Search Results (14)

NASICON-type titanium and zirconium phosphates doped with rare-earth cations, A_0.33M₂(PO₄)₃ (M = Ti, Zr; A = Dy, Y, Yb), were synthesized using the sol–gel method and investigated as catalysts for ethanol dehydration at 300–400 °C. The catalysts were characterized via XRD, SEM, BET, and FTIR spectroscopy. The relationships between the catalyst composition, acidity and the dehydration activity were evaluated. Diethyl ether (DEE) formation is promoted by the presence of the zirconium phosphates (ZrP), while the presence of titanium phosphate (TiP) catalyzes the formation of both ethylene and diethyl ether (DEE). The application of Fourier-transform infrared (FTIR) spectroscopy to the analysis of adsorbed C₆H₆ has revealed the presence of hydroxyl groups exhibiting varying degrees of proton-donating mobility. This finding has enabled the correlation of the structure of the active sites with the process’s selectivity. The results underscore the key function of OH-group localization and framework geometry in the control of form-selective reactions. Full article

Organophosphorus pesticides (OPs), while pivotal for agricultural productivity, pose severe environmental and health risks due to their persistence and bioaccumulation. Existing detection methods, such as chromatography and spectroscopy, face limitations in field adaptability, cost, and operational complexity. To address these challenges, this study introduces a novel dual-mode photoelectrochemical–electrochemical (PEC-EC) sensor based on a Co,N-TiO₂@ZrO₂/3DGH nanocomposite. The sensor synergistically integrates zirconium oxide (ZrO₂) for selective OP capture via phosphate-Zr coordination, cobalt-nitrogen co-doped titanium dioxide (Co,N-TiO₂) for visible-light responsiveness, and a three-dimensional graphene hydrogel (3DGH) for enhanced conductivity. In the PEC mode under light irradiation, OP adsorption induces charge recombination, yielding a logarithmic photocurrent attenuation with a detection limit of 0.058 ng mL⁻¹. Subsequently, the EC mode via square wave voltammetry (SWV) self-validates the results, achieving a detection limit of 0.716 ng mL⁻¹. The dual-mode system demonstrates exceptional reproducibility, long-term stability, and selectivity against common interferents. Parallel measurements revealed <5% inter-mode discrepancy, validating the intrinsic self-checking capability. This portable platform bridges the gap between laboratory-grade accuracy and field-deployable simplicity, offering transformative potential for environmental monitoring and food safety management. Full article

The removal of copper from wastewater of mine origin requires the use of an appropriate method. Sorption methods are considered to be one of the best solutions for removing copper from industrial wastewater at low levels. Metal(IV) phosphates have been reported as excellent sorption materials that can be highly selective for copper. Therefore, the aim of this research was to synthesize titanium(IV), zirconium(IV), and cerium(IV) phosphates with a wide range of P:Metal(IV) molar ratios (0.5–10) in the reaction mixture and under mild conditions, using a simple scalable approach which requires minimal financial outlays. The obtained materials were characterized using XRD, ATR-FTIR, SEM-EDS techniques, and pH titration. To evaluate the performance of the resulting materials, their sorption properties towards copper ions were examined in comparison with selected commercially available ion-exchange resins. In each group of metal(IV) phosphates, the best material has a high ion-exchange capacity: 16.9 meq/g for titanium sorbent, 8.8 meq/g for zirconium sorbent, and 7.0 meq/g for cerium sorbent. Zirconium phosphate synthesized at a P:Zr molar ratio in the reaction mixture of 10:1 exhibits the best sorption properties towards copper ions in a solution similar to mining wastewater (acidic, saline, and containing heavy metals), better than some commercial ion-exchange resins. Full article

