llitlll

Lab-X3500
Benchtop XRF Analyser

OPERATING INSTRUCTIONS

Oxford Instruments Reference No: LXOM3500

Analytical
Halifax Road,
High Wycombe Issue No: 2
Bucks HP12 3SE UK Version 1 0 Software
Tel: +44 (0)1494 442255
Fax: +44(0)1494 524129 October 2001
 Table of Contents

TABLE OF CONTENTS
Safety Information...........................................................................................v
Radiation Safety.............................................................................................................v
Notification......................................................................................................................v
Electrical Safety..................................................................................................................vi
Safety and Electrical Compliance..............................................................................vi
Spillages................................................................................................................................vi

Section 1: System Information.........................................................................1-1

General Description....................................................................................................1-1
Instrument Identification..........................................................................................1-1

Unpacking and setting up...........................................................1-2

Unpacking.....................................................................................................................1-2
Equipment Supplied...................................................................................................1-2
Mains Power Connections..........................................................................................1-3
Switch on......................................................................................................................1-4
Gas Supplies.................................................................................................................1-4
Fitting Printer Paper........................................................................................................1-5
Fitting A Printer Ribbon....................................................................................1-5
Basic Checks......................................................................................................................1-5
General Operation of Instrument............................................................................1-6
Detector Resolution Check.......................................................................................1-8
Preparing the System for Measurement.................................................................1-9
Assembly of Secondary Safety Windows......................................................1-9
Location of Secondary Safety Windows.....................................................1-10

Section 2: ANALYSIS..........................................................................................2-1
Selection of a Calibration.........................................................................................2-1
Analysis using a Calibration......................................................................................2-2

Section 3: RESTANDARDISATION......................................................................3-1
Restandardisation of a Calibration..........................................................................3-1

Section 4: S ECTRUM SCAN........................................................ 4-1

Selecting Measurement Conditions..........................................................................4-1
Output of Spectrum Scan..........................................................................................4-3
Print Scan..........................................................................................................4-3
Identify Peaks...................................................................................................4-3
Change Scale...............................................................................................4-5
Regions of Interest.....................................................................................4-5

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Table of Contents
Superimpose Scans.....................................................................................4-5
Send Scan by RS232....................................................................................4-7
Quit................................................................................................................4-8

Section 5: CALIBRATION....................................................................................5-1
Creating a New Calibration.......................................................................................5-2
Measuring a Set of Calibration Standards and Defining all the
Measurement Conditions................................................................................5-2
Conditions..........................................................................................................5-3
Conditions (summary).....................................................................................5-5
Editing/Adding another Condition................................................................5-6
Segments............................................................................................................5-9
Segments (summary)............................................................................................5-9
Tolerance Limits..................................................................................................5-10
Measuring Calibration Standards.................................................................5-13
Regression.......................................................................................................5-14
Error Analysis..................................................................................................5-15
Graph 1............................................................................................................5-15
Graph 2............................................................................................................5-15
Intensities.............................................................................................................5-15
Manual.....................................................................................................5-15
Quit...................................................................................................................5-15
X-ray Corrections...........................................................................................5-17
Blank Subtraction...........................................................................................5-17
Restrictions on Blank Subtraction Correction.........................................5-18
Overlapping Segment....................................................................................5-18
Ratio Correction.............................................................................................5-19
Mass Absorption Corrections........................................................................5-20
Setting Up Samples for Instrument Corrections.......................................5-21
Edit Blank Correction....................................................................................5-22
Overlap Correction........................................................................................5-22
Low and High SUSSES.....................................................................................5-23

Define Parameters for Routine Analysis....................................................5-25

Printer Format................................................................................................5-27
RS232 Format..................................................................................................5-31
Delete Standards............................................................................................5-32
Save Calibration.............................................................................................5-33
Edit...................................................................................................................5-33
Copy..................................................................................................................5-33
List.........................................................................................................................5-34
Send..................................................................................................................5-34
Delete...............................................................................................................5-34
Measure............................................................................................................5-35
age iv LZOM3500 © Oxford Instruments Analytical 2000 . All Rights
 Table of Contents
Quit...................................................................................................................5-35
Data from RS232.......................................................................................................5-35
Calibrations created as text files................................................................................5-36

Section 6: UTILITIES...................................................................................................6-1
Detector Test....................................................................................................................6-1
Set Date and Time......................................................................................................6-2
Position Turntable.......................................................................................................6-3
Printer Check.....................................................................................................................6-3
Printer On/Off...................................................................................................................6-3
Select Language..........................................................................................................6-3
Setting RS232...............................................................................................................6-4
Test Scan............................................................................................................................6-4
Print Configuration.....................................................................................................6-4
Conditioning On/Off..................................................................................................6-4
Restandardise....................................................................................................................6-5
Connections..................................................................................................................6-5
Quit................................................................................................................................6-5
Setting or Changing Passwords.................................................................................6-5
Reomote Options.........................................................................................................6-6

Section 7: Using the Lab-X with a Computer and

Automation..................................................................7-1
Changing Input/Output..............................................................................................7-2
Changing Keyboard Control......................................................................................7-2
Changing Display Output...........................................................................................7-2
Changing Printer Text Output..................................................................................7-2

Changing Printer Graphics Output...........................................................................7-3

Automation Options...................................................................................................7-4
Automatic Transmission of an energy Lock and Command................................7-4
Automatic Analysis.....................................................................................................7-4
Automatic Restandardisation...................................................................................7-4
Automatic Control and Monitoring of Routine Lab-X Functions........................7-5

Appendix A: RS232 Communication............................................... A-1

Baud Rate, Data Bits, Stop Bits and Parity.......................................................... A-1
At all Times ........................................................................................................... A-1
Transmitting Information .................................................................................... A-1
Receiving Calibration Data or Remote Commands............................................ A-2
Communicating with a PC ................................................................................... A-2

Appendix B: Sample reparation ..................................................... B-1

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Table of Contents
Solids (Metals and Plastics) .................................................................................. B-1
Liquids ................................................................................................................... B-1
Powders (Including Minerals) .............................................................................. B-3
Special Samples .................................................................................................... B-5
Organic Solids............................................................................................. B-5
Papers ......................................................................................................... B-5
Testing for Sampling Errors ................................................................................. B-5

Appendix C: XRF Theory......................................................................... C-1

An Introduction to XRF Analysis ......................................................................... C-1
Selective Excitation and Primary Beam Filtration in EDXRF .............................. C-2
Absorption of X-rays ............................................................................................ C-4
Single Filter Method ............................................................................................ C-5
General Principles of Calibration ........................................................................ C-6
Correction of Interferences ................................................................................. C-8
Corrections............................................................................................................ C-8
Precision .............................................................................................................. C-10
Accuracy .............................................................................................................. C-11

Appendix D: Error Messages ............................................................... D-1

age iv LZOM3500 © Oxford Instruments Analytical 2000 . All Rights

 Safety Information

Radiation Safety The Lab-X 3500 contains a small X-ray tube housed in a fully-shielded and
interlocked radiation enclosure. In normal operation there is no
radiation detectable above background level on any accessible surface.

In Europe, to gain the highest level of official approval for operation of an X-

ray spectrometer in a place of work, the radiation dosage level at a distance of
100 millimetres from any accessible surface of the spectrometer must be less
than 1 (one) microsievert per hour above background levels. On the Lab-X
3500 at 100 millimetres from any surface the radiation dosage is at background
level.

The high inherent safety of the Lab-X 3500, through the use of shielding and
interlocks, means that it can be operated like any other piece of laboratory
equipment and no special procedures, such as wearing radiation safety badges,
are required.

In all foreseeable circumstances the Lab-X 3500 presents no radiation hazard to

the operator, because the operator is well-shielded from the X-rays at all times.
The maximum accessible dose rate to the operator is at background levels for
the body and less than 0.1 microsieverts per hour (0.01 mrem/hr) for fingers.

There are no user serviceable parts inside the Lab-X 3500 and any servicing
required within the instrument must be carried out by an Oxford Instruments-
trained service engineer.

Notification In the United Kingdom, the use of this type of equipment is governed by
the 'Ionising Radiation Regulations 1985'. To comply with these the user
must notify the Health and Safety Executive of his intention to start work
with ionising radiations on Form 2522. This will not be necessary if the user
has previously notified the HSE about similar equipment, such as an X-ray
diffractometer.

Providing that the user follows the instructions in this manual and employs
Oxford Instruments or Oxford Instruments-appointed representatives for all
service work, the only necessary action is to appoint a Radiation Protection
Supervisor (RPS).

a e
Safety Information

The RPS needs to be familiar with the 'Ionising Radiation Regulations' as they
affect the company's work activity, and they must submit the notification to
the HSE and write the 'Local Rules' for radiation work. These should simply
state that the user has no access to the radiation enclosure. There is no
requirement to appoint a Radiation Protection Advisor (RPA) and operators
need not be classified workers nor wear personal dosemeters.

Similar rules apply in other countries and for specific advice please contact
your local Oxford Instruments representative.

Electrical Safety The Lab-X 3500 unit contains high voltages. It is not necessary to remove
covers during routine use and the instrument should never be operated
with its outer case removed. Service work should only be carried out by
Oxford Instruments trained engineers.

Safety The Lab-X 3500 has been designed in accordance with IEC1010 ('Safety
and requirements for electrical equipment for measurement, control and
Electrical laboratory use, Part 1') which encompasses the European Low Voltage
compliance Directive. The instrument must be correctly installed and used only for the
purposes described in this manual. If you have any doubts about the
installation or use of this instrument, contact either Oxford Instruments
Analytical or your local Oxford Instruments representative.

Spilla es In the event of spillage of liquid from the sample cell, first check whether the
liquid has been retained within the secondary (safety) window cell. If so,
remove the liquid and replace the secondary window film. If there is any
possibility that liquid has got into the interior of the unit, isolate the
instrument from the mains supply immediately and contact the service
department at Oxford Instruments Analytical or your local Oxford Instruments
service representative.

Spillages on the outer surface can be wiped with a dry or damp cloth. Do not
use organic solvents.

a e i ..................................................................................................................................
 Section 1: General Information and Operation

SECTION 1: System information

General The Oxford Instruments Lab-X 3500 is a bench-top XRF analyser that uses the
Description principle of energy dispersive X-ray fluorescence (EDXRF) spectrometry to
determine the concentrations of various elements in a range of materials.

It requires single phase mains supply for operation. The Lab-X 3500 may
require a helium gas supply for optimum analytical performance if analysing
for 'low' atomic number elements, typically lower than chlorine in the periodic
table, at low concentrations, i.e. parts per million (ppm).

All operator inputs are accomplished via software control and are activated
using the integral keypad. Software messages and results are shown on the
two column display with analytical results, spectrum scans, etc., printed using
the in-built dot matrix printer. An RS232 connection allows transmission and
receipt of data.

The Lab-X 3500 is available in a range of models, differing mainly in the

excitation and detection mechanism used and application packages supplied.

All Lab-X 3500 instruments are fitted with Oxford Instruments Analytical
Software Package, ASP3500, as standard and may also be fitted with Oxford
Instruments pre-defined calibrations.

There are two levels of password protection in the software: operator and
manager level. These can be set 'on' or 'off' as described in the software
'Utilities' section (Section 6) of this manual

Instrument The instrument is identified by a model and serial number located on a plate at
Identification the rear of the instrument. All enquiries and correspondence relating to the
instrument should quote these numbers.

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1
 Unpackin and settin up

Unpackin Open the packing case carefully, remove the Lab-X 3500 and generally
inspect for any visible damage. Remove the small boxes/polythene bags
containing accessories and spares.
To minimise the risk of damage in transit, the X-ray warning lamp cover
and bulbs are removed from the instrument before shipment and must be
reconnected before any measurements can take place. These items can be
found in the accessories box. Fit the bulbs, ensuring that they are screwed
tightly into the bulb holders, and attach the yellow lamp.

- Note:
1. The Lab-X will not operate if the bulbs are not correctly fitted
2. The Lab-X will continue to operate with only one bulb working.
Place the instrument on a flat topped work surface, away from direct
sunlight, where changes in ambient temperature are minimal.

Equipment Each Lab-X 3500 comes complete with a comprehensive accessories kit
supplied (PartNo.L30) which comprises the following items.
Part No Descripti Quantity
on
L240 Sample cells 1 box (10)
CK-100 Consumable kit, consisting of 100 disposable 1 box (100)
inners and 100 lids
L71 Polycarbonate cell film 1 roll (250
m)
LX5102 Printer paper rolls 5 rolls
A3/LX6544 Paper spindle 1
LX5105 Printer ribbons 2
LX1054 Sample cell window assembly jig 1
LX6037- Secondary safety windows 3
2+
LX6037-
3
LX1032 10-position sample cell rack 1
LX6897-1 Dust port cover (Aluminium) 1
* Set of fuses (1 A) to suit local voltage 1 set
* Mains lead to suit local voltage 1
PR1023 Tube of grease (50 grams) 1
LA1044 X-ray lamp bulbs 5
LX6879-1 Secondary safety window (2 parts) 3
LX320 Assembly tool for above 1
* To suit local voltage

a e12 LZOM3500 © Oxford Instruments Analytical 2000. All Rights Reserved

 Section 1: General Information and Operation

Note: If one of the Oxford Instruments "instrument packages" has been

supplied, the contents of the accessories kit is optimised for the
application, and may differ slightly from the above.

Mains ower This instrument must be connected to an earthed mains supply. If you are in
Connections any doubt about your mains supply, consult a qualified electrician before
proceeding.

The Lab-X 3500 is operated from a single phase supply in the range 100-
120volts or 220-240 volts, 45/65 Hz. Before the instrument is connected to
the mains supply, a check should be made to ensure that the combined
switch/mains input connector has been set to the correct volta e
(Figure 1-1). This connector is on the right-hand side of the instrument
(looking from the front) underneath the profiled edge of the instrument case.
It will be necessary to tilt the instrument to see the switch. The pre-selected
voltage is shown by the position of a white dot in the connector.

USE ONLY WITH 250V FUSES 100V

120V
DISCONNECT POWER BEFORE REPLACING220V
FUSES
240V

Fi ure 1 1: Combined switch and mains input connector showing

position of voltage selector (example shows 220V supply

If the incorrect voltage is shown it can be changed as follows.

1. Check that the mains power is switched off and remove the mains lead.

2. With a small screwdriver, prise open the fuse carrier

3. Pull on the black voltage indicator. It will slide out together with a
small 20mm2 connector board.

4. Slide the voltage indicator (white plastic) around the board until it is on
the opposite side of the board to the required voltage. The voltages are
printed on the surface of the board.

5. Slide the board and indicator back into the connector.

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 6. Refit the fuse carrier and ensure that the indicator is adjacent to the
required voltage setting.

Figure 1.2 shows the label attached at the power inlet/switch.

The power lead

supplied should then
be plugged into the
socket adjacent to the
mains switch and
connected through an
easily accessible
isolation switch to
the mains supply.
Figure 1.2

In the event of the instrument's mains fuses requiring replacement, isolate

the instrument from the mains and fit an approved replacement fuse of the
correct type, according to the fuse specification label adjacent to the mains
switch.

Switch on Once the correct voltage has been set, the instrument can be switched on at
the power switch, which is situated near the mains input connector. The
turntable will reset to the sample loading position and any filters fitted
will also reset.

The following screen should appear on the liquid crystal display:

LAB-X 3500 ANALYTICAL SOFTWARE

LZ xx Press <ENTER>to continue
The software version number is displayed in the bottom left-hand side of the
LCD (indicated by xx above) and the printer will print OXFORD
INSTRUMENTS LAB-X 3500 in red characters.

Gas supplies If a helium purge unit is fitted to the Lab-X 3500 this should be connected
as follows. A helium pipe of 1/8 inch (3mm) bore tubing should be
connected to the barbed connector situated on the left-hand side of the
instrument (when viewed from the front) underneath the profiled edge of
the instrument case.

Helium is used to remove air between the sample and the detector and its
purity should be 99% or greater. The pressure at the inlet to the
instrument should be 5psi ± 1psi (35kPa ± 7kPa) when helium is flowing
(i.e. during a
 Section 1: General Information and Operation

measurement) and the flow rate needs to be 1.7 l/min. Helium is only used
during a measurement, which is defined in the calibration. If helium is
required and is not available, then a warning is printed when a measurement
takes place (see Appendix D). Based on 100 samples per day using a total
analysis time of 100 seconds, a 10 m3 cylinder should last approximately one
month. (Lab-X 35005 300s measurement in 4.1L/sample.)

Fitting printer Paper and the paper spindle will be in the box containing the instrument's
paper accessories.

To fit a roll of paper into the printer, open the printer compartment flap by
gently pressing the back of the flap whilst supporting the front. Cut a straight
edge on the loose end of the paper and push the loose end into the back of
the printer near the printer guide, with the roll unwinding from the bottom.

Press the paper advance key (middle key on the bottom row of
keypad) to advance the paper through the printer mechanism. 5upport the
roll in the printer compartment by fitting the paper spindle through the
centre of the paper roll and locating the spindle in the guides. When the
roll is in place, replace the printer flap.

