Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin cat...Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.展开更多
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 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.展开更多
The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene(CL-20/TNT)composite was prepared by spray-drying method in which sensitive high energy explosive(CL-20)was coated with in...The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene(CL-20/TNT)composite was prepared by spray-drying method in which sensitive high energy explosive(CL-20)was coated with insensitive explosive(TNT).The structure and properties of different formulations of CL-20/TNT composite and CL-20/TNT mixture were characterized by scanning electron microscopy(SEM),Transmission electron microscopy(TEM),Laser particle size analyzer,X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),differential scanning calorimetry(DSC),impact sensitivity test and detonation performance.The results of SEM,TEM,XPS and XRD show that e-CL-20 particles are coated by TNT.When the ratio of CL-20/TNT is 75/25,core-shell structure is well formed,and thickness of the shell is about 20e30 nm.And the analysis of heat and impact show that with the increase of TNT content,the TNT coating on the core-shell composite material can not only catalyze the thermal decomposition of core material(CL-20),but also greatly reduce the impact sensitivity.Compared with the CL-20/TNT mixture(75/25)at the same ratio,the characteristic drop height of core-shell CL-20/TNT composite(75/25)increased by 47.6%and the TNT coating can accelerate the nuclear decomposition in the CL-20/TNT composites.Therefore,the preparation of the core-shell composites can be regarded as a unique means,by which the composites are characterized by controllable decomposition rate,high energy and excellent mechanical sensitivity and could be applied to propellants and other fields.展开更多
In order to improve the hot corrosion resistance of DZ125 alloy,Ce-Y modified aluminum coatings were prepared on DZ125 alloy by pack cementation process at 950°C for 2 h.The microstructure,phase constitution and ...In order to improve the hot corrosion resistance of DZ125 alloy,Ce-Y modified aluminum coatings were prepared on DZ125 alloy by pack cementation process at 950°C for 2 h.The microstructure,phase constitution and formation mechanism of the coatings were investigated.The hot corrosion behaviors of DZ125 alloy and the coatings in molten salt environment of 25%K2SO4+75%Na2SO4(mass fraction)at 900°C were studied.Results show that the obtained Al-Ce-Y coatings were mainly composed of Al3Ni2,Al3Ni and Cr7Ni3,with a thickness of about 120μm.After hot corrosion test,DZ125 alloy suffered catastrophic hot corrosion and serious internal oxidation and internal sulfidation arose.Two layers of corrosion products formed on surfaces of DZ125 alloy,including the outer layer consisting of Cr2O3 and NiCr2O4,and the inner layer of Al2O3,Ni3S2 and Ni-base solid solution.After being coated with Al-Ce-Y coating,the hot corrosion resistance of DZ125 alloy is improved notably,due to the formation of a dense scale mainly consisting of Al-rich Al2O3 in the coating layer.展开更多
A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTF...A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTFE and Al particles were used as starting materials. Under high-power ultrasonic waves, the PTFE powder was dispersed into nano-to sub-micrometer-sized particles and then encapsulated the Al microparticles to form the core-shell structure. The heat of combustion, burning rate, and pressurization rate of the powdered CS-PA were measured. The thermal-initiated reaction behavior was further evaluated using thermogravimetry-differential scanning calorimetry. Subsequently, the bulk CS-PA with a uniform microstructure was obtained via cold isostatic pressing of the powdered CS-PA followed by vacuum sintering. For the bulk CS-PA, the quasi-static compression behavior was characterized, and the impact-initiated reaction processes were conducted using the Split Hopkinson Pressure Bar (SHPB) and evaluated by a high-speed camera. Compared to physically mixed PTFE/Al materials, the powdered and bulk CS-PA demonstrated enhanced thermal- and impact-initiated reaction characteristics respectively, proving the effectiveness of our approach for constructing core-shell structures.展开更多
