Interfacial reinforcement of core-shell HMX@energetic polymer composites featuring enhanced thermal and safety performance

The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)-based polymer-bonded explosives(PBX).A two-step strategy that involves the pretreatment of HMX to endow—OH groups on the surface via polyalcohol bonding agent modification and in situ coating with nitrate ester-containing polymer,was proposed to address the problem.Two types of energetic polyether—glycidyl azide polymer(GAP)and nitrate modified GAP(GNP)were grafted onto HMX crystal based on isocyanate addition reaction bridged through neutral polymeric bonding agent(NPBA)layer.The morphology and structure of the HMX-based composites were characterized in detail and the core-shell structure was validated.The grafted polymers obviously enhanced the adhesion force between HMX crystals and fluoropolymer(F2314)binder.Due to the interfacial reinforcement among the components,the two HMX-based composites exhibited a remarkable increment of phase transition peak temperature by 10.2°C and 19.6°C with no more than 1.5%shell content,respectively.Furthermore,the impact and friction sensitivity of the composites decreased significantly as a result of the barrier produced by the grafted polymers.These findings will enhance the future prospects for the interface design of energetic composites aiming to solve the weak interface and safety concerns.

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.

Activating coordinative conjugated polymer via interfacial electron transfer for efficient CO_(2) electroreduction

With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).

Preparation of Composite Charge-mosaic Hollow Fiber Membrane by Interfacial Polymerization

The preparation of composite charge-mosaic membrane included spinning of hollow fiber as the supporting membrane, preparing a selective layer on the inside surface of the fiber by interfacial polymerization. The charge-mosaic membranes show a high salt permeability while retaining sucrose. The charge-mosaic membrane can be effectively used to separate multivalent salts with organic matter of molecular weight great than 300 g/mol in industry.

Reducing active layer thickness of polyamide composite membranes using a covalent organic framework interlayer in interfacial polymerization

Polyamide(PA)-based thin-film composite membranes exhibit enormous potential in water purification,owing to their facile fabrication,decent performance and desirable stability.However,the thick PA active layer with high transport resistance from the conventional interfacial polymerization hampers their applications.The controllable fabrication of a thin PA active layer is essential for high separation efficiency but still challenging.Herein,a covalent organic framework TpPa-1 interlayer was firstly deposited on a polyethersulfone(PES)substrate to reduce the thickness of PA active layer in interfacial polymerization.The abundant pores of TpPa-1 increase the local concentration of amine monomers by adsorbing piperazine molecules,while hydrogen bonds between hydrophilic groups of TpPa-1 and piperazine molecules slow down their diffusion rate.Arising from those synergetic effects,the PA active layer is effectively reduced from 200 nm to 120 nm.By optimizing TpPa-1 interlayer and PA active layer,the water flux of resultant membranes can reach 171.35 L·m^-2·h^-1·MPa^-1,which increased by 125.4%compared with PA/PES membranes,while the rejection rates of sodium sulfate and dyes solution remained more than 90%and 99%,respectively.Our strategy may stimulate rational design of ultrathin PA-based nanofiltration membranes with high performances.

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.

Preparation of Thin Film Composite Nanofiltration Membrane by Interfacial Polymerization with 3,5-Diaminobenzoylpiperazine and Trimesoyl Chloride

A new aromatic diamine,3,5-diaminobenzoylpiperazine （3,5-DABP）,was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3,5-DABP as aqueous monomer and trimesoyl chloride （TMC） as organic monomer,thin film composite （TFC） nanofiltration membranes were prepared by interfacial polymerization technology.The salt rejection order of these TFC membranes is Na2SO4MgSO4MgCl2NaCl.This sequence indicates that the membranes are negatively charged.

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO_(2) separation

Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.

Composite nanofiltration membranes synthesized from PAMAM and TMC by interfacial polymerization

A novel NF membrane prepared with poly（amidoamine） （PAMAM） dendrimer and trimesoyl chloride （TMC） by interfacial polymerization on polysulfone （PSF） ultrafiltration membrane was investigated. Field emission scanning electron microcopy （ FESEM）, atomic force micrograph （ AFM ） and contact angle （CA） of pure water on PA and PSF substrate were employed to characterize the chemical and physical properties of membranes. The PAMAM concentration, retention of salt solutions and organics were studied on the performance of the NF membrane. From the analyses of SEM and AFM, the polyamide active skin layers of the composite membranes are dense, rough, and finely dispersed nodular structures, packed tightly by the spherical globules. The contact angle of PA nanofitration membrane decreased after polymerization. The higher PAMAM concentra- tion can result in lower flux and higher rejection. The salt rejection of PA membranes decreases in the order K2 SO4 〉 Na2 SO4 〉 MgSQ 〉 MgC12 〉 CaC12 〉 NaC1, which indicates that the resulting membranes is nagatively charged. The pH increases from 3 to 10 in the feed resulting in the decrease of the flux and the increase of the rejection for NazSO4 solution. The molecular weight cut off （MWCO） of the composite NF membrane is nearly 860 kg/mol. The resulted PA membrane can be used to seoarate small organics and salt solutions.

