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Cristian RADU

Assistant Researcher

Laboratory of Atomic Structures and Defects in Advanced Materials (LASDAM)

cristian[DOT]radu[AT]infim[DOT]ro

Publications

1. Structural and magneto-optical investigations of citrate sol-gel derived barium hexaferrite nanocrystalline powder
Authors: Secu, M; Secu, CE; Matei, E; Negrilla, C; Turchenko, V; Radu, C; Polosan, S

Published: MAY 5 2024, JOURNAL OF ALLOYS AND COMPOUNDS, 983, 173897, DOI: 10.1016/j.jallcom.2024.173897

Magneto-optical measurements enable the identification of Fe2+ and Fe3+ in the R and S blocks of BaFe12O19 Mhexaferrite powder obtained by sol -gel processing, followed by thermal annealing at 900 C for 3 hours. The ferromagnetic phase is evidenced by the spin-majority configuration (Fe3+) due to their unpaired electrons between d -d orbitals, while the Fe2+ in the low spin possesses diamagnetic behavior strongly dependent on the surrounded crystal field. Additionally, the irradiation with gamma rays changes the ratio between Fe2+/Fe3+, mainly on the surface of BaFe12O19 nanocrystals. These changes were confirmed by X-ray Photoelectron Spectroscopy measurements, in which the concentration of Fe2+ increased from 69% to 82%, while the one of Fe3+ decreased from 31% to 18%. he thermoluminescent measurements reveal the same changes of Fe3+ in Fe2+ by electron capturing during irradiation, which is released as a red emission after recombination processes. The changes are explained by the increasing of some Fe-O bonds along the c-axis, mainly due to breaking a part of these bonds. The X-ray analysis confirms the changing of the parameters for the BaFe12O19 hexagonal structure.
2. Resistive-like Behavior of Ferroelectric p-n Bilayer Structures Based on Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films
Authors: Boni, AG; Chirila, C; Trupina, L; Radu, C; Filip, LD; Moldoveanu, V; Pintilie, I; Pintilie, L

Published: 2023 JAN 25 2023, ACS APPLIED ELECTRONIC MATERIALS, DOI: 10.1021/acsaelm.2c01497

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.
3. Up-Conversion Luminescence and Magnetic Properties of Multifunctional Er3+/Yb3+-Doped SiO2-GdF3/LiGdF4 Glass Ceramics
Authors: Secu, C; Bartha, C; Radu, C; Secu, M

Published: JAN 2023, MAGNETOCHEMISTRY, 9, 11, DOI: 10.3390/magnetochemistry9010011

Glassy nanocomposites containing Yb3+/Er3+-doped GdF3 and LiGdF4 nanocrystals have been prepared by controlled crystallization of the xerogel and the structural, up-conversion luminescence, and magnetic properties were analyzed and discussed. Structural and morphological analysis showed uniform distribution of both GdF3 and LiGdF4 nanocrystals (tens of nm size), embedded in silica glass matrix as the result of thermal decomposition of the trifluoracetates, revealed as a strong exothermic peak at about 300 degrees C; the Li-ions co-doping showed a strong influence on the GdF3 and LiGdF4 nanocrystalline fraction. The energy dispersive spectrometry mapping showed Gd, F and Yb, Er within the nanocrystals but not in the silica glass matrix. X-ray diffraction pattern analysis indicated the crystalline lattice distortion consistent with the Yb/Er incorporation in both fluoride nanocrystals. The "green" ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and "red" (F-4(9/2)-> I-4(15/2)) up-conversion luminescences at 525, 545, and 660 nm observed under 980 nm laser light pumping were assigned to the Er3+ ions deexcitation through a two-photon process. The magnetic properties of the nanocomposite are strongly temperature dependent. The magnetization hysteresis loops show a ferromagnetic behavior at low temperatures (5K) related to the rare-earth ions contribution and the saturation magnetization of 39 emu/g. At 300 K a paramagnetic behavior was observed that was ascribed to the non-interacting localized nature of the magnetic moment of the rare-earth ions. Hence, such novel, multifunctional magnetic and optical materials can allow the intertwining between magnetism and photonics and might offer new opportunities for new magneto-optical device development.
4. Atomic scale insight into the decomposition of nanocrystalline zinc hydroxynitrate toward ZnO using Mn2+ paramagnetic probes
Authors: Vlaicu, ID; Stefan, M; Radu, C; Culita, DC; Radu, D; Ghica, D

Published: APR 6 2023, FRONTIERS IN CHEMISTRY, 11, 1154219, DOI: 10.3389/fchem.2023.1154219

