Search Results (450)

Multilayer zirconias have recently been introduced as dental biomaterials to combine improved translucency with sufficient mechanical reliability by implementing yttria-driven gradients in phase composition. Such materials can be considered functionally graded ceramics, where local phase stabilization influences strength and crack resistance. However, manufacturer-specific gradient profiles and their structure–property relationships remain insufficiently characterized. This study investigated two commercially available multilayer zirconias with distinct gradient concepts: IPS e.max^® ZirCAD Prime (continuous gradient) and KATANA™ Zirconia YML (stepwise gradient). Ten equidistant sections along the blank height were analyzed using quantitative X-ray diffraction and Rietveld refinement to quantify zirconia phase fractions and estimate local Y₂O₃ content. Mechanical behavior was evaluated by biaxial flexural strength testing (ball-on-three-balls method) and fracture toughness testing using the chevron-notched beam technique. Both materials exhibited pronounced yttria- and phase-dependent gradients consistent with their reported layer designs. Regions with increased yttria content showed higher t″ fractions and reduced fracture toughness and strength, whereas deeper regions displayed increased mechanical performance associated with higher fractions of transformable tetragonal phase. These findings emphasize that multilayer zirconias exhibit spatially dependent mechanical properties, which should be considered in biomaterial selection and restoration design, particularly when balancing aesthetic demands and fracture resistance. Full article

CaFe₂O₄ is a p-type ferrite semiconductor of interest for photo-assisted environmental remediation due to its narrow band gap and high chemical stability. In this work, CaFe₂O₄ powders were synthesized via the Pechini polymeric precursor method and calcined between 550 and 850 °C to investigate the influence of calcination temperature on structural order and material properties. X-ray diffraction combined with Rietveld refinement revealed the progressive stabilization of the orthorhombic Pnma phase, accompanied by relaxation of the FeO₆ octahedral framework. Raman and FT-IR spectroscopies confirmed a significant increase in vibrational coherence with increasing calcination temperature, quantified by a nearly three-fold increase in the global Raman order parameter and phonon lifetimes. Nitrogen physisorption showed a modest specific surface area and a pore system dominated by interparticle meso–macroporosity, typical of thermally treated ferrites. Removal tests using ciprofloxacin under UV-A irradiation showed limited photo-assisted activity, while agar diffusion assays against Escherichia coli and Staphylococcus aureus revealed no inhibition halos, indicating the absence of detectable antibacterial activity under the experimental conditions employed. Overall, CaFe₂O₄ combines photo-assisted response with good structural stability, highlighting its potential as a chemically stable ceramic material with no detectable antibacterial activity under the tested conditions. Full article

(Li_0.4Co_0.2Ni_0.2Cu_0.2Zn_0.2)WO₄ high-entropy ceramics were prepared by a conventional solid-state reaction route. This study thoroughly explores the interrelationships between their crystal structure, bond properties, and microwave dielectric characteristics. X-ray diffraction analysis verified that all specimens crystallized in a single-phase ZnWO₄-type structure. According to Rietveld refinement of the XRD data, the lattice parameters are affected by the ionic radii of the constituent elements, confirming their dissolution and random distribution at Zn sites. Relative density exhibited a strong dependence on sintering temperature. Bonding analysis highlights the crucial role of the W–O bond in governing the dielectric response of the (Li_0.4Co_0.2Ni_0.2Cu_0.2Zn_0.2)WO₄ (LCNCZW) ceramics. Moreover, sinterability can be improved through optimizing the sintering process. Notably, samples sintered at 850 °C attained suitable dielectric performance, characterized by εᵣ = 11.697 ± 0.204, Q × f = 23,851 ± 0.126 GHz, and τ_f = 21.335 ± 0.232 ppm/°C. These results demonstrate that high-entropy design can effectively improve the sinterability and microwave dielectric performance of wolframite-type ceramics, offering a promising strategy for the development of microwave dielectric ceramics for communication devices. Full article

