Inversion,chemical complexity,and interstitial transport in spinels

Spinels with the generic chemical formula AB₂O₄ have potential applications in nuclear energy and batteries. In both cases, their functionality is related to mass transport through the crystal. Here, using long-time atomistic simulations, we examine the impact of the cation structure on interstitial transport in two spinel chemistries, inverse MgGa₂O₄ and double MgAlGaO₄. We emphasize two aspects of the transport properties: the unit mechanisms that are described by individual barriers, for which we introduce pole-figure-like plots, and the aggregate behavior of those unit mechanisms. Compared to previous work on normal spinels, we find that inversion significantly reduces the rate of interstitial transport in these structures and has an impact on the stability of defects as they move through the lattice. In particular, B cation interstitials are found to be kinetically stable only in the inverse MgGa₂O₄. These results provide new insight into relationship between structure, chemistry, and transport in spinels.     

Directed Evolution of a Cp*RhIII-Linked Biohybrid Catalyst Based on a Screening Platform with Affinity Purification

Directed evolution of Cp*Rh^III-linked nitrobindin (NB), a biohybrid catalyst, was performed based on an in vitro screening approach. A key aspect of this effort was the establishment of a high-throughput screening (HTS) platform that involves an affinity purification step employing a starch-agarose resin for a maltose binding protein (MBP) tag. The HTS platform enables efficient preparation of the purified MBP-tagged biohybrid catalysts in a 96-well format and eliminates background influence of the host E. coli cells. Three rounds of directed evolution and screening of more than 4000 clones yielded a Cp*Rh^III-linked NB(T98H/L100K/K127E) variant with a 4.9-fold enhanced activity for the cycloaddition of acetophenone oximes with alkynes. It is confirmed that this HTS platform for directed evolution provides an efficient strategy for generating highly active biohybrid catalysts incorporating a synthetic metal cofactor.     

Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

Images of a First‐Order Spin‐Reorientation Phase Transition in a Metallic Kagome Ferromagnet

First‐order phase transitions, where one phase replaces another by virtue of a simple crossing of free energies, are best known between solids, liquids, and vapors, but they also occur in a wide range of other contexts, including even elemental magnets. The key challenges are to establish whether a phase transition is indeed first order, and then to determine how the new phase emerges because this will determine thermodynamic and electronic properties. Here it is shown that both challenges are met for the spin reorientation transition in the topological metallic ferromagnet Fe₃Sn₂. The magnetometry and variable temperature magnetic force microscopy experiments reveal that, analogous to the liquid–gas transition in the temperature–pressure plane, this transition is centered on a first‐order line terminating in a critical end point in the field‐temperature plane. The nucleation and growth associated with the transition is directly imaged, indicating that the new phase emerges at the most convoluted magnetic domain walls for the high temperature phase and then moves to self‐organize at the domain centers of the high temperature phase. The dense domain patterns and phase coexistence imply a complex inhomogenous electronic structure, which can yield anomalous contributions to the electrical conductivity.     

高强不锈钢绞线网与ECC黏结-滑移关系模型

高强不锈钢绞线网与ECC的黏结是二者协同工作的基础，且黏结 滑移关系模型是其黏结性能的综合反映，故通过对17组51个高强不锈钢绞网增强ECC薄板试件进行单边拉拔试验，研究横向钢绞线间距、纵向钢绞线直径和相对锚固长度等因素对钢绞线网在ECC中黏结性能的影响规律。试验结果表明，横向钢绞线的设置可使黏结破坏由脆性破坏转变为延性破坏；高强不锈钢绞线网与ECC的黏结滑移曲线可分为5个阶段，分别为上升段、微降段、延性强化段、下降段和残余段。基于试验结果，对钢绞线网在ECC中的黏结破坏特征和黏结 滑移机理进行分析，在相关黏结-滑移关系模型的基础上，提出钢绞线网与ECC的黏结 滑移关系模型，并进行模型参数分析。所提模型及模型参数计算公式与试验结果吻合良好，能较好地反映钢绞线网与ECC的界面黏结滑移特征。     

