Raman spectroscopy of silicate glasses and melts in geological...
Transcript of Raman spectroscopy of silicate glasses and melts in geological...
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Raman spectroscopyof silicate glasses and melts
in geological systemsStéphanie Rossano & Bjorn Mysen
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Lava flow (Hawaï)
Melting of crystallinematerials
1100°C
≈ 30°C
Fast cooling (quench)to avoid
crystallization
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Glass/melt science : the scientific issues
Geological interest Information on the Earth historyFormer historyMelt differentiationDynamic behaviourEarth evolution
Build / constrain / complete geochemical models
Stromboli (july 1999) Cré
dit p
hoto
@ S
. Ros
sano
Moldavite (15 Ma) Cré
dit p
hoto
@ S
. Ros
sano
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viscosity, colouration,nucleation, … can bemodulated by a change :• in composition• in thermal treatment
Link composition / thermal historyto physico-chemical properties
Glass/melt science : the scientific issues
Technological interest
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Crédit photo @ S. Rossano
Glass/melt science : the scientific issues
Cultural heritage interest
Understand alteration processesForesee glass durability
PhD J. Sterpenich (1998)
condensation
Meteoric water
Les-Noës-Près-Troyes (Aube)
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Flow of asbestos« lava »
Flow of nuclear waste« lava »
Glass/melt science : the scientific issues
Environmental interest
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Slow coolingRapid cooling
Liquidstable
Glassout of equilibrium
Supercooledliquidmetastable
Crystalstable
mMelting temperatureGlass transition
temperature
Glass vs crystal ?
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Glass vs crystal ?
Crystalline CaFeSi2O6Fe, Ca, Si, O
Glass of hedenbergitecompositionFe, Ca, O, Si
No periodicityNo more special atomic planes / directions
Increase of « disorder »
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Qn species
Q4
Q2
QnTetrahedralentities centredon Si4+ or Al3+
Number of bridgingoxygens
Distribution of environments
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Na2O-4SiO2 (classical MD)
Na, Si, O
Bridging O
Nonbridging O
Glass structure
Q2
Chargecompensationneeded for the
NBO
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• competition betweencations• Distribution ofcationic environments
FeCaOSiNaAl
Tektite (Classical MD snapshot)
Complex compositions
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FeCaOSiNaAl
Tektite (Classical MD snapshot)
Probing glass structureLocal order
Selective techniques 57Fe Mössbauer,
XAS,NMR…
Raman spectroscopy
• Species• Connectivity of the
glass network
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1st order Raman spectrum +Al3+-O + P4+-O + Fe3+-O…
Qn
vibrationsVolatile vibrations CO2,CO, CH4, H2, H2O, N, S…
200 420028001300600
Alkaline earth - OAlkaline - OO - transition metal
800
Regions of interest
Network connectivity
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Pre-treatment steps
Modified from Malfait & Halter (2008)
• Comparison between a seriesof spectra
• Extraction of quantitativeinformation
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Pre-treatment steps
Baseline determination / substraction
• Spectrometer dependent
Modified from Malfait & Halter (2008) 200 400 600 800 1000 1200
K2O-MgO-2SiO
2
Raman shift, cm-1
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• Spectrometer dependent• Fluorescence signal
Pre-treatment steps
Baseline determination / substraction
Modified from Malfait & Halter (2008)
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• Spectrometer dependent• Fluorescence signal• Glass composition
Mercier et al. (2009)
Pre-treatment steps
Baseline determination / substraction
Modified from Malfait & Halter (2008)
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Pre-treatment stepsT / ν correction
Modified from Malfait & Halter (2008) Hass, 1970
€
Icor = Imeasω
(ω0 −ω)4 (1− e
−hvω /kT )
Corrections necessary at high T or low frequency region
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Pre-treatment steps
Daniel et al. 1995
CaAl2Si2O8 @2009 K
(1) Exp. spectrum
(2) Measured Thermalemission (laser off)
(1) - (2)
€
Icor = Imeasω
(ω0 −ω)4 (1− e
−hvω /kT )
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Daniel et al. 1995
CaAl2Si2O8
Liq.
