Robust Metallic Actuators Based on Nanoporous Gold Rapidly Dealloyed from Gold–Nickel Precursors

Dealloyed nanoporous gold (np-Au) has applications as oxygen reduction catalysis in Li-air batteries and fuel cells, or as actuators to convert electricity into mechanical energy. However, it faces the challenges of coarsening-induced structure instability, mechanical weakness due to low relative densities, and slow dealloying rates. Here, monolithic np-Au is dealloyed from a single-phase Au₂₅Ni₇₅ solid-solution at a one-order faster dealloying rate, ultra-low residual Ni content, and importantly, one-third more relative density than np-Au dealloyed from conventional Au₂₅Ag₇₅. The small atomic radius and low dealloying potential of the sacrificing element Ni are intrinsically beneficial to fast produce high relative density np-Au, as predicted by a general model for dealloying of binary alloys and validated by experiments. Stable, durable, and reversible actuation of np-Au takes place under cyclic potential triggering in alkaline and acidic electrolytes with negligible coarsening-induced strain-shift. The thermal and mechanical robustness of bulk np-Au is confirmed by two-order slower ligament coarsening rates during annealing at 300 °C and 45 MPa macroscopic yielding strength distinctive from the typical early onset of plastic yielding. This article opens a rich direction to achieve high relative density np-Au which is essential for porous network connectivity, mechanical strength, and nanostructure robustness for electrochemical functionality.     

可逆感温变色聚丙烯专用料的制备及性能

通过两步法制备可逆感温变色聚丙烯（PP）专用料，首先将乙烯-辛烯共聚物（POE）与可逆感温变色粉于微型双螺杆挤出机中挤出造粒制备色母料，然后将PP与色母料熔融共混挤出制备可逆感温变色PP专用料。探讨了色母料含量对PP专用料感温变色性能、力学性能、热学性能及微观形貌的影响。结果表明，利用POE与PP良好的相容性，实现了可逆感温变色粉在PP基体中均匀的分散，可逆感温变色PP专用料表现出优异的可逆感温变色性能和冲击性能。     

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。     

Deactivation of hydrodesulfurization catalysts during reactor startup

Metal sulfide catalysts for ultra-deep hydrodesulfurization of diesel generally lose a fraction of their catalytically active sites during reactor startup. The underlying mechanisms are discussed. A laboratory diagnostic tool consisting of three probe molecules is developed for testing metal sulfide catalysts' start-of-run (SOR) activity maintenance. It is found that a significant fraction of the active sites on a commercial supported catalyst are deactivated permanently, but this is not the case with a bulk metal sulfide catalyst. The SOR deactivation of the bulk catalyst is completely reversible, while that of the supported catalyst is partially reversible. The diagnostic tool may provide a basis for developing a high-throughput approach for evaluating and enhancing catalyst SOR stability, thereby increasing plant productivity.     

Continuous Flow Fabrication of Block Copolymer–Grafted Silica Micro‐Particles in Environmentally Friendly Water/Ethanol Media

Polymer‐grafted inorganic particles (PGIPs) are attractive building blocks for numerous chemical and material applications. Surface‐initiated controlled radical polymerization (SI‐CRP) is the most feasible method to fabricate PGIPs. However, a conventional in‐batch reaction still suffers from several disadvantages, including time‐consuming purification processes, low grafting efficiency, and possible gelation problems. Herein, a facile method is demonstrated to synthesize block copolymer–grafted inorganic particles, that is, poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMEMA)‐b‐poly(N‐isopropylacrylamide) (PNIPAM)–grafted silica micro‐particles using continuous flow chemistry in an environmentally friendly aqueous media. Immobilizing the chain transfer agent and subsequent SI‐CRP can be accomplished sequentially in a continuous flow system, avoiding multi‐step purification processes in between. The chain length (MW) of the grafted polymers is tunable by adjusting the flow time or monomer concentration, and the narrower molar mass dispersity (Р< 1.4) of the grafted polymers reveals the uniform polymer chains on the particles. Moreover, compared with the in‐batch reaction at the same condition, the continuous system also suppresses possible gelation problems.     

自愈合橡胶材料研究进展

具有自感知、自诊断、自愈合功能的智能聚合物材料是高分子科学领域的前沿材料之一。介绍了自愈合橡胶材料的自愈合机理,综述了自愈合橡胶材料的分类、特性和发展概况,展望了其应用及发展前景。     

Complete Photochemical Regulation of 8–17 DNAzyme Activity by Using Reversible DNA Photo-crosslinking

The regulation of DNAzyme activity is an important problem for its in vivo applications. We achieved photochemical regulation of DNAzyme activity by using reversible DNA photo-crosslinking of 3-cyanovinylcarbazole (^CNVK). The ODN containing ^CNVK photo-crosslinked to a pyrimidine base in the complementary strand after a few seconds of photoirradiation, and its photoadduct was split by photoirradiation of another wavelength. The activity of photo-crosslinked DNAzyme with ^CNVK was completely inhibited (OFF state). In contrast, after 312 nm irradiation, DNAzyme activity was recovered upon addition of a substrate strand (ON state). In addition, the photo-crosslinked DNAzyme is prone to enzymatic digestion by exonuclease. This photochemical OFF to ON switching with reversible DNA photo-crosslinking was regulated at the desired time and position; therefore, it might be possible to use it for in vivo application.     

Emulsifier‐free reversible addition–fragmentation chain transfer emulsion polymerization of alkyl acrylates mediated by symmetrical trithiocarbonates based on poly(acrylic acid)

Emulsifier‐free batch emulsion polymerization of n‐butyl acrylate and its semi‐batch copolymerization with 2,2,3,3,4,4,5,5‐octafluoropentyl acrylate and 2,2,3,4,4,4‐hexafluorobutyl acrylate both mediated by poly(acrylic acid) containing the trithiocarbonate group in the chain was employed to produce amphiphilic triblock copolymers. The polymerization‐induced self‐assembly of these copolymers in aqueous media gave rise to spherical core–shell particles. Irrespective of the experimental conditions, the polymeric product was characterized by a bimodal molecular weight distribution. The apparent violation of the reversible addition–fragmentation chain transfer polymerization mechanism may be attributed to restricted accessibility of the trithiocarbonate group in the self‐assembled block copolymers for propagating radicals that enter into the particle. Mean‐field theoretical arguments were employed to explain the exclusively spherical morphology of the particles observed in the experiment. © 2019 Society of Chemical Industry