Broadband near-infrared(NIR)luminescent materials have shown great promise in applications such as optical communication,biomedicine,and optoelectronic devices.However,the current research is focused on phos⁃phors and...Broadband near-infrared(NIR)luminescent materials have shown great promise in applications such as optical communication,biomedicine,and optoelectronic devices.However,the current research is focused on phos⁃phors and glasses,and it is important to develop broadband NIR luminescent nanomaterials.Here,we report an erbi⁃um-sensitized core-shell nanocrystal design for broadband NIR emission.Based on the structural design with suitable dopings of Tm^(3+)and Ho^(3+),the broadband NIR emission covering 1.5-2.1μm region is achieved under 980 nm and 808 nm excitations.Moreover,the emission intensity is further enhanced by introducing Yb^(3+)and Nd^(3+)into the sam⁃ple,respectively,and the energy transfer processes between them are systematically discussed.Our results present a novel approach for developing broadband NIR luminescent materials and devices.展开更多
本文以30Cr Mn Si A结构钢为研究对象,利用低温等离子体渗氮及低温渗氮-低温氧化复合技术对其进行表面改性研究,重点研究了氧化时间对渗氮30Cr Mn Si A钢表面组织结构和性能的影响。采用扫描电子显微镜、X射线衍射仪分析渗氮层及渗氮-...本文以30Cr Mn Si A结构钢为研究对象,利用低温等离子体渗氮及低温渗氮-低温氧化复合技术对其进行表面改性研究,重点研究了氧化时间对渗氮30Cr Mn Si A钢表面组织结构和性能的影响。采用扫描电子显微镜、X射线衍射仪分析渗氮层及渗氮-氧化复合改性层的表面形貌、截面组织和相结构;利用维氏硬度计、摩擦磨损试验机和电化学工作站对渗氮层及复合改性层的硬度、耐磨性和耐蚀性进行评价。结果表明,渗氮层表面主要由ε-Fe_(23)N、γ'-Fe_(4)N和α_N相组成,经不同时间的氧化处理后,渗氮层表面生成Fe_(3)O_(4)相和Fe_(2)O_(3)相;随着氧化时间的延长,氧化物的含量增大,表面硬度增大,最大可达1012 HV_(0.05),改性层的有效硬化层厚度约为200μm;在防腐耐磨方面,渗氮层和渗氮-氧化复合改性层的耐磨性和耐蚀性均显著提高,且短时间氧化的复合改性层具有更好的耐磨性和耐蚀性。展开更多
The utilization of graded Al powders offers the possibility to adjust the combustion performance of Al powders,while simultaneously safeguarding their energy properties.In this paper,a series of graded Al powder have ...The utilization of graded Al powders offers the possibility to adjust the combustion performance of Al powders,while simultaneously safeguarding their energy properties.In this paper,a series of graded Al powder have been incorporated into the typical Al@AP composites through the spray drying technique.The thermal behavior,ignition and combustion characteristics were comprehensively evaluated and compared.The experimental results showed that with the varying inclusion of the graded Al,the heat of reaction exhibited a significant change,ranging from 9090 J·g^(-1) to 11036 J·g^(-1),which was strongly dependent on the particle size of Al.The combination of Al with diverse range of particle sizes in graded configuration serves to significantly enhance the decomposition of AP,resulting in the disappearance of the LTD stage and a conspicuous decrease of at least 11.7℃ in the peak temperature of the HTD.Furthermore,the maximum burning rate achieved by the Al-3@AP composite was 33.6 mm·s^(-1),which was exactly twice as high as that of the graded Al-1@AP composite with the lowest burning rate.Diffraction peaks corresponding to unburned Al were detected in the condensed combustion products of Al-1@AP,and the combustion images clearly indicated an incomplete combustion tendency for this sample.In contrast,a well-designed gradation of Al powders,such as a combination of fine Al powders with a particle size below 5μm,has proven to be the most conducive to enhancing the combustion efficiency of the composites.展开更多
基金Projects(J21103045,J1210040,J1103312) supported by the National Natural Science Foundation of ChinaProject supported by the Fundamental Research Funds for the Central Universities of China
文摘Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.
基金the support for this work by National Natural Science Foundation of China(Grant Nos.22175139 and 22105156)。
文摘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.
文摘The core-shell 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane/2,4,6-Trinitrotoluene(CL-20/TNT)composite was prepared by spray-drying method in which sensitive high energy explosive(CL-20)was coated with insensitive explosive(TNT).The structure and properties of different formulations of CL-20/TNT composite and CL-20/TNT mixture were characterized by scanning electron microscopy(SEM),Transmission electron microscopy(TEM),Laser particle size analyzer,X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD),differential scanning calorimetry(DSC),impact sensitivity test and detonation performance.The results of SEM,TEM,XPS and XRD show that e-CL-20 particles are coated by TNT.When the ratio of CL-20/TNT is 75/25,core-shell structure is well formed,and thickness of the shell is about 20e30 nm.And the analysis of heat and impact show that with the increase of TNT content,the TNT coating on the core-shell composite material can not only catalyze the thermal decomposition of core material(CL-20),but also greatly reduce the impact sensitivity.Compared with the CL-20/TNT mixture(75/25)at the same ratio,the characteristic drop height of core-shell CL-20/TNT composite(75/25)increased by 47.6%and the TNT coating can accelerate the nuclear decomposition in the CL-20/TNT composites.Therefore,the preparation of the core-shell composites can be regarded as a unique means,by which the composites are characterized by controllable decomposition rate,high energy and excellent mechanical sensitivity and could be applied to propellants and other fields.
