*Kanzaki's Micro-Raman spectroscopy laboratory [#i794fc05]


CENTER:Micro-Raman spectroscopy @ Kanzaki's lab, IPM (as of 2017 08/13)

**Examples of obtained Raman spectra using our instrument [#d7432b0b]
-(2019 04/5) Compiled Raman spectra of tridymite modifications (MC, MX-1, PO-10). Both MC and MX-1 are synthetic, while PO-10 is from natural sample from Slovakia. MC sample actually contains a little MX-1.
-(2019 04/5) Compiled Raman spectra of tridymite modifications (MC, MX-1, PO-10). Both MC and MX-1 are synthetic, while PO-10 is from natural sample from Slovakia. MC sample actually contains a little MX-1. Note intensity difference for two PO-10, which is due to crystal orientation.
-(2019 02/22) Natural zeolites are measrured especially focused to low-frequency rgion. Most zeolites have low-frequency peaks, mostly broad. These peaks are likely due to molecular waters in the cages of the zeolite structures. 
-(2019 02/18) In-situ high-temperature Raman spectra of synthetic tridymite. The temperature-induced changes are consistent with previous study above 100 cmSUP{SIZE(9){-1}}. The spectra below 100 cmSUP{SIZE(9){-1}} are new. At room temperaute, the sample was a mixture of MX-1 and MC phases. It then transformed to OP phase, OC phase and finally HP with temperature. For most phases, we found the low-frequency peaks. Very sharp peaks are from cosmic-rays.
-(2019 02/11) Raman spectrum of natural tridymite (SiOSUB{SIZE(9){2}}). It seems this tridymite is a typical "terrestrial" type (PO phase). Synthetic tridymite generally becomes MC phase. I found a strong peak below 100 cmSUP{SIZE(9){-1}}.
-(2018 9/11) COSUB{SIZE(9){2}}-melanophlogite was heated at 600 ºC for 10 min, and then quenched (top). I found that peaks of Fermi diad in this sample were split, and even observed the split in hot bands. This is likely due to occupation of COSUB{SIZE(9){2}} in both M12 and M14 sites by heat treatment. I suppose initially M12 site was empty. In-situ high-temperature spectra are also shown during heating. Manuscript including this is under revision.
-(2018 09/11) In-situ high temperature Raman measurement of AlPOSUB{SIZE(9){4}} moganite phase. This phase has a displacive phase transition at around 420 ºC. Soft mode of this phase (triangles) was observed as expected, and disappeared at around 420 ºC. This study is already published (https://doi.org/10.2465/jmps.171219 )
-(2018 9/11) Micro Raman measurement of a sandstone from Arizona Meteor Crater. Coesite, a high-pressure phase of quartz, was detected from several spots we measured.
-(2017 08/23) In-situ high temperature Raman measurement of hexacelsian (BaAlSUB{SIZE(9){2}}SiSUB{SIZE(9){2}}OSUB{SIZE(9){8}}). At 325 ˚C, P6SUB{SIZE(9){3}}/mcm to Immm transition was detected.
-(2017 08/20) Test measurement of water (HSUB{SIZE(9){2}}O) at ambient condition.
--(2017/08/06) Below showing spectrum of coesite obtained using combination of new 488 nm Coherent laser and ONDAX filters. Low frequency region can be observed. 

*About Micro-Raman spectrometer in our lab [#ue068cd3]
-Details are given in [[manual:http://www.misasa.okayama-u.ac.jp/~masami/pdfs/raman-man3e.pdf]].
-Schematic diagram (updated) of the spectrometer is shown below. This micro-Raman spectrometer is home-build one, so it is very flexible to accommodate big samples or devices, to modify to accommodate new optic design, such as ONDAX volume filters for measurement of terahertz region.  

