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XRF Fundamentals

Introduction Sample Preparation Calibration Methods Application Guide

SPECTRO Analytical Instruments

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Contents
Contents 2

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2.1 2.2 2.3 2.4

Introduction
Which elements can be analyzed? What are matrix effects? Importance of detector resolution Why use polarization? 4 6 7 8

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3.1 3.2 3.2.1 3.2.2 3.2.3 3.3 3.3.1 3.4 3.4.1 3.4.2 3.4.3 3.4.4 3.4.5

Sample Preparation
Importance of sample preparation Solid Pellets Powders Fusions Liquid Monophased/Polyphased Accessories Mill Press Die Fusion Machine Chemicals 11 11 11 11 12 13 13 13 13 14 15 15 15

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4.1 4.1.1 4.1.2 4.1.3 4.2 4.3

Calibration Methods
TURBOQUANT TURBOQUANT for liquids TURBOQUANT for pellets/powder/metals General Standardless Empirical/Lucas-Tooth 16 18 19 21 21 22

XRF Fundamentals

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5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6 5.1.7 5.1.8 5.1.9 5.1.10 5.1.11 5.1.12 5.1.13 5.1.14 5.1.15 5.1.16

Application Guide
Additives in oil/lubricants Used oil Wear Metals/Cooling Liquids Fuels Waste RoHS, WEEE, ELV Polymers Minerals/Geology/Slags/Ceramics Cement Metals Precious metals Iron ore and Sinter Slag Ferroalloys Pharmaceutical Food 23 23 23 23 23 24 24 24 24 25 25 25 25 25 25 26

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6.1 6.1.1 6.1.2 6.1.3 6.1.4 6.1.5 6.1.6 6.2 6.3

Appendix
Literature Basics Polarization Matrix Correction Methods for Quantification Tables Applications Figures Tables 27 27 27 27 27 28 28 28 29

SPECTRO Analytical Instruments

Table 1: Overview of elements detectable with XRF. in analytical laboratories including applications traditionally handled using atomic absorption spectroscopy (AAS) or inductively coupled plasma-optical emission spectroscopy (ICP-OES). The analysis of the elements Be to F is limited to just a few special applications. Element B C With XRF all elements between Na and U can be analyzed. sample must be re-melted before measurement to avoid inhomogeneities Only special detectors with HT window (cannot measure powders). The advantages are clear: easy sample preparation.Chapter 2 . powders in sample cups Liquids. XRF is becoming the universal tool XRF is becoming the universal tool in analytical laboratories. and for all elements from Pr to U. 2. There is virtually no industry or application field where it isn’t worthwhile to consider the use of the XRF analysis technique. Mg F -Cl K-U All XRF Fundamentals . These elements show low energy x-rays that are easily absorbed by air or a simple polypropylene film. and the possibility to screen completely unknown samples. fusions All Na. particle size must be ~60 µm. pellets. L-lines are used.Introduction 4 2 Introduction The traditional use of XRF has its roots in geology. Not possible with XRF. powders. More and more. The reason for this is the depth of analysis. sample must be extremely homogeneous With increasing atomic number particle size. F F in polymers Be-F Liquids.. For the elements from Na to Ce K-lines are used.. Lines are absorbed in the film which covers the bottom of the cup Only with He-purge or vacuum (pellets+fusion) Depth of analysis is very shallow. Solid samples were the first sample types analyzed by x-rays. polished surface Only WDXRF. effects decrease and penetration of the sample increases.1 Which elements can be analyzed? With XRF all elements between Na and U can be analyzed. Application B in wafers C in steel Remark Only WDXRF. multi-element determination.

Teflon F WDXRF spectrometer Film SPECTRO Analytical Instruments . you need a grain size of 0.305 µm 0.136 µm 0. This is not achievable! Loose Powder and Liquid Teflon F 60 % Pellet Pellet + Mylar 6 µm Pellet + Mylar 12 µm Coarse collimator 24 kV.326 µm Figure 1: Penetration depth of x-rays for light elements.326 µm 0.06 µm 0.5 Pressed Pellet Penetration Depth F O N C B Be 0.045 µm F SiO2 0. 125 mA QP-PX1 Figure 2: Measurement of fluorine. Absorbance of fluorine intensity by films covering the bottom of the sample cup. The main reason why fluorine cannot be measured in a sample cup. F To get reproducible results.02 µm.29 µm 0.

