Transient NOE driven signal enhancement of INADEQUATE solid-state NMR spectroscopy for the structural analysis of rubbers

INADEQUATE(Incredible Natural Abundance DoublE QUAntum Transfer Experiment)is one of the most important techniques in revealing the carbon skeleton of organic solids in solid-state NMR spectroscopy.Nevertheless,its use for structural analysis is quite limited due to the low natural abundance of^(13)C-^(13)C connectivity(~0.01%)and thus low sensitivity.Particularly,in semi-solids like rubbers,the sensitivity will be further significantly reduced by the inefficient cross polarization from 1H to^(13)C due to molecular motions induced averaging of^(1)H-^(13)C dipolar couplings.Herein,in this study,we demonstrate that transient nuclear Overhauser effect(NOE)can be used to efficiently enhance^(13)C signals,and thus enable rapid acquisition of two-dimensional(2D)^(13)C INADEQUATE spectra of rubbers.Using chlorobutyl rubber as the model system,it is found that an overall signalto-noise ratio(SNR)enhancement about 22%can be achieved,leading to significant timesaving by about 33%as compared to the direct polarization-based INADEQUATE experiment.Further experimental results on natural rubber and ethylene propylene diene monomer(EPDM)rubber are also shown to demonstrate the robust performance of transient NOE enhanced INADEQUATE experiment.

Solid-state NMR of vulcanized natural rubber/butadiene rubber blends:Local organization and cross-linking heterogeneities This article is part of the virtual special issue“Solid-state NMR studies on polymers and biological solids”

Elastomer blends,among which natural rubber(NR)and butadiene rubber(BR),are involved in many components of the automotive/tire industry.A comprehensive understanding of their mechanical behavior requires,among other features,a detailed description of the crosslink density in these mixtures.In the case of vulcanized immiscible blends,the distribution of the cross-link density within each of the NR-and BR-rich domains is key information,but difficult to determine using the conventional approaches used for one-component crosslinked elastomers.In this study,the vulcanization within NR/BR blends is investigated using a robust^(1)H double-quantum(DQ)MAS recoupling experiment,BaBa-xy16.Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component.The bulk organization of the resulting blends was first probed by analyzing the^(1)H spin-lattice relaxation behavior.In a second step,BaBa-xy16 was used to investigate,in a selective way,the cross-link heterogeneities within NR/BR blends.In particular,for immiscible NR/BR mixtures,the distribution of the cross-link density between both phases was compared and the observed differences were discussed.

Postmortem ^(7)Li NMR analysis for assessing the reversibility of lithium metal electrodes in lithium metal batteries

Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,we conducted a comprehensive postmortem analysis utilizing ^(7)Li NMR,employing a stan-dard magic angle spinning probe to examine protective-layer coated Li metal electrodes and LiAg alloy electrodes against bare Li metal electrodes within Li metal batteries(LMBs).Our investigation explores the effects of sample burrs,alignment with the magnetic field,the existence of liquid electrolytes,and precycling on the ^(7)Li NMR signals.Through contrasting NMR spectra before and after cycling,we identi-fied alterations in Li^(0) and Li^(+) signals attributable to the degradation of the Li metal electrode.Our NMR analyses decisively demonstrate the efficacy of the protective layer in mitigating dendrite and solid elec-trolyte interphase formation.Moreover,we noted that Li*ions near the Li metal surface exhibit magnetic susceptibility anisotropy,revealing a novel approach to studying diamagnetic species on Li metal elec-trodes in LMBs.This study provides valuable insights and practical guidelines for characterizing distinct lithium states within LMBs.

A review of ^(17)O isotopic labeling techniques for solid-state NMR structural studies of metal oxides in lithium-ion batteries

Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.

Research status and prospects of the fractal analysis of metal material surfaces and interfaces

As a mathematical analysis method,fractal analysis can be used to quantitatively describe irregular shapes with self-similar or self-affine properties.Fractal analysis has been used to characterize the shapes of metal materials at various scales and dimensions.Conventional methods make it difficult to quantitatively describe the relationship between the regular characteristics and properties of metal material surfaces and interfaces.However,fractal analysis can be used to quantitatively describe the shape characteristics of metal materials and to establish the quantitative relationships between the shape characteristics and various properties of metal materials.From the perspective of two-dimensional planes and three-dimensional curved surfaces,this paper reviews the current research status of the fractal analysis of metal precipitate interfaces,metal grain boundary interfaces,metal-deposited film surfaces,metal fracture surfaces,metal machined surfaces,and metal wear surfaces.The relationship between the fractal dimensions and properties of metal material surfaces and interfaces is summarized.Starting from three perspectives of fractal analysis,namely,research scope,image acquisition methods,and calculation methods,this paper identifies the direction of research on fractal analysis of metal material surfaces and interfaces that need to be developed.It is believed that revealing the deep influence mechanism between the fractal dimensions and properties of metal material surfaces and interfaces will be the key research direction of the fractal analysis of metal materials in the future.