LaFeO₃ nanofibers and Ag-doped LaFeO₃ nanofibers were fabricated via an approach combining electrospinning with calcination. Their crystal structures, micro-morphologies, and chemical compositions were determined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. In addition, the conduction mechanisms and magnetic properties of the two samples were investigated using a semiconductor analyzer and a vibrating sample magnetometer. Rietveld refined X-ray diffraction analyses confirmed the orthorhombic structure. The two samples showed a nanofibrous structure. For Ag-doped LaFeO₃, the conduction was dominated by the ohmic conduction mechanism in a low-resistance state, while it was governed by space-charge-limited current conduction in a high-resistance state. It also showed a high on/off ratio of 3.6 × 10³. The coercivity and remanence values of Ag-doped LaFeO₃ were 200 Oe and 0.000404 emu g⁻¹. This, thus, indicates the considerable application potential of Ag-doped LaFeO₃ for resistive random-access memory devices and magnetoresistive random-access memory devices. Full article

Laser Powder Bed Fusion (LPBF) enables the fabrication of complex titanium alloy components with high geometric freedom; however, surface integrity and tribological performance remain critical limitations for sliding-contact applications in biomedical and aerospace systems. In this study, the influence of in-layer laser remelting on the microstructure, surface topography, and dry sliding tribological behavior of LPBF-fabricated Ti-6Al-4V ELI (Grade 23) is systematically investigated. Disc-shaped specimens were produced using single-scan (SS) and double-scan (DS, in-layer remelting) strategies and tested in ball-on-disc configuration against AISI 52100 steel at a constant normal load of 10 N and three sliding speeds of 0.10, 0.15, and 0.20 m·s⁻¹. Microstructural and phase-related characteristics were analyzed by X-ray diffraction combined with Rietveld refinement and Warren–Averbach analysis, revealing that the DS strategy increases retained β-phase fraction (up to 5.2%) and promotes crystallite coarsening relative to the SS condition, without significantly altering bulk hardness. Surface morphology examined by SEM/EDS and AFM revealed a more homogeneous near-surface topography in the DS condition. Tribological results indicate that sliding speed governs steady-state friction and wear, with specific wear rates increasing progressively from 5.13 to 5.44 × 10⁻⁴ mm³·N⁻¹·m⁻¹ for SS and from 6.47 to 7.52 × 10⁻⁴ mm³·N⁻¹·m⁻¹ for DS across the investigated speed range. The DS specimens exhibited higher wear rates than the SS condition across all tested speeds, while steady-state COF values remained comparable between strategies, indicating that remelting-induced microstructural modifications affect material removal mechanisms without proportionally destabilizing the frictional regime. These findings suggest that in-layer laser remelting represents a process-integrated parameter with measurable consequences for surface integrity and tribological performance, though the generalizability of these results warrants validation across broader experimental conditions. Full article

In the current work, the microstructural evolution and CO₂ sensing performance of tungsten trioxide (WO₃) thin films synthesized by reactive DC magnetron sputtering are investigated. Three specific thicknesses of 42, 66, and 131 nm were obtained and annealed at 500 °C, resulting in a stable monoclinic P2₁/n phase with a strong (200) preferred orientation. Gas sensing tests toward 10,000 ppm of CO₂ revealed that the 42 nm film achieves the highest sensitivity (92%) at an optimal operating temperature of 300 °C. Rietveld refinement and texture analysis (texture index, J) demonstrate that the superior performance of the thinnest film is driven by a synergy between its high surface porosity, a grain size comparable to the Debye length, and a high density of active sites on the (200) plane. While all films exhibit n-type semiconductor behavior, increasing thickness leads to microstructural densification and reduced texture, which hinders gas diffusion and operational stability. These findings establish thickness control as a critical parameter for engineering high-performance WO₃-based CO₂ sensors. Full article

