Ion Substitution Research Articles

In situ reconstruction of proton conductive electrolyte from self-assembled perovskite oxide-based nanocomposite for low temperature ceramic fuel cells

In the development of low temperature solid oxide fuel cells (LT-SOFCs), also called ceramic fuel cells, the lack of highly conductive and the high manufacturing cost of dense electrolyte materials severely delay their wide development. In this work, we depart from the classic substitution approach to achieve sufficient ionic conduction (0.01 S cm−2 level at temperature ≥600 °C), a superionic conductive electrolyte material was obtained from a self-assembled hybrid oxide that was derived from the perovskite oxide precursor through alkali metal ion substitution. Moreover, the hybrid oxide was further in-situ reconstructed into a nanocomposite of oxide/carbonate-hydroxide under fuel cell condition. The nanocomposite possesses dominated proton conductivity as verified by the benefited hydration effect, versatile oxygen ionic blocking cell experiment, and concentration cell investigation. Specifically, an outstanding ionic conductivity of 0.185 S cm−1 and an excellent peak power density of 1012 mW cm−2 were demonstrated at 550 °C under an typical H2/air atmosphere. This research offers a rational design strategy to achieve low temperature, high-performance semiconductor-based functional composite electrolytes for efficient and sustainable energy conversion in SOFC technology.

Near-room-temperature magnetic properties and magnetocaloric effect of polycrystalline and nano-scale manganites Pr(0.65-x)NdxSr0.35MnO3 (x ≤ 0.35)

Here we report investigations of structural, electrical and magnetic properties of bulk and nano-sized Pr0.65-xNdxSr0.35MnO3 compounds (x ≤ 0.35). Polycrystalline compounds were produced by solid – state reaction and nanocrystalline samples were obtained by sol–gel method. Analysis of x-ray diffraction patterns revealed a change in lattice structure from ‘Pbnm’ to ‘R3c’ symmetry, with diminishing cell volume upon increasing Nd ions substitution for all samples. Optical microscopy was used for bulk surface morphology and transmission electron microscopy was implemented for nano-sized samples. Iodometric titration showed oxygen deficiency for bulk compounds and oxygen excess for nano-sized particles. Measurements of resistivity of bulk samples revealed a single peak at temperatures associated with grain boundary conditions and with ferromagnetic/paramagnetic transition and negative magnetoresistivity. Critical magnetic behavior analysis disclosed that the polycrystalline samples are governed by a tricritical mean field and by 3D Heisenberg models while nanocrystalline samples are governed by a mean field model. Curie temperature Tc values remain in near room temperature range for all bulk compounds; they lower with increasing Nd ions substitution from 295 K for the parent bulk compound to 268 K for x = 0.35. Tc is lowered from 255 K for the parent nano-sized compound in small temperature intervals. All compounds exhibit second-order magnetic phase transitions and relatively high magnetic entropy change, with the highest value of 5.74 J/kgK for x = 0.25 bulk sample in μ˳∆H = 4 T. Strong magnetocaloric effect, stability and the possibility of fine-tuning Tc by Nd ions substitution make the investigated bulk polycrystalline compounds promising for application in magnetic refrigeration. Nano-sized samples possess lower magnetic entropy changes of maximum 2.4 J/kgK in μ˳∆H = 4 T for x = 0.15, but wider effective entropy change temperature (δTfwhm) and relative cooling power on par with other manganites, bringing them into the conversation as a viable option in cooling materials.

Regulating the electronic and crystal structure of Na3V2(PO4)3 by pillar ionic substitution and p-type doping effects