Layered zinc hydroxynitrate (ZHN), with the chemical formula Zn-5 (OH)(8) (NO3)(2)center dot 2H(2)O, exhibits a range of special properties such as anion-exchange and intercalation capacity, as well as biocompatibility, making it attractive for a large variety of applications in fields from nanotechnology to healthcare and agriculture. In this study nanocrystalline ZHN doped with 1,000 ppm Mn2+ was prepared by two synthesis methods (coprecipitation and solid state reaction) using similar environment-friendly precursors. The complex morpho-structural [X-ray diffraction, scanning and transmission electron microscopy, textural analysis] and spectroscopic [Fourier transform infrared and electron paramagnetic resonance (EPR)] characterization of the two ZHN nanopowders showed similar crystalline structures with Mn2+ ions localized in the nanocrystals volume, but with differences in their morphological and textural characteristics, as well as in the doping efficiency. ZHN obtained by coprecipitation consists of larger nanoplatelets with more than two times larger specific surface area and pore volume, as well as a dopant concentration than in the ZHN sample obtained by solid state reaction. The thermal stability and the on-set of the structural phase transformation have been investigated at atomic scale with high accuracy by EPR, using Mn2+ as paramagnetic probes. The on-set of the ZHN structural phase transformation toward ZnO was observed by EPR to take place at 110 degrees C and 130 degrees C for the samples prepared by coprecipitation and solid state reaction, respectively, evidencing a manganese induced local decrease of the transformation temperature. Our results contribute to the selection of the most appropriate ZHN synthesis method for specific applications and in the development of new green, cost-effective synthesis routes for Mn2+ doped nano-ZnO.
5. Resistive-like Behavior of Ferroelectric p-n Bilayer Structures Based on Epitaxial Pb(Zr0.2Ti0.8)O3 Thin Films
Authors: Boni, AG; Chirila, C; Trupina, L; Radu, C; Filip, LD; Moldoveanu, V; Pintilie, I; Pintilie, L

Published: 2023 JAN 25 2023, ACS APPLIED ELECTRONIC MATERIALS, DOI: 10.1021/acsaelm.2c01497

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.
6. Up-Conversion Luminescence and Magnetic Properties of Multifunctional Er3+/Yb3+-Doped SiO2-GdF3/LiGdF4 Glass Ceramics
Authors: Secu, C; Bartha, C; Radu, C; Secu, M

Published: JAN 2023, MAGNETOCHEMISTRY, 9, 11, DOI: 10.3390/magnetochemistry9010011

Glassy nanocomposites containing Yb3+/Er3+-doped GdF3 and LiGdF4 nanocrystals have been prepared by controlled crystallization of the xerogel and the structural, up-conversion luminescence, and magnetic properties were analyzed and discussed. Structural and morphological analysis showed uniform distribution of both GdF3 and LiGdF4 nanocrystals (tens of nm size), embedded in silica glass matrix as the result of thermal decomposition of the trifluoracetates, revealed as a strong exothermic peak at about 300 degrees C; the Li-ions co-doping showed a strong influence on the GdF3 and LiGdF4 nanocrystalline fraction. The energy dispersive spectrometry mapping showed Gd, F and Yb, Er within the nanocrystals but not in the silica glass matrix. X-ray diffraction pattern analysis indicated the crystalline lattice distortion consistent with the Yb/Er incorporation in both fluoride nanocrystals. The "green" ((H-2(11/2), S-4(3/2)) -> I-4(15/2)) and "red" (F-4(9/2)-> I-4(15/2)) up-conversion luminescences at 525, 545, and 660 nm observed under 980 nm laser light pumping were assigned to the Er3+ ions deexcitation through a two-photon process. The magnetic properties of the nanocomposite are strongly temperature dependent. The magnetization hysteresis loops show a ferromagnetic behavior at low temperatures (5K) related to the rare-earth ions contribution and the saturation magnetization of 39 emu/g. At 300 K a paramagnetic behavior was observed that was ascribed to the non-interacting localized nature of the magnetic moment of the rare-earth ions. Hence, such novel, multifunctional magnetic and optical materials can allow the intertwining between magnetism and photonics and might offer new opportunities for new magneto-optical device development.
7. Synthesis of Nickel and Cobalt Ferrite-Doped Graphene as Efficient Catalysts for Improving the Hydrogen Storage Kinetics of Lithium Borohydride
Authors: Palade, P; Comanescu, C; Radu, C