Fitting printer Spool type (LX5101)

ribbon Remove the printer flap, release the central ribbon tensioners and carefully
manoeuvre the old ribbons from the sprockets. Load the new ribbon with the
red section facing downwards, making sure that the ribbon passes around the
end tensioners. Check that the ribbon is not sagging or twisted before
refitting the printer flap.

Cassette type (LX5105)

Remove the old cassette and replace, ensuring the red section of the ribbon
faces downwards.

Basic checks After initial switch on, certain basic checks should be performed to have the
instrument ready for analytical measurements. From the initial screen press the
(enter) key and the MAIN MENU screen will be displayed :

MAIN MENU
1=ANALYSE 2=OTHER FUNCTIONS
This screen displays two choices: ANALYSE and OTHER FUNCTIONS.
(Note: Press to return to the previous menu). Routine analysis

3 Page 1.5
Section 1: General Information and Operation

(ANALYSE) can only be accessed if a calibration has been generated and, in

addition, the option ALLOW ANALYSIS (defined in a calibration when first
generated) has been specified.

If this function is selected and there are no calibrations in the memory then
the message:

No calibration available
Press <enter> to
continue
will be displayed. When the (enter) key is pressed, the Main Menu will be
redisplayed.

OTHER FUNCTIONS accesses all other routines in the resident Analytical

Software Package (ASP3500).

- Note:
This menu option may be password protected. Passwords are not pre-set
and until a password is defined, press the (enter) key when asked for a
password.

General All of the operating sequences of the Lab-X 3500 are automatically controlled
Operation of by the built-in microprocessor. All instruments are fitted with a standard
Instrument version of the measurement software ASP3500, which includes a Utilities
section. A number of measurement options are available which are shown on
the display as a series of menus. For routine analysis, simply select a calibration,
press the appropriate key for "ANALYSE" (usually 1), enter a sample label
and insert the sample. Measurements are made during the analysis cycle, at the
end of which an analysis report is printed (providing that the PRINTER
ON/OFF function, selected in the Utilities section, is set to on).

In general, when responding to prompts on the display, three different

operator input methods are required:

• When prompted to select a menu option, press the relevant number on

the keypad, e.g.: 1=ANALYSE.

• When asked for a "yes" or "no" response, press the relevant key on the
keypad ( Yes
or No
).

• When asked to input data manually, press the keys for the
numbers/characters required followed by the (enter) key.

Page 1.6 3
 Note:
It is not necessary to press the (enter) key for the first two methods. If a
'beep' is heard, an entry has been made incorrectly.

To select a character in
the upper section of a
key, for example the
letter A, press and hold
down the up  arrow
located on the left-hand
side of the keypad, and
then press the key
containing the character
required. To select a
character in the lower
section of a key, for
example the letter B, use
Figure 1.3: Section of keypad
the same procedure but
press and hold down the down  arrow on the keypad (see Figure 1.3)

Some keys have additional characters in the right-hand side of the keys. To
select one of these characters (for example, when entering characters for a
post-analytical calculation in a customised calibration - see Section 5), press the
key situated on the left side of keypad, and simultaneously press the
required key e.g. for a hash bracket symbol (#) press the and the NO
key. The •
key also has two extra arrows and these are to move the cursor.
For highest stability, always leave the instrument switched on; however
samples, particularly liquids, should be removed from the sample loading
port after analysis. The turntable has three ports, one for the sample and the
other two for setting-up samples (SUSs). The Lab-X 3500 automatically rotates
the correct port to the loading position, as required. Do not place any object
in the ports which might impede the rotation of the turntable.

At the start of each measurement cycle the turntable rotates through 60° and
carries out an energy lock (automatic gain stabilisation) for approximately
10 seconds, after which a further rotation places the sample in the analysis

 a e1
Section 1: General Information and Operation

position. To terminate a measurement, press the Escape

key (possibly more
than once) before the programmed time has
elapsed.

At this stage it is recommended that the correct date and time are set. To do
this, select 2=OTHER FUNCTIONS from the MAIN MENU, followed by
3=UTILITIES (see Section 6). After completing this set up, select
4=TURN PAGE until the menu containing 3=PRINT CONFIGURATION is
displayed. Select this item for a print-out.

Detector After the initial switch on and warm-up, and at regular intervals thereafter
resolution check (typically once a month), the detector resolution should be checked to ensure
that optimum performance is maintained throughout the life of the
instrument.

This function is contained in the Utilities section of the software.

To carry out a detector resolution check select 2 = OTHER FUNCTIONS from

the MAIN MENU display) and enter the operator password, if set. If no
password is in operation, press the (enter) key.

Select 3=UTILITIES
and then
1=DETECTOR TEST.
On selection, the
turntable rotates
automatically and
measures a sample
situated underneath
the turntable
(inaccessible to the
operator). After
approximately 30
seconds the
measurement sequence
is complete and a print- Figure 1.4: Pulse amplitude distribution from
out gives the initial mono-energetic X-rays
and
current DAC value and % resolution of the detector. The DAC value is a
measure of the gain of the system and should be approximately 3000.

Page 1.8 LZOM3500 © Oxford Instruments Analytical 2000. All Rights

 The resolution value is a percentage value expressed as the full width at half
height divided by the peak position, i.e:
h
x100%
H
which is shown in Figure 1.4. A typical value for a neon or argon detector is
22- 26% and for a xenon detector 20%. The last character of the Lab-X3500
model number signifies the type of detector fitted, e.g. LZ3108N is fitted
with a neon detector and LZ3108A an argon detector.

When the resolution value is 6% greater than the initial value, consider
replacing the detector. This work should be carried out by a qualified,
Oxford Instruments-trained service engineer.

Preparing the Secondary safety windows should be fitted into all three ports of the Lab-
system for X3500 before any measurements are made. These prevent dust, accidental
measurement sample spillage, etc., from entering the analysis head and reduce the escape of
helium when using gas purge. For further information see 'Location of
secondary safety windows' on Page 1.10.

- Note: If analysing pressed pellets using Oxford Instruments holder Part No. Q59 for
40mm diameter samples, a secondary safety window cannot be used for
routine analysis, but the two other turntable ports (SUS positions) should
have either the setting-up samples or the secondary windows fitted.

Assembly of secondary safety windows

Safety windows are assembled using a secondary window stage with clamping
ring and a window film. This film should normally be polycarbonate or Mylar
although other films may be used depending on the application (reference
should be made to the application note). It is very important that:

• The correct film is used, as incorrect film could invalidate the

restandardisation procedure. (Where applicable see method sheet.)

• The window is kept very clean and dry - do not touch the surface.

S e c o n d ry
w n d o w s t g e
n n e r
W n d o w
n gr n g
t e r

Figure 1.5: Secondary Window Stage assembly

 Page 1.
Section 1: General Information and Operation

The secondary window is assembled as follows.

1. Place the plastic ring on a flat surface (Note: If the ring has a stepped
end place the stepped end uppermost).

2. Place a piece of window material on top of the ring and press the
secondary window stage inner fully down onto the metal ring, trapping the
window material. The plastic clamping ring has a small chamfer (if it is of
a white material) on its leading edge which helps to prevent the window
material from tearing. Alternatively, the window can be mounted using
the sample assembly tool (see Figure 1.5)

3. Check that the assembled window is perfectly flat. If not, repeat steps 1 and
2 with a new piece of window material. A certain amount of window
tensioning can be achieved after the rings have been assembled, but take
care not to overstretch or tear the window.

4. When the window is satisfactory, trim off the excess material.

5. Repeat steps 1 to 4 for the other two secondary safety windows.

Location of secondary safety windows

The assembled secondary windows now need to be located in the three
turntable ports. This operation is carried out using the Utilities section of the
software.

From the MAIN MENU screen, select 2=OTHER FUNCTIONS and then
=UTILITIES followed by = OSITION TURNTABLE. Select position 4 and
the turntable will rotate to the desired location. Place one of the secondary
window stages into this port. Select position 2 and again place a secondary
window in the port. Finally, select position 0 (the analysis position) and place
the remaining secondary window into the port. When all three windows are
loaded, select 4=TURN AGE three times, followed by the 2=QUIT option
and then 4=MAIN MENU which will then show the MAIN MENU screen.

The Lab-X 3500 is now ready for use.

See Appendix B for details of sample preparation methods.

Page 1.10 LZOM3500 © Oxford Instruments Analytical 2000. All Rights

 This page is intentionally blank

 a e 1 11
 Section 2: Analysis

Section 2: ANALYSIS
The X-ray fluorescence technique is a comparative rather than an absolute
method of analysis, and therefore a calibration curve must first be established
before routine analysis can be carried out. This section assumes that a
calibration has already been established. If not, refer to Section 4 for details on
creating a calibration. The ANALYSE function, which is selectable from the
MAIN MENU display, allows a previously-stored calibration to be accessed and
routine analysis to be performed.

MAIN MENU
l=ANALYSE 2=OTHER FUNCTIONS

l=SULPHUR IN OIL 2=LEAD IN

GASOLINE 3=LIST TITLES 4=TURN

l=ZINC IN ADDITIVES 2=CL IN WASTE

OIL 3=LIST TITLES 4=TURN PAGE

No more calibrations
Press <ENTER> to continue

Selection of a When l=ANALYSE is selected from the MAIN MENU, calibrations that are
calibration in memory are sequentially shown on the liquid crystal display (LCD). Select
the calibration required by pressing the appropriate number from the
keypad. If the required calibration is not shown on the first LCD screen,
then Option 4=TURN PAGE should be selected and further calibrations will
be shown.
Option 3=LIST TITLES will give a printout of the calibrations that can be
used in this routine analysis (ANALYSE) section.

By continuing to select Option 4, all the existing calibrations will be

displayed sequentially until
No more calibrations press <enter> to continue
is displayed. When the (enter) key is pressed the MAIN MENU will be
displayed and 'l=Analyse' or '2=Other functions' can be selected.

If a calibration is selected, for example the first calibration title 'Sulphur in Oil'
shown above, the screen will display:

 a e 2
 SULPHUR IN OIL l=ANALYSE 2=RESTD 3=END
Last restandardised 08/09/9308 35
and a printout of the calibration title and date and time of last
restandardisation is given.

- Note:
If USA date/time is selected, using the 'select language' option in UTILITIES
section, the display will show mm/dd/yy (time) am, where m=month, d=day,
y=year.
From this, routine analysis or a restandardisation of the calibration can be
carried out. Select option 3=END to return to the MAIN MENU.

Analysis using a On selection of l=ANALYSE the title of the calibration selected will be
calibration displayed and a sample label will be requested (as shown below):
Calibration title SULPHUR IN OIL
Enter sample label
The sample label can be alpha/numeric and up to 10 characters long. A 'bar' is
shown on the LCD to indicate the length of the sample label and this is
extinguished as characters are entered. If a mistake is made, the (delete)
function key can be used to correct the error. If the number of characters
exceeds 10, a beep will be heard indicating that an invalid option has been
selected.

Once the correct sample label has been entered, if the calibration includes
options for manual input, the following screen will be displayed:

Enter (parameter) for sample (label as above)

5.7

This is repeated for each manual input segment defined in the calibration. The
name and units of the parameters entered are defined in the calibration
segment. The default value displayed (5.7 in the example above) is the
previous value entered for the segment, providing the selected calibration has
not changed, in which case zero will be displayed.

After the last manual input segment has been entered, the following
screen will be displayed:
Insert sample XXXX
Press <YES> when inserted <NO> to quit
When the sample has been loaded, press either the Yes or key. The
X-ray warning should now be illuminated to indicate that the X-ray tube
is
 powered. The display will show 'Energy lock, please wait' while
the turntable rotates to an intermediate position. (Note: If the option
'conditioning' has been selected [see utilities section] then this will appear for
10 seconds before the energy lock screen).
Energy Lock No l
DAC= 2990SECONDS REMAINING= l0
The 'Energy Lock' function automatically measures a sample located
underneath the turntable and 'locks' the gain of the system electronics, giving
good stability. During the 'Energy Lock' measurement the liquid crystal display
shows the DAC value (a measure of the gain of the system), the time
remaining for the energy lock and a number in the top right-hand side of the
display which indicates the number of attempts at the energy lock. Thus, if
after ten seconds the first 'Energy Lock' has not been successful, then a
second attempt is made and the number in the top right-hand side of the
display changes to 2. This is repeated up to five times. If after five attempts
the 'Energy Lock' cannot be established then an error message is given on the
printout in red: Gain Adjustment Error (see Appendix D). Repeat
the measurement and if the same message appears, contact Oxford
Instruments for remedial action.

Normally the 'Energy Lock' is successful on the first attempt and the turntable
will then rotate to the analysis position and start the measurement. If the
detector conditioning function has been turned on (see Utilities Section) then
the message 'Conditioning detector' will be shown first, followed by
the 'Energy lock' sequence.

For single element calibrations 'sample label', 'calibration title', 'analysis time'
and 'concentration' are displayed during the measurement period. At the end
of the measurement a printout is given, unless the 'printer off' option (see
Utilities Section) has been selected.

During the final condition of analysis up to six segments are displayed. This
includes any manually entered parameters. The normal and condensed results
print-outs also include any manually entered parameters but no intensiities are
printed.

- Note
A number of repeats can be specified in the calibration method to either
measure one sample "n" times or different samples from the same batch
once. In the latter case the display will prompt for insertion of the second
sample (of a total of three measurements) as "2 of 3", etc.
This page is intentionally blank.
 Section 3: Restandardisation

SECTION 3: Restandardisation
Restandardisation involves measuring the Setting Up Samples (SUSs) that
were measured as part of the calibration. Selection of 'Restandardisation' is
via 'Analyse' from the Main Menu and once a calibration has been chosen it
can be restandardised by selection of option 2=RESTD.

The positions of the setting up samples in the turntable are defined in the
initial calibration and can be position O (the sample port), 2 or 4. SUSs are
often located in the instrument turntable and once they have been measured
they correct for any change in the position of the calibration line, both in
terms of background or sensitivity change.

If more than two SUSs are required to restandardise a calibration, then they
will need to be inserted into the instrument following the instructions
shown on the liquid crystal display.

Restandardisation On selection, the following is displayed

of Restandardisation:
a calibration (Calibration title) l=All SUSs2=New blank SUS only
3=Quit
Option 1: measures all the SUSs used in the calibration

Option 2: measures a new blank SUS only and only applies if a blank
subtraction has been carried out. The most frequent use for this
correction is the application measuring silicone coat weight on
paper.

Option 3: returns to the menu allowing analysis or restandardisation of a

calibration.

Selection of 1=ALL SUSs displays:

Restandardisation: (Calibration title)

Are suss inserted in ports? <YEs> / <NO>
If <YES> then the SUS's are automatically measured. If <NO> then the
turntable will automatically rotate to the position for the first SUS and the
LCD will prompt for insertion of the required SUS by the part number
assigned in
Yes
the calibration. Once the SUS is inserted, press the key to measure it. This
procedure is repeated according to the number of SUSs used in the calibration.

 a e31
Section 3: Restandardisation

If the calibration involved a matrix correction, such as an overlap correction

then the SUSs used in the correction are also measured as part of the
restandardisation procedure.

- Note:
If the SUSs are not left in the Lab-X 35OO they should be stored in a secure
place. Fused beads should be stored in a desiccator. It is very important that
SUSs are kept in a good clean condition as they are used to adjust the
calibration lines.
After every restandardisation the Lab-X prints the gross SUS intensities and
the change in sensitivity of the net intensities of the segments since the
calibration was first created. This is printed in the following format (e.g.):

NAME CHANGE SINCE CALIBRATION 0.l23%

CA FE 0.045%

a e3 LZOM3500 © Oxford Instruments Analytical 2000. All Rights

2
 SECTION 4: SPECTRUM SCAN
Selection of the 'Spectrum Scan' function is via the 'OTHER FUNCTIONS' option
of the MAIN MENU and it may be operator password protected. Once a sample
has been measured, its spectrum scan can be investigated, i.e. element peaks
identified, changes of scale carried out, sent to the internal printer,
transmitted via the RS232 output or a second sample can be measured and
the two spectra superimposed.

Selecting On selection, a series of questions will be asked depending on the

Measurement configuration of the instrument. For example, if the instrument does not
Conditions have a helium purge unit fitted then that question would not be asked. The
following example presumes the Lab-X 3500 is fitted with a 25kV power
supply, helium purge, a primary and secondary beam filter and neon
detector.

The initial requirement is to specify the excitation conditions and, hence, the
range of elements to be measured. For a 25kV system the choice is between
'low' energy or 'high' energy ranges, which correspond to the following
elemental range:

l=Al to Cr (LOW) 2=K to Zr (HIGH) (Sr to Ce La) (

The LOW energy range corresponds to the elements Al13 to Cr24 measuring the
principal K alpha and K beta spectral lines and Sr38 to Ce58 measuring the L
series X-ray lines. It should be noted that the L X-ray lines are weaker than
the K lines.

The HIGH energy range corresponds to the elements K19 to Zr40 measuring the
K lines and Rh45 to Am95 measuring the L lines.

