Extended theoretical analysis of crystallisation kinetics being studied by in situ XRD

ABSTRACT

Theoretical simulations were used to study the consequences of simplifying the replacement of the step-wise in situ X-ray diffraction (XRD) temperature programme by simple linear heating (at corresponding effective heating rate) during the kinetic calculations based on the multivariate kinetic analysis. The simulations were performed for a large variety of step-wise non-isothermal in situ XRD temperature programmes, covering most practically used combinations of the temperature step magnitude ΔT, rate of heating, and duration of the isothermal hold Δt. To achieve the universal interpretation of the obtained results, the behaviour of the majority of crystallisation processes with commonly encountered kinetic profiles was explored: simulations were performed for single-process transformations with highly negative, symmetric and highly positive asymmetries; complex multi-process reactions with different degrees of sub-process overlaps and variable activation energy were analysed. It was found that the asymmetry and shape of the crystallisation peaks do not significantly influence the level of distortion of kinetic parameters. The main factors that increase the errors of in situ XRD kinetic evaluations are high Δt, high ΔT and high activation energy (with the latter two being most important). Findings were discussed for the accuracy of the corresponding kinetic predictions. Generalisation of the present conclusions towards their universal utilisation for optimisation of in situ XRD experiments was suggested.     

NaCl-H2O和NaCl-KCl-H2O溶液低温相变过程的原位XRD研究

应用原位X射线衍射法对盐湖卤水体系的两个子体系--NaCl-H₂O和NaCl-KCl-H₂O溶液在低温条件下进行扫描,获得了实验条件下体系的衍射图谱,得到了溶液低温相变过程的信息。图谱解析结果表明：含NaCl 26.25%的溶液在-20~-25℃范围内析出了冰、NaCl、低水合氯化钠和二水氯化钠,含NaCl 25.70%的溶液没有发生相变;对于NaCl-KCl-H₂O体系,含NaCl 20.03%和KCl 10.19%的溶液在0~-25 ℃范围内析出了氯化钾和氯化钠,含NaCl 22.40%和KCl 7.28%的溶液在-10~-25 ℃范围内只有氯化钾析出,含NaCl 21.90%和KCl 6.46%的溶液没有发生相变。实验结果显示：这两个水盐体系低温相变过程析出盐的种类与相图结果有差异,原因在于两者的状态不同;体系中二水氯化钠的析出需要经过氯化钠与水的化合过程,该过程是分步进行的;实验体系在低温条件下发生相变受结晶因素控制,温度只是其中一个因素,体系相变发生与否是结晶因素综合影响的结果。     

Initial oxidation kinetics and energetics of Cu0.5Au0.5 (0 0 1) film investigated by in situ ultrahigh vacuum transmission electron microscopy

The initial oxidation behavior of Cu_0.5Au_0.5 (0 0 1) thin film was investigated by in situ ultrahigh vacuum transmission electron microscopy to model nano-oxidation of alloys with one active component and one noble component. The formation of irregular-shaped octahedron Cu₂O islands with cube-on-cube crystallographic orientation to the substrate film was observed at all temperature studied. The energetics of Cu₂O nucleation for Cu and Cu_0.5Au_0.5 oxidation was compared. Cu_0.5Au_0.5 oxidation has lower nucleation activation energy due to the reduced mismatch strain between Cu₂O and Cu_0.5Au_0.5 films. On the other hand, the reaction kinetics for Cu_0.5Au_0.5 alloy oxidation is slower due to the higher diffusion activation energy of Cu.     

Synthesis of nanocrystalline Zn0.5Mn0.5Fe2O4 via in situ polymerization technique

Nanocrystalline Zn_0.5Mn_0.5Fe₂O₄ was synthesized through the pyrolysis of polyacrylate salt precursors prepared via in situ polymerization of the metal salts and acrylic acid. The pyrolysis behavior of the polymeric precursors was studied by use of thermal analysis. The as-obtained product was characterized by powder X-ray diffraction (XRD), transmission electron microscope (TEM), electron diffraction (ED) pattern, scanning electron microscopy (SEM) and electron dispersive X-ray (EDX) analysis. The results revealed that the particle size is in the range of 15–25 nm for Zn-Mn ferrites with good crystallinity. Magnetic properties of the sample at 300 K were measured using a vibrating sample magnetometer, which showed that the sample exhibited characteristics of superparamagnetism.     

In‐situ and laboratory Raman analysis in the field of cultural heritage: the case of a mural painting

The present work exemplifies, over a mural painting from the 14th century, the advantages of an initial exhaustive research using latest generation hand‐held spectrometers (Raman mainly) in order to perform the characterization of valuable objects of cultural heritage. These in‐situ techniques (meaning on‐site and non‐destructive) are very useful to study the pigments and materials, to identify the nature and causes of some of the main sources of deterioration and to examine past repaints. In addition, the in‐situ measurements are of great importance in the selection of micro‐samples for the laboratory analyses. In this particular case, the combination of these results with the chemical imaging analyses in the laboratory (such as Raman and energy dispersive X‐ray spectrometry imaging) allowed the characterization of the mural painting, including, the identification of all restoration works applied in the past. Copyright © 2014 John Wiley & Sons, Ltd.