Time-Resolved Structural Kinetics of an Organic Mixed Ionic–Electronic Conductor

The structure and packing of organic mixed ionic–electronic conductors have an especially significant effect on transport properties. In operating devices, this structure is not fixed but is responsive to changes in electrochemical potential, ion intercalation, and solvent swelling. Toward this end, the steady-state and transient structure of the model organic mixed conductor, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), is characterized using multimodal time-resolved operando techniques. Steady-state operando X-ray scattering reveals a doping-induced lamellar expansion of 1.6 Å followed by 0.4 Å relaxation at high doping levels. Time-resolved operando X-ray scattering reveals asymmetric rates of lamellar structural change during doping and dedoping that do not directly depend on potential or charging transients. Time-resolved spectroscopy establishes a link between structural transients and the complex kinetics of electronic charge carrier subpopulations, in particular the polaron–bipolaron equilibrium. These findings provide insight into the factors limiting the response time of organic mixed-conductor-based devices, and present the first real-time observation of the structural changes during doping and dedoping of a conjugated polymer system via X-ray scattering.     

基于近似测地线的分层次自动铺带轨迹规划方法

自动铺带技术是一种增量制造技术，适用于制造翼面、壁板等大尺寸、小曲率复合材料构件，具有加工成本低、效率高等特点。轨迹规划是自动铺带技术的关键环节，它直接关系到复合材料构件的成型精度与质量。现有的自动铺带轨迹规划方法难以便捷兼顾调控铺放间隙与防止铺放褶皱，保证铺带产品的最终质量。有鉴于此，提出了一种基于近似测地线的分层次铺放轨迹规划方法。主要目标是合理利用预浸带允许变形能力，在防止铺放褶皱产生的前提下，保证相邻带料不产生覆盖，且间隙不超过2.5 mm。首先，研究了铺放间隙的产生与演化规律，给出了几种典型曲面上初始铺放间隙的优化方法。接下来，提出了近似测地线的数学模型与求解格式。然后，基于铺放褶皱的产生机制与铺放间隙的演化规律，确定了近似测地线的测地曲率大小与符号。最后，在双曲面模具以及自由曲面模具上验证了所提出方法的有效性。     

Novel inorganic precursors [Co4.32Zn1.68(HCO2)18(C2H8N)6]/SiO2 and Co4.32Zn1.68(HCO2)18(C2H8N)6]/Al2O3 for Fischer–Tropsch synthesis

The silica- and alumina-supported Co–Zn catalysts were synthesized by thermal decomposition of new inorganic precursors [Co_4.32Zn_1.68(HCO₂)₁₈(C₂H₈N)₆]/SiO₂ or Al₂O₃. A novel coordination polymer formulated as [Co_4.32Zn_1.68(HCO₂)₁₈(C₂H₈N)₆] (1) was prepared using the solvothermal technique and characterized by elemental analysis, FT-infrared spectroscopy. Thermal stability of the complex 1 was investigated by thermogravimetric analysis and differential scanning calorimetry, and its structure was determined by single-crystal X-ray diffraction. Characterization of catalysts was carried out using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET specific surface area. The catalysts were evaluated for Fischer–Tropsch synthesis (FTS) in the temperature range 200–300 °C. The results revealed that the synthesized catalysts have higher selectivity to the desired products at 260 °C. The performance of the catalysts was compared to those of catalysts constructed via impregnation method and the fabricated catalysts show higher activity and selectivity than the reference catalysts.     

The Electron–Phonon Interaction of Low-Dimensional and Multi-Dimensional Materials from He Atom Scattering

Atom scattering is becoming recognized as a sensitive probe of the electron–phonon interaction parameter λ at metal and metal-overlayer surfaces. Here, the theory is developed, linking λ to the thermal attenuation of atom scattering spectra (in particular, the Debye–Waller factor), to conducting materials of different dimensions, from quasi-1D systems such as W(110):H(1 × 1) and Bi(114), to quasi-2D layered chalcogenides, and high-dimensional surfaces such as quasicrystalline 2ML-Ba(0001)/Cu(001) and d-AlNiCo(00001). Values of λ obtained using He atoms compare favorably with known values for the bulk materials. The corresponding analysis indicates in addition, the number of layers contributing to the electron–phonon interaction, which is measured in an atom surface collision.     

Thermal Management Enables Bright and Stable Perovskite Light-Emitting Diodes

The performance of lead-halide perovskite light-emitting diodes (LEDs) has increased rapidly in recent years. However, most reports feature devices operated at relatively small current densities (<500 mA cm⁻²) with moderate radiance (<400 W sr⁻¹ m⁻²). Here, Joule heating and inefficient thermal dissipation are shown to be major obstacles toward high radiance and long lifetime. Several thermal management strategies are proposed in this work, such as doping charge-transport layers, optimizing device geometry, and attaching heat spreaders and sinks. Combining these strategies, high-performance perovskite LEDs are demonstrated with maximum radiance of 2555 W sr⁻¹ m⁻², peak external quantum efficiency (EQE) of 17%, considerably reduced EQE roll-off (EQE > 10% to current densities as high as 2000 mA cm⁻²), and tenfold increase in operational lifetime (when driven at 100 mA cm⁻²). Furthermore, with proper thermal management, a maximum current density of 2.5 kA cm⁻² and an EQE of ≈1% at 1 kA cm⁻² are shown using electrical pulses, which represents an important milestone toward electrically driven perovskite lasers.     

Physical and thermal properties of l‐lactide/ϵ‐caprolactone copolymers: the role of microstructural design

Understanding the underlying role of microstructural design in polymers allows for the manipulation and control of properties for a wide range of specific applications. As such, this work focuses on the study of microstructure–property relationships in l‐ lactide/?‐caprolactone (LL/CL) copolymers. One‐step and two‐step bulk ring‐opening polymerization (ROP) procedures were employed to synthesize LL/CL copolymers of various compositions and chain microstructures. In the one‐step procedure, LL and CL were simultaneously copolymerized to yield P(LL‐stat‐CL) statistical copolymers. In the two‐step procedure, poly(l‐ lactide) (PLL) and poly(?‐caprolactone) (PCL) prepolymers were synthesized in the first step before CL and LL respectively were added in the second step to yield P[LL‐b‐(CL‐stat‐LL)‐b‐LL] and P[CL‐b‐(LL‐stat‐CL)‐b‐CL] block copolymers as the final products. The findings reveal that, in addition to the copolymerization procedure employed, the length and type of the prepolymer play important roles in determining the chain microstructure and thereby the overall properties of the final copolymer. Moreover, control over the degree of crystallinity and the type of crystalline domains, which is controlled during the polymer chemistry process, heavily influences the physical and mechanical properties of the final polymer. In summary, this work describes an interesting approach to the microstructural design of biodegradable copolymers of LL and CL for potential use in biomedical applications. © 2019 Society of Chemical Industry     

The isothermal reduction kinetics of chromium-bearing vanadium–titanium magnetite sinter

The reduction of chromium-bearing vanadium–titanium magnetite sinter (CVTMS) by CO was investigated at 1123–1223?K. The reduction degree increased with increasing temperature. The isothermal reduction kinetics of CVTMS was analysed, according to Sharp analysis and ln–ln analysis, the kinetic mechanism of reduction process for all samples in different basicity can be represented as f(α)?=?1.61(1?α)[?ln(1?α)]^1–1/1.61. The reaction activation energy of all samples (R?=?1.9, 2.1, 2.3, obtained according to the components of the materials burdening used in sintering process) at different reaction degrees were calculated by the model-free method. And the pre-exponential factors of reaction also were calculated by the mathematical method. The rate controlling step for the reduction process under the present reduction condition was chemical reaction.     

New version of continuous–discrete cubature Kalman filtering for nonlinear continuous–discrete systems

For nonlinear continuous–discrete systems, this paper elaborates a new accurate implementation of continuous–discrete cubature Kalman filter (CD-CKF). As the main contribution of this work, the new Kalman prediction stage begins by integrating the nonlinear continuous model for all the cubature sample vectors; the prior estimate state and covariance prediction are based on the weighted statistics of these integrated cubature sample vectors and the Gauss–Legendre approximation scheme. The new square root form CD-CKF is also derived and accurately implemented by combining with the modified variable stepsize NIRK. As the advantages of proposed approach, the complicated and error-prone processes of solving covariance differential equation or calculating derivatives are avoided, while the positive semi-definiteness of prior error covariance are numerically guaranteed. Simulations of traffic control scenarios further confirm the new approach’s superior filtering performance in both reliability and accuracy.