Intrinsic Defect Limit to the Growth of Orthorhombic HfO2 and (Hf,Zr)O2 with Strong Ferroelectricity: First-Principles Insights

It is believed that promoting the fraction of ferroelectric orthorhombic phase (o-phase) through O-poor growth conditions can increase the spontaneous polarization of HfO₂ and (Hf,Zr)O₂ thin films. However, the first-principles calculations show that the growth may be limited by the easy formation of point defects in the orthorhombic and tetragonal phases of HfO₂, ZrO₂, and (Hf,Zr)O₂. Their dominant defects, O interstitial (O_i) under O-rich conditions and O vacancy (V_O) under O-poor condition, have low formation energies and quite high density (10¹⁶–10¹⁹ cm⁻³ for 800–1400 K growth temperature). Especially, O_i has negative formation energy in tetragonal HfO₂ under O-rich condition, causing non-stoichiometry and limiting the crystalline-seed formation during o-phase growth. High-density defects can cause disordering of dipole moments and increase leakage current, both diminishing the polarization. These results explain the experimental puzzle that the measured polarization is much lower than the ideal value even in O-poor thin films and highlight that controlling defects is as important as promoting the o-phase fraction for enhancing ferroelectricity. The O-intermediate condition (average of O-rich and O-poor conditions) and low growth temperature are proposed for fabricating HfO₂ and (Hf,Zr)O₂ with fewer defects, lower leakage current, and stronger ferroelectricity, which challenges the belief that O-poor condition is optimal.     

Mechanical properties and wear behavior of Tin+1(Al,A)Cn (A = Ga,In, Sn,n = 1, 2) via quasi-high-entropy of single atomic thick A layer

The strengthening method of multi-element M-site solid solution is a common approach to improve mechanical properties of MAX phase ceramic. However, the research on capability of multi-element A-site solid solution to improve mechanical properties has rarely been reported. Thereupon, quasi-high-entropy MAX phase ceramic bulks of Ti₂(Al_1?xA_x)C and Ti₃(Al_1?xA_x)C₂ (A = Ga, In, Sn, x = 0.2, 0.3, 0.4) were successfully synthesized by in situ vacuum hot pressing via multi-elements solid solution. The multi-elements solid solution in single-atom thick A layer was confirmed by X-ray diffraction and X-ray photoelectron spectroscopy as well as by energy dispersive X-ray spectroscopy mappings. Effects of doped multi-elements contents on the phase, microstructure, mechanical properties, and high temperature tribological behaviors were studied. Results demonstrated that the Vickers hardness, anisotropic flexural strength, fracture toughness, and tribological properties of Ti–Al–C based MAX ceramics could be remarkably improved by constitution of quasi-high-entropy MAX phase in A layers. Moreover, the strengthening and wear mechanisms were also discussed in detail. This method of multi-element solid solution at A-site provides new way to enhance mechanical properties of other MAX phase ceramics.     

Liquid-phase epoxidation of propylene with molecular oxygen by chloride manganese meso-tetraphenylporphyrins

Propylene molecule owns two active sites, the direct epoxidation of propylene by dioxygen is still a challenge due to the limitation of selectivity. In this work, the direct liquid-phase propylene aerobic epoxidation protocol by chloride manganese meso-tetraphenylporphyrin (MnTPPCl) was developed. The conversion of propylene was 12.7%, and the selectivity towards PO (propylene oxide) reached up to 80.5%. The formation of PO was attributed to the mechanism via high-valent Mn species, which was confirmed by means of in situ UV–vis spectrum.     

Effect of impact angle on wear behavior of Mo2NiB2–Ni cermets with different Ni content

Herein, the influence of the impact angle and Ni content on the wear behavior of Mo₂NiB₂–Ni cermets was studied using an erodent-carrying slurry comprising artificial seawater and SiO₂ sands. The results reveal that the material loss may be attributed to the wear damage caused by SiO₂ sands because cermets are expected to exhibit good corrosion resistance in artificial seawater. The relative density of cermets markedly influences their resistance to wear damage, and the material loss experienced by cermets with poor relative density is 2–4 times higher than that of cermets with good relative density; this occurs because a higher relative density can markedly enhance the mechanical properties and reduce the defects in the cermets. Moreover, the results indicate that as the impact angle increases from 0° to 60°, the manifestation of the wear mechanism changes from damaging the Ni binder phase (caused by single cutting wear) to damaging both the Mo₂NiB₂ ceramic and Ni binder phases due to the combination of cutting wear and impact wear. The wear damage is dominated by the cutting wear and impact wear from SiO₂ sand at the low and high impact angles, respectively. Furthermore, the severe deterioration of the single ceramic skeleton at high impact angles indicates that the synergistic influence of the Mo₂NiB₂ ceramic and Ni binder phases on enhancing the wear resistance of the cermets intensifies at high impact angles.     

Improvement of a commercial calcium phosphate bone cement by means of drug delivery and increased injectability

Calcium phosphate cements (CPCs) have been increasingly used as synthetic bone substitutes for repair and regeneration of bone defects given their biocompatibility, resemblance to bone and malleability. Moreover, their use as local antibiotic delivery systems is of main interest against bone infections, avoiding the adverse effects of high dosages of conventional therapy. The main goals of this work were to improve the properties of a commercial CPC (Neocement®), turning it injectable, and to provide it with a new functionality as a drug delivery system able to ensure a sustained release of an antibiotic commonly used in orthopaedics (gentamicin sulphate, GS). For this, the influence of the liquid phase amount (%LP) and type of polymer contained in the formulation (chitosan, Chi, or hydroxypropyl methylcellulose, HPMC) on the basic properties of the material was evaluated. It was found that the formulation containing 42%LP + HPMC+1.87% wt GS was the best one. It showed suitable setting and mechanical properties, and injectability around 87% (much superior to the original Neocement®, with 31%). It ensured a sustained release of GS for at least 14 days, at antibacterial levels. The antibiotic released is highly effective against S. epidermidis, but also presents some antibacterial activity against S. aureus. The CPC revealed to be non-cytotoxic. Moreover, it demonstrated good flowability and connectivity with human cadaveric trabecular bone.     