**Spectrometer hardware (home-build) [#jabeee25]
-Lasers available: 
--CW solid 488 nm laser: Coherent Sapphire SF, max 100 mW (new)
--CW air-cooled Ar ion laser: 488 & 514.5 nm, max 100 mW (retired)
--CW solid 785 nm laser for NIR 785nm, max 50 mW
--CW solid 532 nm laser; max 100 mW
-Imaging spectrometer: Acton Spectra_Pro 500i (f=500mm), three gratings:300, 1200, 1800/mm
-Detector: PyLoN 400BR eXcelon 1340x400 pixel, Liquid nitrogen cooled CCD detector (Princeton Instruments)
-Optical system: Mostly constructed using Thorlabs' 30 mm cage system parts.
--scattering geometry: 180˚ back scattering
--objective lenses: various magnification Mitsutoyo's very long working distance objective lenses available. Normal objective lenses are also available.
-Optical filters: 
--ONDAX's volume notch (Sureblock) filter for 488 nm, especially for terahertz region
--ONDAX's Noiseblock ASE filter for 488 nm, especially for terahertz region
--Semrock's Raman edge filters for 488, 514, 532, 632, 785 nm
--Semrock's dichroic mirrors for 488, 514, 532, 632, 785 nm 
-automation: home-made servo-motor controlled rotational ND filter, air-driven retractable half mirrors are available, and are integrated into the system.
**Spectrometer softwares [#k6049f13]
-Measurement software: Winspec/32 software (Roper)
-additional softwares: home-build Raman automation program which calls Winspec/32's functions; ruby fluorescence pressure calculation program, 2D mapping program, all written in Visual Studio.

*Applications of Micro-Raman spectroscopy [#t1073e64]
**Phase identification of natural samples [#xcbbc745]
-Raman spectroscopy is especially suitable to identify small diamond and coesite minerals in natural rocks. Automated XY stage is available for 2D mapping (but slow...).
**Phase identification of synthetic samples [#y7ec6835]
-Laser beam can be focused to about 1 micrometer in diameter, thus very small sample can be measured. Often, a phase not detected by powder X-ray diffraction is identified by micro-Raman spectroscopy, such as graphite and carbonates.
**In-situ high-temperature measurement at 1 bar [#ebe54d7b]
-Wire-heater device is available for in-situ high-temperature measurement up to 1500 ˚C (for Pt wire). A photo of wire-heater during heating is shown below.

-Example of in-situ high-temperature Raman spectra of brianite (Kanzaki, unpublished). A transition was detected between 800 and 850 ˚C, and is consistent with previous studies by XRD and DSC measurements

**In-situ high-pressure Raman measurement [#xb527ab2]
-Example of in-situ high-pressure Raman spectra of ZnSUB{SIZE(9){2}}SiOSUB{SIZE(9){4}} III phase in diamond anvil cell (DAC). Pressure-induced phase transition was observed between 5.0 and 5.5 GPa (Kanzaki 2018, accepted). This high-pressure phase can not be retrieved to ambient pressure. In-situ study is essential for such cases.

-We have an externally heated diamond anvil cell (top photo of this page). By using this cell, Raman spectrum of a sample under high-temperature and high-pressure condition can be measured. 
-Pressure measurement using ruby fluorescence method
--For in-situ high-pressure study of DAC, we need to know pressure of sample in DAC. One commonly used technique is ruby fluorescence method. Ruby has R1 fluorescence peak at around 690 nm which appears when it is irradiated by strong shorter wavelength light, such as 532 nm laser. This peak exhibits red shift with pressure, and this pressure-induced shift is well characterized. So by measuring shift of ruby R1 peak, we can estimate pressure easily. Ruby's fluorescence is much intense than Raman scattering, and can be easily measured using our micro-Raman spectrometer. Shown below are spectra of ruby fluorescence peaks (R1 and R2 double) at 1 bar (upper) and at high pressure (lower). Red shift of latter is apparent. R1 is higher intensity peak of the doublet. Center-right window over the spectra is showing my program to calculate pressure from R1 peak shift in the spectrum. The pressure of the lower spectrum was calculated as 10 GPa. Here, we are using relative wavenumber rather than wave length, because we would like to measure Raman spectra of sample just after ruby measurement in which relative wavenumber is used. 

