Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

Reusable Polyacrylonitrile-Sulfur Extractor of Heavy Metal Ions from Wastewater

Mercury, lead, and cadmium are among the most toxic and carcinogenic heavy metal ions (HMIs), posing serious threats to the sustainability of aquatic ecosystems and public health. There is an urgent need to remove these ions from water by a cheap but green process. Traditional methods have insufficient removal efficiency and reusability. Structurally robust, large surface-area adsorbents functionalized with high-selectivity affinity to HMIs are attractive filter materials. Here, an adsorbent prepared by vulcanization of polyacrylonitrile (PAN), a nitrogen-rich polymer, is reported, giving rise to PAN-S nanoparticles with cyclic π-conjugated backbone and electronic conductivity. PAN-S can be coated on ultra-robust melamine (ML) foam by simple dipping and drying. In agreement with hard/soft acid/base theory, N- and S-containing soft Lewis bases have strong binding to Hg²⁺, Pb²⁺, Cu²⁺, and Cd²⁺, with extraordinary capture efficiency and performance stability. Furthermore, the used filters, when collected and electrochemically biased in a recycling bath, can release the HMIs into the bath and electrodeposit on the counter-electrode as metallic Hg⁰, Pb⁰, Cu⁰, and Cd⁰, and the PAN-S@ML filter can then be reused at least 6 times as new. The electronically conductive PAN-S@ML filter can be fabricated cheaply and holds promise for scale-up applications.     

P91钢管道异常低硬度部位的组织和性能

对电厂运行过程中发现的P91钢主蒸汽管道的低硬度部位进行了微观组织观察、短时力学性能试验和高温持久强度试验,分析了其硬度偏低的原因。结果表明,低硬度区域P91钢组织为铁素体+析出物,位错密度较低,M₂₃C₆相在晶界处粗化聚集,同时析出新相Laves相,使得P91钢的短时力学性能和高温持久强度下降严重。     

Ti-6Al-4V电弧熔丝增材轧制复合制造的有限元模拟

增材制造过程中由于在凝固及随后的冷却阶段易产生残余应力,从而影响部件的成形和使用。在增材过程中引入轧制工序,可望降低宏观残余应力,从而降低部件的变形。本文通过建立Ti-6Al-4V钛合金电弧熔丝增材与层间轧制复合成形过程的有限元模型,研究圆柱形轧辊条件下不同压下量对部件温度、应力、应变及残余应力分布的影响规律。结果表明,层间轧制可显著降低沉积层金属中的残余宏观应力；同时降低对基板的整体应力。采用圆柱形轧辊并增加压下量可显著降低宏观残余应力,还可以通过塑性变形改变材料的微观组织,提高材料性能,为复合增材工艺的优化指明了方向。     

SnSe+Ag_2Se composite engineering with ball milling for enhanced thermoelectric performance

Earth-abundant IV-VI semiconductor SnSe is regarded as a promising thermoelectric material due to its intrinsic low thermal conductivity. In this report, the highly textured SnSe/Ag2 Se composites were first designed by solid solution method followed by spark plasma sintering(SPS) and their thermoelectric properties in two directions were investigated, and then, the performance of composites was further optimized with an additional ball milling. The coexistence of SnSe and Ag2 Se phases is clearly confirmed by energy-dispersive X-ray spectroscopy(EDX) in transmission electron microscopy(TEM). After ball milling, the size of SnSe grains as well as the incorporated Ag2 Se particles reduces effectively, which synergistically optimizes the electrical and thermal transport properties at high temperature range. As a result, a maximum ZT of ～0.74 at 773 K for SnSe+1.0%Ag_2 Se in the direction vertical to the pressing direction is achieved. Composite engineering with additional ball milling is thus proved to be an efficient way to improve the thermoelectric properties of SnSe, and this strategy could be applicable to other thermoelectric systems.     

Centrifuge-aided micromolding of micron- and submicron-sized patterns

Developed from soft lithography, replica molding has been proven to be a good method to prepare micron- and submicron-sized features. However, the fidelity of the features can be compromised by incomplete feature cavity filling and feature shrinkage during the forming process. In this study, centrifuge-aided micromolding is developed to prepare micron- and submicron-sized ZnO features. By introducing a centrifugal force, the shear-thinning behavior of the suspensions is utilized, and the cavity filling process and the diffusion of trapped air out of the features are accelerated. The drying shrinkage is decreased by increasing the density of the wet nanoparticle packing from the centrifugal process. The centrifugal force improves the fidelity of all the designed features. ZnO ridges from 0.4 μm to 2 μm size and rods of 1.6 μm size are prepared successfully. The wide applicability of this strategy has been demonstrated by preparing ZrO₂ features via the same method.     

Biomimetic Engineering of a Scavenger‐Free Nitric Oxide‐Generating/Delivering System to Enhance Radiation Therapy

Nitric oxide (NO) is a potent tumor‐cell radiosensitizer but it can be readily scavenged by hemoglobin (Hb) in vivo. A biomimetic incubator that can generate and deliver NO in a scavenger (Hb)‐free environment to enhance its radiosensitizing effect to maximize its efficacy in radiotherapy is proposed. This NO incubator comprises a poly(lactic‐co‐glycolic acid) (PLGA) hollow microsphere (HM) that contains an NO donor (NONOate) and a surfactant molecule (sodium caprate, SC) in its aqueous core. In acidic tumorous environments, the PLGA shell of the HM allows the penetration of protons from the outside, activating the hydrolytic cleavage of NONOate, spontaneously generating NO bubbles, which are immediately trapped/stabilized by SC. The SC‐stabilized NO bubbles in the HM are then squeezed through the spaces of its PLGA matrices by the elevated internal pressure. Upon leaving the HM, the entrapped NO molecules may passively diffuse through their SC‐stabilized/protected layer gradually to the tumor site, having a long‐lasting radiosensitizing effect and inhibiting tumor growth. The entire process of NO generation and delivery is conducted in a scavenger (Hb)‐free environment, mimicking the development of young ovoviviparous fish inside their mothers' bodies in the absence of predators before birth.     

IF钢退火过程中再结晶行为的EBSD表征

借助EBSD等技术研究了从冷轧到退火过程中IF钢中铁素体再结晶晶粒的取向演变。研究结果表明,从冷轧到退火过程中,铁素体晶粒取向向着平行于法向的[111]晶粒演变,而平行于法向的[100]晶粒逐渐消失;在冷轧变形过程中,铁素体晶粒的晶体取向决定着发生滑移变形的难易程度,与[100]晶粒相比,[111]晶粒更易于发生滑移变形,并在晶粒内部积累大量的位错,储存了大量的应变能,在随后的退火过程中,应变能较高的[111]晶粒优先形核并长大,优先发生再结晶,而应变能较低的[100]晶粒的再结晶受到阻碍。随着退火温度的升高,γ织构([111]//ND)明显增强,其织构组分(111)[112]尤为明显。