Quantitative XRF
Standardless Methods
UniQuant
Denver Conference 2002
Kurt Juchli
Applied Research Laboratories
Ecublens
Switzerland
Thermo ARL
Topics
•
•
•
•
•
Introduction to UniQuant
Differences versus Scanning Programs
Analytical Conditions
Calibration
Analysis of Unknown Samples
Topics
• Introduction to UniQuant
– Main Features
– Evolution
Introduction to UniQuant
Main Features
• 74 elements (F to Am) determined in 15 minutes (4 to 12
seconds / spectral line)
• Peak to Peak Hopping + some Background Positions
• Be, B, C, N and O if appropriate crystals are present
• Samples: Solids, Liquids, Loose Powders, Filter Papers, etc.
• Sample Shape: Flat or uneven, odd shaped, small quantities
or small pieces, etc.
• Determination of Multilayers (Thickness and Mass)
• Balance of unanalysed Elements or Compounds present in
the sample, e.g. Organic Rest or Ultra-light Elements
Introduction to UniQuant
Evolution (1/2)
• Version 1 (1989):
– Calibration required special knowledge
– Background Determination influenced by strong Absorption Edges
• Version 2 (1992):
– Improved Calibration
– Improved Background Determination
– Program split into 2 parts (due to lack of conventional memory)
• Version 3 (1995):
– Improved Alpha and Kappa Coefficients
– Better results on Major Elements
– Improved Handling (only 1 Program)
Introduction to UniQuant
Evolution (2/2)
• Version 4 (1997):
– Improved Background Determination with Manual or Automatic
Selection among up to 32 Background Shapes
– Easy Calibration through Graphical Displays
– Graphical Presentations to check Plausibility of Results
– More Elements and alternative Lines
• Version 5 (2001):
– Parent - daughter principle to derive specific calibrations
– Setup of user specific calibrations
– Thin layer on a substrate: may also employ attenuation of intensity
from a substrate element
– Analysis of predefined compounds for any compound that contains
at least one XRF feasible element.
Topics
• Differences versus Scanning Programs
– Scanning - Peak Hopping
– Impact on Counting Statistics
– Background Determination
Differences versus Scanning Programs
Scanning
Differences versus Scanning Programs
Peak Hopping
Differences versus Scanning Programs
Counting Statistics (1/2)
th = SQR ( R * t )
R = counts/s
t = counting time
Differences versus Scanning Programs
Counting Statistics (2/2)
th = SQR ( R * t )
R = counts/s
t = counting time
Simple rule:
SQR (1’000’000) = 1000

0.1% RSD
Differences versus Scanning Programs
Background Determination - Scanning Method
Differences versus Scanning Programs
Background Determination - UniQuant 4 & 5 (1/2)
Background Shape for Last Elements in Group
?
?
Differences versus Scanning Programs
Background Determination - UniQuant 4 & 5 (2/2)
Background Shape for First Elements in Group
Topics
• Analytical Conditions
Analytical Conditions
UniQuant 4 & 5
Special Crystals - Calibrated on request
Topics
• Calibration
– Measurement of 64 Specimens
– Determination of Background Shapes and Spectral
Impurities
– Determination of Wedge Effect (Geometry of Instrument)
– Determination of Helium and Film Factors
– Determination of Tau values (Fine Tuning of Dead Time
Correction)
– Setup of Drift Correction (5 Setting-up Samples)
Calibration
Measurement of 64 Specimens
• Provides over 100 Spectrometer Channel Sensitivities
(Kappas)
• Establishes over 1500 Line Overlap Coefficients
• Mostly single Compounds, e.g. Elements in the form of pure
Metal foils, Oxides, Quartz, Cryolithe, etc.
Universal Calibration ?
