Strontium and Copper Co-Doped Multifunctional Calcium Phosphates: Biomimetic and Antibacterial Materials for Bone Implants.

ß-tricalcium phosphate (ß-TCP) is a promising material in regenerative traumatology for the creation of bone implants. Previously, it was established that doping the structure with certain cations can reduce the growth of bacterial activity. Recently, much attention has been paid to co-doped ß-TCP, that is explained by their ability, on the one hand, to reduce cytotoxicity for cells of the human organism, on the other hand, to achieve a successful antibacterial effect. Sr, Cu-co-doped solid solutions of the composition Ca9.5-xSrxCu(PO4)7 was obtained by the method of solid-phase reactions. The Rietveld method of structural refinement revealed the presence of Sr2+ ions in four crystal sites: M1, M2, M3, and M4. The M5 site is completely occupied by Cu2+. Isomorphic substitution of Ca2+ → (Sr2+and Cu2+) expands the concentration limits of the existence of the solid solution with the ß-TCP structure. No additional phases were formed up to x = 4.5 in Ca9.5-xSrxCu(PO4)7. Biocompatibility tests were performed on cell lines of human bone marrow mesenchymal stromal cells (hMSC), human fibroblasts (MRC-5) and osteoblasts (U-2OS). It was demonstrated that cytotoxicity exhibited a concentration dependence, along with an increase in osteogenesis and cell proliferation. Ca9.5-xSrxCu(PO4)7 powders showed significant inhibitory activity against pathogenic strains Escherichia coli and Staphylococcus aureus. Piezoelectric properties of Ca9.5-xSrxCu(PO4)7 were investigated. Possible ways to achieve high piezoelectric response are discussed. The combination of bioactive properties of Ca9.5-xSrxCu(PO4)7 renders them multifunctional materials suitable for bone substitutes.

Exploring RF Magnetron Sputtering Growth Composite Thin Film BiFeO3-Bi2Fe4O9 on C-Plane Al2O3 Substrate.

Nanocomposite films of BiFeO3-Bi2Fe4O9 were fabricated on a sapphire substrate Al2O3 using the method of gas discharge high-frequency cathodic sputtering of a ceramic target with a stoichiometric composition in an oxygen atmosphere. The results of the film analysis using X-ray structural analysis, Raman scattering, XPS, and atomic force microscopy are presented. The lattice parameters, surface topography, chemical composition of the films, concentration, and average sizes of the crystallites for each phase were determined. It was shown that the ratio of the BiFeO3 to Bi2Fe4O9 phases in the obtained film is approximately 1:2. The sizes of the crystallites range from 15 to 17 nm. The optical and magnetic properties of the nanocomposite layers were studied, and the band gap width and magnetization hysteresis characteristic of ferromagnetic behavior were observed. The band gap width was found to be 1.9 eV for the indirect and 2.6 eV for the direct interband transitions. The magnetic properties are characterized by a hysteresis loop resembling a "wasp-waist" shape, indicating the presence of magnetic anisotropy.

Oxygen Vacancies and Surface Wettability: Key Factors in Activating and Enhancing the Solar Photocatalytic Activity of ZnO Tetrapods.

This paper reports on the high photocatalytic activity of ZnO tetrapods (ZnO-Ts) using visible/solar light and hydrodynamic water flow. It was shown that surface oxygen defects are a key factor in the photocatalytic activity of the ZnO-Ts. The ability to control the surface wettability of the ZnO-Ts and the associated concentration of surface defects was demonstrated. It was demonstrated that the photocatalytic activity during the MB decomposition process under direct and simulated sunlight is essentially identical. This presents excellent prospects for utilizing the material in solar photocatalysis.

Combination NIPS/TIPS Synthesis of α-Fe2O3 and α/γ-Fe2O3 Doped PVDF Composite for Efficient Piezocatalytic Degradation of Rhodamine B.

Highly porous membranes based on polyvinylidene fluoride (PVDF) with the addition of nanoscale particles of non-magnetic and magnetic iron oxides were synthesized using a combined method of non-solvent induced phase separation (NIPS) and thermo-induced phase separation (TIPS) based on the technique developed by Dr. Blade. The obtained membranes were characterized using SEM, EDS, XRD, IR, diffuse reflectance spectroscopy, and fluorescent microscopy. It was shown that the membranes possessed a high fraction of electroactive phase, which increased up to a maximum of 96% with the addition of 2 wt% of α-Fe2O3 and α/γ-Fe2O3 nanoparticles. It was demonstrated that doping PVDF with nanoparticles contributed to the reduction of pore size in the membrane. All membranes exhibited piezocatalytic activity in the degradation of Rhodamine B. The degree of degradation increased from 69% when using pure PVDF membrane to 90% when using the composite membrane. The nature of the additive did not affect the piezocatalytic activity. It was determined that the main reactive species responsible for the degradation of Rhodamine B were •OH and •O2-. It was also shown that under piezocatalytic conditions, composite membranes generated a piezopotential of approximately 2.5 V.