Currently, low intrinsic conductivity seriously affects the development and large-scale application of Na3V2(PO4)3 (NVP). Herein, the binary K+/Mn2+ co-substituted Na2.96+xK0.04 V2-xMnx(PO4)3 (x = 0.005, 0, 0.01, 0.04) with enwrapped carbon nanotubes (CNTs) are synthesised. The incorporation of CNTs can form an effective conductive framework and provide more conductive paths, thus reducing the resistance of electron and ion migration thereby increasing the overall conductivity. Notably, replacing Na+ by pillar ion K+ with a larger radius can effectively strengthen the crystal structure of NVP, thus increasing the cycling stability of the battery. Besides, due to the differences in atomic radius and electronic structure between Mn2+ and V3+, this substitution can change the local environment of Na+ in the crystal, thus affecting its migration behaviour. Because of the larger ionic radius of Mn2+, it helps to increase the inter-facial distance in the crystal structure, which is favourable to promote the migration of Na+. Meanwhile, divalent Mn2+ occupying V3+ site can generate p-type doping effects, which introduces more hole carriers, thus increasing the intrinsic conductivity of the material. Accordingly, the optimized NVP/C@KMn0.01 achieves a capacity of 106.4 mAh g−1 at 1C, and maintains 98.1 mAh g−1 with a retention rate of 92.19 % after 230 cycles. At 15C, it reveals 106.1 mAh g−1 and keeps 82.5 mAh g−1 after 5800 cycles, corresponding to a capacity retention of 77.76 %. Furthermore, NVP/C@KMn0.01//CHC full cell delivers a high value of 155.0 mAh g−1 and enables to lighten the LED bulbs, indicating its excellent practical application prospects. The improved crystal structure of NVP/C@KMn0.01 is further verified by post-cycled XRD/SEM/XPS measurements.

Regulating the redshift of the charge transfer band edge and antithermal quenching by ion substitution strategy in YP1-xVxO4:Eu3+ phosphor

The redshift of the charge transfer band (CTB) edge of phosphor induced by temperature rise is pervasively accompanied by antithermal quenching. Accordingly, exploring the mechanism of the CTB redshift is thus not only propitious for optimizing the sensitivity of optical thermometry but also tenders a new idea for the design of antithermal quenching phosphors. Herein, a family of YP1-xVxO4:Eu3+ phosphors were designed via the V5+/P5+ ion substitution strategy. With the increase of the V5+ ratio, the relative integral intensity of the 5D0→7F2 transition multiplies from 1.25 to 28.67 times under CTB edge excitation. Moreover, by Gaussian fitting, the reduction degree of vanadate band gap energy 1E (1T1)→1B2 (1T2), 1A2 (1T1)→1B2 (1T2) increased from 0.122 eV and 0.065 eV to0.162 eV and 0.083 eV, respectively, in the range of 303–523 K. Both reveal an enhance in redshift of the excitation spectra. The decrease of charge transfer state (CTS) energy level and the alteration of photoelectron thermal population are two mechanisms that induce CTB redshift. Specifically, the decrease of the CTS level is dominant in the YPO4:Eu3+ sample, and the thermal population of the higher vibrational levels of the VO43−ground state is dominant in the presence of a tiny amount of V5+ doping. In addition, according to the experimental phenomenon, a dual-mode temperature sensing scheme based on excitation intensity ratio (EIR) and single band ratiometric (SBR) is proposed. Y0.9P0.1V0.9O4:0.1Eu3+ achieves a maximum sensitivity of Sr-max = 4.040 % K−1 and a minimum temperature determination uncertainty of δT = 0.124 K at 323 K, which excellent performance indicates that this is a promising non-contact optical thermometer.

Constraining sulfur incorporation in calcite using inorganic precipitation experiments

The sulfur over calcium ratio (S/Ca) in foraminiferal shells was recently proposed as a new and independent proxy for reconstructing marine inorganic carbon chemistry. This new approach assumes that sulfur is incorporated into CaCO3 predominantly in the form of sulfate (SO42−) through lattice substitution for carbonate ions (CO32–), and that S/Ca thus reflects seawater [CO32–]. Although foraminiferal growth experiments validated this approach, field studies showed controversial results suggesting that the potential impact of [CO32–] may be overwritten by one or more parameters. Hence, to better understand the inorganic processes involved, we here investigate S/Ca values in inorganically precipitated CaCO3 (S/Ca(cc)) grown in solutions of CaCl2 − Na2CO3 − Na2SO4 − B(OH)3 − MgCl2. Experimental results indicate the dependence of sulfate partitioning in CaCO3 on the carbon chemistry via changing pH and suggest that faster precipitation rates increase the partition coefficient for sulfur. The S/Ca ratios of our inorganic calcite samples show positive correlation with modelled [CaSO40](aq), but not with the concentration of free SO42− ions. This challenges the traditional model for sulfate incorporation in calcite and implies that the uptake of sulfate potentially occurs via ion-ion pairs rather than being incorporated as single anions. Based on the [Ca2+] dependence via speciation, we here suggest a critical evaluation of this potential proxy. As sulfate complexation seems to control sulfate uptake in inorganic calcite, application as a proxy using foraminiferal calcite may be limited to periods for which seawater chemistry is well-constrained. As foraminiferal calcite growth is modulated by inward Ca2+ flow to the site of calcification coupled to outward H+ pumping, sulfate incorporation as CaSO40 ion-pair in the foraminifer’s shell also provides a mechanistic link for the observed relationship between S/Ca(cc) and [CO32–].