This study investigates the dual mechanisms by which SiO₂ deteriorates magnesium phosphate cement (MPC) performance. MgO-SiO₂ clinkers were prepared using lightly calcined magnesia (MgO) with SiO₂ additions ranging from 1% to 9%, followed by calcination at temperatures between 1100 °C and 1500 °C. Through XRD–Rietveld refinement, workability, compressive strength, and hydration heat analyses, the damaging effects of SiO₂ were systematically evaluated. Results reveal that SiO₂ degrades MPC through two concurrent mechanisms: chemical consumption and physical deactivation of reactive MgO. Chemically, SiO₂ reacts with MgO during calcination to form inert forsterite (Mg₂SiO₄), irreversibly reducing reactive MgO content. Physically, SiO₂ and its reaction products lower the crystallinity and reactivity of remaining MgO while diluting reactive components. A calcination temperature of 1200 °C was optimal, yielding the highest compressive strength (3 d strength > 30 MPa). Increasing SiO₂ dosage monotonically reduced strength; at 1200 °C, 9% SiO₂ reduced 3 d strength by ~40% compared to 1%. Hydration heat analysis showed that both heat flow rate and cumulative heat release increased with SiO₂ content due to enhanced heterogeneous nucleation from Mg₂SiO₄. Critically, this increased heat output did not translate into higher strength, indicating that microstructural quality—not reaction extent—governs mechanical performance. Rietveld quantification confirmed that Mg₂SiO₄ formation increased linearly with SiO₂ dosage and temperature (reaching 72.24% at 1500 °C with 9% SiO₂), providing the material basis for dual damage. This work offers mechanistic insights and experimental support for utilizing low-grade magnesite and optimizing MPC performance. Full article

Titanium dioxide (TiO₂) is a versatile material that exhibits a high refractive index, strong light-scattering capability, effective UV-absorption, wide band gap semiconductor behavior (3.0–3.2 eV), and excellent chemical stability. Owing to this unique combination of properties, TiO₂ is widely used in applications such as cosmetic and healthcare products, architectural and automotive coatings, and photocatalytic degradation of environmental pollutants. In photocatalytic applications, the crystal structure, phase composition and electronic properties of TiO₂ play a critical role in determining its performance. In the present study, TiO₂ nanotubes were synthesized by anodization of Ti° coatings deposited via a semi-industrial arc-PVD process. A post-anodization heat treatment was carried out at 430 °C for 1 h to promote the formation of the anatase phase within the TiO₂ nanotube structures. The structural characterization of the synthesized film was performed using X-ray diffraction (XRD) and Rietveld refinement. This methodology enabled the identification of the formed oxide phases, structure, and crystalline, confirming the formation of mixed oxides in the coating. To address the difficulty of refinement of these crystalline phases, the Le Bail method was applied. This refinement strategy allowed the identification of the crystalline phases that are present in the Ti_xO_y coating, including a hexagonal structure characteristic of α-Ti (space group P63/mmc, No. 194), the tetragonal anatase TiO₂ (space group I41/amd, No. 141) phase, and the trigonal Ti₂O₃ phase (space group R-3/c No. 167). Key crystallographic parameters such as lattice constants, bond lengths and angles, crystallite sizes, unit cell distortion and electron density were systematically evaluated for each phase. In addition, the Wyckoff positions and interatomic distances of the constitutive atoms were calculated, providing a comprehensive description of the TiO₂+Ti₂O₃/Ti° crystallographic system. The topographic and surface oxidation states were recorded by using profilometry and X-ray photoelectron spectroscopy, respectively. Full article

Hafnium carbide (HfC) ceramics are of growing interest due to their exceptional mechanical properties and ultra-high melting points, making them ideal for extreme environmental applications. In this study, we present a synthesis route for HfC nanoparticles via carbothermal reduction of an organic–inorganic hybrid precursor derived from hafnium tetrachloride (HfCl₄) and pectin, followed by thermal treatment at 1500 °C for 1.5 h under an argon atmosphere. According to TGA/DSC analysis of the hybrid precursor, hafnia phases initially formed during pyrolysis and were subsequently converted into HfC at 1500 °C, with the endothermic carbothermal reduction reaction initiating near 1200 °C. Comprehensive characterization using Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), X-ray diffraction (XRD) with Rietveld refinement, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) confirmed the synthesis of hafnium carbide (HfC) exhibiting predominantly cubic morphology. XRD analysis determined a lattice parameter of a = 4.63 Å and an interplanar spacing of d = 2.68 Å. Rietveld refinement revealed a phase composition of 98.08% HfC and 1.92% monoclinic hafnium dioxide (m-HfO₂). Debye–Scherrer analysis indicated an average crystallite size of 67.6 nm. SEM and TEM images showed uniformly distributed nanoparticles with an average particle size of approximately 65–70 nm. Full article

