National Institute Of Materials Physics - Romania

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721 articles found

1. Grain size-driven effect on the functional properties in Ba0.6Sr0.4TiO3 ceramics consolidated by spark plasma sintering

Authors: Patru, RE; Stanciu, CA; Soare, EM; Surdu, VA; Trusca, RD; Nicoara, AI; Vasile, BS; Boni, G; Amarande, L; Horchidan, N; Curecheriu, LP; Mitoseriu, L; Pintilie, L; Pintilie, I; Ianculescu, AC

Published: JUL 2023, JOURNAL OF THE EUROPEAN CERAMIC SOCIETY, 43, DOI: 10.1016/j.jeurceramsoc.2023.02.013

Dense fine-grained Ba0.6Sr0.4TiO3 ceramics with submicronic grains sizes (GS) have been prepared using nanopowders synthesized via sol-gel route and consolidated by Spark Plasma Sintering (SPS). By changing SPS parameters, the GS was reduced from 214 nm to 74 nm. Diffuse ferroelectric-paraelectric phase transitions and low values of dielectric permittivity (<1000) at the Curie temperature (T-C similar to 280 K) were revealed by Impedance Spectroscopy in all sintered ceramics. The GS reduction from submicron to nanoscale range reflects in a gradually diminishment of dielectric constant, tunability, polarisation and storage energy properties. Raman spectroscopy investigations pointed out the presence of polar nanoclusters above the T-C. The short-range polar order is affected by the GS decrease, but becomes more thermally stable. The observed properties of Ba0.6Sr0.4TiO3 nanostructured ceramics are interpreted by considering the interplay between the GS reduction, the role of low-permittivity grain boundaries and the diffuse character of the ferroelectric-to-paraelectric transformation.

2. First Sharp Diffraction Peak features of the intermediate phase glasses and amorphous thin films in the non-stoichiometric (GeS4)x(AsS3)1-x system

Authors: Ciobanu, M; Galca, AC; Sava, F; Zaki, MY; Velea, A; Tsiulyanu, D

Published: MAY 31 2023, THIN SOLID FILMS, 773, 139828, DOI: 10.1016/j.tsf.2023.139828

Grazing incidence X-ray scattering (GIXRS) patterns of thin solid films based on non-stoichiometric chalcogenide glasses (ChG) from the pseudo - binary system (GeS4)x(AsS3)1-x were studied with a focus on the First Sharp Diffraction Peak (FSDP), assigned to the middle range order (MRO) of the glassy material. The films were grown using explosive thermal evaporation in vacuum (10-4 Pa) of pulverized ChG, prepared from previously synthesized bulk glasses, onto mono-crystalline silicon substrates. Scanning Electron Microscopy (SEM) and EnergyDispersive X-ray (EDX) spectroscopy were used to examine the morphology and elemental composition of the films, which were found to have similar composition to the bulk glasses. However, it was revealed that the molecular structure of the grown amorphous films differs from that of the initial ChG bulk material, as indicated by changes in the composition-dependent position and width of the FSDP. Additionally, the intensities of the FSDP in the films were higher compared to those of the bulk samples, suggesting that the molecular-like structure of ChGs is more pronounced in the form of thin films grown from the vapor phase.

3. Structural and Electrical Properties of Novel Cr/Fe Mixed Transition-Metal Phosphates

Authors: Mighri, Z; Souiwa, K; Rostas, AM; Patru, RE; Bocirnea, AE; Iacob, N; Kuncser, V; El Khouja, O; Leonat, LN; Hidouri, M; Nasri, H; Galca, AC

Published: MAY 24 2023, INORGANIC CHEMISTRY, 62, DOI: 10.1021/acs.inorgchem.2c04389

