Powder University of Malaga.

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1 Powder University of Malaga Miguel A. G. Aranda, Laura León-Reina, Ángeles G. De la Torre, José M. Compaña Departamento de Química Inorgánica, Universidad de Málaga, Spain g_aranda@uma.es

2 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

3 # 1 Identification of crystalline compounds: Gemology Top-left. CuK 1 LXRPD pattern for a rock crystal gemstone (quartz) with rutile inclusions. Bottom-left. MoK 1,2 LXRPD pattern of the same gemstone (highly penetrating radiation). Bottom-right. Optical microphotography highlighting the rutile fibre inclusions. 1/20

4 # 1 Identification of crystalline compounds: Gemology Top-left. Photography of a glass showing aventurine effect. Top-right. Optical microphotography of the same gem showing the copper microcrystals. Bottom. MoK 1,2 LXRPD pattern of the same gem (highly penetrating radiation) highlighting the hump due to the glass and the three narrow peaks from the copper microcrystals. 2/20

5 # 2 Identification of crystalline compounds: Archaeometry 1 cm 1 cm a b a b 1 cm c 1 cm d Left. Photographs of four selected Terra Sigillata potsherds [codes (a) GTS001, (b) HTS004, (c) HTS006 and (d) HTS009]. Right. SEM images of the slips for (a) GTS001, (b) HTS004. (c) HTS006 and (d) HTS009. c d 3/20

6 # 2 Identification of crystalline compounds: Archaeometry Qtz Qtz Pl Dp, Pl Qtz Kfs Mca Mca Qtz Qtz Kfs Qtz Intensity (cps) Qtz Qtz Qtz Pl Pl Gp Pl Gp Zeo Pl Qtz Pl Pl Dp Dp Pl Qtz Pl Dp Qtz Kfs Kfs Qtz Pl 2 (º) GI-XRPD laboratory patterns for the slips from top to bottom, GTS001, HTS004, HTS006 and HTS009, with the peaks from the main crystalline phases labelled. 4/20

7 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

8 # 1 Determination of the unit cell parameters: Inorganic pigments & REACH legislation De la Torre, A.G.; León-Reina, L.; Perez, J.; Aranda, M.A.G. Ceramic pigments and the European REACH legislation: black Fe 2 O 3 Cr 2 O 3 a case study International Journal of Applied Ceramic Technology, 2010, on-line doi: /j x Left. Rietveld plot for BLACK-1, (Cr x Fe 1-x ) 2 O 3 x=0.34, ceramic pigment (CuK 1 ). Right. Evolution of the lattice parameters for (Cr x Fe 1-x ) 2 O 3 series (squares and full line from bibliography). The results from our study are superimposed in the previous plot indicating: a single crystalline phase with negligible amorphous phase content! 5/20

9 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

10 Determination of the microstructure of the phase Sources of peak broadening Instrumental Broadening Microstructural features Finite Crystallite Size FWHM α cos -1 θ size < 0.2 μm (if isotropic) 2 θ (º) Lattice Strain (microstrain) A antiphase domain B interstitial atom G, K grain boundary L vacancy S substitutional impurity/doping S interstitial impurity P, Z stacking faults dislocations Extended Defects FWHM α tan θ (if isotropic) fluctuations in cell parameters Anisotropic broadening Antiphase Boundaries, Stacking Faults 6/20

11 7/20 #1 Determination of the microstructure of a given phase: Catalysts CeO 2 standard; a= (6) Å; GSAS, S/L=H/L=0.012; GU=1.95(-); GW= 2.31(2); LX=0.90(2); LY=2.56(4); Rwp=4.55% Parameter Value Error A E-5 B E E R SD N P E-5 14 < CeO 2 nano; a= (9) Å; GSAS, S/L=H/L=0.012; GU=1.95(-); GW= 2.73(-); LX=24.90(3); LY=32.63(6); Rwp=5.9% ( nano - std ) cos D V = 269 Å ó 27(1) nm str = 0.037(2)% sen Williamson Hall method

12 # 2 Determination of the microstructure of a given phase: nanosciences Nano-Y 2 O 3 : 12 nm by E.M. 8/20

13 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

14 # 1 XRPD can be coupled to temperature (heating): Oxygen ion conductors Left: HT-XRPD patterns for La (Ge 6 O 24 )O 2.62 showing a triclinic-to-hexagonal phase transition. Right: Variation of the unit cell volume (a) 636 (b) V/Å T/K /º T/K 9/20

15 I (a.u) I (a.u) I (a.u) (a) (202) (004) 100 K 130 K 160 K 190 K 220 K 250 K 280 K RT Theta (º) La 2 * Sm 0.31 =40 Ca 0.18 Sr 0.20 MnO 3 N A =4 (b) (202) (004) 100 K 130 K 160 K 190 K 220 K 250 K 280 K RT Theta (º) La Pr 5/8 Ca 3/8 MnO Pr 0.35 Ca 3/8 MnO 3 r A =1.191 Å, 3 Phase Segregation σ 2 = Å 2 (c) La 0.26 Nd 2 * =25 Ca 0.23 Sr 0.15 MnO 3 r N A =4 A =1.205 Å σ 2 = Å 2 r A =1.204 Å σ 2 = Å 2 (202) (004) 140 K 170 K 190 K 210 K 230 K 250 K RT Theta (º) # 2 XRPD can be coupled to temperature (cooling): manganites magneto-resistant Selected region of the low-temperature laboratory X-ray powder thermodiffractometries for three Ln 5/8 M 3/8 MnO 3 compositions: (a) La 0.26 Nd 0.37 Ca 0.23 Sr 0.15 MnO 3 (b) La 0.32 Sm 0.31 Ca 0.18 Sr 0.2 MnO 3 (c) La 0.28 Pr 0.35 Ca 3/8 MnO 3 LT-XRPD patterns for (a) and (b) just show thermal contraction (on cooling); but for (c) show phase separation. 10/20

