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Binuclear and Hexanuclear Ti(Ⅳ) Complexes Supported by [OOOO]^(4–)-type Ligand for Preparing Disentangled UHMWPE

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Chinese Journal of Polymer Science 2019年第5期37卷 471-477页

作者： Vladislav A.Tuskaev Svetlana Ch.Gagieva Dmitry A.Kurmaev Viktor G.Vasil'ev Nikolay A.Kolosov Sergey V.Zubkevich Elena S.Mikhaylik Evgenii K.Golubev Galina G.Nikiforova Pavel A.Zhizhko Olga A.Serenko Boris M.Bulychev Department of Chemistry M.V.Lomonosov Moscow State University A.N.Nesmeyanov institute of Organoelement Compounds Russian Academy of Sciences enikolopov institute of synthetic Polymer materials Russian Academy of Sciences

Binuclear and hexanuclear titanium complexes stabilized by tetradentate [OOOO]^(4–)-type ligand were active in ethylene polymerization in the presence of Et2 AlCl/Bu2 Mg binary co-catalyst, giving high molecular weight polyethylene. The binuclear complex showed significantly higher catalytic activity and thermal stability in comparison to mononuclear analogue. Ultra high molecular weight polyethylene(UHMWPE) samples were processed by a solid-state uniaxial deformation into high-strength(up to 2.5 GPa) and highmodulus(over 100 GPa) oriented film tapes, which indirectly indicates a low degree of entanglements between the macromolecular chains.

关键词： Binuclear catalysts Titanium Ethylene Ziegler-Natta polymerization UHMWPE

Scalable nanocomposite parylene-based memristors:Multifilamentary resistive switching and neuromorphic applications

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Nano Research 2023年第2期16卷 3207-3214页

作者： Anna N.Matsukatova Artem Yu.Vdovichenko Timofey D.Patsaev Pavel A.Forsh Pavel K.Kashkarov Vyacheslav A.Demin Andrey V.Emelyanov National Research Centre“Kurchatov institute” Moscow 123182Russia Physics Department Lomonosov Moscow State UniversityMoscow 119991Russia Moscow institute of Physics and Technology DolgoprudnyjMoscow oblast 141701Russia enikolopov institute of synthetic polymeric materials Russian Academy of SciencesMoscow 117993Russia Physics Department Saint Petersburg State UniversitySt.Petersburg 199034Russia

Memristors are promising candidates for synapse emulation in brain-inspired neuromorphic computing *** main obstacle to their usage in such systems is high variability of memristive characteristics and its severe negative effect on the neural network *** paper addresses the issue from two points of view on the example of the parylene-based memristors:(i)the methods of the memristor internal stochasticity decrease and(ii)the methods of the memristive neural network architecture *** introduction of an optimal Ag nanoparticle concentration(3 vol.%–6 vol.%)to the memristive structure leads to a statistically significant decrease in the switching voltage variation and endurance ***,it is shown that post-fabrication annealing improves memristive characteristics,e.g.,resistive switching window increases by an order of magnitude and exceeds 106,the switching voltage variation decreases by a factor of 2(down to 7%for the set and 17%for the reset voltage),and thermostability is *** transmission electron microscopy and impedance spectroscopy analysis allowed establishing a multifilamentary resistive switching mechanism for nanocomposite parylene-based *** simulation of the formal neural network based on these memristors demonstrates high classification accuracy with low variation for an important biomedical task,heart disease prediction,after careful feature selection and network architecture *** prospects of the controlled incorporation of the nanocomposite parylene-based memristors in neural networks are brightened by their scaling possibility in crossbar geometry.

关键词： memristor resistive switching neuromorphic computing parylene nanocomposite

Effect of the Morphology of Leather Surface on the Hydrophobic-Hydrophilic Properties

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Advances in materials Physics and Chemistry 2014年第2期4卷 13-19页

作者： Olga Serenko Zarina Nizamova Mikhail Kalinin Yuri Ostrovsky Ludmila Polukhina Aziz Muzafarov 1enikolopov institute of synthetic polymeric materials Foundation of the Russian Academy of Sciences Moscow Russia enikolopov institute of synthetic polymeric materials Foundation of the Russian Academy of Sciences Moscow Russia Moscow State University of Design and Technology Moscow Russia

