In-situ polymerized PEO-based solid electrolytes contribute better Li metal batteries:Challenges,strategies,and perspectives

Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.

Physical and Chemical Properties of Horns Sheaths Particles for the Manufacture of Composite Materials

Salvaged cow horns from slaughterhouses have been transformed into fine particles for a physical characterization that has led us to determine the humidity rate (2.34% ± 0.054%), the actual density situated between 0.586 g/cm3 and 0.732 g/cm3, the swelling rate (12%), and one chemical characterization that permitted us to determine the rate of dry matters (97.05%), of mineral matters (2.5%), of protein matters (94.52%). From these weak values, it can easily be seen that cow horn case doesn’t absorb much water and improve the mechanical characteristics of the composite;the high rate of protein shows that keratin which is the structural molecule favors its gripping as reinforcing element in the manufacturing of composite materials.

Reliability Based Analysis of Ground Improvement Using a Polymeric Chemical Stabilizer

In view of the challenges posed by the nature of expansive soil to structural stability which makes it necessary in some cases to improve the soils before structures can be placed on them, there is a need to investigate modern trends in ground improvement techniques in order to determine their reliability. This study is thus aimed at using the reliability based approach to analyze the use of polyvinyl alcohol (PVA) in combination with 1,2,3,4 Butane-tetracarboxylic acid (BTCA) for ground improvement. This study is necessary given the challenges posed by the nature of expansive soil to structural stability which makes it necessary in some cases to improve the soils before structures can be placed on them. Simplex lattice design was employed to build the design of experiment before experimental investigations were carried out on the PVA-BTCA treated soft soils. Reliability indices were computed on the basis of the 28th day unconfined compressive strength (UCS) of the treated soil. Reliability index models were developed using the Scheffe’s technique and optimized using excel solver. From analysis of results, reliability model developed proved adequate at 5% level of significance. PVA-BTCA combination provided a potential reliability or probability of success of 99.936% at components combination of: 98.4256% for soil, 1.2352% for PVA, 0.3392% for BTCA and 15.9934% for water. It was therefore recommended that financial implications of using PVA-BTCA for stabilization be compared to those of conventional methods, in order to compare their performance-cost ratio.

Enhanced thermal and electrical properties of poly (D,L-lactide)/ multi-walled carbon nanotubes composites by in-situ polymerization

Biodegradable poly （D,L-lactide） （PLA）/carboxyl-functionalized multi-walled carbon nanotubes （c-MWCNTs） composites were achieved via in-situ polymerization. These as-prepared composite materials were characterized with FT-IR, XRD, TG, DSC, SEM, and high insulation resistance meter. The results demonstrate that the multi-walled carbon nanotube was carboxyl functionalized, which improved the collection between c-MWCNTs and PLA, and further realized the graft copolymerization of c-MWCNTs and PLA. There is a higher glass transition temperature and a lower pyrolysis temperature of PLA/c-MWCNTs composites than pure PLA. The c-MWCNTs gave a better dispersion than unmodified MWCNTs in the PLA matrix, and an even coating of PLA on the surface of c-MWCNTs was obtained, which increased the interfacial interaction. High insulation resistance analysis showed that the addition of c-MWCNTs increased the electric conductivity, and c-MWCNTs performed against the large dielectric coefficient and electrostatic state of PLA. These results demonstrated that c-MWCNTs modified PLA composites were beneficial for potential application in the development of heat-resisting and conductivity plastic engineering.

High-performance imidazole-containing polymers for applications in high temperature polymer electrolyte membrane fuel cells

