Structural, optical and bioactive properties of calcium borosilicate glasses

Glass of composition 40SiO₂–20B₂O₃–30CaO–10M₂O₃ (M = Al, Cr, Y and La) were prepared by the splat quenching technique to investigate the effect of M₂O₃ on their bioactivity, structural and optical properties. Y₂O₃ and Cr₂O₃ containing glasses formed a crystalline hydroxyapatite (HA) layer after dipping in simulating body fluid (SBF) for 25 days. On the other hand, HA layer could not form in Al₂O₃ and La₂O₃ glasses. However, during soaking in SBF solution, these glasses exhibit higher dissolution rate, lower density and increased optical band gap as compared to unsoaked glasses. Their oxygen molar volume was also higher than for Y₂O₃ and Cr₂O₃ glasses. The change in composition affects the cross-link formation in the glass matrix and finally its durability and bioactivity in SBF. The results show that M₂O₃ plays an important role in controlling chemical durability and bioactivity of the glasses.     

The electrical properties of (Ba,Ca, Ce,Ti, Zr)O3 thermistor for wide-temperature sensor architecture

A series of new negative temperature coefficient (NTC) thermal materials based on (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ (0.00 ≤ x ≤ 0.20) ceramics were synthesized by a solid-state method. X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy were used to demonstrate the crystal structure, morphology, and composition of the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics, which were composed of solid solution based on the BaTiO₃ phase. The average grain size of doped ceramic samples experienced the process of first decreasing and then increasing. The doping of Ce has reduced the sintering temperature. The temperature-dependent resistance analysis revealed that with the change of doping amount x, the thermal constant B_300/1200 (1.21 × 10⁴–1.13 × 10⁴ K) and the activation energy E_a300/1200 (0.9777–1.0471eV) was initially increased to maximum values at x = 0.05, followed by the decreasing when x > 0.05. It has been established that the concentration of oxygen vacancies is affected by the transition between Ce⁴⁺ and Ce³⁺ provided by high levels of Ce doping. (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics exhibited excellent negative temperature characteristics in the range of 300–1200 °C. Moreover, the temperature resistance linearity was improved after samples were aged. Hence, the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics were regarded as a promising material for high-temperature NTC thermistors in a wide temperature range.     

Magnetic and bioactive properties of MnO2/Fe2O3 modified Na2O-CaO-P2O5-SiO2 glasses and nanocrystalline glass-ceramics

Glass and in-situ nanocrystalline glass-ceramics of compositions 45SiO₂-25CaO-10Na₂O-5P₂O₅-xFe₂O₃-(15-x) MnO₂ are investigated for their magnetic and in-vitro bioactive properties. The ferrimagnetic character is observed in the high Fe₂O₃ containing in-situ nanocrystalline glass-ceramics. Saturation magnetization and coercivity increases with Fe₂O₃. After soaking in the simulated body fluid (SBF), the powdered as well as the bulk glasses and glass-ceramics are investigated using various characterization techniques. The presence of MnO₂ increases the leaching of Na⁺ ions from the glasses and also attracts the Ca²⁺ cations from the SBF as compared to Fe₂O₃ containing nano-crystalline glass-ceramics. It also increases the tendency to form hydroxyl apatite (HAp) layer. Microwave Plasma Atomic Emission Spectroscopy (MP-AES), Fourier Transform Infrared (FTIR) spectra, X-ray diffraction and Scanning electron micrographs (SEM) after soaking in the SBF confirm the HAp formation on the surface of all the glasses and glass-ceramics. Urbach energy also indicates the structural modifications on the surfaces of the glass and glass-ceramics after soaking in the SBF.     

High configurational entropy for low phase transition temperature and thermal expansion of A2M3O12 oxide ceramics

Transverse vibrations of bridging atoms in framework structure oxides contribute to negative thermal expansion (NTE), increasing the configurational entropy. Herein, the configurational entropy of NTE (Al_1/3Fe_1/3Cr_1/3)₂Mo₃O₁₂ (AFCM) is tuned by introducing ZrMg and W to AlFeCr and Mo sites to lower NTE. The NTE of ((Zr_1/2Mg_1/2)_x(Al_1/3Fe_1/3Cr_1/3)_(1-x))₂Mo₃O₁₂ (ZMAFCM) reduce obviously with increasing the content of ZrMg and also the phase transition temperatures (PTTs) (x = 0∼0.5). For ((Zr_1/2Mg_1/2)_x(Al_1/3Fe_1/3Cr_1/3)_(1-x))₂(Mo_1/2W_1/2)₃O₁₂ (ZMAFCMW), the NTE and PTTs reduce at a faster rate than that of ZMAFM. The configurational entropy increases with the content of ZrMg firstly (x = 0∼0.4) and then decreases. The possible mechanism of thermal expansion change is related to the enhanced lattice configuration, high entropy. The inconsistent transverse vibrations of bridging oxygen atoms could reduce their contribution to NTE, especially for high entropy. The PTT of high configurational entropy oxides is reduced obviously due to the influenced on the effective electronegativity. The investigation paves a high entropy way to lower thermal expansion and PTT of A₂M₃O₁₂ oxide ceramics and explores the further mechanism of NTE.     