Magnetoelectric (ME) materials that exhibit simultaneous coupling between electric polarization and magnetization have attracted significant attention due to their potential technological applications in the emerging generation of multifunctional devices. In this research, Ba_0.85Ca_0.15Ti_0.92Zr_0.08O₃-CoFe₂O₄:x (x = 0.1, 0.2, 0.3% mol) composites were synthesized using solid-state and sol–gel combustion chemical methods to elucidate their ME coupling at ultra-low concentrations of the magnetic phase. Rietveld refinement and Raman spectroscopy results confirm a shift in the morphotropic phase boundary (MPB), evidenced by an increase in the tetragonal phase relative to the orthorhombic structure. High stability of the P4mm and Amm2 symmetries is reached at 1300 °C without diffusion of Fe and Co into the octahedral site. At this temperature, the CoFe₂O₄ spinel structure remains stable without secondary phases. The orthorhombic phase fraction decreases from 55% to 37% as the magnetic phase fraction increases, driven by stress and constraint rather than ionic interactions alone. The Curie temperature decreases from 99 to 90 °C, attributed to the grain-size reduction effect rather than structural disorder. The dielectric permittivity (ε_r) reaches an absolute value of 5070 and progressively decreases with increasing magnetic saturation. An increase in compressive residual stress is observed, which ensures the mechanical stability of the electroceramics. Magnetoelectric (ME) coupling, evaluated through measurements of electric polarization as a function of the magnetic field, shows an increase from 3.8 to 4.9 μC/cm² under a magnetic field of 50 Oe. The composites with x = 0.2 and 0.3 mol% exhibit potential for applications in fast-switching magnetoelectric devices and magnetic field sensors. Full article

This study reports the valorization of oil palm empty fruit bunches into cellulose nanocrystals (CNCs) for the removal of the chemical oxygen demand (COD) from industrial wastewater generated by the same processing sector. Cellulose I_β was first isolated through sequential bleaching, delignification, and mercerization, and two hydrolysis routes were evaluated to obtain CNCs: a concentrated acid route (60% v/v H₂SO₄, 50 °C, 60 min) for CNCs-1 and a low-acid, long-duration route (1% v/v H₂SO₄, 80 °C, 12 h) for CNCs-2. Rietveld refinement of the X-ray diffractograms confirmed the polymorphic transition, assigning cellulose I_β to the intermediate materials and cellulose II to the CNC samples, with crystallite sizes of 4.99 nm for CNCs-1 and 5.43 nm for CNCs-2. Attenuated Total Reflectance–Fourier Transform Infrared (ATR-FTIR) spectroscopy analysis showed the progressive removal of lignin and hemicellulose and supported the cellulose I_β to II transition through changes in hydroxyl bonding and crystallinity-related bands. Preliminary adsorption tests showed better COD removal with CNCs-2, which were therefore selected for optimization using a Box–Behnken design with the adsorbent mass, pH, and contact time as variables. The quadratic model was significant (R² = 0.9675; predicted R² = 0.8908), and the maximum COD removal reached 91.47%, decreasing the COD concentration from 2459.0 to 209.85 mg L⁻¹ under the optimum conditions of 0.09 g CNCs-2, pH 3, and 20 min. These results highlight cellulose II nanocrystals derived from oil palm waste as a promising and scalable adsorbent for industrial wastewater treatment. Full article

Y₂O₃ is widely used in IR windows and optoelectronics, but its vibrational and spectral properties under La³⁺ substitutions remain unclear. This work investigates xLa₂O₃-(1−x)Y₂O₃ with x = 0–0.2 via XRD, SEM, Raman, and IR spectroscopy to address the lack of comprehensive data on structure–property correlations. The solid solution (Y_1−xLa_x)₂O₃ with 0 ≤ x < 0.15 was determined. The cell parameter a increases from 10.6113(5) Å to 10.7116(1) Å as x increases from 0 to 0.15 according to the Rietveld refinements. Both the Raman spectra and infrared (IR) reflection spectra show that (Y_1−xLa_x)₂O₃ is a “one-mode” system, in which eight of the 22 theoretical first-order Raman modes and 12 of 16 theoretical IR modes for the (Y_1−xLa_x)₂O₃ are recognized. A local vibrational mode at approximately 680 cm⁻¹ is observed in the Raman spectra as x > 0. The Raman modes and IR modes of (Y_1−xLa_x)₂O₃ show red shift and obvious peak broadening as x increases, which is caused by the expansion of unit cell and local distortions of the crystal structure. As Y³⁺ is substituted by La³⁺, the extinction coefficient κ decreases significantly, which can lead to a lower IR absorption and should be beneficial for the IR window applications. Full article

