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.

Bifunctional TiO_(2-x)nanofibers enhanced gel polymer electrolyte for high performance lithium metal batteries

Exploration of advanced gel polymer electrolytes(GPEs)represents a viable strategy for mitigating dendritic lithium(Li)growth,which is crucial in ensuring the safe operation of high energy density Li metal batteries(LMBs).Despite this,the application of GPEs is still hindered by inadequate ionic conductivity,low Li^(+)transference number,and subpar physicochemical properties.Herein,Ti O_(2-x)nanofibers(NF)with oxygen vacancy defects were synthesized by a one-step process as inorganic fillers to enhance the thermal/mechanical/ionic-transportation performances of composite GPEs.Various characterizations and theoretical calculations reveal that the oxygen vacancies on the surface of Ti O_(2-x)NF accelerate the dissociation of Li PF_6,promote the rapid transfer of free Li^(+),and influence the formation of Li F-enriched solid electrolyte interphase.Consequently,the composite GPEs demonstrate enhanced ionic conductivity(1.90m S cm^(-1)at room temperature),higher lithium-ion transference number(0.70),wider electrochemical stability window(5.50 V),superior mechanical strength,excellent thermal stability(210℃),and improved compatibility with lithium,resulting in superior cycling stability and rate performance in both Li||Li,Li||Li Fe PO_(4),and Li||Li Ni_(0.8)Co_(0.1)Mn_(0.1)O_(2)cells.Overall,the synergistic influence of nanofiber morphology and enriched oxygen vacancy structure of fillers on electrochemical properties of composite GPEs is comprehensively investigated,thus,it is anticipated to shed new light on designing high-performance GPEs LMBs.

A comprehensive review of in-situ polymer gel simulation for conformance control

Gel treatment has been widely applied in mature oilfields to improve sweep efficiency and control water production.Correct numerical simulation is of major importance to the optimization design and prediction of a successful gel treatment.However,there exist many problems in current simulation studies in published literature.This paper first presents a comprehensive review on the major factors that have been considered at different gelation stages during gel treatment,the models used in the commercial/inhouse simulators,and current numerical simulation studies on both laboratory and field scales.Then we classify the current in-situ gel numerical simulation problems as 1,deficient model problem that has published numerical model but has not been applied in simulator and application studies;2,missing model problem that does not have published quantitative model;and 3,inaccurate application problem that does not consider the major factors of gel performance,based on the reasons from some questionable results of current simulation studies.Finally,we point out the major research efforts that should be made in the future to better simulate in-situ gel treatment process.The review indicates that numerous simulation studies using commercial software packages intend to predigest the gel treatment,many of which,however,ignore important mechanisms and mislead the operation of gel treatment.In fact,a full assessment of simulating in-situ gels cannot be achieved unless the quantitative models can be qualified in terms of transport and plugging mechanisms based on the experimental results.

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.

In Situ High-performance Gel Polymer Electrolyte with Dual-reactive Cross-linking for Lithium Metal Batteries

Lithium metal batteries have been considered as one of the most promising next-generation power-support devices due to their high specific energy and output voltage.However,the uncontrollable side-reaction and lithium dendrite growth lead to the limited serving life and hinder the practical application of lithium metal batteries.Here,a tri-monomer copolymerized gel polymer electrolyte(TGPE)with a cross-linked reticulation structure was prepared by introducing a cross-linker(polyurethane group)into the acrylate-based in situ polymerization system.The soft segment of polyurethane in TGPE enables the far migration of lithium ions,and the-NH forms hydrogen bonds in the hard segment to build a stable cross-linked framework.This system hinders anion migration and leads to a high Li^(+)migration number(t_(Li^(+))=0.65),which achieves uniform lithium deposition and effectively inhibits lithium dendrite growth.As a result,the assembled symmetric cell shows robust reversibility over 5500 h at a current density of 1 mA cm^(-2).The LFP∷TGPE∷Li cell has a capacity retention of 89.8%after cycling 800 times at a rate of 1C.In summary,in situ polymerization of TGPE electrolytes is expected to be a candidate material for high-energy-density lithium metal batteries.