Structural,electrical, and magnetic transport properties of La0.72Ca0.28Mn1−xCrxO3 (0 ≤ x ≤ 0.06) ceramics

To obtain comprehensive materials with both high temperature coefficient of resistivity (TCR) and magnetoresistance (MR) at low magnetic fields, polycrystalline La_0.72Ca_0.28Mn_1?xCr_xO₃ (x = 0, 0.02, 0.04, 0.06) ceramics were prepared herein by sol–gel method. Electronic configuration of Cr³⁺ ions is similar to that of Mn⁴⁺ ions, therefore, successive substitution of Mn with Cr increases electrical resistivity and decreases metal–insulator transition temperature of ceramics, even yielding hump-like feature for Cr-rich (x = 0.06) samples. The best TCR (28.50%·K^?1) and MR (72.37%) values were obtained simultaneously at Cr dopant content of 0.02 (La_0.72Ca_0.28Mn_0.98Cr_0.02O₃). Strong response of the material to temperature and magnetic field was caused by minimal symmetry of orthorhombic structure and the most robust Jahn–Teller distortion. With increasing Cr content, Mn³⁺/Mn⁴⁺ or Mn³⁺/Cr³⁺ double exchange was diluted, and Cr³⁺/Cr³⁺ or Cr³⁺/Mn⁴⁺ superexchange was promoted. However, the internal competition effect was not conducive to the improvement of material properties.     

Role of Ni2+ substituent on the structural,optical and magnetic properties of chromium oxide (Cr2-xNixO3) nanoparticles

Pristine chromium oxide (Cr₂O₃) and nickel ions (Ni²⁺) substituted Cr₂O₃ nanoparticles were synthesized using a simple co-precipitation technique. The main objective of this work is to investigate Ni²⁺ substituent's role at different concentrations on the structural, morphological, optical, and magnetic properties of Cr₂O₃ nanoparticles. Structural analyses based on X-ray diffraction (XRD), Raman and Fourier transform infra-red (FTIR) data confirmed the successful incorporation of Ni²⁺ into Cr₂O₃ nanoparticles up to x = 0.05 of Ni²⁺ content, without affecting the rhombohedral crystal structure of Cr₂O₃ nanoparticles. Rietveld refinement results showed the variation in lattice parameters and cell volumes alongwith the substitution of Ni²⁺ into Cr₂O₃ nanoparticles. Raman and FTIR spectra also depicted a considerable shift in the characteristic vibration modes of Cr₂O₃ nanoparticles due to strain-induced by Ni²⁺ substitution. Beyond x = 0.05, the structural transformation took place from rhombohedral to cubic crystal structure. Subsequently, new peaks (apart from Cr₂O₃ phase modes) have been observed at x = 0.1 of Ni²⁺ content due to the formation of secondary phase i.e., nickel chromate (NiCr₂O₄). Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) illustrated the changes in the morphology of Cr₂O₃ nanoparticles with Ni²⁺ substitution. UV–Vis analysis revealed a narrowing of optical band energy (E_g) of Ni²⁺ substituted Cr₂O₃ nanoparticles from 3 to 1.85 eV as Ni²⁺ content varies from x = 0 to 0.2, respectively. Afterward, there is an increase in optical band gap energy (E_g) when Ni²⁺ content increased from x = 0.3 to 0.5, as NiCr₂O₄ started dominating the Cr₂O₃ phase. Single-phase Ni²⁺ substituted Cr₂O₃ nanoparticles exhibited a superparamagnetic behavior, whereas the multi-phase compound ascribed to both superparamagnetic and paramagnetic. These changes in optical and magnetic properties can lead to novel strategies to render applications in the field of optoelectronics and optomagnetic devices.     