The phosphate KCoCr-(PO4)(2) and iron-substitutedvariants KCoCr1-x Fe x (PO4)(2) (x =0.25, 0.5, and 0.75) were synthesized by a solid-state reaction route,while a high substitution level of Fe was achieved. Their structureswere refined using powder X-ray diffraction and indexed in a monoclinicsystem with a P2(1)/n spacegroup. A 3D framework with six-sided tunnels parallel to the [101]direction was formed in which the K atoms are located. Mo''ssbauerspectroscopy confirms the exclusive presence of octahedral paramagneticFe(3+) ions, with isomer shifts increasing slightly with x substitution. Electron paramagnetic resonance spectroscopyconfirmed the presence of paramagnetic Cr3+ ions. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present higher ionic activity. Relative to the electrochemicalactivity of K, these materials could be good candidates for positiveand/or negative electrode materials for energy storage applications. The synthesized phosphate KCoCr-(PO4)(2) and Fe-substituted variants KCoCr1-x Fe x (PO4)(2) (x = 0.25, 0.5, and 0.75) present a 3D frameworkwith six-sided tunnels in which the K atoms are located. The activationenergy, determined by dielectric measurements, shows that the iron-containingsamples present improved ionic activity, making these materials goodcandidates for positive and/or negative electrode materials for energystorage applications.

4. Structural, Frequency and Temperature Dependent Dielectric Properties of Zn2+ Substituted Ni-Co Based Spinel Ferrite (ZnxNi0.8-xCo0.2Fe2O4)

Authors: Oumezzine, M; Iuga, A; Enculescu, M; Galca, AC

Published: MAY 1 2023, ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY, 12, 053008, DOI: 10.1149/2162-8777/acd6bb

Zinc substituted nickel-cobalt ferrites, i.e., ZnxNi0.8-xCo0.2Fe2O4 (x = 0.0, 0.05, 0.10 and 0.20) with average crystallite size 100 nm were synthesized by citrate-gel auto-combustion method to investigate effects of Zn2+ substitution on the structural and dielectric properties. Both X-ray diffraction (XRD) and IR spectroscopy studies confirms the formation of pure cubic spinel structure. Variation of lattice parameter infers Vegard's law linear dependence with the addition of Zn2+ concentration. The temperature-dependent behavior of dielectric and modulus spectra has been studied within the frequency range 100 Hz-100 kHz for different temperatures between 100 K and 400 K. It was concluded that the dielectric responses of ZnxNi0.8-xCo0.2Fe2O4 are found to be frequency dependent and thermally activated. Also, In the Zn doped ferrites variations of dielectric loss (tan d) and the imaginary part of electric modulus (M") show the presence of the non-Debye type of dielectric relaxation. Rise in Zinc concentration leads to a decrease in dielectric constant (e (r)) due to the declining of Fe3+-O-M2+ conducting network (M is Co or Ni). Here, we report a low loss tangent factor of the order of 8x10-3 0.6Zn(0.2)Co(0.2)Fe(2)O(4) make this composition suitable for high frequency-applications at room temperature. The activation energy is calculated from electric modulus formalism and DC electrical conductivity and found to increase with further substitution of Zn2+ concentration.

5. Sub-Stochiometric Nickel Oxide Hole-Selective Contacts in Solar Cells: Comparison of Simulations and Experiments with Sputtered Films

Authors: Nayak, M; Bergum, K; Stan, GE; Lee, IH; Kuznetsov, A

Published: MAY 2023, PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE, 220, DOI: 10.1002/pssa.202200651

Sub-stochiometric nickel oxide (NiOx) films were investigated as a hole selective contact option in silicon (Si) heterojunction solar cells. Numerical simulations were carried out to evaluate the impacts of the NiOx electronic properties variations and the NiOx/Si interface defect density (D-it) on device performance. Simulation data suggest that the best performance is achievable for wide bandgaps (E-g) and corresponding high valence band edge (E-VB) positions in the NiOx films. Overall, in simulations, the performance remains practically unchanged for the nickel vacancy concentrations [V-Ni] = 10(17)-10(21 )cm(-3), assuming high E-VB and low D-it. The experimental data measured using NiOx films prepared by radio-frequency magnetron sputtering reveal that the increase in [V-Ni] lifts the conductivity, concurrently decreasing E-g and E-VB. As a result, we concluded that the performance of the fabricated sputtered NiOx/Si heterojunction solar cell is limited by high D-it as well as narrow E-g and low E-VB.