In-situ preparation of cross-linked hybrid anion exchange membrane of quaternized poly (styrene-b-isobutylene-b-styrene) covalently bonded with graphene

Introducing graphene into polymer matrix is an effective way to enhance performances of anion exchange membrane (AEM). However, utilizing the advantages of graphene by physical approach is limited due to the weak interface interaction between graphene and polymer matrix. Herein, we report an effective strategy to covalently bond graphene with polymer matrix to improve the interface interaction and further to improve the properties of AEM. A series of cross-linked quaternized graphene-based hybrid AEM were fabricated by covalently bonding poly (vinylbenzyl chloride) grafted graphene (GN-g-PVBC) copolymer with chloromethyl functionalized poly (styrene-b-isobutylene-b-styrene) (SIBS) through the cross-linker (N,N,N′,N′-tetramethyl-1,6-hexanediamine) by in-situ synthetic approach. The interface interaction between graphene and QSIBS is greatly enhanced according to micromorphology characterization of the hybrid membrane. The cross-linked quaternized hybrid AEM containing 0.55 wt% of GN-g-PVBC exhibits obviously improved dynamical mechanical properties (storage modulus: 418 MPa), ion conductivity (1.81 × 10² S cm^?1), methanol barrier property (5.19 × 10^?7 cm² s^?1), selectivity (3.49 × 10⁴ S s cm^?3) at 60 °C and especially a comparably excellent chemical stability to that of Nafion 115 due to the enhanced interface interaction between graphene and the polymer matrix.     

Reduced basis method for managed pressure drilling based on a model with local nonlinearities

To circumvent restrictions of conventional drilling methods, such as slow control actions and inability to drill depleted reservoirs, a drilling method called managed pressure drilling (MPD) has been developed. In MPD, single-phase flow processes can be modeled as a feedback interconnection of a high-order linear system and a low-order nonlinear system. These nonlinearities appear locally both inside and at the boundaries of the computational domain. To obtain a fast simulation platform for real-time purposes (eg, online model-based controller implementation), model order reduction is required for MPD. However, the local nonlinearities render applying model order reduction techniques challenging. In this study, a new approach is proposed to deal with such nonlinearities within the reduced basis (RB) context and it is successfully tested on a model for MPD. Contrary to the classical RB technique, the proposed approach not only does not generate nonphysical spikes at the locations of these local nonlinearities but also yields high speedup factors. The obtained reduced-order model can be used for efficient online simulation and controller design for drilling systems with MPD.     

Hybrid make-to-stock and make-to-order systems: a taxonomic review

Production planning and control (PPC) systems that employ aspects from both make-to-order (MTO) and make-to-stock (MTS) production control are known as hybrid MTS/MTO systems. While both MTO and MTS separately have been studied extensively, their combined use has received less attention. However, the literature on this topic is growing and this paper shows that the review performed in this paper is an important addition to the field. We categorise relevant literature according to a novel taxonomy and show that hybrid MTS/MTO production control can be used in different contexts. In addition, an overview of the modelling techniques and methods used in these papers is provided. Based on the reviewed literature, relevant research questions and directions for future research are identified. Finally, it is shown that hybrid MTS/MTO production control is prevalent in practice by discussing research with industrial applications. The paper contains an overview of research on hybrid MTS/MTO production control to be used as reference for researchers active in the field, and provides managerial insights and directions for future research on this topic.     

Casting methods for the production of rotationally symmetric copper bimetals

ABSTRACT

Multiple-material products are characterised by a complex property profile which is achieved by combining the particular advantages of at least two different materials. Bimetal casting is an energy- and material-efficient technology for the production of multi-metallic objects. This paper describes the development of a semi-continuous casting process for the formation of a rotationally symmetric bimetal with a cohesive bonding character at the interface of a copper–tin alloy (CuSn6) and pure copper (Cu99.5). Initial experiments are conducted by static casting to evaluate the thermal process window. Based on the results of the initial experiments, a vertical semi-continuous compound casting process is developed. A stable cohesive bond between the joining partners is accomplished by forming a solid solution at the interface.

This paper is part of a Thematic Issue on Copper and its Alloys.