Piezo-Enhanced Photocatalytic Activity of the Electrospun Fibrous Magnetic PVDF/BiFeO3 Membrane.

Creating stimulus-sensitive smart catalysts capable of decomposing organic dyes with high efficiency is a critical task in ecology. Combining the advantages of photoactive piezoelectric nanomaterials and ferroelectric polymers can effectively solve this problem by collecting mechanical vibrations and light energy. Using the electrospinning method, we synthesized hybrid polymer-inorganic nanocomposite fiber membranes based on polyvinylidene fluoride (PVDF) and bismuth ferrite (BFO). The samples were studied by scanning electron microscope (SEM), Fourier-transform infrared spectroscopy (FTIR), total transmittance and diffuse reflectance, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), vibrating-sample magnetometer (VSM), and piezopotential measurements. It has been demonstrated that the addition of BFO leads to an increase in the proportion of the polar phase from 86.5% to 96.1% due to the surface ion-dipole interaction. It is shown that the composite exhibits anisotropy of magnetic properties depending on the orientation of the magnetic field. The results of piezo-photocatalytic experiments showed that under the combined action of ultrasonic treatment and irradiation with both visible and UV light, the reaction rate increased in comparison with photolysis, sonolysis, and piezocatalysis. Moreover, for PVDF/BFO, which does not exhibit photocatalytic activity, under the combined action of light and ultrasound, the reaction rate increases by about 3× under UV irradiation and by about 6× under visible light irradiation. This behavior is explained by the piezoelectric potential and the narrowing of the band gap of the composite due to mechanical stress caused by the ultrasound.

Brief Review of PVDF Properties and Applications Potential.

Currently, there is an ever-growing interest in carbon materials with increased deformation-strength, thermophysical parameters. Due to their unique physical and chemical properties, such materials have a wide range of applications in various industries. Many prospects for the use of polymer composite materials based on polyvinylidene fluoride (PVDF) for scientific and technical purposes explain the plethora of studies on their characteristics "structure-property", processing, application and ecology which keep appearing. Building a broader conceptual picture of new generation polymeric materials is feasible with the use of innovative technologies; thus, achieving a high level of multidisciplinarity and integration of polymer science; its fundamental problems are formed, the solution of which determines a significant contribution to the natural-scientific picture of the modern world. This review provides explanation of PVDF advanced properties and potential applications of this polymer material in its various forms. More specifically, this paper will go over PVDF trademarks presently available on the market, provide thorough overview of the current and potential applications. Last but not least, this article will also delve into the processing and chemical properties of PVDF such as radiation carbonization, ß-phase formation, etc.

Morphotropic Phase Boundary Enhanced Photocatalysis in Sm Doped BiFeO3.

This paper presents the results of the synthesis of samarium-doped bismuth ferrite (BFO) nanoparticles by the solution combustion method. The dependence of BFO properties on the amount of the samarium (Sm) in the composition was studied. The synthesized nanocomposites were characterized by scanning electron microscopy SEM), X-ray diffractometry (XRD), Raman, Electron Diffuse Reflectance Spectroscopy (EDRS) and Electron Magnetic Resonance (EMR). The photocatalytic (PC) measurements showed the absence of a strict correlation between the PC activity and the crystallite size and band gap. An increase in the PC activity of BFO samples with 10 and 15% doping was observed and it was concluded that in controlling the PC properties in doped BFO, the processes of interfacial polarization at the boundaries of the morphotropic phase transition are of decisive importance. It was supposed that the internal electric field formed at these boundaries contributes to the efficient separation of photogenerated charge carriers.

Multiferroic/Polymer Flexible Structures Obtained by Atomic Layer Deposition.

The paper considers how a film of bismuth ferrite BiFeO3 (BFO) is formed on a polymeric flexible polyimide substrate at low temperature ALD (250 °C). Two samples of BFO/Polyimide with different thicknesses (42 nm, 77 nm) were studied. As the thickness increases, a crystalline BFO phase with magnetic and electrical properties inherent to a multiferroic is observed. An increase in the film thickness promotes clustering. The competition between the magnetic and electrical subsystems creates an anomalous behavior of the magnetization at a temperature of 200 K. This property is probably related to the multiferroic/polymer interface. This paper explores the prerequisites for the low-temperature growth of BFO films on organic materials as promising structural components for flexible and quantum electronics.

PVDF Fibers Modification by Nitrate Salts Doping.

The method of inclusion of various additives into a polymer depends highly on the material in question and the desired effect. In the case of this paper, nitride salts were introduced into polyvinylidene fluoride fibers prepared by electrospinning. The resulting changes in the structural, chemical and electrical properties of the samples were observed and compared using SEM-EDX, DSC, XPS, FTIR, Raman spectroscopy and electrical measurements. The observed results displayed a grouping of parameters by electronegativity and possibly the molecular mass of the additive salts. We virtually demonstrated elimination of the presence of the γ-phase by addition of Mg(NO3)2, Ca(NO3)2, and Zn(NO3)2 salts. The trend of electrical properties to follow the electronegativity of the nitrate salt cation is demonstrated. The performed measurements of nitrate salt inclusions into PVDF offer a new insight into effects of previously unstudied structures of PVDF composites, opening new potential possibilities of crystalline phase control of the composite and use in further research and component design.

