Microstructure–mechanical properties of Ag0/Au0 doped K–Mg–Al–Si–O–F glass-ceramics

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied. The thermal parameters viz., glass transition temperature (T_g) and crystallization temperature (T_c) were extensively changed by varying NPs (in situ or ex situ). Tc was found to be increased (T_c = 870–875 °C) by 90–110 °C when ex situ NPs were present in the glass system. Under controlled heat-treatment at 950 ± 10 °C, the glasses were converted into glass-ceramics with the predominant presence of crystalline phase (XRD) fluorophlogopite mica, [KMg₃(AlSi₃O₁₀)F₂]. Along with the secondary phase enstatite (MgSiO₃), the presence of Ag and Au particles (FCC system) were identified by XRD. A microstructure containing spherical crystallite precipitates (∼50–400 nm) has been observed through FESEM in in situ doped GCs. An ex situ Ag doped GC matrix composed of rock-like and plate-like crystallites mostly of size 1–3 μm ensured its superior machinability. Vicker''s and Knoop microhardness of in situ doped GCs were estimated within the range 4.45–4.61 GPa which is reduced to 4.21–4.34 GPa in the ex situ Ag system. Machinability of GCs was found to be in the order, ex situ Ag > ex situ Au ∼ in situ Ag > in situ Au. Thus, the ex situ Ag/Au doped SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ GC has potential for use as a machinable glass-ceramic.

In understanding the catalytic efficacy of silver (Ag⁰) and gold (Au⁰) nanoparticles (NPs) on glass-ceramic (GC) crystallization, the microstructure–machinability correlation of a SiO₂–MgO–Al₂O₃–B₂O₃–K₂O–MgF₂ system is studied.     

The preparation,microstructure and mechanical properties of a dense MgO–Al2O3–SiO2 based glass-ceramic coating on porous BN/Si2N2O ceramics

A dense MgO–Al₂O₃–SiO₂ based glass-ceramic coating was prepared by a doctor blade process on a porous BN/Si₂N₂O ceramic surface followed by heat treatment at 1050 °C under nitrogen flow. The phase composition, microstructure, mechanical properties and water absorption of the coating were studied. The coating consisted of α-cordierite phase with a small amount of glass phase. The dense coating without pores and cracks was favorable to seal and densify the porous ceramic surface due to part of the molten glass infiltrating the surface pores. The coating was defect-free and tightly bonded to the substrate because of a larger bonding area between the coating and the substrate. The elastic modulus and bending strength of the glass-ceramic coating were 37.9 GPa and 67.1 MPa, respectively. Moreover, the coated samples had a high Vickers hardness and low water absorption.

A dense MgO–Al₂O₃–SiO₂ based glass-ceramic coating was prepared by a doctor blade process on a porous BN/Si₂N₂O ceramic surface followed by heat treatment at 1050 °C under nitrogen flow.     

Influence of Al2O3 nanoparticle doping on depolarization temperature,and electrical and energy harvesting properties of lead-free 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

In this research article, the effects of Al₂O₃ nanoparticles (0–1.0 mol%) on the phase formation, microstructure, dielectric, ferroelectric, piezoelectric, electric field-induced strain and energy harvesting properties of the 0.94(Bi_0.5Na_0.5)TiO₃–0.06BaTiO₃ (BNT–6BT) ceramic were investigated. All ceramics have been synthesized by a conventional mixed oxide method. The XRD and Raman spectra showed coexisting rhombohedral and tetragonal phases throughout the entire compositional range. An increase of the grain size, T_F–R, T_m, ε_max and δ_A values was noticeable when Al₂O₃ was added. Depolarization temperature (T_d), which was determined by the thermally stimulated depolarization current (TSDC), tended to increase with Al₂O₃ content. The good ferroelectric properties (P_r = 32.64 μC cm⁻², E_c = 30.59 kV cm⁻¹) and large low-field d₃₃ (205 pC N⁻¹) values were observed for the 0.1 mol% Al₂O₃ ceramic. The small Al₂O₃ additive improved the electric field-induced strain (S_max and ). The 1.0 mol% Al₂O₃ ceramic had a large piezoelectric voltage coefficient (g₃₃ = 32.6 × 10⁻³ Vm N⁻¹) and good dielectric properties (ε_r,max = 6542, T_d = 93 °C, T_F–R = 108 °C, T_m = 324 °C and δ_A = 164 K). The highest off-resonance figure of merit (FoM) for energy harvesting of 6.36 pm² N⁻¹ was also observed for the 1.0 mol% Al₂O₃ ceramic, which is suggesting that this ceramic has potential to be one of the promising lead-free piezoelectric candidates for further use in energy harvesting applications.

