called aging. A longer period when the X-rays have
been turned off requires a slower speed to raise the tube voltage and current.
The automatic aging function automatically raises the tube voltage and current at an
appropriate speed according to the period during which the X-rays have been turned off.

GLOSSARY
Analysis Type
The analysis type is a term used to indicate the type of preset analysis using this system.
Examples of the analysis type are qualitative analysis and quantitative analysis, as well
as items for the control analysis such as the drift correction and PHA adjustment.
Analyzing Crystal
The single crystals used for X-ray spectroscopy are called analysis crystals. In a
wavelength dispersive X-ray fluorescence spectrometer, the crystal is located between
the sample and the detector, and the crystal and the detector are moved according to
Bragg’s formula to measure fluorescent X-rays of a specific wavelength. Oriented LiF, Ge,
PET, TAP, etc. are used as crystals.
 Synthetic Multi-Layer
APC
This is an abbreviation for Automatic Pressure Control that is used to keep the vacuum
degree constant when the measuring atmosphere is set to the vacuum mode. Even in the
vacuum mode, the transmittance of X-rays varies depending on the vacuum level.
Therefore, the APC is generally used because a comparison with previous data is easier
if a constant vacuum degree is maintained.
In some cases, however, especially for samples with large surface areas such as activated
carbon and zeolites, measurement without the APC is more advantageous.
Apparent Concentration
An apparent concentration in a standard sample is defined when a matrix correction is

used in the empirical calibration method. This is usually expressed as Xi.
In the matrix correction method [Concentration correction] which is normally used, the
calculation formula for estimation of standard value in case that absorption term Aij and
overlapping term Bij are employed in to the matrix correction term is shown as below.
Wi  BijWj
Xi 
1  AijWj
Wi represents the concentration of component i. The apparent value is the apparent

concentration when it is assumed that no correcting components exist.
In the matrix correction method [Intensity correction], the calculation formula for
estimation of standard value in case that Bij is used as correction term is shown as
below.
Xi  Wi  BijWj
Absorption term Aij is used for correction of X-ray intensity.

GLOSSARY
Application
The application is a set of measuring conditions and calculation conditions that have
been preset and reserved for the qualitative and quantitative analyses. To perform
qualitative analysis, a qualitative application must be prepared. To run quantitative
analysis, a quantitative application must be prepared. All information for analyses is
stored in this application.
Application Package
In the quantitative analysis, an application package contains all the following parts of
the analysis: measured components, measuring conditions, standard sample
information and correction information necessary to prepare calibration curves.
Standard samples to prepare calibration curves are also included. By measuring
standard samples after necessary sample preparation, regression calculations are made
automatically and calibration curves are calculated. Quantitative analysis of unknowns
can then be started.
Application Template
Application templates exist within the software that allows the user to quickly create a
qualitative or quantitative application. Measuring conditions and calculation conditions
optimum to analyses have been registered beforehand. Therefore, one can create either
qualitative or quantitative applications by changing only a few necessary parts.
Attenuator
The attenuator is a mechanism to reduce X-ray intensities counted by the detector to

about 1/10. When counted X-ray intensities are too high, they are not proportional to
real X-ray intensities. This phenomenon is called counting loss. The upper limit of
intensities that do not cause counting loss is about 1000 kcps for the SC system and
about 2000 kcps for the PC system. When X-ray intensities are higher than this upper
limit, linearity between X-ray intensities and counting rates can be maintained by using
the attenuator.

GLOSSARY
Background Function
The following functions can be used for the background calculation. The linear,
quadratic or cubic formula is used to calculate continuous X-rays as background. To
calculate the background of a small peak on the foot of a large peak, the Lorentz or
hyperbolic function is generally used.
 Linear, Quadratic or Cubic Formula
I i  a1  a2  X i  a3  X i  a4  X i
2 3
 Lorentz Function
a1
Ii   a 4  a5  X i
 X i  a2 2  a3
 Hyperbolic Function
a1
Ii   a3  a 4  X i
X i  a2
Item Description
Ii X-ray intensity
Xi 2-theta angle
a1 - a5 Coefficients
Background Ratio Method
In this method, the intensity ratio of net intensity to background intensity is calculated
and used as the ordinate axis of a calibration curve. This is used, for example, to correct
effects in samples when analyzing trace heavy elements in samples that have light
elements as the main components. In the FP method, the background ratio method
cannot be set.
I n et
Ic 
I BG
Item Description
Ic X-ray intensity after correction
Inet Net X-ray intensity

GLOSSARY
Balance Component (Residual)
A component that is treated as the residual when calculating concentrations is the

balance component. The concentration of a balance component is 100 percent minus the
total of the concentrations of the other components.
Bias Correction
In the case of iron and steel samples, when the heat history in the preparation of
standard samples used to prepare a calibration curve is different from that of unknown
samples, a constant analysis error from the calibration curve may appear. The bias
correction fixes this error of analyzed values from the calibration curve. Usually,
samples with known analyzed values are measured after a calibration curve is prepared
and then the bias correction is set if necessary.
For the bias correction, one can correct only the intercept of a calibration curve or apply
a correction function to calculate correction values.
Binder
When a pellet sample prepared by pressing powder sample is breakable, powder and
binder (10% to 20% of sample weight) are mixed before pressing. Many kinds of binders
such as cellulose and boric acid are used.
Bragg’s Formula
Fluorescent X-rays generated from a sample reach the crystal or artificial multi-layer,
and reflect selectively when they satisfy the following formula.  represents the crystal
angle and the detector angle 2 is used for the abscissa axis on a qualitative analysis
chart.
n  2d sin 
Item Description
 Wavelength of diffracted X-rays
d Lattice spacing of crystal
 Crystal angle on diffraction
Order (1 represents the measured element line,
n
and 2 or larger represents the higher-order lines.)

