Optimizing high-temperature energy storage in tungsten bronze-structured ceramics via high-entropy strategy and bandgap engineering.

As a vital material utilized in energy storage capacitors, dielectric ceramics have widespread applications in high-power pulse devices. However, the development of dielectric ceramics with both high energy density and efficiency at high temperatures poses a significant challenge. In this study, we employ high-entropy strategy and band gap engineering to enhance the energy storage performance in tetragonal tungsten bronze-structured dielectric ceramics. The high-entropy strategy fosters cation disorder and disrupts long-range ordering, consequently regulating relaxation behavior. Simultaneously, the reduction in grain size, elevation of conductivity activation energy, and increase in band gap collectively bolster the breakdown electric strength. This cascade effect results in outstanding energy storage performance, ultimately achieving a recoverable energy density of 8.9 J cm-3 and an efficiency of 93% in Ba0.4Sr0.3Ca0.3Nb1.7Ta0.3O6 ceramics, which also exhibit superior temperature stability across a broad temperature range up to 180 °C and excellent cycling reliability up to 105. This research presents an effective method for designing tetragonal tungsten bronze dielectric ceramics with ultra-high comprehensive energy storage performance.

Designs where disorder prevails.

A design strategy boosts electrical properties of ferroelectric materials and devices.

Coating-Free Superhydrophobic Hard Surfaces by Electric Discharge Machining with a Magnetic-Assisted Self-Assembly Sheet Electrode.

Artificial superhydrophobic surfaces hold significant potential in various domains, encompassing self-cleaning, droplet manipulation, microfluidics, and thermal management. Consequently, there is a burgeoning demand for cost-effective, mass-producible, and easily fabricated superhydrophobic surfaces for commercial and industrial applications. This research introduces an efficient, uncomplicated method for constructing hierarchical structures on hard substrates such as binderless tungsten carbide (WC) and glass substrates. The WC substrates were processed by using electrical discharge machining (EDM) with a magnetic-assisted self-assembly sheet electrode. The resultant surfaces comprised micropillars/microgrooves and diminutive craters formed by discharge and ablation, respectively. These surfaces exhibited superior hydrophobic properties, which can be attributed to the modified surface energy and surface texture construction. Our study indicates that a superhydrophobic surface can be achieved on a textured binderless WC. The maximum contact angle and minimum roll-off angle of the hierarchical structure induced by EDM with a magnetic-assisted self-assembly sheet electrode are about 158 and 5°, respectively. The advancing and receding angles are about 161° ± 2 and 157° ± 3, respectively, when the base is tilted at 3°. Furthermore, we have successfully replicated this superhydrophobic structured surface on glass substrates utilizing glass molding technology. This innovative approach to creating superhydrophobic surfaces on hard materials paves the way for the mass production of functional structures on other materials, such as metallic glass, titanium alloy, and mold steel. Most crucially, the proposed fabrication technique offers a straightforward, cost-effective route for creating functional surfaces, rendering it attractive for large-scale industrial production due to its considerable application prospects.

Ultrahigh Energy Storage in Tungsten Bronze Dielectric Ceramics Through a Weakly Coupled Relaxor Design.

Dielectric energy-storage capacitors, known for their ultrafast discharge time and high-power density, find widespread applications in high-power pulse devices. However, ceramics featuring a tetragonal tungsten bronze structure (TTBs) have received limited attention due to their lower energy-storage capacity compared to perovskite counterparts. Herein, a TTBs relaxor ferroelectric ceramic based on the Gd0.03 Ba0.47 Sr0.485-1.5 x Smx Nb2 O6 composition, exhibiting an ultrahigh recoverable energy density of 9 J cm-3 and an efficiency of 84% under an electric field of 660 kV cm-1 is reported. Notably, the energy storage performance of this ceramic shows remarkable stability against frequency, temperature, and cycling electric field. The introduction of Sm3+ doping is found to create weakly coupled polar nanoregions in the Gd0.03 Ba0.47 Sr0.485 Nb2 O6 ceramic. Structural characterizations reveal that the incommensurability parameter increases with higher Sm3+ content, indicative of a highly disordered A-site structure. Simultaneously, the breakdown strength is also enhanced by raising the conduction activation energy, widening the bandgap, and reducing the electric field-induced strain. This work presents a significant improvement on the energy storage capabilities of TTBs-based capacitors, expanding the material choice for high-power pulse device applications.

Strong and ductile titanium-oxygen-iron alloys by additive manufacturing.