In this research article, the effects of Al₂O₃ nanoparticles (0–1.0 mol%) on the phase, microstructure, dielectric, ferroelectric, piezoelectric, electric field-induced strain and energy harvesting of the BNT–6BT ceramic were investigated.     

Realistic dielectric response of high temperature sintered ZnO ceramic: a microscopic and spectroscopic approach

High temperature sintering (1200–1400 °C) has been performed on ZnO ceramics. An X-ray Absorption Fine Structure (XAFS) study shows that high sintering temperature introduces a constant amount of V_O and V_Zn defects without any significant effect on the crystal or electronic structure of Wurtzite ZnO. The combined effects of grain boundaries and voids are considered responsible for the apparent colossal dielectric constant (ε′) > 10⁴ at low frequency (∼10² Hz) for all the sintered ZnO ceramics. The superior contact among grains of the ZnO-1200 sample enhances both the interfacial and orientational polarization of the Zn²⁺–V_O dipoles, which results in the increase of low and high frequency dielectric constants (ε′) and the corresponding dielectric loss (tan δ) also increases. On the other hand, high temperature sintering of ZnO at 1300 °C and 1400 °C introduces voids at the expense of reduced grain and grain boundary contact areas, thus affecting both the interfacial and orientational polarization with corresponding reduction of dielectric constant (ε′) and dielectric loss. Orientational polarizations due to Zn²⁺–V_O dipoles are suggested to remain fixed and it is the microstructure which controls the dielectric properties of high temperature sintered ZnO ceramics.

Superior grain contacts of ZnO-1200 samples enhance low and high frequency dielectric constants (ε′) and dielectric loss (tan δ).     

d-Glucose sensor based on ZnO·V2O5 NRs by an enzyme-free electrochemical approach

A simple wet-chemical technique was used to prepare zinc oxide-doped vanadium pentaoxide nanorods (ZnO·V₂O₅ NRs) in an alkaline environment. The synthesized ZnO·V₂O₅ NRs were characterized using typical methods, including UV-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (XEDS), X-ray photoelectron spectroscopy (XPS), and X-ray powder diffraction (XRD). The d-glucose (d-GLC) sensor was fabricated with modification of a slight coating of nanorods (NRs) onto a flat glassy carbon electrode (GCE). The analytical performances, such as the sensitivity, limit of quantification (LOQ), limit of detection (LOD), linear dynamic range (LDR), and durability, of the proposed d-GLC sensor were acquired by a dependable current–voltage (I–V) process. A calibration curve of the GCE/ZnO·V₂O₅ NRs/Nf sensor was plotted at +1.0 V over a broad range of d-GLC concentrations (100.0 pM–100.0 mM) and found to be linear (R² = 0.6974). The sensitivity (1.27 × 10⁻³ μA μM⁻¹ cm⁻²), LOQ (417.5 mM), and LOD (125 250 μM) were calculated from the calibration curve. The LDR (1.0 μM–1000 μM) was derived from the calibration plot and was also found to be linear (R² = 0.9492). The preparation of ZnO·V₂O₅ NRs by a wet-chemical technique is a good advancement for the expansion of nanomaterial-based sensors to support enzyme-free sensing of biomolecules in healthcare fields. This fabricated GCE/ZnO·V₂O₅ NRs/Nf sensor was used for the recognition of d-glucose in real samples (apple juice, human serum, and urine) and returned satisfactory and rational outcomes.