GLOSSARY
Bulk Sample
A sample that can be regarded as infinitely thick for X-rays is called a bulk sample.
Thick samples such as metal disks and pressed powder samples are treated as bulk
samples. It is impossible to define generally the thickness that can be regarded as that of
bulk samples. Distinctly from bulk samples, finitely thick samples are called thin film
samples.
 Thin Film Sample
Calibration Curve Coefficients
Standard values are concentrations determined with another analysis technique or

known absolutely by some other method. The relationship between those standard
values and X-ray intensities is expressed as a calibration curve formula and analyzed
values of unknown samples are calculated from that formula. Coefficients used in the
calibration curve formula are called calibration curve coefficients.
Wi  AI 3  BI 2  CI  D
Item Description
Wi Analyzed value
A, B, C, D Calibration curve coefficients
I X-ray intensity
Check Analysis
A check analysis is run to determine whether prepared calibration curves are in normal
operation. A sample with known concentrations is analyzed and analyzed values are
calculated. The analyzed values are judged against upper and lower limits registered in
the limit range conditions and judged results are output together with the analyzed
results.
The same check sample can be measured three to five times (specified times) a day and
results can be recorded for X-R control. Output components can be selected in the limit
range condition.
Compound
A compound is a component such as silicon dioxide (SiO2) that consists of two or more
bonded elements. Besides oxides, lithium tetraborate (Li2B4O7) and many other
multi-element materials are also called compounds. In programs using the FP method
such as the SQX analysis, calculation methods such as metal conversion and oxide
conversion are available, and the constituting elements and the ratio of the numbers of
atoms in a compound are important. Standard oxides that are routinely used have been
set in the compound table.

GLOSSARY
Diaphragm
This is a mechanism to limit a measurement area for an analysis. Care must be taken to
make sure that a sample mask with a diameter larger than that of the preset diaphragm
is used. Otherwise, the sample mask will also be measured. Use a diaphragm suitable
for the diameter of a sample mask.
Differential Curve
An energy distribution curve of X-rays that enter the detector after being separated by
wavelength using the crystal is called a differential curve. This is also called a pulse
height distribution curve. This curve is measured to check electronic noises, interference
of higher-order rays and the resolution of a detector.
 PHA
Differential Measurement
Measurement using the upper and lower limits of the PHA is called the differential
measurement. The lower limit is set to eliminate electronic noises and the upper limit to
eliminate higher-order rays. A range between those upper and lower limits is called a
window.
 Integral Measurement
Drift Correction
Since measured X-ray intensities change with time, calibration curves shift (drift) as
they are used for long periods of time. The drift correction adjusts the intensities to
compensate for this shift. The drift correction is performed to continue to use prepared
calibration curves for a long period of time. The same operation is also necessary in the
FP quantification method. The following two methods, the alpha method and the
alpha-beta method, can be used.
 Alpha Method
This is also called the one-point method. Only one sample that has about half the
highest X-ray intensity in the calibration curve range is set.
 Alpha-Beta Method
This is also called the two-point method. Two samples that have a high intensity and a
low intensity in the calibration curve range are set. This method is used when a
concentration range is wide and when X-ray intensities that include background
intensities are used.

GLOSSARY
Excitation Condition
Optical conditions to generate primary X-rays from the X-ray tube and irradiate a
sample with the primary X-rays are called the excitation condition. The target element,
tube voltage, tube current and primary filter are included in the excitation condition.
EZ Analysis
This is an analysis program in which functions necessary for daily routine analyses have
been put together.
It is possible to reserve and make analyses and check analysis results easily on a graphic
screen.
EZ Scan
EZ Scan is an analysis type to carry out the SQX analysis. This is treated as a simplified
mode in the SQX analysis. Though some restrictions are imposed on measurement and
control, advanced SQX analyses can be carried out without preparing applications for
analyses.
Fixed Angle Analysis
Fixed angle analysis is designed to measure a spectral line of a component by fixing the
crystal position and detector position at the peak position and a background position and
by counting in each position for a fixed time.
Fixed Time Analysis
The function that performs a series of analyses automatically at a fixed time is called the
fixed time analysis. This can be applied to a periodical analysis such as the PHA
adjustment and drift correction. The Analysis program must have been started. Even
when a series of sample IDs is being analyzed in the Analysis program, IDs preset for
the fixed time analysis are analyzed preferentially after the analysis of the present ID is
complete.

GLOSSARY
Flow Bar
A guide like a wizard that appears when setting a qualitative application or a

quantitative application is called a flow bar. Both types of applications are created on a
dialog or screen that is started from this flow bar. You can skip an intermediate step and
go back to a previous screen.
Differences from the ordinary wizard are shown below.
Flow Bar Ordinary Wizard
You cannot see the number of the

You can see what step you are now in at a
residual screens or the total number of
glance.
steps.
Preset contents will not be lost even if

Preset contents are not saved till “OK” is
you stop the process halfway.
clicked on the last screen.
Preset contents can be saved any time.
Flux
In the heavy element dilution and in the preparation of a glass fusion bead, material
mixed with sample in a constant proportion is called flux. For example, lithium
tetraborate (Li2B4O7) or sodium tetraborate (Na2B4O7) is generally used in the
preparation of a glass fusion bead.
FP Quantification Method
The quantification method using the fundamental parameter method is called the FP
quantification method. It is assumed that elements are distributed uniformly for X-rays
in a sample in the case of a bulk sample or in each layer in the case of a thin film sample
(homogeneous). On this assumption, fluorescent X-ray intensities can be expressed as a
function of physical constants (fundamental parameters) such as the concentrations of
components, mass absorption coefficients, fluorescence yields and spectrum of the X-ray
source. A correlation between theoretical fluorescent X-ray intensities calculated using
this FP method and measured X-ray intensities is expressed with a sensitivity
calibration curve. The FP quantification method is an analysis method to calculate
quantitative values using this sensitivity calibration curve.