Unlocking the potential of cation vacancy-enriched ZnMn1.75O4 cathode for advanced aqueous aluminum-ion batteries

Manganese oxides are widely utilized in aqueous aluminum-ion batteries (AIBs) due to their high voltage and diverse crystal structures. However, the Jahn-Teller effect induced by Mn-O6 units results in irreversible structural damage. Here, we synthesized ZnMn1.75O4 (ZMO) cathodes loaded onto a carbon framework with manganese vacancies (VMn) for AIBs through ion substitution, manganese extraction, and carbonization on Mn-MIL. VMn stabilizes the ZMO structure by damping Mn-O bond vibrations and fosters Mn-O-C bonds between oxide particles and the carbon framework, effectively suppressing irreversible Mn2+ dissolution. Vacancy-modified cathodes provide more ion insertion sites, promoting ion diffusion. Ex-situ characterization revealed dominant H+ and Al3+ insertion behavior during different voltage regimes. Upon initial discharge, ion insertion into vacant lattice sites causes lattice distortions in adjacent unit cells, prompting ZMO to undergo a crystal structure transition and partial zinc deintercalation, resulting in a more stable cathode structure. Therefore, Al/ZMO batteries exhibit enhanced electrochemical performance.

Physicochemical analysis of Catonyx cuvieri (Mammalia, Xenarthra) remains from the Pleistocene of Paraguay

The fossil-diagenetic characteristics, such as mineralogical aspects present in the ribs of Catonyx cuvieri (Lund, 1839) (Mammalia, Xenarthra), were analyzed in this work. These analyzed remains come from the Risso Cave, San Lazaro's District, Concepción Department, Paraguay. The vibrational response was studied using Raman and Fourier transform infrared (FTIR) and the mineralogy and elemental compositions were examined using multiple characterizations techniques. The main functional groups belong to the mineral part of the bone, and specific functional groups were associated with organic components. The characterization indicated that material was composed of apatites and the original mineral structure was affected by partial ionic substitutions, probably due to the interaction of the fossil with the environment. A Gaussian deconvolution model (GM) was used to identify the individual overlapping bands in the regions of interest in the spectra. A diagenesis pathway for the fossil involved the inclusion of calcium carbonate on the surface of the bone due to the accumulation of moisture, which allowed the recrystallization of hydroxyapatite and the precipitation of calcite in the pores and silicates of the bone. It’s worth mentioning that this work is the first in the ground sloths C. cuvieri in South America. In addition, the material here constitutes the most complete fossil record of a member of the Pleistocene megafaunal of Paraguay.

Influence of purification methods on the extraction of nanocrystals from bio-hydroxyapatite under consideration of the coalescence phenomenon

The coalescence of nanocrystals that occurs during low-temperature thermal treatments during the purification of hydroxyapatite from pigs has not yet been studied in the context of low-temperature environmentally friendly purification. To preserve the nature of hydroxyapatite, two extraction methods were investigated: Route 1 (autoclave and Soxhlet) and Route 2 (calcination at low temperatures with different times). The focus is on observing the effectiveness of removing fats and proteins while maintaining crystallite size and morphology. DSC showed that coalescence of crystallites occurred at 452, 566, 648, and 704 °C. Raw has a higher IR FWHM (phosphate band) due to the organic material; R1 had a lower FWHM (partial removal of lipids and proteins). Increasing the calcination temperature decreases the FWHM, indicating a shift in vibrational states from surface to bulk, leading to an increase in apparent crystallite size due to coalescence. For 20–80 h at quasi-stable temperatures of 400 and 500 °C, no significant changes occur in the IR spectrum. X-ray diffraction indicates the removal of organic material during calcination, as the peaks become clearer with increasing temperature. The crystallite size is not affected and remains in similar ranges. Purification with hydroxide shows an increase in both lattice parameters, in addition to the fluctuations that occur due to the ionic substitutions that naturally occur in biogenic HAp. And the TEM study confirms that the changes in apparent size from 2D to 3D are the result of the phenomenon of interplanar coalescence at low temperatures that occurs in sintering processes.

