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From Prussian blue to iron carbides: high-temperature XRD monitoring of thermal transformation under inert gases

Published online by Cambridge University Press:  08 May 2017

Claudia Aparicio ,
Jan Filip  and
Libor Machala
Claudia Aparicio*
Affiliation:
Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University, Šlechtitelů 27, 783 71 Olomouc, Czech Republic
Jan Filip
Affiliation:
Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University, Šlechtitelů 27, 783 71 Olomouc, Czech Republic
Libor Machala
Affiliation:
Regional Centre of Advanced Technologies and Materials, Faculty of Science, Palacký University, Šlechtitelů 27, 783 71 Olomouc, Czech Republic
*
a)Author to whom correspondence should be addressed. Electronic mail: [email protected]
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Abstract

The thermal behavior and decomposition reaction of Prussian blue (PB) (Fe43+[Fe2+(CN)6]3·xH2O) was studied under inert atmosphere of argon by simultaneous thermogravimetry and differential scanning calorimetry, from room temperature up to 900 °C, with a heating rate of 5 K min−1. Parallel to the thermogravimetric measurements, the thermal process was monitored by in situ X-ray powder diffraction (XRD) technique under nitrogen atmosphere. The thermogravimetric data show six steps, corresponding to different stages of the decomposition reaction; comparable results are also obtained by in situ XRD. In addition, a set of PB samples heated up to selected temperatures (190, 300, 370, 540, 680, and 790 °C) were ex situ analyzed by powder XRD and Mössbauer spectroscopy. It is found that PB exhibits a negative thermal expansion prior to the water release from its crystalline lattice. Above 300 °C, the decomposition is based on the release of cyanogen gas from the PB structure. At 370 °C, a cubic iron cyanide compound is formed, while at higher temperatures several iron carbides were found. The subsequent thermal treatment of these carbides leads to the formation of metallic iron and graphite.

Keywords

solid-state thermal decompositionPrussian blueiron carbides
Type
Technical Articles
Information
Powder Diffraction , Volume 32 , Supplement S1 , September 2017 , pp. S207 - S212
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Copyright
Copyright © International Centre for Diffraction Data 2017 

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