Spirobifluorene Dimers: Understanding How The Molecular Assemblies Drive The Electronic Properties

Spirobifluorene (SBF) is one of the most important scaffolds used in the design of organic semi-conductors (OSCs) for electronics. In recent years, among all the structures developed for these applications, SBF dimers have been highlighted due to their great potential in thermally activated delayed fluorescence and in phosphorescent organic light-emitting diodes. Attaching two SBF units generate 10 dimers, each possessing its own structural specificity, which in turn drives its electronic properties. These ten SBF dimers are gathered herein. Understanding how the molecular assembly determines the electronic properties has been one of the pillars of organic electronics. This is the goal of this article. As positional isomerism is a key tool to design OSCs, defining the design guidelines for the SBF scaffold appears of interest for the future of this building block. Herein, the importance of the two main parameters involved in the electrochemical and photophysical properties, namely the nature of the phenyl linkages and the steric congestion between the two SBF units is discussed. The combination of these two parameters drives the electronic properties but their respective weight is different as a function of the regioisomer involved or of the property considered (frontier orbitals energy level, absorption, fluorescence, phosphorescence).     

Numerical modelling of conjugate heat and mass transfer during hydrofluidisation food freezing in different water solutions

A novel method of hydrofluidisation food freezing is numerically investigated in this paper. This technique is based on freezing small food products in a liquid medium under highly turbulent flow conditions when the heat transfer coefficient is higher than 1 000 W⋅m⁻²⋅K⁻¹, which depends on the operating and flow conditions. A numerical model was developed to characterise the freezing process in terms of the heat transfer and diffusion of liquid solution components into the food product. The study investigates the freezing process of spherical samples in binary solutions of ethanol (30%) and glycerol (40%) and ternary solution of ethanol and glucose (15%/25%). The developed model was employed to determine the concentration of the liquid solution in food samples and to quantify the effect of sample size, heat transfer coefficient, solution temperature and concentration on the process. The food sample size varied from 5 to 30 mm, and the heat transfer coefficients varied from 1 000 to 4 000 W⋅ m⁻²⋅ K⁻¹. The results confirm that a freezing time of 15 min for 30 mm diameter samples or less than 1 min for 5 mm diameter samples can be achieved with the hydrofluidisation method. The solution uptake was influenced by the solution type, sample size and process parameters and varied from 8.9 to 35 g of solute per kg of product for ethanol-glucose and glycerol solutions, respectively. This paper quantifies the advantages and possible limitations of hydrofluidisation, which has not yet been entirely studied, especially in terms of the mass absorption of different solutes.     

A high-performance ternary ferrite-spinel material for hydrogen storage via chemical looping redox cycles

Chemical looping has been proposed as an emerging technology for large-scale hydrogen storage with the advantages of high volumetric hydrogen storage density, environmental compatibility, and safety. However, to ensure sufficient redox activity, conventional oxygen carrier materials must be operated at a temperature higher than 800 °C, leading to the rapid deterioration on the storage capacity over several cycles. In this work, we report a ternary ferrite-spinel material Cu_0.5Co_0.5Fe₂O₄ for chemical looping hydrogen storage and production. The material exhibits high volumetric hydrogen storage density (65.58 g·L⁻¹) and average hydrogen production rate (142 μmol·g⁻¹·min⁻¹) at 550 °C. The performance is maintained with negligible deactivation over repetitive redox cycles. The high performance can be attributed to the ability of Cu and Co to improve the reduction and the reversible phase change during the oxidation stage at moderate temperatures. The performance of the Cu_0.5Co_0.5Fe₂O₄ is comparable to the state-of-the-art Rh-FeO_x containing rare earth metals, which enables its potential in industry application.     

An improved iterative stochastic multi-objective acceptability analysis method for robust alternative selection in new product development

Alternative selection in new product development (NPD) is a multi-criteria decision-making (MCDM) problem. It usually starts with incomplete, imprecise or even partially missing information. Currently, most existing methods in dealing with this problem cannot work well if required information is incomplete or missing. It is acknowledged that stochastic multi-objective acceptability analysis (SMAA) can be applied to address MCDM problem with incomplete preference information and uncertain criteria measurements. In SMAA, alternatives are evaluated based on SMAA measurements (acceptability index, central weight vector and confidence factor). The discriminability of SMAA for the optimum alternative heavily depends on differences of SMAA measurements among different alternatives. Usually, a large number of alternatives and high level of uncertainty are involved in alternative selection in NPD. In this situation, the differences among SMAA measurements are not obvious, and therefore SMAA cannot deal with such problem very well. To this end, this paper proposes an improved SMAA method called Iterative-SMAA (I-SMAA) for alternative selection in NPD. In the I-SMAA, an iterative multi-step decision-making process is suggested to improve differences of SMAA measurements among different alternatives, and thus assist decision makers (DMs) to positively discern from the most preferred alternative. To enhance the decision-making efficiency, sensitive criteria are acquired in each iteration by ranking sensitivity analysis. DMs are guided to provide partial preference information and give more accurate criteria measurements for sensitive criteria rather than all criteria. Eventually, to verify the proposed method, a numerical example of the existing literature is solved with the method, and the results are compared. And then, a practical example of a preparation equipment for coal samples is further employed to verify the practicability of the proposed I-SMAA.     