This work focuses on the development of high temperature polymer electrolyte membranes(HT-PEMs)as key materials for HT-PEM fuel cells(HT-PEMFCs).Recognizing the challenges associated with the phosphoric acid(PA) doped polybenzimidazole(PBI) membranes,including the use of carcinogenic monomers and complex synthesis procedures,this study aims to develop more cost-effective,readily synthesized,and high-performance alternatives.A series of superacid-catalyzed polyhydroxyalkylation reactions have been carefully designed between p-terphenyl and aldehydes bearing imidazole moieties,resulting in a new class of HT-PEMs.It is found that the chemical structure of aldehyde-substituted N-heterocycles significantly impacts the polymerization reaction.Specifically,the use of 1-methyl-2-imidazole-formaldehyde and 1 H-imidazole-4-formaldehyde monomers leads to the formation of high-viscosity,rigid,and ether-free polymers,denoted as PTIm-a and PTIm-b.Membranes fabricated from these polymers,due to their pendent imidazole groups,exhibit an exceptional capacity for PA absorption.Notably,PTIm-a,carrying methylimidazole moieties,demonstrates a superior chemical stability by maintaining morphology and structural stability during 350 h of Fenton testing.After being immersed in 75 wt% PA at 40℃,the PTIm-a membrane reaches a PA content of 152%,maintains a good tensile strength of 13.6 MPa,and exhibits a moderate conductivity of 50.2 mS cm^(-1) at 180℃.Under H_(2)/O_(2) operational conditions,a single cell based on the PTIm-a membrane attains a peak power density of 732 mW cm^(-2) at 180℃ without backpressure.Furthermore,the membrane demonstrates stable cycle stability over 173 h within 18 days at a current density of 200 mA cm^(-2),indicating its potential for practical application in HT-PEMFCs.This work highlights innovative strategies for the synthesis of advanced HT-PEMs,offering significant improvements in membrane properties and fuel cell performance,thus expanding the horizons of HT-PEMFC technology.

In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

In-situ Chemical Age of the Sandstone-hosted Uranium Deposit in Ningdong Area on the Western Margin of the Ordos Basin, North China

Objective The Ordos Basin located in the westem part of the North China Craton bears various energy resources such as oil, gas, coal and uranium. It is one of the richest uranium-bearing basins in China. Since the discovery of the large-scale Dongsheng, Hangjinqi and Daying uranium deposits in the north of the Ordos Basin, a new breakthrough of uranium exploration has been achieved in the Ningdong area （eastern Ningxia） on the western margin of the Ordos Basin （WMOB） in the past two years （Wang Feifei et al., 2017）.

Comprehensive evaluation of chemical breakers for multistage network ultra-high strength gel

Polymer gels have been accepted as a useful tool to address many sealing operations such as drilling and completion,well stimulation,wellbore integrity,water and gas shutoff,etc.Previously,we developed an ultra-high strength gel(USGel)for medium to ultra-low temperature reservoirs.However,the removal of USGel is a difficult problem for most temporary plugging operations.This paper first provides new insights into the mechanism of USGel,where multistage network structure and physical entanglement are the main reasons for USGel possessing ultra-high strength.Then the effects of acid breakers,encapsulated breakers,and oxidation breakers(including H_(2)O_(2),Na_(2)S_(2)O_(8),Ca(ClO)_(2),H_(2)O_(2)+NaOH,Na_(2)S_(2)O_(8)+NaOH,and Ca(ClO)_(2)+NaOH)were evaluated.The effects of component concentration and temperature on the breaking solution were studied,and the corrosion performance,physical simulation and formation damage tests of the breaking solution were carried out.The final formulation of 2%-4%NaOH+4.5%-6%H_(2)O_(2) breaking solution was determined,which can make USGel completely turn into water at 35e105C.The combinations of“acid t breaking solution”,“acid+encapsulated breaker”and“encapsulated breaker+breaking solution”were evaluated for breaking effect.The acid gradually reduced the volume of USGel,which increased the contact area between breaking solution and USGel,and the effect of“4%acid+breaking solution”was 23 times higher than that of breaking solution alone at 35C.However,the acid significantly reduced the strength of USGel.This paper provides new insights into the breaking of high-strength gels with complex network structures.