Published: JAN 2023, MATERIALS, 16, 427, DOI: 10.3390/ma16010427

Featuring a high hydrogen storage content of up to 20 wt%, complex metal borohydrides remain promising solid state hydrogen storage materials, with the real prospect of reversible behavior for a zero-emission economy. However, the thermodynamic barriers and sluggish kinetics are still barriers to overcome. In this context, nanoconfinement has provided a reliable method to improve the behavior of hydrogen storage materials. The present work describes the thermodynamic and kinetic enhancements of LiBH4 nanoconfined in MFe2O4 (M=Co, Ni) ferrite-catalyzed graphene host. Composites of LiBH4-catalysts were prepared by melt infiltration and investigated by X-ray diffraction, TEM, STEM-EDS and TPD. The role of ferrite additives, metal precursor treatment (Ar, Ar/H-2) and the effect on hydrogen storage parameters are discussed. The thermodynamic parameters for the most promising composite LiBH4-graphene-NiFe2O4 (Ar) were investigated by Kissinger plot method, revealing an E-A = 127 kJ/mol, significantly lower than that of neat LiBH4 (170 kJ/mol). The reversible H-2 content of LiBH4-graphene-NiFe2O4 (Ar) after 5 a/d cycles was similar to 6.14 wt%, in line with DOE's target of 5.5 wt% storage capacity, while exhibiting the lowest desorption temperature peak of 349 degrees C. The composites with catalysts treated in Ar have lower desorption temperature due to better catalyst dispersion than using H-2/Ar.
8. Resistive-like Behavior of Ferroelectric p-n Bilayer Structures Based on Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films
Authors: Boni, AG; Chirila, C; Trupina, L; Radu, C; Filip, LD; Moldoveanu, V; Pintilie, I; Pintilie, L

Published: JAN 2023, ACS APPLIED ELECTRONIC MATERIALS, DOI: 10.1021/acsaelm.2c01497

The p-n junctions are the building blocks of nowadays electronic devices. The n- or p-type conductivity is obtained in classic semiconductors, like Si, by doping with atoms acting as donors or acceptors, respectively. Doping was used in ferroelectrics to influence the transition temperature, magnitude of some physical properties, but not necessarily conduction type. Therefore, comprehensive studies to obtain true ferroelectric p-n junctions by controlled doping are missing. Recently, it has been shown that Pb(Zr0.2Ti0.8)O-3 films doped with & AP;1% atomic Nb (n-type doping) or Fe (p-type doping) have different orientations of polarization in the as-grown state. Knowing that polarization orientation depends on doping type, the next step is to build ferroelectric p-n homojunctions and to study their properties in relation to ferroelectric polarization. p-n and n-p structures were grown for this purpose by successive deposition of Nb-doped and Fe-doped Pb(Zr,Ti)O-3 layers with different thicknesses. We find that these p-n homojunctions are ferroelectric, but the magnitude of the polarization and coercive field, as well as the dominant polarization orientation in the as-grown state, depend on the conduction type of the first grown layer. The I-V characteristics are quasi-linear, although the interfaces with the electrodes behaves as Schottky contacts. The resistance extracted from the I-V characteristics displays an exponential dependence on temperature, with an activation energy in the range of 0.14-0.17 eV. These results are explained assuming that the total current in the junction is the total of electron and hole injections at the electrode interfaces. It is shown that for relatively low doping concentrations, the current density contains a dominant term with a linear voltage dependence and an exponential temperature dependence, as observed experimentally, and a secondary (correction) term that is dependent on the free carrier density and can induce non-linear voltage dependence when this density is significant.
9. Atomic scale insight into the decomposition of nanocrystalline zinc hydroxynitrate toward ZnO using Mn2+ paramagnetic probes
Authors: Vlaicu, ID; Stefan, M; Radu, C; Culita, DC; Radu, D; Ghica, D

Published: APR 6 2023, FRONTIERS IN CHEMISTRY, 11, 1154219, DOI: 10.3389/fchem.2023.1154219

Layered zinc hydroxynitrate (ZHN), with the chemical formula Zn-5 (OH)(8) (NO3)(2)center dot 2H(2)O, exhibits a range of special properties such as anion-exchange and intercalation capacity, as well as biocompatibility, making it attractive for a large variety of applications in fields from nanotechnology to healthcare and agriculture. In this study nanocrystalline ZHN doped with 1,000 ppm Mn2+ was prepared by two synthesis methods (coprecipitation and solid state reaction) using similar environment-friendly precursors. The complex morpho-structural [X-ray diffraction, scanning and transmission electron microscopy, textural analysis] and spectroscopic [Fourier transform infrared and electron paramagnetic resonance (EPR)] characterization of the two ZHN nanopowders showed similar crystalline structures with Mn2+ ions localized in the nanocrystals volume, but with differences in their morphological and textural characteristics, as well as in the doping efficiency. ZHN obtained by coprecipitation consists of larger nanoplatelets with more than two times larger specific surface area and pore volume, as well as a dopant concentration than in the ZHN sample obtained by solid state reaction. The thermal stability and the on-set of the structural phase transformation have been investigated at atomic scale with high accuracy by EPR, using Mn2+ as paramagnetic probes. The on-set of the ZHN structural phase transformation toward ZnO was observed by EPR to take place at 110 degrees C and 130 degrees C for the samples prepared by coprecipitation and solid state reaction, respectively, evidencing a manganese induced local decrease of the transformation temperature. Our results contribute to the selection of the most appropriate ZHN synthesis method for specific applications and in the development of new green, cost-effective synthesis routes for Mn2+ doped nano-ZnO.
10. TiO2 Phase Ratio's Contribution to the Photocatalytic Activity
Authors: Stepanova, A; Tite, T; Ivanenko, I; Enculescu, M; Radu, C; Culita, DC; Rostas, AM; Galca, AC

