Thermal behavior and decomposition of cerium(III) butanoate, pentanoate and hexanoate salts upon heating in argon

The thermal behavior and decomposition of Ce-butanoate monohydrate (Ce(C3H7CO2)3·H2O), Ce-pentanoate (Ce(C4H9CO2)3) and Ce-hexanoate (Ce(C5H11CO2)3) were studied in a flow of argon while heating at 5 °C/min. By means of several techniques such as simultaneous TG-DTA, FTIR evolved gas analysis, in-situ x-ray diffraction using a synchrotron source and hot-stage microscopy, it was found that all three compounds undergo melting transitions prior to decomposition and that decomposition involves intermediate stages including at least a Ce2O(CnH2n+1CO2)4 intermediate (n = 3, 4 or 5 for Ce-butanoate, pentanoate or hexanoate respectively). The final decomposition product consists of CeO2, which is formed through a Ce-oxycarbonate. The Ce3+ → Ce4+ oxidation seems to proceed via Ce2O3 that first results from the decomposition of the oxycarbonate phase. During the whole decomposition process, the evolved gas species consist of CO2 and symmetrical ketones

Soft magnetic amorphous alloys in X-ray light: Insights from ultra-fast Joule heating experiments

In this contribution a novel setup for studying rapid crystallization of metallic glasses using a time resolved in situ X-ray diffraction combined with a direct current fast Joule heating (flash-annealing) is presented. The setup was implemented and successfully tested at the P02.1 beamline of the PETRA III storage ring (DESY Hamburg, Germany). Its potential use is demonstrated by studying rapid crystallization of soft magnetic Fe$_{73.5}$Cu$_1$Nb$_3$Si$_{15.5}$B$_7$ (at.%) metallic glass prepared by melt spinning technique. Flash-annealing experiment is realized by bursting 20 rectangular current pulses with a fixed amplitude of 1.5 A and pulse length $\delta$ is varied (30, 40 and 50 ms). A single pulse with duration of 30 ms causes temperature to rise to 770 °C with an average heating rate of 4200 K/s. Phase composition of crystallized material consist of major Fe$_3$Si phase and small traces of boride phase Fe$_{23}$B$_6$. Consecutive pulses result in cyclic thermal expansion of a crystal lattice, which appears fully reversible. Increasing pulse width to 50 ms causes temperature to increase up to 1020 °C with an average heating rate of 5600 K/s. Differentiation of the temperature profile yields exceptionally high value of heating rate 10800 ± 2400 K/s

Influence of the critical Fe atomic volume on the magnetism of Fe-rich metallic glasses evidenced by pressure-dependent measurements

Despite the intensive studies for decades, it is still not well understood how qualitatively different magnetic behaviors can occur in a narrow composition range for the Fe-rich Fe-transition metal (TM) amorphous alloys. In this study of amorphous Fe$_{100−x}$Zr$_x$ (x=7, 9, 12) metallic glasses, normal ferromagnetism (FM) is found at 12 % Zr where only the FM-paramagnetic (PM) transition is observed at the Curie temperature, T$_C$. In contrast, spin-glass (SG)-PM transition at a temperature, T$_g$, called SG temperature, is only observed at 7 % Zr, while in the transient re-entrant composition range (x=8−11), an SG-FM transition at a temperature, T$_f$, called spin-freezing temperature, is also observed at low temperature besides the normal FM-PM transition at T$_C$. In order to understand this unusual behavior, a detailed characterization of pressure (atomic volume), composition, and temperature dependence of the magnetic properties is coupled with high pressure synchrotron x-ray diffraction determination of the pressure dependence of the atomic volume. The results on Fe$_{100−x}$Zr$_x$(x=7, 9, 12) are compared to those obtained for the FM Co$_{91}$Zr$_9$ metallic glass not showing any kind of anomalous magnetic properties. It is confirmed that the unusual behavior is caused by a granularlike magnetic structure where weakly coupled magnetic clusters are embedded into a FM bulk matrix. Since the mechanism of the magnetization reversal was found to be of the curling type rather than homogeneous rotation, the energy barrier determining the blocking temperature of the clusters is calculated as AR, where A is the exchange constant and R is the cluster size, in contrast to the usual characterization of the energy barrier by KV where K is the anisotropy energy and V is the cluster volume. The volume fraction of the FM part is a fast changing function of the bulk composition: Almost 100% FM fraction is found at 12 % of Zr while no trace of real FM is observed at 7 at % Zr. The driving force of this surprising magnetic character is the atomic volume: The lower the Zr content, the higher is the fraction of Fe atoms with compressed atomic volume having low magnetic moment. The percolation of their network separates the clusters from the FM bulk. The complex magnetic behavior of the Fe-rich Fe-Zr amorphous system at low temperatures can thus be interpreted with the only assumption of a cluster-size distribution and a weak coupling of the clusters to the FM matrix. The introduction of this coupling is able to explain the opposite pressure dependence of T$_g$ and T$_f$. The threshold atomic volume in the low magnetic moment regions is found to be comparable to the atomic volume characteristic to the low-spin limit of the face-centered-cubic Fe alloys. The extensive literature results on the anomalous magnetism for various Fe-rich Fe-TM amorphous alloys and especially for the Fe-rich Fe-Zr glassy system are also found to be in agreement with this granular magnetic behavior

