Magnetic Nanoparticles with Fe-N and Fe-C Cores and Carbon Shells Synthesized at High Pressures.

Nanoparticles of iron carbides and nitrides enclosed in graphite shells were obtained at 2 ÷ 8 GPa pressures and temperatures of around 800 °C from ferrocene and ferrocene-melamine mixture. The average core-shell particle size was below 60 nm. The graphite-like shells over the iron nitride cores were built of concentric graphene layers packed in a rhombohedral shape. It was found that at a pressure of 4 GPa and temperature of 800 °C, the stability of the nanoscale phases increases in a Fe7C3 > Fe3C > Fe3N1+x sequence and at 8 GPa in a Fe3C > Fe7C3 > Fe3N1+x sequence. At pressures of 2 ÷ 8 GPa and temperatures up to 1600 °C, iron nitride Fe3N1+x is more stable than iron carbides. At 8 GPa and 1600 °C, the average particle size of iron nitride increased to 0.5 ÷ 1 µm, while simultaneously formed free carbon particles had the shape of graphite discs with a size of 1 ÷ 2 µm. Structural refinement of the iron nitride using the Rietveld method gave the best result for the space group P6322. The refined composition of the samples obtained from a mixture of ferrocene and melamine at 8 GPa/800 °C corresponded to Fe3N1.208, and at 8 GPa/1650 °C to Fe3N1.259. The iron nitride core-shell nanoparticles exhibited magnetic behavior. Specific magnetization at 7.5 kOe of pure Fe3N1.208 was estimated to be 70 emu/g. Compared to other methods, the high-pressure method allows easy synthesis of the iron nitride cores inside pure carbon shells and control of the particle size. And in general, pressure is a good tool for modifying the phase and chemical composition of the iron-containing cores.

Diamond Composites Produced from Fluorinated Mixtures of Micron-Sized and Nanodiamonds by Metal Infiltration.

Improving the operating performance of superhard composites is an important and urgent task, due to a continuing industrial need. In this work, diamond composites with high wear resistance were obtained by sintering fluorinated mixtures of micron-sized diamonds with nanodiamonds at high pressures and temperatures (7-8 GPa, 1550-1700 °C). Aluminum and cobalt powders were added to the diamond mixture to activate the process. The external infiltration of nickel into the diamond layer was carried out additionally during the sintering process, and the effects of nickel infiltration on the structure and properties of composites were studied. The metal melt ensured the mass transfer of carbon within a volume, and the formation of a strong diamond framework. The composition of the additives was selected in such a way that the binding phase became ultimately composed of the intermetallic AlNixCo1-x(x ≤ 1). The Young's modulus of composites synthesized in this way had a value of 850 GPa, and their wear resistance when turning white granite was more than twice as high as that of premium commercial PDC. The obtained results thus demonstrate that by using nickel to increase melt infiltration into diamond-based composites, the mechanical properties of Al/Co/fluorinated diamond compositions, studied previously, can be further improved.

WB5- x : Synthesis, Properties, and Crystal Structure-New Insights into the Long-Debated Compound.

The recent theoretical prediction of a new compound, WB5, has spurred the interest in tungsten borides and their possible implementation in industry. In this research, the experimental synthesis and structural description of a boron-rich tungsten boride and measurements of its mechanical properties are performed. The ab initio calculations of the structural energies corresponding to different local structures make it possible to formulate the rules determining the likely local motifs in the disordered versions of the WB5 structure, all of which involve boron deficit. The generated disordered WB4.18 and WB4.86 models both perfectly match the experimental data, but the former is the most energetically preferable. The precise crystal structure, elastic constants, hardness, and fracture toughness of this phase are calculated, and these results agree with the experimental findings. Because of the compositional and structural similarity with predicted WB5, this phase is denoted as WB5- x . Previously incorrectly referred to as "WB4," it is distinct from earlier theoretically suggested WB4, a phase with a different crystal structure that has not yet been synthesized and is predicted to be thermodynamically stable at pressures above 1 GPa. Mild synthesis conditions (enabling a scalable synthesis) and excellent mechanical properties make WB5- x a very promising material for drilling technology.

High-pressure high-temperature synthesis and structure of α-tetragonal boron.

Microcrystals of α-tetragonal (α-t) boron with unit cell parameters a=9.05077(6) and c=5.13409(6) Å and measured density 2.16-2.22 g cm-3 were obtained by pyrolysis of decaborane B10H14 at pressures of 8-9 GPa and temperatures of 1100-1600 ○C. The crystal structure is in good agreement with the model proposed by Hoard et al (1958 J. Am. Chem. Soc.80 4507). However, compared to the original model, we found small deformations of icosahedra and changes in the interatomic distances within the unit cell of the synthesized α-t boron.