Chapter 2 . Matrix Effect C C O H C Zn O OO H OH O O H H C H C O OC C H ZnC H C CH O Zn C C Zn OH C O C HC O O C O OO H H OOH H C C C H CC O Zn O COH H H H C Zn In this example the matrix is an organic solvent. If the matrix changes (e.. matrix effects occur when one component of the sample changes its concentration by more than 0.2 In general. but very often we are measuring solid samples.e. As long as we know these conditions and keep them constant. fused beads from solids) 3) Use the compton scattering for matrix correction to eliminate matrix effects (i.e. In XRF this is similar. we are able to get reproducible results.. Ecitation Detection The matrix effect can be easily demonstrated with liquids. we will get a “matrix effect” for all the other elements. we have to keep the flame parameters constant. What are matrix effects? The use of an analytical device for the determination of elements or other physical properties is based on special conditions.Introduction 6 2. polymers). If we change the solvent. In AAS this would mean that we have to use the same solvent for standards and samples. The fluorescence radiation (here Zn) is absorbed by the matrix until it leaves the sample. to water) also the absorption of x-rays will change. 2) Make a dilution of your sample to always have the same matrix (i. This will work for trace analysis (i.5 %. If one of the main components of a solid sample changes its concentration.. There are three possibilities to overcome this problem: 1) Always use the same solvent/matrix. Also. the element of interest will show a different intensity.e.g. Figure 3: Exciting x-rays are absorbed by the matrix until they reach the element to excite. used in TURBOQUANT) XRF Fundamentals .

Also the scattering shows matrix dependence. The differences in detection systems can be seen from different spectral resolution. Selecting a special type of sample preparation can do this. 2. theoretically. The behavior of the tube. The Mo radiation from the Mo secondary target used for excitation is scattered at the sample. Disadvantages of the analysis of solids with XRF are the associated matrix effects. For XRF samples. especially for solid samples where collection for a sample cup or even making pressed pellets is less work than a digestion for ICP-OES or AAS. matrix effects occur when one component of the sample changes its concentration by more than 0.7 Figure 4: Each solvent shows a different absorption of x-rays.g. The penetration depth of the x-rays into the material is found in tables stated as mass absorption coefficient and can be calculated for each element. generally less than 0. This can be used for matrix correction (e. in TURBOQUANT). The excitation process as well as the detection of a fluorescence line is always performed in the same constant manner. the geometry of the x-ray beams has to be known. SPECTRO Analytical Instruments . It is well known that one type of digestion is not effective for all elements between Na and U. therefore. target and detector. The software knows all of these parameters. and the geometry must always be the same. it is possible to describe the XRF analysis theoretically. detector. as well as the characteristics of the xray tube. quantities between 3 and 8 g are typical. Some of the detection systems require cooling with liquid nitrogen. The biggest advantage of XRF is its easy sample preparation. The importance of detector resolution There are different types of detectors used in EDXRF. To describe it completely. from the pulse throughput and the asorption characteristics for X-Rays. To get a correct analysis. Another disadvantage of a digestion is the small sample amount. This is very important for inhomogeneous samples where more sample material reduces the influence of the inhomogeneity.5 g.5 %.3 Currently there are four different types of detectors used in EDXRF. In general. others are electrically cooled or do not require any cooling at all. these effects need to be taken into account and corrected. target. using fundamental parameters. but this is usually accomplished by describing the fluorescence process.

Blue: Si(Li) oder SDD Red: Si PIN Black: Prop.Introduction 8 In Figure 5. Here it is important to consider if we are just looking for traces or if we want to analyze traces and main components. If only one element has to be detected. resolution is not important. Counter Figure 5: Comparison of resolution for different types of detectors used in EDXRF. better resolution than the two previous mentioned systems. it is important to choose the right detector. This can have additional benefits for the absorption of some high-energy X-Rays. In classical EDXRF and in WDXRF. The proportional counter detector (PC) is not able to resolve neighboring elements’ lines. Detection systems cooled with liquid nitrogen achieve a very good resolution. 2. direct excitation is used. and it won’t be overlapped by other elements. This leads to a better peak to background ratio and therefore better sensitivity.4 Why use polarization? The main reason for using polarization is to improve analytical sensitivities. too. The essential advantage of SDD’s is the highest available count rate throughput. a semi-conductor detector is required. The Silion PIN-diode shows a much better resolution than the PC and is able to resolve neighboring elements.Chapter 2 . These techniques suffer from a high spectral background which is a result of the excitation x-ray scatter. In the same situation where neighboring elements have to be resolved. In EDXRF bad peak to background ratios are the result. XRF Fundamentals . In this case one may choose a PC. The main reason for using polarization is to reduce the spectral background. In WDXRF the problem is overcome by using high power x-ray tubes .up to 4 kW . For any given application.that require water-cooling. only sensitivity is. In such a case only a Silicon drift detector or Si(Li) detector can do the job. the resolution of the different detection systems are shown for the Mn K lines. which can lead to better precision of the analysis or shorter measuring times. it is important to choose the right detector. A Silicon drift detector (SDD) achieves a For any given application.