A simple wet-chemical technique was used to prepare zinc oxide-doped vanadium pentaoxide nanorods (ZnO·V₂O₅ NRs) in an alkaline environment.     

Study of resistance performance of Al2O3–ZnO–Y2O3 thermal control coating exposed to vacuum-ultraviolet irradiation

As deep space exploration moves farther and farther away, thermal control coating of the in-orbit spacecraft will suffer a serious vacuum-ultraviolet radiation environment, which seriously threatens the reliability of the spacecraft in orbit. Therefore, it is important to improve the vacuum-ultraviolet resistance performance of the thermal control coating. In this work, the inorganic Al₂O₃–ZnO–Y₂O₃ thermal control coating was in situ fabricated on a 6061 aluminum alloy surface by PEO technology, and its vacuum-ultraviolet resistance performance was investigated. The results show that the Al₂O₃–ZnO–Y₂O₃ thermal control coating has a good resistance performance to vacuum-ultraviolet radiation, which is mainly because the large extinction coefficients of the ZnO and Y₂O₃ materials in the ultraviolet band are conducive to improving the ultraviolet resistance performance. Furthermore, the life prediction model of the Al₂O₃–ZnO–Y₂O₃ thermal control coating shows that its Δα_s value first slightly increases and then tends to be stable with the increase of ultraviolet irradiation time from 0 ESH to 25 000 ESH, and the maximum variation of Δα_s is about 0.0536. This work provides a material basis and technical support for the thermal control system of spacecraft with long life and high reliability.

The Al₂O₃–ZnO–Y₂O₃ thermal control coating in situ fabricated by PEO technology, shows a good resistance performance to vacuum-ultraviolet radiation. Further, its life prediction model at vacuum-ultraviolet irradiation is preliminarily established.     

Three hierarchical porous magnesium borate microspheres: a serial preparation strategy,growth mechanism and excellent adsorption behavior for Congo red

The 3D hierarchical porous 7MgO·2B₂O₃·7H₂O (MBH) microspheres were prepared by a phase transformation of chloropinnoite firstly, and anhydrous α-3MgO·B₂O₃ (MBA) microspheres were obtained by thermal conversion of 7MgO·2B₂O₃·7H₂O, and then β-3MgO·B₂O₃ (MBB) microspheres were obtained by phase conversion of α-3MgO·B₂O₃. All samples were characterized by XRD, FT-IR, TG and SEM. The microsphere nanostructures with a hierarchical porous structure were assembled by nanosheets with a thickness of 20–30 nm, and the growth mechanisms were also proposed. By using N₂ adsorption–desorption, the specific surface areas were measured as 103.62 m² g⁻¹ for MBH and 46.10 m² g⁻¹ for MBA. They exhibited excellent selective adsorption performance for Congo red (CR) with maximum adsorption capacities of 202.84 and 170.07 mg g⁻¹ respectively, and the corresponding adsorption mechanisms were also investigated. The adsorption processes were well fitted with the pseudo-second-order rate equation and Langmuir adsorption model. In addition, the corresponding adsorption thermodynamic parameters were also calculated. It is necessary to highlight that the hierarchical porous microspheres could be considered as promising candidates for removal of CR dye pollutants.

Three 3D hierarchical porous 7MgO·2B₂O₃·7H₂O and 3MgO·B₂O₃ microspheres assembled by nanosheets have been prepared by a serial preparation strategy. They exhibited excellent selective adsorption performance for Congo red with high adsorption capacities.     