Published: OCT 25 2023, ACS OMEGA, 8, DOI: 10.1021/acsomega.3c05890

Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N-2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of approximate to 9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.
11. Controlling polarization direction in epitaxial Pb(Zr0.2Ti0.8)O-3 films through Nb (n-type) and Fe (p-type) doping
Authors: Chirila, CF; Stancu, V; Boni, GA; Pasuk, I; Trupina, L; Filip, LD; Radu, C; Pintilie, I; Pintilie, L

Published: JAN 14 2022, SCIENTIFIC REPORTS, 12, 755, DOI: 10.1038/s41598-022-04802-1

Fe (acceptor) and Nb (donor) doped epitaxial Pb(Zr0.2Ti0.8)O-3 (PZT) films were grown on single crystal SrTiO3 substrates and their electric properties were compared to those of un-doped PZT layers deposited in similar conditions. All the films were grown from targets produced from high purity precursor oxides and the doping was in the limit of 1% atomic in both cases. The remnant polarization, the coercive field and the potential barriers at electrode interfaces are different, with lowest values for Fe doping and highest values for Nb doping, with un-doped PZT in between. The dielectric constant is larger in the doped films, while the effective density of charge carriers is of the same order of magnitude. An interesting result was obtained from piezoelectric force microscopy (PFM) investigations. It was found that the as-grown Nb-doped PZT has polarization orientated upward, while the Fe-doped PZT has polarization oriented mostly downward. This difference is explained by the change in the conduction type, thus in the sign of the carriers involved in the compensation of the depolarization field during the growth. In the Nb-doped film the majority carriers are electrons, which tend to accumulate to the growing surface, leaving positively charged ions at the interface with the bottom SrRuO3 electrode, thus favouring an upward orientation of polarization. For Fe-doped film the dominant carriers are holes, thus the sign of charges is opposite at the growing surface and the bottom electrode interface, favouring downward orientation of polarization. These findings open the way to obtain p-n ferroelectric homojunctions and suggest that PFM can be used to identify the type of conduction in PZT upon the dominant direction of polarization in the as-grown films.
12. Relationship between the Formation of Magnetic Clusters and Hexagonal Phase of Gold Matrix in AuxFe1-x Nanophase Thin Films
Authors: Locovei, C; Radu, C; Kuncser, A; Iacob, N; Schinteie, G; Stanciu, A; Iftimie, S; Kuncser, V

Published: APR 2022, NANOMATERIALS, 12, 1176, DOI: 10.3390/nano12071176

AuxFe1-x nanophase thin films of different compositions and thicknesses were prepared by co-deposition magnetron sputtering. Complex morpho-structural and magnetic investigations of the films were performed by X-ray Diffraction, cross-section Transmission Electron Microscopy, Selected Area Electron Diffraction, Magneto Optical Kerr Effect, Superconducting Quantum Interference Device magnetometry and Conversion Electron Mossbauer Spectroscopy. It was proven that depending on the preparation conditions, different configurations of defect alpha-Fe magnetic clusters, i.e., randomly distributed or auto-assembled in lamellar or filiform configurations, can be formed in the Au matrix. A close relationship between the Fe clustering process and the type of the crystalline structure of the Au matrix was underlined, with the stabilization of a hexagonal phase at a composition close to 70 at. % of Au and at optimal thickness. Due to different types of inter-cluster magnetic interactions and spin anisotropies, different types of magnetic order from 2D Ising type to 3D Heisenberg type, as well as superparamagnetic behavior of non-interacting Fe clusters of similar average size, were evidenced.
13. Structural and Optical Characterization of Silica Nanospheres Embedded with Monodisperse CeO2-Eu3+ Nanocrystals
Authors: Secu, C; Bartha, C; Matei, E; Radu, C; Secu, M

Published: FEB 2022, MAGNETOCHEMISTRY, 8, 22, DOI: 10.3390/magnetochemistry8020022

Luminescent nanocrystals embedded into silica microspheres were shown to be useful for silica labeling for biological applications, ensuring mechanical and chemical stability, nontoxicity, biocompatibility and optical properties. We used sol-gel technology to prepare silica nanospheres embedded with fluorescent and magnetic Eu3+(1 mol%)-doped CeO2 nanocrystals. The X-ray diffraction pattern analysis and transmission electron microscopy investigations showed CeO2:Eu3+(1 mol%) nanocrystals of about 9 nm size and Ce3+ ions substitution by the Eu3+ ions; the nanocrystals dispersed inside the nanosized silica spheres of about 400 nm diameters. The photoluminescence spectra recorded under UV-light excitation showed Eu3+ ions luminescence peaks (D-5(0)-F-7(J), J = 0-4) accompanied by a weaker 425 nm luminescence due to the silica matrix; the quantum yield was 0.14. The weak hysteresis loop and magnetization curves recorded up to 20,000 Oe showed dominantly paramagnetic behavior associated with the silica matrix; a slight opening of the hysteresis loop to a very small magnetic field (about 0.005 Oe) was due to the presence of the two rare earth ions. The photonic crystal properties of SiO2-CeO2:Eu3+(1 mol%) silica nanospheres deposited as films on quartz plates were revealed by the two weak attenuation peaks at 420 and 500 nm and were associated with the reflection from different planes. The SiO2-CeO2:Eu3+(1 mol%) nanospheres are attractive potential candidates for photonics-related applications or for multifunctional bio-labels by combining the luminescence and magnetic properties of the nanocrystals.
14. A new method for obtaining the magnetic shape anisotropy directly from electron tomography images
Authors: Radu, C; Vlaicu, ID; Kuncser, AC