Universal Calibration
Sensitivity of Sulfur in various Matrices
Universal Calibration
What are Kappas ? (1/2)
Conventional Sensitivity
cps / %
40’000 cps / % S in Steel
300’000 cps / % S in Oil
Universal Calibration
What are Kappas ? (2/2)
Conventional Sensitivity
cps / %
40’000 cps / % S in Steel
300’000 cps / % S in Oil
Intrinsic Sensitivity = Instrumental Sensitivity =
cps / atom
cps / 0.1mg
(very Thin Layer, Absorption negligible)
Kappa
Universal Calibration
Intrinsic and Overlap Kappas table
Intrinsic Kappas
Overlap Kappas
cps / 0.1 mg
ppm / %
Universal Calibration
Graphical Presentation of Intrinsic Kappas
Ka
La
Lb
Kb
Topics
• Calibration
– Measurement of 64 Specimens
– Determination of Background Shapes and Spectral
Impurities
– Determination of Wedge Effect (Geometry of Instrument)
– Determination of Helium and Film Factors
– Determination of Tau values (Fine Tuning of Dead Time
Correction)
– Setup of Drift Correction (5 Setting-up Samples)
Calibration
Background Shape and Impurities (Teflon)
Spectral Background determined with a Teflon Sample
Spectral Impurities
Mass Absorption Coefficients
Background Shape expressed in cps / 0.1 mg
Calibration
Tables for Background Shapes and Impurities
Impurity Factors
Background Shape
Topics
• Calibration
– Measurement of 64 Specimens
– Determination of Background Shapes and Spectral
Impurities
– Determination of Wedge Effect (Geometry of Instrument)
– Determination of Helium and Film Factors
– Determination of Tau values (Fine Tuning of Dead Time
Correction)
– Setup of Drift Correction (5 Setting-up Samples)
Calibration
The Wedge Effect (1/3)
SAMPLE
GONIOMETER
X-RAY TUBE
Calibration
The Wedge Effect (2/3)
Liquid Sample Cup
Oil
Supporting
Film
SAMPLE
GONIOMETER
X-RAY TUBE
Calibration
The Wedge Effect (3/3)
Liquid Sample Cup
Oil
Wedge
Supporting
Film
SAMPLE
Direction of
Incident
Radiation
GONIOMETER
X-RAY TUBE
Direction of
detected
Radiation
Calibration
Wedge Height
Wedge Height (mm)
Topics
• Calibration
– Measurement of 64 Specimens
– Determination of Background Shapes and Spectral
Impurities
– Determination of Wedge Effect (Geometry of Instrument)
– Determination of Helium and Film Factors
– Determination of Tau values (Fine Tuning of Dead Time
Correction)
– Setup of Drift Correction (5 Setting-up Samples)
Calibration
Absorption Factors for 6µ Polypropylene Film
Film Factor = Intensity without Film / Intensity with Film
Calibration
Table for Helium / Film Factors
Film Impurities (cps)
Helium
Film Film Factor
Factor Factor 1
2
Topics
• Calibration
– Measurement of 64 Specimens
– Determination of Background Shapes and Spectral
Impurities
– Determination of Wedge Effect (Geometry of Instrument)
– Determination of Helium and Film Factors
– Determination of Tau values (Fine Tuning of Dead Time
Correction)
– Setup of Drift Correction (5 Setting-up Samples)
Calibration
Determination of Tau Factors (Measurement)
Calibration
Determination of Tau Factors (Calculation)
Calibration
Tau Values
Topics
• Calibration
– Measurement of 64 Specimens
– Determination of Background Shapes and Spectral
Impurities
– Determination of Wedge Effect (Geometry of Instrument)
