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© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 1
Solid-State Nuclear Magnetic Resonance of glasses: from basics to more advanced concepts
Dominique Massiot, Pierre FlorianCEMHTI-CNRS UPR3079 Orléans
http://www.cemhti.cnrs-orleans.fr/?nom=massiot
Google dmfit nmr
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 2
Since 2008 France has established a nationalnetwork of flagship NMR facilities providingHigh-Resolution and High-Field capabilities,making available the latest cutting edgedevelopments to a broad community of nationaland international users.
From 750 to 1000 MHz1.2GHz to come 2020Liquid & Solid StateCryo-probesFast and ultra-fast MASDNP @800MHzHigh & very High temperature
Open to national and international users uponproposals – constantly open on web
http://www.ir-rmn.fr/
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 3
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 4
Geometrical & Chemical Order
Chemical order / Geometrical disorder Geometrical order / Chemical disorder
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 5
Geometrical & Chemical Order
Chemical order / Geometrical disorder Geometrical order / Chemical disorder
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 6
Materials structure at different scales
a
bc
NM
R X
AS
Ram
an /
IR
Å
nm
Local OrderD
iffraction X-R
ays Neutrons e
-
Order Disorder
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 7
29Si - Silica based materials
Glass Mesoporous Silica SiO2-surfactantMesophase Zeolite
D.Massiot, R.J.Messinger, S.Cadars, M.Deschamps, V.Montouillout, N.Pellerin, E.Veron, M.Allix, P.Florian, F.FayonAccounts Chem. Res. 46 1975–1984 2013
Resolution is gained by averaging out anisotropic signaturesMagic Angle Spinning MAS
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 8
Structure & functions... Proteins / Glasses
Multicomponent Glass SiO2-Al2O3 MOExtended 3D rigid network of tetrahedral
ConnectivityVery similar information from
Dipolar and J-coupling29Si / 23Na / 27Al / 43Ca / 17O
Glass3D interconnected network
Intrinsincally Disordered ProteinIDPs
Macromoleculessecondary and ternary Structure & dynamics
Constraints from identified spin pairsThrough-bond and through space
1H / 13C / 15N
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 9
Glass3D interconnected network
Intrinsincally Disordered ProteinIDPs
Structure & functions... Proteins / Glasses
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 10
NMR TimeLine
1.2 GHz1.5 GHz
MAS 150 kHzDNP
© Pierre Florian
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 11© Histoire de la RMN – d’après H.Desvaux CEA Saclay
The Nuclear Magnetic Resonance
measure of ! in molecular jets
I.I. Rabi, Nobel of Physics 944 for measures in molucular jets
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 12© Histoire de la RMN – d’après H.Desvaux CEA Saclay
The Nuclear Magnetic Resonance
I.I. Rabi, Nobel of Physics 944 for measures in molucular jets
Resonance of LiCl from Rabi's 1938 paper.
measure of ! in molecular jets
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 13
The Magnetic Nuclear Induction approach
Phys. Rev., 69, 127 (1946)
E.M. Purcell et F. Bloch, Nobel of Physics 1952 for the discovery of NMR
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 14
Sensitivity / Observability
H2
He
Li6,7
Be9
B10,11
C N14
O17
F Ne21
Na23
Mg25
Al27
Si P S33
Cl35,37
Ar
K39,41
Ca43
Sc45
Ti47,49
V50,51
Cr53
Mn55
Fe Co59
Ni61
Cu63,65
Zn67
Ga69,71
Ge73
As75
Se Br79,81
Kr83
Rb85,87
Sr87
Y Zr91
Nb93
Mo97
Tc Ru99,101
Rh Pd105
Ag Cd In113-5
Sn Sb121-3
Te I127
Xe129-31
Cs133
Ba135-7
La138-9
Hf177-9
Ta181
W Re185-7
Os187-9
Ir191-3
Pt Au197
Hg201
Tl Pb Bi Po At Rn
Fr Ra Ac
Ce Pr141
Nd143-5
Pm Sm147-9
Eu151-3
Gd155-7
Tb159
Dy161-3
Ho165
Er167
Tm Yb173
Lu175-6
Th Pa U235
Np Pu Am Cm Bk Cf Es Fm Md No Lr
Element n'ayant que des isotopes de spin I=1/2
Element ayant des isotopes de spin quadripolaire (I>1/2)
vObservabilityv abundancevGyromagnetic ratiovQuadrupolar momentum
Numerous possibly sensitive nuclei but fewer easily observed
The most usually observed are «light» nucleivI=1/2 : 1H, 29Si, 31P, 13C,vI=3/2 : 23Na, 11B vI=5/2 : 27Al, 17O (isotopicenrichment)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 15
Larmor Frequency
5 10 15 20 25 30B0(T)
-4.×10-25
-2.×10-25
2.×10-25
4.×10-25ΔE(Joule)
5 10 15 20 25 30B0(T)
-600
-400
-200
200
400
600
ν0 (MHz)1H
13C
15N
3T [128MHz]Whole body (Philips)
Earth Field~50µT (0.5G)magnetometer
23.4T1GHz (Lyon)
1.2GHz Bruker 2019
35 T1.5 GHz (Thallahassee)
40T inhomogeneous
!0="B0 | ΔE=h!0
NMR signalDN a exp(-DE/kT)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 16
Precession – Rotating Frame
Rotating Frame
© P.J. Grandinetti – Ohio State Univ.
