Polymer 4D printing: Advanced shape-change and beyond

4D printing is an exciting branch of additive manufacturing. It relies on established 3D printing techniques to fabricate objects in much the same way. However, structures which fall into the 4D printed category have the ability to change with time, hence the “extra dimension.” The common perception of 4D printed objects is that of macroscopic single-material structures limited to point-to-point shape change only, in response to either heat or water. However, in the area of polymer 4D printing, recent advancements challenge this understanding. A host of new polymeric materials have been designed which display a variety of wonderful effects brought about by unconventional stimuli, and advanced additive manufacturing techniques have been developed to accommodate them. As a result, the horizons of polymer 4D printing have been broadened beyond what was initially thought possible. In this review, we showcase the many studies which evolve the very definition of polymer 4D printing, and reveal emerging areas of research integral to its advancement.     

Insights into MWCNTs/polyimide nanocomposites: from synthesis to application as free-standing flexible electrodes in low-cost micro-supercapacitors

In the pursuit to enlarge the library of polyimide materials for energy applications, new polyimide/MWCNTs composite films have been developed by MWCNTs-assisted polycondensation reaction of a hydroxyl and triphenylmethane-containing diamine with benzophenone tetracarboxylic dianhydride targeting to highlight their electrical storage capability as flexible electrodes in micro-supercapacitors (mSCs). The Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, UV–vis, fluorescence, and Raman spectroscopies were used to demonstrate the evolution of interfacial interactions between MWCNTs and the precursors (diamine monomer and intermediate polyamidic acid) and polyimide matrix that proved to be the origin of MWCNTs homogeneous dispersion. Thus, composite films incorporating 1, 3, 5, and 10 w.t.% MWCNTs were obtained and thoroughly investigated with regard to their morphology, mechanical behavior, thermal stability, and electrical conductivity. The electrochemical performance of these composites was first analyzed in a classical three-electrode cell by cyclic voltammetry and galvanostatic charge-discharge in both aqueous and organic electrolyte systems. By far, the best electrical storage capacity was obtained with the composite polyimide film containing 10% MWCNTs that was further used as both active material and current collector in a flexible symmetric mSC realized by a straightforward and low-cost procedure. In the attempt to better exploit the advantages of this composite film, it was layered with a graphite-containing paint and tested as an electrode in a flexible mSC, which provided satisfactory results. To our knowledge, this is the first report on the electrical charge storage capability of a polyimide/MWCNTs free-standing film as a flexible electrode in mSCs, which do not require time- and resource-consuming processing steps.     

Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt-Fe Alloy Electrocatalysts for Methanol Oxidation Performance

The designs of efficient and inexpensive Pt-based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen-doped carbon (NC) have been successfully prepared via co-engineering of the surface composition and electronic structure. The Pt₁Fe₃@NC/MWCNTs catalyst with moderate Fe³⁺ feeding content (0.86 mA/mg_Pt) exhibits 2.26-fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mg_Pt). Furthermore, the CO oxidation initial potential of Pt₁Fe₃@NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti-corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N-doped carbon (NC) layer, the Pt₁Fe₃@NC/MWCNTs catalyst presents an improved MOR performance and anti-CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.     

Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes

The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g^?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g^?1 for the CNOs/Ppy bilayer (electrochemical deposition).     

Orientation dependent size effects in thermal buckling and post-buckling of nanoplates with cubic anisotropy

In this work, a continuum model is presented for size and orientation dependent thermal buckling and post-buckling of anisotropic nanoplates considering surface and bulk residual stresses. The model with von-Karman nonlinear strains and material cubic anisotropy of single crystals contains two parameters that reflect the orientation effects. Using Ritz method, closed form solutions are given for buckling temperature and post-buckling deflections. Regarding self-instability states of nanoplates and their recovering at higher temperatures, an experiment is discussed based on low pressurized membranes to verify the predictions. For simply supported nanoplates, the size effects are lowest when they are aligned in [100] direction. When the edges get clamped, the orientation dependence is ignorable and the behavior becomes symmetric about [510] axis. The surface residual stress makes drastic increase in buckling temperature of thinner nanoplates for which a minimum thickness is pointed to stay far from material softening at higher temperatures. Deflection of [100]-oriented buckled nanoplates is higher than [110] ones but this reverses at higher temperatures. The results for long nanoplates show that the buckling mode numbers are changed by orientation which is verified by FEM.     