Bacterial Cellulose/Zwitterionic Dual-network Porous Gel Polymer Electrolytes with High Ionic Conductivity

Bacterial cellulose(BC)was innovatively combined with zwitterionic copolymer acrylamide and sulfobetaine methacrylic acid ester[P(AM-co-SBMA)]to build a dual-network porous structure gel polymer electrolytes(GPEs)with high ionic conductivity.The dual network structure BC/P(AM-co-SBMA)gels were formed by a simple one-step polymerization method.The results show that ionic conductivity of BC/P(AM-co-SBMA)GPEs at the room temperature are 3.2×10^(-2) S/cm@1 M H_(2)SO_(4),4.5×10^(-2) S/cm@4 M KOH,and 3.6×10^(-2) S/cm@1 M NaCl,respectively.Using active carbon(AC)as the electrodes,BC/P(AM-co-SBMA)GPEs as both separator and electrolyte matrix,and 4 M KOH as the electrolyte,a symmetric solid supercapacitors(SSC)(AC-GPE-KOH)was assembled and testified.The specific capacitance of AC electrode is 173 F/g and remains 95.0%of the initial value after 5000 cycles and 86.2%after 10,000 cycles.

Supramolecular polymer-based gel fracturing fluid with a double network applied in ultra-deep hydraulic fracturing

A gel based on polyacrylamide,exhibiting delayed crosslinking characteristics,emerges as the preferred solution for mitigating degradation under conditions of high temperature and extended shear in ultralong wellbores.High viscosity/viscoelasticity of the fracturing fluid was required to maintain excellent proppant suspension properties before gelling.Taking into account both the cost and the potential damage to reservoirs,polymers with lower concentrations and molecular weights are generally preferred.In this work,the supramolecular action was integrated into the polymer,resulting in significant increases in the viscosity and viscoelasticity of the synthesized supramolecular polymer system.The double network gel,which is formed by the combination of the supramolecular polymer system and a small quantity of Zr-crosslinker,effectively resists temperature while minimizing permeability damage to the reservoir.The results indicate that the supramolecular polymer system with a molecular weight of(268—380)×10^(4)g/mol can achieve the same viscosity and viscoelasticity at 0.4 wt%due to the supramolecular interaction between polymers,compared to the 0.6 wt%traditional polymer(hydrolyzed polyacrylamide,molecular weight of 1078×10^(4)g/mol).The supramolecular polymer system possessed excellent proppant suspension properties with a 0.55 cm/min sedimentation rate at 0.4 wt%,whereas the0.6 wt%traditional polymer had a rate of 0.57 cm/min.In comparison to the traditional gel with a Zrcrosslinker concentration of 0.6 wt%and an elastic modulus of 7.77 Pa,the double network gel with a higher elastic modulus(9.00 Pa)could be formed only at 0.1 wt%Zr-crosslinker,which greatly reduced the amount of residue of the fluid after gel-breaking.The viscosity of the double network gel was66 m Pa s after 2 h shearing,whereas the traditional gel only reached 27 m Pa s.

Interpenetrating network-reinforced gel polymer electrolyte for ultra-stable lithium−iodine batteries

Li-I_(2) batteries have attracted much interest due to their high capacity,exceptional rate performance,and low cost.Even so,the problems of unstable Li anode/electrolyte interface and severe polyiodide shuttle in Li-I_(2) batteries need to be tackled.Herein,the interfacial reactions on the Li anode and I_(2) cathode have been effectively optimized by employing a well-designed gel polymer electrolyte strengthened by cross-linked Ti-O/Si-O(GPETS).The interpenetrating network-reinforced GPETS with high ionic conductivity(1.88×10^(-3)S cm^(-1)at 25℃)and high mechanical strength endows uniform Li deposition/stripping over 1800 h(at 1.0mA cm^(-2),with a plating capacity of 3.0mAh cm^(-2)).Moreover,the GPETS abundant in surface hydroxyls is capable of capturing soluble polyiodides at the interface and accelerating their conversion kinetics,thus synergistically mitigating the shuttle effect.Benefiting from these properties,the use of GPETS results in a high capacity of 207 mAh g^(-1)(1 C)and an ultra-low fading rate of 0.013%per cycle over 2000 cycles(5 C).The current study provides new insights into advanced electrolytes for Li-I_(2) batteries.