Titanium alloys are advanced lightweight materials, indispensable for many critical applications1,2. The mainstay of the titanium industry is the α-ß titanium alloys, which are formulated through alloying additions that stabilize the α and ß phases3-5. Our work focuses on harnessing two of the most powerful stabilizing elements and strengtheners for α-ß titanium alloys, oxygen and iron1-5, which are readily abundant. However, the embrittling effect of oxygen6,7, described colloquially as 'the kryptonite to titanium'8, and the microsegregation of iron9 have hindered their combination for the development of strong and ductile α-ß titanium-oxygen-iron alloys. Here we integrate alloy design with additive manufacturing (AM) process design to demonstrate a series of titanium-oxygen-iron compositions that exhibit outstanding tensile properties. We explain the atomic-scale origins of these properties using various characterization techniques. The abundance of oxygen and iron and the process simplicity for net-shape or near-net-shape manufacturing by AM make these α-ß titanium-oxygen-iron alloys attractive for a diverse range of applications. Furthermore, they offer promise for industrial-scale use of off-grade sponge titanium or sponge titanium-oxygen-iron10,11, an industrial waste product at present. The economic and environmental potential to reduce the carbon footprint of the energy-intensive sponge titanium production12 is substantial.

Formation of Head/Tail-to-Body Charged Domain Walls by Mechanical Stress.

Domain walls (DWs) in ferroelectric materials are interfaces that separate domains with different polarizations. Charged domain walls (CDWs) and neutral domain walls are commonly classified depending on the charge state at the DWs. CDWs are particularly attractive as they are configurable elements, which can enhance field susceptibility and enable functionalities such as conductance control. However, it is difficult to achieve CDWs in practice. Here, we demonstrate that applying mechanical stress is a robust and reproducible approach to generate CDWs. By mechanical compression, CDWs with a head/tail-to-body configuration were introduced in ultrathin BaTiO3, which was revealed by in-situ transmission electron microscopy. Finite element analysis shows strong strain fluctuation in ultrathin BaTiO3 under compressive mechanical stress. Molecular dynamics simulations suggest that the strain fluctuation is a critical factor in forming CDWs. This study provides insight into ferroelectric DWs and opens a pathway to creating CDWs in ferroelectric materials.

Large Electrocaloric Effect in Nanostructure-Engineered (Bi, Na)TiO3-Based Thin Films.

Although the solid-state cooling technology based on electrocaloric response has been considered a promising refrigeration solution for microdevices, the mediocre dipolar entropy change ΔS impedes its practical applications. In this work, ΔS of a conventional ferroelectric thin film, namely, 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 (BNBT), was greatly improved through engineering the nanodomain structures. The number of zero-field polar states and saturation polarization were greatly increased concomitant with a weakened strength of polar correlation in the thin films, owing to the local stabilization of strongly tetragonally distorted nanoclusters (tetragonality of ∼1.25) by modulating the growth conditions during the thin film deposition process. Consequently, a giant ΔS value of ∼ -48.5 J K-1 kg-1 (corresponding to ΔT = ∼27.3 K) and a wide window of operating temperature (>70 °C) were obtained near room temperature under a moderate electric field of 1330 kV cm-1. Moreover, our engineered BNBT thin film exhibits decent fatigue endurance; i.e., a substantial electrocaloric effect over a broad span of temperature can be sustained after 5 × 107 cyclic loading of the electric field. This work provides a universal design strategy for significantly improving the close-to-room-temperature electrocaloric performance of Bi-based ferroelectric thin films without the need of compositional or architectural complexity.

Interface-Driven Multiferroicity in Cubic BaTiO3-SrTiO3 Nanocomposites.

Perovskite multiferroics have drawn significant attention in the development of next-generation multifunctional electronic devices. However, the majority of existing multiferroics exhibit ferroelectric and ferromagnetic orderings only at low temperatures. Although interface engineering in complex oxide thin films has triggered many exotic room-temperature functionalities, the desired coupling of charge, spin, orbital and lattice degrees of freedom often imposes stringent requirements on deposition conditions, layer thickness and crystal orientation, greatly hindering their cost-effective large-scale applications. Herein, we report an interface-driven multiferroicity in low-cost and environmentally friendly bulk polycrystalline material, namely cubic BaTiO3-SrTiO3 nanocomposites which were fabricated through a simple, high-throughput solid-state reaction route. Interface reconstruction in the nanocomposites can be readily controlled by the processing conditions. Coexistence of room-temperature ferromagnetism and ferroelectricity, accompanying a robust magnetoelectric coupling in the nanocomposites, was confirmed both experimentally and theoretically. Our study explores the 'hidden treasure at the interface' by creating a playground in bulk perovskite oxides, enabling a broad range of applications that are challenging with thin films, such as low-power-consumption large-volume memory and magneto-optic spatial light modulator.

