Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity a...Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance,highly efficient catalytic reduction systems containing sodium borohydride(NaBH_(4))and rare-earth chloride(RECl_(3))were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer,aiming to facilitate the conversion of chainend carboxyl groups into hydroxyl groups and improvement in end-group reactivity.To achieve this,lanthanum chloride(LaCl_(3)),cerium chloride(CeCl_(3)),and neodymium chloride(NdCl_(3))were used separately to form catalytic reduction systems with NaBH_(4).The effects of solvent dosage,reaction temperature,reaction time length,and reductant dosage on carboxylic conversion were investigated,and the molecular chain structure,molecular weight,and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy(FTIR),proton nuclear magnetic resonance(^(1)H-NMR),fluorine-19 nuclear magnetic resonance(^(19)F-NMR),gel permeation chromatography(GPC),and chemical titration.Moreover,the catalytic activity and selectivity of the rare-earth chlorides,as well as the corresponding underlying interactions were discussed.Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups,with a highest conversion up to 87.0%and differing catalytic reduction activities ranked as NaBH_(4)/CeCl_(3)>NaBH_(4)/LaCl_(3)>NaBH_(4)/NdCl_(3).Compared with the conventional lithium aluminum hydride(LiAIH_(4))reduction system,the NaBH_(4)/RECl_(3)systems provide multiple advantages such as mild reaction conditions,high conversion ratio with good selectivity,and environmental innocuity,and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.展开更多
Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to hig...Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to high-content residual solvents.The second,usually consciously overlooked,is the fluoropolymer's inherent instability against alkaline lithium anodes.Here,we propose indium-based metal-organic frameworks(In-MOFs)as a multifunctional promoter to simultaneously address these two challenges,using poly(vinylidene fluoride-hexafluoropropylene)(PVH)as the typical fluoropolymer.In-MOF plays a trio:(1)adsorbing and converting free residual solvents into bonded states to prevent their side reactions with lithium anodes while retaining their advantages on Li~+transport;(2)forming inorganic-rich solid electrolyte interphase layers to prevent PVH from reacting with lithium anodes and promote uniform lithium deposition without dendrite growth;(3)reducing PVH crystallinity and promoting Li-salt dissociation.Therefore,the resulting PVH/In-MOF(PVH-IM)showcases excellent electrochemical stability against lithium anodes,delivering a 5550 h cycling at 0.2 m A cm^(-2)with a remarkable cumulative lithium deposition capacity of 1110 m Ah cm^(-2).It also exhibits an ultrahighσof 1.23×10^(-3)S cm^(-1)at 25℃.Moreover,all-solid-state LiFePO_4|PVH-IM|Li full cells show outstanding rate capability and cyclability(80.0%capacity retention after 280 cycles at 0.5C),demonstrating high potential for practical ASLMBs.展开更多
Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and ...Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and energy efficiency.Fluoride-based surface modification has been developed as an effective approach to address this issue.Here,four classical fluoropolymers(F11,F14,PVDF,PTFE)are employed as coatings to prepare core-shell Al/Fluoropolymer.The combustion experimental results demonstrate that the core-shell Al/PTFE exhibits the highest flame propagation rate(52.88 mm·ms^(-1))and pressure output(109.02 k Pa)performance.Consequently,core-shell Al/PTFE is selected as a high-energy fuel to prepare RDX/Al/PTFE microspheres via the emulsion and solvent evaporation method,which can enhance the energy performance of RDX.The effects of the core-shell Al/PTFE ratio and RDX content on the combustion heat and pressure output are systematically investigated.The peak pressure reaches a maximum of 187.8 k Pa when the mass ratio of RDX,Al,and PTFE is 60:25:10.Additionally,RDX/Al/PTFE microspheres exhibit significantly higher laser-induced air shock velocities,detonation heat,and detonation pressure than those of pure RDX and RDX/Al.The mechanism underlying the enhanced reactivity and energetic performance is attributed to the ability of PTFE to etch the inert Al_(2)O_(3)shell on the surface of Al particles,thereby improving post-combustion reactions and significantly increasing the overall energy output of RDX explosives.This work offers a novel design strategy for high-energy structural thermobaric explosives for the practical applications.展开更多
Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and p...Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and polyfluoroalkyl substances(PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time.The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10^(6) ng/g, and <MDL(method detection limit) to 5.3 × 10^(3) ng/g,respectively.Generally, the levels of PFOA in raw materials were higher than in products,implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps.By tracking a company’s polytetrafluoroethylene(PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10^(6) to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued.High concentrations of HFPO-TrA(2.7 × 10^(5) to 8.2 × 10^(5) ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.展开更多
