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

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

Background Shape for Last Elements in Group Differences versus Scanning Programs Background Determination - UniQuant 4 & 5 (1/2) Background Shape for Last Elements in Group ? ?

Background Shape for First 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 = Kappa cps / atom cps / 0.1mg (very Thin Layer, Absorption negligible)

Universal Calibration Intrinsic and Overlap Kappas table Intrinsic Kappas cps / 0.1 mg Overlap Kappas ppm / %

Universal Calibration Graphical Presentation of Intrinsic Kappas 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)

Calibration The Wedge Effect (2/3) Liquid Sample Cup Oil Supporting Film

Calibration The Wedge Effect (3/3) Liquid Sample Cup Oil Wedge Supporting Film Direction of Incident Radiation 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 Factor Film Factor 1 Film Factor 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 Advanced 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 Advanced 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 Advanced 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-Analysed Compound Select 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 Ratio Diluent / Sample Select 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 Advanced 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 Advanced 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 Advanced 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 Advanced 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

Source: Retsch - The Sample (International Edition Number 5) Layer Thickness (in µm), where 90% of the Fluorescence Radiation originates from (4/4) L Lines K Lines Source: Retsch - The Sample (International Edition Number 5)

Topics Analysis of Unknown Samples Basic Features Advanced 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 SampleWeight

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 Advanced 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

Enter * / Space to select / deselect Alternative Lines 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)

0 = Automatic Shape Selection 1 = Teflon Shape (recommended) 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) Not Set up Not Set up 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 Neighbours in second group Overlapped by Rh Ka Lines Wrong Impurity Factors

Wrong Impurity Factors for Oil Matrix 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 Shape and Impurity Factors calculated with Base Oil Sample Background calculated for Unknown 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 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 Parent Beads Daughter Alloys Parent Pressed Powder Steel Daughter © 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) Homogeneous Samples Beads Copy Kappa List Daughter Mineralogical Effects One or more Standards to firm up calibration of Major Elements Pressed Powder © 2000 Omega Data Systems BV All Rights Reserved Denver conference 2000 W.K. de Jongh (ODS), Kurt Juchli (ARL)

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 High 2 Theta Angles Pd = 16.76 Ir = 56.68 Rh = 17.54 Pt = 54.91

Kappa Lists Practical Example (2/4)

Kappa Lists Practical Example (3/4) 15 mm 29 mm

Kappa Lists Practical Example (4/4) Adjusted Kappas

Kappa Lists Practical Example - Explanation (1/2) Normal Sample Collimator Mask Collimator Mask Crystal at higher angles Crystal at lower angles

Kappa Lists Practical Example - Explanation (2/2) Small Sample Small Sample Collimator Mask Collimator Mask Crystal at higher angles 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 Drill. 90 Drill.180 Drill.360 Pressed Mn % 1.34 1.37 1.38 Si % 0.36 0.30 0.37 0.41 Cr % 18.12 18.37 18.26 18.18 Ni % 10.58 10.61 10.60 10.79 Mo % 1.91 1.47 1.80 1.59 Cu % 0.06 0.08 Ti % 0.021 0.012 0.011 0.014 Fe % 66.4 67.3 67.0 Nb % 0.009 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

Crystal at higher angles Crystal at lower angles Analysed Surface Collimator Mask Collimator Mask Crystal at higher angles Crystal at lower angles