An overview of chemical enhanced oil recovery and its status in India

India is currently producing crude oil from matured fields because of insufficient discoveries of new fields.Therefore,in order to control the energy crisis in India,enhanced oil recovery(EOR)techniques are required to reduce the import of crude from the OPEC(Organization of the Petroleum Exporting Countries).This review mentions chemical EOR techniques(polymers,surfactants,alkali,nanoparticles,and combined alkali-surfactant-polymer flooding)and operations in India.Chemical EOR methods are one of the most efficient methods for oil displacement.The efficiency is enhanced by interfacial tension(IFT)reduction using surfactants and alkali,and mobility control of injected water is done by adding a polymer to increase the volumetric sweep efficiency.This paper also reviews the current trend of chemical EOR,prospects of chemical EOR in Indian oilfields,the development of chemical EOR in India with their challenges raising with economics,and screening criteria for chemical EOR implementation on the field scale.Furthermore,the review gives a brief idea about chemical EOR implementation in Indian oilfields in future prospects to increase the additional oil recovery from existing depleted fields to reduce the import of crude oil.The outcome of this review depicts all chemical EOR operations and recovery rates both at the laboratory scale and field scale around the country.The additional recovery rates are compared from various chemical EOR methods like conventional chemical flooding methods and conventional chemicals combined with nanoparticles on a laboratory scale.The development of chemical EOR in the past few decades and the EOR policy given by the government of India has been mentioned in this review.The analysis provides an idea about enhanced recovery screening and implementation of chemical EOR methods in existing fields will significantly reduce the energy crisis in India.

In-situ wafer bowing measurements of GaN grown on Si(111) substrate by reflectivity mapping in metal organic chemical vapor deposition system

In this work, the wafer bowing during growth can be in-situ measured by a reflectivity mapping method in the 3×2 Thomas Swan close coupled showerhead metal organic chemical vapor deposition（MOCVD） system. The reflectivity mapping method is usually used to measure the film thickness and growth rate. The wafer bowing caused by stresses（tensile and compressive） during the epitaxial growth leads to a temperature variation at different positions on the wafer, and the lower growth temperature leads to a faster growth rate and vice versa. Therefore, the wafer bowing can be measured by analyzing the discrepancy of growth rates at different positions on the wafer. Furthermore, the wafer bowings were confirmed by the ex-situ wafer bowing measurement. High-resistivity and low-resistivity Si substrates were used for epitaxial growth. In comparison with low-resistivity Si substrate, Ga N grown on high-resistivity substrate shows a larger wafer bowing caused by the highly compressive stress introduced by compositionally graded Al Ga N buffer layer. This transition of wafer bowing can be clearly in-situ measured by using the reflectivity mapping method.

Remote plasma enhanced cyclic etching of a cyclosiloxane polymer thin film

The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane)(pV3D3)emerges as a promising candidate.However,previous works have not explored etching for this cyclosiloxane polymer thin film,which is indispensable for potential applications to the back-end-of-line fabrication.Here,we developed an etching process utilizing O2/Ar remote plasma for cyclic removal of iCVD pV3D3 thin film at sub-nanometer scale.We employed in-situ quartz crystal microbalance to investigate the process parameters including the plasma power,plasma duration and O2 flow rate.X-ray photoelectron spectroscopy and cross-sectional microscopy reveal the formation of an oxidized skin layer during the etching process.This skin layer further substantiates an etching mechanism driven by surface oxidation and sputtering.Additionally,this oxidized skin layer leads to improved elastic modulus and hardness and acts as a barrier layer for protecting the bottom cyclosiloxane polymer from further oxidation.

Introducing electrolytic electrochemical polymerization for constructing protective layers on Ni-rich cathodes of Li-ion batteries

LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)is the most promising cathode for high-energy Li-ion batteries,despite its poor cycling stability that originates from the reactions that occur with the electrolyte.Herein,to solve this interfacial issue,a facile electrolytic electrochemical polymerization process was introduced in this paper,and a uniform conductive electrolyte interface(polyaniline)was successfully constructed on the surface of the NCM811 porous electrode(PANI-NCM),which facilitated the charge transfer during charge/discharge.The side reactions at the interface between the cathode and the electrolyte are suppressed,and thereby,the cycling performance and rate capability are considerably improved.PANI-NCM delivers an initial capacity of 157.2 mAh·g^(-1)as well as excellent cyclability(capacity retention of 88%after 500 cycles at 2C),whereas the capacity of the bare NCM811 has dropped to 31.3 mAh·g^(-1).In addition,polypyrrole and polythiophene also can be formed through electrolytic electrochemical polymerization process,which provides a practicable tactic to modify the interfacial stability of cathodes for high-energy Li-ion batteries.