Published: JUL 5 2022, BEILSTEIN JOURNAL OF NANOTECHNOLOGY, 13, DOI: 10.3762/bjnano.13.51

A new methodology to obtain magnetic information on magnetic nanoparticle (MNP) systems via electron tomography techniques is reported in this work. The new methodology is implemented in an under-development software package called Magn3t, written in Python and C++. A novel image-filtering technique that reduces the highly undesired diffraction effects in the tomography tiltseries has been also developed in order to increase the reliability of the correlations between morphology and magnetism. Using the Magn3t software, the magnetic shape anisotropy magnitude and direction of magnetite nanoparticles has been extracted for the first time directly from transmission electron tomography.
15. Green Epoxidation of Olefins with ZnxAl/MgxAl-LDH Compounds: Influence of the Chemical Composition
Authors: Zavoianu, R; Cruceanu, A; Pavel, OD; Bradu, C; Florea, M; Birjega, R

Published: FEB 2022, CATALYSTS, 12, 145, DOI: 10.3390/catal12020145

This contribution concerns the effect of the chemical composition of the brucite-type layer of bi-cationic LDH materials ZnxAl and MgxAl (x = 2-5) and tri-cationic LDH MgyZnzAl (y + z = 4, y = 1, 2, 3) on their catalytic activity for olefin epoxidation with H2O2 in the presence of acetonitrile. LDH materials were prepared by the standard method of co-precipitation at constant pH 10, using an aqueous solution of the corresponding metal nitrates and a basic solution containing NaOH and Na2CO3. The fresh LDHs were calcined to yield the corresponding mixed oxides and then the recovery of the LDH structure by hydration of the mixed oxides was performed. The resulting samples were characterized by AAS, XRD, DRIFT, DR-UV-Vis, BET and determination of basic sites. The results of the catalytic tests for olefin epoxidation were well correlated with the basicity of the samples, which was in turn related to the M2+/Al3+ ratio and the electronegativity of different bivalent metals in the brucite-type layer.
16. Accidental Impurities in Epitaxial Pb(Zr0.2Ti0.8)O-3 Thin Films Grown by Pulsed Laser Deposition and Their Impact on the Macroscopic Electric Properties
Authors: Boni, GA; Chirila, CF; Stancu, V; Amarande, L; Pasuk, I; Trupina, L; Istrate, CM; Radu, C; Tomulescu, A; Neatu, S; Pintilie, I; Pintilie, L

Published: MAY 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11051177

Structural and electrical properties of epitaxial Pb(Zr0.2Ti0.8)O-3 films grown by pulsed laser deposition from targets with different purities are investigated in this study. One target was produced in-house by using high purity precursor oxides (at least 99.99%), and the other target was a commercial product (99.9% purity). It was found that the out-of-plane lattice constant is about 0.15% larger and the a domains amount is lower for the film grown from the commercial target. The polarization value is slightly lower, the dielectric constant is larger, and the height of the potential barrier at the electrode interfaces is larger for the film deposited from the pure target. The differences are attributed to the accidental impurities, with a larger amount in the commercial target as revealed by composition analysis using inductive coupling plasma-mass spectrometry. The heterovalent impurities can act as donors or acceptors, modifying the electronic characteristics. Thus, mastering impurities is a prerequisite for obtaining reliable and reproducible properties and advancing towards all ferroelectric devices.
17. The Physico-Chemical Properties and Exploratory Real-Time Cell Analysis of Hydroxyapatite Nanopowders Substituted with Ce, Mg, Sr, and Zn (0.5-5 at.%)
Authors: Chirica, IM; Enciu, AM; Tite, T; Dudau, M; Albulescu, L; Iconaru, SL; Predoi, D; Pasuk, I; Enculescu, M; Radu, C; Mihalcea, CG; Popa, AC; Rusu, N; Nita, S; Tanase, C; Stan, GE

Published: JUL 2021, MATERIALS, 14, DOI: 10.3390/ma14143808

Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.
18. Homogeneous versus Inhomogeneous Polarization Switching in PZT Thin Films: Impact of the Structural Quality and Correlation to the Negative Capacitance Effect
Authors: Pintilie, L; Boni, GA; Chirila, CF; Stancu, V; Trupina, L; Istrate, CM; Radu, C; Pintilie, I