Nanocrystalline CeO₂ exhibits size-dependent lattice distortions linked to defect chemistry and surface effects. However, the relationships between the oxidation state, surface interactions, and nanoparticle structure remain unclear in the existing literature, particularly when inferred from conventional nanoparticle diffraction techniques, including powder X-ray diffraction. As a result, the atomistic origin of lattice expansion or contraction with the crystallite size of ceria nanoparticles is still debated. Here, synchrotron X-ray powder diffraction data are analyzed using Rietveld refinement supported by advanced peak profile modeling based on whole powder pattern modeling (WPPM), including thermal diffuse scattering (TDS). The latter provides direct access to information on lattice dynamics. Indeed, we simultaneously determine the size distributions of crystalline domains and their atomic displacements, which are then compared and quantitatively validated with molecular dynamics (MD) simulations. Reactive MD simulations further reveal that vacancy-rich surfaces induce lattice contraction at small particle sizes under vacuum, whereas water adsorption causes surface hydroxylation and lattice expansion. These results explain lattice parameter variations in nanocrystalline ceria through the interplay of surface chemistry and environment. This insight is critical for the correct interpretation of diffraction-derived structural parameters in oxide nanocatalysts used in redox and oxygen storage applications. Full article

In the present manuscript, the influence of reaction time on the hexagonal-to-monoclinic phase transition in hydroxyapatite (HAp) nanofibers synthesized via a low-temperature modified hydrothermal method at 100 °C is investigated. The resulting nanofibers were highly crystalline and stoichiometric, with a Ca/P ratio of approximately 1.67. Comprehensive structural and functional characterization, combining X-ray diffraction with Rietveld refinement, Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), and resonance-tracking piezoresponse force microscopy (RT-PFM), was employed to elucidate the role of the non-centrosymmetric monoclinic P2₁/b phase in governing HAp’s structural and piezoelectric properties. The analyses indicated a time-dependent phase evolution from hexagonal (P6₃/m) to monoclinic (P2₁/b), with exclusive formation of the hexagonal phase at 6 h and a clearly dominant monoclinic fraction (73.56%) after 24 h. Nanofibers synthesized for 48 h comprised approximately 98% monoclinic HAp and exhibited elongated morphologies with an average length of 354.82 nm and diameter of 45 nm. RT-PFM measurements confirmed a pronounced piezoelectric response associated with the monoclinic phase, yielding an effective piezoelectric coefficient (d_eff) of 19.85 pm/V. In vitro MTT assays demonstrated that the high monoclinic content did not compromise biocompatibility, as cell viability and cytotoxicity met the requirements of ISO 10993 and ASTM F895 standards. These findings offer new insights into how monoclinic ordering governs the piezoelectric behavior of HAp and suggest a promising strategy for enhancing its performance in biomedical applications. Full article

The aqueous sol–gel preparation technique was successfully employed for synthesizing a homogeneous La–Ti–Mo–O tartrate gel precursor, and thermal treatment at 1000 °C promoted the formation of nanocrystalline complex La_2−xTi_xMo₂O_9+x/2 ceramic. X-ray diffraction analysis revealed a consistent influence of increasing the degree of titanium substitution on the formation of the La₂Mo₂O₃ and La₂MoO₆ impurity phases within the crystalline mixture. Meanwhile, the stability of the high-temperature cubic β-La₂Mo₂O₉ phase in the La_2−xTi_xMo₂O_9+x/2 system at room temperature highlighted the distinct influence of titanium content from structural and thermodynamic perspectives. However, the Raman spectroscopy analysis showed no distinct variations in the spectra of La_2−xTi_xMo₂O_9+x/2 samples, suggesting a substantial effect of titanium on the phase transition behavior between the low-temperature monoclinic α-La₂Mo₂O₉ and the high-temperature cubic β-La₂Mo₂O₉ phases. Full article