- Note:
A 'highlight' will appear over a function to signify that it was the value last
used. If the same value is required again, either re-select the function or simply
press the key. After selection of the required energy range the tube
excitation conditions need to be specified, i.e. voltage and current.
Section 4: Spectrum
Scan

Enter tube kV (4 to 25kV):

Enter tube current (0 to l00uA):

(5µA steps only)
The maximum microamps value displayed on this screen depends on the tube
voltage previously specified

For those systems fitted with primary and secondary filters:

Enter primary filter: 0=NONE
l=A3 2=A5

Enter secondary filter: 0=NONEl=Wl2=Fl

3=0l 4=Vl 5=El

If a helium purge unit is fitted:

Helium path ? <YES> / <NO>

Helium is normally used when determining low concentrations of relatively

low atomic number elements such as Al, Si, P, S, and Cl.
Spectrum Scan Time (seconds)

Any time can be specified up to a maximum of 9999 seconds. Typically 50

or 100 seconds is used, a longer time giving better precision.

Once the parameters have been specified the sample label should be entered,
Yes
then press the key. Load the sample into the turntable and press the
key. The Energy Lock message will be displayed and then a spectrum scan
will be obtained, measuring for the time period specified. The following
will be displayed:
l=PRINT SCAN 2=SUPERIMPOSE SCANS
3=SEND SCAN BY RS232 4=QUIT

Page 4.2 LZOM3500 © Oxford Instruments Analytical 2000. All Rights

 Output of After the sample has been measured, the spectrum scan printout shows an
Spectrum Scan intensity in counts per second on the vertical scale and channel number on
the horizontal scale (0 to 250 channels). For the 'low' energy scale, the range
of elements and their locations is also printed. For the majority of applications
the element will be one of those displayed and detection is accomplished by
measuring the K alpha X-ray line.

However, in some cases the L or M X-ray lines of high atomic number

elements such as Pb could be the peak displayed on the spectrum. It is good
practise to first measure a blank sample (such as liquid paraffin, or a white
nylon plug), as this will identify any X-ray tube lines, diffraction peaks, etc.,
that may occur.

For the 'high' element range the spectrum scan printout does not show the
element locations. A list of possible elements, or X-ray tube lines, etc., is shown
on the following pages and the peak identify function can be used to check
for the most probable element.

Print Scan
This sends and displays the scan on the internal printer. After printing, the
following message will be displayed:
l=IDENTIFY PEAK 3=REGION OF INTEREST 2=CHANGE S
4=TURN
The printout will display the total intensity received across all channels and this
value should be kept below 30,000 counts, normally controlled by the power
on the X-ray tube.

Channel 255 contains all the counts per second from the spectrum above
Note: Channel 254.

Identify peaks
From the spectrum scan, if a peak occurs between the given elements (on the
'low' energy scale) or does not correspond with an expected element, then
by selecting option l=Identify Peaks a printout of the elements to
occur around the position specified ± 10% will be given.

When requested, enter the channel number at which the maximum intensity
for the 'unknown' peak occurs. Once this is done, press the key and a
 Neon and argon detector systems

NOTE: Escape peaks may be present when using an argon detector

LOW ENERGY RANGE HIGH ENERGY
RANGE
Channel Ka La Lf3 Ma
Channel Ka La Channe Ka La Lf3
6 Al Lf3 l
6
40 Rh Ru 132 O
7 Rb
42 Pd Rh 134 s H
6
7 Si Rb 44 Ar Ag Pd 136 G f
8 46 Cd Ag 138 a
8 Sr 48 K In Cd 140
I
0 50 Sn 142
r
8 Sr 52 In 144 T
2 54 Ca Sb Sn 146 a
8 y 56 Te Sb 148
6
58 I 152 P
8 y
60 Sc Xe Te 154 G t
8
9 P Zr P 62 I 156 e w
0 t 64 Cs 158
66 Ti Ba Xe 160
9 Zr A 68 La Cs 164 A
4 u 72 Ce Ba 166 u
74 V Pr La 168 R
9 Nb 78 Nd Ce 170 A e
6
80 Cr Pm 174 s
9 H
82 Pr 176 H
8 g
84 Sm Nd 178 g
86 Eu 180 O
1 Nb T
88 Mn Pm 182 s
0 l T
0 90 Gd 186 l
1 S M 92 Tb Sm 192 S
0 o 94 Fe 196 e
2 P I
96 Dy Eu 198
1 P b r
100 Ho Gd 202
0 b
102 Co Er 206
4
1 Mo 104 Tb 210
0 106 Tm 212
B B P
6 108 Dy 216 t
r i
1 Tc B 110 Ni yb 218
0 i 112 Ho 222
8 114 Lu 226 P
1 Tc 116 Hf Er 232 o
1
118 Cu 234 A
2
120 Ta Tm 240 u
1 Ru K
124 w yb 246
1 r
4
1 Cl
1
6
1 Ru
1
8
1 Rh
2
0
1 Pd Rh
2
6
Xenon detector HIGH ENERGY RANGE
LOW ENERGY
RANGE
Chan Ka La Lf3
Channel La L M Channel La Lf3 M nel
Ka a Ka a 34 Ti La Cs
44 P 122 Pr 36 V Ce Ba
46 126 Sm Nd 38 Pr Nd La Ce
Z 130 n u
48 r Z A 40 Cr Pm Pr
132 Pm
r u 42 Sm Nd
134 Gd
50 H 44 n u Gd Pm
N 138 Sm
52 S g 140 Tb 46 Tb Sm
54 b 48 e u
T 142 e
56 N 144 u 50 Ho Gd
l
58 b P 148 Gd 52 Co r Tb
o b 150 Ho 54 Tm Yb
154 Co r Tb 56 Ni Lu Ho
B
Cl 160 Tm 58 Hf r
i
60 T 164 Yb 60 Cu Ta Tm
62 c o 166 Ni Ho
62 w Yb
66 170 Lu
174 r 64 Zn Re Lu
R T 66 Os Hf
176 Hf
u c 68 Ga Ir
Ar 178 Cu
180 Ta Tm 70 Pt Ta
70
186 w Yb 72 Au w
72
192 Zn Re 74 Ge Hg Re
74 K R 194 Lu
R 76 Tl Os
76 u 198 Os
h 78 As Pb
78 200 Hf
80 Bi Ir
80 204 Ir
P R 82 Se Po Pt
82 206 Ga
d h 208 Ta 84 At Au
210 Pt 86 Rn
Ca 214 w 88 Br r Hg
A P
84 216 Au 90 Tl
g d
86 220 Ge 92 Ra
88 222 Hg Re 94 Kr Ac Pb
A 228 Tl 96 Th Bi
90 C
g 230 Os 98 Pa
d
100 Rb u Po
Sc 102 At
92 I
104 Sr Np
106 Pu Rn
108 Am
110 Y r
112 Ra
116 Zr Ac
120 Th
124 Nb Pa
128 u
130 o
132 Np
136 Tc Pu
140 Am
142 Ru
150 Rh
156 Pd
 table will be listed on the printer detailing the various elements X-ray lines
that can occur at that peak position ±10%. From this list the most
probable element can be determined.

The complete list of probable lines is given on page 4.4 for both the 8 and
25kV version instruments.

- Note:
The element positions are only approximate (typically ± 5 divisions) and could
be confused by background peaks, escape peaks, detector wall fluorescence,
etc. It is best to confirm the element with a known, single element sample.

Change scale
Use this option to change the scaling of the spectrum scan. On selection,
input from the keypad the maximum intensity (in counts per second) on the
vertical axis required for the spectrum scan and press the key. (The
current value is displayed). A new spectrum scan will then be printed with
the new scaling factor applied.

Regions of Interest
Use the Regions of Interest option to obtain counts per second (cps)
information for a particular area of the spectrum scan.

Select 3=Region of Interest and the display shows:

Region of interest:
Enter lower channel:
Once the figure representing the lowest channel of the region of interest has
been entered then the display shows:
Region of interest:
Enter upper channel:
and the upper channel figure should be entered. The Lab-X prints the total
intensities in cps for the sample measured.

Superimpose Scans
Select 2=SUPERIMPOSE SCANS to compare the spectra of two
samples. The display will show:
Superimpose XXX with l=Another measured scan
2=Quit
 where XXX is the sample label of the first sample measured.

If option 1 is selected, then the measurement conditions for the second scan
can be specified as for the first sample, i.e.:

Enter tube kV (0 to 25kV):

Enter tube current (0 to l00uA):

(5µA steps only)

For those systems fitted with primary and secondary filters:

Enter primary filter: 0=NONE
l=A3 2=A5

Enter secondary filter:

0=NONE l=Wl 2=Fl 3=0l 4=Vl 5=E2
If a helium purge unit is fitted:

Helium path ? <YES> / <NO>

Helium is normally used when determining low concentrations of relatively

low atomic number elements such as Al, Si, P, S, and Cl.
Spectrum Scan Time (seconds)

Once the parameters have been specified, enter the sample label of the second
sample, e.g.: YYY, then press either Yes
or the key. Load the sample
into the turntable and press the Yes
key. The Energy Lock message will be
displayed and when the scan is completed it will be automatically
superimposed on the initial sample and printed on the internal printer.

This function can be re-selected to superimpose other samples onto the initial
sample measured, e.g.: a series of 'unknowns' can be compared to a 'standard'.
The options of 'Identify peak', 'Change scale' and "Region of Interest" will be
available.

On selection of "Region of Interest" (selected when one sample has been

superimposed on another) an estimation of the theoretical limit of detection
and mid-range precision can be obtained using a "straight line two point
calibration procedure". On selection, a value for the lower and upper
channel is required, (default values are displayed if this function has already
been
 used) which defines the area of interest, followed by the concentration value
(concentration specified in units) for the two samples measured.

Based on a linear two point calibration from the measured intensity and
concentration values, the following parameters are calculated and printed:
sensitivity (expressed in counts per second per concentration unit); background
equivalent concentration; theoretical limit of detection (3 sigma at zero
concentration) and mid-range precision (2 sigma). See appendix C for
information on these terms.

This function allows investigation of different instrument parameters, such as

lower and upper channel values, for method development work and only
requires the measurement of two standards.

Note: • If the background equivalent concentration is a negative value (as shown

on the printout) then the limit of detection and mid-range precision is
not printed.
• The background equivalent concentration = -A0 (See Appendix C)

Send scan by RS232

An RS232 cable must be used for this function (a schematic of a suitable cable
is shown in Appendix 1). It should be connected to the RS232 connector which
is located underneath the side panel at the rear left-hand side of the
instrument. The following spectrum scan information will be transmitted:

• Version
• Sample label
• Time and date of transmission
• Measurement conditions (i.e.: kV, µA, primary and secondary filter types,
helium [if used], scan time and range [44.37 or 14.79 channels/keV for a
argon or neon detectors; 22.18 or 7.39 for xenon detectors])
• Channel numbers
• Intensity measured in each of these channels (raw data, i.e.: no smoothing
has been applied)

On selection, the display will show

Transmitting scan: 'sample label'

Please wait
The scan will now be transmitted at the baud rate, parity, etc., set up (see
'Utilities' section). If the scan is not received or there is a problem in the
communication, check the connections and try again.

Quit
This option returns to the initial menu of Spectrum Scan, Calibration, Utilities,
and Main Menu, shown in the flow diagram.
This page is intentionally blank
 Section 5: Calibration

Section 5: CALIBRATION
Since the X-ray fluorescence technique is a comparative rather than absolute
method of analysis a calibration curve must first be established before routine
analysis can be accomplished.

A new calibration can basically be generated in four ways:

• By manually measuring a set of calibration standards and defining all

the measurement conditions

• By measuring a set of calibration standards using an Oxford

Instruments pre-programmed calibration, e.g.: LZMET005.

• By 'direct data' entry, typing in the regression coefficients

• From data received via the RS232.

Before a calibration can be derived, a spectrum scan must be carried out on

standards that are typical of those to be analysed on a routine basis to ensure
that the correct 'window' settings are used. This is not necessary when using
an Oxford Instruments pre-programmed calibration. The series of 'standards'
needs to be similar to the unknown samples in composition, with a
concentration range encompassing, and often exceeding, the range of
interest. The 'standards' can be certified reference materials, samples that have
been analysed well using another analytical technique or, in some cases,
synthetics covering the requirements mentioned above.

Using these standards, a calibration can be derived by first specifying the

instrumental measurement conditions (not necessary on Oxford Instruments
pre-programmed calibrations), then measuring the standards and
performing regression work (which may be a simple straight line correlation
of intensity versus concentration, or involve some instrument or matrix
corrections). The resulting calibration can then be saved and, if required,
used in routine analysis.

If an Oxford Instruments pre-programmed calibration has been provided, the

analytical parameters have already been derived and it is not possible to edit
or delete the calibration. The creation of a new calibration based on an
Oxford

 a e 5
 Instruments calibration involves first copying the Oxford Instruments
calibration and then simply measuring a series of standards and
SUSs.

Creatin a new
calibration MAIN MENU
l=ANALYSE 2=OTHER FUNCTIONS
Select Option 2=Other Functions (this function may be operator password
protected).
l=SPECTRUM SCAN 3=UTILITIES 2=CALIBRATION
4=MAIN MENU

Select Option 2=Calibration (this function may be manager password

protected). Manager password stops unauthorised access to the various
calibration options. Once the correct password has been entered the
following is displayed:

l=New calibration 2=Existing calibration

Select Option 1=New Calibration and the following is displayed:

Please refer to manual to verify correct parameters used
<Enter> to continue

For example, it is essential that the correct excitation and detection parameters
are used.
l=CREATE CALIBRATION 2=DATA FROM RS232

Option 1 allows a new calibration to be derived and Option 2 allows a

previously derived calibration to be received via the RS232 (see Data from
RS232).

Measurin a set of calibration standards and definin all

the measurement conditions
A new calibration can be created by defining a set of measurement
parameters and segments, then measuring standards and Oxford Instruments
supplied Setting Up Samples.

Select Option 1=Create Calibration.

Enter calibration title

Up to 15 alpha/numeric characters may be chosen. When completed, press
and a printout of the calibration title will be given. The calibration title
will also be shown on the printout for routine analysis.

(Calibration title)
l=CONDITIONS 2=SEGMENTS 3=CONTINUE

Conditions
See pages 5.4 and 5.5.
Flow Diagram for Conditions (see opposite)
 Section 5: Calibration

Conditions (summary)
This specifies a set of measurement conditions, i.e. the instrument's excitation
and detection parameters, such as x-ray tube voltage, current, primary and
secondary filters, helium path, calibration and restandardisation times. This
allows elements to be measured under different, but optimised, measurement
parameters.

Various inputs will be requested. The example shown in the Flow Diagram
assumes that the instrument used is a 25kV Lab-X 3500 fitted with primary
and secondary beam mechanisms and a helium purge unit. The questions you
will be asked may be different, according to the configuration of your own
instrument.

Select Option 1 or 2 as appropriate.

C
Enter as appropriate.
D
Enter as appropriate.
E
For systems fitted with primary and secondary filters. Note: A
F 'highlight' is shown on the previously entered value, and either the
same number can be re-entered or the key can be pressed
and this will accept the previous value.
Enter as appropriate.
G
If a helium purge unit is fitted. Helium is normally used when
H determining low concentrations of relatively low atomic number
such as Al, Si, P, S, and Cl.
The calibration time (and the time subsequently used in routine
analysis) can be specified between 1 and 9999 seconds. This is the
measurement time for the first set of measurement conditions
and a default setting of 1 second is displayed.
This is the time taken to measure the setting up samples. As
J a guide, it should be twice the calibration time because the
calibration line will be adjusted for any change in
instrument performance and the precision of measurement
increases as measurement time increases.

 a e5
5
 Once the conditions are correct press <<YES>> and another set of
measurement conditions can be specified if required, e.g. for a different
element or element range.

Editing/adding another condition

Re-selection of Option 1=Conditions allows a condition to be edited or a new
condition to be specified. Note: A condition cannot be deleted.

Specify instrument condition No l ?

<YES>/<NO>

Yes
Select on the keypad to modify the first set of instrument conditions or
No
to select the second, third, etc., conditions. When all the previously
entered conditions have been shown the screen will display:

Enter condition No N ? <YES> / <NO>

where N is a new set of conditions to be added to the current list. On

completion, this screen will be displayed:
(Calibration title)
l=CONDITIONS 2=SEGMENTS 3=CONTINUE

Se ments
See pages 5.8 and 5.9.

Page 5.6 LZOM3500 © Oxford Instruments Analytical 2000. All Rights Reserved
 Section 5: Calibration

This page is
intentionally blank

 a e 5
Flow Diagram for Segments and Tolerance Limits
Se ments (Summary)
This section allows the elements or analytes to be measured and specified in
detail (including any segments required for X-ray corrections such as
'backscatter'). This includes the set of measurement conditions (defined above)
under which the element(s) is to be measured, element name, 'window'
conditions, i.e. lower and upper channel values, concentration units, and
number of decimal places.

This is the name required for the segment, e.g. S for sulphur in
C oil, or SALT if measuring crisps, or Si if silicone on paper etc.. The
name will be used for all subsequent reference to this segment
of the spectrum and in the printout.