Sodium alginate synergises with copper ion deposition on LDH surface to enhance the fire resistance of waterborne epoxy coatings

Layered double hydroxide (LDH) possesses the effect of interlayer barrier and dilute the concentration of flammable gases due to its unique lamellar structure, which enables it to perform excellent flame retardancy in both gas and condensed phases. In this paper, the abundant hydroxyl and carboxyl groups on the surface of sodium alginate (SA) were utilized to confer excellent hydrophilicity to LDH. Meanwhile, through ion substitution at the carboxyl site of sodium alginate, thus introducing Cu to catalysis charring into LDH@SA for the synthesis of a novel organometallic ion flame retardant (LSCu). Combination of flame retardants with intumescent fireproofing coatings to prepare composite coatings and test them for fire performance. The large panel test indicated that when the LSCu content was 4 %, the backside temperature of the steel panel dropped to 174.7°C, and the char layer surface remained intact, without any holes or cracks. In the furnace test, the composite coating had the highest expansion height (15.6 mm) and expansion rate (13.28 %) with uniform expansion. SEM illustrated that the char layer of the composite coating had a honeycomb structure, which enhanced the adsorption of heat and smoke. In addition, the composite coating retained the highest residual char content (28.1 %), which had to do with the synergistic effect between LDH and Cu complexes. Furthermore, through analyzing the residual char, it was demonstrated that the formation of metal oxides by LSCu at elevated temperatures improved the sustained barrier performance of the char layer.

Mn‐doped Pb(In1/2Nb1/2)O3‐Pb(Mg1/3Nb2/3)O3‐PbTiO3 relaxor ferroelectric ceramics for high‐power piezoelectric applications

AbstractAchieving comprehensive improvement in both piezoelectric coefficient (d33) and mechanical quality factor (Qm) has become a key issue in the research of high‐power piezoelectric ceramics. Here, we focused on Mn‐doped Pb(In1/2Nb1/2)O3‐Pb(Sc1/2Nb1/2)O3‐PbTiO3 (PIN‐PSN‐PT) relaxor ferroelectric ceramics, where Mn‐doping is employed to enhance Qm. The effects of doping concentration and PT content on phase structure, ferroelectric, dielectric, and electromechanical properties were systematically studied. The well radius matching between Mn ions and B‐site ions facilitates the ion substitution and significantly increases the concentration of oxygen vacancies, thereby enhancing the domain wall pinning effect. A significantly weakened mutual constraint relationship between d33 and Qm is observed in the 2 mol% Mn‐doped PIN‐PSN‐PT ceramics with tetragonal phase, which exhibits Qm exceeding 3000 while maintaining d33 higher than 320 pC/N and Curie temperature higher than 300°C, leading to the vibration velocity over 1.15 m/s. Rayleigh analysis reveals the higher intrinsic piezoelectric response in high PT components compared to that in low PT components, which was thought to be the origin for the weakened mutual constraint relationship between d33 and Qm in tetragonal Mn‐doped PIN‐PSN‐PT ceramics.

Structural analysis, relaxor-ferroelectric behavior and optical properties of Mn3+-doped CaBi3NdTi4O15 synthesized via hydrothermal technique

In this study, the synthesis of the Aurivillius Ca1-xBi3+xNdTi4-xMnxO15 (CBNTMx), where x is 0, 0.2, and 0.4, was carried out using the hydrothermal technique. The X-ray diffraction (XRD) data showed that the polar orthorhombic structure in space group of A21am was adopted by all powder samples. All samples possessed anisotropic plate-like particle shapes, and the particle size increased with increase in x value. The phase transition temperature (Tm) is decreased by the ionic substitution owing to the decrease in orthorhombic distortion reflected by the reduction of orthorhombicity. Relaxor-ferroelectric behavior was observed for CBNTM0.4 because of its strong frequency dispersion, while CBNTM0 and CBNTM0.2 only showed a diffused-phase transition (DPT) indicated by the broad dielectric constant at the transition temperature (Tm). The electrical conductivity exhibited an enhancement at higher x value since the ionic substitution with acceptor Mn3+ ions introduced the charge carrier in the lattice. Similarly, the reduction of optical band gap energy from 3.43 eV for the parent CBNTM0 to 2.75 eV and 2.71 eV for CBNTM0.2 and CBNTM0.4, respectively, was described as the contribution of the lower energy level of Mn 3d orbital than that of Ti 3d in the conduction band and also the less distorted structure.