Fluoropolymer and different kinds of silica particles were used for controlling surface chemistry and morphology, respectively. A superhydrophobic surface originated from strawberry-like or quincunx-shaped composite s...Fluoropolymer and different kinds of silica particles were used for controlling surface chemistry and morphology, respectively. A superhydrophobic surface originated from strawberry-like or quincunx-shaped composite silica particles was obtained. The dual size particles are obtained by utilizing the graft of different modified silica particles with epoxy functional group and amine functional group, This makes the surface of film form a composite interface to have irregular binary structure which plays an essential role in trapping air between the substrate surface and the liquid droplets to be necessary for high contact angle and low contact angle hysteresis. The maximum contact angle for water on the hybrid film is about 174±2° and the contact angle hysteresis is less than 2°. The surface morphologies, roughness and the wettability on the surface of films containing different structural silica particles were compared. It was shown that the hierarchical irregularly structure with a low roughness factor and high air-trapped ratio is indispensable for superhydrophobic surface. Although this structural surfaces based on composite silica particles play a vital role in governing the surface wettability, it is necessary to combine with a low surface energy to make the surface superhydrophobic.展开更多
Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface ele...Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.展开更多
Fluorinated polymers are important materials that are widely used in many areas as taking the advantage of inertness to chemical corrosion,prominent weather resista nee,low flammability,and good thermal stability.Poly...Fluorinated polymers are important materials that are widely used in many areas as taking the advantage of inertness to chemical corrosion,prominent weather resista nee,low flammability,and good thermal stability.Poly(vinylidene fluoride)(PVDF)based fluoropolymers is the most commontype of commercial fluoropolymer especially used as dielectric materials.However,there are always some shortcomings in practical applications,so it is necessary to modify PVDF-based fluoropolymers for better application.Controlled/living radical polymerization(CRP)and related techniques have become a powerful approach to tailoring the chemical and physical properties of materials and have given rise to great advances in modification of PVDF-based fluoropolymers.展开更多
UV-curable perfluoropolyether (PFPE)-based fluoropolymer (PFPE-DMA) was synthesized and the photocuring behaviors of PFPE-DMA/HDDA systems with and without tertiary triethyl amine (TEA) were investigated using photo-D...UV-curable perfluoropolyether (PFPE)-based fluoropolymer (PFPE-DMA) was synthesized and the photocuring behaviors of PFPE-DMA/HDDA systems with and without tertiary triethyl amine (TEA) were investigated using photo-DSC under air and nitrogen atmospheres. Photo-DSC analysis revealed that N2 purging and the presence of TEA mitigated oxygen inhibition in the photopolymerization of the UV-curable free-radical PFPE-DMA/ HDDA system. In addition, TEA synergistically acted as a coinitiator or photosynergist under nitrogen atmosphere, which increased the cure rate and percentage conversion for the photopolymerization of PFPE-DMA/ HDDA. TEA acted as both oxygen scavenger and photosynergist. The results presented here demonstrate that investigating the photocuring behaviors of PFPE-DMA/HDDA systems is very helpful to determine the optimal curing conditions for the PFPE-DMA fluoropolymer.展开更多
The experimental results and numerical modeling of penetration process of fluoropolymer projectiles in aluminum-based targets are presented. Analysis of mathematical models for interaction of elastoplastic projectile ...The experimental results and numerical modeling of penetration process of fluoropolymer projectiles in aluminum-based targets are presented. Analysis of mathematical models for interaction of elastoplastic projectile and target without taking additional energy released during interaction of fluoropolymer and aluminum into consideration is carried out. Energy fraction which is spent effectively on the increase in cavity volume is determined. The experimental and calculated results of penetration by combined and inert projectiles are compared.展开更多
In this paper, the relationship between radiation crosslinking parameter β and the molecular internal rotating steric factor (σ) for fluoropolymers were studied. An expression calculating the molecular internal rota...In this paper, the relationship between radiation crosslinking parameter β and the molecular internal rotating steric factor (σ) for fluoropolymers were studied. An expression calculating the molecular internal rotating steric factor of fluoropolymers, σ=1.44+(β-0.206)/1.946, was established. σ value obtained by this method is in agreement with that given in the literature.展开更多
In this paper, the effect of irradiation temperature on sol fraction-dose relationship of tluoropolymers was studied. It was found that the increasing of irradiation temperature can result in the decreasing of β valu...In this paper, the effect of irradiation temperature on sol fraction-dose relationship of tluoropolymers was studied. It was found that the increasing of irradiation temperature can result in the decreasing of β value of fluoropolymer, which increases the crosslinking probability of fluoropolymer. The relationship between crosslinking parameter β and irradiation temperature (T_i)of fluoropolymer is established as follows:β=2.2×10^(-3) T_g+4×10^(-4)(T_g-T_i)+0.206.values of some tluoropolymers calculated from the above expression are in agreement with the experimental values.展开更多
We report a method for the coacervation micro-encapsulation of several forms of CaCO3 microparticles with the fluoropolymer poly(heptadecafluorodecyl acrylate) (poly (HDFDA)) by pressure-induced phase separation of a ...We report a method for the coacervation micro-encapsulation of several forms of CaCO3 microparticles with the fluoropolymer poly(heptadecafluorodecyl acrylate) (poly (HDFDA)) by pressure-induced phase separation of a supercritical CO2 solution.? A suspension of CaCO3 in CO2 and dissolved poly(HDFDA) were mixed in supercritical CO2.? After the system pressure was slowly decreased to atmospheric pressure, the microcapsules were obtained.? Coacervation was achieved by the precipitation of poly(HDFDA) during the decrease in the pressure of CO2;the solubility of poly(HDFDA) in CO2 decreased with the pressure.? The structure and morphology of the microparticles were investigated by using a scanning electron microscope (SEM) and an electron probe microanalyzer (EPMA) equipped with a wavelength dispersive X-ray spectroscope (WDX).展开更多