Settin up manual input se ment

To define a manually entered segment in a calibration, the
segment is set to use condition number 0. In this case only the
decimal places and units are entered for such a segment. The
calibration print out and template for a manual segment
contain the segment name, condition number 0, decimal places
and units only:

Segments:
Name No Channels Dp Tolerances Units:
LOI 0 - - 2 - - %

The standards and SUS's in a print out or template show no

values for a manually input segment. When measuring a
standard or SUS, or restandardising a SUS, no values for the
manual segment are entered or printed. The total number of
segments, including normal segments, manual segments and
barometric segments, cannot exceed 10.

NOTE: Manually entered parameters can be used in any post-

analytical calculations, just like any other concentration
segment.

This refers to the measurement conditions that are used to

D measure Seg1.
Section 5: Calibration

These questions define a region of interest in the spectrum. Any

E F channel number from 25 to 255 can be specified, e.g. 30. The
default value for the lower channel is 25. The values required
for the lower and upper channels are derived from a spectrum
scan that should have been accomplished previously. If the
lower channel was specified as 30, the upper channel can be
any value from 30 up to 255. Note that the upper channel value
must be greater than the lower channel value. If a lower value
is specified it will not be accepted, the value must be erased
using
Del
the (delete) key and the correct value inserted.

Normally a segment to be measured, e.g. Si, S, P, etc., will have a

H concentration value in %, ppm, g/l, etc. (Note: some segments,
such as a 'backscatter' signal that is only used for X-ray
correction purposes, will not have a designated concentration
but that segment will still need to be specified for correction
purposes). Up to 8 characters can be specified. Typical examples
are %, PPM, G/LITRE, LBS/REAM, etc.

Insert the number of decimal places from zero to four required

for this element segment. If the calibration is for a multi-
element application, such as sulphur and chlorine in oil, then, as
an example, the sulphur could be measured in percent to two
decimal places and the chlorine measured in ppm quoted to
zero decimal places. These are the values that will be shown on
the printout obtained in routine analysis and can be edited
later if required under the 'edit calibration' option. Only values
between 0 and 4 will be accepted. If an error is made, delete the
Del
value using the key and enter the correct value.

Tolerance limits
Often in quality control applications a lower and upper concentration limit is
specified for a process. If these 'tolerance values' are specified, then any
sample in routine analysis where the measured concentration is outside the
specified band produces a printout with 'out of specification' in red.
Tolerance limits can be specified for each element or just a lower or upper
value, as required. A value can be entered for each segment regressed or No
press the
key if tolerances are not used.

a e5 0 
 The lower tolerance value is specified in the concentration units
K previously defined.

The value is specified for this segment and a printout is given of

M all the parameters.
No
If the parameters are not correct, select and the values can
N be re-entered. Note: Press the key to accept the previous
value shown.

(Calibration title)
l=CONDITIONS 2=SEGMENTS 3=CONTINUE
After the conditions and segments required have been fully specified, select
Option 3=Continue.
l=STANDARDS 3=CORRECTIONS 2=REGRESSION
4=CONTINUE
Section 5: Calibration

Flow Diagram for

measuring Calibration
Standards

Page 5.12 LZOM3500 © Oxford Instruments Analytical 2000. All Rights Reserved
 Section 5: Calibration

Measurin Calibration Standards

This function allows the following:

• Measurement of a series of calibration standards so that a regression can

be performed.

• Concentration values to be assigned to a standard.

• Measurement, rejection, recall of a standard.

• A 'direct data' entry mode for standards that have previously

been measured to be added to a calibration.

A standard label can be entered that can be up to 10 characters

C long and alphanumeric. This label will also appear on the printout
given after measuring a calibration standard.

Concentrations for this standard can now be entered or the

D standard can just be measured if a concentration value is not
currently known.

In addition for a multi-element application, e.g. measuring P, S,

E and Ca in lubricating oil, some standards may have a sulphur and
calcium concentration but no phosphorus concentration. In this
case the concentrations for S and Ca can be entered and no
concentration for phosphorus specified. On the printout if a
concentration has not been specified for a segment then a # sign
is given. Only those segments specified as having a concentration
(as defined when specifying the segments) will be included.

Enter the concentration value.

F
The standard (in this example STDX) can be measured. If already
G measured, then the intensity can be input or the standard can be
rejected manually.
Yes
Measure: Once the standard has been inserted and the
key pressed the measurement on the
calibration standard takes place.

 a e 5
 Manual: This function allows a standard that has
previously been measured to be added to a
calibration by manual data input. The intensity in
counts per second can be input from the keypad.
If this function is selected after a standard has
been measured using Option 1=Measure, the
current intensity value(s) are shown for the
number of segments measured, i.e. this is a repeat
of the intensities given on the printout.

Reject: If the standard measured needs to be rejected

from the calibration, for example if a liquid
standard had leaked during the measurement time,
then by selecting this option the standard will be
removed from the calibration. On selection a
printout is given in red print indicating that the
standard has been removed, in addition the LCD
display will change from the word reject to recall
which allows the standard to be recalled if
required.

After one of the above operations has been completed, select Option
4=Continue to return to the menu:
Enter new standard?<YES> / <NO>

No
Another standard can be measured or is selected then the previous
if screen is displayed i.e.:
l=STANDARDS 3=CORRECTIONS 2=REGRESSION
4=CONTINUE

Re ression
A regression can now be performed. Selection of Option 2=Re ression gives:
l=Error analysis 2=Graph 3=Graph 2
l
4=Intensities S=Manua 6=Quit
l

a e5 4 LZOM3500 © Oxford Instruments Analytical 2000. All Rights Reserved

 Section 5: Calibration

Error Analysis
Select Option l=Error Analysis to perform a regression of the raw
intensity data against the given concentration for a particular segment. The
error analysis for a specific element, or all elements, can be selected by
highlighting the required element(s) and then pressing the key. This
function can only be used when six or more standards with concentration
data have been analysed.

Note: If there are more segments than fit on the display, then the menu looks
like this:
SELECT SEGMENTS
O=Turn pagel=ABCD 2=EFGH 3=IJKL 4=MNOP

Select O=Turn page to display the extra segments available for regression.
Graph 1
Select Option 2=Graph l to print out a graph of intensity (raw data)
against concentration for the particular segment specified.

Graph 2
Select Option 3=Graph 2 to print out a graph of the given concentration
against the calculated concentration for the particular segment specified.

Intensities
Select Option 4=Intensities for a printout of the original, i.e. raw
data, intensities for the standards and the corrected intensities. If a straight
line regression has been performed then the original and corrected will be the
same value. However, if a correction, such as a line overlap of ratio, has been
applied then the corrected intensity is the value of the intensity after the
correction has been applied.

Manual
Select Option S=Manual to enter the calibration coefficients, i.e. the A0
and A1 values, manually if a calibration has been previously derived on a Lab-
X 3500.

Quit
Select Option 6=Quit to return to the screen:
l=STANDARDS 3=CORRECTIONS 2=REGRESSION
4=CONTINUE

 a e5 5
Flow Diagram for X-ray corrections
 Section 5: Calibration

X-ray Corrections
After the calibration standards have been analysed, the correlation of X-ray
intensity to the given concentrations can be observed either by the error
analysis or the graph. If a poor correlation of X-ray intensity against
concentration is seen, then a correction may be necessary to improve the
calibration fit.

Corrections should only be applied where appropriate, e.g. if a spectrum scan

shows an overlap of one element on another, then this correction should be
applied. It may not be relevant to carry out a correction, depending on the
application, and some knowledge of the theory of X-ray fluorescence is
required to check on its validity. Normally only one or two corrections should
be required. If a calibration is over-corrected, i.e. many corrections applied,
then although the correlation looks good, the analysis of unknown samples of
the same material type will produce inaccurate results. A good procedure to
check the validity of a calibration is to obtain ten standards, calibrate using
eight of them and run the remaining two as 'unknown'. Please refer to the
flow diagram on Page 5.16>.

Select Option 3=Corrections.

A
Select Option l=Corrections to specify the various
B corrections available, i.e. blank subtraction, overlap correction,
ratio or mass absorption correction. For the blank subtraction
and overlap corrections a Setting Up Sample must also be
measured. If a particular correction is not required then press
the enter key to display the next correction.

C Blank Subtraction

This correction 'forces'

the graph to pass
through zero intensity
for zero concentration
and requires a blank
sample to be analysed.
The correction is
normally applied for Figure 5.1
the
silicone on paper application. Diagrammatically the correction
is as shown in Figure 5.1.

LZOM3500 © Oxford Instruments Analytical 2000 . All Rights a e 5

 Restrictions on blank subtraction correction:
When applying blank subtraction the same blank must be
used. Also, do not subtract a blank from a 'backscatter' signal
because the blank will give the highest intensity reading and
the correction will not be valid.

The segment requiring correction, (the example shows three

segments specified in a calibration by SEG1, SEG2, SEG3),
should be specified and on selection a 'highlight' will appear.
To implement this, a blank sample must be measured as a
SUS (using the SUS routine shown in the Screen then when a
regression is performed the blank subtraction correction will
automatically be applied and this will be seen by a change
in the A0 value of the calibration line. If the blank
subtraction has been selected by mistake or you wish to
remove the correction then press the key corresponding to
the segment highlighted and the highlight will disappear.
When a new regression is applied the correction will be
removed.

Overlappin se ment
D From a spectrum scan it can be seen that if the element of
interest is overlapped by an adjacent or nearby element, then
the intensity measured for this element cannot be correlated
to the given concentration because of the interference of
this element. To correct for this an overlap correction can be
applied.

To calculate the amount of one element overlapping onto

the element of interest, a setting up sample (SUS) needs to
be measured which should contain only the overlapped
element and not the element of interest. By first specifying
the overlap required (see below), then measuring the setting
up sample followed by a new regression, the software will
calculate the overlap factor and apply this during the
regression. The overlap correction can be applied on more
than one element (segment).

Note: A segment cannot be overlapped onto itself.

 In the example SEG 1 requires to be corrected for an overlap
coming from (caused by) SEG2.

Select Option 2=SEG2, i.e. the segment that is causing the

overlap.

Next the segment that is being overlapped, in this example

E SEG1, should be selected by pressing the number 1 key and a
'highlight' will appear on this segment. When completed press
the key to return to D and now SEG2 has a 'highlight'
applied. When completed press the key and the
next correction will be shown.

Note: For this correction to be implemented a Setting

Up Sample must be measured before a regression
is carried out using the SUS function shown in B
screen

If an overlapping segment has been selected by

mistake or you wish to remove the correction then
press the key corresponding to the segment
highlighted and the highlight will disappear. When a
new regression is applied the correction will be
removed.

Ratio Correction
F This option is used when two element segments need to be
ratioed. One of the main uses is in the analysis of oils where
oils of different matrix types can be analysed using one
calibration line by applying a ratio of the element being
measured to a 'backscatter' or background signal..

Select the element segment to be ratioed, in this example

segment SEG1 requires to be ratioed to SEG2 so press '1' to
select SEG1.

SEG1 can now be ratioed to another segment, e.g. SEG2, by

G pressing '1'.
 This allows the denominator to be raised to the power
H required between 0.1 and 2. If a zero is entered then the
correction is not implemented, normally a simple ratio is
required so the value would be entered as 1 (one).

A 'highlight' is now shown on SEG1 because this segment has

had a ratio to segment 2 applied in F above.

To remove the correction the same segments can be specified

and at the prompt Raise SEG2 to what power?, a zero should
be entered which removes the correction (and the 'highlight')
and when a new regression is performed a ratio will not be
applied.

Note: A segment can be ratioed to itself only as a special

case. Experienced XRF users should only carry this out during
method development.

Mass absorption corrections

I This correction should be applied when the intensity of
radiation coming from a sample for one element has been
modified by the presence of another element in the sample.

For example, when an element has been fluoresced by incident

radiation from the X-ray tube, the element emits secondary or
characteristic X-rays. Each element requires a certain minimum
energy to excite it and this is called the X-ray absorption edge,
e.g. for calcium this value is 4.04keV. Therefore, if a primary X-
ray has an energy of 4keV then the calcium will not be excited
because the incoming radiation is not energetic enough but if
it is greater than 4.04keV the calcium will be excited.

In a sample containing sulphur and chlorine the chlorine

radiation will be emitted at 2.622keV. The absorption edge
for sulphur is 2.47keV, therefore the sulphur in the samples will
be excited by the chlorine radiation and the intensity of
chlorine radiation emanating from the sample will be reduced
by the presence of sulphur. A mass absorption correction of
sulphur on chlorine will correct for this effect.
 Section 5: Calibration

The element segment that requires a mass absorption to be

applied is first specified, e.g. SEG1.

The interfering segment should now be specified, e.g. press

J '2' for SEG2, which will put a 'highlight' on that segment. More
than one segment can be specified at this stage, if required.
On completion press to return to I
In the example a 'highlight' will be applied to SEG1. When a
I regression is accomplished a mass absorption correction of
SEG2 interfering on SEG1 will be applied and SEG1 will be
corrected. This correction is an intensity correction based on
the collected intensities in the two segments.

To remove the correction the same procedure should be

followed and re-selection of the same element segments
will remove the 'highlight'. If a regression is now
accomplished a mass absorption correction will not be
applied.

Note: When applying mass absorption corrections some

knowledge of X-ray spectrometry is required as corrections
should only be applied where appropriate.

On completion, press to re-display Screen B

Settin Up Samples for Instrument corrections
B When an X-ray correction is to be applied such as fixed
background or overlap correction then a setting up sample(s)
must be measured using this routine before a regression is
performed.

If the only corrections specified are 'Ratio' or 'Mass Absorption'

then setting up samples do not need to be measured and
Option 2=SUSSES cannot be accessed.

If a blank subtraction has been specified then a blank sample

needs to be measured as a SUS. Select Option 2=SUSSES.

LZOM3500 © Oxford Instruments Analytical 2000 . All Rights a e52

 Enter the sample label (e.g. BLANK)
K
The BLANK SUS can be measured in one of the three turntable
L positions, i.e. 0, 2 or 4. Specify the desired position.

l=MEASURE: This will measure the blank SUS in the port

M specified.
Yes
Press when the SUS is inserted.
N
After the measurement has taken place a printout is
given specifying the SUS name, turntable position (TTP)
and the intensity (labelled original) of the SUS measured
under the element segments specified in the calibration.

M 2=MANUAL DATA ENTRY: If the intensity for the setting

up sample is known for all the element segments then this
can be typed in directly on request, without measuring the
setting up samples. When all element segments have been
entered a M
printout is given and screen is re-displayed.

Select OPTION 3=CONTINUE and Screen is re-displayed.

Edit Blank Correction

If a correction, i.e. blank subtraction is subsequently removed -
that is not required - then whenOption 2=SUSSES
(Screen B ) is selected the message:

BLANK SUS NOT USED

DELETE Y/N
is given. This allows the SUS to be removed if no longer
required.

From Screen B select Option 2=SUSSES

Overlap Correction
O If an overlap correction has been specified, then using the
example shown in Screens D and E, a setting up sample
that contains only the element corresponding to SEG2
should be measured so that the software can calculate the
overlap factor for SEG2 into SEG1. This is repeated for the
number of E.
overlaps specified in D Enter the SUS label.
and
 Section 5: Calibration

Enter the SUS position in the turntable, i.e. 0, 2 or 4.

l=MEASURE: This will measure the instrument SUS in the

Q port specified.
Yes
Press when the SUS is inserted.
R
After the measurement has taken place a printout is
given specifying the SUS name, turntable position (TTP)
and the intensity (labelled original) of the SUS measured
under the conditions specified in the calibration.

2=MANUAL DATA ENTRY: If the intensity for the setting

Q up sample is known for all the element segments then this can
be typed in directly on request, without measuring the setting
up samples. When all element segments have been entered a
printout is given and Screen Q is re-displayed.
Select OPTION 3=CONTINUE and Screen B is re-
displayed. Select OPTION 3=CONTINUE and Screen A is
re-displayed. Select OPTION 4=CONTINUE.

l=LOW AND HIGH SUSSES 3=RESTANDARDISATION WARNING 2=REPEATS

4=CONTINUE

Low and Hi h SUSSES

Select l=LOW AND HIGH SUSSES. On selection a printout is given of the
SUSs required for restandardisation of the calibration line(s). A high and low
SUS will need to be measured for each segment regressed, plus any SUSs
used for instrument corrections, i.e.: if a blank subtraction or overlap
corrections have been applied. If the application involves the determination
of two elements then four SUSs will be required that represent the low and
high intensity values for the two elements. Often the SUSs can be chosen to
be either the low value for both elements, or low for one and high for the
other.

If a SUS has been measured once in a specific turntable position and the same
SUS is specified again then it is not necessary to re-measure the SUS. By
selecting the Manual Data Entry option the intensity will be displayed and by

 a e52
 pressing the enter key the value is accepted and a printout given. SUSs can
be chosen from three areas:

• Fused beads provided by Oxford Instruments, Analytical

• Samples located underneath the turntable
• Customers own SUSs

If the SUSs underneath the turntable are chosen then a specific part number
should be used so that the software recognises the samples. These are:

IAGPS1: The Oxford Instruments Ti sample

IAGPS2: The Oxford Instruments Al sample

If any of these sample labels are used then the sample will be measured and
the intensity data printed, i.e. the turntable position will not be requested.