Deep eutectic solvents for separation and purification applications in critical metal metallurgy:Recent advances and perspectives

Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.

Molecule‑Level Multiscale Design of Nonflammable Gel Polymer Electrolyte to Build Stable SEI/CEI for Lithium Metal Battery

The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.

Porous Organic Cage‑Based Quasi‑Solid‑State Electrolyte with Cavity‑Induced Anion‑Trapping Effect for Long‑Life Lithium Metal Batteries

Porous organic cages(POCs)with permanent porosity and excellent host–guest property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.

用于电梯曳引机减振的MR-SRC减振器设计与分析

针对现有曳引机减振常采用的高分子减振垫因环境因素而引发性能大幅退化问题,以电梯曳引机减振器的工程应用需求为导向,确定减振器所需阻尼元件的刚度后,采用真空渗流技术将硅橡胶填充入金属橡胶孔隙并形成包覆,研制出一款耐环境影响的高性能金属橡胶/硅橡胶连续互穿相复合减振材料(metal rubber-silicone rubber continuous interwoven phase composite damping material, MR-SRC)。然后基于实际结构建立电梯曳引机的有限元数值模型。对加装MR-SRC减振器前后的电梯曳引机进行了模态分析,确定了整体结构的固有频率和振型。对MR-SRC减振器进行冲击响应分析,对比不同MR-SRC材料和冲击载荷对响应的影响,校核减振器的强度。接着,基于MR-SRC的近似等效,对减振器系统的冲击响应进行了理论计算,得出金属橡胶密度为1.8 g/cm^(3)的MR-SRC减振器对减振效果最佳。最后将所制备的MR-SRC减振器安装于实际电梯曳引机,按照电梯减振国标要求,测试电梯在运行过程中的加速度和速度变化,计算并校核电梯运行的相关特性参数。该文章提出的减振器为电梯安全可靠运行提供了一种新途径。

Energy dissipation of a ring-like metal rubber isolator

Metal rubber （MR） is a kind of homogeneous poroelastic damping material made of metal wire. In this paper, by ana- lyzing the forces on the MR isolator and the MR element, the hysteresis loops of the force and deformation are studied and verified by experiments. The results show that the force and displacement hysteresis loop of the MR isolator is described by the force and deformation hysteresis loops of the MR elements. In addition, the relationship between the energy dissipation coefficient of the MR element and that of the MR isolator is derived. The energy dissipation coefficient is programmed and calculated by MATLAB using experimental data, and the results are compared with the theoretical value. It is the basis for the design and applied research of the MR isolator in a future study.

Damping characteristics analysis of squeeze film damper with metal rubber

A squeeze film damper (SFD) with metal rubber (MR) ring installed on the end and the radial direction of rotor are implemented in this paper. Based on the hypothesis of π film, the description of the new SFD/MR flux and nonlinear oil film damping force is derived according to the Reynolds Eq. and Darcy’s law. It proves that the SFD/MR has better damping characteristics than the traditional SFD after comparatively analyzing characteristics of oil film between the traditional short SFD and the SFD/MR.

CALCULATION OF ELASTIC DAMPING CHARACTERISTICS OF ROTOR SUPPORT MADE OF METAL RUBBER MATERIAL UNDER VARIABLE LOADS

A metal rubber（MR） dry friction damper was designed based on the load supported by the rotor. An experimental apparatus for obtaining hysteresis loops of support under the precession load was designed. The elastic-damping characteristics of the ring-shaped MR damper used as a rotor support under variable loads were presented by studying the hysteresis loops of the damper. The vibration rigidity and the energy dissipation coefficient were calculated from the hysteresis loops, based on the description of the deformation process of the MR element with simple structure in a dimensionless coordinating system. The calculation results showed that the energy dissipation coefficient in the inner of MR element and on the boundary between the damper and the frame of the rotor support were approximately equal. The comparison of the hysteresis loops for a precession load and a one-axial load indicated a large difference when the coefficient of the energy dissipation and the stiffness of the MR damper were concerned.

Lifetime of metal rubber isolator with different vibration amplitudes

The lifetime of metal rubber isolator and its characteristics during lifetime experiment were studied. The stepped-up test principle was adopted to study the lifetime of resonant frequency, the breakage form of metal rubber isolator was obtained, and the relation between the energy dissipation, resonant frequency and stiffness was obtained in (available) lifetime of the isolator. Furthermore, the reason for the changes of properties of metal rubber isolator was analyzed with contact model of metal rubber material. The results show that if the resonant amplitude is large, the stiffness of metal rubber isolator will be kept steadily for a long time, its resonant frequency will be stable and the effective working time in the protecting area will be long. The lifetime of metal rubber isolator is more than 1376 h in the experiment. The main failure forms of metal rubber isolator are accumulative wear and breaking of metal wires and spirals. In protecting area the metal rubber isolator can work effectively for a long time, and the effective working time depends on the concrete working condition.