Meticulously tailoring phase boundary in KNN-based ceramics to enhance piezoelectricity and temperature stability

Although KNN-based ceramics with high electrical properties are obtained through a variety of strategies, the temperature sensitivity is still one of the key technical bottlenecks hindering practical applications. Here, we use a new strategy, meticulously tailoring phase boundary, to refine the ferroelectric boundary of KNN-based ceramics, leading to high piezoelectricity companied with improving temperature stability. The highest d₃₃ value in this system reaches 501 pC/N with a T_C ∼ 240°C, whereas a large strain of ∼0.134% can be kept with 10% lower deterioration until 100°C. The origin of high piezoelectricity is mainly attributed to the well-preserved multiphase coexistence and the appearance of nanodomains, which greatly facilitate the polarization rotation. Instead of the changed intrinsic thermal insensitivity, the precision phase boundary engineering plays an important role in strengthening the temperature stability of electric-induced strain. This work provides a simple and effective method to obtain both high electrical properties and excellent thermal stability in KNN-based ceramics, which is expected to promote the practical applications in the future.     

Effect of temperature on the structure and mechanical properties of SiC–TiB2 composite ceramics by solid-phase spark plasma sintering

SiC composite ceramics have good mechanical properties. In this study, the effect of temperature on the microstructure and mechanical properties of SiC–TiB₂ composite ceramics by solid-phase spark plasma sintering (SPS) was investigated. SiC–TiB₂ composite ceramics were prepared by SPS method with graphite powder as sintering additive and kept at 1700 °C, 1750 °C, 1800 °C and 50 MPa for 10min.The experimental results show that the proper TiB₂ addition can obviously increase the mechanical properties of SiC–TiB₂ composite ceramics. Higher sintering temperature results in the aggregation and growth of second-phase TiB₂ grains, which decreases the mechanical properties of SiC–TiB₂ composite ceramics. Good mechanical properties were obtained at 1750 °C, with a density of 97.3%, Vickers hardness of 26.68 GPa, bending strength of 380 MPa and fracture toughness of 5.16 MPa m^1/2.     

Evolution of core–rim structures and phase transformations in infra-red transmitting Y-α-SiAlON ceramics

Core–rim structures were observed as common features in Y-α-SiAlON ceramics hot-pressed between 1550?1950 °C. We found most dopants were taken into α’-rims, and a transition layer grown first on α-cores from liquid-phase over-saturated with metal solutes. Elongated β’-grain were formed as minor phase with α’- or AlN-cores thus only after the α’ matrix had consumed up all Y solutes, revealing that the α’ → β’ transformation is controlled by the transient liquid-phase and similar defects and dangling bonds could be detected in both SiAlON phases by cathodoluminescence. Quantitative assessment of Y_m/3Si_12?(m+n)Al_m+nO_nN_16?n demonstrates the multiphase evolution, initiated by over-saturation of Y solutes at low temperatures thus retaining α-phase as cores to lower the infra-red transmittance, dictated by homogenization of Al solutes at higher temperature. The elimination of those phase boundaries leads to better dopant and sintering design for achieving transparent and high-performance SiAlON ceramics.     

Effect of metallurgical evolution during post-weld aging treatment on localised corrosion of resistance spot welding joints of A286 superalloy

The combined effect of resistance spot welding and precipitation hardening on the localised corrosion of A286 superalloy is studied. The specimens tested by double loop electrochemical potentiokinetic reactivation were welded in the solution treated condition, and then subjected to different precipitation hardening treatments. For both base metal and weld nugget, the maximum localised corrosion is reached when η phase is clearly observable. The fact that the localised corrosion resistance of weld nugget is different from that shown by base metal may be explained by the segregation of Ni and Ti towards the interdendritic region of weld nugget (studied by using scanning electron microscope/energy dispersive X-ray analysis).     

退火温度对新型锆合金薄板带材析出相和织构的影响

采用扫描电镜和超高分辨透射电镜,对具有良好冲制性能的新型锆合金薄板成品带材进行含晶粒、第二相粒子等在内的显微组织研究,并探索真空退火处理条件下温度对带材显微组织的影响。结果显示:新型锆合金薄板成品带材晶粒平均尺寸2.17 μm,存在{0001}<1010>和{0001}<1120>两种织构,大部分晶粒<1120>平行带材RD方向,较少晶粒<1010>平行带材RD方向;第二相粒子分布在晶粒内部及晶界,平均尺寸114 nm,尺寸较大的为不规则椭圆形的Zr-Nb-Fe相,尺寸较小的为圆形的β-Nb相;热处理退火温度降低,带材晶粒尺寸减小,第二相粒子细小弥散分布;新型锆合金薄板成品带材良好冲制性能主要源于轧制积累应变诱发再结晶过程进行充分,导致晶粒细小及孪晶发生破碎;相对轧制变形,退火对带材冲制性能影响不显著。