Magnetic Properties of Crystalline NiFe Alloy Prepared by High-Energy Ball Milling and Compacting

The structure and magnetic properties of compacted microcrystalline NiFe (81 wt% of Ni) powder is investigated. The powder of NiFe alloy prepared by ball milling of ribbon (prepared by melt spinning) remains single phase material suitable for compaction in order to prepare soft magnetic material. The bulk samples were consolidated by uniaxial compaction of the powder in vacuum. By measuring of AC and DC magnetic properties it was found out that in bulk samples the displacement of domain walls is the dominant magnetization process, while rotation of magnetization vectors prevails in powder material

Isobaric Thermal Expansion and Isothermal Compression of Powdered NiFe Based Alloys Studied by In-Situ EDXRD

The aim of the present work was to study the isothermal compression and isobaric thermal expansion behaviour of ball-milled NiFe (81 wt.% of Ni) and NiFeMo (79 wt.% of Ni, 16 wt.% of Fe) alloy and follow its phase evolution when exposed to high pressure and temperature. In-situ pressure-temperature energy dispersive X-ray (EDXRD) diffraction experiments were performed at the MAX80 instrument (beamline F2.1). The compressibility of NiFe alloy at 400 °C was evaluated for pressure values of up to 3.5 GPa. The EDXRD spectra revealed the presence of cubic FeNi_{3} phase as determined from the shift of (111), (200) and (220) reflection lines in corresponding EDXRD spectra

Isobaric Thermal Expansion and Isothermal Compression of Powdered NiFe Based Alloys Studied by In-Situ EDXRD

The aim of the present work was to study the isothermal compression and isobaric thermal expansion behaviour of ball-milled NiFe (81 wt.% of Ni) and NiFeMo (79 wt.% of Ni, 16 wt.% of Fe) alloy and follow its phase evolution when exposed to high pressure and temperature. In-situ pressure-temperature energy dispersive X-ray (EDXRD) diffraction experiments were performed at the MAX80 instrument (beamline F2.1). The compressibility of NiFe alloy at 400 °C was evaluated for pressure values of up to 3.5 GPa. The EDXRD spectra revealed the presence of cubic FeNi_{3} phase as determined from the shift of (111), (200) and (220) reflection lines in corresponding EDXRD spectra

Magnetic Properties of Crystalline NiFe Alloy Prepared by High-Energy Ball Milling and Compacting

The structure and magnetic properties of compacted microcrystalline NiFe (81 wt% of Ni) powder is investigated. The powder of NiFe alloy prepared by ball milling of ribbon (prepared by melt spinning) remains single phase material suitable for compaction in order to prepare soft magnetic material. The bulk samples were consolidated by uniaxial compaction of the powder in vacuum. By measuring of AC and DC magnetic properties it was found out that in bulk samples the displacement of domain walls is the dominant magnetization process, while rotation of magnetization vectors prevails in powder material

Structure and Magnetic Properties of Three-Dimensional Gadolinium-Based Hybrid Framework

In the present work we have focused on the preparation and magnetic study of coordination polymer formed by Gd(III) cations as nodes and formate (HCOO¯; FOR) anions as charge compensating linkers. The prepared complex with formula ${[Gd(μ_{3}-FOR)_{3}]}_{n}$ was characterized by single-crystal X-ray diffraction, and high-energy powder X-ray diffraction. The structural study showed that complex is formed by 3D polymeric network with the shortest Gd-Gd, distances of 3.998 Å. The magnetic properties of the complex were studied by magnetic susceptibility $χ_{M}(T)$ and magnetization M(H) measurements. The results show on the weak antiferromagnetic coupling at low temperatures represented by the Weiss constant θ=-0.468 K. The value of effective magnetic moment $μ_{eff}=7.57μ_{B}$, which was estimated from the experimental data is close to the theoretical value for systems with S=7/2. Correlation between crystal structure of complexes and magnetic properties is presented

Correlation between atomic structure evolution and strength in a bulk metallic glass at cryogenic temperature

A model Zr41.25Ti13.75Ni10Cu12.5Be22.5 (at.%) bulk metallic glass (BMG) is selected to explore the structural evolution on the atomic scale with decreasing temperature down to cryogenic level using high energy X-ray synchrotron radiation. We discover a close correlation between the atomic structure evolution and the strength of the BMG and find out that the activation energy increment of the concordantly atomic shifting at lower temperature is the main factor influencing the strength. Our results might provide a fundamental understanding of the atomic-scale structure evolution and may bridge the gap between the atomic-scale physics and the macro-scale fracture strength for BMGs