Paul Callaghan applying a pulse in the gravitational fieldhttps://www.youtube.com/watch?v=7aRKAXD4dAg
Top in a Gravitational field "Spin" in Magnetic Field
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 17
Bloch Equations – with B1 on - Pulses
pacqu
p/2
p
3p/2
2p
p
Precession in the B1 field [n1 = g B1] – remaining far from thermal equilibrium
B1
Equilibrium Pulse Evolution (t2)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 18
Pulsed NMR – long lasting coherence
E.L. Hahn, Phys. Rev., 77, 297 (1950)
Bloch Equations
50 100 150 200
-1.0
-0.5
0.0
0.5
1.0
1-Exp[-t/T1]
ms to sLong coherence lifetime
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 19
T1 measurement – Inversion Recovery
200 400 600 800 1000
-1.0
-0.5
0.5
1.0
d1
p p/2
vd acqu
vd 0 T1/8 T1 √ln2 2 T1 ∞
I(t)=I0[1-2 Exp[-vd/T1]
5 T1
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 20© Histoire de la RMN – d’après H.Desvaux CEA Saclay
Spin Echo – signal can be refocused
E.L. Hahn, Phys. Rev., 80, 580 (1950)
The spectroscopist isan actor of the experiment
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 21
Hahn Echo – Spin Echo
p/2 p
d1 t t
acqu
-1.0 -0.5 0.0 0.5 1.0 -1.0 -0.5 0.0 0.5 1.0
t=0t=0
100 200 300 400 500
0.2
0.4
0.6
0.8
1.0
I(t)=I0 Exp[-2 t /T2]
Measurement of T2
the life time of the coherence in the XY [transverse] plane
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 22
Nuclear Magnetic Resonance
Spectroscopy
Chemistry
In a magnetic field - ν0=γ B0/2π
Spatial EncodingField Gradients
Local FieldHomogeneous Principal Field (<ppm)
Imaging anatomy / function
Diffusion / Rheology
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 23
Coding of position - Imaging
Paul C. Lauterbur – Nature 1973Nobel Physiology & Medecine 2003
-1.0 -0.5 0.0 0.5 1.0
Projection on the Field Gradient
Gradient along B0!" = $ %" + ' ()
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 24© Histoire de la RMN – d’après H.Desvaux CEA Saclay
The Discovery of Chemical Shift
Phys. Rev., 77, 716 (1950) Phys. Rev., 77, 736 (1950)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 25
Visibility of each family of nuclei
Zn O3P C2H4 CO2H - 0.5 C6H5NH2Phosphonate (B.Bujoli – Nantes)
17O I=5/20.037% ab.
54 MHz
14N I=199.6 % ab.
29 MHz
67Zn I=5/24.11% ab.
25 MHz
13P I=1/2100% ab.162MHz
*
1020304050(ppm)
13C I=1/21.18% ab.
100MHz
050100150200(ppm)
C6H5
C2H4
COOH
-100-50050100150(ppm)
1H I=1/299.9% ab.
400MHz
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 26
PulpChannels
b)a)
31P / 1H MAS MRI
PulpChannels
b)a)
1H/31P CPMAS
1H Chemical Shift Imaging
V.Sarou-Kanian et al., Scientific Report 5, 9872 (2015)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 27
The different perturbating interactions
Q2
Q1
Chemical Shift Anisotropyelectronic shielding
first shells, coordinence and geometry
~10s of kHz
Dipolar interactionneighboring spins
Distances
~kHz 1/r3Q2
Q1
Indirect J Coupling chemical bonding
Connectivity
Q2
Q1
< 100s of Hz I>1/2 up to MHz
Quadrupolar interaction Electric Field GradientSurrounding Charges,
electrons and nucleigeometry
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 28
Powder Pattern
Interactions are ansiotropic and take the following form (at 1st order):
÷øöç
èæ abh--b+n=n 2cos²sin22
1²cos3A0
Single Crystal rotation pattern
w
Crystalline Powderoverlapping Broad lines
h=0.2aAzz
Axx
Ayy b
xy
z
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 29
Magic Angle Spinning
Static
-50050100
31P Spin 1/2 CSA
MAS
-50050100(ppm)
Modulation into sharp lines
MAS54.74°
P2(cosq)
q
0°static1
-0.5
90°H0
Dipolar -> 0Chem. Shift -> diso
Jcoupling
Quad 1st -> 0Quad 2nd -> d2nd
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 30
Zn O3P C2H4 CO2H - 0.5 C6H5NH2Phosphonate (B.Bujoli – Nantes)
Getting to High Resolution
Static
unresolved spectrumCSA + Dipolar
-50-250255075100125(ppm)
31P
high speed MA
S spinning attenuate dipolar couplingand m
odulates chemical shift anisotropy
-50-250255075100125(ppm)
MAS
CSA + Dipolar
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 31
Getting to High Resolution
-50-250255075100125(ppm)
simplified resolved spectrum
Static
unresolved spectrumCSA + Dipolar
-50-250255075100125(ppm)
31P
high speed MA
S spinning attenuate dipolar couplingand m
odulates chemical shift anisotropy
-50-250255075100125(ppm)
MAS
CSA + Dipolar
-50-250255075100125(ppm)
Proton decoupling averages strong 31P-1H dipolar interaction
CSA + Dipolar
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 32
Magic Angle Spinning 13C
(ppm) 2030
39.5Hz42.5Hz
R {14N}13C
(ppm)120130140
(ppm)50100150
C6H5
C2H4
COOH
31P-13C 1J
C2H4C6H5NH2
D.Massiot, F.Fayon, M.Deschamps, S.Cadars, P.Florian, V.Montouillout, N.Pellerin, J.Hiet, A.Rakhmatullin, C.Bessada‘Detection and use of small J couplings in solid state NMR experiments.'