Thick-film organic solar cells(OSCs)are critical for large-scale manufacturing,yet they face persistent challenges of severe energy loss and complex morphology control.The integration of molecular design and device en...Thick-film organic solar cells(OSCs)are critical for large-scale manufacturing,yet they face persistent challenges of severe energy loss and complex morphology control.The integration of molecular design and device engineering is widely recognized as a promising strategy to address these bottlenecks.Here,we report the synthesis of a fluoropolymer PF8 and its application in combination with fluorous solvent vapor annealing(FSVA)post-treatment to fabricate high-performance thick-film OSCs.The fluorination strategy and FSVA process synergistically enhance the polymer’s crystallinity and induce an intrinsic fibrous morphology.As a result,the FSVA-treated PF8:L8BO device with a thickness of 110 nm achieves a power conversion efficiency(PCE)of 18.89%.Notably,even when the film thickness is increased to 300 and 500 nm,the devices maintain high efficiencies of 17.54%and 15.59%,respectively.More importantly,the 300-nm FSVA-treated blend films exhibit enhanced packing order and well-defined fibrillar morphology,leading to suppressed non-radiative recombination and efficient charge transport along the fiber network.This study demonstrates the potential of combining fluoropolymers with fluorous solvent-based device engineering for advanced thick-film optoelectronic applications,providing a viable pathway for scalable OSC manufacturing.展开更多
A Pd-catalyzed multi-component carbonylative difluoroalkylation/perfluoroalkylation through the alkyne difunctionalization process has been developed. Besides, new functional fluoropolymer materials have been successf...A Pd-catalyzed multi-component carbonylative difluoroalkylation/perfluoroalkylation through the alkyne difunctionalization process has been developed. Besides, new functional fluoropolymer materials have been successfully synthesized. Owing to the presence of the fluorine element, the materials present excellent chemical resistance, high-temperature-resistance and outstanding hydrophobicity simultaneously, which may significantly make them great appealing in the industrial production and life science as well.展开更多
As the application scenarios of aerogels expand,higher requirements are put forward for the materials used to prepare aerogels.Due to the unique chemical structure,polytetrafluoroethylene(PTFE)has excellent properties...As the application scenarios of aerogels expand,higher requirements are put forward for the materials used to prepare aerogels.Due to the unique chemical structure,polytetrafluoroethylene(PTFE)has excellent properties such as high-temperature resistance,hydrophobicity,and chemical stability.However,the PTFE aerogels are difficult to be molded due to the weak interaction between resin particles.In this work,poly(ethylene oxide)(PEO)was selected as the carrier to assist the PTFE aerogels molding.The pure PTFE aerogels were prepared by homogeneously mixing PTFE aqueous dispersion and PEO,freeze-drying,and high-temperature sintering.When the mass fraction of PTFE and PEO were appropriate,the porosity of PTFE aerogels exceeded 90%and had a hierarchical honeycomb structure.Results showed that the PTFE aerogels not only had excellent hydrophobicity but also possessed superior acoustic insulation,mechanical strength,thermal insulation,and heat resistance properties.Specifically,the water contact angle is about 140°.The noise reduction coefficient is 0.34 and the average sound absorption coefficient is greater than 88%in the frequency range of 2000-6400 Hz.Meanwhile,the thermal conductivity in the air is about 0.045 W/(m·K),and the initial thermal decomposition temperature is 450℃.More importantly,the PTFE aerogels had excellent temperature and corrosion resistance.Even after extremely thermal and chemical treatment,they remained unchanged porous structure as well as acoustic and thermal insulation properties,which exhibits great potential for application in many harsh environments.展开更多
The advancement in material science and engineering technology has led to the development of antifouling(AF) coatings which are cheaper, durable, less toxic, and safe to the environment. The use of AF coatings contain...The advancement in material science and engineering technology has led to the development of antifouling(AF) coatings which are cheaper, durable, less toxic, and safe to the environment. The use of AF coatings containing tributyltin compounds was prohibited at the beginning of 2003, this necessitated the development of environmentally friendly coatings. The fouling release coating(FRC) lacks biocides and has low surface energy, low elastic modulus with smooth surface properties, hence a better release effect to fouling organisms. Several functional coatings have been recently developed based on fouling release(FR) technology to combat the effects of biofouling. Here, we provide a brief overview of innovative technologies and recent developments based on FRCs, including silicone, modified fluorinated polymer,cross-linked coatings, amphiphilic copolymer coating, hydrogel coatings, and biomimetic coatings. We also highlight the key issues and shortcomings of innovative technologies based on FRCs. This may give new insights into the future development of marine AF coatings.展开更多
