Thermally-induced Transformation Research Articles

Multidimensional thermally-induced transformation of nest-structured complex Au-Fe nanoalloys towards equilibrium

Bimetallic nanoparticles are often superior candidates for a wide range of technological and biomedical applications owing to their enhanced catalytic, optical, and magnetic properties, which are often better than their monometallic counterparts. Most of their properties strongly depend on their chemical composition, crystallographic structure, and phase distribution. However, little is known of how their crystal structure, on the nanoscale, transforms over time at elevated temperatures, even though this knowledge is highly relevant in case nanoparticles are used in, e.g., high-temperature catalysis. Au-Fe is a promising bimetallic system where the low-cost and magnetic Fe is combined with catalytically active and plasmonic Au. Here, we report on the in situ temporal evolution of the crystalline ordering in Au-Fe nanoparticles, obtained from a modern laser ablation in liquids synthesis. Our in-depth analysis, complemented by dedicated atomistic simulations, includes a detailed structural characterization by X-ray diffraction and transmission electron microscopy as well as atom probe tomography to reveal elemental distributions down to a single atom resolution. We show that the Au-Fe nanoparticles initially exhibit highly complex internal nested nanostructures with a wide range of compositions, phase distributions, and size-depended microstrains. The elevated temperature induces a diffusion-controlled recrystallization and phase merging, resulting in the formation of a single face-centered-cubic ultrastructure in contact with a body-centered cubic phase, which demonstrates the metastability of these structures. Uncovering these unique nanostructures with nested features could be highly attractive from a fundamental viewpoint as they could give further insights into the nanoparticle formation mechanism under non-equilibrium conditions. Furthermore, the in situ evaluation of the crystal structure changes upon heating is potentially relevant for high-temperature process utilization of bimetallic nanoparticles, e.g., during catalysis.

Superelasticity of micropillar of single crystalline Fe3Pt

Mechanical behaviors of partly ordered (S~0.75) single crystalline Fe-25Pt (at%) micropillars were studied by compressive tests in the [001] direction. The pillar with the diameter of 400 nm exhibited recoverable strain of ~10.8% at room temperature. The recoverable strain is most likely caused by the stress-induced martensitic transformation from the face-centered-cubic (FCC) phase to the body-centered-tetragonal (BCT) phase although the thermally-induced transformation to the BCT phase does not occur down to 4.2 K. In this alloy superelasticity occurs in a wide temperature window of more than 200 K.

Inner tube growth and electronic properties of metallicity-sorted nickelocene-filled semiconducting single-walled carbon nanotubes

In the present work, we have obtained metallicity-sorted nickelocene-filled semiconducting single-walled carbon nanotubes (SWCNTs) by density gradient separation of metallicity mixed filled nanotubes. Double-walled carbon nanotubes (DWCNTs) were obtained by annealing of filled SWCNTs in vacuum. The diameter distribution of inner tubes was analyzed by multifrequency Raman spectroscopy. The chemical transformation of nickelocene upon annealing was studied by X-ray photoelectron spectroscopy (XPS) at the Ni 2p core level. The thermally-induced transformation of nickelocene to nickel carbides and metallic nickel was revealed. The electronic properties of the filled SWCNTs and DWCNTs were investigated by XPS at the C 1s core level. By tracing the C 1s binding energy, it was shown that the annealing of nickelocene-filled SWCNTs at low temperatures (360–600 °C) led to electron doping of SWCNTs, whereas annealing at high temperatures and formation of DWCNTs (680–1200 °C) resulted in hole doping of nanotubes.

Monitoring real time polymorphic transformation of sulfanilamide by diffuse reflectance visible spectroscopy

This study investigated the development of a novel approach to surface characterization of drug polymorphism and the extension of the capabilities of this method to perform ‘real time’ in situ measurements. This was achieved using diffuse reflectance visible (DRV) spectroscopy and dye deposition, using the pH sensitive dye, thymol blue (TB). Two polymorphs, SFN-β and SFN-γ, of the drug substance sulfanilamide (SFN) were examined. The interaction of adsorbed dye with polymorphs showed different behavior, and thus reported different DRV spectra. Consideration of the acid/base properties of the morphological forms of the drug molecule provided a rationalization of the mechanism of differential coloration by indicator dyes. The kinetics of the polymorphic transformation of SFN polymorphs was monitored using treatment with TB dye and DRV spectroscopy. The thermally-induced transformation fitted a first-order solid-state kinetic model (R2=0.992), giving a rate constant of 2.43×10−2s−1.

(C5H14N2) [Zn3(HPO4)4], a New 3D Open‐Framework Zincophosphate Synthesized by Hydrothermal Reversible Transformation of (C5H14N2) [Zn2(HPO4)3]×H2O.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Phase Transformation of Hexacelsians Doped with Li, Na and Ca

A series of hexacelsians with different compositions were synthesized by thermally induced transformation of a LTA zeolite. Various forms of hexacelsians have been characterized by XRPD, IR, Raman and 29Si MAS NMR method. The phase transformation ab hexacelsian was investigated by DSC method. This phase transformation is sensitive to synthesis conditions, doping and thermal treatment. The peak maximum temperature, Tm, varies from 302 up to 353 oC. Heat of transformation changes from 0.42 to 1.77 kJ/mol.

Thermal effects on an enzymatically latent conformation of coagulation factor VIIa.

Activation of the zymogen factor VII yields an enzyme form, factor VIIa, with only modest activity. The thermal effect on this low activity of factor VIIa and its enhancement by the cofactor tissue factor was investigated. Factor VIIa activity measured with a chromogenic peptide substrate is characterized by an unusual temperature dependency which indicates that the activated protease exists in an equilibrium between a latent (enzymatically inactive) and an active conformation. As shown by calorimetry and activity measurements the thermal effects on factor VIIa are fully reversible below the denaturation temperature of 58.1 degrees C. A model for factor VIIa has been proposed [Higashi, S., Nishimura, H., Aita, K. & Iwanaga, S. (1994) J. Biol. Chem. 269, 18891-18898] in which the protease is supposed to exist primarily as a latent enzyme form because of the poor incorporation into the protease structure of the N-terminal Ile153 released by proteolytic cleavage during activation of factor VII. Binding of tissue factor to factor VIIa is assumed to shift the equilibrium towards an active conformation in which the N-terminal Ile153 forms a salt bridge with Asp343. We corroborate the validity of this model by: (a) chemical modification of factor VIIa; this suggests that the thermal effect on the equilibrium between the active and inactive conformation is reflected in the relative accessibility of the active site and the N-terminal Ile153; (b) measurements of factor VIIa binding to tissue factor indicating that complex formation is favoured by stabilization of the active conformation; and (c) activity measurements of a cross-linked factor VIIa-tissue factor complex; this showed that cross-linking stabilized the active conformation of factor VIIa and essentially prevented its thermally-induced transformation into the inactive state.

Some Observetions Concerning the Growth Kinetics of Biotite During the Thermally-Induced Transformation of White Mica (Phengite) in the Contact Aureole of the Traversella Intrusion (N-Italy)

Some Observetions Concerning the Growth Kinetics of Biotite During the Thermally-Induced Transformation of White Mica (Phengite) in the Contact Aureole of the Traversella Intrusion (N-Italy)