Natural leathers (split, velour split, nubuck) ware investigated. Solution of fluorine silane in ethanol was applied as the hydrophobic agent. It is shown that the microstructure of the leather surface, provided its structural elements possess hydrophilic properties, determines the wetting regime and duration of the induction period of changeover from heterogeneous to homogeneous wetting. The heterogeneous regime of wetting is distinguished by low rates of spreading and absorbing. The homogeneous wetting is characterized by high rates of spreading and absorbing of a water drop. A necessary condition of the stable heterogeneous wetting regime and achieving hydrophobicity of leather with structurally inhomogeneous face layer is to preserve the microstructure features of their surface at hydrophobic treatment. The morphological peculiarities of split and ground leather ensure stable hydrophobic properties after application of efficient hydrophobizators.

关键词： Leather Surface Modification Water Contact Angle Wetting Hydrophobic Effect

Sustainable and untethered soft robots created using printable and recyclable ferromagnetic fibers

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Bio-Design and Manufacturing 2024年第6期7卷 926-937页

作者： Wei Tang Yidan Gao Zeyu Dong Dong Han Vadim V.Gorodov Elena Y.Kramarenko Jun Zou State Key Laboratory of Fluid Power and Mechatronic Systems Zhejiang UniversityHangzhou 310058China School of Mechanical Engineering Zhejiang UniversityHangzhou 310058China institute of Process Equipment College of Energy EngineeringZhejiang UniversityHangzhou 310027China Faculty of Physics Lomonosov Moscow State UniversityMoscow 119991Russia enikolopov institute of synthetic polymeric materials of Russian Academy of Sciences Moscow 117393Russia

Integrated printing of magnetic soft robots with complex structures using recyclable materials to achieve sustainability of the soft robots remains a persistent ***,we propose a kind of ferromagnetic fibers that can be used to print soft robots with complex *** ferromagnetic fibers are recyclable and can make soft robots *** ferromagnetic fibers based on thermoplastic polyurethane(TPU)/NdFeB hybrid particles are extruded by an *** use a desktop three-dimensional(3D)printer to demonstrate the feasibility of printing two-dimensional(2D)and complex 3D soft *** printed soft robots can be recycled and reprinted into new robots once their tasks are ***,these robots show almost no difference in actuation capability compared to prior versions and have new *** applications include lifting,grasping,and moving objects,and these functions can be operated untethered *** addition,the locomotion of the magnetic soft robot in a human stomach model shows the prospect of medical ***,these fully recyclable ferromagnetic fibers pave the way for printing and reprinting sustainable soft robots while also effectively reducing e-waste and robotics waste materials,which is important for resource conservation and environmental protection.

关键词： Ferromagnetic fibers Sustainable soft robots Three-dimensional printing Recyclable soft materials Medical applications

Shape estimation for a TPU-based multi-material 3D printed soft pneumatic actuator using deep learning models

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Science China(Technological Sciences) 2024年第5期67卷 1470-1481页

作者： HU Yu TANG Wei QU Yang XU HuXiu KRAMARENKO Yu.Elena ZOU Jun State Key Laboratory of Fluid Power and Mechatronic Systems Zhejiang UniversityHangzhou310058China School of Mechanical Engineering Zhejiang UniversityHangzhou310027China institute of Process Equipment College of Energy EngineeringZhejiang UniversityHangzhou310027China Faculty of Physics Lomonosov Moscow State UniversityMoscow119991Russia enikolopov institute of synthetic polymeric materials of Russian Academy of Sciences Moscow117393Russia

Real-time proprioception presents a significant challenge for soft robots due to their infinite degrees of freedom and intrinsic *** studies mostly focused on specific sensors and *** is still a lack of generalizable technologies for integrating soft sensing elements into soft actuators and mapping sensor signals to proprioception *** tackle this problem,we employed multi-material 3D printing technology to fabricate sensorized soft-bending actuators(SBAs)using plain and conductive thermoplastic polyurethane(TPU)*** designed various geometric shapes for the sensors and investigated their strain-resistive performance during *** address the nonlinear time-variant behavior of the sensors during dynamic modeling,we adopted a data-driven approach using different deep neural networks to learn the relationship between sensor signals and system states.A series of experiments in various actuation scenarios were conducted,and the results demonstrated the effectiveness of this *** sensing and shape prediction steps can run in real-time at a frequency of50 Hz on a consumer-level ***,a method is proposed to enhance the robustness of the learning models using data augmentation to handle unexpected sensor *** the methods are efficient,not only for in-plane 2D shape estimation but also for out-of-plane 3D shape *** aim of this study is to introduce a methodology for the proprioception of soft pneumatic actuators,including manufacturing and sensing modeling,that can be generalized to other soft robots.