Microencapsulation of Chlorocyclophosphazene by Interfacial Polymerization

A polyurea-chlorocyclophosphazene microcapsule flame retardant is prepared by an interfacial polymerization process using 2,4-toluene diisocyanate (TDI) and hexanediamine as the raw materials. TG tests show that the thermal decomposition temperature of chlorocyclophosphazene in microcapsule obviously rises. The flame retardancy of HDPE/chlorocyclophosphazene in microencapsules is better than that of HDPE/chlorocyclophosphazene. Mechanical properties of HDPE/chlorocyclophosphazene microencapsule turn out to be superior to those of HDPE/chlorocyclophosphazene.

Highly permeable reverse osmosis membranes incorporated with hydrophilic polymers of intrinsic microporosity via interfacial polymerization

Enhancing the water permeation while maintaining high salt rejection of existing reverse osmosis(RO)membranes remains a considerable challenge.Herein,we proposed to introduce polymer of intrinsic microporosity,PIM-1,into the selective layer of reverse osmosis membranes to break the trade-off effect between permeability and selectivity.A water-soluble a-LPIM-1 of low-molecular-weight and hydroxyl terminals was synthesized.These designed characteristics endowed it with high solubility and reactivity.Then it was mixed with m-phenylenediamine and together served as aqueous monomer to react with organic monomer of trimesoyl chloride via interfacial polymerization.The characterization results exhibited that more“nodule”rather than“leaf”structure formed on RO membrane surface,which indicated that the introduction of the high free-volume of a-LPIM-1 with three dimensional twisted and folded structure into the selective layer effectively caused the frustrated packing between polymer chains.In virtue of this effect,even with reduced surface roughness and unchanged layer thickness,the water permeability of prepared reverse osmosis membranes increased 2.1 times to 62.8 L·m^(-2)·h^(-1) with acceptable Na Cl rejection of 97.6%.This attempt developed a new strategy to break the trade-off effect faced by traditional polyamide reverse osmosis membranes.

Fabrication of Solvent-Resistant Nanofiltration Membrane via Interfacial Polymerization Based on Cellulose Acetate Membrane

Although a great progress has been achieved for the development of NF membranes and technologies and SRNF do show a great potential in the separation of organic components, an NF membrane with good separation performance and good resistance to organic solvents are urgently needed for a more complicated situation in practical. In this study, a kind of solvent-resistant nanofiltration (SRNF) membrane was fabricated via interfacial polymerization on a laboratory optimized cellulose acetate (CA) basic membrane. The effects of interfacial polymerization parameters, such as water phase concentration, immersed time in the water phase and in the organic phase, on the pure water flux and rejection rate of C-2R yellow dyestuffs were investigated. A highest dye rejection rate of 72.9% could be obtained by water phase solution containing 1% m-xylylenediamine (mXDA) and organic phase solution with 0.2% trimesoyl chloride (TMC) under immersed time in water phase of 6 minutes and in organic phase of 40 seconds. This membrane demonstrated better resistance to methyl alcohol compared to commercial membrane. This study may offer an avenue to develop a solvent-resistant nanofiltration membrane.

Characterization on Surface and Interfacial Properties of Nitramine Crystal Fillers and Polymeric Bonding Agents

The surface and interfacial properties of polymeric bonding agents and nitramine crystal fillers were studied. The surface free energy and adhesion work of polymeric bonding agents and nitramine fillers were calculated by using Kaeble′s equations. It was observed that the hydroxyl values of neutral polymeric bonding agents (NPBA) correlate well with the polar components of surface free energies. On the basis of the measurements of swelling ratio and initial modulus, the interfacial bonding through highly crosslinked polymeric shell formation around the nitramine particles and generating interfacial reinforcement were rationalized. The application of Tapping Mode AFM (atomic force micro scope) to observing the surface morphology of NPBA reveals that methyl acrylate monomer appears to play a role for aiding the formation of network like structure when nanometer scale images of NPBA are created.

Breaking Through Bottlenecks for Thermally Conductive Polymer Composites:A Perspective for Intrinsic Thermal Conductivity,Interfacial Thermal Resistance and Theoretics

Rapid development of energy,electrical and electronic technologies has put forward higher requirements for the thermal conductivities of polymers and their composites.However,the thermal conductivity coefficient(λ)values of prepared thermally conductive polymer composites are still difficult to achieve expectations,which has become the bottleneck in the fields of thermally conductive polymer composites.Aimed at that,based on the accumulation of the previous research works by related researchers and our research group,this paper proposes three possible directions for breaking through the bottlenecks:(1)preparing and synthesizing intrinsically thermally conductive polymers,(2)reducing the interfacial thermal resistance in thermally conductive polymer composites,and(3)establishing suitable thermal conduction models and studying inner thermal conduction mechanism to guide experimental optimization.Also,the future development trends of the three above-mentioned directions are foreseen,hoping to provide certain basis and guidance for the preparation,researches and development of thermally conductive polymers and their composites.