Ultrahigh Energy Storage Density in Glassy Ferroelectric Thin Films under Low Electric Field.

The current approach to achieving superior energy storage density in dielectrics is to increase their breakdown strength, which often incurs heat generation and unexpected insulation failures, greatly deteriorating the stability and lifetime of devices. Here, a strategy is proposed for enhancing recoverable energy storage density (Wr ) while maintaining a high energy storage efficiency (η) in glassy ferroelectrics by creating super tetragonal (super-T) nanostructures around morphotropic phase boundary (MPB) rather than exploiting the intensely strong electric fields. Accordingly, a giant Wr of ≈86 J cm-3 concomitant with a high η of ≈81% is acquired under a moderate electric field (1.7 MV cm-1 ) in thin films having MPB composition, namely, 0.94(Bi, Na)TiO3 -0.06BaTiO3 (BNBT), where the local super-T polar clusters (tetragonality ≈1.25) are stabilized by interphase strain. To the knowledge of the authors, the Wr of the engineered BNBT thin films represents a new record among all the oxide perovskites under a similar strength of electric field to date. The phase field simulation results ascertain that the improved Wr is attributed to the local strain heterogeneity and the large spontaneous polarization primarily is originated from the super-T polar clusters. The findings in this work present a genuine opportunity to develop ultrahigh-energy-density thin-film capacitors for low-electric-field-driven nano/microelectronics.

The ion-imprinted oyster shell material for targeted removal of Cd(II) from aqueous solution.

In order to realize the sustainable utilization of waste oyster shell and develop a targeted removal technology for cadmium. A novel ion-imprinted oyster shell material (IIOS) was prepared by surface imprinting technique. The prepared samples were characterized by scanning electron microscope, Fourier infrared spectrometer, X-ray diffractometer, thermogravimetric analysis and N2 adsorption-desorption. The adsorption performances of IIOS for Cd(II) from aqueous solution were studied by the single factor sequential batch, kinetics, isotherms, selectivity and recycling experiments. The characterization researches showed that IIOS was successfully prepared. The adsorption experiments indicated that the adsorption process reached equilibrium within 240 min; the maximum adsorption capacity was up to 69.1 mg g-1 with the initial Cd(II) concentration of 75 mg L-1 at pH 5; the adsorption process fitted well to the pseudo-second-order model and the Langmuir isotherm model, which revealed the chemisorption characteristic of Cd(II). Moreover, IIOS exhibited a good targeted adsorption of Cd(II) in several binary competition systems owing to the present of these imprinted cavities. The recycling experiment showed that the targeted removal ratio of IIOS for Cd(II) remained above 80% after used six times. The results of this study indicated that it is a promising prospect for waste oyster shell used as IIOS to dispose heavy metals in wastewater.

Manipulating ferroelectric behaviors via electron-beam induced crystalline defects.

Ferroelectric nanoplates are attractive for applications in nanoelectronic devices. Defect engineering has been an effective way to control and manipulate ferroelectric properties in nanoscale devices. Defects can act as pinning centers for ferroelectric domain wall motion, altering the switching properties and domain dynamics of ferroelectrics. However, there is a lack of detailed investigation on the interactions between defects and domain walls in ferroelectric nanoplates due to the limitation of previous characterization techniques, which impedes the development of defect engineering in ferroelectric nanodevices. In this study, we applied in situ biasing transmission electron microscopy to explore how dislocation loops, which were judiciously introduced into barium titanate nanoplates via electron beam irradiation, affect the motion of ferroelectric domain walls. The results show that the motion was dramatically suppressed by these localized defects, because of the local strain fields induced by the defects. The pinning effect can be further enhanced by multiple domain walls embedded with defect arrays. These results indicate the possibility of manipulating domain switching in ferroelectric nanoplates via the electron beam.

Doping Process of 2D Materials Based on the Selective Migration of Dopants to the Interface of Liquid Metals.