Effect of substituted cobalt–chromium–iron oxides’ dissolution kinetics in oxidizing formulation on decontamination process

Removing radioactive corrosion products from Cr-containing iron oxides require a multi-step and multi-cycle decontamination process. The present article brings out the effect of divalent metal ion substitution on the release rate of chromium in the oxidative pre-treatment step. The non-stoichiometric cobalt chromium ferrites were synthesized, characterized and effect of Zn2+/Ni2+ substitution on the dissolution behavior was probed. The dissolution rates decreased with increasing the degree of inclusion and showed minima at ~ 0.4–0.6 atom% which is explained on the basis of lattice structure. It is concluded that the dissolution kinetics of native nickel–chromium ferrites in reactors increases with metal ion inclusion.

Synthesis and characterization of lithium fluoride-doped hydroxyapatite by aqueous precipitation

Hydroxyapatite is an essential material for bone and dental composition, widely used in biomaterials due to its biocompatibility and bioactivity. Its crystalline structure, similar to human bone, facilitates integration with biological tissues, promoting bone and dental regeneration. Applications include implants, orthopedic coatings, and bone grafts. The aim of this work was to synthesize hydroxyapatite with different percentages of lithium fluoride by aqueous precipitation. The produced powders were sintered at 1100 °C, and their properties were characterized by XRD, FTIR, and SEM. The results indicated the presence of fluorapatite and calcium oxide phases in the hydroxyapatite with lithium fluoride, with ion substitution occurring, while samples without LiF addition revealed the presence of hydroxyapatite and calcium oxide phases. SEM images showed that the samples with LiF addition exhibited morphological anisotropy, while pure hydroxyapatite samples showed equiaxed grains. The addition of LiF reduced the porosity of the samples after sintering. FTIR results indicated that fluoride ions replaced the hydroxyl groups originally present in the pure hydroxyapatite structure.

Study of the effect of Sr2+ ions substitution on the dielectric behaviour of BaCr2O4 chromites synthesized by solution combustion method

Study of the effect of Sr2+ ions substitution on the dielectric behaviour of BaCr2O4 chromites synthesized by solution combustion method

Manipulating and investigating the room-temperature magnetic memory phenomenon: The impact of rare-earth ion doping on nickel oxide nanoparticles

This study investigates the relationship between point defect density and magnetic properties in nickel oxide (NiO) nanoparticles (NPs). Specifically, we explore the effects of 0.5 % trivalent rare-earth ion (RE3+: Ce3+, Pr3+, Nd3+, Sm3+, and Dy3+) doping on NiO NPs, considering the influence of RE3+ ionic radius on structural modulation and magnetic properties. Our findings reveal important trends: increased microstrain (0.08 %–0.17 %) and decreased crystalline size (36–17 nm) with increasing ionic radius (r = 0.91 to 1.01 Å), along with a preference for growth along the (1 1 1) plane over (2 0 0). Additionally, multivalent point defects increase with the increase of ionic radius. Substituting Ni2+ site with RE3+ ion promotes nearest-neighbor weak ferromagnetic interaction over next-nearest-neighbor strong antiferromagnetic (AF) interaction. This leads to a redshift of two magnons (2 M) frequency by 50 cm−1 and enhanced room temperature (RT) magnetization (0.23–0.43 emu/g) with increasing ionic radius. Ce-doped NiO (r = 1.01 Å) shows the smallest crystalline size (17 nm), maximum 2 M redshift, and enhanced RT magnetization (0.43 emu/g) based on interacting bound magnetic polaron model. Ce-, Pr-, Nd-, and Sm-doped NiO NPs exhibit RT magnetic memory effects, while Dy-doped NiO NPs (r = 0.912 Å) display AF properties. Our analysis provides valuable insights for designing RT magnetic memory materials with tailored properties through suitable RE3+ ion substitutions.