Characterization of Polyvinylidene Fluoride (PVDF) Electrospun Fibers Doped by Carbon Flakes.

Polyvinylidene fluoride (PVDF) is a modern polymer material used in a wide variety of ways. Thanks to its excellent resistance to chemical or thermal degradation and low reactivity, it finds use in biology, chemistry, and electronics as well. By enriching the polymer with an easily accessible and cheap variant of graphite, it is possible to affect the ratio of crystalline phases. A correlation between the ratios of crystalline phases and different properties, like dielectric constant as well as piezo- and triboelectric properties, has been found, but the relationship between them is highly complex. These changes have been observed by a number of methods from structural, chemical and electrical points of view. Results of these methods have been documented to create a basis for further research and experimentation on the usability of this combined material in more complex structures and devices.

Piezoelectric Current Generator Based on Bismuth Ferrite Nanoparticles.

Bismuth ferrite nanoparticles with an average particle diameter of 45 nm and spatial symmetry R3c were obtained by combustion of organic nitrate precursors. BiFeO3-silicone nanocomposites with various concentrations of nanoparticles were obtained by mixing with a solution of M10 silicone. Models of piezoelectric generators were made by applying nanocomposites on a glass substrate and using aluminum foil as contacts. The thickness of the layers was about 230 µm. There was a proportional relationship between the different concentrations of nanoparticles and the detected potential. The output voltages were 0.028, 0.055, and 0.17 V with mass loads of 10, 30, and 50 mass%, respectively.

Atomic Layer Deposition of Mixed-Layered Aurivillius Phase on TiO2 Nanotubes: Synthesis, Characterization and Photoelectrocatalytic Properties.

For the first time, one-dimensional phase-modulated structures consisting of two different layered Aurivillius phases with alternating five and six perovskite-like layers were obtained by atomic layer deposition (ALD) on the surface of TiO2 nanotubes (Nt). It was shown that the use of vertically oriented TiO2 Nt as the substrate and the ALD technology of a two-layer Bi2O3-FeOx sandwich-structure make it possible to obtain a layered structure due to self-organization during annealing. A detailed study by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the coating is conformal. Raman spectroscopic analysis indicated the structure of the layered Aurivillius phases. Transient photocurrent responses under Ultraviolet-Visible (UV-Vis) light irradiation show that the ALD coating benefits the efficiency of photon excitation of electrons. The results of the photoelectrocatalytic experiments (PEC) with methyl orange degradation as a model demonstrate the significant potential of the synthesized structure as a photocatalyst. Photoluminescent measurement showed a decrease in the probability of recombination of photogenerated electron-hole pairs for ALD-coated TiO2 Nt, which demonstrates the high potential of these structures for use in photocatalytic and photoelectrochemical applications.

Surface Modification and Enhancement of Ferromagnetism in BiFeO3 Nanofilms Deposited on HOPG.

BiFeO3 (BFO) films on highly oriented pyrolytic graphite (HOPG) substrate were obtained by the atomic layer deposition (ALD) method. The oxidation of HOPG leads to the formation of bubble regions creating defective regions with active centers. Chemisorption occurs at these active sites in ALD. Additionally, carbon interacts with ozone and releases carbon oxides (CO, CO2). Further annealing during the in situ XPS process up to a temperature of 923 K showed a redox reaction and the formation of oxygen vacancies (Vo) in the BFO crystal lattice. Bubble delamination creates flakes of BiFeO3-x/rGO heterostructures. Magnetic measurements (M-H) showed ferromagnetism (FM) at room temperature Ms ~ 120 emu/cm3. The contribution to magnetization is influenced by the factor of charge redistribution on Vo causing the distortion of the lattice as well as by the superstructure formed at the boundary of two phases, which causes strong hybridization due to the superexchange interaction of the BFO film with the FM sublattice of the interface region. The development of a method for obtaining multiferroic structures with high FM values (at room temperature) is promising for magnetically controlled applications.

Complementary SEM-AFM of Swelling Bi-Fe-O Film on HOPG Substrate.

The objective of this work is to study the delamination of bismuth ferrite prepared by atomic layer deposition on highly oriented pyrolytic graphite (HOPG) substrate. The samples' structures and compositions are provided by XPS, secondary ion mass spectrometry (SIMS) and Raman spectroscopy. The resulting films demonstrate buckling and delamination from the substrates. The composition inside the resulting bubbles is in a gaseous state. It contains the reaction products captured on the surface during the deposition of the film. The topography of Bi-Fe-O thin films was studied in vacuum and under atmospheric conditions using simultaneous SEM and atomic force microscopy (AFM). Besides complementary advanced imaging, a correlative SEM-AFM analysis provides the possibility of testing the mechanical properties by using a variation of pressure. In this work, the possibility of studying the surface tension of the thin films using a joint SEM-AFM analysis is shown.