A novel combined method for the formation of composite coatings on the Mg-Mn-Ce alloy is developed.Ceramic like matrix was formed on the Mg alloy surface by the plasma electrolytic oxidation.Then the samples were subs...A novel combined method for the formation of composite coatings on the Mg-Mn-Ce alloy is developed.Ceramic like matrix was formed on the Mg alloy surface by the plasma electrolytic oxidation.Then the samples were subsequently processed by dip-coating in an alcohol suspension of superdispersed polytetrafluoroethylene and spraying with the tetrafluoroethylene telomers solution.SEM,OSP,and SPM was used to study structure of formed surfaces.It was established by measurements of CA and CAH,as well as surface free energy calculations that formed coatings demonstrate superhydrophobic properties due to the presence of an irregular hierarchical surface structure and low surface free energy of fluoropolymers.The coating preserves its hydrophobic properties after exposure to high and low temperatures,for a long time as well as being in corrosive environments.EDS and XRD data analysis confirmed the presence of organofluorine compounds in the composite layers,including in the form of crystalline polytetrafluoroethylene.Using potentiodynamic polarization test and EIS,it was found that the resulting coatings significantly increase the corrosion resistance of Mg material.These data are also confirmed by salt spray tests for 40 days.Incorporation of fluoropolymers additionally decrease coatings coefficient of friction.展开更多
A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared ...A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared by coupling reactions of end-functlonal PMTFPS and PEO homopolymers. Copolymers were shown to be well defined and narrow molecular weight distribution （MWD） （1.07-1.3） by characterizations such as gel permeation chromatography （GPC） and ^1H-nudear magnetic resonance （^1H-NMR）.展开更多
The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By vi...The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling,a robust organic/inorganic hybrid interlayer(lithiophilic LiF/LiC_(6)framework hybridized-CF_(2)-O-CF_(2)-chains)was formed atop Li metal.The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface.The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h(1.0 mA cm^(-2)and 1.0 mAh cm^(-2))and 1,350 cycles even at a harsh condition(18.0 mA cm^(-2)and 3.0 mAh cm^(-2)).When paired with high-loading LiFePO4 cathodes,the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%.This work provides a new friction-induced strategy for producing high-performance thin LMAs.展开更多
Fluoropolymers get increasing attention in energetic materials application due to the high fluorine content.To explore the effect of poly(vinylidene fluoride-co-hexafluoropropylene)(P(VDF-HFP))on Al/MnO_(2) nanothermi...Fluoropolymers get increasing attention in energetic materials application due to the high fluorine content.To explore the effect of poly(vinylidene fluoride-co-hexafluoropropylene)(P(VDF-HFP))on Al/MnO_(2) nanothermite,the samples with different contents are prepared and characterized by SEM,TGDSC,XRD,and their ignition and combustion behavior are tested and recorded.The results show that P(VDF-HFP)as an energetic binder can combine the nanothermite components together,even exist in the gaps.The integrity of energetic materials has been improved.Thermal analysis shows that the addition of P(VDF-HFP)greatly changes the thermal reaction processes,and the exothermic peaks appear early,but the utilization of fuel and oxidizer is not efficient from the XRD results.Furthermore,the appropriate addition of P(VDF-HFP)can directly reduce the ignition energy threshold and increase the combustion time,which is necessary for the potential ignition charge application.The possible reasons for above phenomena are discussed and analyzed.This research provides a reference for improvement of thermitebased ignition charge formulation.展开更多
文摘Herein the use of rare-earth compounds in catalytic reduction systems for the end-group functionalization of carboxyl-terminated low-molecularweight fluoropolymers was explored.Leveraging the high catalytic activity and selectivity of rare-earth compounds along with no residual impact on polymer product's performance,highly efficient catalytic reduction systems containing sodium borohydride(NaBH_(4))and rare-earth chloride(RECl_(3))were specifically designed for a telechelic carboxyl-terminated liquid fluoroeslastomer,aiming to facilitate the conversion of chainend carboxyl groups into hydroxyl groups and improvement in end-group reactivity.To achieve this,lanthanum chloride(LaCl_(3)),cerium chloride(CeCl_(3)),and neodymium chloride(NdCl_(3))were used separately to form catalytic reduction systems with NaBH_(4).The effects of solvent dosage,reaction temperature,reaction time length,and reductant dosage on carboxylic conversion were investigated,and the molecular chain structure,molecular weight,and functional group content of the raw materials and the products were analyzed and characterized by means of infrared spectroscopy(FTIR),proton nuclear magnetic resonance(^(1)H-NMR),fluorine-19 nuclear magnetic resonance(^(19)F-NMR),gel permeation chromatography(GPC),and chemical titration.Moreover,the catalytic activity and selectivity of the rare-earth chlorides,as well as the corresponding underlying interactions were discussed.Results indicated that the rare-earth-containing catalytic reduction systems studied in this work could efficiently convert the chain-end carboxyl groups into highly active hydroxyl groups,with a highest conversion up to 87.0%and differing catalytic reduction activities ranked as NaBH_(4)/CeCl_(3)>NaBH_(4)/LaCl_(3)>NaBH_(4)/NdCl_(3).Compared with the conventional lithium aluminum hydride(LiAIH_(4))reduction system,the NaBH_(4)/RECl_(3)systems provide multiple advantages such as mild reaction conditions,high conversion ratio with good selectivity,and environmental innocuity,and are potentially applicable as new reduction-catalysis combinations for the synthesis and functionalization of polymer materials.
