Corrélation homonucléaire par le J : INADEQUATE refocalisé

L’expérience INADEQUATE (Incredible Natural Abundance DoublE Quantum Transfer Experiment) refocalisée avec filtre Z a prouvé sa grande efficacité pour déterminer les corrélations homonucléaires associées aux liaisons chimiques dans les solides inorganique [52]. Au cours de cette thèse nous avons utilisé ce type d’expérience pour analyser les corrélations homonucléaires entre les noyaux 29Si-29Si sur des échantillons enrichis en isotope 29Si ou 11B-11B. La séquence d’impulsion rf ainsi que le chemin de cohérence correspondant à cette expérience sont donnés sur la figure 49.

-10 -5 0 5 10 15 20 25 -10 -5 0 5 10 15 20 25

B

3

-B

3

B

4

-B

4

B

3

-B

4 11 B ¹ Q di m ens ion (pp m ) 11B 1Q dimension (ppm)

II-51

Figure 49: Séquence d’impulsion de l’expérience INADEQUATE refocalisée avec filtre Z (haut) et chemins de cohérences (bas) [52-54]

Le chemin de cohérences montre que le spectre 2D résultant est une corrélation entre un spectre 2Q (dimension indirecte) et un spectre 1Q (dimension directe). La figure 50 illustre les types de spectres obtenus après une expérience de type INADEQUATE refocalisée. Le spectre brut comme nous venons de l’évoquer montre une corrélation 2Q-1Q (figure 50a). Pour obtenir un spectre plus simple à simuler on effectue un processus de cisaillement appelé sharing qui permet de passer d’un spectre 2Q-1Q à un spectre 1Q-1Q (figure 50b).

Figure 50: Spectres 2D INADEQUATE correspondant à trois spins A, B et C faiblement couplés. B est couplé à A et C (JAB ≠0, JBC≠ 0), et A et C ne sont pas couplés (JAC = 0). a) spectre brut de corrélations 2Q-1Q : la présence des deux pics à égale distance de la diagonal à la fréquence (ωA + ωB), par exemple, correspond à la proximité entre les deux spins A et B b) spectre traité avec la procédure de cisaillement de corrélation 1Q-1Q. [21]

Séquence de pulse Chemin de cohérence ⁰ t₁ -2 -1 +1 +2 𝜋 2 𝜋

II-52

Conclusion

Au cours de mon travail de thèse j’ai élaboré et caractérisé des verres homogènes et des verres présentant des séparations de phases, celles-ci étant exploitées dans l’objectif de synthétiser des vitrocéramiques. Ce chapitre détaille les modes de synthèse que j’ai adoptés afin d’élaborer les échantillons des systèmes aluminosilicates, borosilicates et aluminoborosilicates. Les méthodes de caractérisation qui m’ont permis de définir l’ensemble des spécificités des échantillons à différentes échelles (macroscopique, microscopique et échelle locale) ont été détaillées : il s’agit des propriétés thermiques (Tg, Tc, Tf), microstructurales (MEB, TEM, STEM) et structurales (DRX en température, RMN). La RMN étant l’outil de diagnostic privilégié dans le cadre de cette thèse, cette spectroscopie a été développée plus longuement afin de présenter ses principes, les principales interactions et leur influence sur le signal RMN et les expériences d’acquisition du signal RMN, des spectres 1D aux spectres 2D tels que les spectres MQMAS essentiels pour les noyaux quadripolaires (aluminium et bore notamment dans cette étude), et les méthodes de corrélation et de découplage hétéro et homonucléaire (INADEQUATE, D-HMQC, 𝑅2₁2).

II-53

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III-i

Chapitre III : Etudes structurales des verres d’oxydes : Point

bibliographique

III.1. Les verres silicatés, preuve de l’ordre à courte distance ... III-1

III.1.1. La silice vitreuse : verre SiO2 ... III-1 III.1.2. Système SiO2-MOz/2 (M = alcalins, alcalino-terreux, terres rares) ... III-2

III.2. Les verres aluminosilicates ... III-5

III.2.1. Configurations structurales de l’aluminium ... III-5 III.2.2. Modèle structural des aluminosilicates SiO2-Al2O3-MOz/2 ... III-5 III.2.2.a. Le principe de la compensation de charge et la coordinence de l’aluminium .... III-6 III.2.2.b. Principe d’évitement de Loewenstein ... III-6 III.2.2.c. Distribution de NBO dans le réseau aluminosilicate ... III-7 III.2.2.d. Les limites du modèle de structure des aluminosilicates ... III-8

III.3. Les borates et les unités superstructurales associées ... III-8

III.3.1. Le verres pure B2O3 ... III-9 III.3.2. L’anomalie du bore et les borates alcalins et alcalino-terreux : B2O3 - MOz/2 ... III-11 III.3.3. Modèle Théorique de Krogh-Moe et les unités supertructurales dans les borates III-14 III.3.4. Les borates de terre rare : système B2O3-Tr2O3... III-15

III.4. Les borosilicates du système SiO

2

-B

2

O

3

-MO

z/2

... III-17

III.5. Les borosilicates de terre rare du système SiO

2

-B

2

O

3

-Ln

2

O

3

... III-19

III.6. Les aluminoborosilicates du système SiO

2

-B

2

O

3

-Al

2

O

3

-MO

z/2

... III-21

Conclusion ... III-23

Références : ... III-25

III-1

Dans le document Etude structurale des phénomènes de séparation de phases dans des verres d'oxydes aluminosilicatés et borosilicatés : application à la synthèse de vitrocéramiques (Page 106-115)