Comptes Rendus de Chimie 13 117-129 2010
13CI=1/2
p/2 Spin Lock
1H
contact
13C (X)
t2
Decoupling
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 33
Solid State NMR Concepts & Methods tool box
Zeeman Interaction100s of MHz
Sensitivity & spectral resolution (CSA)
Perturbating InteractionPhysical & Chemical informations
(from Hz to MHz)
Sample ManipulationOrientation
rotation (Hz to 30 to 150 kHz)
Spin Manipulationcoherent radio frequency fields
(few Hz to 100/300 kHz)
Evolution times(µs to s)
Long lasting relaxation times T1 up to 100s sec – T2 up to 100s ms
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 34
29Si - Silica based materials
Glass Mesoporous Silica SiO2-surfactantMesophase Zeolite
D.Massiot, R.J.Messinger, S.Cadars, M.Deschamps, V.Montouillout, N.Pellerin, E.Veron, M.Allix, P.Florian, F.FayonAccounts Chem. Res. 46 1975–1984 2013
Average Chemical Shift ~ local fieldelectronic shielding a B0 -> first shells, coordinence and geometry
Chemical Shift Anisotropyelectronic shielding
first shells, coordinence and geometry
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 35
S.Ispas, T.Charpentier, F.Mauri, D.Neuvllle – Solid State Science 2010 12 183
The combination of molecular dynamics simulations with first-principles (or ab initio) calculations with density functional theory (DFT) enable the prediction of NMR spectra from a structural model (here oxygen-17 MQMAS). Two spectra are compared, the first from classicalmolecular dynamics (EP, Effective Potential) and the second from ab-initio molecular dynamics (CP, Car-Parinello). Differences between the two models in Si-NBO distances induce a difference in the position of isotropic peaks of non-bridging oxygens. This can be explained by the high sensitivity of the quadrupole interaction (CQ) to the Si-NBO distance
T.Charpentier, D.Massiot, in From glass to crystal phase separation, nucleation and growth, from research to applications, EDP Sciences, 2017
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 36
OB
Non-ring
B
B BRing
S(q) 17O NMR
22% ringsMD
75% ringsMD
G.Ferlat, T.Charpentier, A.P.Seitsonen, A.Takada, M.Lazzeri, L.Cormier, G.Calas, F.Mauri"Boroxol Rings in Liquid and Vitreous B2O3 from First Principles"
Phys. Rev. Lett. 101 065504 2008
Diffusion / Model / NMR : local order
B2O3 Glass
T.Charpentier, D.Massiot, in From glass to crystal phase separation, nucleation and growth, from research to applications, EDP Sciences, 2017
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 37T.Charpentier, D.Massiot, in From glass to crystal phase separation, nucleation and growth, from research to applications, EDP Sciences, 2017
Computing NMR parameters
Angeli F., et al. Geochim. Cosmochim. Acta, 75, 2453-2469, 2011 - Ispas S., et al. Solid State Sci., 12, 183-192, 2010
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 38
Computing NMR parameters
T.Charpentier, D.Massiot, in From glass to crystal phase separation, nucleation and growth, from research to applications, EDP Sciences, 2017
Angeli F., et al. Geochim. Cosmochim. Acta, 75, 2453-2469, 2011 - Ispas S., et al. Solid State Sci., 12, 183-192, 2010
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 39
Silicate (phosphate) network: Qn units(SiO4, PO4 tetrahedra with n bridging oxygen atoms)
2.6 P2O5
3.8 P2O5
5.0 P2O5
Ca/Si = 1.11
P 2O
5
Broad chemical shift distribution(disordered materials)
-140-120-100-80-60-40
9.4 T14kHz
Lack of resolution: Qn unitsquantification ?
Q1
Q2
Q3
Q4
29Si
Mainly orthophosphate units(Q0 : PO4
3-)
-30-20-100102030
Q0 Q1 Q2
31PQ0
Q1
Q3
Q2Q0
1D MAS spectra of CaO-SiO2-P2O5 glasses
Structure of CaO-SiO2-P2O5 Bioglasses
F.Fayon, C.Duée, T.Poumeyrol, M.Allix, D.Massiot, J. Phys. Chem. 117 2283-2288 2013
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 40
Distribution of PO43- units in bioactive glasses
TEM (5.0 mol.% P2O5)
§Very weak Z-contrast between Si and P: No information from SAXS and TEM
Counting 31P neighbors by spin-counting dipolar NMR ?
Chemical homogeneity ?(Random distribution)
Silicate chains
Q0 (PO43-)
Phosphate clusters ?
F.Fayon, C.Duée, T.Poumeyrol, M.Allix, D.Massiot, J. Phys. Chem. 117 2283-2288 2013
CaO-SiO2-P2O5
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 41
Counting neighboring 31P spins
0 2 4 6 8 10 12 140
1
2
3
4
5
6
7
8
N (s
pins
)T (ms)
N≈5.5
Highest coherence order ≈ 4Q
Coherence order0 2 4 6 8 10 12 14
0.0
0.2
0.4
0.0
0.2
0.4
0.0
0.2
0.4
0.6
0 2 4 6 8 10 12 14
0 2 4 6 8 10 12 14
T = 4.0 ms
T = 7.2 ms
T = 12 ms
Int.
Int.
Int.