GLOSSARY
Full Range Qualitative Analysis
Measurement to scan a wide range of the 2-theta angle with a combination of a crystal
and a detector is called the full range qualitative analysis. For example, “Heavy” is a full
range qualitative analysis to measure a range of 5 to 90 degrees with the LiF-SC optical
system. This full range qualitative analysis can check the existence of components from
Ti to U and the measured element lines of two or more components can be used for the
SQX calculation. On the other hand, the qualitative analysis method for the light
element region is called the partial qualitative analysis. This means measurement to
scan a partial 2-theta range with a combination of a crystal and a detector.
Function Peak Deconvolution
To separate overlapping peaks using a function, the following function is used for
approximation. Up to four peaks can be separated. The peak deconvolution function is a
combination of Gaussian and Lorentzian factors.
I i  h  r  fg  1  r   fl   a  i 2  b  i  c
 ln 2i u 2
fg  e W2
1
fl 
(i  u ) 2
1
W2
Item Description
fg Gauss function
fl Lorentz function
 Fitting intensity (intensity of channel i)
h Peak intensity
Proportion of Gauss function to total
r
(0.0 -1.0)
u Data channel No. of peak
i Data channel No.
w Half width at half maximum of peak
a, b, c Coefficients
 Standard Profile Peak Deconvolution

GLOSSARY
Glass Fusion Bead
Samples of oxide powders are fused using a high-frequency furnace or an electric

furnace with flux such as lithium tetraborate (Li2B4O7) and formed into a glass disks.
Such a sample is free of characteristics of powder samples such as grain size effects and
mineral effects and can be analyzed more accurately. The ratio of flux mass to sample
mass is called a dilution ratio. For example, when 2g of sample and 10g of flux are mixed,
the dilution ratio is 5.
Glass Fusion Bead Correction
This software has optional correction functions for a dilution ratio and a loss on ignition
in a glass fusion bead analysis using the empirical method. These matrix correction
coefficients are calculated using the theoretical matrix correction coefficient calculation.
In the matrix correction method [Concentration correction] which is normally used,
following calibration equation is used.
Wi  ( BIi 2  CIi  D )( 1  Ki  AijWj  AiLOIWLOI  AFRF  AORO )
Term Description Term Description

Correction coefficient for
Aij
correcting component
Wi Quantification value
Correction coefficient for LOI
ALOI
(GOI)
Correction coefficient for
Ii X-ray intensity AF
dilution ratio
Constant for dilution Correction coefficient for
Ki AO
ratio/oxidizer correction oxidizer
Calibration curve
B,C,D RF Dilution ratio
coefficients
RO Oxidizer addition ratio
When a loss on ignition component is set as a balance component (residual) in the loss on
ignition correction, a correction term for the loss on ignition component is not included,
and information on the concentration of the loss on ignition component is unnecessary.
The loss on ignition component of a glass fusion bead is named “Ig” when used in this
software. The dilution ratio is flux weight divided by sample weight, and the oxidizer
addition ratio is the residual weight of oxidizer divided by sample weight.
When the evaporation correction is made for flux, the value of (Bead Weight/Sample
Weight - 1) is used as the dilution ratio.
Besides, the meaning of correction of matrix correction method of [Intensity correction]

is same. Refer to the matrix correction in the glossary.

GLOSSARY
Grain Size Effect
The X-ray fluorescence analysis is a method that analyzes sample surfaces 1 to several
micrometers deep. Therefore, in the case of powder samples, X-ray intensities may vary
depending on grain sizes and their non-uniformity. That phenomenon is called the grain
size effect. In such a case, the effect can be reduced using glass fusion beads or
pulverization.
 Mineralogical Effect
Gross Intensity
An intensity before subtracting a background is called a gross intensity.
 Net Intensity
Higher-Order Line
All fluorescent X-rays that satisfy the Bragg’s formula at a certain angle enter the
detector. When the analyzed line has a certain wavelength , a line having the
wavelength ’ that satisfies =n’ (n>1) also enters the detector and is counted. The
X-rays with that wavelength ’ are called a higher-order line of the wavelength . The
wavelength  with n=1 is called the primary line. For example, when Pb-L1 is analyzed
and a sample contains Sn, Sn-K1 appears as a secondary line.
Since the wavelength is inversely proportional to the energy, when equals 2’, E’
equals 2E in the term of energy. So a higher-order line can be separated using the
difference of detected energy.
Higher-Order Line of Pb-L1
Spectral Line Order Wavelength (nm) Energy (10-15J)

Pb-L1 1 0.09828 2.02195
Sn-K1 2 0.04906 4.04871
 PHA

GLOSSARY
Identification Analysis
One of the data processing features in the qualitative analysis is the automatic
identification analysis of detected peaks. A marker is attached to each peak detected in
the peak search. For example, Fe-K andSi-K are used as markers.
Impurity Correction
This is a correction method used in the SQX analysis. The impurity correction can be
used, for example, to correct for impurities in the flux of a glass fusion bead and impurity
lines from the X-ray tube. Selection can be made from concentration correction and
intensity correction. To correct impurity lines from the X-ray tube, it is generally
recommended that concentration correction be used because the intensities of impurity
lines vary depending on the matrix of a sample.
Integral Measurement
The integral measurement uses only the lower limit of the PHA with no upper limit.
This method eliminates electronic noise. However, care must be taken because all
higher-order lines are counted. To select the integral measurement, designate 0 (zero)
for the upper limit. This method can be used when main components with very high
intensities are measured and there is no effect of higher-order lines. In that case, stable
measurement is possible with almost no counting loss or variation in intensities caused
by changes in pulse heights.
 Differential Measurement
Intensity Integration Measurement
In the ordinary quantitative analysis, an analysis element is measured with the

fixed-time counting method, in which measurement is made at a peak angle (and at a
background angle if necessary) for a specified time. In the intensity integration
measurement, a step scan is carried out over a specified angle range like the qualitative
analysis and the average of the intensities at each angle is used for analysis.
Background subtraction can be selected in this method. This method is effective in
special cases such as when the peak of an analysis line shifts depending on the
combination form of its element in a sample or when a peak width changes.