关键词： shape estimation soft sensors and actuators 3D printing deep learning in robotics

Olefin Polymerization Behavior of Titanium(IV) Complexes with Fluorinated and Non-fluorinated Aliphatic Phenoxyimine Ligands

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Chinese Journal of Polymer Science 2024年第1期42卷 52-62,I0007页

作者： Vladislav A.Tuskaev Kasim F.Magomedov Svetlana Ch.Gagieva Dmitry A.Kurmaev Yulia V.Nelyubina Evgenii K.Golubev Maria D.Evseeva Viktor G.Vasil'ev Galina G.Nikiforova Mikhail I.Buzin Vyacheslav S.Bogdanov Boris M.Bulychev Department of Chemistry M.V.Lomonosov Moscow State UniversityMoscow 119992Russian Federation A.N.Nesmeyanov institute of Organoelement Compounds Russian Academy of SciencesMoscow119991Russian Federation enikolopov institute of synthetic Polymer materials Russian Academy of SciencesMoscow 117393Russian Federation

A series of Ti(Ⅳ) dichloride and dialkoxide com plexes with phenoxyimine ligands containing fluorinated and nonfluorinated aliphatic imine fragments have been *** molecular structures of complexes 1 and 4 were established by single-crystal X-ray diffraction *** complexes adopt a distorted octahedral coordination structure around the titanium atom and two oxygen atoms are situated in trans position while two nitrogen atoms and two outgoing ligands(Cl or iPrO) are situated in cis *** of activators(MMAO-12 and combinations Et_nAICl_(3-n)+Bu_(2)Mg) and outgoing ligand(Cl or iPrO) nature on the catalytic activity and properties of the resulting polymers was *** Ti complexes,despite the nature of the outgoing ligands(Cl or iPrO) in the presence of Al/Mg activators,was found to display a high ethylene polymerization activity in the range 1600-3830 kg_(polymer)·mol_(Ti)^(-1)·h^(-1)·atm^(-1) with a viscosity average molecular weight(M_v) value in the range 1.1×10~6-7.1×10~6 Dalton(Da).The resulting UHMWPE can be processed by a solventless method into high-strength and high-modulus oriented *** rheological characteristics of a polymer melt have been *** absence of a cross-over point did not allow to compare the values of the molecular weight distribution of polymers obtained on fluorinated and non-fluorinated pre-catalysts,however,the estimation of the entanglement density is in good agreement with the mechanical characteristics of oriented film *** activation with methylalumoxane,the activity of the com plexes decreased very significantly;however,a polymer with a molecular weight of about 12 million Da was *** the process of ethylene/octene-1 copolymerization,fluorine-containing precatalysts showed a clear advantage over non-fluorinated analogues both in activity and in comonomer content.

关键词： FI catalysts Titanium(IV) (Co)polymerization Al/Mg co-catalyst Ultra-high molecular weight polyethylene

Luminescent Composite Films Based on Mechanically Strong Ladder-like Polyphenylsilsesquioxane and Oligophenyleuropiumsiloxane

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Chinese Journal of Polymer Science 2024年第11期42卷 1793-1801,I0013页

作者： E.E.Kim T.O.Ershova A.S.Belova D.A.Khanin E.V.Bashkova G.G.Nikiforova Yu.N.Kononevich A.A.Anisimov O.I.Shchegolikhina A.M.Muzafarov A.N.Nesmeyanov institute of Organoelement Compounds Russian Academy of SciencesMoscow119334Russian Federation Tula State Lev Tolstoy Pedagogical University Tula300026Russian Federation V.Topchiev institute of Petrochemical Synthesis Russian Academy of Sciences Moscow119991Russian Federation Moscow institute of Physics and Technology(National Research University) DolgoprudnyMoscow Region141700Russian Federation N.S.enikolopov institute of synthetic polymeric materials Russian Academy of SciencesMoscow117393Russian Federation