Then the polarization plane is the same as for the target. this means that the nonpolarized x-rays from the tube are polarized at the target. To polarize x-rays you need a certain geometry: tube.Secondary Target SPECTRO Analytical Instruments . Polarization is performed by changing the direction of x-rays by 90°. sample. Once these polarized x-rays hit the sample. target. WDXRF with direct excitation and EDXRF with polarized excitation: EDPXRF. Tube Sample Target z Figure 7: Cartesian geometry for polarization of exciting x-rays. it can only be scattered orthogonal to the plane and because the detector is placed inside the plane. Polarization is performed by changing the direction of x-rays by 90°. y x Detector Targets: .Polarizer . The x-rays coming out of the tube are reflected or scattered by the target with an angle of 90° to the sample. sample and detector must be arranged in a Cartesian geometry. and detector. it can only detect the fluorescence radiation coming from the elements in the sample. it is not important which physical process is involved in polarizing x-rays. However.9 Figure 6: Different XRF techniques: EDXRF.

like alloys. Figure 8 shows the comparison between direct and polarized excitation. These are the applications where the polarization technique performs best and generates the highest sensitivities in XRF. One of the main causes for background is the scattering of the exciting x-rays at the sample. This gives a good impression of how the peak to background ratio improves when background is reduced and the reduction is compensated by higher fluorescence lines due to polarization. Heavy sample materials. XRF Fundamentals . Both spectra are normalized to the height of Fe and Zn.. Light sample materials. liquids.Introduction 10 Figure 8: Comparison of spectra of certified reference material (BCR-186) with direct excitation (yellow) and polarized radiation (blue). show virtually no scattering.. which means polarization won’t give an advantage. the reasons for spectral background have to be understood. polymers. Polarization will always show a big improvement over the classical direct excitation when the spectrum exhibits a high background.background is the scattering of the exciting x-rays at the sample. . To understand now how polarization will improve the analysis. silicates and even a lot of minerals generate a high level of scattering.Chapter 2 . like organics.

Solid Pellets 4 g of a powder (< 100 µm) is mixed well. After pouring. In particular.9 g Wax Powder Clariant micropowder C Mill Container for grinding and mixing Die (diameter 32 or 40 mm) Press min.9 g of Clariant micropowder C. The bottom of the sample cup is covered typically with a 4 µm polypropylene film.Sample Preparation Sample Preparation Importance of sample preparation The error of the analysis goes along with the sample preparation. 3 3.e. the error of the sample preparation must be in agreement with the required precision of the analytical method.. homogenized with 0.1 + 4 g Powder Sample: Additives: Preparation Utilities: 0. 15 ton Pellet Powders 4 g of a powder ground down to < 100 µm is poured into a sample cup with an inner diameter of 28 mm.2 4 g Powder Sample: Additives: Preparation Utilities: Powder None Mill for grinding Sample Cup sample cups (outer diameter 32 or 40 mm) Polypropylene foil 4 µm thickness Pistil SPECTRO Analytical Instruments .11 Chapter 3 .1 The error of the analysis goes along with the sample preparation.2 3. the error of the light elements Na to Cl decreases by using pressed pellets in the preparation technique... and then pressed with 15 tons to pellet with 32 mm diameter.2. For liquids. 3. 3. the powder will be slightly pressed with a pistil to form a good surface to avoid any air holes on the bottom.2. simply pouring into a sample cup is acceptable. The available preparation techniques for solids are powder or pressed pellets. i.

The flux should be selected carefully in order to create a completely dissolved sample in the fused bead. carbides are also dangerous. 0.7 g Powder 6 g Li2B4O7 Crucible + Crucible Burner/Furnace Bead Sample: Additives: Preparation Utilities: Powder Flux.2 g. wetting agent Platinum/gold crucible and mould Fusion machine or furnace ! XRF Fundamentals There are some materials that may destroy your Pt/Au crucible. the use of a wetting agent (e. time and temperature may vary. As a standard procedure. The most dangerous for the Pt/Au crucibles are metals. boron. especially elemental silicon. In some cases it is necessary to reduce the sample amount down to 0. . If a lot of fusion remains in the crucible.Chapter 3 . or iron. Depending on the material and the fusion machine. For some materials a pre-oxidation may be necessary. a 10-minute fusion time should be sufficient.7 g of the powder is homogenized with 6. 12 + 0.g.2.3 Fusions The sample material must be dried and milled to a grain size lower than 100 µm.Sample Preparation 3. NH4I) may be required.0 g of Flux and then fused at 1100°C to a 40 mm bead.

1 4 g Liquids Sample Cup Polyphased Liquids: To analyze polyphased liquids (liquid / liquid or solid / liquid) or highly volatile liquids.4 3. it is very important that the particle size is < 100 µm. water based. charcoal for polyphased liquids Sample cups (outer diameter 32 or 40 mm) Prolene foil 4 µm thickness Mixing containers for polyphased liquids Accessories Mill For preparation of pellets or loose powder. SPECTRO Analytical Instruments . The bottom of the sample cup is covered with a 4 µm polypropylene film. polyphased liquids None. the use of a mill is quite common. + 6 g Liquids 2 g Charcoal Mixture 4 g Mixture Sample: Additives: Preparation Utilities: Sample Cup Liquid: oil based. it is very important that the particle size is < 100 µm. Monophased Liquids: 3.13 Liquid Monophased / Polyphased 4 g of a liquid is poured into a sample cup with an outer diameter of 32 mm. The TURBOQUANT programs need powder and pellet samples prepared to < 100 µm! 3.3.4. it is advised to use 4 g of a well-homogenized mixture prepared using 6 g sample and 2 g charcoal (Merck). To mill the samples.3 3.1 For preparation of pellets or loose powder. Also it is recommended to use a Zirconium dioxide grinder (volume 25 ml good for 10 g of material) Zirconium dioxide is hard enough to grind most all materials.