– Determination of Helium and Film Factors
– Determination of Tau values (Fine Tuning of Dead Time
Correction)
– Setup of Drift Correction (5 Setting-up Samples)
• Samples 223, 246, 295, 298, 299
Calibration
Setup of Drift Correction
Day 0
Today
Drift
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
– Advanced Features
Analysis of Unknown Samples
Import Intensities (1/5)
Analysis of Unknown Samples
Import Intensities (2/5)
Analysis of Unknown Samples
Import Intensities (3/5)
Drift Range Indication
Analysis of Unknown Samples
Import Intensities (4/5)
Select Results File
Analysis of Unknown Samples
Import Intensities (5/5)
Each Result is stored in an individual file
with the extension 000 to 999
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
– Advanced Features
Analysis of Unknown Samples
Select Job
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
– Advanced Features
Analysis of Unknown Samples
Specify General Data (1/12)
Analysis of Unknown Samples
Specify General Data (2/12)
Specify
Chemistry
Analysis of Unknown Samples
Specify General Data (3/12)
Select Helium
or Vacuum
Analysis of Unknown Samples
Specify General Data (4/12)
Specify Film
Analysis of Unknown Samples
Specify General Data (5/12)
Enter Sample
Diameter
Analysis of Unknown Samples
Specify General Data (6/12)
Calculated for
Effective Diameter
Compensation for
Non-Infinite Sample
Thickness
Effective Mass
Enter Sample
Weight
Analysis of Unknown Samples
Specify General Data (7/12)
Enter Sample Thickness
to compensate for Wegde
Effect
Analysis of Unknown Samples
Specify General Data (8/12)
Density is only used to calculate the
XRF measuring Depth and to check
Weight and Height (esp. for Liquids)
Analysis of Unknown Samples
Specify General Data (9/12)
Enter Concentration of Known
Non-AnalysedSelect
Compound
Compound / Material
Analysis of Unknown Samples
Specify General Data - Materials (10/12)
Analysis of Unknown Samples
Specify General Data (11/12)
Specify your
own, if necessary
Enter Dilution
Select
Ratio Diluent / Sample
Compound / Material
Analysis of Unknown Samples
General Data - Summary (12/12)
• Specify everything you know about the Sample
– Choice of Chemistry
– Weight (Effective Mass) to compensate for Non-Infinite
Thickness
– Height (Thickness) to compensate for Wedge Effect
– Known unmeasured Compounds
– Dilution
• Specify everything you know about the Analysis
– Helium or Vacuum
– Film
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
– Advanced Features
Analysis of Unknown Samples
Calculate Concentrations (1/2)
! Only in Version 5 !
Analysis of Unknown Samples
Calculate Concentrations (2/2)
Result
Display
Options
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
– Advanced Features
Analysis of Unknown Samples
Display Result (1/7)
Result
Display
Options
Analysis of Unknown Samples
Display Result (2/7)
< 18 ppm
Analysis of Unknown Samples
Display Result (3/7)
< 18 ppm
Analysis of Unknown Samples
Display Result (4/7)
Analysis of Unknown Samples
Display Result (5/7)
Analysis of Unknown Samples
Display Result (6/7)
Result
Display
Options
Analysis of Unknown Samples
Display Result (7/7)
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