In Ukrainian

The paper discusses the results of saponite research from the Tashkiv deposit of Ukraine. X-ray structural analysis proved the necessity of preliminary cleaning of saponites from mineral impurities. The study of the morphology, nanoprofile and topography of the surface of saponite by the methods of SEM-microscopy and Atomic Force Microscopy revealed that the mineral is represented by aggregates of nano- and microparticles of a pyramidal shape. Its characteristic feature is the heterogeneity of isomorphic substitutions of ions in the tetrahedral and octahedral sheets of the structural elementary package. According to X-ray fluorescence analysis, saponite contains a significant amount of Fe3+, which isomorphically replaces magnesium Mg2+ and, accordingly, is located mastly in the octahedral sheet of the structural package with a charge from +0.37 to +0.35. The number and mechanism of isomorphic substitutions determine the presence of a total negative charge of the crystal lattice (from –0.38 to –0.3), the value of which ensures intensive interaction with water molecules of the interpacket space with the formation of surface OH groups. Accordingly, both acidic and alkaline Lewis and Brønsted centers are present on the surface with a predominance of acidic ones, so the acidity function is 5.82, and the point of zero proton charge is pH = 5.5. During dispersion in water, a part of the alkaline centers of the side surface are transformed into Brønsted acid centers as a result of their protonation, which causes an increase in the pH of the dispersion medium to pH = 8–8.6. Accordingly, the isoionic state is reached at pH = 7.5. The difference in pH values characterizing the isoionic state of the surface and the point of zero net proton charge (PZNPC) indicates the presence of weak acid-alkaline centers on the surface. The study of the adsorption of acid-alkaline dyes showed the adsorption of alkaline (pK = 1¸3) and acid (pK = 7¸14) dyes on saponites. The latter is significantly reduced due to the preliminary hydration of the solid surface - mainly the lateral edges of the particles. Acidic dyes are not adsorbed from a dispersion medium with pH < 5.5 (PZNPC), and basic dyes are adsorbed at pH > 5,5( PZNPC).

Unlocking the high-capacity operation of P2-type cathode through bifunctional spectator ions substitution

The high specific capacity of the P2-type cathode endowed by the synergistic cation and anion redox makes it one of the most promising cathode materials for sodium-ion batteries (NIBs). However, the structural rearrangement and the irreversible oxygen release under highly desodiated states engender stability issues upon high-capacity operation. Herein, we show specifically how the structural degradation of the P2-type cathode is effectively stabilized by the substitution of bifunctional spectator ions. The rational incorporation of Ti and Si ions triggers the “pillar effect” and “inductive effect”, which eliminates the P2-O2/P2-P2′ structural evolution and mitigates the irreversible oxygen oxidation. Benefited from the highly reversible anion redox, the obtained Na0·67Li0·21Mn0·59Si0·01Ti0·19O2 represents a high reversible capacity of 220 mAh g−1 at 0.1C (20 mA g−1) within a Na-metal half-cell. Ex-situ XRD reveals a solid solution reaction without the formation of additional phases among the charge/discharge process, thus favoring stable cycling performance for up to 200 cycles at 2.5C (with a capacity retention rate of 88 %). This work shows, not only the specific strategies for improving the electrochemical performance of cathode materials, but also offers insights into the intrinsic mechanisms underlying the performance enhancement achieved through spectator ion substitution.

Effect of Physicochemical Surface Properties of Silicon-Substituted Hydroxyapatite on Angiogenesis.

Synthetic hydroxyapatite (HA) is a widely studied bioceramic for bone tissue engineering (BTE) due to its similarity to the mineral component of bone. As bone mineral contains various ionic substitutions that play a crucial role in bone metabolism, the bioactivity of HA can be improved by adding small amounts of physiologically relevant ions into its crystal structure, with silicate-substituted HA (Si-HA) showing particularly promising results. Nevertheless, it remains unclear how distinct material characteristics influence the bioactivity due to the intertwined nature of surface properties. A coculture methodology was optimized and applied for in vitro quantification of the biological response. Initially, HA and Si-HA samples were produced and characterized. To compare the bioactivity of the samples, a method was developed to measure interactions in an increasingly complex environment, first including fibronectin (FN) adsorption and subsequently cell adhesion in mono and coculture using primary human osteoblasts (hOBs) and human dermal microvascular endothelial cells (HDMECs), with and without FN precoating. An experimental set-up was designed to assess to what extent different surface features of the samples contribute to the induced biological response. An 8-nm gold sputter coating was applied to eradicate the electrochemical differences and polishing and abrading was used to reduce the differences in surface topographies. Overall, 1.25 wt% Si-HA exhibited most nanoscale variations in surface potential. In terms of bioactivity, 1.25 wt% Si-HA samples induced the highest osteoblast attachment and vessel formation. Additionally, in vitro vessel formation was established on Si-HA surfaces using a hOB:HDMEC cell ratio of 70:30 and a methodology was established that enabled the assessment of the relative effect of topographical and electrochemical features induced by silicon substitution in the HA lattice on their bioactivity. It was found that the difference in the amount of protein attached to HA and 1.25 wt% Si-HA after 2 h was affected by topographical differences. Conversely, electrochemical differences induced different vessel-like structure formation in coculture with a FN precoating. Without an FN precoating, both topographical and electrochemical differences dictated the differences in angiogenic response. Overall, 1.25 wt% Si-HA surface features appear to induce the most favorable protein adsorption and cell adhesion in mono and coculture with and without FN precoating.