The introduction of trace impurities within the doping processes of semiconductors is still a technological challenge for the electronics industries. By taking advantage of the selective enrichment of liquid metal interfaces, and harvesting the doped metal oxide semiconductor layers, the complexity of the process can be mitigated and a high degree of control over the outcomes can be achieved. Here, a mechanism of natural filtering for the preparation of doped 2D semiconducting sheets based on the different migration tendencies of metallic elements in the bulk competing for enriching the interfaces is proposed. As a model, liquid metal alloys with different weight ratios of Sn and Bi in the bulk are employed for harvesting Bi2 O3 -doped SnO nanosheets. In this model, Sn shows a much stronger tendency than Bi to occupy surface sites of the Bi-Sn alloys, even at the very high concentrations of Bi in the bulk. This provides the opportunity for creating SnO 2D sheets with tightly controlled Bi2 O3 dopants. By way of example, it is demonstrated how such nanosheets could be made selective to both reducing and oxidizing environmental gases. The process demonstrated here offers significant opportunities for future synthesis and fabrication processes in the electronics industries.

Direct observation of nanoscale dynamics of ferroelectric degradation.

Failure of polarization reversal, i.e., ferroelectric degradation, induced by cyclic electric loadings in ferroelectric materials, has been a long-standing challenge that negatively impacts the application of ferroelectrics in devices where reliability is critical. It is generally believed that space charges or injected charges dominate the ferroelectric degradation. However, the physics behind the phenomenon remains unclear. Here, using in-situ biasing transmission electron microscopy, we discover change of charge distribution in thin ferroelectrics during cyclic electric loadings. Charge accumulation at domain walls is the main reason of the formation of c domains, which are less responsive to the applied electric field. The rapid growth of the frozen c domains leads to the ferroelectric degradation. This finding gives insights into the nature of ferroelectric degradation in nanodevices, and reveals the role of the injected charges in polarization reversal.

The mechanism for the enhanced piezoelectricity in multi-elements doped (K,Na)NbO3 ceramics.

(K,Na)NbO3 based ceramics are considered to be one of the most promising lead-free ferroelectrics replacing Pb(Zr,Ti)O3. Despite extensive studies over the last two decades, the mechanism for the enhanced piezoelectricity in multi-elements doped (K,Na)NbO3 ceramics has not been fully understood. Here, we combine temperature-dependent synchrotron x-ray diffraction and property measurements, atomic-scale scanning transmission electron microscopy, and first-principle and phase-field calculations to establish the dopant-structure-property relationship for multi-elements doped (K,Na)NbO3 ceramics. Our results indicate that the dopants induced tetragonal phase and the accompanying high-density nanoscale heterostructures with low-angle polar vectors are responsible for the high dielectric and piezoelectric properties. This work explains the mechanism of the high piezoelectricity recently achieved in (K,Na)NbO3 ceramics and provides guidance for the design of high-performance ferroelectric ceramics, which is expected to benefit numerous functional materials.

Manganese-Doped Silica-Based Nanoparticles Promote the Efficacy of Antigen-Specific Immunotherapy.

Prophylactic human papillomavirus (HPV) vaccines are commercially available for prevention of infection with cancerogenic HPV genotypes but are not able to combat pre-existing HPV-associated disease. In this study, we designed a nanomaterial-based therapeutic HPV vaccine, comprising manganese (Mn4+)-doped silica nanoparticles (Mn4+-SNPs) and the viral neoantigen peptide GF001 derived from the HPV16 E7 oncoprotein. We show in mice that Mn4+-SNPs act as self-adjuvants by activating the inflammatory signaling pathway via generation of reactive oxygen species, resulting in immune cell recruitment to the immunization site and dendritic cell maturation. Mn4+-SNPs further serve as Ag carriers by facilitating endo/lysosomal escape via depletion of protons in acidic endocytic compartments and subsequent Ag delivery to the cytosol for cross-presentation. The Mn4+-SNPs+GF001 nanovaccine induced strong E7-specific CD8+ T cell responses, leading to remission of established murine HPV16 E7-expressing solid TC-1 tumors and E7-expressing transgenic skin grafts. This vaccine construct offers a simple and general strategy for therapeutic HPV and potentially other cancer vaccines.

Giant tuning of ferroelectricity in single crystals by thickness engineering.

Thickness effect and mechanical tuning behavior such as strain engineering in thin-film ferroelectrics have been extensively studied and widely used to tailor the ferroelectric properties. However, this is never the case in freestanding single crystals, and conclusions from thin films cannot be duplicated because of the differences in the nature and boundary conditions of the thin-film and freestanding single-crystal ferroelectrics. Here, using in situ biasing transmission electron microscopy, we studied the thickness-dependent domain switching behavior and predicted the trend of ferroelectricity in nanoscale materials induced by surface strain. We discovered that sample thickness plays a critical role in tailoring the domain switching behavior and ferroelectric properties of single-crystal ferroelectrics, arising from the huge surface strain and the resulting surface reconstruction. Our results provide important insights in tuning polarization/domain of single-crystal ferroelectric via sample thickness engineering.