The display will prompt for the required SUSs and the SUSs should be
analysed in their final positions, i.e.: either in one of the ports of the Lab-X
3500 turntable or measured in port zero which is the analysis position. For
example, if a regression is a straight line correlation measuring one segment
(SEG1) then the following will be displayed:

Enter SUS label for low SEGI

The SUS label should be entered followed by the SUS position in the turntable,
i.e. 0, 2 or 4. The following screen is then displayed:
Instrument SUS for SEGI (label) l=MEASURE2=MANUAL DATA ENTRY
3=CONTINUE
Select l=MEASURE
This will measure the instrument SUS in the port specified. Enter the SUS
Yes
required and press when inserted. After the measurement has taken
place a printout is given specifying the SUS name, turntable position (TTP)
and the intensity (labelled original) of the SUS measured under the conditions
specified in the calibration. After correct measurement select
OPTION 3=CONTINUE.

Select 2=MANUAL DATA ENTRY

 Section 5: Calibration

If the intensity for the setting up sample is known for all the element segments
then this can be typed in directly without measuring the setting up sample.

The above procedure is then repeated according to the number of SUSs

required for the calibration.
l=LOW AND HIGH SUSSES 3=RESTANDARDISATION WARNING 2=REPEATS
4=CONTINUE

Define parameters for routine analysis

Select Option 2=REPEATS. This option allows one sample to be
measured "n" times for routine analysis, or if sample inhomogeneity is
considered to be a problem then "n" samples can be taken from the bulk
sample and each "sub-sample" measured once.

On selection the following is displayed:

Enter number of measurements (l-99)

Note: The default value is 1 (for software version 1.8 or earlier then the
number of repeats was required, where 0 repeats = one measurement).
Repeat measurements l=Same sample
2=Different samples
If a series of measurements is required on the same sample then select l if
different samples are to be measured then select 2.

If l is selected: routine analysis will be performed as follows:

Once a sample label is entered and the sample

placed in the port, the sample will be rotated to the
analysis position and measured "n" times, with each
result shown and the average printed at the end of
the number of measurements specified. When the
calibration method details are printed, at the bottom
of the printout will be shown (assuming three
measurements on the same sample):

Number of repeats 2 Same sample YES

 a e5
25
NOTE: When repeat measurements are defined in the calibration, the
manual segments are entered only once at the start of the analysis
after the sample name is entered. The same value is used for each
repeat measurement. This applies to repeats on the same sample and
repeats on different samples.

If 2 is selected: routine analysis will be performed as follows:

Once a sample label is entered and the sample placed in the port, the
sample will be rotated to the analysis position. The result from the first
"sub-sample" will be printed out, the automatic turntable rotates back
to the analysis position and the software prompts for the next sample.
This sequence is repeated until the last sample is measured, the average
result is then displayed and printed out. When the calibration method
details are printed, at the bottom of the printout will be shown
(assuming three measurements on the same sample):

Number of repeats: 2 Same Sample NO

For routine analysis one sample can be measured 'n' times without operator
intervention. If two measurements are required on a sample then the
number of repeats is one, i.e.: one standard measurement and one repeat.
Select Option 3=RESTANDARDISATION WARNING.

On selection the following is displayed:

Enter time interval before warning:

(hours from l to 99)
Restandardisation involves the re-measuring of the Setting Up Samples (SUSs)
that were measured when the calibration was first derived. These
measurements correct for any 'long term' change in the instruments
performance. To determine when a restandardisation should be accomplished
a quality control 'check sample' is often measured as an 'unknown' against the
calibration. If the values shown on the concentration reading for this sample
are outside the required limits, restandardisation should be carried out and
the QC check sample re-measured. This approach will determine when
restandardisation should be carried out, depending on a particular
application and location of the instrument.
 Section 5: Calibration

If required, this time limit can be specified above, for example 8 hours, and
after this time period when the ANALYSE function is selected the message:

Restandardisation recommended, Restandardise?

<YES/<NO>

is given. Select Option 4=Continue.

Printer Format
Three formats are possible, i.e. normal, customised or condensed. It is
suggested that normal is used when first deriving the calibration.
Printer format l=Normal
2=Condensed 3=Customised

For the Normal printout the default parameters are set and a standard
printout is obtained. This is shown below. If required the standard could be
changed to either condensed or customised at a later date.
The Condensed printout is again a default value and saves on the usage of
paper. For a one element application the printout is simply the sample label,
time, date and results. No Oxford Instruments heading or instrument type is
shown.

The Customised printout allows many designs to be incorporated. The input

of the parameters is via a 'dot command' and a list of possible dot commands
is given below:

.Sl.-.SO Segment name (where .S1 = Segment 1,, .S0 = Segment 10)
.CT. Calibration title
.L. Sample label
. Concentration where 1 and 0 again refer to the segment and:
ClXY.-.COXY.
X = number of digits before decimal
point Y = number of digits after
decimal point
.CMlXY. Mean concentration for Segment 1
. Intensity
IlXY.-.IOXY.
.IMlXY. Mean intensity
.Ul.-.UO. Units of measurement
.D. Current date
.T. Current time
.X. Line of *****
.R. Specified at the start of a line if the line is to be printed in red
characters (normal size) and automatically cancelled for next line

 a e52
.B. Specified at the start of a line if the line is to be printed in
large (black characters) and automatically cancelled for next
line
.RB. Specified at the start of a line if the line is to be printed in
large red characters and automatically cancelled for next
line
.I. Continued on next line
.-. Allows a calculation to be incorporated (see Example B).

If a customised printout is required similar to Example A, then the printout

can be derived as follows by specifying the required parameters for each line
on the printout.

Line No. Comments

1 *********************** Normal black
2 OXFORD INSTRUMENTS Large red
LAB-X 3500
3 04/06/1997 09:26 Large black
4 SULPHATE IN CEMENT Large black
5
6 SAMPLE LABEL Normal black
7 CONCENTRATION Normal black
8 *********************** Normal black

Example A
To generate this printout the following dot commands should be entered
and the key pressed when the line is finished:

Li Message Commen
ne ts
1 .X. Prints a row of stars
2 .RB. , OXFORD Prints large red and name
INSTRUMENTS LAB-X
3500
3 .B..D. .T. Prints large black date and time
4 .B.SULPHATE IN CEMENT Prints large black the characters specified
5 Press for blank line
6 SAMPLE LABEL Prints characters specified
7 CONCENTRATION Prints characters specified
8 .X. Prints a row of stars
 Line No Comments
OXFORD INSTRUMENTS Large red
LAB-X 3SOO
2 ANALYSIS REPORT Large black
3 04/06/1997 09:26
Normal black
4 Calibration title: SALT1 Normal black
5 SAMPLE: 2 Normal black
6 2367 cps Normal black
7 ***********************
Normal black
8 Sample 2 = 11.47% SALT
Normal black
9 = 6.16% BUTTER Normal black
10 *********************** Normal black
Example B
To generate this printout the following dot commands should be entered
and the key pressed when the line is finished:

Li Message Commen
ne ts
1 .RB.OXFORD Prints large red and name
INSTRUMENTS LAB-X
3500
2 .B.ANALYSIS REPORT Prints large black the characters specified
3 .D. .T. Prints normal black date and time
4 Calibration title: SALT1 Prints normal black the characters
specified
5 SAMPLE .L. Prints characters specified
6 .IM150.cps Prints the characters specified
7 .X. Prints a row of stars
8 Sample.L. = .CM132. % Prints the characters specified
Salt
9 =.=22.SALT/10+5 % Performs a calculation and prints the
BUTTER characters specified (see below for details
Similar customised printouts can be specified as required.

Post Analytical calculations

Post analytical calculations can be inserted into calibration print-outs and
templates. The calculation is evaluated at the time of analysis. If the equation
is inserted in a print format the result of the calculation will be printed. If the
equation is inserted in a RS232 format the result of the calculation will be
transmitted. The equation is started by a new dot
command, eg:.=23., where 23 specifies the format of the result (2 digits before
decimal point, 3 digits after decimal point in this example).

Simple calculations using + - * / operators and nested brackets ( ) can be used.

Only segment concentration values and constant numbers can be used in

calculations. Concentrations are specified by the segment name which must
begin with a letter and must contain only letters and numbers.

Equations must not contain spaces. The maximum length of a line containing
an equation is 255 characters.

Equations are evaluated from left to right. Multiply and divide take priority
over add and subtract.

Evaluation of an equation is terminated by the end of the line or a space or

any invalid character or invalid segment name or invalid number. In this case,
the result of the calculation is printed (or transmitted) and the remainder of
the line (if any) is printed (or transmitted). The rest of the line may also
contain other dot commands, including more calculations.

For example, the calculation for LSF (Lime Saturation Factor) should be entered
as follows:

LSF - .-23.(CA-0.7*S)I(2.8*SI+l.l8*AL+0.65*FE)

Use the keys (see section 1 page 1.7) to enter the special characters.

Any constant or part of the calculation can be edited.

 Section 5: Calibration

The cursor can be moved by using the •

key in conjunction with the Shift Up
and Shift Down keys See section 1 page 1.7
Divide by zero or other overflow errors in post-analytical calculations are
handled in the same way as similar errors are handled in existing calculations
(ie: the result so far is set to zero and the calculation continues).

After specifying the printer format the following screen will appear:
l=RS32 format 3=DELETE STANDARDS 2=OTHER
4=CONTINUE
Select Option l = RS232 format

RS232 format
This can be set up as required for the transmission of results data. Three
options are available, as shown below:
RS32 format l=Off
2=Default format 3=Customised

This selects what data will be transmitted for this calibration along the RS232
cable when the calibration is selected for routine analysis. Whichever option is
chosen can be changed subsequently in the 'Edit Calibration' section if
required.

Option l=Off: In routine analysis the results will not

be transmitted via the RS232.

Option 2=Default format: Uses a default setting and the parameters

transmitted are similar to the 'normal
printout' used in the printer format of the
previous section.

 a e 5
 Option 3=Customised: Allows many designs to be incorporated.
The input of the parameters is via the
'dot command' and the dot commands
possible are the same as for printer
format.

After specifying the RS232 format (if required) the following screen will be
re- displayed:
l=RS32 FORMAT 3=DELETE STANDARDS 2=OTHERS
4=CONTINUE

Select Option 2=Others

For routine analysis an operator can select a calibration and carry out routine
analysis work. In many cases calibration work involves trying out new methods
of analysis that may not result in a good calibration. This function allows only
those calibrations which are required to be used by the operator to appear in
the ANALYSE section of the software, ie: the operator need not be presented
with a list of all the calibrations in the instrument but only those relevant for
routine analysis.

On selection the following is displayed:

Use for routine analysis?

O=Not available l=Available
If 1 then this calibration will appear in the routine analysis section of the
software if 0 then it will not.
l = RS32 format 2 = OTHER
3 = DELETE STANDARDS 4 = CONTINUE
Select Option 3 = Delete Standards

Delete Standards
This function will delete the standards measured during the calibration. It will
not delete the calibration itself, ie: the co-efficients of the slope (sensitivity),
background level, SUS data etc, but will delete the standards data, ie: standard
name, concentration and intensity. The function is used purely to save on
memory space when many calibrations are used on the instrument. Generally,
unless there is a problem with memory space, it is preferable to retain the
standards data in memory. On selection the following is displayed:

Delete all standards

Please confirm ? <YES>/<NO>
 Confirmation is required with a YES/NO answer.

This screen will then re-appear:

l=RS32 FORMAT 3=DELETE STANDARDS 2=OTHERS
4=CONTINUE
Select Option 4=Continue

Save calibration
This function will save the calibration in the Lab-X 3500's memory.
The following is displayed:

Save Calibration <YES> / <NO>

Confirmation is required with a YES/NO answer. If YES is given to the 'Save

Calibration' screen then the following screen will be displayed:
l=EDIT 2=COPY 3=LIST 4=SE
ND
S=DELETE 6=MEASURE ?=QUIT
If NO then further confirmation is required before the calibration is deleted, ie:
Delete (Calibration title)
Please confirm ? <YES> / <NO>
If the calibration is to be deleted then by answering YES to the above
question all data for this calibration will be erased and a printout in red will
be given stating:

(Calibration title) deleted

Once the calibration is saved the following screen is displayed:

l=EDIT 2=COPY 3=LIST 4=SE

ND
S=DELETE 6=MEASURE ?=QUIT

Edit
This allows a parameter used in the calibration to be modified to a new
value. Examples are changing the analysis time, adding another standard,
changing the number of repeats etc.

It should be noted that if a calibration has been derived where a series of

standards have been measured then the instrument parameters, i.e.. kV on
tube, microamps, etc cannot be changed. This is because it would make the
intensity values for the standards incorrect. If different conditions are required
then a new calibration should be derived.
Copy
This feature allows a calibration to be copied. On selection the following is
displayed:

Enter new calibration title

(Current calibration title shown)
The new calibration title can be specified.

Note: The same calibration title cannot be used as a copy.

After specifying the new title, the following is displayed. The example shown
is for a calibration called SULPHUR copied into a second calibration called
SULPHUR COPY.

Select old or new calibration

l=SULPHUR 2=SULPHUR
COPY
From this the required calibration can be selected and the following screen is
displayed:
l=EDIT 2=COPY 3=LIST 4=SE
ND
S=DELETE 6=MEASURE ?=QUIT
From which the required function can be selected.

List
This will give a printout of the calibration, i.e.. All parameters stored including
the standards used to derive the calibration providing these have not been
deleted under the option 'delete standards' in the calibration.

Send
This will allow a calibration to be downloaded to a PC using an RS232
interface lead. This feature allows a back up calibration to be stored on a PC,
which can be edited and transmitted back to the Lab-X when required.

Select Option 4=Send. The display will show:

Transmitting calibration
Please Wait

Delete
This allows a calibration to be deleted. On selection the following is displayed:
 Section 5: Calibration

Delete (calibration title)

Please confirm ? <YES> / <NO>
If confirmed, then the calibration will be deleted and a printout will be given
in red stating (Calibration title) deleted.

Measure
This routine is the same format as used in the routine analysis section. Samples
can be measured against this calibration when in this calibration section.

Quit
On selection the calibration section will be finished and the following
screen displayed.
l=SPECTRUM SCAN 3=UTILITIES 2=CALIBRATION
4=MAIN MENU

Data from RS232 See Page 5-2

l=CREATE CALIBRATION 2=DATA FROM RS232

Select 2=DATA FROM RS232 and the display will show:

SELECT PORT l=RS232 l
2=RS232 2
Select Option l=RS232 l to receive a calibration on Port 1 or 2=RS232 2
to receive a calibration on Port 2.

Receiving calibration
Please Wait
and then:

l=EDIT 2=COPY 3=LIST 4=SE

ND
S=DELETE 6=MEASURE ?=QUIT
If this message appears:
TRANSMITTED CALIBRATION INVALID
Press <Escape> to continue
It means that the calibration has not been transmitted correctly. Select
and the screen will again display:

l=EDIT 2=COPY 3=LIST 4=SE

ND
S=DELETE 6=MEASURE ?=QUIT
Select Option 3=List to ascertain what information has been received

 a e5 5
 and, based on that, Options 5 or 7 can be used. Option 7=Quit exits the
Calibration routine.

If an Oxford Instruments pre-programmed calibration has been provided, the

analytical calibration parameters have already been derived and the
calibration involves first copying the Oxford Instruments calibration and then
simply measuring a series of standards and SUSs.

Calibrations When a calibration is created on the Lab-X 3500 and then copied to a PC, the
created as file can be transmitted back to the Lab-X using the above procedure if no
text changes have been made to the file.
files
If changes have been made or if a text file is created on a PC to be used as
a calibration, then the format in Figure 5. must be followed in order for
the calibration to be successfully recognised by the Lab-X.
 Section 5: Calibration

Calibration Format

Fi ure 5 2: Lab-X 3500 Calibration Printout

Only UK or USA date formats are recognised (i.e.. UK format "d/m/y h:m or USA m/d/y h:m am

Calibration title may contain

spaces. This must be the very first
line and must contain a colon (:) calibration has not been restandardised this line should not contain a valid
f the
character before the start of the
title.