3D Modeling of the preparation process of metal rubber material

Based on the analysis of the preparation of metal rubber （MR） and two pivotal hypotheses, the uniform distribution and the unaltered topological structure of wires in the radial direction of columns in the punch process, a 3D parametrical model was established based on four approaches： helix-making, planar roughcast-weaving, planar roughcast-rolling, and 3D roughcast punching. In the modeling process, 5 lattice types of weave patterns in planar roughcast were put forward, and 10 quantificational modeling parameters were picked up to exclusively define the column MR component structure. The wire distribution was visualized by CAD techniques. The important performance parameter of column MR components （relative density ρ^- ） can be forecasted by modeling computing, which provides the necessary foundation for the design and optimization of MR materials.

RuRh Bimetallic Nanoparticles Stabilized by 15-membered Macrocycles-terminated Poly(propylene imine) Dendrimer:Preparation and Catalytic Hydrogenation of Nitrile–Butadiene Rubber

A new fourth-generation poly(propylene imine) dendrimer(G4-M) containing 32 triolefinic 15-membered macrocycles on the surfaces has been synthesized. The bimetallic Ru Rh dendrimer-stabilized nanoparticles(DSNs) were first prepared within G4-M by a co-complexation route. The new G4-M dendrimer has been characterized by 1H nuclear magnetic resonance, infrared radiation, and elemental analysis.The dendrimer-stabilized bimetallic ions and reduction courses were analyzed by UV-vis spectroscopy. Highresolution transmission electron microscopy and energy dispersive spectrometer were used to characterize the bimetallic nanoparticle size, size distribution, and particle morphology. The Ru Rh bimetallic DSNs showed high catalytic activity for the hydrogenation of nitrile-butadiene rubber.

~2H-NMR CHARACTERIZATION OF CLAY DISPERSION AND CONFINEMENT EFFECT ON PROBE MOLECULES IN RUBBER/CLAY NANOCOMPOSITE-GELS

~2H-NMR spectroscopy of the probe molecule,deuterated benzene,was applied to characterize organo-clay dispersion and confinement effect on the local motion of benzene in rubber/clay nanocomposite-gels.The observed ~2H line shapes of benzene in intercalated and exfoliated nanocomposites were obviously different,which can be used to estimate clay-dispersion quality.~2H-NMR line shapes also reflect the different influence of intercalated or exfoliated layered-silicates on local motions of benzene,implying that...

Memristive Devices Based on Two-Dimensional Transition Metal Chalcogenides for Neuromorphic Computing

Two-dimensional(2D)transition metal chalcogenides(TMC)and their heterostructures are appealing as building blocks in a wide range of electronic and optoelectronic devices,particularly futuristic memristive and synaptic devices for brain-inspired neuromorphic computing systems.The distinct properties such as high durability,electrical and optical tunability,clean surface,flexibility,and LEGO-staking capability enable simple fabrication with high integration density,energy-efficient operation,and high scalability.This review provides a thorough examination of high-performance memristors based on 2D TMCs for neuromorphic computing applications,including the promise of 2D TMC materials and heterostructures,as well as the state-of-the-art demonstration of memristive devices.The challenges and future prospects for the development of these emerging materials and devices are also discussed.The purpose of this review is to provide an outlook on the fabrication and characterization of neuromorphic memristors based on 2D TMCs.

Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.

Deuterium NMR Studies on the Orientational Order Generated in Strained Rubbers

The present paper deals with the induced orientational order of the probe molecules dissolved in the uniaxially strained rubbers measured by using deuterium NMR. The distinctive dependence of the quadrupolar splitting on the swelling, elongation and crosslinking density was observed. The orientational order arising from the correlation between chain segments decreases with the increase of the numbers of both links between junctions and solvent molecules around segments.

Low-temperature characteristicsof rubbers and performance testsof type 120 emergencyvalve diaphragms

Purpose–The type 120 emergency valve is an essential braking component of railway freight trains,butcorresponding diaphragms consisting of natural rubber(NR)and chloroprene rubber(CR)exhibit insufficientaging resistance and low-temperature resistance,respectively.In order to develop type 120 emergency valverubber diaphragms with long-life and high-performance,low-temperatureresistant CR and NR were processed.Design/methodology/approach–The physical properties of the low-temperature-resistant CR and NRwere tested by low-temperature stretching,dynamic mechanical analysis,differential scanning calorimetryand thermogravimetric analysis.Single-valve and single-vehicle tests of type 120 emergency valves werecarried out for emergency diaphragms consisting of NR and CR.Findings–The low-temperature-resistant CR and NR exhibited excellent physical properties.The elasticityand low-temperature resistance of NR were superior to those of CR,whereas the mechanical properties of thetwo rubbers were similar in the temperature range of 0℃–150℃.The NR and CR emergency diaphragms metthe requirements of the single-valve test.In the low-temperature single-vehicle test,only the low-temperaturesensitivity test of the NR emergency diaphragm met the requirements.Originality/value–The innovation of this study is that it provides valuable data and experience for futuredevelopment of type 120 valve rubber diaphragms.