16 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

17 # 1 Quantitative phase analysis (sample purity): Magnetic water treatment 11/20

18 # 2 Quantitative phase analysis (high resolution needed): Cements emitting less CO 2 Aftitalite - C2 S - C2 S C4 AF C C3 S C3A C4AF - C2 S - C2 S C3 A C4 AF C4 AF I (a.u.) I (a.u.) I (a.u.) C3 S I (a.u.) I (a.u.) I (a.u.) C3 C C C3 S S C3 S C3 C S C3 S C3 C S C3 C S C4 AF C3 S C3 S - C2 S - C2 S - C2 S C3A C4AF - C2S - C2 S - C2 S C3 S C3 A - C2 S C3 S - C2 S - C2 S - C2S C3A C4 AF C3 S - C2 C S - C2 S C3 C S - C2 C S C C3 A C 4 AF - C2 S C4 AF -C2S - C2 S - C2S - C2S C3 S - C2 S CuK 1,2 radiation CuK 1 radiation Top. LXRPD patterns for an activated Belite cement (more reactive). Intermediate. LXRPD patterns for a non-activated Belite cement. Bottom. LXRPD patterns for an Ordinary Portland Cement. 12/20

19 K2 SO 4 C2S C2S C4AF C4AF C4AF C4AF C3A C4 AF C4 AF C3 S Clinker F6 Provided sample D5000 data Clinker F6 Aluminates fraction C3 S C2S C2S Salicylic C3 A C3 S C3 S C4 AF C3A # 3 Quantitative phase analysis: Ordinary Portland Cements Grey Portland clinker Main phases C 3 S C 2 S, C 4 AF C 3 A Selective dissolution Aluminate rich fraction Selective dissolution Silicate rich fraction Clinker F6 Silicates fraction 13/20

20 # 4 Quantitative phase analysis: Methodological study for better cement analyses # 3 commercial samples were also studied: (i) white Portland clinker, (ii) grey Portland clinker (iii) a type-i grey Portland cement 14/20

21 # 4 Quantitative phase analysis: Methodology study for better analysis of cements Just a brief summary for artificial mixture #2 15/20

22 # 5 Quantitative phase analysis: Alternative fuel study in Portland cement fabrication C 3 S Phase CEM-1 CEM-2 Ca 3 SiO 5 (C 3 S) 62.4 ± ± 0.5 Ca 2 SiO 4 (C 2 S) 8.5 ± ± 0.5 C 3 S C 3 S Ca 3 Al 2 O 6 (C 3 A) 5.3 ± ± 0.2 Ca 2 AlFeO 5 (C 4 AF) 5.7 ± ± 0.3 basanita C 3 S CaSO 4 1/2H 2 O (basanite) 3.8 ± ± 0.2 CaSO 4 (anhidrite) 1.3 ± ± 0.2 SiO 2 (quartz) 0.8 ± ± 0.1* C 3 S C 2 S ZnO C 3 A C 4 AF ZnO C 3 S calcita CaCO 3 (calcite) 10.8 ± ± 0.2 CaMg(CO 3 ) 2 (dolomite) 0.3 ± 0.2* 1.0 ± 0.2 ZnO (zincite) 1.1 ± /20

23 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

24 # 1 Reactivity: Laboratory X-ray Powder data collection in-situ hydration Goniometer circle X-Rays tube Mirror Sample Divergent incident beam Convergent beam Focus Transmission Much better particle statistics Convert the divergent X-ray beam from a tube in line focus position to an intense beam that focuses onto the goniometer circle. 17/20

25 # 1 Reactivity: Laboratory X-ray Powder data collection in-situ hydration -C 2 S 4^200 4^000 3^800 3^600 3^400 3^200 3^000 2^800 2^600 2^400 2^200 2^000 1^800 1^600 1^400 1^200 1^ Counts Time Wt (%) Gypsum C 4 A 3 S C 2 AS CA Free Water C-A-H-H Position [ 2Theta] (Copper (Cu)) Ettringuite t (h) 18/20

26 Outline: powder UMA 1. Phase identification 2. Unit cell parameters evolution 3. Microstructure 4. Thermodiffractometry phase transition 5. Quantitative phase analysis 6. Reactivity 7. Conclusions

27 Conclusions Powder diffraction is a versatile technique that may give interesting answers. However, the utility of these results will depend on the problem and very importantly, on the experimental setting used. Several optical configurations are highly desirable if the laboratory is managed by well-skilled/trained scientist(s). 19/20

28 Acknowledgements Thanks to MICINN and J. A. for funding Thanks to all collaborators from UMA and other research institutions ESRF is thanked for providing X-ray synchrotron beamtime Finally, to all of you for your attention!! 20/20