4. Figure 10: Mill with an Al2O3 grinding vessel for grinding of up to 60 g. a press with a pressure up to 15 tons is sufficient Figure 11: Manual press up to 15 tons.Sample Preparation 14 Figure 9: Mill with a ZrO2 grinding vessel for grinding of up to 10 g.1 Press For preparation of pellets. To grind larger amounts of sample material (up to 60 g). XRF Fundamentals . a disc vibration grinding mill is recommended. 3.Chapter 3 .

4. Program 2 melts the flux + sample. and program 4 pours it into the pre-heated mould. burners fusion machine. This machine fuses samples fully automatically. The mixture is then poured into the die and pressed with 15 tons. Program 1 will dry the sample. one may use the 2 burners or 4 Figure 13: Fusion Machine (2 burners. 3. and then the crucible is placed into the fusion machine. Program 3 stirs the melt. To make the preparation procedure as easy as possible.4.5 Chemicals Clariant micropowder C Pellets Charcoal (Merck) Flux Polyphased liquids Fused beads SPECTRO Analytical Instruments .3 Die To prepare pellets. also available with 4 burners).4. The bead then cooled and can be used for analysis. you need a die.15 3. Figure 12: Example for different types of dies.4 Fusion Machine Fused beads give the most accurate results for those elements which suffer from grain size effects on their fluorescence radiation. 3. The sample is weighed into the Platinum crucible together with the flux. The powder is homogenized with the wax using a mixing container in the mill MM2.

XRF Fundamentals .U (L) Zr . The only distinction is made between solids. Whenever it is possible to limit the possible matrices. The excitation of all elements (Na-U) is split into three single measurements using different targets. The method is able to analyze the elements from Na to U in completely unknown samples.V Table 2: Targets and Corresponding Elements in TURBOQUANT.Y (K). Target Mo Al2O3 HOPG Target Type of Target secondary Barkla Bragg Excited Elements Cr . The light elements Na-V are excited using a HOPG target (intense monochromatic polarized x-rays). liquids and alloys (there is a separate program for each).1 TURBOQUANT is able to analyze the elements from Na to U in completely unknown samples. the accuracy is between 10 to 20 % relative. This means that all matrix effects which will occur are taken into account. The elements Cr-Zr and Pr-U are excited using a Mo secondary target (intense monochromatic non polarized x-rays).Chapter 4 .Calibration Methods 16 4 Calibration Methods 4. only for organic matrices.Ce Na . the relative accuracy can be improved. i.. HOPG-Target Mo-Secondary-Target Mo-Target Al2O3-Target Figure 14: Excitation of K and L lines with different targets. With this highly flexible mode. Pr . The high-energy elements Y-Ce are excited using a Barkla Al2O3 target (intense polychromatic polarized x-rays). TURBOQUANT TURBOQUANT is the brand name for a SPECTRO method that is used for screening analysis.e.

The calculation of the theoretical mass absorption coefficients for 2. This method is based on the fact that all elements contained in a sample contribute to the Compton scattering of the excitation radiation. That means the intensity of the Compton peak is related to the mass absorption coefficient of the specimen. ethylene glycol / water (86 % / 14 %). This can be accomplished using the well-known Compton Method (One may understand that this line is used as internal standard). SPECTRO Analytical Instruments . This can be used for an unknown sample to calculate the mass absorption coefficient based on the Compton peak and then the intensities of the element lines are subsequently corrected based on the mass absorption (this is valid for liquids and solids). the correlation between intensity and concentration is calculated. To handle different matrices with one calibration. One of the main features of TURBOQUANT is the automatic matrix correction. and kerosene. The detected intensities show a difference between water and kerosene of a factor 2.17 Four solutions of 1 % Chlorine were prepared with 4 different solvents: water.6. For calibration. a Fundamental Parameter (FP) approach is used. 10 kV. Measurement was done using a HOPG-target. This evaluation technique is used for solid and liquid samples. the intensities first have to be corrected for the matrix effect. Figure 15: Influence of different matrices on the intensity of the chlorine Kα-line.7. 200 s. This is caused by the variation of the oxygen and carbon contents in the liquids. Based on the corrected intensities for each element.6 keV gives a factor of 2. The main advantage of FP versus empirical methods is its capacity to take into account all possible inferences between the elements. 2-propanol.

5 17. XRF Fundamentals .Chapter 4 . Measurement time 200 s. containing ICP standards (Merck.8 27 55 39 21 104 *Impurity of charcoal Known Conc.Calibration Methods 4.5 28.1. 1% Clorine in TURBOQUANT[%] Kerosene 1. total measurement time 600 s. 16 demonstrates the performance of the method for the analysis of halogens over a large concentration range from 10 µg/g to 10 %. 3 g sample + 1 g charcoal as absorbing material.05 Water Ethyl. Bernd Kraft) and oil standards (Conostan) were used.88 Water Water 0. For example.5 10 40 25 25 75 40 25 115 Cr Mn Fe Co Ni Cu Zn Ga Ag Cd Pb Table 4: Results of a polyphased sample. water and oil based samples can be analyzed in the same way as solvents or even polyphased liquids. For an optimum calibration. a special set of standards.98 Table 3: Results of TURBOQUANT liquid for Cl in different solvents. [µg/g] 21 30 <100* 10 35.5 22. Fig. [µg/g] 27.1 18 TURBOQUANT for liquids The use of an automatic matrix correction makes it possible to analyze liquids of different origins with the same calibration. Element SPECTRO X-LAB 2000 Conc. It is possible to extend the calibration range for Cl up to 80 %.glcol / Water 0. Figure 16: Calibration of halogens in liquids with TURBOQUANT.01 2-Propanol 2-Propanol 1.