基金the financial support from the 261 Project of MIITNatural Science Foundation of Jiangsu Province(No.BK20240179)。
文摘Fluoropolymers promise all-solid-state lithium metal batteries(ASLMBs)but suffer from two critical challenges.The first is the trade-off between ionic conductivity(σ)and lithium anode reactions,closely related to high-content residual solvents.The second,usually consciously overlooked,is the fluoropolymer's inherent instability against alkaline lithium anodes.Here,we propose indium-based metal-organic frameworks(In-MOFs)as a multifunctional promoter to simultaneously address these two challenges,using poly(vinylidene fluoride-hexafluoropropylene)(PVH)as the typical fluoropolymer.In-MOF plays a trio:(1)adsorbing and converting free residual solvents into bonded states to prevent their side reactions with lithium anodes while retaining their advantages on Li~+transport;(2)forming inorganic-rich solid electrolyte interphase layers to prevent PVH from reacting with lithium anodes and promote uniform lithium deposition without dendrite growth;(3)reducing PVH crystallinity and promoting Li-salt dissociation.Therefore,the resulting PVH/In-MOF(PVH-IM)showcases excellent electrochemical stability against lithium anodes,delivering a 5550 h cycling at 0.2 m A cm^(-2)with a remarkable cumulative lithium deposition capacity of 1110 m Ah cm^(-2).It also exhibits an ultrahighσof 1.23×10^(-3)S cm^(-1)at 25℃.Moreover,all-solid-state LiFePO_4|PVH-IM|Li full cells show outstanding rate capability and cyclability(80.0%capacity retention after 280 cycles at 0.5C),demonstrating high potential for practical ASLMBs.
基金supported by the National Natural Science Foundation of China(Grant Nos.T2222027 and 12202416)。
文摘Aluminum(Al)powder is widely applied in thermobaric explosives due to its high energy density and favorable reaction kinetics.However,the inert oxide layer(Al_(2)O_(3))on Al particles limits combustion reactivity and energy efficiency.Fluoride-based surface modification has been developed as an effective approach to address this issue.Here,four classical fluoropolymers(F11,F14,PVDF,PTFE)are employed as coatings to prepare core-shell Al/Fluoropolymer.The combustion experimental results demonstrate that the core-shell Al/PTFE exhibits the highest flame propagation rate(52.88 mm·ms^(-1))and pressure output(109.02 k Pa)performance.Consequently,core-shell Al/PTFE is selected as a high-energy fuel to prepare RDX/Al/PTFE microspheres via the emulsion and solvent evaporation method,which can enhance the energy performance of RDX.The effects of the core-shell Al/PTFE ratio and RDX content on the combustion heat and pressure output are systematically investigated.The peak pressure reaches a maximum of 187.8 k Pa when the mass ratio of RDX,Al,and PTFE is 60:25:10.Additionally,RDX/Al/PTFE microspheres exhibit significantly higher laser-induced air shock velocities,detonation heat,and detonation pressure than those of pure RDX and RDX/Al.The mechanism underlying the enhanced reactivity and energetic performance is attributed to the ability of PTFE to etch the inert Al_(2)O_(3)shell on the surface of Al particles,thereby improving post-combustion reactions and significantly increasing the overall energy output of RDX explosives.This work offers a novel design strategy for high-energy structural thermobaric explosives for the practical applications.