Interfacial fusion-enhanced 11 μm-thick gel polymer electrolyte for high-performance lithium metal batteries

In the pursuit of ultrathin polymer electrolyte(<20 μm) for lithium metal batteries, achieving a balance between mechanical strength and interfacial stability is crucial for the longevity of the electrolytes.Herein, 11 μm-thick gel polymer electrolyte is designed via an integrated electrode/electrolyte structure supported by lithium metal anode. Benefiting from an exemplary superiority of excellent mechanical property, high ionic conductivity, and robust interfacial adhesion, the in-situ formed polymer electrolyte reinforced by titanosiloxane networks(ISPTS) embodies multifunctional roles of physical barrier, ionic carrier, and artificial protective layer at the interface. The potent interfacial interactions foster a seamless fusion of the electrode/electrolyte interfaces and enable continuous ion transport. Moreover, the built-in ISPTS electrolyte participates in the formation of gradient solid-electrolyte interphase(SEI) layer, which enhances the SEI's structural integrity against the strain induced by volume fluctuations of lithium anode.Consequently, the resultant 11 μm-thick ISPTS electrolyte enables lithium symmetric cells with cycling stability over 600 h and LiFePO_(4) cells with remarkable capacity retention of 96.6% after 800 cycles.This study provides a new avenue for designing ultrathin polymer electrolytes towards stable, safe,and high-energy–density lithium metal batteries.

Research Progress of Polymer Fire Extinguishing Gel and Its Application in Forest Fire Prevention

The paper summarizes the structure and water-absorbing mechanism,classification,and preparation method of polymer fire extinguishing gel,and prospects for its application in aerial firefighting,forest ground fire extinguishing,opening of firebreaks,and mitigating human casualties in forest fire extinguishing.

Variation in Polymerization Degree of C-A-S-H Gels and Its Role in Strength Development of Alkali-activated Slag Binders

To investigate the variation in the degree of polymerization calcium aluminium silicate hydrate(C-A-S-H)gel and its role in the evolution of the strength of waterglass slag binders,the compressive strength,hydration products,degree of hydration of the slag,and the degree of polymerization of C-A-S-H gels of binders were examined.The experimental results indicate that the pH of the pore solution increased with an increase in the Na_(2)O concentration.However,mortar with an optimum compressive strength value of 81.0 MPa at 28 d was obtained when water glass modulus was 1.5.The main hydration product is a C-A-S-H gel for which the quantity and the degree of polymerization depend strongly on the Na_(2)O concentration;for a given range,both increase with increasing Na_(2)O concentration,thus yielding an enhanced strength.A further increase in the Na_(2)O concentration continuously increases the quantity of C-A-S-H gels while drastically reducing the degree of polymerization.The positive effect of the former is counteracted by the adverse effect of the latter,ultimately,leading to a decreased strength.Furthermore,we reveal that the degree of polymerization for C-A-S-H gels may be affected by pH,through a series of complex chemical reactions.

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.

A NOVEL EOR POLYMER (Ⅱ)——INVESTIGATION ON IN-SITU GELATION OF SMRF SYSTEM IN BEREA CORE

In-situ gelation of aqueous sulfomethylated resorcinol formaldehyde (SMRF) system inBerea core has been investigated. Two sets of displacement experiments were conducted with thissystem (containing 5% NaCl, 0. 036% CaCl_2. 2H_2O). The brine permeabilities of the coreswere reduced significantly from about 600 to 0.1 md. The in-situ gelation in Berea core occurreda little bit earlier than gelation anticipated from bulk test in the experiments. The gel time waseasier to control at initial pH between 6 and 8. During injection of SMRF system, the apparentviscosity was less than 1 mPa·s at 41℃.

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.