6. Structural and Electrical Properties of Novel Cr/Fe Mixed Transition-Metal Phosphates

Authors: Mighri, Z; Souiwa, K; Rostas, AM; Patru, RE; Bocirnea, AE; Iacob, N; Kuncser, V; El Khouja, O; Leonat, LN; Hidouri, M; Nasri, H; Galca, AC

Published: 2023 MAY 24 2023, INORGANIC CHEMISTRY, DOI: 10.1021/acs.inorgchem.2c04389

7. Physico-chemical characterization and in vitro biological study of manganese doped beta-tricalcium phosphate-based ceramics for bone regeneration applications

Authors: Arpak, MC; Daglilar, S; Kalkandelen, C; Balescu, LM; Sasmazel, HT; Pasuk, I; Stan, GE; Durukan, K; Gunduz, O

Published: 2023 MAY 12 2023, JOURNAL OF THE AUSTRALIAN CERAMIC SOCIETY, DOI: 10.1007/s41779-023-00889-5

This work evaluates the effects of manganese (Mn) doping on the morpho-structural features, mechanical performance, and in vitro biological response of beta-tricalcium phosphate (beta-TCP) derived bioceramics for bone tissue engineering applications. Five different Mn doping levels (i.e., 0.01%, 0.05%, 0.1%, 0.5%, and 1 wt.%) were investigated, with the beta-TCP-based bioceramics being sintered at four temperatures (i.e., 1000, 1100, 1200, and 1300 degrees C). A densification improvement was induced when using Mn in excess of 0.05 wt.%; the densification remained stationary in the sintering temperature range of 1200 - 1300 degrees C. The structural analyses evidenced that all samples sintered at 1000 and 1100 degrees C were composed of beta-TCP as major phase and hydroxyapatite (HA) as a minor constituent (similar to 4-6 wt.%). At the higher temperatures (1200 and 1300 degrees C), the formation of alpha-TCP was signalled at the expense of both beta-TCP and HA. The Mn doping was evidenced by lattice parameters changes. The evolution of the phase weights is linked to a complex inter-play between the capacity of the compounds to incorporate Mn and the thermal decomposition kinetics. The Mn doping induced a reduction in the mechanical performance (in terms of compressive strength, Vickers hardness and elastic modulus) of the beta-TCP-based ceramics. The metabolic activity and viability of osteoblastic cells (MC3T3-E1) for the ceramics were studied in both powder and compacted pellet form. Ceramics with Mn doping levels lower than 0.1 wt.% yielded a more favorable microenvironment for the osteoblast cells with respect to the undoped beta-TCP. No cytotoxic effects were recorded up to 21 days. The Mn-doped beta-TCPs showed a significant increase (p < 0.01) in alkaline phosphatase activity with respect to pure beta-TCP.

8. Development of ceramic coatings on titanium alloy substrate by laser cladding with pre-placed natural derived-slurry: Influence of hydroxyapatite ratio and beam power

Authors: Mocanu, AC; Miculescu, F; Stan, GE; Tite, T; Miculescu, M; Tierean, MH; Pascu, A; Ciocoiu, RC; Butte, TM; Ciocan, LT

Published: APR 1 2023, CERAMICS INTERNATIONAL, 49, DOI: 10.1016/j.ceramint.2022.11.227

The attraction towards Ti and its alloys reside in their superior mechanical and tribological features, as compared to CaPs, which are renowned for their compositional and structural features similar to those of natural bones. However, Ti-based materials suffer from limited biocompatibility and inertness when implanted for extended periods. As such, surface modification with ceramic coatings is required in order to achieve proper biomedical features and enhance their overall behavior in the human body. Hence, this study outlined for the first time the prospect of coating several Ti6Al4V substrates (disks) with bovine-bone derived hydroxyapatite (HA) by laser cladding technique with pre-placed slurry. During laser processing the input materials merge depending on the heating rate/temperature and clad materials. The proposed sample preparation set-up, followed for the first time in this study, involved the concomitant modulation of two parameters: the natural HA ratio (100 wt%, and 50 wt % HA + 50 wt% Ti blends) and laser beam power (500-1000 W range). The laser beam was applied after the ceramic slurries (prepared HA/HA-based blends mixed with polyvinyl alcohol) were placed inside the priorly machined channels on the metallic Ti disks. Partially overlapped cladding tracks (similar to 30% overlapping ratio) resulted and the investigations were further performed in cross-section view. The structural analyses confirmed the formation of calcium titanate as main phase for all samples and the arrest of HA only for those prepared with 100% HA ratio at low to medium laser powers. In addition, the morpho-compositional evaluation revealed the formation of a fully ceramic coating only for the latter sample sets. Further, the surface wettability (contact angle and surface free energy) and Vickers micro-hardness results led to the selection of the optimal technological parameters for the development of ceramic cladded layers with prospect compatibility with regenerative med-icine applications.