Synthesis of silicon-substituted hydroxyapatite by a hydrothermal method with two different phosphorous sources

Silicon-substituted hydroxyapatite (Si-HA) with up to 1.8 wt% Si content was prepared successfully by a hydrothermal method, using Ca(NO₃)₂, (NH₄)₃PO₄ or (NH₄)₂HPO₄ and Si(OCH₂CH₃)₄ (TEOS) as starting materials. Silicon has been incorporated in hydroxyapatite (HA) lattice by partially replacing phosphate (PO₄³⁻) groups with silicate (SiO₄⁴⁻) groups resulting in Si-HA described as Ca₁₀(PO₄)_6−x(SiO₄)_x(OH)_2−x. X-ray diffraction (XRD), Fourier transform IR spectroscopy (FTIR), inductively coupled plasma AES (ICP-AES) and scanning electron microscopy (SEM) techniques reveal that the substitution of phosphate groups by silicate groups causes some OH⁻ loss to maintain the charge balance and changes the lattice parameters of HA. The crystal shape of Si-HA has not altered compared to silicon-free reference hydroxyapatite but Si-incorporation reduces the size of Si-HA crystallites. Based on in vitro tests, soaking the specimens in simulated body fluid (SBF), and MTT assays by human osteoblast-like cells, Si-substituted hydroxyapatite is more bioactive than pure hydroxyapatite.     

Crystal structure and luminescence properties of novel Sr10−x(SiO4)3(SO4)3O:xEu2+ phosphor with apatite structure

In this paper, a series of novel luminescent Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors with apatite structure were synthesized by a high temperature solid-state reaction. The phase structure, photoluminescence (PL) properties, as well as the PL thermal stability were investigated. Sr_9.92(SiO₄)₃(SO₄)₃O:0.08Eu²⁺ phosphor exhibits better thermal quenching resistance, retaining the luminance of 66.55% at 150 °C compared with that at 25 °C. The quenching concentration of Eu²⁺ in Sr₁₀(SiO₄)₃(SO₄)₃O was about 0.08 (mol) with the dipole–quadrupole interaction. The Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors exhibited a broad-band green emission at 538 nm upon excitation at 396 nm. The results indicate that Sr_10−x(SiO₄)₃(SO₄)₃O:xEu²⁺ phosphors have potential applications as near UV-convertible phosphors for white-light UV LEDs.     

Superior hybrid improper ferroelectricity and enhanced ferromagnetism of Ca3(Ti1-xCox)2O7 ceramics through the superexchange interaction

Ca₃(Ti_1-xCo_x)₂O₇ ceramics were prepared by a tartaric acid sol-gel method and sintered in an oxygen atmosphere. The introduction of Co²⁺/Co³⁺ as acceptor dopants leads to the formation of more oxygen vacancies and defect dipoles in Ca₃(Ti_1-xCo_x)₂O₇ ceramics. Oxygen vacancy and defect dipoles lead to the transition of dielectric, leakage, and ferroelectric behaviors of Ca₃(Ti_1-xCo_x)₂O₇ ceramics. The coexistence of hybrid improper ferroelectricity and ferromagnetism at room temperature in Ca₃(Ti_1-xCo_x)₂O₇ ceramics has been successfully realized through the superexchange interaction of Co–O–Co. Ca₃(Ti_1-xCo_x)₂O₇ ceramics exhibit superior ferroelectricity (the remnant polarization is 3.29 μC/cm²) and enhanced ferromagnetism (the remnant magnetization reaches 6.4×10^?3 emu/g). This strategy based on the introduction of transition metal ions with unfilled 3d shells at B sites is an important approach to realize novel room-temperature single-phase multiferroic materials for Ca₃Ti₂O₇-based materials.     

Gel-derived SiO2–CaO–P2O5 bioactive glasses and glass-ceramics modified by SrO addition