Zr-50Ti alloys are promising biomaterials due to their excellent mechanical properties and low magnetic susceptibility. However, Zr-50Ti alloys do not inherently bond well with bone. This study aims to enhance the bioactivity and bonding strength of Zr-50Ti alloys for orthopedic implant materials. Initially, the surface of Zr-50Ti alloys was treated with a sulfuric acid solution to create a microporous structure, increasing surface roughness and area. Subsequently, low crystalline calcium phosphate (L-CaP) precipitation was controlled by adding Mg²⁺ and/or CO₃²⁻ ions in modified simulated body fluid (m-SBF). The treated Zr-50Ti alloys were then subjected to cold isostatic pressing to force m-SBF into the micropores, followed by incubation to allow L-CaP formation. The apatite-forming process was tested in simulated body fluid (SBF). The results demonstrated that the incorporation of Mg²⁺ and/or CO₃²⁻ ions enabled the L-CaP to cover the entire surface of Zr-50Ti alloys within only one day. After short-term soaking in SBF, the L-CaP layer, modulated by Mg²⁺ and/or CO₃²⁻ ions, formed a uniform hydroxyapatite (HA) coating on the surface of the Zr-50Ti alloys, showing potential for optimized bone integration. After soaking in SBF for 14 days, the bonding strength between the apatite layer and alloy has the potential to meet the orthopedic application requirement of 22 MPa. This study demonstrates an effective method to enhance the bioactivity and bonding strength of Zr-50Ti alloys for orthopedic applications. Full article

The use of hybrid abutment crowns bonded extraorally to a titanium bonding base has aesthetic and biological benefits for the prosthetic rehabilitation of oral implants. The objective of this study was to evaluate the effects of luting agents between a zirconium dioxide crown and the titanium bonding base on crown/abutment retention and the subsequent durability of the prosthetic superstructure. Fifty-six implant abutment samples, all restored with a lower first premolar zirconium dioxide crown, were used and divided into seven groups (n = 8/group) according to the type of luting agent used: group 1, SpeedCEM Plus; group 2, Panavia SA Cement Universal; group 3, Panavia V5; group 4, RelyX Unicem 2 Automix; group 5, VITA ADIVA IA-Cem; group 6, Ketac CEM; and group 7, Hoffmann’s Phosphate Cement. All specimens were subjected to thermomechanical loading (load of 49 N, 5 million chewing cycles and 54.825 thermocycles in water with temperatures of 5 °C and 55 °C). The surviving samples were exposed to a pull-off force until crown debonding from the bonding base. Overall, 55 samples survived the thermomechanical load. Group 2 showed the highest mean pull-off force value (762 N), whereas group 6 showed the lowest mean value (55 N). The differences between the seven groups were statistically significant (ANOVA, p < 0.001). The debonding failure pattern was mainly adhesive and was noticed predominantly at the zirconium dioxide–luting agent interface. Within the scope of the present investigation, it was shown that most of the luting agents are suitable for “cementation” of a zirconium dioxide crown onto a titanium base since the debonding forces are above a recommended value (159 N). Full article

Achieving lightweight, high-strength, and biocompatible composites is a crucial objective in the field of tissue engineering. Intricate porous metallic structures, such as lattices, scaffolds, or triply periodic minimal surfaces (TPMSs), created via the selective laser melting (SLM) technique, are utilized as load-bearing matrices for filled ceramics. The primary metal alloys in this category are titanium-based Ti6Al4V and iron-based 316L, which can have either a uniform cell or a gradient structure. Well-known ceramics used in biomaterial applications include titanium dioxide (TiO₂), zirconium dioxide (ZrO₂), aluminum oxide (Al₂O₃), hydroxyapatite (HA), wollastonite (W), and tricalcium phosphate (TCP). To fill the structures fabricated by SLM, an appropriate ceramic is employed through the spark plasma sintering (SPS) method, making them suitable for in vitro or in vivo applications following minor post-processing. The combined SLM-SPS approach offers advantages, such as rapid design and prototyping, as well as assured densification and consolidation, although challenges persist in terms of large-scale structure and molding design. The individual or combined application of SLM and SPS processes can be implemented based on the specific requirements for fabricated sample size, shape complexity, densification, and mass productivity. This flexibility is a notable advantage offered by the combined processes of SLM and SPS. The present article provides an overview of metal–ceramic composites produced through SLM-SPS techniques. Mg-W-HA demonstrates promise for load-bearing biomedical applications, while Cu-TiO₂-Ag exhibits potential for virucidal activities. Moreover, a functionally graded lattice (FGL) structure, either in radial or longitudinal directions, offers enhanced advantages by allowing adjustability and control over porosity, roughness, strength, and material proportions within the composite. Full article

