Presentation is loading. Please wait.

Presentation is loading. Please wait.

1 T. CharpentierActinet Workshop, September 23th, 2005 A Solid State NMR Study of a Mixed Alkali Aluminoborosilicate Glass Structure and its Evolution.

Published byJasper Daniel Modified over 9 years ago

Similar presentations

Presentation on theme: "1 T. CharpentierActinet Workshop, September 23th, 2005 A Solid State NMR Study of a Mixed Alkali Aluminoborosilicate Glass Structure and its Evolution."— Presentation transcript:

1 1 T. CharpentierActinet Workshop, September 23th, 2005 A Solid State NMR Study of a Mixed Alkali Aluminoborosilicate Glass Structure and its Evolution Under  Irradiation T. Charpentier, M. Gaillard, D. Sakellariou, J. Virlet Laboratoire de Structure et Dynamique par Résonance Magnétique Laboratoire Claude Fréjacques, URA 331 CEA / CNRS Service de Chimie Moléculaire CEA Saclay, France. N. Ollier, B. Boizot Laboratoire des Solides Irradiés CEA-CNRS-Ecole Polytechnique, France.

2 2 T. CharpentierActinet Workshop, September 23th, 2005 Overview of the study Understanding the effects of ionizing radiations (here  e-) on structural changes of nuclear waste glasses, in order to predict the modification of the glass during storage. Simulation of the  dose (auto) irradiation accumulated during storage by external electron irradiations: Van de Graaff accelarator,1.8 MeV, 20  A beam, ~ 1GGy dose. Use of simplified borosilicate glasses (mol.%) 63.47 SiO2- 16.8 B2O3 – 4.04 Al2O3 – 2.35 ZrO2 – 13.34 A2O A2O = 1) x Na2O - (1-x) Li2O 2) x Na2O - (1-x) K2O Vitrified waste (CSD-V)

3 3 T. CharpentierActinet Workshop, September 23th, 2005 (Microscopic) Structural changes induced by  irradiations Increase of glass polymerization : Si(Q2)  Si(Q3) Increase of boron in trigonal environments : BO4  BO3 Formation of molecular oxygen Production of paramagnetic defects B. Boizot et al., NIM B 166-167, (2000) 500 N. Ollier et al., JNCS 323, (2003) 200. Most of the structural changes are assigned to the migration of alkali  Segregation of alkali under  irradiation ? These changes are less important in complex glass composition (close to the French Nuclear glass SON68) than simple ones : this could be explained by the decrease of the alkaline ions mobility The Mixed Alkali Effect (decreases considerably the alkali motion ) /  irradiations

4 4 T. CharpentierActinet Workshop, September 23th, 2005 The Mixed Alkali Effect Electrical conductivity (300°C) Tg MAE : significant decrease of the ionic conductivity Can the MAE cause a reduction of alkali migration under irradiation ?

5 5 T. CharpentierActinet Workshop, September 23th, 2005 MAS NMR of Quadrupolar Nuclei +3/2 +1/2 -1/2 -3/2 Central transition

6 6 T. CharpentierActinet Workshop, September 23th, 2005 11B (I=3/2) MAS NMR

7 7 T. CharpentierActinet Workshop, September 23th, 2005 11B MAS / MQMAS NMR MAS (1d) MQMAS (2d)

8 8 T. CharpentierActinet Workshop, September 23th, 2005 11B MQMAS NMR BO3 2 sites BO4 2 sites

9 9 T. CharpentierActinet Workshop, September 23th, 2005 11B MAS NMR

10 10 T. CharpentierActinet Workshop, September 23th, 2005 11B MAS NMR : Mixed Alkali Effect

11 11 T. CharpentierActinet Workshop, September 23th, 2005 11B MAS NMR : Mixed Alkali Effect Non-linear variation of the BO 3 /BO 4 ratio Na/Li : BO 3 /BO 4 minimum Na/K : BO 3 /BO 4 maximum

12 12 T. CharpentierActinet Workshop, September 23th, 2005 11B MAS NMR :  irradiation effects Na/Li BO 4 to BO 3 conversion

13 13 T. CharpentierActinet Workshop, September 23th, 2005 11B MAS NMR :  irradiation effects Na/K BO 4 to BO 4 /BO 3 conversionNo conversion

14 14 T. CharpentierActinet Workshop, September 23th, 2005 27Al MAS NMR

15 15 T. CharpentierActinet Workshop, September 23th, 2005 27Al MAS NMR : Mixed Alkali Effect AlO 4 - : Na + preferential charge compensator ?

