the structure of glass - lectures 12 and 13: nuclear magnetic
TRANSCRIPT
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The Structure of Glass - Lecture 13: Nuclear Magnetic Resonance Spectroscopy
of Glass Structure: Practice and Application of Dipolar Nuclei
Be able to predict alkali silicate glass structures from 29Si MASS-NMR spectra Be able to predict alkali phosphate glass structure from 31P MASS NMR Spectra Be able to use 29Si MASS NMR spectra to examine the glass structure of mixed glass former M2O + B2O3+SiO2
Be able to use 31P MASS NMR spectra to examine the glass structure of mixed glass former M2O +SiO2+ P2O5 Be able to use 29Si MASS NMR spectra to examine the glass structure of M2O + Al2O3+SiO2
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 2
Application to Alkali Silicate Minerals - 29Si MASS NMR
29Si MASS NMR, spin ½, 4.5 % atomic abundance, 8.467 MHz/T
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 3
Quiz…
For the different Q groups in M2O + SiO2 Write out the Chemical formula Draw out the chemical structure Calculate the mole fraction of M2O Calculate the fraction of bridging and non-bridging
oxygens
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 4
Alkali Silicate Phase Diagram Compounds are formed at
stoichiometric ratios of M2O to SiO2
Disilicate is M2O + 2SiO2 Metasilicate is M2O + SiO2 Orthosilicate is 2M2O + SiO2 From composition, write out
SRS for each phase From Zacharaisen's Rules,
which do you expect to be glass forming, which do you expect not to be?
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 5
Alkali Silicate Glasses Reflect Local SRS Units Pure SiO2 is made of SiO4/2 units
Q4 units with all “bridging” oxygens Na2O + 2SiO2 is made of NaOSiO3/2 units
Q3 units with one “non-bridging” and three bridging oxygens Na2O + SiO2 is made of (NaO)2SiO2/2
Q2 units with two non-bridging and two bridging oxygens 3Na2O +2SiO2 is made of (NaO)3SiO1/2 units
Q1 units with three non-bridging oxygens and one bridging oxygens
2Na2O + SiO2 is made of (NaO)4Si units Q0 units with four non-bridging and no bridging oxygens
Alkaline earth silicates (MO + SiO2) behave similarly
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 6
“Qi” Units in Alkali Silicate Glasses
Q4
Q0 Q1
Q2 Q3
O
Si
Na+
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 7
Calculating the Fraction of Non-Bridging Oxygens
Modifier M2O or MO creates two NBOs per M2O or MO added
xNa2O + (1-x)SiO2 creates 2x NBOs fNBO = NBOs/(NBOs + BOs)
= 2x/(x + 2(1-x)) = 2x/(2-x)
fBO = 1- fNBO
Calculate knob & fBO for all the alkali silicate phases
Q4 Q4 Q3 Q3
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 8
Qi Unit Structures in Alkali Silicate Glasses Mixture of Q4 and Q3
sites Can you determine the
fraction of Q4 and Q3 units in this structure?
Can you determine the fraction of NBOs and BOs in this structure?
Can you determine the alkali modifier oxide concentration?
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 9
Qi sites and NBO/BO ratios are related Q4 unit, all O are
BO Q0 unit, all O are
NBO 2Q4 + M2O >> 2 Q3 2Q3 + M2O >> 2 Q2 …. 2Q1 + M2O >> 2 Q0
0 0.25 0.50 0.75 1.0 0
1.0
xM2O
Q4
Q3
Q2 Q1
Q0
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 10
29Si MASS NMR of Simple Alkali Silicates
Li2O + 2SiO2
Li2O + SiO2
2Li2O + SiO2
2Li2O + 3SiO2
Q4 Q3 Q2 Q1 Q0
Less shielded
More shielded
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 11
Amorphous versus Crystalline Silicates
Li2O + 2 SiO2 = Li2SiO3
Q2
2Li2O + 3SiO2 =Li2SiO3 +
Li2Si2O5 = Q2 + Q1
Amorphous
Crystalline
Amorphous
Crystalline
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 12
“Simple” silicate crystals
Ca2Mg2[Si4O11]2(OH)2
Synthetic Ca3Si2O7
-O-Si-O- +Ca+ -O-Si-O-
O- -O +Ca+
O- -O +Ca+
Can you sketch this structure?
How many predicted Si sites?
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 13
29Si MASS of 3CaO + SiO2, Ca3SiO5
Can you predict this structure?
Crystalline compound possess multiple chemical sites, each with their unique chemical shift
Chemical shift difference is greater than dipolar broadening, “spun down”
So that individual sites can be observed
Note long relaxation time of 29Si required 12 hour accumulation!
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 14
29 Si MASS NMR of Crystalline Silicates
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 15
29Si MASS NMR Chemical Shifts for Silicates
SiO4/2
Si(MO)4
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 16
29Si MASS NMR of Aluminosilicate Zeolites
Less alkali, mostly Al and Si
Single Si site
Two Si sites
More alkali, more Si sites
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 17
Affect of Si/Al ratio
Few Si Sites Multiple Si Sites Few Si Sites
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 18
Typical Aluminosilicate Zeolite Structure
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 19
Affect of Al coordination upon 29Si MASS shift
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 20
29Si MASS NMR of Glasses – Amorphous Materials
PPM scale in terms of glass chemistry
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 21
29 Si MASS NMR of Silicate Glasses
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 22
Speciation of Silicate Groups in Silicate Glasses
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 23
31P MASS NMR Na2O + P2O5
xM2O + (1-x)P2O5
x = 0, P2O5
P O
O O O
O
P O
O O O
Na+ P O
O O O
Na+
Na+
P O
O O O
Na+
Na+ Na+
P3
P0 x =?
P1 x =?
P2 x=?
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 24
31P MASS NMR
15Li2O + 85P2O5
35Li2O + 65P2O5
55Li2O + 45P2O5
*
* * * *
* * *
* * *
* * Spinning side bands
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 25
Site specific 31P MASS 2D NMR
15Li2O + 85P2O5 35Li2O + 65P2O5
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 26
Site specific 31P MASS 2D NMR 55Li2O + 45P2O5
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 27
Composition dependence of Phosphate groups
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 28
29Si MASS NMR of Potassium borosilicate glasses
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 29
29Si MASS NMR of Potassium borosilicates
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 30
Chemical Shift for different B/Si ratios
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 31
Chemical Shift versus added O/Si ratio
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 32
Chemical Shift versus calculated chemical shift
ALL added K2O is equally shared between B2O3 and SiO2 from 0K2O
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 33
Na2O + P2O5 + SiO2 Glasses Two NMR active
nuclei add to the level of structural analysis
Site specific information around Si and P nuclei
Combine this information to determine complete structure of the glass
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 34
29MASS NMR of Na2O + Al2O3 + SiO2 Glasses
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Ternary Na2O + Al2O3 + SiO2 System
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 36
Composition dependence of Chemical Shift
Na2O + Al2O3 + SiO2 Glasses
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SWMartin ISU Lecture 13 NMR Spectroscopy of Glass Structure: Dipolar Nuclei 37
Composition dependence of Q fractions