SupercooledLiq.
Glass
-
T
T0
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Na2TiSi2O7
Reynard & Webb 1998
The Long formula does notcorrect for T dependence ofsd order Raman scattering
€
I (2) (ω) =Icorr (T )− Icorr (T0 )
n T − n T0
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€
Icorr (T )− I(2) (ω)
€
Icorr (T )
€
I (2) (ω)
Daniel et al. 1995
Minimize misinterpretations
Changes observed are due toconfigurational changes oranharmonic effects
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Pre-treatment stepsNormalization
Modified from Malfait & Halter (2008)
Comparison of relativeintensities among spectra of asame family
• in a region with no Raman signal• to the most intense point• to the integrated Raman signal
Comparison between studiesdifficult
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Tsujimura et al., 2004
Fingerprinting
Identification of Ramanbands due to dissolved
species
1st order Raman spectrum +Al3+-O + P4+-O + Fe3+-O…
Qn
vibrationsVolatile vibrations CO2,
CO, CH4, H2, H2O, N, S…
200 420028001300600
Alkaline earth - OAlkaline - O
O - transition metal
800
Isolated SO42- S6
2- Isolated SO42-
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Quantification (external standard)
Lenoir et al., 2009
• Magmatic systems• industrial glasses : refining agent
Without refining agent2 Na2SO4 2Na2O + O2 + 2 SO2 With refining agent
Calibration lines are composition dependent
Sulfur At 1450°CA bubble of 0.1 mm140h = elevation of 1m
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Lenoir et al., 2009
Application to melts
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Fingerprinting
• Identification of pigments• Classification of samples
Tournié et al., 2011
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Fingerprinting
Brawer & White (1977)
Comparison between glass and crystal
200
400
600
800
1000
0 200 400 600 800 1000 1200
verre CaMgSi2O6cristal CaMgSi2O6
cm-1
glass & crystal of CaMgSi2O6 composition
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Statistical analysis
• Decomposition intoGaussian components• Least squares refinement• A posteriori assignment
Na2O-MgO-8SiO2
Modified from Trcera et al. (2011)
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Polymerization
Na2O-MgO-xSiO2 with 2 < x < 10
Trcera et al. (2011)
Please : verify that theenvironment around atoms donot change
Trcera (personal com.)
1290 1300 1310 1320 1330 1340 1350
NMS2 norm.NMS3NMS4NMS6NMS8NMS10
Rel
ativ
e in
tens
ity
(arb
. uni
ts)
energy (eV)
Mg K-edge
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Guide to interpret the trends Polymerization
Controversies : • Shape of the individual bands• Number of components• Assignments
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Quantification of Qn species
29Si NMR spectroscopy
Not easy for meltsFrantz & Mysen (1995)
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Statistical analysis
• Principal components analysis
• Linear combinations of partialspectra
• Optimization procedure
No need of external calibration melts
Necessity of a large number ofspectra in the same glass family
Number of independentcontributions
Internal standard for Qn
quantification
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Statistical analysisExtraction of individual signals
assigned to Qn species
Malfait et al., JNCS 353 p4029 (2007) Zotov (1999)
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Toplis & Reynard (2000)
melt dynamics0.9Na2O-0.1Al2O3-2SiO2+ 6mol% P2O5
Na3PO4 Na4P2O7
Reaction extent : A910-950/A800-1350
Phase separation
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Conclusions and perspectives
• Raman has been extensivelyused to try to get insight intoglass connectivity
• Simple experiments
• Difficulty to analyze /interpret the spectra
GLASS MELT
Zotov, 1999 ; Spiekermann, 2012
• Quite easy to perform ascompared to other techniques(such as NMR for ex.)
• Access to the dynamics /kinetics of melt transformation
• Necessity to correct for sd
order Raman effect
Calculation could help to assign the peaks