Enhanced mechanical quality factor of BiScO3–PbTiO3 piezoelectric ceramics using glass composition

Compared with pure Pb-based perovskite ferroelectric materials, Bi(Me)O₃–PbTiO₃ (Me = Sc³⁺, In³⁺, Yb³⁺) have attracted attention due to their remarkable advantage in their Curie temperature. Among them, BiScO₃–PbTiO₃ piezoelectric ceramic is a potential piezoelectric material in high-temperature applications for its high Curie temperature and excellent piezoelectric coefficient. However, its shortcomings are high dielectric loss and low mechanical quality factor. Herein, we report the improvement of the mechanical quality factor of 0.36BS–0.64PT ceramics through the addition of glass composition (GeO₂). There is a small change in the Curie temperature after GeO₂ addition. The piezoelectric coefficient d₃₃ and planar electromechanical coupling factor k_p increase first and then decrease, and the mechanical quality factor Q_m monotone increases with an increase in GeO₂. The 0.36BS–0.64PT + 0.5 mol%GeO₂ ceramics have optimal electrical properties with T_C of 455 °C, d₃₃ of 385 pC N⁻¹, k_p of 58%, and Q_m of 90. In addition, the thermal stability of 0.36BS–0.64PT + xGeO₂ and 0.36BS–0.64PT ceramics is almost the same. It was concluded that the mechanical quality factor of BS–PT ceramics can be enhanced by the addition of GeO₂ with other properties remaining unchanged.

The mechanical quality factor Q_m of BS–PT ceramics increased to 90 and the thermal depolarization temperature T_d remained above 300 °C after GeO₂ doping.     

Colossal dielectric permittivity,reduced loss tangent and the microstructure of Ca1−xCdxCu3Ti4O12−2yF2y ceramics

Ca_1−xCd_xCu₃Ti₄O_12−2yF_2y (x = y = 0, 0.10, and 0.15) ceramics were successfully prepared via a conventional solid-state reaction (SSR) method. A single-phase CaCu₃Ti₄O₁₂ with a unit cell ∼7.393 Å was detected in all of the studied ceramic samples. The grain sizes of sintered Ca_1−xCd_xCu₃Ti₄O_12−2yF_2y ceramics were significantly enlarged with increasing dopant levels. Liquid-phase sintering mechanisms could be well matched to explain the enlarged grain size in the doped ceramics. Interestingly, preserved high dielectric permittivities, ∼36 279–38 947, and significantly reduced loss tangents, ∼0.024–0.033, were achieved in CdF₂ codoped CCTO ceramics. Density functional theory results disclosed that the Cu site is the most preferable location for the Cd dopant. Moreover, F atoms preferentially remained close to the Cd atoms in this structure. An enhanced grain boundary response might be a primary cause of the improved dielectric properties in Ca_1−xCd_xCu₃Ti₄O_12−2yF_2y ceramics. The internal barrier layer capacitor model could well describe the colossal dielectric response of all studied sintered ceramics.

CdF₂ defect clusters result in enhancement of dielectric properties of the Ca_1−xCd_xCu₃Ti₄O_12−2yF_2y ceramics.     

Exploring color tunable emission characteristics of Eu3+-doped La2(MoO4)3 phosphors in the glass–ceramic form

The glass–ceramic form of phosphor materials can overcome the many serious issues of phosphor/silicone composite in commercial phosphor-converted LEDs and are considered as new-generation color converters. In this report, we have shown a novel approach of developing inorganic red phosphor [Eu³⁺:La₂(MoO₄)₃] in the glass–ceramic form based on lanthanum molybdate system. The ceramic form of the compound was found to have a glass transition temperature of 1002 °C, as confirmed by TGA and DSC studies. Further, XRD, FTIR and Raman studies also confirmed that the compounds prepared at 1050 °C are in glass–ceramic form, while those prepared at 750 °C are in ceramic form. Photoluminescence studies showed that both the ceramic and glass–ceramic forms of the phosphor are red color-emitting materials. However, the glass–ceramic forms have better color purity and more radiation transition probabilities. Further, the decay kinetics of both ceramic and glass–ceramic forms confirmed that only those Eu³⁺ ions which exist in the grain boundaries of the ceramics go inside the glass network structure upon heating the compound at or above the glass transition temperature. On the other hand, Eu³⁺ ions which exist at the La-site in the bulk of the particles are retained in the ceramic form in the glass–ceramic mixture.

The glass–ceramic Eu-LMO-1050 is more suitable as a red-color-emitting phosphor material than the ceramic Eu-LMO-750. Further, Eu-LMO-1050 can overcome the problems related to the phosphor/silicone composite in commercial LEDs.     

