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Instituto de Cerámica y Vidrio, CSIC Francisco Muñoz, Nicolas Hémono, Araceli de Pablos,

Work Package 7. NMR Structural characterisation of the nano-crystallised glass-ceramics. Instituto de Cerámica y Vidrio, CSIC Francisco Muñoz, Nicolas Hémono, Araceli de Pablos, Mª Jesús Pascual, Alicia Durán. Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008.

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Instituto de Cerámica y Vidrio, CSIC Francisco Muñoz, Nicolas Hémono, Araceli de Pablos,

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  1. Work Package 7 NMR Structural characterisation of the nano-crystallised glass-ceramics Instituto de Cerámica y Vidrio, CSIC Francisco Muñoz, Nicolas Hémono, Araceli de Pablos, Mª Jesús Pascual, Alicia Durán Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  2. Outline  Nuclear Magnetic Resonance Facilities Materials Science Institute of Madrid, CSIC J. Sanz and I. Sobrados NMR and Glasses groups at the University of Lille, France L. Montagne and L. Delevoye • NMR experiments have been performed on: LAS glass-ceramics (OSI, Jena) (Pb,Cd)F2 system (OSI,Jena) BaF2 system (OSI, Jena) LaF3 system (ICV-CSIC, Madrid) • Further work Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  3. Work Package 7 Crystallisation of Li-Al-Si-O phases in (Li,Na,K)2O-(Mg,Ba,Zn)O-(Ti,Zr)O2-Al2O3-SiO2 OSI Jena Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  4. LAS system possibly 2 different Si sites glass-ceramic samples From 29Si: Q3 SiO4 tetrahedra (and Q2 + Q4) 29Si (I=1/2) f=79.49 MHz 7 mm probe /2 = 5 s 800 scans 5 kHz Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  5. LAS system 1 broad resonance band: 60 to 0 ppm Al (V) or Al (IV) distorted tetrahedra Contribution of different Al species ? 27Al (I=5/2) f=104.27 MHz 4 mm probe /2 = 3 s 400 scans 10 kHz Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  6. LAS system >  Li+ in the crystalline phase might be in a more covalent environment 6Li (I=1/2) f=379 MHz 7 mm probe 10 kHz XRD Rietveld + Neutron diffraction Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  7. Work Package 7 (Pb,Cd)2-containing glass-ceramics OSI Jena Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  8. (Pb,Cd)F2 system -125 ppm -122 ppm 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Paramagnetic effect of RE elements !! GC 8B4357 Glass 8B Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  9. Work Package 7 BaF2-containing glass-ceramics (1-x)(2Na2O.16K2O.8Al2O3.74SiO2).xBaF2 OSI Jena Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  10. BaF2-system  (19F) = - 15 ( 1) ppm • 19F in base glass: Al-F-Ba(2+1) ref.: BaAlF5 (-125 ppm) F-background * * * * * * * * * * * *  (19F) = - 125 ppm * * * * * * * * • 19F in glass-ceramics: -15 ppm F-Ba(4) ref.: BaF2 * * * * (*) spinning side bands 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  11. BaF2-system  19F in B6-500-20h glass-ceramic: 2 components • 19F in glass-ceramics: -15 ppm F-Ba(4) ref.: BaF2 -19 ppm F-Ba(n) ref.: Ba3Al2F12; Ba3AlF9 dmfit software -15 ppm -18 ppm * * * *  19F chem. shift in base glass: 1 component Al-F-Ba(2+1) species Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  12. BaF2-system Al-F-Ba BaF2 Al-F-Na 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Kinetics at 500 ºC Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  13. BaF2-system Al-F-Ba BaF2 Al-F-Na Al-F-Ba 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Kinetics at 500 ºC Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  14. BaF2-system  (29Si) = 97  1 ppm • 29Si indicates glass network formed by Q3 (+Q2+Q4) tetrahedra 29Si (I=1/2) f=79.49 MHz 7 mm probe /2 = 5 s 400 scans 5 kHz There is no measurable change in 29Si chem. shift with treatment T for 20 h Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  15. BaF2-system Al (IV) 60 ppm Al (V) 20 ppm Al (VI) 0 ppm No change in Al (IV) chem. shift However, Al (V) and Al (VI) decrease with increasing Tc F may move from Al (V,VI)-F-Ba to Ba-F bonds Al (IV) Al (V) Al (VI) 27Al (I=5/2) f=104.27 MHz 4 mm probe /2 = 3 s 400 scans 10 kHz Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  16. BaF2-system 23Na chem. shift is not affected by crystallisation 23Na (I=3/2) f=105.84 MHz 4 mm probe 600ºC - 20 h 580ºC - 20 h 540ºC - 20 h 520ºC - 20 h 500ºC - 20 h B6 base glass Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  17. BaF2-system Conclusions: • F is involved in the Al coordination polyhedra, likely in Al (V,VI)-F-Ba • 19F NMR clearly indicates formation of Ba-F bonds • Two different F species might be present in BaF2 glass-ceramics • 29Si NMR does not show quantitative influence from fluorine crystallisation • Al (V,VI) polyhedra disappear from the network when BaF2 