9. An improved balanced replicated sampling design for preliminary screening of the tailings ponds aiming at zero-waste valorization. A Romanian case study

Authors: Pencea, I; Turcu, RN; Popescu-Arges, AC; Timis, AL; Priceputu, A; Ungureanu, C; Matei, E; Nedelcu, L; Petrescu, MI; Niculescu, F

Published: APR 1 2023, JOURNAL OF ENVIRONMENTAL MANAGEMENT, 331, 117260, DOI: 10.1016/j.jenvman.2023.117260

The scope of this study consists of setting up of an integrated cost-effective sampling & laboratory analyses procedure which delineates sampling, sub-sampling and analytical uncertainties in case of fine-grained extractive waste deposits. This procedure is designed to support the decision makers towards fine-grained waste deposits upcycling and land reclamation. This procedure consists of a balanced replicated sampling design (BRSD) coupled with a three split levels ANOVA data processing. The paper provides the readership with the mathematical backgrounds of the three split level ANOVA analysis (3L-ANOVA) and an Excel algorithm for its implementation. Also, the paper presents an example of implementation of the developed methods in the case of a Romanian iron ore tailings (IOT) old pond. The findings of the paper consist of: a) argues, based on OM, SEM-EDS, XRFS and XRD observations, that classical TOS is ineffective for fine-grained waste deposits; b) BRSD in conjunction with 3L-ANOVA analysis is the only approach fit for reliable characterization of the fine-grained stockpiles; c) sampling uncertainty is the critical factor of the uncertainty budget of the analyte concentration; d) Lilliefors approach is adequate for the hypothesis testing where or not the measurand is normal distributed; e) The outcomes of the BRDSD&3L-ANOVA investigations carried on Teliuc tailings, estimated at circa 5.5* 106 m3, consist mainly of mineral quantification at lot level i.e. quartz-54% (+/- 7%), hematite-15% (+/- 3%), calcite-11% (+/- 3%), MgO 3% (+/- 1%), Al2O3 9% (+/- 2%). The concentrations of some CRMs like Ti, V, Ba, Y, W were found at ACE limits and their associated relative expanded uncertainties overpass 50%. Thus, the expanded uncertainties clearly depict the reliability of acquired data for the decision makers regarding waste valorization. f) The IOT into Teliuc can be upcycled as minerals for cement and ceramic industries as well as for geopolymer manufacture. Also, IOT can be downcycles as filler in road construction and mine closure. Finally, the Teliuc yard can be rehabilitated with zero-waste left behind. The data exactness provided by this procedure can be increased to any desirable level through increasing the number of collected items, but the cost of sampling and analyses increases proportionally. In such circumstances, the posted approach can be tailored at the stakeholder request as to safely underpin the decision to turn fine-grained by-products into valuable secondary resources, facilitating a greater circularity of the mining industry.

10. Partial replacement of Pb2+ in MAPbI(2.6)Cl(0.4) perovskite films and their photovoltaic performance

Authors: Derbali, S; Nouneh, K; Leonat, LN; Stancu, V; Tomulescu, AG; Galca, AC; Touhami, ME; Pintilie, I; Florea, M

Published: APR 2023, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 34, 903, DOI: 10.1007/s10854-023-10318-9

Replacing lead atoms in halide perovskite materials is of significant importance for the development of environmentally friendly perovskite solar cells. In this paper, we investigated the effect of doping the MAPbI(2.6)Cl(0.4) hybrid perovskite (MA-methyl ammonium) with non-toxic elements, such as alkaline earth metal ions (Mg2+) and transition metal ions (Zn2+). The structural, morphological, and optical properties of the prepared samples were analyzed using X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV-Vis. spectroscopy. Finally, the doped films were used as photoactive layers in solar devices in order to evaluate their photovoltaic performance. Zn proved to be more appropriate to replace partially Pb and films with higher quality were obtained. As a result, the MAPb1(-x)Zn(x)I(2.6)Cl(0.4) based solar cells have demonstrated a slight improvement of the photovoltaic performances, resulting in a uniform and narrower PCEs (power conversion efficiency) range, compared to pristine MAPbI(2.6)Cl(0.4) based devices.