Nowadays organosilicon luminescent materials are of increasing interest due to the variety of their synthetic or modification techniques and application *** polyphenylsilsesquioxanes(L-PPSQ)are a unique class of organosilicon polymers,which can be ideal matrices for the luminescent composites due to their high thermal stability,optical transparency and mechanical *** this work,new mechanically strong,heat-resistant,transparent and sensitive to ammonia vapor luminescent composite films based on L-PPSQ have been *** the source of Europium ions oligophenyleuropiumsiloxane was used,demonstrating perfect compatibility to the matrix due to the similar *** improve luminescent properties of the films,new organosilicon ligands were introduced into the composites and their influence on the properties of the materials was *** properties of described composites may allow their further application as multifunctional coatings.

关键词： Luminescent composite films Ladder-like polyphenylsilsesquioxane Oligophenyleuropiumsiloxane

Hofmeister Effect-Assisted Strong Natural Biopolymer-Based Hydrogels with Multi-Functions

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Chinese Journal of Chemistry 2021年第11期39卷 3085-3092页

作者： Yaqian Cai Jiachuan Shi Fangzhe Liu Haichao Li Xinya Man Shuang Guan Department of polymeric and Soft materials Laboratory School of Chemistry and Life Science and Advanced Institute of Materials ScienceChangchun University of TechnologyChangchunJilin130012 China

Natural biopolymer-based hydrogels have been extensively studied in recent years due to their excellent ***,the preparation of multi-functional and tough natural biopolymer-based hydrogels is still a challenging ***,a natural biopolymer-based hydrogel is prepared using gelatin and carboxymethyl chitosan(CMCS)through a one-step soaking *** prepared hydrogel without any synthetic polymers and crosslinking agents has a fully physical crosslinking *** to the hydrophobic interaction brought by the Hofmeister effect,the mechanical properties of soaked hydrogels(tensile stress and strain can reach 3.77 MPa and 1082%)are superior to conventional protein *** addition,the prepared gelatin/carboxymethyl chitosan(Gel/CMCS)hydrogels exhibit a variety of appealing properties,including good shape memory,fatigue resistance,electrical conductivity,water retention,drug releasing,antibacterial property,and *** strategy opens up a new horizon to fabricate hydrogels with excellent mechanical properties and multiple functions,which can extend their applications in the biomedicine area and other related fields.

关键词： Natural biopolymer-based hydrogels Mechanical properties Polymers Hofmeister effect Multi-Fuctions

A 2D NiFe Bimetallic Metal–Organic Frameworks for Efficient Oxygen Evolution Electrocatalysis

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Energy & Environmental materials 2019年第1期2卷 18-21页

作者： Yongchao Hao Qinglin Liu Ying Zhou Zeqian Yuan Yanan Fan Zhuofeng Ke Cheng-Yong Su Guangqin Li MOE Laboratory of Bioinorganic and synthetic Chemistry Lehn Institute of Functional MaterialsSchool of ChemistrySun Yat-Sen UniversityNo.135Xingang Xi RoadGuangzhou 510275China Key Laboratory for polymeric Composite and Functional materials of Ministry of Education School of Materials Science and EngineeringSun Yat-Sen UniversityGuangzhou 510275China

The oxygen evolution reaction(OER) is the cornerstone for many important energy conversion devices, including metal–air battery and water ***, an optimized NiFe-based metal–organic framework is developed as highly efficient active material for OER. It just needs a low overpotential of 0.31 V to deliver a current density of 10 mA cm-2 with a favorable Tafel slope of 43.7 mV dec-1 in 0.1 M KOH electrolyte for the as-prepared Ni0.75Fe0.25 BDC, which is superior to RuO2. This efficient catalytic performance is due to the introduction of Fe in Ni-based MOFs could benefit the kinetics and charge transfer efficiency, resulting in the optimal activity toward OER. Besides, the obtained active material demonstrates good stability, suggesting the great potential value in sustainable electrochemical energy storage and conversion devices.

关键词： iron-doping metal-organic frameworks oxygen evolution reaction two-dimension