–
–
–
–
Sum before Normalisation
Information contained in the Intensity Table
Influence of Wrong Sample Weight
Alternative Lines
– Advanced Features
Analysis of Unknown Samples
Check Result - Sum before Normalisation (1/2)
Analysis of Unknown Samples
Check Result - Sum before Normalisation (2/2)
Reasons for Bad Sum before Normalisation
–
–
–
–
–
–
Wrong Chemistry
Dilution not specified (Binder - Fused Bead)
Helium not selected
Film not specified
Wrong Effective Sample Diameter
Known or Unknown Rest not specified (Not analysable
Elements)
– Grain Size Effects
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
–
–
–
–
Sum before Normalisation
Information contained in the Intensity Table
Influence of Wrong Sample Weight
Alternative Lines
– Advanced Features
Analysis of Unknown Samples
Check Result - Intensity Table (1/4)
Analysis of Unknown Samples
Check Result - Intensity Table (2/4)
For all these lines
the L lines are also
measured
Analysis of Unknown Samples
Check Result - Intensity Table (3/4)
11.48
Ka Lines
0.202
L
Lines
Layer Thickness (in µm), where 90% of the
Fluorescence Radiation originates from (4/4)
Analyte Line Graphite Glass
Iron
Lead
Analyte Line Graphite Glass
Iron
Lead
U
La1
28000
1735
154
22.4
Mn
Ka
2110
155
131
9.01
Pb
Lb1
22200
1398
125
63.9
Cr
Ka
1619
122
104
7.23
Hg
La1
10750
709
65.6
34.9
Ti
Ka
920
73.3
63
4.52
W
La1
6289
429
40.9
22.4
Ca
Ka
495
54.3
36.5
3.41
Ce
Lb1
1484
113
96.1
6.72
K
Ka
355
40.2
27.2
3.04
Ba
Sn
La1
La1
893
399
71.3
44.8
61.3
30.2
4.4
3.34
Cl
S
Ka
Ka
172
116
20.9
14.8
14.3
10.1
2.19
4.83
Cd
Ka
144600
8197
701
77.3
Si
Ka
48.9
16.1
4.69
2.47
Mo
Ka
60580
3600
314
36.7
Al
Ka
31.8
10.5
3.05
1.7
Zr
Ka
44130
2668
235
28.9
Mg
Ka
20
7.08
1.92
1.13
Sr
Ka
31620
1947
173
24.6
Na
Ka
12
5.56
1.15
0.728
Br
Ka
18580
1183
106
55.1
F
Ka
3.7
1.71
0.356
0.262
As
Kb
17773
1132
102
53
Zn
Ka
6861
466
44.1
24
O
N
Ka
Ka
1.85
0.831
Cu
Ni
Fe
Ka
Ka
Ka
5512
4394
2720
380
307
196
36.4
29.8
164
20
16.6
11.1
C
Ka
13.6 0.424 0.0311 0.0312
B
Ka
4.19 0.134
2.5 0.178 0.143
1.11 0.0802 0.0713
Source: Retsch - The Sample (International Edition Number 5)
0.01 0.0117
K
Lines
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
–
–
–
–
Sum before Normalisation
Information contained in the Intensity Table
Influence of Wrong Sample Weight
Alternative Lines
– Advanced Features
Analysis of Unknown Samples
Check Result - Wrong Sample Weight (1/3)
Specification of Wrong
Sample Weight
! Recalculate !
Analysis of Unknown Samples
Check Result - Wrong Sample Weight (2/3)
11.48
0.202
Correct
Sample
Weight
Analysis of Unknown Samples
Check Result - Wrong Sample Weight (3/3)
11.48
60.64
0.202
Since Version 5.04
99.6
Topics
• Analysis of Unknown Samples
– Basic Features
•
•
•
•
•
•
Import Intensities
Select Job
Specify General Data
Calculate Concentrations
Display Result
Check Result
–
–
–
–
Sum before Normalisation
Information contained in the Intensity Table
Influence of Wrong Sample Weight
Alternative Lines
– Advanced Features
Analysis of Unknown Samples
Check Result - Select Alternative Lines (1/2)
Move Cursor here
or Click here
Enter * / Space to
select / deselect
Alternative Lines
! Recalculate !