BioGlass – 2.6%P2O5
Coherence Order
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
T =8.8ms
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
T = 0.8 ms
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
T = 5.6 ms
Inte
nsity
Ca4P2O9
0 2 4 6 8 10 120
50
100
150
200
N (s
pins
)
T (ms)
170
More than 32Q
F.Fayon, C.Duée, T.Poumeyrol, M.Allix, D.Massiot, J. Phys. Chem. 117 2283-2288 2013
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 42
Static 31P-31P Dipolar network
0 2 4 6 8 10 12 140
1
2
3
4
5
6
7
8
N (s
pins
)T (ms)
N≈5.5
Highest coherence order ≈ 4Q
Coherence order0 2 4 6 8 10 12 14
0.0
0.2
0.4
0.0
0.2
0.4
0.0
0.2
0.4
0.6
0 2 4 6 8 10 12 14
0 2 4 6 8 10 12 14
T = 4.0 ms
T = 7.2 ms
T = 12 ms
Int.
Int.
Int.
BioGlass – 2.6%P2O5
Coherence Order
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
T =8.8ms
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
T = 0.8 ms
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34
T = 5.6 ms
Inte
nsity
Ca4P2O9
0 2 4 6 8 10 120
50
100
150
200
N (s
pins
)
T (ms)
170
More than 32Q
Phosphate clusters of 1 nm size !!
F.Fayon, C.Duée, T.Poumeyrol, M.Allix, D.Massiot, J. Phys. Chem. 117 2283-2288 2013
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 43
207Pb / 31P NMR in PbO-P2O5 glasses
-120-80-4004080 (ppm)
66% PbO
60% PbO
55% PbO
50% PbO
45% PbO
40% PbO
68% PbO
Q0Q1 Q2 Q3
31P MAS NMR spectra
Fayon et al., JACS 119 (1997), JNCS 232-234 (1998)., JNCS 243 (1999), JMR 137 (1999), Inorg. Chem. 38 (1999) .
68% PbO
60% PbO
50% PbO
40% PbO
35% PbO
-8000-6000-4000-2000020004000 0 0.2 0.4 0.6 0.8d (ppm) R (nm)
P2O5-PbOÄCN ~ 9 to 7Äd(Pb-O) ~ 0.26-7nm
NMRstatic or MAS XAFS
207Pb static NMR spectra
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 44
X
p/2 p pppp
t2
1
-1
PASS-SE
n/wR
DT1 DT2DT5+k/ wRDT4DT3
DT6+k/ wR
Recoupling CSA2D PASS SE
Isotropic Dimension (ppm)
-1200 -1600 -2000 -2400 -2800 -3200
800
400
0
-400
-800
Ani
sotr
opic
Dim
ensio
n (p
pm)
Large and Continuous distributionof coupled isotropic & anisotropic CSA
CSA : 207Pb NMR in PbO-P2O5 glasses
68% PbO
60% PbO
50% PbO
40% PbO
35% PbO
-8000-6000-4000-2000020004000 0 0.2 0.4 0.6 0.8d (ppm) R (nm)
P2O5-PbOÄCN ~ 9 to 7Äd(Pb-O) ~ 0.26-7nm
NMRstatic or MAS XAFS
Fayon et al., JACS 119 (1997), JNCS 232-234 (1998)., JNCS 243 (1999), JMR 137 (1999), Inorg. Chem. 38 (1999) .
dii (ppm)
d ISO (ppm)
d33d22d11
D=d11- d33
Distribution of isotropic chemical shift
Dis
tribu
tion
of a
niso
tropy
-3200-3000-2800-2600-2400-2200-2000-3500
-3000
-2500
-2000
-1500
-1000
Distribution of ionic to covalentchemical binding of Pb in the network
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 45
31P NMR in PbO-P2O5 glasses
0.0 0.5 1.0 1.5 2.0 2.5 3.00
20
40
60
80
Q3Q2
Q1
Q0
I (%)
R = [PbO]/[P 2O5]
K2 = 5.10 -4
K1 = 0.022
-120-80-4004080 (ppm)
66% PbO
60% PbO
55% PbO
50% PbO
45% PbO
40% PbO
68% PbO
Q0Q1 Q2 Q3
31P MAS NMR spectra
Fayon et al., JACS 119 (1997), JNCS 232-234 (1998)., JNCS 243 (1999), JMR 137 (1999), Inorg. Chem. 38 (1999) .
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 46
(ppm)-40-30-20-10010
Q1 (end of chain)750 Hz
Q2 (middle of chain)1200 Hz
[Q1] = [Q2]
Average chain lengthNav. ~ 4
Chain length distribution?Chemical disorder
Chain geometries?Topological or geometrical disorder
? Nature of disorder at
the nanometricscale ?
(PbO) 0.61(P2O
5)0.39glass
Phosphate Glasses : 31P MAS NMR
P-O-P chemical bonds can be viewed from J based P-P experiments
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 47© Histoire de la RMN – d’après H.Desvaux CEA Saclay
2D NMR
J. Chem. Phys., 64, 2229 (1974)
In « NMR and More », M. Goldman et M. Porneuf Eds (1994)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 48
Hahn Echo – Spin Echo
p/2 p
d1 t t
acqu
-1.0 -0.5 0.0 0.5 1.0 -1.0 -0.5 0.0 0.5 1.0
t=0t=0
100 200 300 400 500
0.2
0.4
0.6
0.8
1.0
I(t)=I0 Exp[-2 t /T2]
Measurement of T2
the life time of the coherence in the XY [transverse] plane
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 49
2D Exchange (NOESY - EXSY)
tm = 5 ms tm = 100 ms
6 4 2 0 6 4 2 0(ppm)
6
4
2
0
(ppm
)
Si-H (TH)Si-H (DH)Si-CH3 (DH)Si-H (DH) Si-CH3 (DH)
Si-H (TH)
f1 f2
01
-1
f3t1 mixing
t2
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 50
Principle of a 2D homonuclear experiment
t1evolution
preparation
6 4 2 0
6
4
2
0
(ppm
)
t2 evolutionmixing
t1sp
ectru
m
t2 spectrum
(ppm)
Mixing:
• Spin diffusion• Chemical exchange• Dipolar interaction• Multiple quantum filter• …
t1 : evolution of coherent state built duringPreparation
• Single quantum• Multiple quantum• …
tm = 100 ms
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 51
Anisotropic nature of local structure
M.Davis, D.Kaseman, S.Parvani, K.Sanders, P.J.Grandinetti, P.Florian, D.MassiotQ(n)-Species Distribution in K2O • 2 SiO2 Glass by 29Si Magic Angle Flipping NMR
J. Phys. Chem. A 114 5503–5508 (2010)
29Si MAF Spectrum of K2O-2SiO2
Q4
Q3
Q2
Isotropic MAS Isotropic/anisotropic MAF
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 52
(ppm)-40-30-20-10010
Q1 (end of chain)750 Hz
Q2 (middle of chain)1200 Hz
[Q1] = [Q2]
Average chain lengthNav. ~ 4
Chain length distribution?Chemical disorder
Chain geometries?Topological or geometrical disorder
? Nature of disorder at
the nanometricscale ?
