1. Claylab Applied Geology & Mineralogy X-ray diffraction A tool for material characterization and mineral quantification 1 Rieko Adriaens rieko.adriaens@ees.kuleuven.be 23/01/2013

2. X-ray diffraction on mineral powders Divergence slit Detector- slit Tube Antiscatter- slit Sample Mono- chromator

3. Diffraction pattern Tube measurement circle focusing- circle θ θ 2 Detector Sample

4. Unique fingerprint for anorganic substances 4 a b c a = b = c === 90 o

5. crystalline Amorphous

6. Errors in XRD – analysis: Vendor competition Sample preparation Measurement Identification Quantification 6

7. Sample preparation: Classical approach Manual grinding using mortar & pestle Back/top loading of holder applying pressure 7

8. Classical approach: disadvantages Presence of coarse particles and bad loading cause several negative effects: – Extreme preferred orientation – Pattern shifts – Very poor reproducibility  Complex identification & wrong quantification 8

9. XRD pattern: Ideal case Classical approach: disadvantages – Preferred orientation & pattern shifts 9

10. Classical approach: disadvantages – Preferred orientation: Cleavage planes & prominent crystal faces 10 Halite Gypsum Mica Quartz

11. Classical approach: disadvantages – Preferred orientation & pattern shifts – Very poor reproducibility !!! 11

12. Bulk XRD – analysis Disadvantages impede accurate Q-XRD  Neccessity of standardized preparation procedures We need a procedure which makes sure that: -Particles should be finer than <50µm -Wet grinding instead of dry grinding -Particles are randomly oriented in the measurement holder -Sample surface should be smooth and perfectly flat -Reproducible & representative measurements 12

13. Standardized procedure after Srodon, 2001 Powder mixed with internal standard (ZnO, Al2O3, TiO2 ) Grinding media (Al2O3, Yttria stabilized Zr) Grinding agent: methanol/ ethanol McCrone micronizing mill (5min.) Side load filling / no pressure top load 13

14. Standardized procedure after Srodon, 2001  Good random orientation of crystallites obtained BUT can be improved by the making of spherical granules: use of Vertrel XF treatment, spray drying equipment, elvacite treatment,… 14 Kaolinite Portland cement

15. Standardized procedure: Validation 15 Classic methodology Renewed methodology

16. Standardized procedure: Validation 16 Much less preferred orientation Classic methodology Renewed methodology

17. Standardized procedure after Srodon, 2001  Allows accurate Q-XRD analysis 17

18. Other possibilities 18

19. [The Rietveld Method] Most powerful method for combined quantification and structure analysis Relies on the refinement of basic theoretical structures Minimize difference between calculated XRD pattern and measured XRD pattern

20. Rietveld refinement: procedure 1.Measure the diffraction pattern of the sample 3.Compare both patterns 4.Refine parameters and recalculate pattern 5.Draw info from the refined data (crystallite sizes / quantitative phase information / …) 2.Introduce reasonable starting models / values to calculate a diffraction pattern

21. What can be evaluated with a Rietveld refinement ? Example: Cement Fully amorphous blast furnace slag ZnO as internal standard

22. What can be evaluated with a Rietveld refinement ? 2.Crystallite Sizes / Strain – Absolute Crystallite sizes Useful for: – Process optimisation – Product characterisation – Product quality assesment Finer crystallites are prone to react faster (or to react better as catalysts, etc.) – Assessment of crystallite shape (in case of anisotropic peak size broadening) <10nm crystallites

23. What can be evaluated with a Rietveld refinement ? 3.Solid Solution – Example: Fe-rich Dolomite (CaMg(CO3)2) – Ankerite (CaFe(CO3)2) Change in lattice parameters as a function of the Fe-content With a Rietveld refinement; Lattice parameters and hence Fe-contents can be accurately determined Example: Fe-rich Dolomite/Ankerite in Sedimentary rock: Exact average formula: Ca(Fe 0,46 Mg 0,54 )(CO 3 ) 2 Fe-Dolomite

24. Practical information 24

25. Practical information 25 1st floor Ground floor XRD rooms Software computers

26. Practical information 26 Reservations https://ees.kuleuven.be/reservations/xrd/calendar/index.html https://ees.kuleuven.be/reservations/xrd/calendar/index.html

27. Practical information 27 Measurements overview list

28. Practical information 28 Technical support: Dirk Steeno dirk.steeno@ees.kuleuven.be 200C – 00.89 General support: Rieko Adriaens rieko.adriaens@ees.kuleuven.be 200E – 03.217 Responsible professor: Jan Elsen jan.elsen@ees.kuleuven.be 200E – 02.207

29. Questions / more information Contact rieko.adriaens@ees.kuleuven.be 29