National Bureau of Standards (USA). either loose powder or pellet.49 104 117 120 120 122 116 135 125 123 116 121 120 ± 0. The small RMS-value proves the performance of the matrix correction. The matrix correction is able to handle matrices starting from a ‘light’ matrix like wax (Hoechst) up to PbO. TURBOQUANT for pellets/powder/metals A matrix correction is done for solids in the same way as for liquids. 4.5 %)* 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g 125 µg/g (*Value in brackets are not certfied) Table 5: Reproducibility of an ICP multielement standard prepared 3 times with charcoal (3 g sample + 1 g charcoal). CoO or PbO or certified reference materials from BCR (Brussels).2 The high dynamic range from the ppm up to % level is significant.9999. RMS1 = 0. Canadian Certified Reference Materials (Canada). the matrix of the sample is detected by the Compton Method.19 Element Cl Ti Cr Mn Fe Co Ni Cu Zn Sr Cd Ba La Value Average Value (n=3) 6.04 % ± 18 µg/g ± 3 µg/g ± 4 µg/g ± 17 µg/g ± 14 µg/g ± 7 µg/g ± 4 µg/g ± 3 µg/g ± 2 µg/g ± 3 µg/g ± 3 µg/g ± 2 µg/g Value certified Value (6. R=0. Figure 17: Calibration of Pb in pellets. which represents the ‘heaviest’ matrix. 59 standards. The TURBOQUANT calibrations are based on 120 standard samples which are either pure chemicals like NaCl. pellets will give the most precise results. State Bureau of Metrology (China). Zentrales Geologisches Institut (Berlin). Independent of the sample preparation. The high dynamic range from the ppm up to % level is significant. Figure 17 shows the calibration curve for Pb. and the South African Committee for Certified Reference Materials (South Africa). For light elements like Na-S.006%. SPECTRO Analytical Instruments Pb cacluated (ug/g) . The selection of the sample preparation depends on the desired precision.1.

2 < 1.7 15 8 0.0 Br Br Br Table 7: Results using TURBOQUANT for the analysis of Br in polystyrene.29 (0.7 0.04 0.0 < 2.007 ± ± ± ± ± ± ± ± ± ± 0. Element SPECTRO X-LAB 2000 Conc. Table 8: Results using TURBOQUANT for an alloy: stainless steel.058 Certified Conc.02 0.06 (9. BS 84h.7 ± 1.0 50.5 mm.03 0.7 13. total measurement time 150 s.5 0.4 13.39 (64.Calibration Methods 20 Tables 6-9 show the results using TURBOQUANT for different kinds of solid materials.027 2.005 Value in brackets are not certified.1 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 60 28 300 60 60 20 4 1.02 0.4 < 1. prepared as loose powder.2 0. 316.5 51 97 Known Conc.6 1.0 100.1[%] (0.0022 0.81) 0.02 ± 0.42 65. Element SPECTRO X-LAB 2000 Conc.028 0.1 0. [µg/g] 2420 601 11000 7850 2780 9940 116 10.02 0.2 0.3 0.63 0. [µg/g] 10.7 ± 1.006 0.004) 0.00 0.25 0.025) 2.5 0. NIST-1577 represents a ‘light’ matrix whereas BCR-176 represents a ‘heavy’ matrix.4 12.16 0.2 12.0 10.08 0.08 0.05 1 Al Si P S V Cr Mn Fe Co Ni Cu Nb Mo W ± 0. [µg/g] ± 500 <1000 10750 ± 100 7661 ± 64 2739 ± 50 9790 ± 200 123 ± 46 < 12 189 ± 17 167 ± 11 < 1. [µg/g] 9.6 1000 Certified Conc.08 16.5 0.15 0. total measurement time 150 s.0 3.7 0.5 0.004 Na Mg P S Cl K Ca Mn Fe Cu Se Br Rb Sr Mo Cd Pb Table 6: Results using TURBOQUANT for a ‘light’ matrix: reference material NIST1577b (bovine liver) prepared as pellet. [%] <0.2 ± 1. total measurement time 150 s.001 0.5 184 160 0.86 1. XRF Fundamentals .7) 1.1 3.15 17.Chapter 4 .04 <0. Element SPECTRO X-LAB 2000 Conc. particle size 0.9 0.01 0.