(PbO) 0.61(P2O
5)0.39glass
Phosphate Glasses : 31P MAS NMR
P-O-P chemical bonds can be viewed from J based P-P experiments
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 53
31P NMR in PbO-P2O5 glasses
Individual 31P
(ppm)0 -8 -16 -24 -32
(ppm)
0
-8
-16
-24
-32
tmix = 6.4 ms
Q1-Q2
Q1-Q1
Q2-Q2
"Spin diffusion"Spatial proximity
Pairs of 31P
(ppm)
(ppm)0 -8 -16 -24 -32
0.0
-10.0
-20.0
-30.0
-40.0
-50.0
-60.0
Q2-Q2
Q2-Q1
Q1-Q1 Dimer
End
Mid
Double Quantum editionDipolar : spatial proximityJcoupling : chemical bond
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 54
1 to 3 tetraedra – 31P J-couplings
Q1 Q2
0 -8 -16 -24 -32
40
0
-40
J2 ~ 17 to 25 Hz
750 Hz 1200 Hz
~ 2Å
-40-30-20-100
Q1-Q1
Q1-Q2Q2-Q2
~ 5Å
(ppm)-40-30-20-100
Q2-Q2-Q2
Q1-Q2-Q2
Q1-Q2-Q1
~ 7-8Å
F. Fayon, I.J. King, R.K. Harris, J.S.O. Evans, D. Massiot Comptes Rendus de Chimie 7 351-361 (2004)
F.Fayon, C.Roiland, L.Emsley, D.Massiot, Journal of Magnetic Resonance 179 50-58 (2006)
(Pb
O) 0
.61(P
2O
5) 0
.39
gla
ss
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 55
1 to 3 tetraedra – 31P J-coupligs
Q1 Q2
0 -8 -16 -24 -32
40
0
-40
J2 ~ 17 to 25 Hz
750 Hz 1200 Hz
-40-30-20-100
Q1-Q1
Q1-Q2Q2-Q2
(ppm)-40-30-20-100
Q2-Q2-Q2
Q1-Q2-Q2
Q1-Q2-Q1
F. Fayon, I.J. King, R.K. Harris, J.S.O. Evans, D. Massiot Comptes Rendus de Chimie 7 351-361 (2004)
F.Fayon, C.Roiland, L.Emsley, D.Massiot, Journal of Magnetic Resonance 179 50-58 (2006)
(Pb
O) 0
.61(P
2O
5) 0
.39
gla
ss
(ppm)-40-30-20-100
Q1-Q1
Q1-Q2-Q2
Q1-Q2-Q1
Q2-Q2-Q2Q1
Q2
Geometry
“Chem
istry”
Topology
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 56
{27Al} 29Si(O-29Si)n? Spin Counting
Q33 Q4
4 Q43 Q4
2 Q41 Q4
0
RMN 29SiAnorthite
Crystalline & Glass
(ppm) -100-90-80-70
Q44
Q??
J.Hiet, M.Deschamps, N.Pellerin, F.Fayon, D.Massiot"Probing chemical disorder in glasses using silicon-29 NMR spectral editing" Phys. Chem. Chem. Phys. 11 6935–6940 2009
3Si
2Si
1Si
4Si
CaO
-Al 2O
3G
lass
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 57J.Hiet, M.Deschamps, N.Pellerin, F.Fayon, D.Massiot
"Probing chemical disorder in glasses using silicon-29 NMR spectral editing" Phys. Chem. Chem. Phys. 11 6935–6940 2009
{27Al} 29Si(O-29Si)n? Spin Counting
Q33 Q4
4 Q43 Q4
2 Q41 Q4
0
NMR29SiAnorthite
Crystalline & Glass
(ppm) -100-90-80-70
Q44
Q??
CaO
-Al 2O
3G
lass
CaAlLaY Glass
1Si
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 58J.Hiet, M.Deschamps, N.Pellerin, F.Fayon, D.Massiot
"Probing chemical disorder in glasses using silicon-29 NMR spectral editing" Phys. Chem. Chem. Phys. 11 6935–6940 2009
4Si
{27Al} 29Si(O-29Si)n? Spin Counting
Q33 Q4
4 Q43 Q4
2 Q41 Q4
0
NMR29SiAnorthite
Crystalline & Glass
(ppm) -100-90-80-70
Q44
Q??