--We use diamond's Raman peak (1332 cmSUP{SIZE(9){1}} at 1 bar) as pressure marker as well. One advantage is that it can be used at high-temperature. Ruby fluorescence quickly reduces its intensity with temperature, and can not be used at more than few hundred ˚C. For diamond Raman measurement, you can introduce small diamond crystal in the sample chamber. Much simpler way is to use central region of diamond anvil curret plane as a pressure marker, so no need to introduce diamond in the sample chamber.

*Information for users [#pe2b36d4]
-This spectrometer is available for both domestic and international cooperative research programs. Please contact to Dr. Kanzaki. 
**Manuals [#be11b396]
-Manual is available in both English and Japanese. For English manual (pdf), click [[here:http://www.misasa.okayama-u.ac.jp/~masami/pdfs/raman-man3e.pdf]].For Japanese version (PDF), click [[here:http://www.misasa.okayama-u.ac.jp/~masami/pdfs/raman-man3j.pdf]].
**Text books of Raman spectroscopy [#w21429ac]
-"Raman spectroscopy applied to Earth Sciences and cultural heritage", EMU Notes in Mineralogy vol. 12, Edited by J. Dubessy, M.-C. Caumon and F. Rull, European Mineralogical Unions, 2012.
-"Modern Raman Spectroscopy - A Practical Approach", by E. Smith and G. Dent, J Wiley&Sons, 2005 (Paperback)
-"Practical Raman Spectroscopy", D.J.Gardiner and P.R. Graves (Eds), 1989, Springer-Verlag.
-"Raman Microscopy", G. Turrell & J. Corset Eds., 1996, Academic Press.
-Also see spectroscopy issues of "Reviews of Mineralogy and Geochemistry"
**Raman spectra database [#k5262774]
-[[ENS-Lyon:http://www.ens-lyon.fr/LST/Raman/index.php]] Natural minerals
-[[University of Parma:http://www.fis.unipr.it/phevix/ramandb.php]] Minerals
-[[RRUFF database:http://rruff.info]] Minerals Raman, XRD, IR database. Also Crystalsleuth software provided from same site can be used to identify minerals from measured Raman spectra (for Windows). This program is installed in the PC in the Raman lab.
**Published papers in which this spectrometer is used [#h90b5585]
-Kanzaki, M. (2019) High-temperature Raman spectroscopic study of COSUB{SIZE(9){2}}-containing melanophlogite, J. Mineral. Petrol. Sci., 114, (accepted).
-Kanzaki, M. (2018) Pressure-induced phase transitions of ZnSUB{SIZE(9){2}}SiOSUB{SIZE(9){4}} III and IV studied by in-situ Raman spectroscopy, J. Mineral. Petrol. Sci., 113, 126-134 (https://doi.org/10.2465/jmps.180409 ).
-Kanzaki, M. (2018) Temperature-induced phase transition of AlPOSUB{SIZE(9){4}}-moganite studied by in-situ Raman spectroscopy, J. Mineral. Petrol. Sci., 113, advanced publication (https://doi.org/10.2465/jmps.171219 ).
-Kanzaki, M. and Xue, X. (2017) Protoenstatite in MgSiOSUB{SIZE(9){3}} samples prepared by conventional solid state reaction, J. Mineral. Petrol. Sci., 112, 359-364 (https://doi:10.2465/jmps.170616 ).
-Xue, X., Kanzaki, M., Turner, D. and D. Loroch (2017) Hydrogen incorporation mechanisms in forsterite: New insights from SUP{SIZE(9){1}}H and SUP{SIZE(9){29}}Si NMR spectroscopy and first-principles calculation, American Mineralogist, in Special Collection: "Water in nominally hydrous and anhydrous minerals", 102, 519-536.
-Tomioka, N., T. Okuchi, N. Purevjav, J. Abe and S. Harjo (2016) Hydrogen sites in the dense hydrous magnesium silicate phase E: a pulsed neutron powder diffraction study, Phys. Chem. Minerals, 43, 267-275. (DOI 10.1007/s00269-015-0791-4)