The effect of SrO substitution for CaO in two sol–gel glasses with different chemical compositions (mol%) A2Sr: (54−x)CaO–xSrO–6P₂O₅–40SiO₂ and S2Sr: (16−x)CaO–xSrO–4P₂O₅–80SiO₂ (x=0, 1, 3 and 5) stabilized at 700 °C on their structure (XRD, FTIR) and bioactive properties (SBF test) was investigated. Preliminary in vitro tests using human articular chondrocytes of selected A2Sr glass were also conducted. Moreover, the subject of this study was to detect the changes on material properties after heat treatment at 1300 °C. The results show that the effect of strontium substitution on structure, bioactivity and crystallization after treatment at both the above temperatures strongly depends on CaO/SiO₂ molar ratio. The presence of 3–5 mol% of strontium ions creates more expanded glass structure but does not markedly affect crystallization ability after low temperature treatment. Sintering at 1300 °C of A2 type glasses results in crystallization of pseudowollastonite, hydroxyapatite and also Sr-substituted hydroxyapatite for 3–5 mol% of SrO substitution. The increase of strontium concentration in silica-rich materials after sintering leads to appearance of calcium strontium phosphate instead of calcium phosphate. Bioactivity evaluation indicates that substitution of Sr for Ca delays calcium phosphate formation on the materials surface only in the case of silica-rich glasses treated at 700 °C. Calcium-rich glasses, after both temperature treatments, reveals high bioactivity, while crystal size of hydroxyapatite decreases with increasing Sr content. High temperature treatment of high-silica glasses inhibits their bioactivity. Preliminary in vitro tests shows Sr addition to have a positive effects on human articular chondrocytes proliferation and to inhibit cell matrix biomineralization.     

Calcium Sulfoaluminate Sodalite (Ca4Al6O12SO4) Crystal Structure Evaluation and Bulk Modulus Determination

The predominant phase of calcium sulfoaluminate cement, Ca₄(Al₆O₁₂)SO₄, was investigated using high‐pressure synchrotron X‐ray diffraction from ambient pressure to 4.75 GPa. A critical review of the crystal structure of Ca₄(Al₆O₁₂)SO₄ is presented. Rietveld refinements showed the orthorhombic crystal structure to best match the observed peak intensities and positions for pure Ca₄(Al₆O₁₂)SO₄. The compressibility of Ca₄(Al₆O₁₂)SO₄ was studied using cubic, orthorhombic, and tetragonal crystal structures due to the lack of consensus on the actual space group, and all three models provided similar results of 69(6) GPa. With its divalent cage ions, the bulk modulus of Ca₄(Al₆O₁₂)SO₄ is higher than other sodalites with monovalent cage ions, such as Na₈(AlSiO₄)₆Cl₂ or Na₈(AlSiO₄)₆(OH)₂·H₂O. Likewise, comparing this study to previous ones shows the lattice compressibility of aluminate sodalites decreases with increasing size of the caged ions. Ca₄(Al₆O₁₂)SO₄ is more compressible than other cement clinker phases such as tricalcium aluminate and less compressible than hydrated cement phases such as ettringite and hemicarboaluminate.     

Bond characteristics,sintering behavior and microwave dielectric properties of Ce2[Zr1−x(Ca1/3Sb2/3)x]3(MoO4)9 ceramics

Ce₂[Zr_1?x(Ca_1/3Sb_2/3)_x]₃(MoO₄)₉ (CZ_1?x(CS)_xM) (x = 0.02–0.10) ceramics were prepared by the conventional solid-state reaction method. The correlations between the chemical bond parameters and microwave dielectric properties were calculated and analyzed by using the Phillips–Van Vechten–Levine (P–V–L) theory. Phase composition and microstructures were evaluated by scanning electron microscopy and X-ray diffraction patterns. Lattice parameters were obtained by Rietveld refinements based on XRD data. Excellent properties for Ce₂[Zr_0.96(Ca_1/3Sb_2/3)_0.04]₃(MoO₄)₉ ceramic sintered at 775 °C: ε_r = 10.68, Q×f = 85,336 GHz and τ_f = ?7.58 ppm/°C were achieved.     

Iron and chromium doped perovskite (CaMO3 M = Ti,Zr) ceramic pigments,effect of mineralizer

Solid solutions Ca(D_xM_1?x)O₃ (M = Ti, Zr and D = Fe,Cr), have been studied as ceramic pigment in conventional ceramic glazes using 0.5 mol/mol of NH₄Cl as flux agent by solid state reaction and by ammonia coprecipitation route. Ca(Cr_xTi_1?x)O₃ compositions obtained without addition of NH₄Cl as mineralizer, produce pink color in glazes at low x but CaCrO₄ crystallizes when x increases, producing undesired green colors. The crystallization of chromates can be avoided using NH₄Cl as mineralizer, giving a complete solid solution that produce pink color in glazes at low x and dark blue shades at high x. Coprecipitated sample produce blue colors at low x and at low temperature than ceramic sample (1000 °C instead 1200 °C for CE sample). Cr⁴⁺ ion acts as red chromophore, but at higher x values (blue samples) Cr³⁺ ion entrance affects the color. Ca(Fe_xTi_1?x)O₃ system crystallizes perovskite CaTiO₃ and pseudobrookite Fe₂TiO₅ together with rutile as residual crystalline phase, glazed samples change from a yellow to a pink color associated to the increase of pseudobrookite with firing temperature. Ca(Fe_xTi_1?x)O₃ and Ca(Cr_xZr_1?x)O₃ systems crystallize perovskite CaZrO₃ and zirconia (ZrO₂) in both monoclinic and cubic polymorphs, but iron or chromium oxides are not detected in the powders. Coprecipitated sample stabilises cubic form. The solid solution is not reached completely in these samples and is not stable in glazes.     