Preparation of Gd2Zr2O7 nanoceramics from two-step thermal treatment and the aqueous durability analysis

Gd₂Zr₂O₇ ceramics demonstrate important prospect in the immobilization of high-level radioactive wastes (HLWs). In this study, Gd₂Zr₂O₇ nanoceramics were fabricated using two-step method, where Gd₂Zr₂O₇ nanopowder was firstly synthesized by solvothermal method and Gd₂Zr₂O₇ nanoceramics were subsequently sintered via self-propagating chemical furnace plus quick pressing (SCF/QP). The characterization results display that the Gd₂Zr₂O₇ nanocrystalline ceramics with average grain size of 78 nm and bulk density of 5.53 g cm⁻³ were successfully prepared. The results of MCC-1 static leaching experiments show that the normalized release rate (LR_i) of Gd is 2.2 × 10⁻² g m⁻²•d⁻¹ on the first day and converges to 1.2 × 10⁻³ g m⁻²•d⁻¹ after 42 days. Zr shows superior chemical stability as the 21 days LR_Zr value is as low as 2.7 × 10⁻⁶ g m⁻²•d⁻¹, which becomes constant as the leaching duration prolongs.     

Multi-objective optimization of shield construction parameters based on random forests and NSGA-II

Metro shield construction will inevitably cause changes in the stress and strain state of the surrounding soil, resulting in stratum deformation and surface settlement (SS), which will seriously endanger the safety of nearby buildings, roads and underground pipe networks. Therefore, in the design and construction stage, optimizing the shield construction parameters (SCP) is the key to reducing the SS rate and increasing the safe driving speed (DS). However, optimization of existing SCP are challenged by the need to construct a unified multiobjective model for optimization that are efficient, convenient, and widely applicable. This paper innovatively proposes a hybrid intelligence framework that combines random forest (RF) and non-dominant classification genetic algorithm II (NSGA-II), which overcomes the shortcomings of time-consuming and high cost for the establishment and verification of traditional prediction models. First, RF is used to rank the importance of 10 influencing factors, and the nonlinear mapping relationship between the main SCP and the two objectives is constructed as the fitness function of the NSGA-II algorithm. Second, a multiobjective optimization framework for RF-NSGA-II is established, based on which the optimal Pareto front is calculated, and reasonable optimized control ranges for the SCP are obtained. Finally, a case study in the Wuhan Rail Transit Line 6 project is examined. The results show that the SS is reduced by 12.5% and the DS is increased by 2.5% with the proposed framework. Meanwhile, the prediction results are compared with the back-propagation neural network (BPNN), support vector machine (SVM), and gradient boosting decision tree (GBDT). The findings indicate that the RF-NSGA-II framework can not only meet the requirements of SS and DS calculation, but also used as a support tool for real-time optimization and control of SCP.     

Electrically conductive aluminosilicate/graphene nanocomposite

Highly electrically conductive ceramic material based on aluminosilicate/graphene nanocomposite has been prepared by high pressure (400 MPa) compaction of montmorillonite intercalated with polyaniline followed with the high temperature (1400 °C) treatment in argon atmosphere. Tablets pressed from polyaniline/montmorillonite intercalate exhibits strong texture due to the disk-shaped montmorillonite particles and, consequently, the high anisotropy in conductivity. The high temperature induced phase transformation of montmorillonite into cristobalite and mullite preserved the aluminosilicate layered structure and created good conditions for formation of graphene sheets from polyaniline layers intercalated in montmorillonite. Therefore, the texture and anisotropy in conductivity remain preserved in resulting aluminosilicate/graphene tablets, while the in-plane conductivity in aluminosilicate/graphene tablets is 23,000× higher than the conductivity of uncalcined polyaniline/montmorillonite tablets. Simple fabrication method of aluminosilicate/graphene tablets is very promising for the manufacturing of the electrically conductive and tough ceramic material, which can be exposed to corrosive environment as well as to high temperatures.     

Role of zirconia phase transformation,interface processes,and Ta2O5 doping on the blistering phenomenon of molten glass in contact with zirconia-based refractories

Bubble formation and removal within the molten glass is an important issue in glass industry. Various sources of bubbles have been identified in glass manufacturing: decomposition of the glass components, air trapping, oxidation/reduction reactions, precipitation resulting from insufficient refining, etc. It has been demonstrated in a previous paper that the blistering phenomenon at the interface between a molten glass and a zirconia-based refractory can be ascribed to the oxygen semipermeability through the zirconia phase. The objective of this study is to clarify the role of temperature on the blistering process, and especially, below and above the phase transition temperature of zirconia (monoclinic/tetragonal transformation) and to evaluate the role of zirconia doping on the blistering level. The influence of the kinetics of the surface processes at the glass/refractory interface is emphasized. Quantitative measurement of the slight blistering ascribed to the so-called “redox shock” is also given.     

Effect of low content sintering aids addition on β-SiC sintered by spark plasma sintering

The influence of low content of sintering aids addition on the properties of β-SiC sintered by spark plasma sintering was studied based on X-ray diffraction and SEM observations. Three dopants, respectively Al₂O₃, Al₂O₃-Y₂O₃ and Al₂O₃-AlN were chosen, and the investigation was undertaken in the [0.5–5 wt%] content range. The analyses revealed the possibility to increase the density of sintered pellets close to 100% of theoretical density (T.D.), even with the addition of very low sintering aids contents, as low as 0.5 wt%, for each dopant. The combination with high sintering pressure allowed keeping a fine microstructure and a pristine cubic crystalline structure while avoiding the formation of secondary phases.