PREPARATION OF POLYSULFONAMIDE AND MODIFIED TITANIUM OXIDE NANOCOMPOSITES BY IN-SITU POLYMERIZATION

A kind of new nano composite with ultraviolet （UV） ray resistance and high temperature stability was prepared by in-situ polymerization in low temperature. Polysulfonamide （PSA） was synthesized with 4, 4＇-diaminodiphenyl sulfone （DDS） and terephthaloyl chloride （TPC） in the common solvent N, N-Dimethyl- -acetamide （DMAc）. Nano filler is a certain nano titanium oxide modified by silicon oxide （TMS）, which plays the role of UV resistance additives. Properties of the novel composite materials were characterized by Atomic Force microscopy （AFM）, thermal gravimetric Analysis （TGA） and Ultraviolet Spectroscopy. AFM had showed the sizes and distributions of TMS particles in the nanocomposite. Ultraviolet Spectroscopy for the nanocomposites showed a large absorption in UV band. TGA showed the decomposition temperature was increased over ten degrees with 0.5% wt TMS for this nanocomposite compared with pure PSA.

Rate of elapsed polymerization of hydroxyethylacrylate gel induced by gamma irradiation

The rate of elapsed polymerization of polyhydroxyethylacrylate in gelatin has been studied to investigate the effect of co-monomers consumption at a given dose. The polymer gel dosimeters consisted of 2%～4% N,N-methyelene-bis-acrylamide cross-linker,2%～4% 2-hydroxyethylacrylate monomer and gelatin at 3% and 5%. The dosimeters were irradiated by using 60Co teletherapy γ-ray source up to 20 Gy at a constant dose rate. The relaxation rate of water proton in the dosimeters at different doses and co-monomer concentrations were measured using a nuclear magnetic resonance spectroscopy. The rate of elapsed polymerization decreases with increasing the dose and the initial concentration of co-monomers. The rate of consumption of co-monomers increases with an increase of the polymerization and the gelatin content of the polymer gel.

PREPARATION AND PROPERTIES OF GEL POLYMER ELECTROLYTE BASED ON PVDF/ACRYLATE INTERPENETRATING POLYMER NETWORK FOR DYE-SENSITIZED SOLAR CELL

The gel polymer electrolytes（GPEs）based on poly（vinylidence fluoride）（PVDF）/acrylate interpenetrating polymer network（IPN）are prepared.The micro-phase separation type GPEs are characterized by Fourier transform infrared（FTIR）spectroscopy,scanning electron microscope（SEM）,respectively.Moreover,the conductivity and the voltage-current curves of the electrolytes are measured by electrochemical workstation.The higher porosity and electrolyte uptake are observed in the membranes prepared at lower crosslinker concentration.The suitable cross-linking acrylate monomer improves the porosity and the electrochemical behavior of GPE.A dye-sensitized solar cell（DSSC）employing PGE based on PVDF/poly（ethylene glycol dimethacrylate）（PEGDMA）IPN yields an open-circuit voltage of 0.674 V,short-circuit current of 8.476 mA·cm-2and the conversion efficiency of 2.710% under 100 mW·cm-2illumination.

On the Scaling Study for the A_f-A_g Type Free Radical Polymerization

根据Ａｆ－Ａｇ自由基加聚反应的数量分布函数，导出凝胶点附近的渐进分布函数和高分子矩的表示式．进一步应用标度变换，得到了描述溶胶－凝胶相变的广义标度律，从而揭示了Ａｆ－Ａｇ自由基加聚的固化反应是一个相变过程．

Recent advances in gel polymer electrolyte for high-performance lithium batteries

Lithium batteries (LBs) have become increasingly important energy storage systems in our daily life. However, their practical applications are still severely plagued by the safety issues from liquid electrolyte, especially when the batteries are exposed to mechanical, thermal, or electrical abuse conditions. Gel polymer electrolytes (GPEs) are being considered as an effective solution to replace currently available organic liquid electrolyte for building safer LBs. This review provides recent advancements in GPEs applied for high-performance LBs. On the one hand, from the environmental and economic point of view, the skeletons of GPEs changed from traditional polymer to renewable and degradable polymer. On the other hand, in addition to being as a component with good electrochemical and physical characterizations, the GPEs also need to provide some functions for addressing the concerns of lithium (Li) dendrites, unstable cathode electrolyte interface, dissolution and migration of transition metal ions,"shuttle effect" of polysulfides, and so on. Finally, to synchronously meet the challenges from the advanced cathode and Li metal anode, the bio-based GPEs with multi-functionality are proposed to develop high-energy/powerdensity batteries in the future.