Effects of Mg‐Doping and of Reinforcing Multiwalled Carbon Nanotubes Content on the Structure and Properties of Hydroxyapatite Nanocomposite Ceramics

Surfactant‐assisted hydrothermal synthesis of magnesium‐doped hydroxyapatite (Ca_10?xMg_x(PO₄)₆(OH)₂) with 0 ≤ x ≤ 1) was realized in aqueous solution at 90°C. β‐TCP phase was formed in the Mg_0.6‐HA sample after heat treatment at 1000°C. Magnesium was found to degrade the sintering ability of Mg_x‐HA ceramics. Flexural strength (σ_f) was found to decrease as a function of Mg‐doped HA. The using of carbon nanotubes as reinforcing agents mitigated the strength loss of Mg‐HA ceramics. The flexural strength of Mg_0.6‐HA was then increased by nearly 20% from approximately 33 to 39 MPa with an optimum addition of 3 wt% of multi‐walled nanotubes.     

Dependence of antimicrobial properties on site-selective arrangement and concentration of bioactive Cu2+ ions in tricalcium phosphate

Cu-doped solid solutions Ca_10.5–xCu_x(PO₄)₇ with β-Ca₃(PO₄)₂ (β-TCP) structure were synthesized using high-temperature solid-state synthesis. Correctly characterizing the location of Cu²⁺ in the structure is important for a correct understanding of the biological properties formation. The limit of Ca_10.5–xCu_x(PO₄)₇ solid solutions without impurity phases was found at x = 1.5. The crystal-chemical analysis reveals that the Cu²⁺ ions cannot be located in the M4 site of the β-TCP-type structure due to the very distorted environment. The Cu²⁺ ions preferably occupy the M5 site (x ≤ 1.00) and then located in the M3 and M2 sites (x > 1.00). The chemical composition, local environment, and structural features of Ca_10.5–xCu_x(PO₄)₇ phosphates were investigated by a complex of methods. The antibacterial properties were studied on one fungus (C. albicans) and four bacteria (E. coli, E. faecalis S. aureus and P. aeruginosa). Biocompatibility tests were performed on human bone marrow mesenchymal stem cells (hMSCs). The biological response of the Cu²⁺ strongly depends on the occupied ion position and its concentration. The concentration-dependent behavior of the bacteria growth inhibition was observed, and the sample with x = 1.33 exhibits the highest activity between single-phase samples. Further increasing of bacteria growth inhibition is attributed to Ca₃Cu₃(PO₄)₄ impurity phase. Also, antimicrobial properties depend on the Cu²⁺ location in the β-TCP crystal structure in accordance with ion release behavior. The Cu²⁺ location in the large M3 polyhedra leads to a noticeable increase in ion release. Biocompatibility assays on hMSCs showed the absence of cytotoxicity in direct and indirect contact for single-phase samples. In the biphasic sample the presence of impurity Ca₃Cu₃(PO₄)₄ phosphate at 2 wt% causes a cytotoxicity effect. Thus, phase purity plays a critical role in understanding the regularities of bioactive properties formation. This work can be an initial basis for further investigations of the site-selective arrangement of bioactive ions, such as Cu²⁺ and other similar ions, in the β-TCP structure to enhance biological potential.     

Formation of chromium borides by combustion synthesis involving borothermic and aluminothermic reduction of Cr2O3