Published: AUG 2021, NANOMATERIALS, 11, DOI: 10.3390/nano11082124

Polarization switching in ferroelectric films is exploited in many applications, such as non-volatile memories and negative capacitance field affect transistors. This can be inhomogeneous or homogeneous, depending on if ferroelectric domains are forming or not during the switching process. The relation between the polarization switching, the structural quality of the films and the negative capacitance was not studied in depth. Here, Pb(Zr0.2Ti0.8)O-3 (PZT) layers were deposited by pulse laser deposition (PLD) and sol-gel (SG) on single crystal SrTiO3 (STO) and Si substrates, respectively. The structural quality was analyzed by X-ray diffraction and transmission electron microscopy, while the electric properties were investigated by performing hysteresis, dynamic dielectric measurements, and piezo-electric force microscopy analysis. It was found that the PZT layers grown by PLD on SRO/STO substrates are epitaxial while the layers deposited by SG on Pt/Si are polycrystalline. The polarization value decreases as the structure changes from epitaxial to polycrystalline, as well as the magnitude of the leakage current and of the differential negative capacitance, while the switching changes from homogeneous to inhomogeneous. The results are explained by the compensation rate of the depolarization field during the switching process, which is much faster in epitaxial films than in polycrystalline ones.
19. EFFECTS OF ANNEALING ON THE PHYSICAL PROPERTIES OF ITO THIN FILMS GROWN BY RADIO FREQUENCY MAGNETRON SPUTTERING
Authors: Radu, A; Locovei, C; Antohe, VA; Socol, M; Coman, D; Manica, M; Dumitru, A; Dan, L; Radu, C; Raduta, AM; Ion, L; Iftimie, S; Antohe, S

Published: JUL-SEP 2020, DIGEST JOURNAL OF NANOMATERIALS AND BIOSTRUCTURES, 15, 687, DOI:

Indium-doped tin oxide (ITO) thin films were fabricated by radio frequency magnetron sputtering and were subjected to in-situ and ex-situ annealing, at 200 degrees C, 300 degrees C and 400 degrees C, respectively. The in-situ thermal treatment consisted to intentionally heating the samples' substrates, while the ex-situ annealing was performed using an oven, under ambient atmosphere. For the ITO samples subjected to ex-situ annealing, the density of oxygen vacancies increased leading to the decrease of the electrical resistivity. No significant changes were noticed in terms of transmission spectroscopy after the thermal treatment; while by evaluating the Skewness parameter was determined that the annealing improves the planarity of samples' surface.
20. Pd-Cu catalysts supported on anion exchange resin for the simultaneous catalytic reduction of nitrate ions and reductive dehalogenation of organochlorinated pollutants from water
Authors: Bradu, C; Capat, C; Papa, F; Frunza, L; Olaru, EA; Crini, G; Morin-Crini, N; Euvrard, E; Balint, I; Zgura, I; Munteanu, C

Published: JAN 25 2019, APPLIED CATALYSIS A-GENERAL, 570, 129, DOI: 10.1016/j.apcata.2018.11.002

The present work proposes the simultaneous removal of these classes of pollutants by a catalytic hydrotreatment processes. For this purpose, bimetallic Pd-Cu catalysts (with mass ratio Pd:Cu of 4:1) supported on macroporous strong base anion resin were prepared by different methods. The catalysts were characterized (by XRD, SEMEDX, XPS, AAS and H-2 chemisorption) and tested in a continuous flow system. The selected catalyst preparation protocol consists in a two-step method, which implies the deposition of palladium by ion exchange and the subsequent deposition of copper by controlled reaction on the surface of the pre-reduced palladium. The effectiveness of the catalyst in the simultaneous reduction of nitrate and hydrodechlorination of 4-chlorophenol was demonstrated. By adjusting the initial pH and the flow rate of the aqueous solution, nearly complete hydrodechlorination of 4-chlorophenol can occur together with selective nitrate reduction at a conversion of 95% and a selectivity to N-2 of 92% (this value contains the contribution of all gaseous products, including the eventually formed NOx). The bimetallic catalyst was found to remains relatively stable after 100 h of test time.
21. New ways to use the red mud waste as raw material for inorganic-organic hybrid hydrogels
Authors: Sandu, T; Sarbu, A; Zavoianu, R; Spatarelu, CP; Florea, M; Bradu, C; Mara, EL; Dragut, DV; Alexandrescu, E; Zaharia, A; Radu, AL

Published: DEC 10 2017, , DOI: 10.1016/j.minpro.2017.11.005

22. Nanostructured Titanium Doped Iron Oxide Photoelectrodes for Water Splitting
Authors: Miclea, C; Amarande, L; Cioangher, MC; Miclea, CT; Mihailescu, M; Radu, C; Ivanov, A

