Investigate the capability of INAA absolute method to determine the concentrations of 238U and 232Th in rock samples

This work aimed to study the capability of INAA absolute method in determining the elemental concentration of ²³⁸U and ²³²Th in the rock samples. The INAA absolute method was implemented in PUSPATI TRIGA Mark II research reactor, Malaysian Nuclear Agency (NM). The accuracy of INAA absolute method was performed by analyzing the IAEA certified reference material (CRM) Soil-7. The analytical results showed the deviations between experimental and certified values were mostly less than 10 % with Z-score in most cases less than 1. In general, the results of analysed CRM Soil-7 show a good agreement between certified and experimental results which mean that the INAA absolute method can be used accurately for elemental analysis of uranium and thorium in various types of samples. The concentration of ²³⁸U and ²³²Th ranged from 1.77 to 24.25 and 0.88 to 95.50 ppm respectively. The highest value of ²³⁸U and ²³²Th was recorded for granite rock sample G17 of ²³⁸U and sample G9 of ²³²Th, whereas the lower value was 1.77 ppm of ²³⁸U recorded in sandstone rock and 0.88 ppm of ²³²Th for gabbro. Moreover, a comparison of the ²³⁸U and ²³²Th results obtained by the INAA absolute method shows an acceptable level of consistency with those obtained by the INAA relative method.     

Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. ³¹P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.     

A Rechargeable Hydrogen Battery Based on Ru Catalysis

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H₂ battery which is based on the principle of the Ru‐catalyzed hydrogenation of CO₂ to formic acid (charging process) and the Ru‐catalyzed decomposition of formic acid to CO₂ and H₂ (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure‐free conditions (discharging process). Up to five charging–discharging cycles were performed without decrease of storage capacity. The resulting CO₂/H₂ mixture is free of CO and can be employed directly in fuel‐cell technology.     

Synthesis of Soluble,Alkyne‐Substituted Trideca‐ and Hexadeca‐Starphenes

Two literature‐known TIPS‐ethynyl‐dibromoacenes were prepared and employed to synthesize cyclotrimers by using Yamamoto coupling conditions. Two large, well‐soluble starphenes were isolated in good yields. Crystallographic characterization verifies the triangular shape and shows significant differences in crystal packing.     

Highly Tin‐Selective Stille Coupling: Synthesis of a Polymer Containing a Stannole in the Main Chain

The incorporation of heavier Group 14 element heteroles into semiconducting polymers leads to unusual optoelectronic properties. However, polymers containing stannoles have not been accessible to date. We report a synthetic route to a well‐defined, stannole‐containing polymer, the first example of this class of π‐conjugated polymers. This route was made possible by developing difunctionalized stannole monomers and highly tin‐selective Stille coupling reactions that leave the tin in the stannole untouched. Compared to poly(3‐n‐hexylthiophene), the resulting polymer displays a remarkable bathochromic shift in its absorption.     

GC–MS with photoionization of cold molecules in supersonic molecular beams—Approaching the softest ionization method

A new type of photoionization ion source was developed for the ionization of cold molecules in supersonic molecular beams (named Cold PI). The system was based on a GC–MS with supersonic molecular beams and its fly‐through EI of cold molecules ion source (Cold EI) plus quadrupole mass analyzer. A continuously operated deuterium VUV photoionization lamp was added and placed above and between the supersonic nozzle and skimmer whereas the Cold EI ion source served only as a portion of the ion transfer ion optics. The supersonic nozzle and skimmer were voltage biased and the VUV light crossed the supersonic expansion about 10 mm from the nozzle. We obtained over three orders of magnitude enhancement in the relative abundance of the molecular ion of squalane in Cold PI versus in photoionization of this compound as a thermal compound. Accordingly, we also proved that standard photoionization is not as soft ionization method as previously perceived for large compounds. We found that Cold PI is as soft as and possibly softer than field ionization; thus, it could be the softest known ionization method. The ionization yield was about 200–300 times weaker than with Cold EI yet our limit of detection was about 200 femtogram in SIM mode for cholesterol and pyrene which is reasonable. Practically, all hydrocarbons gave only molecular ions with rather uniform response whereas alcohols gave some molecular ions plus major fragment ions particularly with a loss of water (similarly to field ionization). We tested Cold PI in the GC–MS analysis of diesel fuels and analyzed the time averaged data for group type information. We also found that we can analyze the diesel fuels by fast under 20‐s flow injection analysis in which the generated averaged mass spectrum of molecular ions only could serve for the characterization of fuels.     

Beitrag zur Züchtung von ZnSiP2 unter nichtstöchiometrischen Bedingungen aus der Gasphase in Auswertung mikroanalytischer Untersuchungen

Röntgenographically identified single-phase ZnSiP₂ of stoichiometric composition which has been grown in gas phase has a specific resistance of > 10³ Ωcm and locally limited luminescence spectra. The presence of foreign phases and inhomogeneities as well as stoichiometric deviations in the ZnSiP₂ are possible causes of these physical properties. An attempt was made to grow, in the gas phase, ZnSiP₂ containing foreign phases. For this purpose, synthesis and crystallization of ZnSiP₂ were carried out using non-stoichiometric proportions of silicon. The phase composition of the crystals was investigated by means of light microscopy and electron-beam microanalysis. In the case of hypostoichiometric silicon amounts (–50 mole% Si) the ZnSiP₂ matrix contains the binary phases ZnP₂ and Zn₃P₂. Under hyperstoichiometric conditions (> 100 mole% Si) ZnS₁₃P₂ layers are deposited on the ZnSiP₂. Distinct differences between the physical properties of stoichiometric single-phase ZnSiP₂ and ZnSiP₂ containing foreign phases could not be detected.