Standard-less programs will only give accurate results (error 20-30 % relative) as long as the matrix is known.55) (4.64 45 472 437 33 1.11 % ± 4. Value in brackets are not certified General The results for the different sample types show the excellent performance of TURBOQUANT. Total measurement time is 150 s.086 2.51 4.0085 2.02 0.97 0.2 µg / g ± 26 µg / g ± 0.2 One of the biggest advantages of the theoretical methods is that they don’t need standards to calibrate the inter-elemental effects.04 0. Analyzing samples on the basis of liquid or solid calibration gives a high degree of flexibility.13 123.34 4. 4. Error (1σ).02 12 15 11 5 0. 4.04 % ± 2.12 0.18) (10. SPECTRO Analytical Instruments . the instrument geometry has to be measured on at least one sample.1 µg / g ± 9 µg / g ± 18 µg / g ± 1.2 9.015 1 0.087 % % % % % % % ± 0.3 2. Table 9: Comparison of results using TURBOQUANT for BCR-176 (ash) prepared as loose powder or pellet.5 1302 2.0 0.37 0.2 470 412 31. The only unknown is the instrument itself. Therefore.3) (2.46) (4.014 (4.02 0.017 % stat.5 0.1 3.4 0.084 2. In table 9. It is a useful tool for classification and identification of unknown samples. The comparison shows that for the analysis of the heavy elements (Z > 22) the preparation as loose powder is sufficient.13 13.15) 14.04 (0. Na Mg Al Si P S Cl Cr Fe Ni Cu Zn Se Cd Sb Hg Pb ± ± ± ± ± ± ± ± ± ± ± ± ± ± 0.003 % ± 0. No special calibrations adapted to the sample type are required.05 22 50 0.44 5.21 Element SPECTRO X-LAB 2000 Loose powder Conc.06 0.066 ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± ± 2 Certified2 Unit Conc.3 Standardless Standardless programs are based on fundamental parameters and describe the fluorescence process theoretically.06 SPECTRO X-LAB 2000 Pellet Conc.16 0.04 22 54 0.1 µg / g ± 0.58 41.012 0.018 0. The precision achieved for the heavy elements is generally <10 % relative and <20 % for the light elements.47 41.1 14. The major advantage of the TURBOQUANT method compared with these classic standardless methods is its matrix independence.15 125 1232 2. the results of BCR-176 are compared with two different sample preparation techniques.06 0.02 11 15 12 6 0.00 134 1299 2.08 0.016 0.12 0.1.8) 0.16 5.4 1.2 510 421 21 1.

concentration).3 Empirical / Lucas-Tooth & Price The classical way to calibrate is to use standards with the same matrix and known composition. The measured intensities are then used to create a calibration curve (intensity vs. Empirical methods do not correct for any of these effects. However. This is only possible as long as standards with and without these components are available. The biggest difference between the theoretical method (fundamental parameters FP) and the empirical method is found in the use of inter-elemental corrections. which will show a better degree of accuracy than theoretical methods. Empirical methods are used to calibrate only a few elements in a fixed matrix. XRF Fundamentals . if the Lucas/Tooth method is used. corrections for inter-elemental effects can be introduced into the calibration.Calibration Methods 22 4. In XRF this is called an empirical calibration. One of the biggest advantages of the theoretical methods is that they don’t need standards to calibrate the inter-elemental effects.Chapter 4 .

draft norm ASTM WK 7530/EI polarization EDXRF 5.23 Chapter 5 .1. ASTM 4294-90.1 Used oil Application: Sample Prep: Precision: LOD: Quantification: check of wear metals Homogenize the used oil.5 ppm Fundamental parameters with automatic matrix correction (e. ASTM D6552-97.TURBOQUANT) 5. EN ISO 20847. powders and liquids in sample cups 10-20 % >0. empirical ASTM D6481-99 5 5.3 Fuels Application: Sample Prep: Precision: LOD: Quantification: Test methods: Check of S Pouring liquid into sample cup 1-3 % ~1 ppm Fundamental Parameters.Application Guide Application Guide Additives in Oil/Lubricants Application: Sample Prep: Precision: LOD: Quantification: Test method: Check of the elements Na-Zn in oil Pouring liquid into sample cup 1-3 % >100 ppm Fundamental Parameters.g.1.5 SPECTRO Analytical Instruments .1.4 Waste Application: Sample Prep: Precision: LOD: Quantification: Test methods: Screening of all elements between Na and U Pellets..g.1. IP 496. empirical 5.. pour it into a sample cup 10-20 % ~ 1-10 mg/kg Fundamental Parameters.2 Wear Metals/Cooling Liquids Application: Sample Prep: Precision: LOD: Quantification: Check of additive elements Na-Zn and wear metals in oil/emulsions Pouring liquid into sample cup 10 % >1 ppm Fundamental parameters with automatic matrix correction (e. draft norm CEN TC 292 WG3 5.TURBOQUANT) ASTM D5839-96.1. empirical ASTM 6445-99.

