Status and progress of ion-implanted βNMR at TRIUMF

Beta-detected NMR is a type of nuclear magnetic resonance that uses the asymmetric property of radioactive beta decay to provide a “nuclear” detection scheme. It is vastly more sensitive than conventional NMR on a per nuclear spin basis but requires a suitable radioisotope. I briefly present the general aspects of the method and its implementation at TRIUMF, where ion implantation of the NMR radioisotope is used to study a variety of samples including crystalline solids and thin films, and more recently, soft matter and even room temperature ionic liquids. Finally, I review the progress of the TRIUMF βNMR program in the period 2015–2021.

Predicting conductivities of alkali borophosphate glasses based on site energy distributions derived from network former unit concentrations

For ion transport in network glasses, it is a great challenge to predict conductivities specifically based on structural properties. To this end it is necessary to gain an understanding of the energy landscape where the thermally activated hopping motion of the ions takes place. For alkali borophosphate glasses, a statistical mechanical approach was suggested to predict essential characteristics of the distribution of energies at the residence sites of the mobile alkali ions. The corresponding distribution of site energies was derived from the chemical units forming the glassy network. A hopping model based on the site energy landscape allowed to model the change of conductivity activation energies with the borate to phosphate mixing ratio. Here we refine and extend this general approach to cope with minimal local activation barriers and to calculate dc-conductivities without the need of performing extensive Monte-Carlo simulations. This calculation relies on the mapping of the many-body ion dynamics onto a network of local conductances derived from the elementary jump rates of the mobile ions. Application of the theoretical modelling to three series of alkali borophosphate glasses with the compositions 0.33Li2O–0.67[xB2O3–(1 − x)P2O5], 0.35Na2O–0.65[xB2O3–(1 − x)P2O5] and 0.4Na2O–0.6[xB2O3–(1 − x)P2O5] shows good agreement with experimental data.

Site preferences and ion dynamics in lithium chalcohalide solid solutions with argyrodite structure: II. Multinuclear solid state NMR of the systems Li6PS5−x Se x Cl and Li6PS5−x Se x Br

A comprehensive multinuclear (7Li, 31P, 35Cl, 77Se, 79Br) nuclear magnetic resonance (NMR) study has been conducted to characterize local structural configurations and atomic distributions in the crystallographically disordered solid solutions of composition Li6PS5−x Se x X (0 ≤ x ≤ 1, X = Cl, Br) with the Argyrodite structure. In contrast to the situation with the corresponding iodide homologs, there is no structural ordering between the 4a and 4c sites, with the halide ions occupying both of them with close to statistical probabilities. Nevertheless, throughout the composition range, the 16e Wyckoff sites of the Argyrodite structure are exclusively occupied by the chalcogen atoms, forming PY4 3− (Y = S, Se) tetrahedra, indicating the absence of P-halogen bonds. 31P magic-angle spinning (MAS)-NMR can serve to differentiate between the various possible PS4−n Se n 3− tetrahedral units in a quantitative fashion. Compared to the case of the anion-ordered Li6PS5−x Se x I solid solutions, the preference of P–S over P–Se bonding is significantly stronger, but it is weaker than in the halide free solid solutions Li7PS6−x Se x . Each individual PS4−n Se n 3− tetrahedron is represented by a peak cluster of up to five resonances, representing the five different configurations in which the PY4 3− ions are surrounded by the four closest chalcogenide and halide anions occupying the 4c sites; this distribution is close to statistical and can be used to deduce deviations of sample compositions from ideal stoichiometry. Non-linear 7Li chemical shift trends as a function of x are interpreted to indicate that the Coulombic traps created by sulfur-rich PS4−n Se n 3− ions (n ≤ 2) within the energy landscape of the lithium ions are deeper than those of the other anionic species present (i.e., selenium-richer PY4 3− tetrahedra, isolated chalcogenide or iodide ions), causing the Li+ ions to spend on average more time near them. Temperature dependent static 7Li NMR linewidths indicate higher mobility in the present systems than in the previously studied Li6PS5−x Se x I solid solutions. Unlike the situation in Li6PS5−x Se x I no rate distinction between intra-cage and inter-cage ionic motion is evident. Lithium ionic mobility increases with increasing selenium content. This effect can be attributed to the influences of higher anionic polarizability and a widening of the lithium ion migration pathways caused by lattice expansion. The results offer interesting new insights into the structure/ionic mobility correlations in this new class of compounds.

Back to the roots: the concepts of force and energy

The concepts of force and energy are analyzed in the context of state and process equations. In chronological order, the application of the cause-effect principle in process equations is studied in mechanics, thermodynamics, special relativity, general relativity, and quantum theory. The differences in the fundamental approaches to nature and the significance of a consistent physical interpretation of formulas and state variables are emphasized. It is shown that the first origins for the crisis of modern theoretical physics are to be found in the concepts of force and energy in mechanics, which partly violate the cause-effect principle. This affects all theories based on mechanics and underlines their historical conditionality. The systematic application of driving forces and the cause-effect principle in process equations suggests a return to causal realistic physics. It meets the wave character of matter, is compatible with the experiment, and allows a unified description of interaction.