-Kanzaki, M., X. Xue, J. Amalberti and Q. Zhang (2012) Raman and NMR spectroscopic characterization of high-pressure K-cymrite (KAlSiSUB{SIZE(9){3}}OSUB{SIZE(9){8}}.HSUB{SIZE(9){2}}O) and its anhydrous form (kokchetavite), J. Mineral. Petrol. Sci., 107, 114-119.
-Tomioka, N., Kondo, H., Kunikata, A. and Nagai, T., Pressure-induced amorphization of albitic plagioclase in an externally heated diamond anvil cell, Geophys. Res. Lett., 37, L21301, 2010.
-Xue, X., Kanzaki, M., and Fukui, H., Unique crystal chemistry of two polymorphs of topaz-OH: a multi-nuclear NMR and Raman study. American Mineralogist, 95, 1276-1293 (2010)
-S. Zhai, M. Kanzaki, T. Katsura, E. Ito, Synthesis and characterization of strontium-calcium phosphate gamma-Ca3-xSrx(PO4)2 (0≤x≤2), Materials Chemistry and Physics, 120, 348-350, 2010.
-Malfait, W., The 4500 cm-1 infrared absorption band in hydrous aluminosilicate glasses is a combination band of the fundamental (Si,Al)-OH and O-H vibrations. Am. Min., 94, 849-852, 2009.
-N. Noguchi, K. Shinoda and K. Masuda, Quantitative analysis of binary mineral mixtures using Raman microspectroscopy: Calibration curves for silica and calcium carbonate minerals and application to an opaline silica nodule of volcanic origin, Journal of Mineralogical Petrological Sciences,104, 253-262, 2009
-B. Mysen, S. Yamashita, and N. Chertkova, Solubility and solution mechanisms of NOH volatiles in silicate melts at high pressure and temperature - amine groups and hydrogen fugacity, Geochim. Cosmochim. Acta, 93, 1760-1770, 2008.
-M. Kanzaki, Elastic wave velocities and Raman shift of MORB glasses at high pressures-Comment, Journal of Mineralogical Petrological Sciences, 103, 427-428, 2008
-S. Zhai, A. Yoneda and E. Ito, Effects of pre-heated pyrophyllite gaskets on high-pressure generation in the Kawai-type multi-anvil experiments, High Pressure Research, 28, 265-271, 2008.
-T. Ota, K. Kobayashi, T. Kunihiro and E. Nakamura, Boron cycling by subducted lithosphere; insights from diamondferous tourmaline from the Kokchetav ultrahigh-pressure metamorphic belt, Geochim. Cosmochim. Acta., 72, 3531-3541, 2008
-S. Zhai and E. Ito, Phase relations of CaAl4Si2O11 at high-pressure and high-temperature with implications for subducted continental crust into the deep mantle, Phys. Earth Planet. Int., 167, 161-167, 2008.
-X. Xue, M. Kanzaki and A. Shatskiy, Dense hydrous magnesium silicates, phase D and superhydrous B: New structural constrains from one- and two-dimensional 29Si and 1H NMR, Am. Mineral., 93, 1099-1111, 2008. 
-X. Xue and M. Kanzaki, High-Pressure delta-Al(OH)3 and delta-AlOOH Phases and Isostructural Hydroxides/Oxyhydroxides: New Structural Insights from High-Resolution 1H and 27Al NMR, Journal of Physical Chemistry B, 111, 13156-13166, 2007.
-X. Xue, M. Kanzaki, H. Fukui, E. Ito, and T. Hashimoto, Cation order and hydrogen bonding of high-pressure phases in the Al2O3-SiO2-H2O system: An NMR and Raman study, Am. Mineral., 91, 850-861, 2006
-T. Tsujimura, X. Xue, M. Kanzaki and M.J. Walter, Sulfur speciation and network structural changes in sodium silicate glasses: Constraints from NMR and Raman spectroscopy, Geochim. Cosmochim. Acta., 68, 5081-5101, 2004

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