Thermal-stability of the enhanced piezoelectric,energy storage and electrocaloric properties of a lead-free BCZT ceramic

The lead-free Ba_0.85Ca_0.15Zr_0.10Ti_0.90O₃ (BCZT) relaxor ferroelectric ceramic has aroused much attention due to its enhanced piezoelectric, energy storage and electrocaloric properties. In this study, the BCZT ceramic was elaborated by the solid-state reaction route, and the temperature-dependence of the structural, electrical, piezoelectric, energy storage and electrocaloric properties was investigated. X-ray diffraction analysis revealed a pure perovskite phase, and the temperature-dependence of Raman spectroscopy, dielectric and ferroelectric measurements revealed the phase transitions in the BCZT ceramic. At room temperature, the strain and the large-signal piezoelectric coefficient reached a maximum of 0.062% and 234 pm V⁻¹, respectively. Furthermore, enhanced recovered energy density (W_rec = 62 mJ cm⁻³) and high-energy storage efficiency (η) of 72.9% at 130 °C were found. The BCZT ceramic demonstrated excellent thermal stability of the energy storage variation (ESV), less than ±5.5% in the temperature range of 30–100 °C compared to other lead-free ceramics. The electrocaloric response in the BCZT ceramic was explored via the indirect approach by using the Maxwell relation. Significant electrocaloric temperature change (ΔT) of 0.57 K over a broad temperature span (T_span = 70 °C) and enhanced coefficient of performance (COP = 11) were obtained under 25 kV cm⁻¹. The obtained results make the BCZT ceramic a suitable eco-friendly material for energy storage and solid-state electrocaloric cooling devices.

High-thermal stability of the recovered energy density and significant electrocaloric temperature change over a broad temperature span in a lead-free BCZT ceramic.     

Improvement of electric field-induced strain and energy storage density properties in lead-free BNKT-based ceramics modified by BFT doping

In this research, the effects of Ba(Fe_0.5Ta_0.5)O₃ (BFT) additive on the phase evolution, the dielectric, ferroelectric, piezoelectric, electric field-induced strain responses, and energy storage density of the Bi_0.5(Na_0.80K_0.20)_0.5TiO₃–0.03(Ba_0.70Sr_0.03)TiO₃ (BNKT–0.03BSrT) ceramics have been systematically investigated. The ceramics have been prepared by a solid-state reaction method accompanied by two calcination steps. X-ray diffraction indicates that all ceramics coexist between rhombohedral and tetragonal phases, where the tetragonal phase becomes dominant at higher BFT contents. The addition of BFT also promotes the diffuse phase transition in this system. A significant enhancement of electric field-induced strain response (S_max = 0.42% and = 840 pm V⁻¹) is noted for the x = 0.01 ceramic. Furthermore, the giant electrostrictive coefficient (Q₃₃ = 0.0404 m⁴ C⁻²) with a giant normalized electrostrictive coefficient (Q₃₃/E = 8.08 × 10⁻⁹ m⁵ C⁻² V⁻¹) are also observed for this composition (x = 0.01). In addition, the x = 0.03 ceramic shows good energy storage properties, i.e. it has a high energy storage density (W = 0.65 J cm⁻³ @ 120 °C) with very high normalized storage energy density (W/E = 0.13 μC mm⁻²), and good energy storage efficiency (η = 90.4% @ 120 °C). Overall, these results indicate that these ceramics are one of the promising candidate piezoelectric materials for further development for actuator and high electric power pulse energy storage applications.

The effects of Ba(Fe_0.5Ta_0.5)O₃ additive on phase, dielectric, ferroelectric, piezoelectric, electric field-induced strain, and energy storage density of the Bi_0.5(Na_0.80K_0.20)_0.5TiO₃–0.03(Ba_0.70Sr_0.03)TiO₃ ceramics have been investigated.     