A General Approach to Direct Growth of Oriented Metal-Organic Framework Nanosheets on Reduced Graphene Oxides.

Ultrathin metal-organic framework nanosheets (UMOFNs) deposited on graphene are highly attractive, however direct growth of UMOFNs on graphene with controlled orientations remains challenging. Here, a low-concentration-assisted heterogeneous nucleation strategy is reported for the direct growth of UMOFNs on reduced graphene oxides (rGO) surface with controllable orientations. This general strategy can be applied to construct various UMOFNs on rGO, including Co-ZIF, Ni-ZIF, Co, Cu-ZIF and Co, Fe-ZIF. When UMOFNs are mostly attached perpendicularly on rGO, a 3D foam-like hierarchical architecture (named UMOFNs@rGO-F) is formed with an open pore structure and excellent conductivity, showing excellent performance as electrode materials for Li-ion batteries and oxygen evolution. The contribution has provided a strategy for improving the electrochemical performance of MOFs in energy storage applications.

Effects of CDKN2B-AS1 polymorphisms on the susceptibility to coronary heart disease.

BACKGROUND: Coronary heart disease (CHD) is one of the most severe cardiovascular diseases. Cyclin-dependent kinase inhibitor 2B antisense RNA 1 (CDKN2B-AS1) is a significant susceptibility locus for cardiovascular disease by regulating inflammation response and cell cycle. The aim of this study was to assess whether CDKN2B-AS1 polymorphisms are associated with CHD risk in the Chinese Han population. METHODS: A total of 501 CHD patients and 496 healthy controls were recruited from Central South University Xiangya School of Medicine Affiliated Haikou Hospital, five CDKN2B-AS1 polymorphisms (rs10115049, rs75227345, rs2383205, rs10738606, and rs1333049) were analyzed by the Agena MassARRAY platform. The association of CDKN2B-AS1 polymorphisms and CHD risk was determined by odd ratios (OR) and 95% confidence intervals (CI) using logistic regression. RESULTS: CDKN2B-AS1 rs10738606 was significantly associated with CHD under codominant (p = .03), dominant (p = .019), recessive (p = .010), additive (p = .003), and allele (p = .003) models. Gender-based subgroup tests showed that four polymorphisms (rs75227345, rs2383205, rs10738606 and rs1333049) were associated with CHD in males (p < .05). And age-based subgroup tests indicated that rs2383205 and rs10738606 were associated with CHD among individuals, respectively (p < .05). For CHD patients, rs1333049 decreased the risk of diabetes under heterozygote (p = .014) and dominant (p = .024) models. CONCLUSIONS: In conclusion, CDKN2B-AS1 polymorphisms were associated with CHD risk in the combined or subgroup tests, suggesting an important role of CDKN2B-AS1 in CHD susceptibility.

CYP17A1 Polymorphisms Are Linked to the Risk of Coronary Heart Disease in a Case-Control Study.

BACKGROUND: Cytochrome P450 17A1 (CYP17A1) catalyzes the formation and metabolism of steroid hormones and is required for cortisol and androgens. There is increasing evidence that CYP17A1 plays an important role in the development of coronary heart disease (CHD). However, the association of CYP17A1 polymorphisms and CHD susceptibility is still not clear. METHODS: We conducted a case-control study with 396 CHD cases and 461 healthy controls from Hainan province, China. Using the Agena MassARRAY platform, we genotyped 4 genetic variants (rs3740397, rs1004467, rs4919687, and rs3781286) in CYP17A1. Logistic regression analysis was used to assess the association of CYP17A1 polymorphisms with CHD risk by odds ratios (ORs) and 95% confidence intervals (CIs). RESULTS: It showed that A allele of CYP17A1 rs4919687 carried with a 1.59-fold increased risk of CHD (OR = 1.59; 95% CI = 1.26-1.99; P < 0.001). Also, rs4919687 was significantly associated with CHD risk under various models (homozygote: OR = 3.60; 95% CI = 1.64-7.83; P = 0.001; dominant: OR = 1.51; 95% CI = 1.06-2.13; P = 0.021; recessive: OR = 3.28; 95% CI = 1.51-7.14; P = 0.003; additive: OR = 1.56; 95% CI = 1.17-2.07; P = 0.002). Moreover, analysis showed that Ars1004467 Ars4919687 haplotype was a protective factor of CHD (OR = 0.64; 95% CI = 0.48-0.86; P = 0.002). CONCLUSIONS: Our study suggests that CYP17A1 polymorphisms are associated with CHD susceptibility in the Hainan Han Chinese population.