NDLI: Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions

Content Provider	Springer Nature Link
Author	Schmid Beurmann, Peter Ottolini, Luisa Hatert, Frédéric Geisler, Thorsten Huyskens, Magdalena Kahlenberg, Volker
Copyright Year	2012
Abstract	The topotactic oxidation and delithiation reaction from triphylite, Li(Fe,Mn)PO4, leading to ferrisicklerite, Li<1(Fe3+,Mn2+)PO4, was investigated under hydrothermal conditions. A cuboid cut from a triphylite single-crystal (Palermo Mine, New Hampshire, USA) with the composition Li0.93(3)(Fe2+ 0.733(6),Fe3+ 0.015(1),Mn2+ 0.210(4),Mg0.063(2))1.021(8)P1.00(2)O4 in addition with ground bulk material were treated with KMnO4 and 30 % H2O2(aq) as oxidizing agent in a 0.1 N hydrochloric acid solution in the temperature range between 60 and 200 °C. At 120 °C a rim of 0.1 mm thickness of ferrisicklerite had formed around the core of unreacted triphylite. The sharp reaction boundary was clearly visible, due to the reddish brown absorption colors of ferrisicklerite, compared to colorless triphylite. Using single-crystal X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron probe micro-analysis (EPMA) and 57Fe-Mössbauer spectroscopy the product ferrisicklerite was characterized and its composition determined as Li0.30(7)(Fe2+ 0.049(1)Fe3+ 0.65(2)Mn2+ 0.218(5)Mg0.062(2))0.98(1)P1.01(3)O4, with unit cell parameters a = 4.795(1), b = 9.992(4), and c = 5.886(2) Å. EPMA investigations across the reaction boundary showed no changes in the concentrations of Fe, Mn, Mg, and P. In contrast, SIMS measurements clearly proved the delithiated state of the ferrisicklerite product. Polarization microscopy revealed that the orientation of the ferrisicklerite rim was the same as that of the original triphylite single-crystal, confirming the strictly topotactic character of the reaction.
Starting Page	501
Ending Page	515
Page Count	15
File Format	PDF
ISSN	09300708
Journal	Mineralogy and Petrology
Volume Number	107
Issue Number	4
e-ISSN	14381168
Language	English
Publisher	Springer Vienna
Publisher Date	2012-12-01
Publisher Place	Vienna
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Mineralogy Inorganic Chemistry Geochemistry
Content Type	Text
Resource Type	Article
Subject	Geophysics Geochemistry and Petrology

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