Mechanoluminescent Materials Enable Mechanochemically Controlled Atom Transfer Radical Polymerization and Polymer Mechanotransduction

Organic mechanophores have been widely adopted for polymer mechanotransduction.However,most examples of polymer mechanotransduction inevitably experience macromolecular chain rupture,and few of them mimic mussel’s mechanochemical regeneration,a mechanically mediated process from functional units to functional materials in a controlled manner.In this paper,inorganic mechanoluminescent(ML)materials composed of CaZnOS-ZnS-SrZnOS:Mn2+were used as a mechanotransducer since it features both piezoelectricity and mechanolunimescence.The utilization of ML materials in polymerization enables both mechanochemically controlled radical polymerization and the synthesis of ML polymer composites.This procedure features a mechanochemically controlled manner for the design and synthesis of diverse mechanoresponsive polymer composites.

Syntheses,crystal structures,and quantum chemistry calculation of two Ni(Ⅱ)coordination polymers

Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.

Performance improvement in polymeric thin film transistors using chemically modified both silver bottom contacts and dielectric surfaces

An efficient interface modification is introduced to improve the performance of polymeric thin film transistors. This efficient interface modification is first achieved by 4-fluorothiophenol（4-FTP） self-assembled monolayers（SAM） to chemically treat the silver source–drain（S/D） contacts while the silicon oxide（SiO2） dielectric interface is further primed by either hexamethyldisilazane（HMDS） or octyltrichlorosilane（OTS-C8）. Results show that contact resistance is the dominant factor that limits the field effect mobility of the PTDPPTFT4 transistors. With proper surface modification applied to both the dielectric surface and the bottom contacts, the field effect mobilities of the bottom-gate bottom-contact PTDPPTFT4 transistors were significantly improved from 0.15 cm^2·V^-1·s^-1 to 0.91 cm^2·V^-1·s^-1.

SYNTHESIS AND CHARACTERIZATION OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES VIA AN in-situ POLYMERIZATION APPROACH

Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).

Preparation of Polysulfonamide/ZnO Nanocomposite by In-Situ Polymerization

Polysulfonamide/zinc oxide(PSA/ZnO) nanocomposite films with w(ZnO)=0.5% were prepared by in-situ polymerization based on 4,4′-diaminodiphenylsulfone and terephthaloyl chloride in the common solvent N,N-Dimethylacetamide(DMAc). Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA and mechanical property was characterized by DXLL-1000 electromechanical material testing machine. The results showed that the breaking strength of the film containing 0.5% ZnO was great enhanced. The average size of ZnO particles was below 100 nm. The introduction of ZnO as nano filler in PSA react as UV shield effect and make the composite mechanical property improved.

CHEMICALLY DEPOSITED SILVER FILM USED AS A SERS-ACTIVE OVER-COATING LAYER FOR POLYMER FILM

When colloidal silver particles were chemically deposited onto polymer film as an over-coating layer, surface-enhanced Raman scattering (SERS) spectra could be collected for the surface analysis. SERS measurements of liquid crystal film were successfully performed without disturbing the surface morphology.

CHANGES OF STRUCTURE AND PROPERTIES OF POLY (ETHYLENE TEREPHTHALATE) CAUSED BY IN-SITU POLYMERIZATION OF PYRROLE

Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly （ethylene terephthalate） （PET） film. The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5×10;Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.

<i>In-Situ</i>Monitoring of Chemical Vapor Deposition from Trichlorosilane Gas and Monomethylsilane Gas Using Langasite Crystal Microbalance

Using the langasite crystal microbalance (LCM), the trends in film thickness produced by means of the chemical vapor deposition using trichlorosilane gas, monomethylsilane gas and their mixed gas were observed at 600?C and evaluated by comparison with the information from a transmission electron microscope (TEM). The crystalline silicon film thickness from trichlorosilane gas was comparable to that of an amorphous silicon carbide film from monomethylsilane gas. The film obtained from the gas mixture was amorphous and was the thinnest in this study. Because the thickness trend obtained by the LCM agreed with that by the TEM, the LCM is shown to be a convenient evaluation tool for the behavior of various film deposition.