GLOSSARY
The internal standard correction is a type of matrix correction where the intensity ratio
of an analysis spectral line to an internal standard spectral line is calculated. A certain
amount of a standard substance that can generate a peak near the peak of an analyzed
component is added. That standard substance is called the internal standard substance.
Since both peaks are affected by coexisting elements in similar ways, the matrix effects
can be corrected.
In some cases, the scattered rays of the characteristic X-rays of the X-ray tube or a
background intensity near the analyzed line are used as an internal standard spectral
line. This method is called the scattered rays internal standard.
The internal standard correction cannot be set in the case of the FP method.
Ii
Iic 
Ij
Item Description
Iic X-ray intensity after correction
Ii X-ray intensity before correction
Ij X-ray intensity of internal standard
Loss on Ignition
This means a decrease in sample weight due to the evaporation of H2O and CO2 during
fusion when analyzing a powder sample containing water of crystallization or carbonate
using the glass fusion bead method. It is also called the LOI. This software has an
optional function to correct this loss on ignition in the quantitative analysis using the
glass fusion bead method. There is another method in which a powder sample is ignited
before an analysis using the powder method. On the other hand, Fe3O4 in a sample may
oxidize to Fe2O3 in the glass fusion bead method. This phenomenon is called a gain on
ignition (GOI).
Manual Input Data
Data entered from the keyboard on sample ID setting instead of measuring X-ray
intensities to calculate analyzed values are called the manual input data. Data is
entered for a component for which “Input” has been set for “Analysis” on the
“Component Selection” screen in the application information. Since this data is entered
on individual sample ID setting unlike fixed value setting, a value obtained with
another analysis method can be entered for a specific component in an unknown sample.

GLOSSARY
Matrix Correction
The calculation to correct the effects of coexisting elements in the empirical calibration
method is called the matrix correction.
Matrix correction method is selectable from [Concentration correction] and [Intensity
correction].
In case of [Concentration correction] which is normally used, the matrix correction
equation is expressed as general formula below and used for the calculation.
RijFj
1  Wi / 100

Aij, aij
Quantified coefficient
Wi
value Absorption/enhancement correction
Qij, qij
coefficient
Calibration
Analyzed values or X-ray intensities of
A, B, C, D curve Fj, Fk
coexisting elements j and k
coefficients
be used for either concentration correction or intensity correction. When expressed in
uppercase characters, concentration corrections are used. When expressed in lowercase
characters, intensity corrections are used.
or bij term for overlap correction.
In case of [Intensity correction], the matrix correction equation including overlapping

correction is expressed as general formula below and used for the calculation.
RijFj
1  Wi / 100

GLOSSARY
The meaning of each correction term is same as [Concentration correction]. Basic

calibration formula when [Intensity correction] is selected is Wi = CIi+D of which
intercept D is cared differently. Calibration graph is plotted with the intensity after
matrix correction. Besides, [Intensity and BG correction] is selectable as a special
correction method for fusion bead case. This method becomes available when the
optional fusion bead correction is included in the order. Intercept D of calibration curve
of [Intensity correction method] is changed to D (1+RF) and intercept D is corr3ected
with dilution rate RF. Correction with residual oxidant/sample weight ratio is also
added when the oxidant correction is made.
 Theoretical Matrix Correction Coefficients
Measurement Atmosphere
In the X-ray fluorescence analysis, measurement is generally made in the vacuum

condition. This is important to reduce the absorption of fluorescent X-rays generated
from a sample by elements in the X-ray path (atmosphere). Although X-rays of heavy
elements with short wavelengths are not affected so much, X-rays of lighter elements,
especially very light elements, are affected dramatically. However, in the case of liquid
sample that cannot be run in the vacuum condition, measurement is usually made in the
helium or air condition.
Mineralogical Effect
The phenomenon that X-ray intensities vary depending on the differences of the
configuration of analyzed components and the kind of a mineral crystal is called the
mineral effect. In general, this is often seen in powder or block samples of rock and
mineral. This effect can be reduced by using glass fusion beads or by pulverizing
samples.
 Grain Size Effect
Net Intensity
In general, an intensity after background subtraction is called a net intensity. In this

system, the intensity after background subtraction and drift correction is called a net
intensity. An intensity after background subtraction in the qualitative analysis is also
called a net intensity.
→ Gross Intensity

GLOSSARY
Overlap Correction
This is the correction for the overlap of interfering rays with analysis rays. Correction
can be made for net intensities after the drift correction using up to three peaks. Since
this correction employs X-ray intensities, this can be used for both the empirical
calibration method and the FP method.
Oxidizer
This is an additive to oxidize a sample when a glass fusion bead is made from sulfide,
carbide or a metal sample. NaNO3, LiNO3, etc. are used as oxidizer.
→ Glass Fusion Bead
PC
This is an abbreviation of Proportional Counter, which is a detector for light elements.

This is generally used to count X-rays with wavelengths longer than 0.3nm. Since this
detector is used with P-10 gas flowing, it is called the flow-type PC or F-PC. A sealed
type proportional counter, which has detector gas sealed in the detector, can also be
mounted and is called the S-PC. The expression PC is used throughout this instruction
manual.
 SC
PC Wire Cleaning
The PC uses the P-10 gas as its detector gas. The P-10 gas consists of Ar gas and
methane gas mixed in a proportion of 9 to 1. When one X-ray quantum enters the
detector, Ar gas is ionized to emit electrons that ionize other Ar atoms in an avalanche
process. A large number of electrons reach the center wire and one pulse is counted. In
such a case, the methane gas, which is added to prevent subsequent discharges, absorbs
electrons, ionizes and sticks to the center wire. Since the methane gas that sticks to the
wire is not conductive, electrons cannot transfer appropriately, resulting in bad energy
resolution. PC wire cleaning is executed to restore the original condition.

GLOSSARY
Peak Deconvolution
Adjacent spectral lines in 2-theta scan data are separated into individual spectral lines.
Peak deconvolution has the following two methods.
 Function Deconvolution
Overlapping peaks are separated by fitting those using functions. The waveform of each
peak is calculated as a combination function of the Gauss function and the Lorentz
function.
 Standard Profile Deconvolution
Overlapping peaks are separated using peak profiles that were measured and extracted
beforehand. More accurate separation can be carried out using the standard profile
deconvolution.
 Function Deconvolution, Standard Profile Deconvolution
Peak Search
This is one of the qualitative data processing items. Peak search detects a peak from a
qualitative analysis chart. Using several points on the right and left of each measured
data point, the position where a parabola can replace those points is found. The program
takes statistical fluctuations of X-rays into consideration when setting requirements for
locating a peak.
Threshold  3  k    3  k  I BG
Item Description
k Peak detection sensitivity constant (k=0.3-2.0)
Due to statistical fluctuations of X-rays, the following phenomena may occur.
 A small peak is not detected as a peak.

 A peak near the detection condition is detected as a peak in some cases and is not in
others.
 A fluctuation of background is detected as a peak.
By increasing the measuring time to suppress statistical fluctuations, the detection

sensitivity for peaks can be improved. The same effect can also be obtained by setting a
larger peak detection sensitivity constant.

GLOSSARY
PHA
A unit that discriminates pulse heights according to the energy of X-rays that enter the
detector is called the PHA (Pulse Height Analyzer). The pulse heights of electronic
signals vary depending on incident energy. The PHA selects only signals in an objective
range using differences in pulse height. Pulse height is expressed by a scale with
arbitrary units and an adjustment is made so that the maximum of measured X-ray
pulses will be at 200. X-ray signals captured by the detector consist of the following.
Signal Component Description
Electronic noises Electronic noises
X-ray pulses with the wavelength that satisfies the Bragg’s

Measured X-ray pulses formula with n=1. These pulses are generally adjusted at
scale 200.
X-ray pulses with wavelengths that satisfy the Bragg’s

Higher-order pulses
formula with n1.
This is observed as an energy loss peak, for example, when
Signal pulses of escape
Ar, which is a component in detector gas used for the PC, is
peaks
excited by incident X-rays.
Signal pulses of For example, pulses generated when the Tl-M line of the
fluorescent X-rays from crystal TAP used is excited and enters the detector when
crystal the Na-K line is measured.
 PHA Scan
Measurement of the energy distribution of incident X-rays with a fixed detector angle is
called the PHA scan. The energy distribution is expressed with a pulse height
distribution curve. This scan is used to check electronic noises and the interference of
higher-order lines. It is also used to check the energy resolution of a detector.
 PHA Adjustment
The PHA adjustment is carried out to set the pulse height of a measured element line to
200. The PHA adjustment can be made automatically using PHA adjustment samples.

GLOSSARY
Preparatory Evacuation
In the case where measurement is to be made in vacuum, if a sample is transported

to/from the analysis chamber directly, the vacuum level is disturbed when the sample
enters or goes out of the chamber. In the case of a sample with a large surface area, it
takes a very long time until the vacuum degree necessary for measurement is restored,
resulting in a long measuring time. The ZSX Guidance has an evacuation chamber
dedicated to loading a sample and evacuates it before moving the sample to the sample
chamber. That function is called the preparatory evacuation. Since evacuation is done
until an appropriate vacuum degree is attained in the evacuation chamber, transfer of
the sample into the analysis chamber is performed in the vacuum condition and rapid
analyses can be made.
P-10 Gas
Gas for the detector that is always flowing through the PC is called the P-10 gas. In
general, P-10 gas, which is the mixed gas of Ar 90% and methane 10%, is employed.
Primary Filter
This is located between the X-ray tube and the sample and is used to reduce the
interference of continuous X-rays or characteristic X-rays generated from the X-ray tube
on the analysis X-rays. This is also used to lower background. When the primary filter is
used, X-ray intensities lower relatively. However, since lower background results in
smaller calibration curve coefficients, analyses can be made with higher precision.
Detection limits are also improved. The kinds and purposes of the main filters are shown
below.
Filter Description
Absorbs the Rh K-line.
Ni400
Effective for analyses using the K-lines of Ru, Rh, Pd, Ag, Cd, etc.
Ni40 Effective for trace analyses using the Pb L-line and As K-line.
Al125 Effective for trace analyses of Ti, Cr and Fe.
Absorbs the Rh L-line.

Al25
Effective for analyses of Cd-L etc. in thin samples such as films.
Used to avoid damaging the spectrometer by dropping sample on

a part such as the X-ray tube window during analyses of liquid or
Be30
powder. This can also be used to reduce a rise in the temperature
of a sample caused by radiant heat from the X-ray tube.

GLOSSARY
Qualitative analysis is used to determine the kinds of unknown components in a sample.

The full range qualitative analysis and the partial qualitative analysis can be used in
the qualitative analysis.
 Full Range Qualitative Analysis
Qualitative analysis to determine whether elements in a range from F to U exist in a

sample is called the full range qualitative analysis. In the case of a system with a special
configuration, the full range qualitative analysis for a range from Be to U is also
possible.
 Partial Qualitative Analysis
The qualitative analysis to see whether a specific element exists in a sample is called the
partial qualitative analysis.
 Quantitative Analysis
Quant Scattering FP Method
This method makes it possible to perform the FP quantitative analysis by internal

standard method adopting scattered X-rays and also to calculate theoretical coefficients of
matrix correction when the calibration curve is prepared with the ratio of fluorescent
X-rays and scattered X-rays as internal standard line.
Also, this FP program has further features such as the automatic subtraction function of
background intensities, which are theoretically calculated without measuring the unknown
sample actually.
 Scattered Rays
Quantitative Analysis
The analysis to determine the quantity of a known component is called the quantitative
analysis. The standard sample comparison method with the empirical calibration
method or the FP quantification method is used for analyses. In general, a qualitative
analysis is made first to know components that comprise a sample and then a
quantitative analysis is made.
 Qualitative Analysis

GLOSSARY
Reproducibility
The standard deviation of analyzed values obtained by measuring the same sample
many times is called the repeatability. This value is used to know the so-called stability
of the spectrometer. The standard deviation of X-ray intensities is generally calculated
with the following formula.
( Ii  I M ) 2
 
n 1
Item Description
Ii Each measured X-ray intensity (kcps)
IM Average X-ray intensity (kcps)
n Number of repetitions
The theoretical standard deviation of X-ray intensities is calculated with the following
formula.
IM
 cal 
t  1000
t : Measuring time (sec.)
Resolution
The following two kinds of resolution are defined in the X-ray fluorescence analysis.
 Energy Resolution
The energy resolution shows the performance of a detector and is expressed as the
percentage of the half-value width of a differential curve to the peak position. The
half-value width is an energy width where the intensity is half of the peak.
 Angular Resolution
This term is used to describe the performance of an optical system and is the angle width
of a peak on a qualitative analysis chart. This is assessed with the half-value width or
the 10% width. The 10% width is an angular width where the intensity is 10% of the
peak.

GLOSSARY
Sample Film Correction
The sample film correction adjusts for the absorption of X-rays by the film when making
a measurement using a polypropylene film (P.P. Film) or a polyester film (P.E. Film) for
analyses of a liquid sample or the like in the SQX analysis. Though a film designated by
Rigaku must be used, a library need not be registered beforehand using a sample with
the film.
Sample ID
Information that identifies each sample is called the sample ID. Identification
information such as the type of an analysis, an application name and a sample name,
and information about processing after an analysis such as result output are set on an
analysis. After an analysis is completed, a sample ID is used to retrieve an analyzed
result.
Sample ID Table
A series of specific analyses on certain samples can be set into a sample ID table. This
can be loaded as an individual analysis and designated for the program operation or
cycle repeat analysis. One can save time and trouble by registering a series of sample
IDs used frequently and routinely such as ones for the PHA adjustment and check
analysis.
Sample Model
Sample models must be set to calculate concentrations with an FP program such as the
SQX analysis. Those models are classified into the metal and the oxide.
 Metal
Concentrations are calculated assuming that each component in a sample exists as a

single element. For metal samples such as iron, steel and a copper alloy, select this
model.
 Oxide
This choice is used for samples in which each element exists as a compound such as an
oxide. In the case of powder sample such as glass, concentrations are generally
calculated assuming that each component exists as an oxide. Standard oxides to be used
have been registered beforehand in the compound table.

GLOSSARY
Sample Spin
To rotate a sample during measurement is called the sample spin. When a sample
surface has directivity (in the case where a metal sample was ground using a belt or in a
similar case), measured intensities may vary depending on the sample direction if the
sample is not spun. By rotating a sample during measurement, directivity can be
canceled and analysis precision can be improved. In the case of liquid samples, however,
measurement is generally made without the sample spin.
SC
This is an abbreviation of Scintillation Counter, which is a detector for heavy elements.

This is used to measure X-rays with high energy to a wavelength range of about 0.3nm.
 PC
Scattered Rays
Primary X-rays generated from the X-ray tube contain the characteristic rays of the
X-ray tube target element and continuous X-rays. Those X-rays are reflected and
scattered by a sample and become the scattered rays. There are two types of scattered
rays: Thomson scattered rays, which maintain the same energy, and Compton scattered
rays, which are observed with some loss of energy. Since these scattered rays contain
information about a sample, they can be used for analyses using the FP method. To
analyze the two types of scattered rays generated from the X-ray target used is the first
step of the identification analysis. Most of the background of fluorescent X-rays can
generally be regarded as scattered rays of continuous X-rays from the X-ray tube.
Sealing
In the analyses of liquid samples, the measuring chamber is filled with helium so as to
reduce the absorption of X-rays by the atmosphere. A seal with a thin film is placed
between the spectroscopic chamber and the sample chamber to separate the two
chambers in this spectrometer. By using the seal, it is possible to set only the sample
chamber in the helium atmosphere keeping the spectroscopic chamber in a vacuum. And
this method can reduce the consumption of helium gas.

GLOSSARY
Secure
The spectrometer ordinarily evacuates the analysis chamber before measurement.

When measurement is completed and the system is shut down and turned off, the
vacuum pump is also stopped. At that time, shutting down the system with the analysis
chamber in the depressurized condition is called “secure”. Since crystals in the analysis
chamber may deliquesce when exposed to air and it takes a long time until the system is
stabilized after evacuation is started if the analysis chamber has been open to the
atmosphere, the system should be shut down in the secure condition. Since the pump is
stopped, the depressurized condition cannot be kept for a long period of time. Therefore,
one should start up the system at least once a week for evacuation.
When the system is to be stopped for a very long period of time, open the spectrometer to
the atmosphere and remove the crystals and keep them in a desiccator or the like.
Finally, disconnect the piping connector and turn off the P-10 gas.
Sensitivity Library
The relationship between X-ray intensities obtained by measuring library samples such
as pure metals and reagents and theoretical X-ray intensities calculated with the FP
method is called the spectrometer sensitivity. A collection of sensitivity values is called
the sensitivity library. A collection of sensitivity values obtained by measuring
representative elements using library samples without using standard samples for each
kind of samples is called the common library. It is also possible to analyze elements that
have not been registered in the library by estimating the sensitivity values of those
elements using the sensitivity values of elements before and after those elements in the
periodic table. Even when conditions for the diaphragm and the attenuator are different,
correction is made automatically. The sensitivity library can be used for both qualitative
and quantitative analyses.
Sensitivity Library Division
A sensitivity library is a collection of sensitivity values obtained from data of a small

number of elements. Even for elements that are not registered in the library, analyzed
values can be calculated by estimating the sensitivity values of those elements using the
measured sensitivity values of elements before and after those elements in the periodic
table. Libraries are classified into several divisions so that they can be used for all
components by changing the crystal and excitation condition. A range obtained with the
same crystal and excitation condition where the sensitivity changes continuously is
called a library division.
Sensitivity Library Sample
A sample measured to create a sensitivity library is called a sensitivity library sample.

Standard substances such as pure metals and reagents are used for the common library,
while standard samples for each kind such as stainless steel and copper alloys are used
for the matching library.

GLOSSARY
Slit
The slit is a mechanism to make the fluorescent X-rays generated from a sample parallel.
By changing the type of slit, the angular resolution for spectral lines can be changed.
When spectral lines overlap, interference can be lessened by using a slit with high
resolution (Fine slit). For an artificial multi-layer such as RX61 to be used for the
measurement of boron (B) or carbon (C), when there is no adjacent spectral line, high
intensities are obtained by using a slit with high sensitivity.
Slit Description
S2 Standard slit for the detector SC. High resolution is obtained.
S4 Standard slit for the detector PC.

S8 Resolution lowers, but high X-ray intensities are obtained.
S1 Resolution higher than that of the S2 is obtained.
Smoothing
This is the function of smoothing processing for a qualitative spectrum. As the number of
points used for smoothing becomes larger, the chart becomes smoother. But if the
number of points is too large, the spectrum will be deformed.
Spectrometer Sensitivity Coefficients
Coefficients used for a sensitivity calibration curve, which is a correlation between

measured intensities and theoretical intensities in the FP method, are called the
spectrometer sensitivity coefficients. These correspond to calibration curve coefficients
in the empirical calibration method.
It  BI 2  CI  D
Item Description
It Theoretical X-ray intensity
I Measured X-ray intensity
B, C, D Spectrometer sensitivity coefficients
SQX Analysis
An FP program to calculate semiquantitative analysis values using built-in sensitivity

libraries without standard samples is called the SQX analysis. This is an FP program
that has new functions such as the automatic overlap correction and photoelectron FP.
When creating a qualitative application, the fixed angle measurement can be added.

GLOSSARY
SQX Overlap Correction
If interfering rays overlap with a peak for analysis in the SQX analysis, overlap
correction can be made using overlap correction coefficients stored beforehand in each
spectrometer. Analyzed values can be calculated using net intensities after the
correction. This correction has been registered mainly for the overlap of primary X-rays
and may not have been registered for higher-order rays etc.
SQX Scattering FP Method
When the samples of industrial wastes and organism materials are analyzed by
conventional FP method, the difficulty on XRF analysis takes place because the samples
mentioned before contain non-measurable components by XRF such as carbon and
hydrogen. In this application, SQX Scattering FP Method becomes the preferred
technique, which can calculate the concentration of such components by monitoring
scattered X-rays (Rh-KA Compton and Rh-KA Thomson scatterings).
 Scattered Rays
Standard Profile
A standard profile is the spectral data of a single line such as the Ti-K or Zn-L line.
This is registered using a pure material etc., and is used for the standard profile peak
deconvolution. In the ZSX Guidance, this file is created in the standard profile
extraction in the Qualitative Data Handling program.
Standard Profile Peak Deconvolution
A peak deconvolution is made using waveforms registered beforehand as standard

profiles by measuring standard substances. Since this method employs measured peak
profiles for separation, accurate results are obtained. Up to four peaks can be separated.
The following formula, which is a combination of a real spectrum and standard profiles,
is used for calculation.
I i  j  Gji  j   a  i 2  b  i  c
Item Description
 Fitting intensity (intensity of channel i)
j Contribution coefficient of standard profile j
Gj Standard profile intensity (intensity of channel i+j)
i Data channel
j Channel direction correction value for standard profile j
a, b, c Coefficients
 Function Peak Deconvolution

GLOSSARY
Synthetic Multi-Layer
Analyzing crystals that are artificially made of a heavy element that behaves as a
reflection layer and a light element that behaves as a spacer are called synthetic
multi-layers. These are used to analyze components in the longer wavelength region
where the Bragg’s formula cannot be satisfied with a single crystal. Synthetic
multi-layers are employed mainly for analyses of elements lighter than O and are
labeled as the RX series.
 Analyzing Crystal
Theoretical Matrix Correction Coefficients
Matrix correction coefficients obtained by calculating theoretical intensities using the

FP method assuming the composition of a sample are called theoretical matrix
correction coefficients. To obtain reliable matrix correction coefficients with the
regression method, many standard samples are generally required. On the other hand,
theoretical matrix correction coefficients can be calculated by using the FP method
without any standard sample. The matrix correction coefficients mentioned here
correspond to the matrix correction coefficient type Aij.
 Matrix Correction
Thin Film Sample
This term describes a sample that has a finite thickness for X-rays, such as metal-coated
electronic material or a coated sample. This sample does not have an enough film
thickness that all X-rays are coming from the film. The measurement intensities are
affected by its thickness. In analyses with the FP method, a film thickness and
concentrations can be analyzed simultaneously using this principle.
 Bulk Sample
Tube Voltage and Current
These are the voltage applied to the target of the X-ray tube and the current that flows
through the filament. The tube voltage and current are limited by the restrictions on the
filament current as well as the maximum load of the X-ray tube. If an improper selection
is made, an error message will be displayed. The X-ray intensity is roughly proportional
to the current. It is not linearly proportional to the voltage and depends on an X-ray tube
target, element and measured element line. In general, for heavier elements (shorter
wavelengths), the intensity becomes higher than a linearly proportional value as the
voltage becomes higher.

