An ultra-high-entropy rare earth orthoferrite (UHE REO): solution combustion synthesis, structural features and ferrimagnetic behavior.

A novel ultra-high-entropy rare earth orthoferrite (UHE REO) of Sc1/16Y1/16La1/16Ce1/16Pr1/16Nd1/16Sm1/16Eu1/16Gd1/16Tb1/16Dy1/16Ho1/16Er1/16Tm1/16Yb1/16Lu1/16FeO3 nominal composition was successfully synthesized for the first time through a simple and efficient solution combustion approach. PXRD, Raman, and 57Fe Mössbauer spectroscopy confirmed the high chemical and phase purity of the synthesized UHE REO (hereafter denoted as ΣREFeO3), which belonged to the Pnma space group, typical of the perovskite-like rare earth orthoferrites. Despite the fact that the main X-ray reflections, vibration modes, and spectral Mössbauer components unambiguously indicate the single-phase nature of the sample, the results of SEM and TEM make it possible to establish the presence of a main (about 50 nm) and a minor ultrafine (about 10 nm) fraction of ΣREFeO3 nanoparticles. The bimodal size distribution of nanoparticles was also reflected in the magnetic behavior of this substance: the presence of several sextet components in the Mössbauer spectra, the hard single-domain magnetic nature of the main fraction of 50 nm UHE REO nanoparticles, and the superparamagnetic state of the minor fraction of 10 nm UHE REO nanoparticles. Thus, the unusual features of nanostructured ΣREFeO3 can potentially be used for the creation of new generations of transformers, magnetic memory systems, magnetic screens, radio devices, etc.

Enhanced Osseointegrative Properties of Ultra-Fine-Grained Titanium Implants Modified by Chemical Etching and Atomic Layer Deposition.

An integrated approach combining severe plastic deformation (SPD), chemical etching (CE), and atomic layer deposition (ALD) was used to produce titanium implants with enhanced osseointegration. The relationship between morphology, topography, surface composition, and bioactivity of ultra-fine-grained (UFG) titanium modified by CE and ALD was studied in detail. The topography and morphology have been studied by means of atomic force microscopy, scanning electron microscopy, and the spectral ellipsometry. The composition and structure have been determined by X-ray fluorescence analysis, X-ray diffraction, and X-ray photoelectron spectroscopy. The wettability of the surfaces was examined by the contact angle measurement. The bioactivity and biocompatibility of the samples were studied in vitro and in vivo. CE of UFG titanium in basic (NH4OH/H2O2) or acidic (H2SO4/H2O2) piranha solution significantly enhances the surface roughness and leads to microstructures, nanostructures, and hierarchical micro-/nanostructures on the surfaces. In vitro results demonstrate deterioration of adhesion, proliferation, and differentiation of MC3T3-E1 osteoblasts cell for CE samples as compared to the non-treated ones. Atomic layer deposition of crystalline titanium oxide onto the CE samples increased hydrophilicity, changed the surface composition, and enhanced significantly in vitro characteristics. In vivo experiments demonstrated non-toxicity of the implants. Etching in basic piranha solution with subsequent ALD significantly improved implant osseointegration as compared with the non-modified samples.

Modification of the Surface Topography and Composition of Ultrafine and Coarse Grained Titanium by Chemical Etching.

In this study, we present the detailed investigation of the influence of the etching medium (acidic or basic Piranha solutions) and the etching time on the morphology and surface relief of ultrafine grained (UFG) and coarse grained (CG) titanium. The surface relief and morphology have been studied by means of scanning electron microscopy (SEM), atomic force microscopy (AFM), and the spectral ellipsometry. The composition of the samples has been determined by X-ray fluorescence analysis (XRF) and X-ray Photoelectron Spectroscopy (XPS). Significant difference in the etching behavior of UFG and CG titanium has been found. UFG titanium exhibits higher etching activity independently of the etching medium. Formed structures possess higher homogeneity. The variation of the etching medium and time leads to micro-, nano-, or hierarchical micro/nanostructures on the surface. Significant difference has been found between surface composition for UFG titanium etched in basic and acidic Piranha solution. Based on the experimental data, the possible reasons and mechanisms are considered for the formation of nano- and microstructures. The prospects of etched UFG titanium as the material for implants are discussed.

Formation of Micro- and Nanostructures on the Nanotitanium Surface by Chemical Etching and Deposition of Titania Films by Atomic Layer Deposition (ALD).

In this study, an integrated approach was used for the preparation of a nanotitanium-based bioactive material. The integrated approach included three methods: severe plastic deformation (SPD), chemical etching and atomic layer deposition (ALD). For the first time, it was experimentally shown that the nature of the etching medium (acidic or basic Piranha solutions) and the etching time have a significant qualitative impact on the nanotitanium surface structure both at the nano- and microscale. The etched samples were coated with crystalline biocompatible TiO2 films with a thickness of 20 nm by Atomic Layer Deposition (ALD). Comparative study of the adhesive and spreading properties of human osteoblasts MG-63 has demonstrated that presence of nano- and microscale structures and crystalline titanium oxide on the surface of nanotitanium improve bioactive properties of the material.