16 16 T. CharpentierActinet Workshop, September 23th, 2005 27Al MAS NMR :  irradiation effects Na/K,Na/Li Cq increases (site distortion increase). MAE : minimized effect K,NaNa,Li

17 17 T. CharpentierActinet Workshop, September 23th, 2005 27Al MAS NMR : Mixed Alkali Effect Na/K,Na/Li Analytical model for f(Cq,nq) : Gaussian Isotropic Model (Cjzjek)

18 18 T. CharpentierActinet Workshop, September 23th, 2005 27Al MAS NMR : Mixed Alkali Effect Na/K,Na/Li

19 19 T. CharpentierActinet Workshop, September 23th, 2005 29Si MAS NMR Na,K Li,Na

20 20 T. CharpentierActinet Workshop, September 23th, 2005 29Si RAMAN :  irradiation effects Na/K,Na/Li Na/Li Na/K 50/50 Q2Q2 Q3Q3 Irradiated Pristine MAE: modifier migration blocked Q2Q2 Q3Q3

21 21 T. CharpentierActinet Workshop, September 23th, 2005 29Si MAS NMR / RAMAN Q2Q2 Q3Q3 Na/Li : Stable polymerizationLi : Polymerization increase

22 22 T. CharpentierActinet Workshop, September 23th, 2005 23Na NMR Localisation of the alkali after the migration processes 1)migration to the surface XPS : No 2) bulk segregation Can NMR provides measurements to detect it ? Static (Non-rotating ) sample approach : Relaxation Time Measurment and SEDOR NMR

23 23 T. CharpentierActinet Workshop, September 23th, 2005 23Na NMR : longitudinal relaxation 18090 inversion recovery experiment

24 24 T. CharpentierActinet Workshop, September 23th, 2005 23Na NMR :  irradiation effects Na/Li

25 25 T. CharpentierActinet Workshop, September 23th, 2005 23Na Spin Echo / SEDOR NMR 90 TT E(T) 23Na 7Li E(T) (Hahn Echo): Na-Na dipolar interactions 180 E(T) (SEDOR): Na-Na + Na-Li dipolar interactions 180

26 26 T. CharpentierActinet Workshop, September 23th, 2005 23Na Spin Echo / SEDOR NMR

27 27 T. CharpentierActinet Workshop, September 23th, 2005 23Na Spin Echo/SEDOR NMR :  irradiation effects Na/Li  : decrease of Na-Li dipolar interactions  Na clusterization ?

28 28 T. CharpentierActinet Workshop, September 23th, 2005 Conclusion MAE on the glass network structure Na/K : BO3/BO4 minimum - Na/Li : BO3/BO4 maximum MAE /  irradiation effects Na/K blocks the migration of BO4 compensators Na/Li blocks the migration of modifiers AlO4 – stable : site distortion increase Na preferential charge compensator ? Na clusterization? Ionic Irradiation (Au n+ ) (underway) N.Ollier et al, Journal of Physics : Condensed Matter 16 (2004) 7625. N.Ollier et al, Journal of Non-Crystalline Solids 341, (2004) 26.

29 29 T. CharpentierActinet Workshop, September 23th, 2005 Perpectives NMR of active materials : Auto-irradiation effects Special containment (rotor) system See D. Sakellariou

30 30 T. CharpentierActinet Workshop, September 23th, 2005 Perpectives : Heteronuclear correlation spectrosocopy Static sample NMR can be useful

Download ppt "1 T. CharpentierActinet Workshop, September 23th, 2005 A Solid State NMR Study of a Mixed Alkali Aluminoborosilicate Glass Structure and its Evolution."

Similar presentations

Relaxation Time Phenomenon & Application

Relaxation Time Phenomenon & Application
Elliptic flow of thermal photons in Au+Au collisions at 200GeV QNP2009 Beijing, Sep 21 - 26, 2009 F.M. Liu Central China Normal University, China T. Hirano.

Elliptic flow of thermal photons in Au+Au collisions at 200GeV QNP2009 Beijing, Sep , 2009 F.M. Liu Central China Normal University, China T. Hirano.
Zero-Phonon Line: transition without creation or destruction of phonons Phonon Wing: at T = 0 K, creation of one or more phonons 7. Optical Spectroscopy.

Zero-Phonon Line: transition without creation or destruction of phonons Phonon Wing: at T = 0 K, creation of one or more phonons 7. Optical Spectroscopy.
Molecular Orbitals An approach to bonding in which orbitals encompass the entire molecule, rather than being localized between atoms.

Molecular Orbitals An approach to bonding in which orbitals encompass the entire molecule, rather than being localized between atoms.
Measuring concentration using electrodes Indicator electrodes used with reference electrode to measure potential of unknown solution E cell = E indicator.

Measuring concentration using electrodes Indicator electrodes used with reference electrode to measure potential of unknown solution E cell = E indicator.
Chapter 7 Summary  Here’s what you need to know Trends for and explanations of:  Electron Shells and Sizes of Atoms  Electronegativity  Ionization.