Analysis of Unknown Samples
Check Result - Select Alternative Lines (2/2)
11.48
60.64
0.202
99.6
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
–
–
–
–
•
•
•
•
•
General Information
How to make a New Shape
Example Oil Standard Conostan S-21 / 50 ppm
Example Chemplex 55 Elements Standard
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
Small Samples
Analysis of Unknown Samples
Background Shapes - Select Shape (1/8)
Analysis of Unknown Samples
Background Shapes - Selection Criteria (2/8)
Analysis of Unknown Samples
Background Shapes - Define Default Shape (3/8)
0 = Automatic Shape Selection
1 = Teflon Shape (recommended)
Since Version 5
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
–
–
–
–
•
•
•
•
•
General Information
How to make a New Shape
Example Oil Standard Conostan S-21 / 50 ppm
Example Chemplex 55 Elements Standard
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
Small Samples
Analysis of Unknown Samples
Background Shapes - Table of Shapes (4/8)
Analysis of Unknown Samples
Background Shapes - Shapes and Impurity Factors (5/8)
N
o
t
N
o
t
S
e
t
u
p
S
e
t
u
p
Impurity Factors
Background Shapes
Analysis of Unknown Samples
Background Shapes - Make New Shape (6/8)
Analysis of Unknown Samples
Background Shapes - Select Sample (7/8)
Analysis of Unknown Samples
Background Shapes - Check / Refine Shape (8/8)
Fe Absorption Edge
Smoothed Shape
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
–
–
–
–
•
•
•
•
•
General Information
How to make a New Shape
Example Oil Standard Conostan S-21 / 50 ppm
Example Chemplex 55 Elements Standard
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
Small Samples
Analysis of Unknown Samples - Oil Sample
Conostan S-21 / 50ppm (1/5)
Last Element in
first group
Problem of Shape
Overlapped by Rh
Ka Lines
Wrong Impurity
Factors
Neighbours
in second
group
Analysis of Unknown Samples - Oil Sample
Inappropriate Background Shape (2/5)
Background
too low
Wrong Impurity
Factors for Oil
Matrix
Analysis of Unknown Samples - Oil Sample
Shape and Impurity Factors for Oil Matrix (3/5)
Analysis of Unknown Samples - Oil Sample
Appropriate Background Calculation (4/5)
Background calculated
for Unknown Oil Sample
Background Shape
and Impurity Factors
calculated with Base
Oil Sample
Analysis of Unknown Samples - Oil Sample
Conostan S-21 / 50ppm with Oil Background (5/5)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
–
–
–
–
•
•
•
•
•
General Information
How to make a New Shape
Example Oil Standard Conostan S-21 / 50 ppm
Example Chemplex 55 Elements Standard
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
Small Samples
Analysis of Unknown Samples
Special Case - Chemplex 55 Elements Standard
Look ahead in Background Calculation
Analysis of Unknown Samples
Special Case - Chemplex 55 Elements Standard
Look ahead of 8 Lines (Default Setting)
Analysis of Unknown Samples
Special Case - Chemplex 55 Elements Standard (1/2)
Look ahead of 20 Lines (Special Setting)
Analysis of Unknown Samples
Special Case - Chemplex 55 Elements Standard (2/2)
Look ahead of 20 Lines (Special Setting)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
•
•
•
•
•
•
Background Shapes
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
Small Samples
Analysis of Unknown Samples
Compensation for Grain Size Effects (1/2)
Analysis of Unknown Samples
Compensation for Grain Size Effects (2/2)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
• Shadow Loss
• Special Cases
–
–
–
–
–
Case 1 Unknown Area
Case 2 Unknown % Rest
Case 3 Unknown Dilution
Case 4 Unknown g/cm2 (Monolayer)
Case 5 Unknown Masses/Area (Multilayer)
• Subset Programs
• Kappa Lists
• Small Samples
Analysis of Unknown Samples
Special Cases - Unknown Area (1/2)
Analysis of Unknown Samples
Special Cases - Unknown Area (2/2)
Case 1:
Unknown Area
Same
Result !