Si(OSi) n≥3
CaO
-Al 2O
3G
lass
CaAlLaY Glass
1Si
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 59J.Hiet, M.Deschamps, N.Pellerin, F.Fayon, D.Massiot
"Probing chemical disorder in glasses using silicon-29 NMR spectral editing" Phys. Chem. Chem. Phys. 11 6935–6940 2009
4Si
{27Al} 29Si(O-29Si)n? Spin Counting
Q33 Q4
4 Q43 Q4
2 Q41 Q4
0
NMR29SiAnorthite
Crystalline & Glass
(ppm) -100-90-80-70
Q44
Q??
Si(OSi) n≥3
Si(OSi) n≥23Si
CaO
-Al 2O
3G
lass
CaAlLaY Glass
1Si
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 60
CaAlLaY Glass
J.Hiet, M.Deschamps, N.Pellerin, F.Fayon, D.Massiot"Probing chemical disorder in glasses using silicon-29 NMR spectral editing" Phys. Chem. Chem. Phys. 11 6935–6940 2009
4Si
{27Al} 29Si(O-29Si)n? Spin Counting
Q33 Q4
4 Q43 Q4
2 Q41 Q4
0
NMR29SiAnorthite
Crystalline & Glass
(ppm) -100-90-80-70
Q44
Q??
Si(OSi) n≥3
Si(OSi) n≥23Si
2Si Si(OSi) n≥1
CaO
-Al 2O
3G
lass
1Si
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 61
chemistry
CaAlLaY Glass
J.Hiet, M.Deschamps, N.Pellerin, F.Fayon, D.Massiot"Probing chemical disorder in glasses using silicon-29 NMR spectral editing" Phys. Chem. Chem. Phys. 11 6935–6940 2009
Chemical and Geometrical disorder
Q33 Q4
4 Q43 Q4
2 Q41 Q4
0
NMR29SiAnorthite
Crystalline & Glass
(ppm) -100-90-80-70
Q44
Q??
2Si Si(OSi) n≥1
CaO
-Al 2O
3G
lass
geometry
1Si
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 62
Verres : Ordre Chimique & Géomatrique
F.Fayon, et al. Journal of Magnetic Resonance 179 50-58 (2006) J.Hiet, et al. Phys. Chem. Chem. Phys. 11 6935–6940 2009
Si(OSi) n≥3
Si(OSi) n≥2
Si(OSi) n≥1
4Si
3Si
2Si
Calcium REE-Alumino-Silicate glasses
1Si-40-30-20-100
-40
-30
-20
-10
0
Q1-Q1
Q1-Q2
Q2-Q2
(ppm)-40-30-20-100
-100
-80
-60
-40
-20
0
Q2-Q2-Q2
Q1-Q2-Q2
Q1-Q2-Q1
(ppm) -40-30-20-100Q1-Q1
Q1-Q2-Q2
Q1-Q2-Q1
Q2-Q2-Q2Q1
Q2
“Chem
istry”
Lead Phosphate glasses
31P
29Si
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 63
MAS Quadrupolar nuclei
-100-50050100(kHz)
076 (ppm)
750 MHz
600 MHz
500 MHz
400 MHz
300 MHz
200 MHz
27Al in YAG two sites AlIV and AlVI
Second order shift and width goes with nQ²/n0 (Hz)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 64
A multi level system of transitions II
2I+1 energy levels, 2I single quantum transitions
I=3/2
Zeeman 1st orderQuadrupolar
2nd orderQuadrupolar
n0+n(1)Q
n0
n0
n0
n0+n(1)Q
n03n0
+n(2)Q<m>
+n(2)Q<m>
+n(2)Q<m>
1st order quadrupolar interaction
2nd order quadrupolar interaction
( )[ ]1III3A61CH 2
zQ20Q
)1(Q +-=
( ){ }( ){ }úúû
ù
êêë
é
--++
--+
w=
-
-
1I21II2AA
1I81II4AA2C
H2z
Q22
Q22
2z
Q21
Q12
0
2Q)2(
Q
( )gban+n+n=n >-<>-<>-< ,,)2(1m,m
)2(iso1m,m01m,m
( ) ( )3
130
1mm931II 2
0
2Q)2(iso
1m,mh
+n
n---+-=n >-<
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 65
Magic Angle Spinning - 2nd order
( ) ( )å=
f+w-ba>-< +n
-q+n=n
2
1n
tnin,Q201m,m
reAC2
)m21(CosP
First order HI <<Hz
P4(cosq)
( ) ( )åå=
f+w-
=>-< +q+n=n
4
1n
tni)2(n
4,2,0ll
)2(l
lI,m01m,m
reACosPBCSecond order HI <Hz
MAS54.74°
P2(cosq)
q
0°static1
-0.5
90°H0
ppm
30.56°
90°
70.12°
0°=static
~MAS
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 66
27Al in A9B2 (Al18B4O33) 750 MHz
(Hz)-450000-300000-1500000150000300000450000
Satellite transitions Satellite transitions
Central transition27Al in A9B2
750 MHz - 15 kHz
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 67
A9B2 – 750 MHz 31.25kHz
.. APM Kentgens.. Solid State NMR 5 175-180 1995.. Z. Gan .. J. Am. Chem. Soc. 124 5634-5635 2002
Z.Gan... JMR 2017
1GHz
1.5GHz
1.7GHz
(Hz)-1000001000020000
n=0 CT
n≠0 ST
All
AlO4
AlO5I AlO5IIAlO6
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 68
DAS, MQ-MAS & STMAS
0
-3
+33Q 1Q
t1 t2
0
-1
+1
t1 t2hop
q1 q2
Pulsesequence
Coherencepathway
DAS MQ-MAS
angle
0
-1
+1
t1 t2
Sat Central
STMAS
Pulse duration (µs)
Inte
nsity
(a.u
.)