Chapter 7 Summary  Here’s what you need to know Trends for and explanations of:  Electron Shells and Sizes of Atoms  Electronegativity  Ionization.
DIAMOND Decommissioning, Immobilisation and Management of Nuclear Wastes for Disposal Effects of Zinc Addition on the Structure of Sodium Silicate Glass.

DIAMOND Decommissioning, Immobilisation and Management of Nuclear Wastes for Disposal Effects of Zinc Addition on the Structure of Sodium Silicate Glass.
 Single crystals of YBCO: P. Lejay (Grenoble), D. Colson, A. Forget (SPEC)  Electron irradiation Laboratoire des Solides Irradiés (Ecole Polytechnique)

 Single crystals of YBCO: P. Lejay (Grenoble), D. Colson, A. Forget (SPEC)  Electron irradiation Laboratoire des Solides Irradiés (Ecole Polytechnique)
DIAMOND Decommissioning, Immobilisation and Management of Nuclear Wastes for Disposal Density Functional Theory study of defects in zirconolite Jack Mulroue.

DIAMOND Decommissioning, Immobilisation and Management of Nuclear Wastes for Disposal Density Functional Theory study of defects in zirconolite Jack Mulroue.
核磁共振光譜與影像導論 Introduction to NMR Spectroscopy and Imaging Lecture 08 Introduction to Solid State NMR (Spring Term, 2011) Department of Chemistry National.

核磁共振光譜與影像導論 Introduction to NMR Spectroscopy and Imaging Lecture 08 Introduction to Solid State NMR (Spring Term, 2011) Department of Chemistry National.
Institut des NanoSciences de Paris CNRS et Universités de Paris 6 et 7 Isotopes and ion beams in the study of dielectric/semiconductor interfaces. Ian.

Institut des NanoSciences de Paris CNRS et Universités de Paris 6 et 7 Isotopes and ion beams in the study of dielectric/semiconductor interfaces. Ian.
Towards a Clearer Picture of Complex Borosilicates NMR of Borate Model Glasses Scott Kroeker Department of Chemistry, University of Manitoba Solid-State.

Towards a Clearer Picture of Complex Borosilicates NMR of Borate Model Glasses Scott Kroeker Department of Chemistry, University of Manitoba Solid-State.
Physics 440 Condensed Matter Physics a.k.a. Materials Physics Solid-State Physics.

Physics 440 Condensed Matter Physics a.k.a. Materials Physics Solid-State Physics.
1 Lecture 12 The cooperative relaxation of water at the pore surface of silica glasses.

1 Lecture 12 The cooperative relaxation of water at the pore surface of silica glasses.
Rinat Ofer Supervisor: Amit Keren. Outline Motivation. Magnetic resonance for spin 3/2 nuclei. The YBCO compound. Three experimental methods and their.

Rinat Ofer Supervisor: Amit Keren. Outline Motivation. Magnetic resonance for spin 3/2 nuclei. The YBCO compound. Three experimental methods and their.
Dieter Freude, Institut für Experimentelle Physik I der Universität Leipzig METU-Center Workshop on Solid State NMR, 1 November 2007 Solid-state NMR studies.

Dieter Freude, Institut für Experimentelle Physik I der Universität Leipzig METU-Center Workshop on Solid State NMR, 1 November 2007 Solid-state NMR studies.
Extensions of the Stochastic Model of the Overdamped Oscillator Applied to AC Ionic Conductivity in Solids Juan Bisquert Departament de Ciències Experimentals.

Extensions of the Stochastic Model of the Overdamped Oscillator Applied to AC Ionic Conductivity in Solids Juan Bisquert Departament de Ciències Experimentals.
ELECTRICAL PROPERTIES OF GLASSES INORGANIC GLASSES CONDUCTIVITY NATURE AND APPLICATIONS Pure ionic conductivity : Pure electronic conductivity : - demonstrated.

ELECTRICAL PROPERTIES OF GLASSES INORGANIC GLASSES CONDUCTIVITY NATURE AND APPLICATIONS Pure ionic conductivity : Pure electronic conductivity : - demonstrated.
March 2, 2010Global Network Symposium 1 Physics of compression of liquids Implication for the evolution of planets Shun-ichiro Karato Yale University Department.

March 2, 2010Global Network Symposium 1 Physics of compression of liquids Implication for the evolution of planets Shun-ichiro Karato Yale University Department.
Carbon Dioxide Clusters and Copper Complexes Formed in Argon Matrices Michael E. Goodrich & David T. Moore Chemistry Department, Lehigh University Bethlehem.

Carbon Dioxide Clusters and Copper Complexes Formed in Argon Matrices Michael E. Goodrich & David T. Moore Chemistry Department, Lehigh University Bethlehem.

Similar presentations

Ads by Google