Case 0:
Everything is known
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
• Shadow Loss
• Special Cases
–
–
–
–
–
Case 1 Unknown Area
Case 2 Unknown % Rest
Case 3 Unknown Dilution
Case 4 Unknown g/cm2 (Monolayer)
Case 5 Unknown Masses/Area (Multilayer)
• Subset Programs
• Kappa Lists
• Small Samples
Analysis of Unknown Samples
Unknown Rest % (1/2)
Analysis of Unknown Samples
Unknown Rest % (2/2)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
• Shadow Loss
• Special Cases
–
–
–
–
–
Case 1 Unknown Area
Case 2 Unknown % Rest
Case 3 Unknown Dilution
Case 4 Unknown g/cm2 (Monolayer)
Case 5 Unknown Masses/Area (Multilayer)
• Subset Programs
• Kappa Lists
• Small Samples
Analysis of Unknown Samples
Unknown Dilution (1/2)
Analysis of Unknown Samples
Unknown Dilution (2/2)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
• Shadow Loss
• Special Cases
–
–
–
–
–
Case 1 Unknown Area
Case 2 Unknown % Rest
Case 3 Unknown Dilution
Case 4 Unknown g/cm2 (Monolayer)
Case 5 Unknown Masses/Area (Multilayer)
• Subset Programs
• Kappa Lists
• Small Samples
Analysis of Unknown Samples
Unknown g/cm2 (Monolayer) (1/6)
Analysis of Unknown Samples
Unknown g/cm2 (Monolayer) (2/6)
“Schmauchspuren”
Residues of unburnt powder
after a gun shot
Analysis of Unknown Samples
Unknown g/cm2 (Monolayer) (3/6)
La
Lb
Case 0
(Bulk Sample)
Analysis of Unknown Samples
Unknown g/cm2 (Monolayer) (4/6)
Analysis of Unknown Samples
Unknown g/cm2 (Monolayer) (5/6)
Analysis of Unknown Samples
Unknown g/cm2 (Monolayer) (6/6)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
• Background Shapes
• Shadow Loss
• Special Cases
–
–
–
–
–
Case 1 Unknown Area
Case 2 Unknown % Rest
Case 3 Unknown Dilution
Case 4 Unknown g/cm2 (Monolayer)
Case 5 Unknown Masses/Area (Multilayer)
• Subset Programs
• Kappa Lists
• Small Samples
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (1/7)
• Up to 9 unknown (Masses) and 6 fixed layers can be specified
• Layers can be specified by an Element, Oxide or Compound (Material)
• Each Layer must have at least one Element of which the Intensity can be
measured
• The order of the layers must be specified (Substrate = 0)
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (2/7)
Select Case 5
Calculate
Background
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (3/7)
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (4/7)
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (5/7)
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (6/7)
Check !
Analysis of Unknown Samples
Unknown Masses/Area (Multilayer) (7/7)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
•
•
•
•
Background Shapes
Shadow Loss
Special Cases
Subset Programs
– Reasons
– How to create a Subset
– Example
• Kappa Lists
• Small Samples
Subset Programs
Reasons
• To speed up the Analysis
– measure only Elements present in the Samples
– measure only Elements that can be measured (e.g. eliminate F to Be
in He and/or with Foil)
• To optimise the Analysis
– measure only Elements present in the Samples
– increase Counting Times for important Traces
– decrease Counting Times for Majors
The analysis of oils or polymers does not require to measure
lanthanides and precious metals.