crystallises Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  18. LaF3-system LaF3-containing glass-ceramics Na2-K2O-Al2O3-SiO2-LaF3 ICV-CSIC Madrid Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  19. LaF3-system Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  20. LaF3-system -19.3 ppm LaF3 -185.5 ppm Al-F-Na -15.3 ppm LaF3 -185.5 ppm Al-F-Na -187.6 ppm Al-F-Na 40SiO2.30Al2O3 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Remaining F in glass matrix Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  21. LaF3-system -17.2 ppm LaF3 -187.2 ppm Al-F-Na -3.06 ppm LaF3 -188.3 ppm Al-F-Na -189.5 ppm Al-F-Na 55SiO2.20Al2O3 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Remaining F in glass matrix Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  22. LaF3-system -12.6 ppm NaLaF4 -128 ppm Si-F-K, Al-F-K ?? -189.5 ppm Al-F-Na -12.6 ppm NaLaF4 -129 ppm Si-F-K, Al-F-K ?? -189.3 ppm Al-F-Na -187.7 ppm Al-F-Na -125 ppm Si-F-K, Al-F-K ?? 70SiO2.7Al2O3 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz Remaining F in glass matrix Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  23. LaF3-system 23Na (I=3/2) f=105.84 MHz 4 mm probe 10 KHz 40SiO2.30Al2O3 55SiO2.20Al2O3 Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  24. LaF3-system Glass matrix Czjzek distribution 23Na NaLaF4 Quadrupolar 2nd order 3 % 23Na crystals  1.24 wt.% NaLaF4 23Na (I=3/2) f=105.84 MHz 4 mm probe 10 KHz 70SiO2.7Al2O3 Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  25. LaF3-system 27Al (I=5/2) f=104.27 MHz 4 mm probe /2 = 3 s 400 scans 10 kHz 40SiO2.30Al2O3 AlO4, AlO5, AlO6 Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  26. LaF3-system 27Al (I=5/2) f=104.27 MHz 4 mm probe /2 = 3 s 400 scans 10 kHz 55SiO2.20Al2O3 AlO4, AlO5, AlO6 Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  27. LaF3-system 27Al (I=5/2) f=104.27 MHz 4 mm probe /2 = 3 s 400 scans 10 kHz 70SiO2.7Al2O3 AlO4 tetrahedra only AlO5? Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  28. Comparative study Comparison between systems: Determining crystallisation from structural considerations and its relationship with composition Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  29. Comparative study 19F(I=1/2) f= 376.49 MHz 4 mm probe /2 = 1 s 400 scans 10 kHz ~ -190 ppm Al-F-Na 70Si: ? Al-F-K, Si-F-K ? Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  30. Comparative study 23Na (I=3/2) f=105.84 MHz 4 mm probe 10 kHz 23Na resonance in 70 SiO2 (and B6 glass) shifted to lower field. Increased c.s. distribution < CN (Na), stronger Na-O bonds 23Na resonance in 55 SiO2 shifted to higher field compared to 40 SiO2 > CN (Na), weaker Na-O bonds Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  31. Comparative study Al(IV) 27Al (I=5/2) f=104.27 MHz 4 mm probe /2 = 3 s 400 scans 10 kHz B6 glass : AlO4, AlO5 AlO6 40 – 55 SiO2 : AlO4, AlO5 AlO6 70 SiO2 : AlO4 predominantly Al(V) Al(VI) Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  32. Comparative study Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  33. Comparative study Current experiments NMR center University of Lille (L. Montagne) NMR ICMM-CSIC Madrid Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  34. Current experiments 70Si-7La 70SiO2.7Al2O3.8Na2O.8K2O.7LaF3 • 19F NMR : crystals vs residual glass • 23Na MQMAS: • separate crystals vs residual glass • Determine fraction of crystals (quantify 23Na, weighted samples) • 123La: crystals vs residual glass? • 27Al: check for Al (VI,V, IV) (broad resonance), CP Al-F if broad resonance is observed from 0 to 60 ppm that would indicate multiple coordination. Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  35. Current experiments B6 glass 2Na2O.16K2O.8Al2O3.64SiO2.6BaF2 • 27Al ( IV, V, VI) in base glass: CP Al-F to confirm F connection to Al (VI or V) • 19F: asymmetric resonance in the GC: check for Ba-F (-15 ppm) and Al-F-Ba (-18 ppm): CP Al-F (significant only if all F is in crystals, no F in residual glass), TRAPDOR Al-F ? Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  36. Current experiments (Cd,Pb)F2 glass 6Al2O3.13.5B2O3.20SiO2.20PbF2.13.3CdF2.10YbF3.0.5ErF3.10PbO.6.6CdO • 207Pb: PbF2 crystals (quantification on weighed samples, but paramagnetism may influence!!) • 113Cd: (Cd,Pb)F2 crystals ? • 19F: strong spinning sidebands: 25 kHz MAS increases resolution? Paramagnetic effect of Yb, Er? Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

  37. Comparative study B6 glass : very little Na2O and BaO  BaF2 higher I.F.S. of Ba2+ 40Si, 55Si : high Na2O and Al2O3 LaF3 Na+ as modifier and charge compensator 70Si : medium Na2O and low Al2O3  NaLaF4 Na+ as modifier ions Mid-term INTERCONY meeting: report on work and results WP7, Mainz, May 2008

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