The article presents the distribution coefficient (K_d) values of ¹³⁷Cs and ⁹⁰Sr tracer radionuclides in solutions of sodium and calcium salts for a wide range of commercially available inorganic sorbents: natural and synthetic aluminosilicates, manganese, titanium and zirconium oxyhydrates, titanium and zirconium phosphates, titanosilicates of alkali metals, and ferrocyanides of transition metals. The results were obtained using a standard technique developed by the authors for evaluating the efficiency of various sorption materials towards cesium and strontium radionuclides. It was shown that bentonite clays and natural and synthetic zeolites are the best for decontaminating low-salt natural water from cesium radionuclides, and ferrocyanide sorbents are the choice for decontaminating high-salt-bearing solutions. The manganese (III, IV) oxyhydrate-based MDM sorbent is the most effective for removing strontium from natural water; for seawater, the barium silicate-based SRM-Sr sorbent is the first-in-class. Results of the study provide a possibility of making a reasonable choice of sorbents for the most effective treatment of natural water and technogenic aqueous waste contaminated with cesium and strontium radionuclides. Full article

Eudialyte-group minerals are of scientific interest as important concentrators of rare elements (mainly Zr and REE) in agpaitic alkaline rocks and a potential source of REE, Zr, Hf, Nb, and Ta for industrial use. Extraction of uranium(VI), thorium(IV), zirconium(IV), hafnium(IV), titanium(IV), and scandium(III) by a binary extractant based on 1,5-bis[2-(hydroxyethoxyphosphoryl)-4-ethylphenoxy]-3-oxapentane and methyl trioctylammonium nitrate from eudialyte breakdown solutions is studied. Extraction isotherms were obtained and exhaustive extraction was investigated. It is shown that uranium, thorium, hafnium, zirconium, scandium, and titanium are almost completely recovered in two-stage extraction by a mixture of 1,5-bis[2-(hydroxyethoxyphosphoryl)-4-ethylphenoxy]-3-oxapentane and methyltrioctylammonium nitrate in 1,2-dichloroethane. Quantitative characteristics were compared for uranium(VI), thorium(IV), zirconium(IV), hafnium(IV), titanium(IV), and scandium(III). It was shown that the extraction efficiency of the metals by the binary extractant based on 1,5-bis[2-(hydroxyethoxyphosphoryl)-4-ethylphenoxy]-3-oxapentane and methyltrioctylammonium nitrate in 1,2-dichloroethane is much higher in comparison with the commercially available tributyl phosphate. Full article

In this work, new solid electrolytes Li_1+yTi_2−x−yZr_xAl_y(PO₄)₃ (0 ≤ x ≤ 0.2, 0 ≤ y ≤ 0.2) were prepared by the sol-gel and solid-state methods (sintering temperatures: 800–1000 °C). The prepared materials were characterized by X-ray powder diffraction and scanning electron microscopy. Their conductivity was investigated by impedance spectroscopy in the temperature range of 25–200 °C. The activation energies of Li⁺ transfer were calculated. The Li_1.2Ti_1.7Zr_0.1Al_0.2(PO₄)₃ material prepared by solid-state reaction exhibits the highest conductivity at 25 °C (6.2 × 10⁻⁴ S/cm). Full article

Metal phosphates represent an important group of materials with established industrial applications that are still attracting special scientific interest, owing to their outstanding physical and chemical properties. In this review, we account on the different synthetic routes and applications of zirconium and titanium phosphates, with a special focus on their application in the medicinal field. While zirconium phosphate has been extensively studied and explored with several reported industrial and medicinal applications, especially for drug delivery applications, titanium phosphates have not yet attracted the deserved attention regarding their established applications. However, titanium phosphates have been the focus of several structural studies with their different polymorphic forms, varied chemical structures, and morphologies. These variations introduce titanium phosphates as a strong candidate for technological and, particularly, biomedical applications. Full article

In this study, the composite of silica-based sandwich-layered zirconium-titanium phosphate was prepared by a layer-by-layer grafting method and its adsorption properties in a diluted solution of Ni ions were specifically researched by the bath experiment method. The field-emission scanning electron microscope (FESEM) results presented the smooth surface morphology of the pristine adsorbent and a rough surface morphology of the adsorbed adsorbent and the energy dispersive analysis (EDS) results ensured the presence of the original metal element (Si, O, Ti, P, Zr) and the captured nickel element on the adsorbent. The Fourier transformed infrared spectroscopy (FTIR) revealed the new band formation of -Si-Ti-O-, -Si-Ti-O-P-, and -Si-Ti-O-P-Zr-O-, which ensured the successful modification of the silica substrate by zirconium-titanium phosphate. The specific surface area and pore size distribution analysis indicated that the pore structure was changed from type-Ⅳ to H2-type and the specific surface area (BET) of the modified composite was 337.881 m²/g. In the bath experiment, the optimal pH for adsorbing Ni ions on the composite was ~8 with the equilibrium time 30 min at room temperature and the maximum sorption amount was 50.1 mg/g. The adsorption kinetics of the sorption process were corresponded to the pseudo-second-order kinetic equation and the isothermal adsorption data were fitted well to the Redlich-Peterson Model. Thermodynamic simulation results revealed the species of Ni ions and provided a reasonable pH scope for better removal of the Ni element in wastewater. Full article