X-ray photoemission studies of the interaction of metals and metal ions with DNA

X-ray Photoelectron Spectroscopy (XPS) has been used to study the interactions of heavy metal ions with DNA with some success. Surface sensitivity and selectivity of XPS are advantageous for identifying and characterizing the chemical and elemental structure of the DNA to metal interaction. This review summarizes the status of what amounts to a large part of the photoemission investigations of biomolecule interactions with metals and offers insight into the mechanism for heavy metal-bio interface interactions. Specifically, it is seen that metal interaction with DNA results in conformational changes in the DNA structure.

Impacts of polyols and temperature on the micellization, interaction and thermodynamics behavior of the mixture of tetradecyltrimethylammonium bromide and polyvinyl alcohol

Herein, the aggregation manner of the mixture of polyvinyl alcohol (PVA) and tetradecyltrimethylammonium bromide (TTAB) was performed in polyols (glucose, maltose and galactose) media over 300.55–320.55 K temperatures range with 5 K interval through conductivity measurement method. The micelle formation of TTAB + PVA mixture was identified by the assessment of critical micelle concentration (CMC) from the plots of specific conductivity (κ) versus TTAB concentration. The degree of micelle ionization (α), the extent of bound counter ions (β) as well as thermodynamic properties ( Δ G m 0 ${\Delta}{G}_{m}^{0}$ , Δ H m 0 ${\Delta}{H}_{m}^{0}$ and Δ S m 0 ${\Delta}{S}_{m}^{0}$ ) of TTAB + PVA systems have been estimated. The CMC values reveal that the micelle formation of TTAB + PVA mixture experience an enhancement in the manifestation of polyols. The values of free energy of micellization ( Δ G m 0 ${\Delta}{G}_{m}^{0}$ ) are negative for the TTAB + PVA system in aqueous polyols media, suggesting a spontaneous aggregation phenomenon. The Δ H m 0 ${\Delta}{H}_{m}^{0}$ and Δ S m 0 ${\Delta}{S}_{m}^{0}$ values of TTAB + PVA systems direct that the PVA molecule interacts with TTAB through the exothermic, ion-dipole, and hydrophobic interactions. The thermodynamic properties of transfer were also determined for the move of TTAB + PVA mixture from H2O to water + polyols mixed solvents. The values of compensation temperature (T c) and intrinsic enthalpy gain ( Δ H m 0 , ∗ ${\Delta}{H}_{m}^{0,\ast }$ ) were evaluated and discussed for the studied system.

Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study

The chemical expansion of Pr0.1Ce0.9O2–δ (PCO) and CeO2–δ thin films is investigated in the temperature range between 600 °C and 800 °C by laser Doppler vibrometry (LDV). It enables non-contact determination of nanometer scale changes in film thickness at high temperatures. The present study is the first systematic and detailed investigation of chemical expansion of doped and undoped ceria thin films at temperatures above 650 °C. The thin films were deposited on yttria stabilized zirconia substrates (YSZ), operated as an electrochemical oxygen pump, to periodically adjust the oxygen activity in the films, leading to reversible expansion and contraction of the film. This further leads to stresses in the underlying YSZ substrates, accompanied by bending of the overall devices. Film thickness changes and sample bending are found to reach up to 10 and several hundred nanometers, respectively, at excitation frequencies from 0.1 to 10 Hz and applied voltages from 0–0.75 V for PCO and 0–1 V for ceria. At low frequencies, equilibrium conditions are approached. As a consequence maximum thin-film expansion of PCO is expected due to full reduction of the Pr ions. The lower detection limit for displacements is found to be in the subnanometer range. At 800 °C and an excitation frequency of 1 Hz, the LDV shows a remarkable resolution of 0.3 nm which allows, for example, the characterization of materials with small levels of expansion, such as undoped ceria at high oxygen partial pressure. As the correlation between film expansion and sample bending is obtained through this study, a dimensional change of a free body consisting of the same material can be calculated using the high resolution characteristics of this system. A minimum detectable dimensional change of 5 pm is estimated even under challenging high-temperature conditions at 800 °C opening up opportunities to investigate electro-chemo-mechanical phenomena heretofore impossible to investigate. The expansion data are correlated with previous results on the oxygen nonstoichiometry of PCO thin films, and a defect model for bulk ceria solid solutions is adopted to calculate the cation and anion radii changes in the constrained films during chemical expansion. The constrained films exhibit anisotropic volume expansion with displacements perpendicular to the substrate plane nearly double that of bulk samples. The PCO films used here generate high total displacements of several 100 nm’s with high reproducibility. Consequently, PCO films are identified to be a potential core component of high-temperature actuators. They benefit not only from high displacements at temperatures where most piezoelectric materials no longer operate while exhibiting, low voltage operation and low energy consumption.

How the cation size impacts on the relaxational and diffusional dynamics of supercooled butylammonium-based ionic liquids: DPEBA–TFSI versus BTMA–TFSI

Li-bis(trifluoromethylsulfonyl)imide based ionic liquids with either butyl-trimethylammonium or N,N-dimethyl-N-(2-(propionyloxy)-ethyl)butan-1-ammonium as the anion were studied using proton and fluorine relaxometry as well as using field-gradient diffusometry to gain separate access to cation and anion dynamics in these compounds. The transport parameters obtained for these ionic liquids are compared with the estimates based on the conductivity data from literature and from the present work. The impact of cation size on correlation effects, the latter parameterized in terms of various Haven ratios, is mapped out.