Cold sintering of YBa2Cu3O7−δ

Cold sintering is a sintering technique which enables ceramic powders to be densified at greatly reduced temperatures compared to traditional solid state techniques, which often require temperatures in excess of 1000 °C. These temperatures often preclude the exploitation of size or orientational effects in ceramics as these are lost during heating. One such effect is the orientation of the crystallographic c axis in YBa₂Cu₃O_7−δ (YBCO) which can be controlled through applied pressure. This effect is of interest for increasing critical current density which is highly dependent on the orientation of the a–b (CuO₂) planes within the ceramic. Using cold sintering, we demonstrate that dense YBCO can be created at 180 °C (vs. 1000 °C using solid state) and demonstrate that the likely sintering mechanism is mediated by the cracking which occurs in YBCO when exposed to water. In addition, the ceramics produced show and retain the orientational effect, representing a unique opportunity to study the effect on critical current density. We show that the intergranular critical current when the a–b planes are parallel to the applied field is around 15% higher than when perpendicular.

Cold sintered superconducting YBa₂Cu₃O_7−δ densified at 180 °C shows enhanced critical current densities by exploiting grain alignment created during pressing.     

A novel microwave dielectric ceramic Li2NiZrO4 with rock salt structure

Low loss Li₂NiZrO₄ ceramics with rock salt structure were successfully prepared by the solid-phase reaction method. The relationship between sintering temperature, phase composition and dielectric properties of Li₂NiZrO₄ ceramics was reported for the first time. The grain size gradually increased and the porosity decreased with the sintering temperature increasing. When the sintering temperature exceeds 1300 °C, the grains grow abnormally and some grains begin to melt. The XRD patterns indicated the second phase ZrO₂ appeared due to the volatilization of lithium. The grains grow abnormally and a second phase of ZrO₂ increased the loss of Li₂NiZrO₄ ceramics. The samples sintered at 1300 °C possessed the best dielectric properties: ε_r = 12.3, Q_f = 20000 GHz, τ_f = −23.4 ppm °C⁻¹, which would make the ceramic a possible candidate for millimeter-wave applications.

Low loss Li₂NiZrO₄ ceramics with rock salt structure were successfully prepared by the solid-phase reaction method.     

Electrical properties of Sb2O3-modified BiScO3–PbTiO3-based piezoelectric ceramics

Compared with pure Pb-based perovskite ferroelectric materials, BiMeO₃–PbTiO₃ (Me = Sc³⁺, In³⁺, and Yb³⁺) systems have remarkable advantages in their Curie temperatures. As a member of this group, the BiScO₃–PbTiO₃ (BS–PT) solid solution has drawn considerable attention from scientists for its high Curie temperature and excellent piezoelectric coefficient. However, BS–PT ceramics still have some shortcomings, such as high dielectric loss and low mechanical quality factor, which make them unsuitable for high-temperature applications. Herein, we report the effect of the addition of complex ions on the electrical properties of BS–PT ceramics. Sb₂O₃-doped 0.36BiScO₃–0.64PbTi_0.97Fe_0.03O₃ + 1 mol% MnO₂ (BS–PTFMn + x% Sb₂O₃) ceramics were fabricated and their electrical properties were studied. BS–PTFMn + 0.75% Sb₂O₃ had an optimal piezoelectric coefficient, exhibiting which indicates that Sb₂O₃ doping can improve the piezoelectric properties of the BS–PT ceramics, exhibiting a “soft” effect of Sb₂O₃ doping. In addition, the thermal depolarization temperature (T_d) of BS–PTFMn + 0.75% Sb₂O₃ ceramics remained above 300 °C, such as 325 °C for BS–PTFMn + 0.75% Sb₂O₃. It was concluded that the piezoelectric properties of BS–PT ceramics were enhanced by the addition of Sb₂O₃.

Compared with pure Pb-based perovskite ferroelectric materials, BiMeO₃–PbTiO₃ (Me = Sc³⁺, In³⁺, and Yb³⁺) systems have remarkable advantages in their Curie temperatures.     