This section must be terminated by a blank line Calibration title: GRC 123
Created: 1/2/1997 1:28
Last restandardised: 3/4/1997 0:58
Instrument:
Pd Ne f helium is not used this must be marked by some character (hyph

Conditions
# Range kV uA Filters CT RT
1 HIGH 19 30 L3 K3 - 28 56
Ranges in any languages are recognised (i.e.. 2 LOW 4 100 - X3 He 30Unused
60 filters must be marked by some character (hyphen for
AUT or O ) are valid
Segments:
Name No Channels Dp Tolerances Units
C 1 4 73 2 - - %
Segments may contain spaces A 0
F 1 7 11 2 - - This section must be
E 6 0
This section must be terminated by a blank line. S 2 5 95 2 terminated by a blank line.
I 0 Unused tolerances must be marked by some character (hyphen
Standards:
SAMPLE NAME CONC INT (CPS)
STD1 CA 1.23% 12.34
Standard names may contain spaces
FE 2.34% 23.45
SI # 34.56
STD2 CA 12.3% 123.4
FE 23.4 ppm 234.5
SI # g/m3 345.6
STD3 CA # % 1234
This section must be FE # 2345
terminated by a blank line. f SI 345 3456
There must be a space between a concentration value (if any) and th
there is no standards section STD4 CA # 12340
FE # ppm 23450
then the whole section must SI 3450 g/m3 34560
be replaced by a blank line
SUSSES
SUS TTP NAME ORIGINAL CURRENT
SUS names may contain SUCM04B2 CA 1.1E+00 2.1E+00
spaces FE 1.2E+00 2.2E+00 Current SUS data need not be
ed by a blank line. f there is no standards section then the whole section must be replaced
SI by 1.3E+00
a blank line 2.3E+00
SUCM03B 4 CA 1.4E+00 2.4E+00 present
FE 1.5E+00 2.5E+00
SI 1.6E+00 2.6E+00
IAGBLANK 1 CA 1.7E+00 2.7E+00
FE 1.8E+00 2.8E+00
SI 1.9E+00 2.9E+00

 a e 5
 Fi ure 5 : Lab-X 3500 Calibration Printout (continued)
line. If there is no blank subtraction section, then the whole section must be replaced by a blank line.

This section must be terminated by a blank line. If there is no instrument corrections section, then the whole section must be replaced

Blank Subtraction: IAGBLANK on CA FE SI

Instrument Corrections: SUSNAME

k line. If there is no ratio corrections section, then the whole section must be replaced by a blank
OVERLAPPED line
SEGMENTS FESI
SUCM04B CA SUCN03B FE CA

Ratio Corrections:
NAMERATIOED BYTO THE POWER OF CAFE1.8
This section must be terminated by a blank line. If there is no coefficients section, then the whole section must be replaced by a blank line.
FECA2.0 Note: Intercept=AO, Slope=A1

Coefficients:
NAMEINTERCEPT SLOPEEFFECT 1
CA0must be replaced by a blank
lank line. If there is no SUS usage section, then the whole section 3 line.
FE1 FE9
5
SI 2

:
GH
SUCM04B This must be the sixth line from the end of the calibration.
SUCM03B
SUCM03B
end of the calibration. If there is no restandardisation warning time, this line must be:
ing
Repeats: 7Same Sample: NO Restandardisation warning after 8 hoursType numbers
Printer for printer
format format0are
type: type O (normal),
(Normal) RS232type 1 (condensed),
format type: type 2 (customised)
0 (Off)
Allowed: YES Locked: No

Type numbers for RS232 format

are type O (off), type 1 (default),
type 2 (customised)
Section 5: CALIBRATION...............................................................................................................................5.1
Creating a new calibration.....................................................................................................................................5.2
Measuring a set of calibration standards and defining all the measurement conditions......................5.2
Conditions..............................................................................................................................................................5.3
Conditions (summary).........................................................................................................................................5.5
Editing/adding another condition.....................................................................................................................5.6
Segments.......................................................................................................................................................................5.6
Segments (Summary)...........................................................................................................................................5.9
Tolerance limits.........................................................................................................................................................5.10
Measuring Calibration Standards.....................................................................................................................5.13
Regression...................................................................................................................................................................5.14
Error Analysis......................................................................................................................................................5.15
Graph 1.............................................................................................................................................................5.15
Graph 2.............................................................................................................................................................5.15
Intensities................................................................................................................................................................5.15
Manual.................................................................................................................................................. 5.15
Quit...................................................................................................................................................................5.15
X-ray Corrections.......................................................................................................................................................5.17
Blank Subtraction...........................................................................................................................................5.17
Restrictions on blank subtraction correction:..........................................................................................5.18
Overlapping segment.....................................................................................................................................5.18
Ratio Correction.............................................................................................................................................5.19
Mass absorption corrections.........................................................................................................................5.20
Setting Up Samples for Instrument corrections.......................................................................................5.21
Edit Blank Correction....................................................................................................................................5.22
Overlap Correction.........................................................................................................................................5.22
Low and High SUSSES.........................................................................................................................................5.23
Define parameters for routine analysis.........................................................................................................5.25
Printer Format............................................................................................................................................................5.27
Post Analytical calculations.................................................................................................................................5.29
RS232 format...................................................................................................................................................5.31
Delete Standards............................................................................................................................................5.32
Save calibration.....................................................................................................................................................5.33
Edit...........................................................................................................................................................................5.33
Copy..................................................................................................................................................................5.33
List............................................................................................................................................................................5.34
Send..................................................................................................................................................................5.34
Delete......................................................................................................................................................................5.34
Measure............................................................................................................................................................5.35
Section 5: Calibration

Quit...................................................................................................................................................................5.35
Data from RS232.............................................................................................................................................5.35
Calibrations created as text files........................................................................................................................5.36
Calibration Format.........................................................................................................................................5.37

a e5 

40
 SECTION 6: UTILITIES
This function allows various checks to be performed on the Lab-X 3500.
Selection of this is via the 'other functions' option on the MAIN MENU
and may be password protected. A software flow diagram for this section is
shown below:

Detector Test This function can be used to automatically check the resolution of the
detector. The type of detector used in the Lab-X 3500 is a sealed
proportional counter, containing either neon, xenon or argon gas and one
parameter that defines the performance of a detector is its resolution. After
selecting the 'Detector test' option, a measurement automatically starts and a
sample (fitted at the factory underneath the turntable and inaccessible to the
user) is used to check the resolution.

The measurement time is 20 seconds after the 'Energy Lock' measurement (plus
the conditioning time if selected on) and, at the end of this time, the display
will show:
Sectiion 6:
Utilities

RESOLUTION 3500-23.5-2995
Press <ENTER> to continue
with the corresponding information, including time and date, being
reproduced on the printout. The display shown signifies that the resolution is
currently 23.5%, the DAC (digital \ analog converter) value before the
measurement was 3500 and after the measurement 2995.

If the resolution changes by more than +6% of the initial value, the Oxford
Instruments Analytical Service Department or its representative should be
consulted to discuss remedial action.

From this screen press to return to the 'Detector Test / Set

date and time / Position turntable' screen.

Set d te nd time This function is used when the date and/or time need to be changed.

Enter the hour:

This should be entered in 24 hour format, i.e. if the time is 9 o'clock in
the morning, select '9' or '09' (for 0900 hours), if 9 in the evening enter
'21' (for 2100 hours), then press . A single digit number may be entered
with or without a zero prefix (e.g. 09).

Enter the minutes:

Between 0 and 59. A single digit number may be entered with or without a
zero prefix (e.g. 09).

Enter the d y:
Between 1 and 31. A single digit number may be entered with or without a
zero prefix (e.g. 09).

Enter the month:

Between 1 and 12. A single digit number may be entered with or without a
zero prefix (e.g. 09).

Enter the ye r:
Between 00 and 99. For the year 2000, enter 00.
When the above has been completed a printout of the revised time and date
is given.

e 62 LZOM3500 © Oxford Instruments Analytical 2000. All Rights

 Note: Two formats are given on the printout, depending on whether the
UK or USA selection was specified in 'Select Language'. These are:
UK printout dd/mm/yy 15:20 and USA printout mm/dd/yy 3:20 pm.

osition turnt ble Use this function whenever the turntable needs to be rotated, for example
to change or check a SUS, or if the movement of the turntable is suspect.
The positions are labelled from 0 to 5. SUSs are normally located in positions
2 and 4.

Oxford Instruments samples are located underneath the turntable in positions

1, 3 and 5 and correspond to measuring IAGPSI (Ti) and IAGPS2(Al). They are
inaccessible to the operator. The sample port position is position 0. On
selection of a position the turntable will rotate to that location.

rint This function prints the configuration of the instrument. The printout given
confi ur specifies the instrument serial number, model number, software version, tube
tion voltage, tube target, type of detector, helium purge, energy lock conditions
and any primary or secondary filters fitted. Also prints whether printer is
off during analysis, conditioning on and restandardisation option on.

Rest nd rdise This determines whether the Rest nd rdise option should appear on the
analysis menu. Only Manager-level users can re-set the option so
unauthorised restandardisation can be prevented.

Select l=RESTANDARDISE and the display will show:

Restandardisation
option: O=oFF l=oN
Select 1=ON and the analysis menu displays will show:
Calibration title: XXX
l=ANALYSE2=RESTANDARDISE 3=END
If 0=OFF is selected the analysis menu displays will show:
Calibration title: XXX
l=ANALYSE 2=END

Conditionin This function can be used if an instrument is often left for many hours
without measuring any samples. Under these circumstances, if a sample,
particularly one containing a high concentration of the element of interest,
e.g. 40% Ca in cement, is measured, then it is advisable to first 'condition'
the detection system. If conditioning is 'On', then an Oxford Instruments
standard located
 underneath the turntable (and inaccessible to the operator) is measured
automatically before every measurement of a production sample and before
the Energy Lock takes place. Use of this procedure will give the best instrument
stability.

On selection of this function, the display will show:

Conditioning required:
0=OFF l=ON
and the required option can be selected.

rinter on/off If a printout is not required during routine analysis, the printer can
be switched off. On selection, the following message is displayed:

Printing during analysis

0=OFF l=ON
Selection of 0=OFF will switch off the printer and a printout is given
confirming that the printer has been switched off.

If a calibration or spectrum scan is subsequently performed, the printer will

operate as normal for these functions but not for routine analysis.

Select l n u e This function may be manager password protected.

Various language options are available for the Lab-X 3500 Analytical
Software. The release version is English. If the English version is chosen, the
display will show:

l=UK Date/Time 2=USA Date/Time

The UK option shows the date and time as dd/mm/yy 15:20, i.e. day (d), month
(m) and year (y), followed by the time using the 24 hour clock notation.

For the USA version the format is mm/dd/yy 3:20pm, i.e. month, day, year, with
the time shown according to the 12 hour clock, with am or pm showing
morning or afternoon.
 Settin RS2 2 This function sets such items as Baud rate, data bits, parity, etc., to give
compatibility between the data from the Lab-X 3500 and the receiving
system.

Select l=RS232 and the display will show:

Select Port: l=PoRT l
2=PoRT 2
Select the appropriate port number and the display will show::

Select Baud rate: XXXX

(l5O,3OO,6OO,l2OO,24OO,48OO,96OO,l92OO)
(XXXX is the current value).

Select number of data bits (5, 6, 7 or 8): X

(X is the current value). Press when correct.

Select number of stop bits (l or 2): X

(X is the current value). Press when correct.

Select parity:
O=NoNE l=oDD 2=EVEN
Press the key to return to the 'Setting RS232, Test Scan, Print
Configuration' menu.

Test scan This function tests the Lab-X 3500 by performing a spectrum scan, using
factory set conditions, on a sample (IAGPS1) located underneath the Lab-X
3500 turntable.
On selection, the measurement routine is carried out automatically. A
spectrum scan is automatically printed at the end of the measurement period.

Printer check On selection, a printout is given of all the functions of the integral printer as
a means of ensuring that all characters and colours are working correctly.

Connections See section 7

Remote options This function is for use when connecting the Lab-X to a PC. Please refer
to Section 7.

Quit This function returns to the 'Spectrum scan, Calibration, Utilities' menu.
Sectiion 6:
Utilities

Settin or Select 'the second screen' in the Utilities section labelled print configuration,
Ch n in operator options, select language and then press the YeS
when this screen is
sswords shown. Enter the Manager password (or press the key if a password has
not previously been set) and, if correct, the screen will show:
Change Passwords l=Operator
2=Manager 3=Quit
The required operator or manager password can be selected and changed.
When completed select 3=Quit which will display the 'Printer check, Printer
on/off, select language" screen.

Note: A "Manager" password allows access to both operator and

manager functions.

Page 6.6 LZOM3500 © Oxford Instruments Analytical 2000. All Rights Reserved
 Section 7: Using the Lab-X with a computer and automation

SECTION 7: Using the Lab-X with a computer and

automation

Contents Page

Changing input/output..........................................................................................7.2
Changing Keyboard Control...................................................................................7.2
Changing display output........................................................................................7.2
Changing printer text output................................................................................7.3
Changing printer graphics output........................................................................7.3
Automation options................................................................................................7.5
Automatic transmission of an energy lock command......................................7.5
Automatic analysis..................................................................................................7.5
Automatic restandardisation................................................................................7.5
Automatic control and monitoring of routine Lab-X functions......................7.6

The Lab-X 3500 can be controlled by a PC via either of the two serial ports and
results, etc, can be transmitted to the PC for display on its screen.
Before using any serial ports for output or input, ensure that the other end of
the RS232 connection is properly set up.

Before disconnecting any RS232 connections, ensure that the Lab-X is reset
not to use any serial ports.

When the Lab-X is switched on, it will remember the screen, display, etc, last
used. To revert to the default settings (i.e.: the Lab-X's own keypad, LCD
display and internal printer), hold down the paper feed key when
switching on the Lab-X.

From Option 1=CONNECTIONS in Utilities (see Section 6).

Change mode:
0=LOCAL l=ON-LINE 2=PC 3=SPECIAL
Select 0=LOCAL to switch off all communications through Lab-X serial parts.
In this mode all external commands will be ignored and no displays or
printouts or calibrations will be transmitted although calibrations can be
received. The internal printer is also enabled. Adjustments to the default
local mode can be made by selecting 3=SPECIAL (see below).

 Page 7
 Select 1=ON-LINE to switch on external computer control through the first or
second Lab-X serial port. In this mode the Lab-X can be controlled and
monitored and results transmitted to an external computer using the
Automation Options described later in this chapter. Adjustments to the
default on-line mode can be made by selecting 3=SPECIAL (see below). Select
2=PC to switch on external control and monitoring using the Lab-X control
software package. In this mode the internal printer is disabled and all print-
outs are displayed on the PC. In addition, some menus can be optimised for
PC control (e.g. spectrum scan and regression). To select this option select
2=PC on the menus style menu. Otherwise select 1=LAB-X. Adjustments to the
default PC mode can be made by selecting 3=SPECIAL (see below).

Changing From Option 3=SPECIAL in connections menu:

input/output
Change connections:
l=KEY 2=LCD3=PRINTER 4=GRAPHS S=EXPORT

Changing
Keyboard Control Select l=KEY to change the control input. The display becomes:
Select control inputs:
l=PORT l 2=PORT 2
The current control inputs are highlighted. Select 1=PORT 1 or 2=PORT 2 to
switch on or off the first or second Lab-X serial port for control input.
The selection will be highlighted to show that the Lab-X can be
controlled through that port. (N.B. It is not possible to switch off keypad
control of Lab-X.) In this way simultaneous keypad and serial port control
is possible.

Press (Enter) to return to the Change Connections menu.

Change connections:
l=KEY 2=LCD 3=PRINTER 4=GRAPHS S=EXPORT

Changing display Select 2=LCD to change where displays are sent to. The display becomes:
output Select display outputs:
l=PORT l 2=PORT 2
The current display outputs are highlighted. Select l=PORT l or
2=PORT 2 to switch on or off the first or second Lab-X serial port for display
output. If the selection is highlighted, displays will be output to that port.
(NB: It is not possible to switch off the LCD display on the Lab-X). In this way
simultaneous display and serial output of displays is possible.
 NB: If a port is selected for display output, then printer text and printer
graphics are automatically switched off for that port.

Press (enter) to return to the Change Connections menu.

Change connections:
l=KEY 2=LCD 3=PRINTER 4=GRAPHS S=EXPORT

Changing printer Select 3=PRINTER to change where text print-outs are sent. The current
text output printer text outputs are highlighted on the display. Select 0=PRINTER to
switch on or off the Lab-X printer for text print-outs. Select l=PORT l or
2=PORT 2 to switch on or off the first or second Lab-X serial port for text
print-outs. If the selection is highlighted, text print-outs are sent to that port.
In this way simultaneous printer and serial output of print-outs is possible.

NB: If a port is selected for printer text or printer graphics output then
display output is automatically switched off for that port.

Press ENTER to return to the Change connections menu.

Change connections:
l=KEY 2=LCD 3=PRINTER 4=GRAPHS S=EXPORT

Changing printer Select 4=GRAPHS to change where graphics print-outs are sent to. The
graphics output display becomes:
Select graphs outputs:
0=PRINTER l=PORT l 2=PORT 2
The current graph outputs are highlighted. Select 0=PRINTER to switch on
or off the Lab-X printer for graphical print-outs. Select l=PORT l or
2=PORT 2 to switch on or off the first or second Lab-X serial port for
graphical print-outs. If the selection is highlighted, graphical print-outs are
sent to that port. In this way simultaneous printer and serial output of
graphical print-outs is possible. Press (enter) to return to the
Change Connections menu.

Change connections:
l=KEY 2=LCD 3=PRINTER 4=GRAPHS S=EXPORT

NB: It is not possible to use the same port for both display and
printer outputs.
The Lab-X remembers the last used keyboard, display, printer and graph
setups. At switch on the Lab-X restores the last used keyboard, display, printer
and graph setups. To override this feature, hold down the paper-feed key at
switch on and the Lab-X will then use its own keyboard, display and printer
only.