8 Minerals/Geology/Ceramics Application: Sample Prep: Precision: LOD: Quantification: Test methods: Application: Sample Prep: Precision: LOD: Quantification: Check of main components Fused beads 0.1.6 RoHS. direct. powder.g.9 Cement Application: Sample Prep: Precision: LOD: Quantification: Test methods: Check of main components Fused beads or pressed pellets 0..Application Guide 5.1. Pb.1. empirical IEC draft norm 24 5. PBDE.2 % >100 ppm Fundamental parameters or alpha coefficients DIN 51001 Check of trace elements Pellets 1-10 % >0. powder.2 % >100 ppm empirical ASTM C114.2 ppm Fundamental parameters or empirical method 5.Chapter 5 . XRF only determine the overall content of Cr and Br direct. granulates Fundamental parameters with automatic matrix correction (e. powder..TURBOQUANT). ISO DIS 680 XRF Fundamentals . granulates ~ 5 mg/kg Fundamental parameters with automatic matrix correction (e.1. PBB. Cd.TURBOQUANT). direct. ELV Application: Sample Prep: LOD: Quantification: Test methods: Analysis of Cr(VI). Hg.g. empirical Application: Sample Prep: Quantification: Analysis of additive elements pressed pellets. empirical 5.7 Polymers Application: Sample Prep: LOD: Quantification: Analysis of flame retardant elements containg Br and Sb pressed pellets.TURBOQUANT).g. WEEE. granulates ~ 5 mg/kg Fundamental parameters with automatic matrix correction (e..

standards must represent the same grain size effects as the samples do.1.. powder in a sample cup 1-10 % >0.1.g.15 SPECTRO Analytical Instruments . Therefore.01 % Fundamental parameters 5.g.1.10 Precious metals Application: Sample Prep: Precision: LOD: Quantification: Quantification of alloying elements Polishing surface ~ 0.25 Metals Application: Sample Prep: Precision: LOD: Quantification: Screening of metals Polishing surface 10-20 % >100 ppm Fundamental parameters with automatic matrix correction (e. 5. pressed pellets or powders in cups empirical DIN 51001 5.14 Pharmaceutical Application: Sample Prep: Precision: LOD: Quantification: Check of trace elements Pellets.13 Ferroalloys Application: Sample Prep: Precision: LOD: Quantification: Remark: Check of main components Pellets 1-3 % >100 ppm Empiric calibration Ferroalloys show big particle size effects.11 Iron ore and Sinter Application: Sample Prep: Precision: Quantification: Check of main components Fused beads 1-3 % empirical 5.TURBOQUANT) 5.1 % >0..12 Slag Application: Sample Prep: Quantification: Test methods: Check of main components Fused beads.1.2 ppm Fundamental parameters with automatic matrix correction (e. No international standards can be used for calibration.1.1.TURBOQUANT for pharmaceuticals) 5.

powders in sample cups 1-5 % >0. P Cl. K.Application Guide 5. Zn in milk powder .16 Food Application: Sample Prep: Precision: LOD: Quantification: Na. Mg. Fe.Chapter 5 .5 ppm Fundamental parameters or empirical methods 26 XRF Fundamentals .1. Pellets. Ca.

C. 20. Anal. Anal. Jr. german. M. X-Ray Spectrom. 6. M. Schindler.. german. Adv.1. 6 6. 6. A Simple Method for Background and Matrix .V.1. Nucl.1. (5) T. Swoboda. (4) R.M. Heckel. A Mathematical Method for the Investigation of Interelement Effects in X-Ray Fluorescence Analysis. 149 (1961). 297 (1974).3 Methods for Quantification (12)H. Andermann and J. B. Lucas-Tooth. Vieweg Braunschweig-Wiesbaden (1984). Brumme. Trace Microprobe Tech. 13(2) (1995) 97. J. (7) J.E. Kemp. (13)J. Atom. Irmer. Reynolds. Dzubay. 1133 (1963).J. (6) E. Metallurgia 64. Scattered X-Rays as Internal Standard in X-Ray Emission Spectroscopy.2 Matrix Correction (9) G. (11)C. Methods 115. Kanngiesser.P Willis. A Theoretical Derivation of the Composition of Mixable Specimens from Fluorescent X-Ray Intensities. Using Barkla polarized X-ray radiation in energy dispersive X-Ray fluorescence analysis (EDXRF). K. Haschke. 20.W. Chem. Instrum. J. 6. A.4 SPECTRO Analytical Instruments . 5. Heckel. Multi-Element Trace Analysis of Rocks and Soils by EDXRF Using Polarized Radiation. Sherman. Gerhard-Mercator-Universität Duisburg (1995). R. (10)R.1. 41 (1976). Beckhoff. Heckel. 30. 287-292 (1991). Jaklevic. Mineral. X-Ray Anal. Price. 331 (1991). B. Brumme.J. Correction of Spectral Peaks in Trace Element Determination by X-Ray Fluorescence Spectrometry. 281 (1992). X-RaySpectrom. Comparison of Highly Oriented Pyrolytic and ordinary Graphite as Polarizers of Mo Ka Radition in EDXRF. Spectrom.27 Chapter 6 . J. Scheer and W.G. Taggart. 7. X-Ray Anal. Schramm. Weinert. 17 (1985). 28. 1 (1958) 231.1 6. 1306 (1958). (3) B. Diplomathesis. 48.. M. B.1 Polarization (2) J. Untersuchungen zur Optimierung der Energiedispersiven Röntgenfluoreszenzanalyse als Methode der Instrumentellen Analytik. J. Matrix Corrections In Trace Element Analysis by X-Ray Fluorescence: Estimation of the Mass Absorption Coefficient by Compton Scattering. (8) J. Principles and Applications of Energydispersive X-ray Fluorescence Analysis With Polarized Radiation. Am. X-Ray Spectrom. Feather and J.J. Jarrett. Röntgenfluoreszenzanalyse.Appendix Appendix Literature Basics (1) P Hahn-Weinheimer. Grundlagen und praktische Anwendung der . Adv.

