Novel Melt‐Castable Energetic Pyrazole: A Pyrazolyl‐Furazan Framework Bearing Five Nitro Groups

Continuing advances in energetic pyrazole construction foster further its rational use. This work establishes an approach for the first synthesis of nitropyrazole that bear both furazan and trinitromethyl moieties. The approach to the installation of the C(NO₂)₃ group exploits the destructive nitration of N‐acetonyl group. The target 3‐(3,4‐dinitro‐1‐(trinitromethyl)‐1H‐pyrazol‐5‐yl)‐4‐methylfurazan ( 6 ) has promising explosive properties.     

5‐Amino‐3,4‐dinitropyrazole as a Promising Energetic Material

The nitrogen‐rich energetic compound 5‐amino‐3,4‐dinitropyrazole (5‐ADP) was investigated using complementary experimental techniques. X‐ray diffraction indicates the strong intermolecular hydrogen bonding in 5‐ADP crystals. Compound exhibits low impact sensitivity (23 J) and insensitivity to friction. The activation energy of thermolysis determined to be 230±5 kJ mol⁻¹ from DSC measurements. Accelerating rate calorimetry indicates the lower thermal stability (173 °C) of 5‐ADP than that of RDX, which is probably the main concern about using this compound. 5‐ADP also exhibits good compatibility with common energetic materials (viz. TNT, RDX, ammonium perchlorate), including an active binder. The burning rate of 5‐ADP monopropellant is higher than that of benchmark HMX, while the pressure exponent 0.51±0.04 is surprisingly low. Addition of ammonium perchlorate does not affect the pressure exponent of 5‐ADP, while the burning rate increases. The 5‐amino‐3,4‐dinitropyrazole exhibits a notable combination of combustion performance, low sensitivity, and good compatibility, which renders it as a promising energetic material.     

Bio-based poly(ethylene terephthalate) copolyesters made from cyclic monomers derived from tartaric acid

Two cyclic acetal compounds, 2,3-O-methylene L-threitol and dimethyl 2,3-O-methylene L-threarate, both coming from naturally-occurring tartaric acid, were used as comonomers to replace ethylene glycol and dimethyl terephthalate respectively, in the preparation of PET-based copolyesters by polycondensation in the melt. Synthesis results, structure and thermal properties of the two afforded copolyester series were evaluated and compared regarding composition and type of comonomer used in each case. All the copolyesters had a random microstructure and molecular weights in the 25,000–35,000 g·mol⁻¹ range. Their thermal properties varied logically with composition along each series but they significantly changed according to which acetal comonomer was used. PET copolyesters made from acetalized L-threitol displayed thermal stability and T_g comparable to PET, whereas these two properties were depressed in the copolyesters containing threarate units. Both types of copolyesters were able to crystallize for contents in tartaric acid derived units up to around 30% by adopting the crystal structure of PET. Crystallization rates and melting temperatures decreased with copolymerization in the two series but this effect was more noticeable in copolyesters made from threitol.     

Comparison of release behaviour from microcapsules and microspheres

The plasticizing effect of core oil in the polymer shell of core–shell particles, so-called microcapsules, was here examined. The study involved release measurements of 4-nitroanisole into aqueous solution from two types of microparticles. In the first study, a microcapsule with PMMA shell and hexadecane core was examined. The second type of particle was a homogeneous PMMA microsphere containing no oil. Experimental data were compared to models that describe release by a diffusion mechanism out from core–shell particles as well as homogeneous spherical particles. Results clearly show that the alkane oil has a plasticizing effect on the PMMA shell, thereby generating a faster release of 4-nitroanisole. In both types of microparticles, the diffusion coefficients of 4-nitroanisole could be determined. The findings increase our understanding of important parameters in the microcapsule design with regard to tuning the release behaviour. Using microparticles, the ambition is to prolong the protection of paint and other coatings against fouling.     

Dust dispersal and Pb enrichment at the rare-metal Orlovka-Spokoinoe mining and ore processing site: insights from REE patterns and elemental ratios

Different geological, technogenic and environmental samples from the Orlovka-Spokoinoe Ta-Nb-Sn-W mining site and ore processing complex in Eastern Transbaikalia (Russia), were analysed for Pb, Y, Zr, Hf and rare earth elements (REE) to assess the effect of dust and metal dispersal on the environment within the Orlovka-Spokoinoe mining site. Potential source material analysed included ore-bearing and barren granites, host rocks, tailing pond sediments, and ore concentrates. Lichens and birch leaves were used as receptor samples. The REE enrichment relative to chondrite, the extent of the Eu anomalies, the enrichments of heavy REE (HREE), and Zr/Hf and Yb/Y ratios suggest that tailings, barren granites, and metasedimentary host rocks are the main sources of dust in the studied mining environment. In addition, calculated lead enrichment (relative to host rocks) suggests that the environment is polluted with Pb. Our results clearly demonstrate the potential of REE patterns and elemental ratios as a reliable technique to trace dust and metals sources and dispersal within a confined mining area offering a new tool for environmental assessment studies.     

Characterization of Ni-Coated WS2 Nanotubes for Hydrodesulfurization Catalysis

A reactivity screening of new nano-hydrodesulfurization (HDS) catalysts was conducted using an ambient pressure flow reactor as well as ultra-high vacuum kinetics techniques. Thiophene was used as a probe molecule. Clean multiwall WS₂ nanotubes (INT-WS₂) as well as Ni- and Co-coated INT-WS₂ were considered. In addition, undoped MoS₂ and Re-doped nanoparticles with fullerene-like structures were studied. Commercial Ni and Co HDS catalysts from Haldor Topsoe (Denmark) as well as “nano MoS₂” from Impex Corp. (USA) were considered as reference materials. The lab-synthesized and commercial systems broke down thiophene into quite similar non-sulfur containing products, as identified by a gas chromatograph. The Ni and Co promoted catalysts showed similar thiophene conversion rates. Although the commercial catalysts had larger thiophene conversion rates than the laboratory-synthesized systems, the Re-doped nano-HDS catalyst showed quite low rates of formation of H₂S, an undesirable by-product.     

A general framework for tree-based morphology and its applications to self-dual filtering

This paper presents a tree-based framework for producing self-dual morphological operators, based on a tree-representation complete inf-semilattice (CISL). The idea is to use a self-dual tree transform to map a given image into the above CISL, perform one or more morphological operations there, and map the result back to the image domain using the inverse tree transform. We also present a particular case of this general framework, involving a new tree transform, the Extrema-Watershed Tree (EWT). The operators obtained by using the EWT in the above framework behave like classical morphological operators, but in addition are self-dual. Some application examples are provided: pre-processing for OCR and dust and scratch removal algorithms, and image denoising. We also explore first steps towards obtaining tree transforms that induce a CISL on the image domain as well.