Design of broadband achromatic metasurface device based on phase-change material Ge2Sb2Te5

Based on the phase-change material Ge₂Sb₂Te₅ (GST), achromatic metasurface optical device in the longer-infrared wavelength is designed. With the combination of the linear phase gradient GST nanopillar and the adjustment of the crystalline fraction m value of GST, the polarization insensitive achromic metalenses and beam deflector metasurface within the longer-infrared wavelength 9.5 μm to 13 μm are realized. The design results show that the achromatic metalenses can be focused on the same focal plane within the working waveband. The simulation calculation results show that the full-width at half-maximum (FWHM) of the focusing spot reaches the diffraction limit at each wavelength. In addition, the same method is also used to design a broadband achromatic beam deflector metasurface with the same deflection angle of 19°. The method proposed in this article not only provides new ideas for the design of achromatic metasurfaces, but also provides new possibilities for the integration of optical imaging, optical coding and other related optical systems.     

从废水到新能源:光催化燃料电池的优化与应用

随着经济的飞速发展,社会对能源的需求日益扩大,对工业废水的无害化处理也提出了更高的要求。光催化燃料电池 (photocatalytic fuel cell, PFC) 在燃料电池中引入半导体光催化材料作为电极,实现了有机污染物高效降解和同步对外产电的双重功能,在废水无害化与资源化利用方面具有潜在的应用价值。半导体光催化电极是PFC系统高效运行的核心组件,增强其可见光响应和光生载流子分离是提高PFC性能的关键策略。反应器结构设计和运行参数优化也有利于改善PFC性能。本文从PFC基本原理和应用入手,综述了PFC在环境污染物资源化处理中的研究进展,并详细阐述了提高PFC的污染控制性能和产电效率的优化手段,为进一步设计高效稳定的PFC系统并实现其在水污染控制和清洁能源生产中的应用提供理论指导。     

Influence of the Degree of Deacetylation of Chitosan and BMP-2 Concentration on Biocompatibility and Osteogenic Properties of BMP-2/PLA Granule-Loaded Chitosan/β-Glycerophosphate Hydrogels

Compositions based on chitosan/β-glycerophosphate hydrogels with highly porous polylactide granules can be used to obtain moldable bone graft materials that have osteoinductive and osteoconductive properties. To eliminate the influence of such characteristics as chain length, degree of purification, and molecular weight on a designed material, the one-stock chitosan sample was reacetylated to degrees of deacetylation (DD%) of 19.5, 39, 49, 55, and 56. A study of the chitosan/β-glycerophosphate hydrogel with chitosan of a reduced DD% showed that a low degree of deacetylation increased the MSCs (multipotent stromal cells) viability rate in vitro and reduced the leukocyte infiltration in subcutaneous implantation to Wistar rats in vivo. The addition of 12 wt% polylactide granules resulted in optimal composite mechanical and moldable properties, and increased the modulus of elasticity of the hydrogel-based material by approximately 100 times. Excessive filling of the material with PLA (polylactide) granules (more than 20%) led to material destruction at a ~10% strain. Osteoinductive and osteoconductive properties of the chitosan hydrogel-based material with reacetylated chitosan (39 DD%) and highly porous polylactide granules impregnated with BMP-2 (bone morphogenetic protein-2) have been demonstrated in models of orthotopic and ectopic bone formation. When implanted into a critical-size calvarial defect in rats, the optimal concentration of BMP-2 was 10 μg/mL: bone tissue areas filled the entire material’s thickness. Implantation of the material with 50 μg/mL BMP-2 was accompanied with excessive growth of bone tissue and material displacement beyond the defect. Significant osteoinductive and osteoconductive properties of the material with 10 μg/mL of BMP-2 were also shown in subcutaneous implantation.     

A model for crack formation during active solid pyrolysis of a char-forming solid: crack patterns; surface area generation; volatile mass efflux

A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests.