Maths Karlsson

Liquid 1-propanol studied by neutron scattering, near-infrared, and dielectric spectroscopy

Liquid monohydroxy alcohols exhibit unusual dynamics related to their hydrogen bonding induced structures. The connection between structure and dynamics is studied for liquid 1-propanol using quasi-elastic neutron scattering, combining time-of-flight and neutron spin-echo techniques, with a focus on the dynamics at length scales corresponding to the main peak and the pre-peak of the structure factor. At the main peak, the structural relaxation times are probed. These correspond well to mechanical relaxation times calculated from literature data. At the pre-peak, corresponding to length scales related to H-bonded structures, the relaxation times are almost an order of magnitude longer. According to previous work [C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E. Rössler, and R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)] this time scale difference is connected to the average size of H-bonded clusters. The relation between the relaxation times from neutron scattering and those determined from dielectric spectroscopy is discussed on the basis of broad-band permittivity data of 1-propanol. Moreover, in 1-propanol the dielectric relaxation strength as well as the near-infrared absorbance reveal anomalous behavior below ambient temperature. A corresponding feature could not be found in the polyalcohols propylene glycol and glycerol.

Inorganic Phosphor Materials for Lighting

This chapter addresses the development of inorganic phosphor materials capable of converting the near UV or blue radiation emitted by a light emitting diode to visible radiation that can be suitably combined to yield white light. These materials are at the core of the new generation of solid-state lighting devices that are emerging as a crucial clean and energy saving technology. The chapter introduces the problem of white light generation using inorganic phosphors and the structure–property relationships in the broad class of phosphor materials, normally containing lanthanide or transition metal ions as dopants. Radiative and non-radiative relaxation mechanisms are briefly described. Phosphors emitting light of different colors (yellow, blue, green, and red) are described and reviewed, classifying them in different chemical families of the host (silicates, phosphates, aluminates, borates, and non-oxide hosts). This research field has grown rapidly and is still growing, but the discovery of new phosphor materials with optimized properties (in terms of emission efficiency, chemical and thermal stability, color, purity, and cost of fabrication) would still be of the utmost importance.

Perspectives of neutron scattering on proton conducting oxides

Understanding the fundamental properties of materials of relevance for alternative energy technologies is crucial in addressing the global challenge of cleaner sources of energy. This Perspective article aims to demonstrate the important role that neutron scattering now plays in advancing the state of the art of the basic understanding of proton conducting oxides, which show potential as electrolytes in next-generation intermediate temperature fuel cells. In particular, the breadth of neutron scattering work on perovskite structured oxides, which continue to be the most promising class of electrolytes for intermediate-temperature applications, is reviewed. Key fundamental properties that are addressed include structures, proton sites, hydrogen-bonding interactions, proton dynamics, and concentration of protons in materials. Furthermore, the perspectives for future neutron studies within this field of research are discussed.

Proton dynamics in oxides: insight into the mechanics of proton conduction from quasielastic neutron scattering

This article is concerned with the use of quasielastic neutron scattering as a technique for investigation of the dynamical properties of proton conducting oxides. Currently, the main interest in these materials comes from their promise as electrolytes in future electrochemical devices and particularly through their use as electrolytes in next-generation, intermediate-temperature, fuel cells. However, the realization of such devices depends critically on the development of new, more highly proton conducting oxides. Such a development depends on increasing the current understanding of proton conduction in oxides and for this purpose quasielastic neutron scattering is an important mean. The aim of this article is to introduce the non-specialist reader to the basic principles of quasielastic neutron scattering, its advantages and disadvantages, to summarize the work that has been done on proton conducting oxides using this technique, as well as to discuss future opportunities within this field of research.

Proton conduction in Perovskite Oxide BaZr0.5Yb0.5O3-δ Prepared by Wet Chemical Route

A wet chemical route has been used to synthesize the oxygen deficient perovskite BaZr 0.5 Yb 0.5 O 3-δ . Analysis of X-ray powder diffraction data showed that both dried and hydrated samples adopt cubic crystal structures of space group Pm3m. Dynamic thermogravimetric analysis showed a significant mass loss for the hydrated sample compared to the dried sample, indicating that ∼28% of the oxygen vacancies are filled by protonic defects. The strong O-H stretch band, 2500-3500 cm -1 , in the IR absorbance spectrum also clearly manifests the presence of significant levels of protons in the hydrated material. Proton conductivity was investigated on prehydrated (under dry Ar) and as-prepared (under wet Ar) samples. The heating cycle of the prehydrated sample showed higher proton conductivity compared to the cooling cycle, especially in the intermediate temperature range (150-550°C). Finally, comparison with data for BaZr 0.9 Yb 0.1 O 3-δ revealed that the more heavily doped sample showed higher proton conductivity compared to the more lightly doped sample.

Proton Conduction in Perovskite Oxide BaZr0.5Yb0.5O3 − δ Prepared by Wet Chemical Synthesis Route

A wet chemical route has been used to synthesize the oxygen deficient perovskite BaZr 0.5 Yb 0.5 O 3-δ . Analysis of X-ray powder diffraction data showed that both dried and hydrated samples adopt cubic crystal structures of space group Pm3m. Dynamic thermogravimetric analysis showed a significant mass loss for the hydrated sample compared to the dried sample, indicating that ∼28% of the oxygen vacancies are filled by protonic defects. The strong O-H stretch band, 2500-3500 cm -1 , in the IR absorbance spectrum also clearly manifests the presence of significant levels of protons in the hydrated material. Proton conductivity was investigated on prehydrated (under dry Ar) and as-prepared (under wet Ar) samples. The heating cycle of the prehydrated sample showed higher proton conductivity compared to the cooling cycle, especially in the intermediate temperature range (150-550°C). Finally, comparison with data for BaZr 0.9 Yb 0.1 O 3-δ revealed that the more heavily doped sample showed higher proton conductivity compared to the more lightly doped sample.

Structural and vibrational properties of silyl (SiH3(-)) anions in KSiH3 and RbSiH3: new insight into Si-H interactions.

The alkali metal silyl hydrides ASiH3 (A = K, Rb) and their deuteride analogues were prepared from the Zintl phases ASi. The crystal structures of ASiH3 consist of metal cations and pyramidal SiH3(-) ions. At room temperature SiH3(-) moieties are randomly oriented (α modifications). At temperatures below 200 K ASiH3 exist as ordered low-temperature (β) modifications. Structural and vibrational properties of SiH3(-) in ASiH3 were characterized by a combination of neutron total scattering experiments, infrared and Raman spectroscopy, as well as density functional theory calculations. In disordered α-ASiH3 SiH3(-) ions relate closely to freely rotating moieties with C3v symmetry (Si-H bond length = 1.52 Å; H-Si-H angle 92.2 °). Observed stretches and bends are at 1909/1903 cm(-1) (ν1, A1), 1883/1872 cm(-1) (ν3, E), 988/986 cm(-1) (ν4, E), and 897/894 cm(-1) (ν2, A1) for A = K/Rb. In ordered β-ASiH3 silyl anions are slightly distorted with respect to their ideal C3v symmetry. Compared to α-ASiH3 the molar volume is by about 15% smaller and the Si-H stretching force constant is reduced by 4%. These peculiarities are attributed to reorientational dynamics of SiH3(-) anions in α-ASiH3. Si-H stretching force constants for SiH3(-) moieties in various environments fall in a range from 1.9 to 2.05 N cm(-1). These values are considerably smaller compared to silane, SiH4 (2.77 N cm(-1)). The reason for the drastic reduction of bond strength in SiH3(-) remains to be explored.

Polarized neutron Laue diffraction on a crystal containing dynamically polarized proton spins

A polarized neutron Laue diffraction experiment on a single crystal of neodymium-doped lanthanum magnesium nitrate hydrate containing polarized proton spins is reported. By using dynamic nuclear polarization to polarize the proton spins, it is demonstrated that the intensities of the Bragg peaks can be enhanced or diminished significantly, whilst the incoherent background, due to proton spin disorder, is reduced. It follows that the method offers unique possibilities to tune continuously the contrast of the Bragg reflections and thereby represents a new tool for increasing substantially the signal-to-noise ratio in neutron diffraction patterns of hydrogenous matter.

Structure of glassy lithium sulfate films sputtered in nitrogen: Insight from Raman spectroscopy and ab initio calculations

Raman spectra of thin solid electrolyte films obtained by sputtering a

Neutron Scattering of Proton-Conducting Ceramics

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