Published: 2015, ROMANIAN JOURNAL OF INFORMATION SCIENCE AND TECHNOLOGY, 18, 105, DOI:

Water splitting by means of semiconducting photoelectrodes and solar light represents a promising alternative to conventional fossil fuel economy. In this process the photoactive electrode absorb sunlight directly thus initiating the photochemical reaction which create excess electrons in the conduction band of the semiconducting electrode. Titanium doped iron oxide seems to be a promising semiconducting material for photoelectrodes. Consequently, we investigated the effect of Ti doping on the structure, electrical and photoelectrochemical properties alpha-Fe2O3. The Ti doped alpha-Fe2O3 were prepared by a slightly modified mixed oxide route, consisting in a prolonged mixing of the raw materials in a high energy planetary ball mill until the particles decreased to the nanometric sizes. Optimum results were obtained for samples doped with 5 at. % titanium and sintered at 1200 degrees C. Photocurrents as high as 8.4 mA/cm(2), for illumination from a 300 W xenon lamp, were recorded for such samples. It is hoped that such photoelectrodes show promise for water splitting.
23. Supported Pd-Cu Nanoparticles for Water Phase Reduction of Nitrates. Influence of the Support and of the pH Conditions
Authors: Papa, F; Balint, I; Negrila, C; Olaru, EA; Zgura, I; Bradu, C

Published: DEC 10 2014, INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 53, 19103, DOI: 10.1021/ie503070f

PdCu nanoparticles were synthesized by the alkaline polyol method and further supported on alumina or titania. The nanoparticles show a crystalline Pd core and a shell rich in amorphous copper as was put in evidence by complex characterization methods (X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and CO chemisorption). The performances of as-prepared catalysts in the water phase reduction of nitrate were assessed in comparison with catalysts obtained by impregnation. Supported nanoparticle catalysts show a high activity in the reduction of nitrates, better than the impregnated catalysts. The importance of the support choice was discussed. The catalyst based on PdCu nanoparticles supported on titania (PCT-np) is the most active, selective, and stable among those investigated. Also, the influence of pH conditions on the PCT-np catalyst performances was emphasized.
24. Large scale microstructuring on silicon surface in air and liquid by femtosecond laser pulses
Authors: Ulmeanu, M; Jipa, F; Radu, C; Enculescu, M; Zamfirescu, M

Published: SEP 15 2012, APPLIED SURFACE SCIENCE, 258, 9317, DOI: 10.1016/j.apsusc.2011.08.110

Large-scale microstructures were imprinted on the surface of silicon with dimensions of 1 mm x 1 mm by femtosecond laser line-by-line scanning irradiation. The scanning was made under air and under chlor/hydrogen based liquid layers. Scanning electron microscope investigations evidenced homogeneous surface microstructures, such as: ripples with sub-wavelengths dimensions, Si pillars and directional oriented bacilliform structures. The dependence of the surface morphology on laser energy, scanning speed and irradiation media was analyzed. In air, the microstructure changes from directional-arranged bacilliform structures to well-known ripple structures with a width of about 525 nm. When using the liquid media, we observe ripple structures with a width of about 370 nm and an overlapping of those that evolve in certain regions into Si pillars. The surfaces show interesting gradient topography behaviour which could be used as model scaffolds for the systematic exploration of the role of 3D micro/nano morphology on cell adhesion and growth. By using chlor and hydrogen based liquids we were able to explore the microstructuring of the silicon by line-by-line irradiation process using the femtosecond laser. (C) 2011 Elsevier B. V. All rights reserved.
25. Vaterite Synthesis via Gas-Liquid Route under Controlled pH Conditions
Authors: Udrea, I; Capat, C; Olaru, EA; Isopescu, R; Mihai, M; Mateescu, CD; Bradu, C

Published: JUN 20 2012, INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 51, 8193, DOI: 10.1021/ie202221m

The purpose of this work was to obtain precipitated calcium carbonate (PCC) particles in polymorphic form of vaterite via gas-liquid route in controlled pH conditions. The effect of CO2 concentration (12.5-100%), feed gas (CO2-air) flow rate, pH, and conductivity of solution upon the PCC particles properties was studied. On the basis of the experimental data, the main factors leading to vaterite formation as major product were established. It was found that the buffer solution has a decisive role in determining polymorphic phase of PCC while CO2 concentration and feed gas flow rate have no significant influence. It was demonstrated that spherical vaterite particles of high purity can be produced under controlled reaction conditions. Also, some considerations on the mechanism of carbonation process were formulated.
26. Silicon structuring by etching with liquid chlorine and fluorine precursors using femtosecond laser pulses
Authors: Radu, C; Simion, S; Zamfirescu, M; Ulmeanu, M; Enculescu, M; Radoiu, M