Preparation of Poly-α-Olefin Microcapsule Particles Coated with Polyurethane as a Drag Reducer Based on Interface Polymerization

The molecular behavior of polyurethane(PU)coating materials during the surface adsorption of poly-α-olefin as a drag reducing polymer was explored by a molecular dynamics simulation.Three different PU capsule wall materials were synthesized using two reaction monomers,and a poly-α-olefin/PU drag reducer microcapsule was prepared based on interface polymerization.The structure,morphology,thermal stability,compressive strength,and drag reduction performance of the microcapsules were characterized and compared.The results showed that a non-bonding interaction induced the adsorption of the PU coating material,poly-α-olefin and PU then fused at the interface,and the PU coating material was embedded into the inner grooves of poly-α-olefin in the form of a local mosaic,thereby forming a stable core–shell structure.The morphological characterization indicated that PU and poly-α-olefin could form microcapsule structures.The thermal decomposition temperature of the microcapsule was dependent on the type of capsule wall material.The microcapsule structure had a slight effect on poly-α-olefin drag reduction.The system enabled poly-α-olefin to exist in powdered particles through microcapsulation,and had a good dispersion effect that facilitated storage and transport processes.The method effectively inhibited the accumulation and bonding of poly-α-olefin at room temperature.

Electrochemical performance of interfacially polymerized polyaniline nanofibres as electrode materials for non-aqueous redox supercapacitors

H+ doped polyaniline nanofibre(PH) was synthesized by interfacial polymerization and polyanilines doped with Li salt(PLI and PHLI) were prepared by immersing emeraldine base(EB) and H+ doped polyaniline in 1 mol/L LiPF6/(EC-EMC-DMC),respectively.PH,PLI and PHLI were all characterized by scanning electron microscopy(SEM) and Fourier transform infrared(FT-IR) spectrometry.With 1 mol/L LiPF6/(EC-EMC-DMC) as electrolyte,PH,PHLI and PLI were used as the active materials of symmetric non-aqueous redox supercapacitors.PLI shows the highest initial specific capacitance of 120 F/g(47 F/g for PH and 66 F/g for PHLI) among three samples.After 500 cycles,the specific capacitance of PLI remains 75 F/g,indicating the good cycleability.

Enhancing interfacial stability in solid-state lithium batteries with polymer/garnet solid electrolyte and composite cathode framework

The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^(-4) S cm^(-1) at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^(-1) and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.

Boosting the cycling stability of all-solid-state lithium metal batteries through MOF-based polymeric protective layers

Solid-state electrolytes(SSEs)play a pivotal role in advancing next-generation lithium metal battery technology.However,they commonly encounter substantial interfacial resistance and poor stability when interfacing with lithium metal,hindering practical applications.Herein,we introduce a flexible metal-organic framework(MOF:NUS-6)-incorporated polymeric layer,denoted as NP,designed to protect the sodium superionic conductor(NASICON)-type Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)electrolyte from Li metal anodes.The NP matrix establishes a soft interface with the LATP surface,effectively reducing voids and gaps that may arise between the LATP electrolyte and Li metal.Moreover,the MOF component in NP enhances ionic conductivity,offers abundant Li^(+)transport sites,and provides hierarchical ion channels,ensuring a homogeneous Li^(+)flow and thus effectively inhibiting Li dendrite formation.Utilizing NP,we fabricate Li symmetrical cells cycled for over 1600 h at 0.2 mA cm^(-2)and all-solid-state LiINP-LATPI LiFePO_(4)batteries,achieving a remarkable 99.3%capacity retention after 200 cycles at 0.2 C.This work outlines a general strategy for designing long-lasting and stable solid-state Li metal batteries.

Interfacial Actions and Adherence of an Interpenetrating Polymer Network Thin Film on Aluminum Substrate

The interpenetrating polymer networks (IPN) thin film with the –C=O group in one network and the terminal –N=C=O group in another network on an aluminum substrate to reinforce the adherence between IPN and aluminum through interfacial reactions, were obtained by dip-pulling the pretreated aluminum substrate into the viscous-controlled IPN precursors and by the following thinning treatment to the IPN film to a suitable thickness. The interfacial actions and the adhesion strengths of the IPN on the pretreated aluminum substrate were investigated by the X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and strain-stress(?-?) measurements. The XPS and FTIR detection results indicated that the elements’ contents of N, O, and Al varied from the depths of IPN. The in-terfacial reaction occurred between the –N=C=O group of IPN and the AlO(OH) of pretreated aluminum. The in-creased force constant for –C=O double bond and the lower frequency shift of –C=O stretching vibration absorption peak both verified the formation of hydrogen bond between the –OH group in AlO(OH) and the –C=O group in IPN. The adherence detections indicated that the larger amount of –N=C=O group in the IPN, the higher shear strengths between the IPN thin film and the aluminum substrate.