基金supported by the National Natural Science Foundation of China (No.21625702)。
文摘Perfluorooctanoic acid(PFOA), its salts, and related compounds were listed as new persistent organic pollutants by the Stockholm Convention in 2019.In this study, the occurrence of residues of PFOA and other per-and polyfluoroalkyl substances(PFASs) in raw materials and fluoropolymer products from the Chinese fluoropolymer industries are reported for the first time.The PFOA concentrations in raw materials and fluoropolymer products were in the range of 6.7 to 1.1 × 10^(6) ng/g, and <MDL(method detection limit) to 5.3 × 10^(3) ng/g,respectively.Generally, the levels of PFOA in raw materials were higher than in products,implying that PFOA in the emulsion/dispersion resin could be partly removed during the polymerization or post-processing steps.By tracking a company’s polytetrafluoroethylene(PTFE) production line, it was found that over a 5 year period, the residual levels of PFOA in emulsion samples declined from 1.1 × 10^(6) to 28.4 ng/g, indicating that the contamination of PFOA in fluoropolymer products from production source gradually decreased after its use had been discontinued.High concentrations of HFPO-TrA(2.7 × 10^(5) to 8.2 × 10^(5) ng/g) were detected in some emulsion samples indicating this alternative has been widely applied in fluoropolymer manufacturing in China.
基金the National Natural Science Foundation of China(Grant No.20506005).
文摘Fluoropolymer and different kinds of silica particles were used for controlling surface chemistry and morphology, respectively. A superhydrophobic surface originated from strawberry-like or quincunx-shaped composite silica particles was obtained. The dual size particles are obtained by utilizing the graft of different modified silica particles with epoxy functional group and amine functional group, This makes the surface of film form a composite interface to have irregular binary structure which plays an essential role in trapping air between the substrate surface and the liquid droplets to be necessary for high contact angle and low contact angle hysteresis. The maximum contact angle for water on the hybrid film is about 174±2° and the contact angle hysteresis is less than 2°. The surface morphologies, roughness and the wettability on the surface of films containing different structural silica particles were compared. It was shown that the hierarchical irregularly structure with a low roughness factor and high air-trapped ratio is indispensable for superhydrophobic surface. Although this structural surfaces based on composite silica particles play a vital role in governing the surface wettability, it is necessary to combine with a low surface energy to make the surface superhydrophobic.
基金supported by the startup funding at University of Delaware
文摘Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.92066204,52003214,51773166 and 51603167)China Postdoctoral Science Foundation Funded Project(Nos.2019M663699 and 2020T130507)+3 种基金Key Laboratory Construction Program of Xi'an Municipal Bureau of Science and Technology(No.201805056ZD7CG40)Natural Science Foundation of Jiangsu Province(No.BK2020245)Suzhou Science and Technology Project(No.SYG202028)the Fundamental Research Funds for the Central Universities(No.xzy012020035).
文摘Fluorinated polymers are important materials that are widely used in many areas as taking the advantage of inertness to chemical corrosion,prominent weather resista nee,low flammability,and good thermal stability.Poly(vinylidene fluoride)(PVDF)based fluoropolymers is the most commontype of commercial fluoropolymer especially used as dielectric materials.However,there are always some shortcomings in practical applications,so it is necessary to modify PVDF-based fluoropolymers for better application.Controlled/living radical polymerization(CRP)and related techniques have become a powerful approach to tailoring the chemical and physical properties of materials and have given rise to great advances in modification of PVDF-based fluoropolymers.
文摘UV-curable perfluoropolyether (PFPE)-based fluoropolymer (PFPE-DMA) was synthesized and the photocuring behaviors of PFPE-DMA/HDDA systems with and without tertiary triethyl amine (TEA) were investigated using photo-DSC under air and nitrogen atmospheres. Photo-DSC analysis revealed that N2 purging and the presence of TEA mitigated oxygen inhibition in the photopolymerization of the UV-curable free-radical PFPE-DMA/ HDDA system. In addition, TEA synergistically acted as a coinitiator or photosynergist under nitrogen atmosphere, which increased the cure rate and percentage conversion for the photopolymerization of PFPE-DMA/ HDDA. TEA acted as both oxygen scavenger and photosynergist. The results presented here demonstrate that investigating the photocuring behaviors of PFPE-DMA/HDDA systems is very helpful to determine the optimal curing conditions for the PFPE-DMA fluoropolymer.
文摘The experimental results and numerical modeling of penetration process of fluoropolymer projectiles in aluminum-based targets are presented. Analysis of mathematical models for interaction of elastoplastic projectile and target without taking additional energy released during interaction of fluoropolymer and aluminum into consideration is carried out. Energy fraction which is spent effectively on the increase in cavity volume is determined. The experimental and calculated results of penetration by combined and inert projectiles are compared.
基金The project was supported by the research foundation of IAEA, Agency Research Contract No. 4316/RB
文摘In this paper, the relationship between radiation crosslinking parameter β and the molecular internal rotating steric factor (σ) for fluoropolymers were studied. An expression calculating the molecular internal rotating steric factor of fluoropolymers, σ=1.44+(β-0.206)/1.946, was established. σ value obtained by this method is in agreement with that given in the literature.