Textural and chemical variations in cassiterite from the Yuanlinzi Sn-Cu deposit, NE China: Insights into ore-forming processes

Microtextural, U–Pb isotopic, and trace element analyses were conducted on magmatic and hydrothermal cassiterites from the Yuanlinzi Sn–Cu deposit (NE China) to determine the timing of mineralization and investigate the ore-forming process. Magmatic cassiterites are disseminated in pegmatite, while hydrothermal cassiterites can be classified into three types: cassiterite-bearing stockworks in pegmatite, disseminated cassiterite in wall rock, and cassiterite-quartz-feldspar veins. U–Pb dating of the four types of cassiterite yields a similar age of ∼ 139 Ma, which is consistent with the ages of regional tin mineralization and granites within the mining district. These results suggest a strong association between Early Cretaceous magmatism and tin mineralization. The four types of cassiterite exhibit comparable textural features, characterized by alternating oscillatory CL zonation and dark homogeneous bands, with the latter commonly enriched in W, Nb, Ta, and U. The direct substitution of tetravalent ions, including Zr, Hf, Ti, and V, with Sn4+ and the coupled substitutions of Fe3+ + OH– = Sn4+ + O2– or Fe3+ + H+ = Sn4+, 2Sb3+ + U6+ = 3Sn4+ and Sc3+ + V5+ = 2Sn4+ are responsible for the incorporation of these elements in cassiterite. The enrichment of W, Nb, Ta, and U in the dark domains of cassiterite is related to the coupled substitution of W + U and Nb + Ta, while the excess of Nb and Ta in the oscillatory-zoned domains may be attributed to the substitution of 4(Nb, Ta)5+ + □ = 5Sn4+. The trace element variations observed in the four types of cassiterite, particularly Al, Sc, Ti, V, and Fe, reflect the ongoing enhancement of the water–rock reaction during the mineralization process. The examination of redox-sensitive elements such as Fe, U, and V suggested that tin mineralization in the Yuanlinzi deposit occurred in an oxidizing environment where oxygen fugacity gradually increased. Additionally, we proposed that the Sc/V ratio of cassiterite could serve as an indicator of the redox state of the associated melt/fluid.

Low dielectric loss and high temperature stability of tri-rutile NiO–SnO2–Ta2O5 ceramics simultaneously achieved by component optimization design

The structural analysis and microwave dielectric characteristics of ionic-modified tri-rutile Ni0·5Sn0·5TaO4 ceramics, focusing on ionic non-stoichiometry and substitution strategies, were systemically studied in this work. A tri-rutile solid solution was unequivocally identified via X-ray diffraction, Raman scatting spectra analysis, and transmission electron microscopy characterization under [110] direction. The unit cell of the tri-rutile structure experiences a contraction primarily due to the compression of the [M2O6] octahedron. An excess of Ni content and the incorporation of (Al1/2Nb1/2)4+ complex cations notably halved the grain size. Conversely, deliberate Sn deficiency led to enlarged grain sizes; however, grain boundaries blurred when the deficiency exceeded 0.03 mol. The microwave dielectric properties are intricately linked to structural characteristics and sintering behavior. Ionic polarizabilities and bulk density predominantly affect the εr value, while grain growth governs variations in the Q × f value. The distortion of [M2O6] octahedra primarily influences the τf value. All measured τf values demonstrated exceptional temperature stability within the range of -5 ∼ +5 ppm/°C. Notably, the Ni0·5Sn0·47TaO4 ceramic displayed outstanding microwave dielectric characteristics: εr = 21.9, Q × f = 45,055 GHz (at f = 10.7 GHz), and τf = -2.07 ppm/°C post-sintering at 1425 °C, rendering it ideal for applications in extreme environmental conditions.