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
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
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
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
Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepare...Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.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.
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.
基金supported by Wuxi HIT New Material Research Institute and China Academy of Engineering Physics。
文摘Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives(PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks(semiIPNs) were prepared using different catalyst amounts(denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing.An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs;these factors can be feasibly controlled using an appropriate catalyst amount.