文摘In this paper, the effect of irradiation temperature on sol fraction-dose relationship of tluoropolymers was studied. It was found that the increasing of irradiation temperature can result in the decreasing of β value of fluoropolymer, which increases the crosslinking probability of fluoropolymer. The relationship between crosslinking parameter β and irradiation temperature (T_i)of fluoropolymer is established as follows:β=2.2×10^(-3) T_g+4×10^(-4)(T_g-T_i)+0.206.values of some tluoropolymers calculated from the above expression are in agreement with the experimental values.
文摘We report a method for the coacervation micro-encapsulation of several forms of CaCO3 microparticles with the fluoropolymer poly(heptadecafluorodecyl acrylate) (poly (HDFDA)) by pressure-induced phase separation of a supercritical CO2 solution.? A suspension of CaCO3 in CO2 and dissolved poly(HDFDA) were mixed in supercritical CO2.? After the system pressure was slowly decreased to atmospheric pressure, the microcapsules were obtained.? Coacervation was achieved by the precipitation of poly(HDFDA) during the decrease in the pressure of CO2;the solubility of poly(HDFDA) in CO2 decreased with the pressure.? The structure and morphology of the microparticles were investigated by using a scanning electron microscope (SEM) and an electron probe microanalyzer (EPMA) equipped with a wavelength dispersive X-ray spectroscope (WDX).
基金supported by the National Natural Science Foundation of China(22379095)the Natural Science Foundation of Shanghai(21ZR1435100)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2022MS015).
文摘Thick-film organic solar cells(OSCs)are critical for large-scale manufacturing,yet they face persistent challenges of severe energy loss and complex morphology control.The integration of molecular design and device engineering is widely recognized as a promising strategy to address these bottlenecks.Here,we report the synthesis of a fluoropolymer PF8 and its application in combination with fluorous solvent vapor annealing(FSVA)post-treatment to fabricate high-performance thick-film OSCs.The fluorination strategy and FSVA process synergistically enhance the polymer’s crystallinity and induce an intrinsic fibrous morphology.As a result,the FSVA-treated PF8:L8BO device with a thickness of 110 nm achieves a power conversion efficiency(PCE)of 18.89%.Notably,even when the film thickness is increased to 300 and 500 nm,the devices maintain high efficiencies of 17.54%and 15.59%,respectively.More importantly,the 300-nm FSVA-treated blend films exhibit enhanced packing order and well-defined fibrillar morphology,leading to suppressed non-radiative recombination and efficient charge transport along the fiber network.This study demonstrates the potential of combining fluoropolymers with fluorous solvent-based device engineering for advanced thick-film optoelectronic applications,providing a viable pathway for scalable OSC manufacturing.
基金Acknowledgement China We thank the National Natural Science Foundation of （NSF 21472073 and 21532001）, and the ＂111＂ Project.
文摘A Pd-catalyzed multi-component carbonylative difluoroalkylation/perfluoroalkylation through the alkyne difunctionalization process has been developed. Besides, new functional fluoropolymer materials have been successfully synthesized. Owing to the presence of the fluorine element, the materials present excellent chemical resistance, high-temperature-resistance and outstanding hydrophobicity simultaneously, which may significantly make them great appealing in the industrial production and life science as well.
基金supported by the National Natural Science Foundation of China(No.52233003)the Department of Sichuan Province(No.2022JDJQ0023)。
文摘As the application scenarios of aerogels expand,higher requirements are put forward for the materials used to prepare aerogels.Due to the unique chemical structure,polytetrafluoroethylene(PTFE)has excellent properties such as high-temperature resistance,hydrophobicity,and chemical stability.However,the PTFE aerogels are difficult to be molded due to the weak interaction between resin particles.In this work,poly(ethylene oxide)(PEO)was selected as the carrier to assist the PTFE aerogels molding.The pure PTFE aerogels were prepared by homogeneously mixing PTFE aqueous dispersion and PEO,freeze-drying,and high-temperature sintering.When the mass fraction of PTFE and PEO were appropriate,the porosity of PTFE aerogels exceeded 90%and had a hierarchical honeycomb structure.Results showed that the PTFE aerogels not only had excellent hydrophobicity but also possessed superior acoustic insulation,mechanical strength,thermal insulation,and heat resistance properties.Specifically,the water contact angle is about 140°.The noise reduction coefficient is 0.34 and the average sound absorption coefficient is greater than 88%in the frequency range of 2000-6400 Hz.Meanwhile,the thermal conductivity in the air is about 0.045 W/(m·K),and the initial thermal decomposition temperature is 450℃.More importantly,the PTFE aerogels had excellent temperature and corrosion resistance.Even after extremely thermal and chemical treatment,they remained unchanged porous structure as well as acoustic and thermal insulation properties,which exhibits great potential for application in many harsh environments.