-1.00
-0.50
0.00
0.50
1.00
0.00 5.00 10.00 15.00 20.00
1 kHz
25 kHz
50 kHz
100 kHz
250 kHz
1000 kHz
I=3/2
( ) ( )W p lp
ll lC A P= -
=å0 2 4, ,
, cosq j b
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 69
Ultimate resolution at ultra high field (40T)
80 40 0 -40
MQ-MAS 400
(ppm)
STMAS 830
(ppm)40 20 0 -20 -40
27Al A9B2
Models
experimental
Gan, Gor’kov, Cross, Samoson, Massiot, JACS 124 5634-5635 (2002)
NHMFL – Z. Gan
Hours / Minutes
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 70
Ca 50_25 / 30 fit 1D & 2D 750/400 MHz
100
80
60
40
20
120
100
80
60
40
20400 MHzExperiment
Model
Exp.
Model
750 MHzExperiment
Model
120 80 40 0 -40
120
100
80
60
40
20400 MHzExperiment
Model
80 40 0 -40
100
80
60
40
20750 MHzExperiment
Model
-200-1000100200300
(ppm)-200-1000100200300
Exp.
Model
MAS 750 MHz MQMAS 400 MHz MQMAS 750 MHz
CA
50.
25C
A 5
0.30
Gla
ss (S
iO2,
Al 2O
3,CaO
)
D.R.Neuville, L.Cormier, D.Massiot 'Al coordination and speciation in calcium aluminosilicate glasses : effects of composition determined by 27Al MQ-MAS NMR and Raman spectrocospy' Chem. Geol. 229 173-185 (2006)
D.R. Neuville, L. Cormier, D. Massiot 'Al environment in tectosilicate and peraluminous glasses: a NMR, Raman and XANES investigation' Geochim. Cosmochim. Acta 68 5071-5079 (2004)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 71
27Al - Ternary SiO2-Al2O3-CaO
D.R.Neuville, L.Cormier, D.Massiot 'Al coordination and speciation in calcium aluminosilicate glasses : effects of composition determined by 27Al MQ-MAS NMR and Raman spectrocospy' Chem. Geol. 229 173-185 (2006)
AlO5 is present in mostof the glass
compositions
CaO
-Al 2O
3G
lass
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 72
“In silico” 2D colloidal glass simulation
1 particle size: crystallization
2 particle sizes: no long-range orderè Glass
Hexatic order in a 2D colloidalglass with two particle sizes :
Medium Range Crystalline OrderAndLocally Favored Structures LFS
Qnm, SiO5, AlO5, µ3O, Al-O-Al…
From the model to the real glass?
Correlation between Dynamic Heterogeneity and Medium-Range Order in Two-Dimensional Glass-Forming Liquids Takeshi Kawasaki, Takeaki Araki, and Hajime Tanaka
PRL 99, 215701 (2007)
Similarity to Hexatic order
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 73
Chemical Disorder in a Structural Order
T1 : Al only5 configurations
Al-Al4Al-SiAl3Al-Si2Al2Al-Si3Al
Al-Si4
Si-SiAl2Si-Al3
T2 : (Al0.5,Si0.5)2 configurations
Al-SiAl2Al-Al3
Gehlenite Ca2Al2SiO7
P.Florian, E.Veron, T.F.G.Green, J.R.Yates, D.Massiot Chem. Mater. 24 4068–4079 2012
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 74P.Florian, E.Veron, T.F.G.Green, J.R.Yates, D.Massiot Chem. Mater. 24 4068–4079 2012
Chemical Disorder in a Structural Order
27Al MAS @ 17.6T
-82-80-78-76-74-72-70-68-66-64
29Si MAS
T1 & T2 Al T2 Si
Gehlenite Ca2Al2SiO7
Si-Al3
Si-SiAl2
Al-Si2Al2
Al-Al4Al-SiAl3Al-Si3Al
Al-Si4
Al-SiAl2
Al-Al3
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 75
Local Order in Gehlenite from 29Si
p(AlOAl) = p(SiOSi) = 0.11
{27Al}29Si INEPT
-82-80-78-76-74-72-70-68-66-64
Si-(Al3)
Si-(Al2Si)
{29Si}29Si INADEQUATE
-72.5ppm / 92Hz / 88.9%-74.7ppm / 99Hz / 11.1%
T1100% Al
T2Si 50% /Al 50%
Si-(O-Si) x≥1
Si-(O-Al) x≥1
GehleniteCa2Al2SiO7
Tf = 1590°C
P.Florian, E.Veron, T.F.G.Green, J.R.Yates, D.Massiot Chem. Mater. 24 4068–4079 2012
Si-SiAl2Si-Al3
Si-SiAl2
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 76
Al spectra: how to decipher?
{29Si}27Al J-couplingà Bond angles from DFT
50 100 150 200 250
Build-up time texc.(ms)
0
T1 sites:J(Si-Al) ~ 1.5 – 3.5 Hz
T2 sites:J(Si-Al) ~ 4.0 Hz
27Al Echo t=50µs
27Al
29Sit1/2 t1/2
t2t t
{29Si}27Al HMQC
27Al Echo t=50msT1Al-Al4 ?T2Al-Al3 gone
AlSi4 =
Al27Al Dipolar filter
{29Si}27Al HMQC
T1Al-SiAl3 ?