J. Atomic Form Factors. Heckel. Data Tables 27. This can be used for matrix correction (e.A. The Mo radiation from the Mo secondary target used for excitation is scattered at the sample. No. (18)K. Main reason why fluorine cannot be measured in sample cups. R. J. Fujikawa. J.02 µm. 431 (1969). The fluorescence radiation (here Zn) is absorbed until it leaves the sample by the matrix. IV France 8.H. to water) also the absorption of x-rays will change. Cosmochim Acta 33.1. In this example. Fast Analysis of Traces and Major Elements with ED(P)XRF Using Polarized X-Rays: TURBOQUANT. 12.K. James. Norrish and J. the matrix is an organic solvent. Ref. Brown. May . J. Briggs.5 Tables (14)J. R. If the matrix changes (e. Vol. This is not achievable! Figure 2: Measurement of fluorine. Veigele. W. Also the scattering shows a matrix dependence. 4. in TURBOQUANT).Appendix 6. An accurate X-ray spectrographic method for the analysis of a wide range of geological samples. Spectra Analyse 196. E.T. Henke. Data. A. Data Nucl.J. and Photon Scattering Cross Sections. Cromer. Hubbell. Phys. Hutton. XRF Fundamentals . Heckel.g. T. Shimabukuro and B. Incoherent Scattering Functions. J. 25 (1997). 3 (1975). Chem. Journal of Analytical Atomic Spectrometry.2 Figures Figure 1: Penetration depth of x-rays for light elements. To get reproducible results. . (19)R. Schramm.. Comparison of peak to background ratios of different types of Si(Li) detectors used in EDXRF. Figure 4: Each solvent shows a different absorption of x-rays. R. 28 6.June (1997).L. 335-342 (1998). (15)P Russell. you need a grain size of 0. Phys. T.. Figure 7: Cartesian geometry for polarization of exciting x-rays. Figure 3: Exciting x-rays are absorbed by the matrix until they reach the element to excite.L. Tanaka. . Schramm. Contrôle d’entrée de rejets organiques et d’hydrocarbures halogénés par EDXRF. J. Geochim.g.1.Chapter 6 . Howerton. R.6 Applications (17)R. 1 (1982). (16)B. At. 6. D. Figure 5: Figure 6: Comparison of resolution of different types of detectors used in EDXRF. P Lee. Absorbance of fluorine intensity by films covering the bottom of a sample cup.

12 and 13: With friendly permission by Fluxana. Manual press up to 15 tons. Figure 17: 1 2 Calibration of Pb in pellets. Table 5: Reproducibility of an ICP multi-element standard prepared 3 times with charcoal (3 g sample + 1 g charcoal). Table 6: Results using TURBOQUANT for a ‘light’ matrix: reference material NIST-1577b (bovine liver) prepared as pellet. SPECTRO Analytical Instruments . 200 s. Example for different types of dies. Fusion Machine (2 burners. 11. Targets and corresponding elements in TURBOQUANT. Results of a polyphased sample. 59 standards. Figure 102: Figure 111: Figure 121: Figure 131: Figure 14: Figure 15: Figure 16: Calibration of halogens in liquids by TURBOQUANT. prepared as loose powder. Influence of different matrices to the intensity of chlorine Kα-line.29 Figure 8: Figure 9 : 1 Comparison of spectra of certified reference material (BCR-186) with direct excitation (1) and polarized radiation (2).5 mm.9999. 10 kV. Mill with a Al2O3 grinding vessel for grinding of up to 60 g. Accessories & Application Support for X-Ray Fluorescence Analysis Figure 10: With friendly permission by Breitländer 6. total measurement time 600 s. total measurement time 150 s. Table 7: Results using TURBOQUANT for the analysis of Br in polystyrene. Figure 9. Measurement time 200 s. total measurement time 150 s. RMS = 0. particle size 0. also available with 4 burners). Excitation of K and L lines with different targets. R=0.006 %.3 Tables Table 1: Table 2: Table 3: Table 4: Overview of elements detectable with XRF. 3 g sample + 1 g charcoal as absorbing material. Mill with a Zr02 grinding vessel for grinding of up to 10 g. Measurement was done by an HOPG-target. Results of TURBOQUANT liquid for Cl in different solvents.

BS 84h. Total measurement time is 150 s. total measurement time 150 s.Chapter 6 . 316. Table 9: Comparison of results by TURBOQUANT of BCR-176 (ash) prepared as loose powder or pellet. XRF Fundamentals .Appendix 30 Table 8: Results using TURBOQUANT for an alloy: stainless steel.