GLOSSARY
2-Theta Angle
A crystal is used for the spectral analysis of fluorescent X-rays. When the crystal angle is
theta, the detector angle is 2-theta because of the conformal reflection according to the
Bragg’s formula. Both the crystal and the detector move according to the wavelength to
be measured. The detector angle 2-theta is conventionally used for the abscissa axis of
the qualitative analysis spectral chart.
2-Theta Scan
The crystal and detector are rotated from low angle to high angle to measure an X-ray
intensity at each angle (wavelength or energy). This is used for the qualitative analysis
and the measurement of a peak shape. In general, a chart is drawn with the 2-theta
angle as the abscissa axis and the X-ray intensity as the ordinate axis. A chart can also
be drawn with its abscissa axis converted to the wavelength or energy.
Unit
The following units are used in this software. Units for thickness are used for thin film
samples.
Concentration Description
mass% Mass%
ppm 1/10000 of mass%
at% Ratio of numbers of atoms
mol% Ratio of numbers of molecules
Thickness, length Description

Angstrom Angstrom (10-10m)
nm Nanometer (10-9m)
m Micrometer (10-6m)
Weight Description
g/m2 g/m2
mg/m2 mg/m2
mg/cm2 mg/cm2
g/cm2 g/cm2
The unit for density is fixed to g/cm3. The density of a layer can be selected from a value
fixed to the layer or one calculated from the density of each component. It is also possible
to add a unit.

GLOSSARY
Universal Standard Samples
The database that has information about standard samples on the market such as NIST
(National Institute of Standards and Technology) and JSS (Japanese Steel Standard) is
called the Universal Standard Samples. When you have a sample in this database, you
can set the information for that standard sample without entering standard values
manually. Furthermore, by adding your standard sample to the database, you can
handle it as a universal standard sample.
Weight Thickness
This means sample weight per unit area, for example, g/cm2. It corresponds to the mass
thickness in the case of a unit of mass. In the case of a coating sample, the coating
weight of a coating layer is also the weight thickness. It is also called an area density.
X-Ray Intensity
In the X-ray analysis, the X-ray intensity is expressed as the number of X-ray photons
that enter through the detector window in a unit time. In general, the number of counts
per second is expressed in units of kcps (kilo-counts/second). In the International System
of Units (SI), the X-ray intensity is expressed as the total electrical charge of ions
generated in air by electrons generated by interactions with 1kg of air through which
X-rays pass. Its unit is C/kg (Coulomb/kilogram).
X-R Control
Check analyses are carried out three to five times a day to control the precision of
analyzed values. Variations of check analysis results are monitored using an X-R control
chart. Check samples are registered with limit range conditions and the averages (X)
and ranges (R) (maximum values minus minimum values) of analyzed results are
assessed daily. Upper and lower limits in limit range conditions are used as control
limits for averages on an X-R control chart. R upper limits are used as control values for
ranges.

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X-RAY FLUORESCENCE SPECTROMETER

ZSX Primus Series

SOFTWARE OPERATION MANUAL

1. OUTLINE OF ZSX GUIDANCE SCREEN .................................................... 1

3. QUALITATIVE ANALYSIS .........................................................................116

ZSX Primus IV/IVi Software Operation Manual i-1

e. Setting of Measuring Conditions .................................................................................... 146

i-2 ZSX Primus IV/IVi Software Operation Manual

3.5.4.CUSTOMIZATION OF TEMPLATE........................................................................... 289

4. QUANTITATIVE ANALYSIS ..................................................................... 293

ZSX Primus IV/IVi Software Operation Manual i-3

e. Unknown Sample Quantification.................................................................................... 541

5. MAPPING ANALYSIS (OPTION) ............................................................. 576

6. UTILITY AND MAINTENANCE ................................................................ 614

i-4 ZSX Primus IV/IVi Software Operation Manual

d. Universal Standard Samples ......................................................................................... 631

ZSX Primus IV/IVi Software Operation Manual i-5

i-6 ZSX Primus IV/IVi Software Operation Manual

1. Outline of ZSX Guidance Screen

1.1 Main screen

Title Bar Menu Bar

Status Bar Task Bar of

ZSX Primus IV/IVi Software Operation Manual 1

Marks and Expressions

Marks and expressions used in this manual are explained below.

OK or Cancel Means a button in a screen.

1. Click OK . Means an operating procedure.

Means a selection operation for a

<Vacuum> or <Air> Means a selection item.

ZSX Guidance Screen Operation Tool Buttons

Button Name Function

2 ZSX Primus IV/IVi Software Operation Manual

ZSX Guidance Common Tool Buttons

Button Name Function

Execute Scale change after designating an area is executed.

The display scale of a graph is returned to the default

Clear The designated point or area is cleared.

Move to left The field of view of a graph is moved to the left.

Move to right The field of view of a graph is moved to the right.

X-axis The abscissa axis (X-axis) of a graph is expanded around

ZSX Primus IV/IVi Software Operation Manual 3

Logon User Display Function

4 ZSX Primus IV/IVi Software Operation Manual

An indicator of an operation flow that appears when creating a qualitative analysis

Main menu Submenu No submenu

ZSX Primus IV/IVi Software Operation Manual 5

1.2. Program Menu

6 ZSX Primus IV/IVi Software Operation Manual

ZSX Primus IV/IVi Software Operation Manual 7

 Micro Mapping (Option)

This menu is used to make an analysis by specifying measurement positions while

8 ZSX Primus IV/IVi Software Operation Manual

1.3 Software Options

ZSX Primus IV/IVi Software Operation Manual 9

1.4 About ZMonitor

Restart ZSX Guidance

1. Double-click the icon of (ZSX Guidance) on the desktop.

ZMonitor is not started, it starts from ZMonitor.

Display Measuring Control Programs in Operation

 1. Select [Status] on the pop-up menu of ZMonitor.

10 ZSX Primus IV/IVi Software Operation Manual

1.5 Sample Preparation

Sample Preparation for Analysis