T1Al-Al4 goneAl-(O-Si)x≥1 J filter
(ppm)2030405060708090100110
{29Si}x2 27Al HTQC
T2Al-SiAl2 gone
T1Al-SiAl3 goneAl-(O-Si)x≥2 J filter
P.Florian, E.Veron, T.F.G.Green, J.R.Yates, D.Massiot Chem. Mater. 24 4068–4079 2012
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 77
The 27Al point of view
% diso(ppm) Ddiso CQ(MHz) DCQ hQ T2 (ms)-----------------------------------------------------------------------------------------------------------------------------#1 - T1a AlAl4 3 82.5 n/a 1.75 n/a n/a 9 (±1)#2 - T1b AlAl3Si1 11 79.2 1.50 5.82 2.00 0.3 21 (±1)#3 - T1c AlAl2Si2 24 76.7 1.50 7.27 2.00 0.3 28 (±1)#4 - T1d AlAl2Si3 16 73.4 1.50 7.59 2.00 0.6 47 (±2)#5 - T1e AlSi4 3 70.2 1.50 6.89 2.00 0.3 86 (±12)#6 - T2a AlAl3 7 89.4 1.48 8.31 2.20 0.24 12 (±2)#7 - T2b AlAl2Al1 36 87.7 1.49 10.7 1.84 0.61 38 (±2)
AlSi4
AlSi3Al
AlSi2Al2
AlSiAl3
AlAl4
AlSiAl2AlAl3
27Al quantitativeMAS at 17.6T
27Al MQMAS @17T
3 ppm shift per Si/Al substitution in T1 sites
T2
T1
T1
T2
P.Florian, E.Veron, T.F.G.Green, J.R.Yates, D.Massiot Chem. Mater. 24 4068–4079 2012
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 78
CaO-Al2O3-SiO2 – the 17O viewpoint
Lee et al., Geochim. Cosmochim. Acta 70 4275-4286 (2006)
SiO2
Al2O3CaO
S.Sukenaga, P.Florian, K.Kanehashi, H.Shibata, N.Saito, K.Nakashima, D.Massiot – J.Phys.Chem. Lett. 8, 2274, 2017
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 79
CaO-Al2O3-SiO2 – the 17O viewpoint
36.5 CaO – 51 SiO2 – 12.5 Al2O3
Lee et al., Geochim. Cosmochim. Acta 70 4275-4286 (2006)
S.Sukenaga, P.Florian, K.Kanehashi, H.Shibata, N.Saito, K.Nakashima, D.Massiot – J.Phys.Chem. Lett. 8, 2274, 2017
17O frequency (ppm)050100150200
17O single resonance
SiObAl
{27Al} 17O INEPT
* *
SiOnbCa
SiObAl:Ca
SiObSi
SiOnb
(Si,Al)Ob(Si,Al)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 80
CaO-Al2O3-SiO2 + Na2O – the 17O viewpoint
S.Sukenaga, P.Florian, K.Kanehashi, H.Shibata, N.Saito, K.Nakashima, D.Massiot – J.Phys.Chem. Lett. 8, 2274, 2017
10.8 Na2O – 31.9 CaO – 44.7 SiO2 – 12.6 Al2O3
17O frequency (ppm)050100150
SiOnb(Ca,Na)8.8%
SiObAl:Ca
SiObSi
SiObAl:Na23.2%
SiOnbCa
17O single resonance
{27Al} 17O INEPT
SiObAl:Ca(from CAS)
SiObAl:Na
{23Na} 17O INEPT SiObAl:Na
SiOnb(Ca,Na)
SiOnb
(Si,Al)Ob(Si,Al)
17O frequency (ppm)050100150200
17O single resonance
SiObAl
{27Al} 17O INEPT
* *
SiOnbCa
SiObAl:Ca
SiObSi
SiOnb
(Si,Al)Ob(Si,Al)
36.5 CaO – 51 SiO2 – 12.5 Al2O3
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 81
Separation, Simplification… and gains
27Al (ppm)-250255075100
-100
-80
-60
29Si
(ppm
)
{29Si}27Al
SiO2
C(A)S
Network TopologyPhase separation Local structures
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 82
Accounts Chem. Res. 46 1975–1984 (2013)
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 83
James Keeler – University of Cambridgehttp://www-keeler.ch.cam.ac.uk/lectures/
Malcom Levitt – University of Southamptonhttp://www.spindynamica.soton.ac.uk/author/mhl/
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 84
http://www.tgir-rmn.org/
Dmfit~8700 reg. users~2500 citations
Googledmfit nmr
© Dominique Massiot – USTV-ESRF school - IV School How to assess the structure of glasses ? – Grenoble Nov. 2019 85
AcknowledgementsFranceF. BabonneauC. SanchezCh. Bonhomme…D. NeuvilleCh. Le LosqL. CormierB. AlonsoF. TaulelleB. BujoliB. BureauT. Charpentier
Germany U. Scheler
JapanS. SukenagaK. KanehashiN. SaitoK. Nakashima
OrléansC.BessadaF. FayonM. AllixP. FlorianM. DeschampsV. MontouilloutN. PellerinE. VéronS. CadarsV. Sarou-KanianJ. HietS. ChenuL. MartelS. AlahrachéM. YonR. ShakhovoyA. NovikovCh. Martineau
UKR.K. HarrisJ.R. YatesN. GreavesM. SmithR. DupreeI. Farnan
Denmark T. Vosegaard
USAP.J. GrandinettiZ. GanB.F. ChmelkaR.J. Messinger
Australia T. Bastow
Spain M. Alba J Sanz Dmfit~8700 reg. users~2500 citations
Bruker : D. Muller, H. Forster, S. Steurnagel, M. Ziliox, S. Wegner et al.
LyonGrenoble
LilleOrléans
BordeauxParis
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