Option S=EXPORT is for selecting which serial port is used for routine
analysis results output, spectrum scan data output and calibration output.
 Automation options
Some Lab-X functions can be performed by a single letter key press and a
single letter can be transmitted by the process software to the Lab-X if used
in a fully-automated system.

Automatic When the Main, Other Functions or Utilities menu is displayed (on the Lab-
transmission X LCD panel), if a capital letter E is transmitted to the Lab-X (either directly
of an energy via the keypad/keyboard or from previously programmed software on a
lock process computer) an energy lock is carried out. When the energy lock is
command complete, the Lab-X returns to the original menu (displayed on the LCD
panel on the Lab-X). In this way an energy lock can be performed at any
time.

Automatic When the Main, Other Functions or Utilities menu is displayed (on the Lab-X
analysis LCD panel), if a capital letter A is transmitted to the Lab-X (either directly via
the keypad/keyboard or from previously programmed software on a process
computer) a calibration title must be entered. Again, this can be done
either directly via the keypad/keyboard or from previously programmed
software on a process computer. The Lab-X LCD panel will show:

Enter calibration title:

If a valid calibration title is entered (one that appears in those allowed for
analysis) a sample label is then required (the Lab-X LCD panel will display the
message shown below) or the label can be transmitted automatically by
previously programmed software on a process computer.

Calibration title: XYZ

Enter label:

After a sample label is entered, the Lab-X analyses the given sample against
the selected calibration. When the analysis is complete (or if there is any
error) the Lab-X LCD display returns to the sample menu.

Automatic When the Main, Other Functions or Utilities menu is displayed (on the Lab-X
restandardisation LCD panel), if a capital letter R is transmitted to the Lab-X (either directly via
the keypad/keyboard or from previously programmed software on a process
computer) a calibration title must be entered. Again, this can be done
either directly via the keypad/keyboard or from previously programmed
software on a process computer. The Lab-X display panel will show:

Enter calibration title:

 If a valid calibration title is entered (one that appears in those allowed
for analysis) then the calibration is restandardised. When restandardisation
is complete (or if there is an error) the Lab-X LCD display returns to the
same menu.

Automatic When the Lab-X is used in a fully-automated system, automatic control and
control and monitoring of routine Lab-X functions by a PC or process computer is
monitoring of necessary to ensure that the system operates correctly.
routine Lab-X
functions NOTE: When selecting a calibration with manual segments remotely, the
following sequence is required to enter the calibration name,
sample name and each manually entered segment in turn:
A calibration name
sample name
first manual segment
next manual segment
etc

In each of the following displays, enter a sequence of up to seven characters

in each case or leave the entry blank if the feature is not required. The sequence
will be transmitted on whichever serial port is defined in the EXPORT option
in the CONNECTIONS menu (see Utilities section) at the appropriate time.

From the Main Menu select OTHER FUNCTIONS, then 3=UTILITIES, then
continue to select 4=TURN page until the screen shown below is
displayed:
l=CONNECTIONS 3=QUIT 2=REMOTE OPTIONS

Select 2=REMOTE OPTIONS and the following screens will be displayed in

order:

Enter a sequence for transmission from the Lab-X to the PC or process

computer whenever the Lab-X is switched on:

Enter characters transmitted at start-up

Enter a sequence for transmission from the Lab-X to the PC or process

computer whenever the Lab-X successfully performs an energy lock (only as
described above).
Characters sent on remote energy lock

Enter a sequence for transmission from the Lab-X to the PC or process

 Section 7: Using the Lab-X with a computer and automation

computer whenever the Lab-X unsuccessfully performs an energy lock (only as

described above).

Characters sent on energy lock fail

Enter a sequence for transmission from the Lab-X to the PC or process

computer whenever the Lab-X unsuccessfully performs an analysis (see above).
This sequence is followed by the date and time (in the currently selected UK or
US format) and the text of the error message (as in Appendix D).
Enter characters sent on analysis error

This sequence is followed by the date and time (in the currently selected UK or
US format) and the text of the error message (as in Appendix D).

When the next screen is displayed press YES if you want the Lab-X to transmit
restandardisation results* to the process computer whenever it successfully
restandardises an analysis.

Transmit restandardisation ? <YES> / <NO>

*The restandardisation results are in the format of relative percentage change

in sensitivity since the calibration was created (see Section 3).

Enter a sequence for transmission from the Lab-X to the PC or process

computer whenever the Lab-X unsuccessfully restandardises an analysis:

Characters sent on restandardise error:

This sequence is followed by the date and time (in the currently selected UK or
US format) and the text of the error message (as in Appendix D).

Press (enter) and the display returns to the Remote Options menu.

To abort any of the energy lock, analyse or restandardise functions press the
X key or the ESCAPE key. This also works whenever the Lab-X is performing a
measurement. When aborting a remote analysis the whole analysis is
aborted, including any repeats, and there is no option to reload the sample.
When aborting a remote or manual restandardisation the whole
restandardisation is aborted instead of just the current SUS measurement.

Each transmitted analysis result, or spectrum scan, or calibration, or remote

output sequence (start-up, failed or successful energy lock, failed analysis,
failed or successful restandardisation) is terminated by an end-of-file or
control-Z character (ASCII 26).

 Page 7 7
 Appendix A : RS232 Communication
The RS232 cable can be connected to either the 25-way 'D' socket or the 9-
way 'D' socket which are situated 'underneath' the rear left hand fairing of
the Lab-X 3500. If this cable is used, then transmission and receipt of data
and remote control of the Lab-X can be achieved. The 25-way socket is Port
1, or RS232 1, and the 9-way socket is Port 2, or RS232 2.

The Lab-X can transmit six types of information:

• Spectrum scan data

• Routine analysis data
• Calibration data
• Lab-X displays
• Lab-X print-outs (text)
• Lab-X graphics (spectrum scans and regression data).

It can also receive calibration data and be controlled remotely.

Baud rate, On either of the two ports the Lab-X can transmit at any of eight baud
data bits, stop rates, 19200, 9600, 4800, 2400, 1200, 600, 300 or 150 providing
bits and handshaking is used as described below.
parity
The Lab-X can transmit and receive 8-bit, 7-bit, 6-bit or 5-bit data with 1 or 2
stop bits using even, odd or no parity.

When setting up serial communication, it is important that both ends of

the link are set to the same protocol.

At all times For Port 1 and Port 2 the Lab-X:

• Asserts DTR true when it is switched on.

Transmitting For Port 1 and Port 2 the Lab-X:

information • Requires DSR to be true for transmission to be enabled.
• Requires CTS to be true for transmission to continue. If CTS goes false, then
Lab-X will halt transmission and will resume from where it left off when
CTS subsequently goes true.
Appendix A: RS232 Communication

• Terminates successfully transmitted data with a Control-Z character

(ASCII 26)
• If the communication is aborted, at the Lab-X or the receiving end, then
the communication must also be aborted at the other end.

Receiving For Port 1 and Port 2 the Lab-X:

calibration data
or remote • Asserts RTS true when it is ready to receive data. The Lab-X may assert RTS
commands false, which should halt data being transmitted. It expects received data to
resume from where it left off if RTS is subsequently asserted true

• Detects the end of the received calibration data automatically. No special

character (e.g. Control-Z) is required. Only valid calibration data (i.e. any
text format calibration) may be successfully received. Special care must be
taken to transmit calibrations only when the Lab-X is ready to receive them
and on the correct port, otherwise they may be interpreted as remote
commands.

• If the communication is aborted, at the Lab-X or transmitting end, then

the communication must also be aborted at the other end. If invalid data
is received then the communication must be aborted at the transmitting
end. Special care must be taken when aborting calibration transmission at
the Lab-X end because incomplete calibrations may be interpreted as
remote commands

Communicating To transmit to and receive information from an PC using WINDOWS the

with an IBM following lead should be used on Port 2 or on Port 1 using a suitable 9 to 25
C way adaptor.

Na in Directi in Name
me on
GN 1 - 1 GND
D
RX 2  3 TX
TX 3  2 RX
DTR 4  6 DSR
LAB-X GN 5 - 5 GND IBM
D PC
DSR 6  4 DTR
RTS 7  8 CTS
CTS 8  7 RTS

Before communicating, make sure that the PC is using the same protocol as
the Lab-X. For example, using a WINDOWS terminal program to communicate
at 9600 baud, 8 data bits, 1 stop bit and no parity on port one, select

age A 2 LZOM3500 © Oxford Instruments Analytical 2000 All Rights Reserved

 Appendix A: RS232 Communication

the appropriate communications properties. Select the hardware flow control

option.

Received information will be displayed in the window. To store a

calibration in a file on disk select the required calibration on the Lab-X and
select the receive text or capture text option in the WINDOWS terminal
program.

Press a key on the Lab-X to send the calibration in text format.

To transmit a calibration, select the send text option. For example, to transmit
the calibration received in the example above, select receive calibration on the
Lab-X and select and send text option in the WINDOWS terminal program.

If you experience problems either sending or receiving calibration text files, try
again at a slower baud rate and/or select the no flow control option in
communications properties.

To send remote commands to the Lab-X, simply type directly into the
WINDOWS terminal program. Make sure the Lab-X is set up for external
control. e.g. control input and display output using the same port, in the
connections menu.

Version 1.8 or greater software now allows:

• A single letter command to be sent from a PC for key Lab-X

commands, such as analysis and restandardisation.
• A calibration can now be selected from a PC by name for routine
analysis and calibration.
• ASCII is the only format used for loading calibrations from a PC.

 age A 3
 Appendix B: Sample Preparation
X-ray fluorescence spectrometry is a non-destructive method of analysis and it
is possible to measure a wide range of sample types using this technique.
The nature of the sample is very important and can adversely affect the
accuracy of the analysis, however, sample preparation is usually very simple.
Basic requirements are that the sample should have a flat surface, be
homogeneous, have an adequate thickness and fit into the sample port of the
instrument.

The Lab-X 3500 will accept samples of diameter between 28 and 41mm and
height less than 39mm. Information on the preparation of several different
sample types is given below, however if information of a more specific nature
is required, then contact the Sales Support Department of Oxford Instruments
Analytical or your local Oxford Instruments representative.

Solids (metals Normal machine shop techniques, such as lathe turning, milling, linishing and
and plastics) surface grinding, have all been used for obtaining a suitable smooth and flat
surface to give consistent analytical results.

Lathe turning is the most widely applicable method (e.g. brasses, steels, nylons)
although for materials with a tendency to smear, such as highly leaded brasses
or antimonial lead alloys, an end milled surface is far superior. Linishing will
cope with hard materials (e.g. cast iron) but surface grinding is more
reproducible.

Consistency of preparation is important and the unknown samples should be

prepared in the same way as the standards. If inhomogeneity is a problem
then the operator, with specialised knowledge of the samples, is probably in
the best position to eliminate or reduce inhomogeneity caused by, for
example, inclusions, occlusions, blowholes or preferential separations.

Liquids Liquids are poured directly into Lab-X sample cups. The component parts of
the cup are shown in Figure B-2 and assembly should be carried out as
follows:

1 Place the white polypropylene inner, with leading edge uppermost, on

a clean, flat surface.

2 Position the window support tool centrally around the cell inner.
Appendix B: Sample Preparation

3 Lay a piece of window material over the support tool so that the material
is flat at the rim of the cell inner.

4 Push the aluminium cell outer, with O-ring uppermost, vertically down
onto the cell inner. If necessary, use the assembly tool to help push the
outer fully down. Figure B-2 shows the use of the window assembly tool
for the assembly of sample cups.

The window assembly tool is also used to dismantle the cell and to fit a
secondary window. Note that the secondary window clamping ring has a small
chamfer on its leading edge and this should face upwards when placed in the
recess of the assembly tool.

Window
assembly tool

Cell outer 'O' ring

Windo
w
mater
ial

Window
support tool Cell inner
Figure B-2: Sample cup assembly using assembly tool

When assembling a sample cup or a secondary window it is important to use

a clean piece of window material. Disregard the outer layer of material if
the roll has been unused for a long time and only handle the window
material at its edge. Always visually inspect the assembled cell for leakages
when filled with liquid and renew the window if it is wrinkled or creased.
The plastic cell inners are reusable after cleaning but are inexpensive so
should be considered disposable.

Do not assemble the cell outer and inner without a window and do not leave
sample cells filled with liquid in the instrument port after completion of a
measurement. It is advisable to store cells in the Lab-X sample rack to minimise
window contamination.

Page B.2
 A thin layer of grease must occasionally be applied to the O-ring in the cell
outer. The standard O-ring is made of neoprene but certain organic solvents
(e.g. aromatics) may attack this material, in which case a Viton O-ring should
be used.

A polyethylene sample cell lid is provided for use with volatile samples such as
gasoline to reduce evaporation to a negligible level. Any evaporation usually
results in a change in composition of the sample which may give incorrect
results.

To measure elements below calcium in the periodic table a minimum sample

depth of 2-3mm is sufficient. For heavier elements fill the cups to the step in
the internal diameter of the cell inner (approximately 22mm/13ml) to ensure a
constant volume.

Several types of window material are available, each one providing a

different compromise of strength, solvent resistance, X-ray transmission and
purity, although some films, such as Hostaphan, produce diffraction peaks in
certain parts of the spectrum and should not be used. It is advisable to run a
spectrum scan with an empty sample cell to check for this effect.

Two types of suitable window material are:

• Polycarbonate film (6 micrometres thick, light green) is the general

purpose film for elements below calcium. It is free of impurities, reasonable
strong and moderately resistant to solvents.
• Mylar film (6 micrometres thick, clear) contains definite traces of calcium as
an impurity but this does not affect its performance for elements above
calcium. Its extra strength makes it the easiest material to handle.
Reference should be made the Oxford Instruments application report to
confirm the type of film used
• Poly4 film has the best transmission and extremly low impurities but will
not resist organic liquids with high solvent action.
• Hostaphan is similar to mylar but higher transmission, lower impurities
but mechanically less strong.

Powders For many applications satisfactory results are obtained by pouring the powder
(including into a standard sample cell. The cell should be lightly tapped on a clean bench
minerals) to settle the contents - use the white plastic assembly tool to prevent damage
to the cell window during this procedure. For other applications it is necessary
to compact the powder into a briquette/pellet.
The choice of method depends on the required speed, cost and precision,
balanced against what can be achieved at the energy of the X-ray being
measured. Obviously, for maximum speed and lowest cost the simplest
preparation is best but the resulting precision is often unacceptable and a
compromise must be reached.

In the rapid determination of sulphur in cement the limiting factor is

counting statistics and a powder (50-100 micrometres) easily provides the
achievable precision. Pressing the samples into briquettes would not improve
the results and it would unnecessarily extend the time of preparation.
However, for the related application of calcium in cement a higher precision
is not only required but is readily obtainable by pressing the cement powder
into a briquette. This provides a flat, smooth sample of consistent density that
is readily reproduced, thus minimising the errors of sample preparation and
allowing the high precision of the counting statistics to be realised.

A gyratory disc, or swing, mill (e.g. GyRo mill) is generally used to reduce
samples to a fine powder, being both rapid and efficient in operation. The
powder may then be compacted into briquettes using a hydraulic press
capable of loads up to 25 tonnes. This can be done using a die to form a
simple pellet, a die and cap to form a very strong bound pellet or precise
diameter or a steel cap between flat plates, which is sufficient for routine use.

It is unlikely that a particular material will possess all the qualities needed for
grinding and briquetting, in which case a suitable additive must be used.
Before choosing an additive, it is necessary to identify the basic physical
properties of the material under test. Some softer samples such as limestone,
cement or barytes will compact and clog the mill which reduces grinding
efficiency and makes it tedious to clean the mill between samples. By adding
one part of granular stearic acid to twenty five parts of sample it remains a
free flowing powder which greatly increases efficiency.

Harder minerals, such as silica sand, remain free in the mill but are extremely
difficult to form into briquettes. A suitable additive for this purpose is a
finely powdered wax which is used one part to ten parts sample in the mill.
By the same action that binds pellets, the wax may also cause samples to
compact inside the mill. Experiments with a mixed additive of stearic acid and
wax may yield a mixture that remains free but still forms a good briquette.
 Some polymer powders can also act as a binder, especially in combination with
wax and they exhibit less tendency to clog the mill.

Special Samples
Organic solids
There is an increasing demand for the determination of metals in a variety of
organic materials used in the food industry, e.g. chelates, organo-metallic
additives, catalysts and trace catalysts. Such materials are very soft and cannot
be ground in a gyratory disc mill. Those samples still in powder form can be
prepared in a shaker/mixer mill, which is simply a metal vessel containing hard
metal or ceramic balls, which is shaken in a 'figure of eight' motion. Very soft
materials, e.g. fats, can be pulverised in a food chopper and then pressed in a
die.

Papers
A special device is available from Oxford Instruments Analytical for analysing
paper samples on the Lab-X 3500. It was originally designed for the
measurement of thickness of silicone coatings but can be used for other thin
samples. The sample holder includes a suitable support which reduces
unwanted background signals.

Testing for The operator can perform a few simple tests to determine whether the
sampling errors sample preparation is adequate for a particular application and is not
contributing errors to the analysis.