The total exposure time to X-Rays for Samples using a thin Foil is
limited (15 to 20 minutes) - Risk of Damage
Subset Programs
How to create a Subset
Counting
Time = 0

will not be
measured
Subset Programs
Example - PetroQuant (1/4)
• Additives in Oil
– Ca, Zn, P, Mg, Mo (0 - 5000 ppm)
– Cl, S (0 - 2.5 %)
– Si (few ppm)
• Following elements are sometimes present
– Na, K, Ba (0 - 5000 ppm)
– Cu, Fe (0 - 1000 ppm)
• Abrasion Elements (0 - 500 ppm)
– Al, Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Sn, Sb, Pb
Total Measuring Time : 11 minutes
Subset Programs
Example - PetroQuant (2/4)
Subset Programs
Example - PetroQuant (3/4)
Subset Programs
Example - PetroQuant (4/4)
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
•
•
•
•
•
Background Shapes
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
– Principle
– Practical Example
• Small Samples
Kappa Lists
Principle - New Calibration derived from a Parent (1/3)
AnySample
Beads
Daughter
Parent
Alloys
Parent
Pressed Powder
Daughter
Steel
© 2000 Omega Data Systems BV All Rights Reserved
Denver conference 2000 W.K. de Jongh (ODS), Kurt Juchli (ARL)
Kappa Lists
Principle - New Calibration derived from a Parent (2/3)
Parent
Beads
Homogeneous
Samples
Copy Kappa List
One or more Standards
to firm up calibration
of Major Elements
Daughter
Pressed Powder
© 2000 Omega Data Systems BV All Rights Reserved
Denver conference 2000 W.K. de Jongh (ODS), Kurt Juchli (ARL)
Mineralogical
Effects
Kappa Lists
Principle - Create New Kappa List (3/3)
Kappa Lists
Practical Example (1/4)
Difference in Sensitivity Reduction between High and
Low Crystal Angles versus Sample Surface Size
(Opening of Sample Holder)
– Sample with 90% Pt / 10% Rh (CAL 278) analysed with
29 and 15 mm Sample Holder Openings
– Sample with 10% Ir / 90% Pd (CAL 246) measured to
adjust Kappas for 15 mm Sample Holder Opening
– Sample with 90% Pt / 10% Rh (CAL 278) recalculated
with new Kappa list
Low 2 Theta Angles
Pd = 16.76
Rh = 17.54
High 2 Theta Angles
Ir = 56.68
Pt = 54.91
Kappa Lists
Practical Example (2/4)
Sample
29 mm
15 mm
CAL 278
Pt 89.98%
Rh 10.00%
Pt 83.84%
Rh 16.15%
CAL 246
Pd 89.98%
Ir
9.99%
Pd 94.08%
Ir 5.90%
CAL 278
Pt 89.98%
Rh 10.00%
?
?
Kappa Lists
Practical Example (3/4)
15 mm
29 mm
Kappa Lists
Practical Example (4/4)
Sample
29 mm
15 mm
CAL 278
Pt 89.98%
Rh 10.00%
Pt 83.84%
Rh 16.15%
CAL 246
Pd 89.98%
Ir
9.99%
Pd 89.99%
Ir 10.01%
CAL 278
Pt 89.98%
Rh 10.00%
Pt 89.94
Rh 10.05
Adjusted
Kappas
Kappa Lists
Practical Example - Explanation (1/2)
Normal
Sample
Collimator Mask
Crystal at higher angles
Collimator Mask
Crystal at lower angles
Kappa Lists
Practical Example - Explanation (2/2)
Small
Sample
Collimator Mask
Crystal at higher angles
Small
Sample
Collimator Mask
Crystal at lower angles
Topics
• Analysis of Unknown Samples
– Basic Features
– Advanced Features
•
•
•
•
•
•
Background Shapes
Shadow Loss
Special Cases
Subset Programs
Kappa Lists
Small Samples
Small Samples
Irregular Shaped Small Sample
Polypropylene Insert
to keep sample in place
Small Samples
Stainless Steel Drillings
Lowest Angle
Element
Mn
Si
Cr
Ni
Mo
Cu
Ti
Fe
Nb
%
%
%
%
%
%
%
%
%
Drill. 90
1.34
0.36 18.12 10.58 1.91
Drill.180
1.37
0.30 18.37 10.61 1.47
0.06
0.012 67.3
Drill.360
1.37
0.37 18.26 10.60 1.80
0.08
0.011 66.4
0.009
Pressed
1.38
0.41 18.18 10.79 1.59
0.08
0.014 67.0
0.009
0.021 66.4
• Drill.90, Drill.180 and Drill.360 were analysed under helium
environment with a film support (6µ PP)
• The pressed sample was analysed under vacuum
Thank you very much for
your Attention
Kurt Juchli
Applied Research Laboratories
Ecublens
Switzerland
Thermo ARL
Analysed
Surface
Collimator Mask
Crystal at higher angles
Collimator Mask
Crystal at lower angles