Ti surface doping of LiNi0.5Mn1.5O4−δ positive electrodes for lithium ion batteries

The particle surface of LiNi_0.5Mn_1.5O_4−δ (LNMO), a Li-ion battery cathode material, has been modified by Ti cation doping through a hydrolysis–condensation reaction followed by annealing in oxygen. The effect of different annealing temperatures (500–850 °C) on the Ti distribution and electrochemical performance of the surface modified LNMO was investigated. Ti cations diffuse from the preformed amorphous ‘TiO_x’ layer into the LNMO surface during annealing at 500 °C. This results in a 2–4 nm thick Ti-rich spinel surface having lower Mn and Ni content compared to the core of the LNMO particles, which was observed with scanning transmission electron microscopy coupled with compositional EDX mapping. An increase in the annealing temperature promotes the formation of a Ti bulk doped LiNi_(0.5−w)Mn_(1.5+w)−tTi_tO₄ phase and Ti-rich LiNi_0.5Mn_1.5−yTi_yO₄ segregates above 750 °C. Fourier-transform infrared spectrometry indicates increasing Ni–Mn ordering with annealing temperature, for both bare and surface modified LNMO. Ti surface modified LNMO annealed at 500 °C shows a superior cyclic stability, coulombic efficiency and rate performance compared to bare LNMO annealed at 500 °C when cycled at 3.4–4.9 V vs. Li/Li⁺. The improvements are probably due to suppressed Ni and Mn dissolution with Ti surface doping.

LiNi_0.5Mn_1.5O_4−δ surface is doped with Ti ion maintaining the spinel structure at 500 °C, higher annealing temperatures cause Ti diffusion from surface towards the core.     

Influence of surface coating on the microstructures and dielectric properties of BaTiO3 ceramic via a cold sintering process

We present herein a modified cold sintering process (CSP) for BaTiO₃ ceramics using a surface coating at the particle surface which could enhance the relative density of BaTiO₃ up to ∼93.5% at 220 °C and 500 MPa. The surface coating greatly enhances the ceramic density, mainly because it facilitates the dissolution–precipitation process during CSP. Ba vacancies form at the surface of the coated powders, so Ba(OH)₂ solution is used to compensate Ba ions in the as-cold-sintered ceramics, which increases the dielectric permittivity. Post-annealing at 700 and 900 °C increases the relative density to 97%, and the resulting relative dielectric permittivities are 810 and 1550, respectively, at room temperature and 1 kHz. This technique may also be extended to materials with very small, incongruent solubility in water or volatile solutions that use the cold sintering process.

Surface coating facilitates to dissolution–precipitation process and improves the dielectric properties of barium titanate ceramics during cold sintering process.     

Composition design,electrical properties,and temperature stability in (1 − x)K0.44Na0.56Nb0.96Sb0.04O3-xBi0.45La0.05Na0.5ZrO3 lead-free ceramics

In this work, we designed a new system of (1 − x)K_0.44Na_0.56Nb_0.96Sb_0.04O₃-xBi_0.45La_0.05Na_0.5ZrO₃ (KNNS-xBLNZ, 0 ≤ x ≤ 0.06) ceramics, and systemically investigated both their electrical performance and temperature stability. Through optimizing the composition, a relatively good comprehensive performance (e.g., d₃₃ ∼ 455 ± 10 pC N⁻¹, k_p ∼ 0.47 ± 0.02, T_C ∼ 266 °C, strain ∼ 0.148%, and ) is obtained in the ceramics with x = 0.040, which is attributed to the construction of a rhombohedral–orthorhombic–tetragonal (R–O–T) phase boundary. Moreover, a good temperature stability of remnant polarization (P_r) as well as strain value (P_{r100 °C}/P_rRT ∼ 89.6%, P_{r180 °C}/P_rRT ∼ 73.2%, S_{100 °C}/S_RT ∼ 92.6%, S_{180 °C}/S_RT ∼ 74.1%) is gained in KNNS-0.040BLNZ ceramics with a broad temperature range from room temperature to 180 °C. Hence, we believe that KNNS-xBLNZ ceramics opens a window for the practical application of lead-free ceramics.

