Solid-State Nuclear Magnetic Resonance of glasses: from ... · Solid-State Nuclear Magnetic Resonance of glasses: from basics to more advanced concepts Dominique Massiot, ... Structure

© 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

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http://www.cemhti.cnrs-orleans.fr/?nom=massiot


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Geometrical & Chemical Order

Chemical order / Geometrical disorder Geometrical order / Chemical disorder


Geometrical & Chemical Order

Chemical order / Geometrical disorder Geometrical order / Chemical disorder


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


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


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


Glass3D interconnected network

Intrinsincally Disordered ProteinIDPs

Structure & functions... Proteins / Glasses


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


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


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


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)


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)


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

https://www.youtube.com/watch?v=7aRKAXD4dAg


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)


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


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


Spin Echo – signal can be refocused

E.L. Hahn, Phys. Rev., 80, 580 (1950)

The spectroscopist isan actor of the experiment


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


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


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!" = $ %" + ' ()


The Discovery of Chemical Shift

Phys. Rev., 77, 716 (1950) Phys. Rev., 77, 736 (1950)


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


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)


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


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


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


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


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


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

http://dx.doi.org/10.1016/S1293-2558(00)01133-X


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


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


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


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


© 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


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


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


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 ?


CaO-SiO2-P2O5


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



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 !!



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


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


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


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



(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


2D NMR

J. Chem. Phys., 64, 2229 (1974)

In « NMR and More », M. Goldman et M. Porneuf Eds (1994)


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


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


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


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

http://dx.doi.org/10.1021/jp100530m


(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


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


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


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


{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


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



4Si


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



4Si


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


CaAlLaY Glass


4Si


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


chemistry

CaAlLaY Glass


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


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


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)


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 >-<


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


27Al in A9B2 (Al18B4O33) 750 MHz

(Hz)-450000-300000-1500000150000300000450000

Satellite transitions Satellite transitions

Central transition27Al in A9B2

750 MHz - 15 kHz


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


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


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


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)

http://dx.doi.org/10.1016/j.chemgeo.2006.01.019

http://dx.doi.org/10.1016/j.gca.2004.05.048


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


“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


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


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


Si-SiAl2Si-Al3

Si-SiAl2


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



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



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


CaO-Al2O3-SiO2 – the 17O viewpoint

36.5 CaO – 51 SiO2 – 12.5 Al2O3

Lee et al., Geochim. Cosmochim. Acta 70 4275-4286 (2006)


17O frequency (ppm)050100150200

17O single resonance

SiObAl

{27Al} 17O INEPT

* *

SiOnbCa

SiObAl:Ca

SiObSi

SiOnb

(Si,Al)Ob(Si,Al)


CaO-Al2O3-SiO2 + Na2O – the 17O viewpoint


10.8 Na2O – 31.9 CaO – 44.7 SiO2 – 12.6 Al2O3


SiOnb(Ca,Na)8.8%

SiObAl:Ca

SiObSi

SiObAl:Na23.2%

SiOnbCa


{27Al} 17O INEPT

SiObAl:Ca(from CAS)

SiObAl:Na

{23Na} 17O INEPT SiObAl:Na

SiOnb(Ca,Na)

SiOnb

(Si,Al)Ob(Si,Al)



SiObAl

{27Al} 17O INEPT

* *

SiOnbCa

SiObAl:Ca

SiObSi

SiOnb

(Si,Al)Ob(Si,Al)

36.5 CaO – 51 SiO2 – 12.5 Al2O3


Separation, Simplification… and gains

27Al (ppm)-250255075100

-100

-80

-60

29Si

(ppm

)

{29Si}27Al

SiO2

C(A)S

Network TopologyPhase separation Local structures


Accounts Chem. Res. 46 1975–1984 (2013)

http://dx.doi.org/10.1021/ar3003255


James Keeler – University of Cambridgehttp://www-keeler.ch.cam.ac.uk/lectures/

Malcom Levitt – University of Southamptonhttp://www.spindynamica.soton.ac.uk/author/mhl/

http://www-keeler.ch.cam.ac.uk/lectures/

http://www.spindynamica.soton.ac.uk/author/mhl/


http://www.tgir-rmn.org/

Dmfit~8700 reg. users~2500 citations

Googledmfit nmr

http://www.tgir-rmn.org/


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

Gif sur Yvette

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