There is an increasing demand on synthesizing pharmaceuticals and biomaterials that possess antimicrobial and/or antiviral activities. In this respective silver nanoparticles are known for their excellent antimicrobial activity. Nevertheless, their uncontrolled release in a biological medium can induce a cytotoxic effect. For this, we explored the use of nanolayered metal phosphates based on titanium and zirconium as materials that can be enriched with silver nanoparticles. Employing the hydrothermal route, crystalline α-phases of zirconium and titanium phosphates (α-ZrP, α-TiP) were synthesized and there after surface-enriched with silver nanoparticles. The structural assessment confirmed the stability of the structures and their sizes are in the nanoscale at least in one dimension. The cytocompatibility assays confirmed the biocompatibility of the pristine phases and the antimicrobial assay confirmed that both silver-enriched nanolayered structures maintain an antibacterial effect at reasonably low concentrations. Full article

Calcium (titanium, zirconium) hexaorthophosphates with a [NZP] (sodium zirconium phosphate) structure belonging to the NaSiCon (Na Superionic Conductor) family were deposited by atmospheric plasma spraying onto the surfaces of Ti6Al4V substrates. (NaSiCon sensu strictu refers to solids with the chemical formula Na_1+xZr₂Si_xP_3−xO₁₂, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements). The microstructure of the coatings revealed the incongruent melting of the precursor material as ascertained by electron probe microanalysis (EPMA). The adhesion of the coatings to the substrate surface was within the limits specified for biomedical coatings. The solubility of the coatings was tested by immersion in 0.2 molar tris–hydroxymethyl–amino–methane–HCl (TRIS–HCl) buffer and found to be at least one order of magnitude lower than that of conventional hydroxylapatite coatings deposited under comparable conditions. In vitro biocompatibility tests with primary rat bone marrow cells (BMCs) showed a substantial cell proliferation in the presence of fetal bovine serum. Animal tests confirmed that coatings based on calcium (titanium, zirconium) hexaorthophosphates applied to Ti6Al4V rods implanted in the femoral medulla of sheep led to the strong neoformation of dense bone at a stable interface implant-bioceramic coating without coating delamination. Hence, based on their multifarious advantageous properties in the biomedical context, CaTi_4-xZr_x(PO₄)₆ ceramics may be considered the ‘Sleeping Beauty’ of osseoconductive coatings for the stem of hip endoprostheses and dental root implants, osteosynthetic fixation devices, and bioelectric devices including bone growth stimulators. Full article

The clinical success of dental implantation is associated with the phenomenon of osteointegration. Geometry and topography of the implant surface are critical for the short- and long-term success of an implantation. Modification of the surface of endosseous part of the implant with sandblasting was of special interest for our study. Taking into account the advantages of currently used ceramic abrasives: aluminum oxide, titanium oxide, calcium phosphate, these materials are able to break down during collision with the treated surface, the possibility of incorporation of their residues into the implant surface, as well as the difficulty of removing these residues. This paper aimed to determine the preferred composition and the shape of the abrasive, as well as the treatment regime for ZrO₂ sandblasting modification of the surface of the endosseous part of the dental implant. Tetragonal and cubic solid solutions are based on ZrO₂, as an abrasive that is applied for zirconium-niobium alloy sandblasting under different pressures. Optical and scanning electron microscopy, the physical and chemical state of the surface of implants as well as contact angle measurement and cell viability were used to assess surface after sandblasting. The results demonstrate the potential of using granular powders that are based on zirconium dioxide as an abrasive to create a rough surface on endosseous part of dental implants made from zirconium-based alloys. It does not lead to a significant change in the chemical composition of the surface layer of the alloy and it does not require subsequent etching in order to remove the abrasive particles. Based on structural and chemical characterization, as well as on cell viability and contact angle measurement, sandblasting by tetragonal ZrO₂ powder in 4 atm. and an exposure time of 5 s provided the best surface for dental implant application. Full article