If a sample of material is placed in the instrument and ten repeat readings

are taken without disturbing the sample, then the standard deviation
calculated from these readings is a measure of instrument precision or
repeatability of analysis.

Removing the sample between readings and comparing the standard deviation
calculated from ten such readings with that from the first set will indicate any
error introduced by the presentation of the sample to the instrument.

If the ten measurements are repeated using different samples of the same
material for each of the readings, any difference between this standard
deviation and the repeatability will represent an error in preparation of the
sample.
Many applications will not be affected by variations in thickness (or depth)
of the sample. A simple test is to take a measurement on a sample and then
either increase the volume (if the sample is a liquid), or place another sample
of the same material on top of the first sample (if it is a solid or powder)
and repeat the measurement. An increase in signal will imply that the X-ray
penetration depth has not been reached and the operator must either use
thicker samples or, if this is not possible, then samples of constant thickness
must be prepared.

Calibration lines for elements in light organic matrices can be curved, leading
to a decrease in sensitivity at high levels. It is sometimes desirable to dilute the
samples to obtain linear calibrations. Suitable diluents for powder samples are
starch or sugar both readily obtainable cheaply in pure form.
 Appendix C: XRF
Theory

Appendix C: XRF Theory

An introduction X-rays, which form a part of the electromagnetic spectrum as shown in
to XRF Figure C-3 are generated when atoms of elements are struck either by
Analysis particles, such as electrons, or other higher energy radiation. The process of
primary X-ray emission which takes place inside an X-ray tube can be
considered simply as the release of characteristic X-ray wavelengths of the
tube anode element when it is irradiated by a beam of high energy
electrons.

Figure C-3: Part of the electromagnetic radiation spectrum

Although the X-ray region could be defined by frequency in MHZ, it is more convenient to use
wavelengths specified in either angstrom units (1A or AU=10 cm) or the SI unit nanometers (1nm
-B

= 10 m) or energy keV.
-9

As the Atomic Number of the element increases, the wavelength of the most
sensitive characteristic emission spectral line, known as the K line, decreases.
Low atomic number elements are often called 'light elements' and their
radiations are absorbed by air. Conversely, high atomic numbers are called
heavy elements.

Page C.1
Appendix C: XRF
Theory
Characteristic X-rays are often also expressed in terms of energy in keV
(inversely proportional to wavelength). This means that the energy of the
X- ray emission lines in keV increase with increasing Atomic Number. The
relationship between energy and wavelength is as follows:
12.4
E (keV ) =
wavelength( A)
It is necessary to understand that each element has a number of characteristic
lines and that these occur as a result of internal electronic transitions within
the atom. These lines occur as the result of the excess energy liberated when
electrons from higher energy levels 'fall down' to take the place of K, L and
M electrons which have been ejected by the exciting radiation.

These discrete energy differences give rise to characteristic element lines and
are shown in Figure C-4. Here the classical Siegbahn description of the line is
used, i.e.Ka, K�, etc.

When X-rays are used as a source of radiation to excite other elements the
process is known as X-Ray Fluorescence.

Selective The energy dispersive spectrometer has a single detector which sees X-rays of
excitation and all energies simultaneously. This advantage has to be used carefully to ensure a
primary beam maximum countrate of typically, 30,000 counts per second, which the detector
filtration in will accept.
EDXRF
In the EDXRF spectrometer, therefore, we must lower the percentage of the
spectrum taken up by background counts and this is done by selective
excitation and primary beam filtration. In practice, this means that the
excitation voltage used for a particular range of elements is only that which
effectively excites the highest energy line and no more. This avoids producing
large amounts of continuum background above the highest element to be
analysed under these conditions. In addition, the use of a fiter may be placed
between the X-ray tube and the sample to modify the position of the peak
energy available for excitation.

In this way, the X-ray beam reaching the sample has a spectral distribution
which favours good excitation and low backgrounds for a particular region of
the spectrum. To accomplish this, the Lab-X 3500 energy dispersive
spectrometer is fitted with programmable multiple filter changers which
provide automatic changing between different ranges of elements in multi-
element applications. The choice of filter is matched with an appropriate

Page C.2
 Appendix C: XRF Theory

Incident X-ray

e-
Characteristic X-ray

16 s

e- ejected electron L

Figure C-4: Fluorescence of sulphur atom

Page C.3
 combination of tube voltage and beam current. Such analytical procedures
may be stored for automatic repeat use, where the stored sets (methods) of
analytical conditions are re-used.

Absorption of Knowledge of the nature of absorption of X-rays is fundamental to the

X-rays understanding of nearly everything that happens in X-ray analysis. Two basic
facts need to be grasped as follows:

(i) X-rays are absorbed exponentially according to Beer's law.

Ix= µpx
I 0 e-
Where
I
X
= the intensity passing through a thickness x
I
O
= the initial incident intensity
µ = the mass absorbtion coefficient
p = the density
x = the thickness of the absorber

(ii) The value of the mass absorption coefficient changes with

wavelength and a plot of the variation between absorption and
wavelength shows maxima followed by a sharp drop - the absorption
edge. Figure C-5 shows this effect.

Absorption edges
occur when energy
is close to the
critical value
needed to excite a
particular spectral
line of an element
and is absorbed
very strongly. An
abrupt fall in
absorption takes
place when the
energy is just
Figure C-5
insufficient to eject
the appropriate electron.
 Appendix C: XRF Theory

From this it follows that an element is effectively transparent to its own

radiation and that elements a few atomic numbers lower will be strong
absorbers. For example, Al will absorb SiKa radiation as strong as Fe, even
though Fe is much more dense and has a much higher atomic number.

Elements of higher atomic number are normally called heavy elements and
because they have many extra nuclear electrons they have a series of
absorption edges K, L, M, etc. The higher the atomic number the higher
the energy (shorter the wavelength) of the K spectral lines. Conversely,
elements of low atomic number are called light elements and have K
spectral lines of low energy (or long wavelength).

From a study of a set of mass absorption tables it will be seen that the
magnitude of the mass absorption coefficient at the energy being studied
plays a principle role. This is the whole basis of inter-element (matrix)
correction procedures, which are needed in the analysis of multi-element
materials. The make-up of the material or the matrix decides how much of
the excited characteristic radiation escapes from the sample which is measured
and related by calibration to the concentration of the element.

Single Filter
Method
A single filter may
be employed where
the line of the
element to be
measured (analyte)
is lower in energy
than the element(s) Figure C-6
to be discriminated
against and where the absorption edge of the filter lies to the high energy
side of the analyte line. This is shown diagrammatically in Figure C-6.

The use of a single filter mounted in front of the detector, known as a

secondary filter, plays a very important role. Filters may be programmed to
selectively absorb elements of higher energy (normally higher Atomic
Number).

These filters work particularly well in the region from Al to Ti, where it is now
possible to separate Al from Si, P from S, S from Cl and so on. Special

Page C.5
 techniques have been used for these elements to fabricate filters of high
efficiency.

Another powerful tool in limiting interference from higher energy elements is

the use of specific programmed kilo voltages on the X-ray tube. For example,
it is possible to nearly eliminate the excitation of Ca, while still retaining a
useful signal from an element such as S in, for example, a finished cement
sample.

General Principles X-ray analysis, as with other forms of spectroscopy, is a comparative technique.
of Calibration This means it is necessary to have a series of reference standards which cover
the elements to be measured in the ranges of interest. These are measured
and the intensities for the elements to be analysed are recorded so that
calibrations of concentration versus intensity can be derived and stored in the
data processing computer for future analysis of unknown samples of the same
type.

Before the standard samples can be measured it is necessary to decide the

sample preparation methods that will be employed (see Appendix B).

It must always be
remembered that even
though XRF analysis is a
volume analysis, the depth
of sample involved in the
analysis depends greatly on
the matrix material (i.e.
absorption) and the energy
of the X-rays being
measured. For example, Pb
being measured as the PbL
spectral line in a steel comes
from only some 10 microns
deep, whereas Pbl measured
in a gasoline comes from
more than 10mm depth in Figure C-7

the sample.

Solid samples therefore need a flat surface for analysis and because the surface
of dense solids represent the mechanical reference with the
 Appendix C: XRF Theory

instrument, it is important that these are flat to 10-20 microns, if the ultimate
of accuracy is to be achieved. This point will be touched on again in the
sections describing precision and accuracy.

The simplest form of calibration is a straight line as shown in Figure C-7 and
this basic relationship between concentration and intensity is the sensitivity of
the instrument. The equation of the straight line is given by:

C = a + a 1* I
o n

such that the concentration for an 'unknown' sample can be calculated by

measuring the intensity from the instrument and using the a and a
O 1

coefficients. This equation is derived from the following:

y = mx + c

From Figure C-7, y is the intensity measured (Im), m is the sensitivity (Q) and c
is I0. The equation becomes:

I = (Q x C) + I
m 0

Rearrangement of this
gives:

Q –
Q

The magnitude of the term a , which is normally negative, is called the

O

Background Equivalent Concentration commonly known as the BEC. It is

possible to use an intensity intercept 1 , but this is less common.
O

The inverse of the slope term 1/a is equal to the number of

1

counts/second/unit of concentration used. This is referred to as Q in our

documentation and will be used in formulae to express the precision of the
instruments.

As it is required to use a calibration over a very long time, it is necessary to

compensate for instrument drift which, even though small, will occur. This is
done by the use of high and low reference points for each element. Special
samples known as SUSs (Setting Up Samples), which are long term stable, are

Page C.7
 made to contain enough of the elements being checked to give these high
and low intensity values for each element.

Correction of There are two main types of interference to be considered:

interferences
(i) Instrument imperfections (Overlaps due to insufficient resolution)
(ii) Matrix effects (due to large changes of matrix absorption)

In addition to these problems occurring between elements in the sample being

measured, there can also be changes of spectral background affecting the
measurement of elements in low concentration. As a general rule, if it is
necessary to measure below 1000 ppm it will be necessary to consider some
form of background correction unless the overall matrix is quite constant.

The spectral background varies inversely with the average atomic number of
the samples. That is to say the higher the average atomic number (and mass
absorption coefficient) of the sample, the lower the scattered background. This
effect is also shown in the intensities measured from the scattered X-Ray tube
anode lines. These characteristic lines are scattered from the sample and the
lower the average atomic number of the sample the higher their intensities
will be.

Scattered intensities are directly related to the spectral background and, if

measured, can be used to make measured background corrections of other
element gross peak intensities.

Corrections It can be seen that the simplest form of background correction is the
subtraction of a fixed amount equal to I0 from each measured intensity,
commonly referred to as 'Blank Subtraction'. Such a procedure produces
a series of net intensities related to concentration by:

C = a1 * I

The principal use of this form of background correction is for the

determination of silicone on paper.
 Appendix C: XRF Theory

An overlap correction can be applied to either a tube line or an overlapping

N
element line. The corrected, or net, intensity (1 ) is calculated as follows:

IN = - K*IB
I
measure

The value of K for a tube line is determined by measuring a 'blank' base

material. For example, if measuring sulphur in a diesel oil, a suitable blank
would be a low viscosity mineral oil which does not contain any sulphur.

Spectral overlaps are corrected in a similar way but here the special samples
needed to calculate the correction factor must contain both a significant
amount of the overlapping element and none of the analyte element present.
Oxford Instruments supply Setting Up Samples (SUSs) which are suitable for
this purpose.

Once all the corrections to intensity have been made and a set of 'pure' net
intensities exist for all elements, correction for change of sensitivity (a1) can be
made. These corrections rely on the basic premise that the change of
sensitivity, either positive or negative, is proportional to both the
concentration of the analyte being measured and that of the interfering
element causing the change:

C1 = (a + a l 1)(1+ L
k *l1)
i 0 1 i n n
1-n

As concentration is directly proportional to the net intensity of each element,

the matrix correction equation is expressed as an intensity, where a and a
O 1

have the same meaning, as explained earlier, and I n is the intensity of the nth
1

element.

2
If there are N values to be calculated empirically then a minimum of N
standards are normally required for a good statistical fit.

The intensity model is the easiest to apply because not all the element
percentages need to be known. The sign and magnitude of the calculated
factors will depend on the number of elements used in the equation, because
elements omitted contribute to the 'balance of the matrix.' It must be
remembered that the effect of changing an element for another depends on
Appendix C: XRF
Theory Page C.9
 Appendix C: XRF Theory

the resultant change of absorption for the analyte radiation by what is

considered the balance of the matrix.

Precision The term 'precision' is used to describe the repeatability of the instrument and,
to give it some numerical significance, it is normally described as the standard
deviation.

Figure C-8 shows a

typical Gaussian
distribution which can 66%
be used for any
measured value where
random events are
involved. From this it is 95%
seen that the
deviation from the -2-  2
mean value for
approximately 66% of (5 -

(n 1 )
all the measured
values is a number Figure C-8
which is called sigma
(cr). Twice this value
takes in 95% of all the measured values and three times cr 99.97% of all.
These break-points are used frequently to describe various levels of
confidence..

That is to say, there is a 1 in 20 chance in getting a result with a deviation

larger than twice the one sigma (cr) value.

With X-ray analysis the measurements are made up of a series of numbers

accumulated by counting photons of a particular energy entering a detector.
This counting process obeys a Gaussian distribution and the standard
deviation 1 sigma (cr) is equal to:

1 = total number of photons counted

but

total number of photons counted = (C + BEC) * Q)

 See Figure C-7, where:

BEC = Background Equivalent Concentration

Q = Sensitivity
T = Counting/analysis time
C = Concentration

1 = (C + BEC) * QT counts

however:

QT counts =
so that: 1%

( A )A 1
1
O

( + BE ) * QT
% T
QT

( + BE )
1 NOTE: A is negative
%
QT
O

From this it is seen that:

BE % A X A1
 at e o
O

QT T

BE
Three times this value, ie: is known as the limit of detection LOD.
QT

Accuracy The terms 'accuracy and 'precision' are often interchanged and wrongly used.
The definition is, however, quite clear: Precision is the ability of the
instrument to repeat a result from the same sample.

It should be remembered that precision and time are intimately related. For
example, if it is required to improve the sigma at a particular concentration
level by a factor of 2, then the counting time must be increased by a factor
of
4. That is to say, the time must increase by the square of the improvement
required.
Page C.11
Appendix C: XRF
Theory
Accuracy is the correctness of this result compared with other reference
methods of analysis.

A useful way of expressing the accuracy is in terms of the standard error,

(standard deviation of differences between X-ray and given values) of the
calibration curve.

From this, it follows that an instrument can have excellent precision or

reproducibility but that the value being produced could be quite wrong. A
classical cause for this would be a poor calibration, possibly caused by
insufficient calibration standards, inaccurate concentration values, errors in
sample preparation, etc.

Page C.12
 Appendix D: Error Messages

Appendix D: Error Messages

The following is a list of error messages which may appear on the printout in
red if your Lab-X 3500 is not functioning correctly. In some instances you may
be able to correct the fault yourself, in some cases simply by repeating the
operation, in others you will need to contact your Oxford Instruments service
representative.

All error messages are printed with date and time of occurrence. Error
messages may also be optionally transmitted using the Remote Options facility
(see Section 7).

GAIN ADJUSTMENT ERROR Energy Lock Routine has made five attempts
and DAC change between measurements is
>9. Implies that peak from IAGPSI is not
within the range of control and DAC needs to
be reset. Spectrum Scan <TEST> will confirm
true position of peak.
The following errors fall into two categories - errors relating to an
incompatibility in instrument configuration and errors due to hardware faults.

For example, if a calibration is created and the hardware configuration is

subsequently changed or if a calibration is imported and the hardware is not
compatible, then a message such as "CANNOT SET SECONDARY FILTER 'a'" will
be reported at the start of the first measurement which involves the
incompatible conditions.

The following parameters are monitored continuously during a measurement.

An error will stop the measurement, report the fault on the printer in red
capitals and switch X-rays off.

INTERLOCK FAULT Both bulbs in the X-ray warning lamp have

failed.

OR The bottom cover key-operated microswitch is

not made.

HV FAULT Tube HV not set within predefined limits.

Page D-1
Appendix D: Error Messages

EMISSION CURRENT FAULT Tube emission current not set within

predefined limits.

PRIMARY FILTER FAULT Failure at position 0, e.g. has not reset itself to
the 'home' position between measurements.
SECONDARY FILTER FAULT Failure at position 0, e.g. has not reset itself to
the 'home' position between measurements.
HELIUM PURGE FAULT Insufficient helium inlet pressure and flow.

SOFTWARE FAILURE x at y Report the error message.

UNKNOWN CALIBRATION Named calibration in remote analysis or

restandardisation does not exist.

INVALID CALIBRATION Named calibration in remote analysis or

restandardisation contains no segments
or invalid SUS's.

INCORRECT SUSSES Remote restansardisation results in calibration

with invalid SUS's.
Note: It is very unlikely that any software errors will occur during normal
operation. If a failure does occur, it will usually indicate a software
bug and the particular circumstances (with printouts) should be
reported.

Error 203 is trapped and if caused by insufficient room in battery backed RAM
will report 'battery backed memory full - press any key to continue'. All other
error conditions will reset processor, i.e. will return to 'switch on' menu.

Page D-2