A new system of (1 – x)K_0.44Na_0.56Nb_0.96Sb_0.04O₃-xBi_0.45La_0.05Na_0.5ZrO₃ (KNNS-xBLNZ, 0 ≤ x ≤ 0.06) ceramics was designed, and systemically investigated both their electrical performance and temperature stability.     

High temperature structure evolution of SiBZrOC quinary polymer derived ceramics

SiBZrOC quinary ceramics were obtained through the modification of a SiOC precursor with B(OH)₃ and Zr(OnPr)₄. The results showed that both B and Zr atoms were involved in the SiOC network through Si–O–B and Si–O–Zr bonds, respectively. The combined effects of B and Zr on the chemical structure and the thermal stability of the SiBZrOC system were investigated in detail. The sp³–C/Si ratio of SiBZrOC ceramics was between the values for SiZrOC and SiBOC. The presence of B promotes the crystallization of t-ZrO₂, which precipitated at 1000 °C and transformed to m-ZrO₂ at 1400 °C. At 1600 °C, ZrO₂ reacted with the matrix and formed ZrSiO₄, which consumed SiO₂ and thus inhibited the carbothermal reaction. The very small I(D)/I(G) ratio of 0.13 in the Raman spectra indicated the high graphitization of free carbon in SiBZrOC ceramics, which was observed by TEM with 10–20 graphene layers. The SiBZrOC ceramics showed excellent thermal stability in argon at 1600 °C for 5 h with a mass loss of 6%. Both the formation of ZrSiO₄ and the highly graphitized free carbon play important roles in inhibiting the carbothermal reaction and thus improving the thermal stability of SiBZrOC ceramics.

SiBZrOC quinary ceramics were obtained through the modification of a SiOC precursor with B(OH)₃ and Zr(OnPr)₄.     

n–n ZnO–Ag2CrO4 heterojunction photoelectrodes with enhanced visible-light photoelectrochemical properties

In this study, ZnO nanorods (NRs) were hydrothermally grown on an Au-coated glass substrate at a relatively low temperature (90 °C), followed by the deposition of Ag₂CrO₄ particles via a successive ionic layer adsorption and reaction (SILAR) route. The content of the Ag₂CrO₄ particles on ZnO NRs was controlled by changing the number of SILAR cycles. The fabricated ZnO–Ag₂CrO₄ heterojunction photoelectrodes were subjected to morphological, structural, compositional, and optical property analyses; their photoelectrochemical (PEC) properties were investigated under simulated solar light illumination. The photocurrent responses confirmed that the ability of the ZnO–Ag₂CrO₄ heterojunction photoelectrodes to separate the photo-generated electron–hole pairs is stronger than that of bare ZnO NRs. Impressively, the maximum photocurrent density of about 2.51 mA cm⁻² at 1.23 V (vs. Ag/AgCl) was measured for the prepared ZnO–Ag₂CrO₄ photoelectrode with 8 SILAR cycles (denoted as ZnO–Ag₂CrO₄-8), which exhibited about 3-fold photo-enhancement in the current density as compared to bare ZnO NRs (0.87 mA cm⁻²) under similar conditions. The improvement in photoactivity was attributed to the ideal band gap and high absorption coefficient of the Ag₂CrO₄ particles, which resulted in improved solar light absorption properties. Furthermore, an appropriate annealing treatment was proven to be an efficient process to increase the crystallinity of Ag₂CrO₄ particles deposited on ZnO NRs, which improved the charge transport characteristics of the ZnO–Ag₂CrO₄-8 photoelectrode annealed at 200 °C and increased the performance of the photoelectrode. The results achieved in the present work present new insights for designing n–n heterojunction photoelectrodes for efficient and cost-effective PEC applications and solar-to-fuel energy conversions.

ZnO NRs hydrothermally grown on Au coated glass substrate, followed by deposition of Ag₂CrO₄ particles via SILAR route. The content of the Ag₂CrO₄ particles on the ZnO NRs were controlled by changing the number of SILAR cycles.