Chromium borides of various phases were fabricated through combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) by adopting the powder compacts of Cr₂O₃ + xB (with x = 4–9) and Cr₂O₃ + 2Al + yB (with y = 1–8). Because aluminothermic reduction of Cr₂O₃ is more exothermic than borothermic reduction, the reaction temperature and combustion front velocity of the Al-added samples are much higher than those of the Cr₂O₃–B samples. In agreement with the composition dependence of reaction exothermicity, the fastest combustion wave was observed in the compact with x = 6 for the Cr₂O₃–B sample and y = 4 for the Cr₂O₃–Al–B sample. According to the XRD analysis, Cr₅B₃, CrB, and CrB₂ were produced in the monolithic form respectively from the Cr₂O₃–B samples of x = 4, 5, and 9, or in the composite form from samples of other stoichiometries. On the other hand, five different borides were identified in Al₂O₃-added products. Among them, Cr₂B, CrB, and CrB₂ were yielded as the sole boride compound from the Al-added samples of y = 1.2, 3, and 7 or 8, respectively. Cr₅B₃ and Cr₃B₄ were produced along with CrB as the secondary phase. Based upon experimental evidence, it was found that an excess amount of boron in the reactant mixture was required to facilitate the formation of chromium borides.     

Microstructures and microwave dielectric properties of (1 − y)La1−xSmx(Mg0.5Sn0.5)O3–yCa0.8Sm0.4/3TiO3 ceramics

The (1 ? y)La_1?xSm_x(Mg_0.5Sn_0.5)O₃–yCa_0.8Sm_0.4/3TiO₃ ceramics were prepared by the conventional solid-state method. The X-ray diffraction patterns of the La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics revealed that La_1?xSm_x(Mg_0.5Sn_0.5)O₃ is the main crystalline phase, which is accompanied by a little La₂Sn₂O₇ as the second phase. An apparent density of 6.59 g/cm³, a dielectric constant (?_r) of 19.9, a quality factor (Q × f) of 70,200 GHz, and a temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained when the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were sintered at 1500 °C for 4 h. The temperature coefficient of resonant frequency (τ_f) increased from ?77 to +6 ppm/°C as y increased from 0 to 0.6 when the (1 ? y)La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃–yCa_0.8Sm_0.4/3TiO₃ ceramics were sintered at 1500 °C for 4 h. 0.425La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃–0.575Ca_0.8Sm_0.4/3TiO₃ ceramic that was sintered at 1500 °C for 4 h had a τ_f of ?3 ppm/ °C.     

Optimization of electrical conductivity in the Na2O-P2O5-AlF3-SO3 glass system

We report on the individual roles of charge carrier density and network modification in sodium ion conducting glasses from the Na₂O-P₂O₅-SO₃-AlF₃ (NAPFS) system. For this, a broad range of glass compositions was considered across the series of 44Na₂O/(56 – x − y)P₂O₅/xAlF₃/ySO₃, 47Na₂O/(53 − x − y)P₂O₅/xAlF₃/ySO₃, and 50Na₂O/(50 − x − y)P₂O₅/xAlF₃/ySO₃, with x = 8, 12, 16, 20 and y = 0, 5, 7, 10, 12. Impedance spectroscopy was conducted on these glasses at frequencies from 10⁻² to 10⁶ Hz and over temperatures from 50 to 250°C, and complemented by structural analyses using Raman spectroscopy and nuclear magnetic resonance data. While the trends in dc conductivity and activation energy follow that of Na₂O content (increasing from 44 to 50 mol%), substantial enhancement of conductivity (by about two orders of magnitude) and correspondingly lower activation energy were also found for constant Na₂O concentration when adjusting SO₃ or AlF₃ within specific limits of glass structure.     

Preparation and electrochemical performance studies on Cr-doped Li3V2(PO4)3 as cathode materials for lithium-ion batteries

Cr-doped Li₃V_2−xCr_x(PO₄)₃/C (x = 0, 0.05, 0.1, 0.2, 0.5, 1) compounds have been prepared using sol–gel method. The Rietveld refinement results indicate that single-phase Li₃V_2−xCr_x(PO₄)₃/C with monoclinic structure can be obtained. Although the initial specific capacity decreased with Cr content at a lower current rate, both cycle performance and rate capability have excited improvement with moderate Cr-doping content in Li₃V_2−xCr_x(PO₄)₃/C. Li₃V_1.9Cr_0.1(PO₄)₃/C compound presents an initial capacity of 171.4 mAh g⁻¹ and 78.6% capacity retention after 100 cycles at 0.2C rate. At 4C rate, the Li₃V_1.9Cr_0.1(PO₄)₃/C can give an initial capacity of 130.2 mAh g⁻¹ and 10.8% capacity loss after 100 cycles where the Li₃V₂(PO₄)₃/C presents the initial capacity of 127.4 mAh g⁻¹ and capacity loss of 14.9%. Enhanced rate and cyclic capability may be attributed to the optimizing particle size, carbon coating quality, and structural stability during the proper amount of Cr-doping (x = 0.1) in V sites.