文摘The advancement in material science and engineering technology has led to the development of antifouling(AF) coatings which are cheaper, durable, less toxic, and safe to the environment. The use of AF coatings containing tributyltin compounds was prohibited at the beginning of 2003, this necessitated the development of environmentally friendly coatings. The fouling release coating(FRC) lacks biocides and has low surface energy, low elastic modulus with smooth surface properties, hence a better release effect to fouling organisms. Several functional coatings have been recently developed based on fouling release(FR) technology to combat the effects of biofouling. Here, we provide a brief overview of innovative technologies and recent developments based on FRCs, including silicone, modified fluorinated polymer,cross-linked coatings, amphiphilic copolymer coating, hydrogel coatings, and biomimetic coatings. We also highlight the key issues and shortcomings of innovative technologies based on FRCs. This may give new insights into the future development of marine AF coatings.
基金The study was supported by the Russian Science Foundation grant no.22-73-10149,https://rscf.ru/project/22-73-10149/.
文摘A novel combined method for the formation of composite coatings on the Mg-Mn-Ce alloy is developed.Ceramic like matrix was formed on the Mg alloy surface by the plasma electrolytic oxidation.Then the samples were subsequently processed by dip-coating in an alcohol suspension of superdispersed polytetrafluoroethylene and spraying with the tetrafluoroethylene telomers solution.SEM,OSP,and SPM was used to study structure of formed surfaces.It was established by measurements of CA and CAH,as well as surface free energy calculations that formed coatings demonstrate superhydrophobic properties due to the presence of an irregular hierarchical surface structure and low surface free energy of fluoropolymers.The coating preserves its hydrophobic properties after exposure to high and low temperatures,for a long time as well as being in corrosive environments.EDS and XRD data analysis confirmed the presence of organofluorine compounds in the composite layers,including in the form of crystalline polytetrafluoroethylene.Using potentiodynamic polarization test and EIS,it was found that the resulting coatings significantly increase the corrosion resistance of Mg material.These data are also confirmed by salt spray tests for 40 days.Incorporation of fluoropolymers additionally decrease coatings coefficient of friction.
基金the National Natural Science Foundation of China (No. 20606029)the Postdoctoral Science Foundation of China (No. 20070420230)
文摘A series of new amphiphilic poly[methyl（3,3,3-trifluoropropyl）siloxane]-b-poly（ethylene oxide） （PMTFPS-b-PEO） diblock copolymers with different ratios of hydrophobic segment to hydrophilic segment were prepared by coupling reactions of end-functlonal PMTFPS and PEO homopolymers. Copolymers were shown to be well defined and narrow molecular weight distribution （MWD） （1.07-1.3） by characterizations such as gel permeation chromatography （GPC） and ^1H-nudear magnetic resonance （^1H-NMR）.
基金This work was supported by the National Natural Science Foundation of China(U1904216 and U22A20141)the Natural Science Foundation of Changsha City(kq2208258).
文摘The practical application of Li metal anodes(LMAs)is limited by uncontrolled dendrite growth and side reactions.Herein,we propose a new friction-induced strategy to produce high-performance thin Li anode(Li@CFO).By virtue of the in situ friction reaction between fluoropolymer grease and Li strips during rolling,a robust organic/inorganic hybrid interlayer(lithiophilic LiF/LiC_(6)framework hybridized-CF_(2)-O-CF_(2)-chains)was formed atop Li metal.The derived interface contributes to reversible Li plating/stripping behaviors by mitigating side reactions and decreasing the solvation degree at the interface.The Li@CFO||Li@CFO symmetrical cell exhibits a remarkable lifespan for 5,600 h(1.0 mA cm^(-2)and 1.0 mAh cm^(-2))and 1,350 cycles even at a harsh condition(18.0 mA cm^(-2)and 3.0 mAh cm^(-2)).When paired with high-loading LiFePO4 cathodes,the full cell lasts over 450 cycles at 1C with a high-capacity retention of 99.9%.This work provides a new friction-induced strategy for producing high-performance thin LMAs.
基金This work was supported by the National Natural Science Foundation,project no.51704302was also supported by China Scholarship Council,no.201903170086.
文摘Fluoropolymers get increasing attention in energetic materials application due to the high fluorine content.To explore the effect of poly(vinylidene fluoride-co-hexafluoropropylene)(P(VDF-HFP))on Al/MnO_(2) nanothermite,the samples with different contents are prepared and characterized by SEM,TGDSC,XRD,and their ignition and combustion behavior are tested and recorded.The results show that P(VDF-HFP)as an energetic binder can combine the nanothermite components together,even exist in the gaps.The integrity of energetic materials has been improved.Thermal analysis shows that the addition of P(VDF-HFP)greatly changes the thermal reaction processes,and the exothermic peaks appear early,but the utilization of fuel and oxidizer is not efficient from the XRD results.Furthermore,the appropriate addition of P(VDF-HFP)can directly reduce the ignition energy threshold and increase the combustion time,which is necessary for the potential ignition charge application.The possible reasons for above phenomena are discussed and analyzed.This research provides a reference for improvement of thermitebased ignition charge formulation.