Published: AUG 1 2011, JOURNAL OF APPLIED PHYSICS, 110, DOI: 10.1063/1.3619856

The aim of this study is to investigate the micrometer and submicrometer scale structuring of silicon by liquid chlorine and fluorine precursors with 200 fs laser pulses working at both fundamental (775 nm) and frequency doubled (387 nm) wavelengths. The silicon surface was irradiated at normal incidence by immersing the Si (111) substrates in a glass container filled with liquid chlorine (CCl(4)) and fluorine (C(2)Cl(3)F(3)) precursors. We report that silicon surfaces develop an array of spikes with single step irradiation processes at 775 nm and equally at 387 nm. When irradiating the Si surface with 400 pulses at 330 mJ/cm(2) laser fluence and a 775 nm wavelength, the average height of the formed Si spikes in the case of fluorine precursors is 4.2 mu m, with a full width at half maximum of 890 nm. At the same irradiation wavelength chlorine precursors develop Si spikes 4 mu m in height and with a full width at half maximum of 2.3 mu m with irradiation of 700 pulses at 560 mJ/cm(2) laser fluence. Well ordered areas of submicrometer spikes with an average height of about 500 nm and a width of 300 nm have been created by irradiation at 387 nm by chlorine precursors, whereas the fluorine precursors fabricate spikes with an average height of 700 nm and a width of about 200 nm. Atomic force microscopy and scanning electron microscopy of the surface show that the formation of the micrometer and sub-micrometer spikes involves a combination of capillary waves on the molten silicon surface and laser-induced etching of silicon, at both 775 nm and 387 nm wavelength irradiation. The energy-dispersive x-ray measurements indicate the presence of chlorine and fluorine precursors on the structured surface. The fluorine precursors create a more ordered area of Si spikes at both micrometer and sub-micrometer scales. The potential use of patterned Si substrates with gradient topography as model scaffolds for the systematic exploration of the role of 3D micro/nano morphology on cell adhesion and growth is envisaged. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3619856]
27. Removal of Reactive Black 5 azo dye from aqueous solutions by catalytic oxidation using CuO/Al2O3 and NiO/Al2O3
Authors: Bradu, C; Frunza, L; Mihalche, N; Avramescu, SM; Neata, M; Udrea, I

Published: JUN 7 2010, APPLIED CATALYSIS B-ENVIRONMENTAL, 96, 556, DOI: 10.1016/j.apcatb.2010.03.019

CuO/Al2O3 and NiO/Al2O3 catalysts prepared by incipient wetness impregnation were used for the oxidation of Reactive Black 5 (RB5) in aqueous solution. Removal of the dye was assessed by High Performance Liquid Chromatography (HPLC) and Total Organic Carbon (TOC) measurements and the generation of the hydroxyl radicals in the process was evaluated by chemiluminescence measurements. To put in evidence the interaction RB5 - catalyst and the surface species formed onto catalysts during the oxidation, Diffuse Reflectance Infrared Fourier Transform (DRIFT) analysis was performed. A different behavior of the two catalytic systems was revealed by the comparative analysis of the data obtained from the adsorption and oxidation tests. Only CuO/Al2O3 was effective in the RB5 degradation, NiO/Al2O3 acted as a simple adsorbent. In the presence of CuO/Al2O3, at H2O2 concentration of 40 mM the azo dye was totally eliminated from both solution and catalyst surface after 4 h, with a mineralization degree higher than 90%. However, a strong inhibition of the catalytic oxidation of RB5 was observed in the presence of phosphate ions. In the conditions of hydrogen peroxide excess, the rate equation in the case of copper catalyst was simply expressed by a pseudo-first order equation and the model was found to fit well the data. The amount of copper leached from catalyst during the oxidation process was only 1.0-1.6% per cycle leading to the conclusion that the decrease of the dye mineralization with the number of cycles has to be explained mostly by the surface covering with the reaction products, at least to a certain extent. (C) 2010 Elsevier B.V. All rights reserved.
28. Modified ruthenium exchanged zeolites for enantioselective hydrogenation
Authors: Parvulescu, VI; Parvulescu, V; Coman, S; Radu, C; Macovei, D; Angelescu, E; Russu, R

Published: 1995, PREPARATION OF CATALYSTS VI: SCIENTIFIC BASES FOR THE PREPARATION OF HETEROGENEOUS CATALYSTS, 91, 570, DOI:

Preparation of modified ruthenium molecular sieves has been investigated in two steps deposition of ruthenium and modifying of ruthenium molecular sieves in presence of ligands. As support sieve there were used two molecular sieves with large pore apertures and low acidity strength (zeolite L and APO-34). Correlation of in situ W-VIS ruthenium deposition measurements with catalyst characterisation revealed that ruthenium deposition takes place not only through ionic exchange but also through adsorption of ruthenium hydrolysed species. Modifying of the ruthenium molecular sieves catalysts with ligands has as effect a diminution of electronic charge on metal. The experimental data indicate that the presence of ligand favours an enantioselective hydrogenation of D-fructose to D-mannitol even if the yields are not very high.
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