基金Project(51961003)supported by the National Natural Science Foundation of ChinaProject(NGY2018-148)supported by the Science and Technology Research of Ningxia Colleges,ChinaProject(NZ16083)supported by Key Program of Natural Science Foundation of Ningxia,China
文摘In order to improve the hot corrosion resistance of DZ125 alloy,Ce-Y modified aluminum coatings were prepared on DZ125 alloy by pack cementation process at 950°C for 2 h.The microstructure,phase constitution and formation mechanism of the coatings were investigated.The hot corrosion behaviors of DZ125 alloy and the coatings in molten salt environment of 25%K2SO4+75%Na2SO4(mass fraction)at 900°C were studied.Results show that the obtained Al-Ce-Y coatings were mainly composed of Al3Ni2,Al3Ni and Cr7Ni3,with a thickness of about 120μm.After hot corrosion test,DZ125 alloy suffered catastrophic hot corrosion and serious internal oxidation and internal sulfidation arose.Two layers of corrosion products formed on surfaces of DZ125 alloy,including the outer layer consisting of Cr2O3 and NiCr2O4,and the inner layer of Al2O3,Ni3S2 and Ni-base solid solution.After being coated with Al-Ce-Y coating,the hot corrosion resistance of DZ125 alloy is improved notably,due to the formation of a dense scale mainly consisting of Al-rich Al2O3 in the coating layer.
基金This work was supported by the National Natural Science Foundation of China(No.51571033,11804022)the Science and Technology on Transient Impact Laboratory Foundation(No.6142606183208).
文摘A facile and economical approach was developed for the large-scale production of powdered core-shell structured PTFE/Al (CS-PA) energetic materials through ultrasonic-assisted mixing. The low-cost micrometer-sized PTFE and Al particles were used as starting materials. Under high-power ultrasonic waves, the PTFE powder was dispersed into nano-to sub-micrometer-sized particles and then encapsulated the Al microparticles to form the core-shell structure. The heat of combustion, burning rate, and pressurization rate of the powdered CS-PA were measured. The thermal-initiated reaction behavior was further evaluated using thermogravimetry-differential scanning calorimetry. Subsequently, the bulk CS-PA with a uniform microstructure was obtained via cold isostatic pressing of the powdered CS-PA followed by vacuum sintering. For the bulk CS-PA, the quasi-static compression behavior was characterized, and the impact-initiated reaction processes were conducted using the Split Hopkinson Pressure Bar (SHPB) and evaluated by a high-speed camera. Compared to physically mixed PTFE/Al materials, the powdered and bulk CS-PA demonstrated enhanced thermal- and impact-initiated reaction characteristics respectively, proving the effectiveness of our approach for constructing core-shell structures.
文摘Broadband near-infrared(NIR)luminescent materials have shown great promise in applications such as optical communication,biomedicine,and optoelectronic devices.However,the current research is focused on phos⁃phors and glasses,and it is important to develop broadband NIR luminescent nanomaterials.Here,we report an erbi⁃um-sensitized core-shell nanocrystal design for broadband NIR emission.Based on the structural design with suitable dopings of Tm^(3+)and Ho^(3+),the broadband NIR emission covering 1.5-2.1μm region is achieved under 980 nm and 808 nm excitations.Moreover,the emission intensity is further enhanced by introducing Yb^(3+)and Nd^(3+)into the sam⁃ple,respectively,and the energy transfer processes between them are systematically discussed.Our results present a novel approach for developing broadband NIR luminescent materials and devices.
文摘本文以30Cr Mn Si A结构钢为研究对象,利用低温等离子体渗氮及低温渗氮-低温氧化复合技术对其进行表面改性研究,重点研究了氧化时间对渗氮30Cr Mn Si A钢表面组织结构和性能的影响。采用扫描电子显微镜、X射线衍射仪分析渗氮层及渗氮-氧化复合改性层的表面形貌、截面组织和相结构;利用维氏硬度计、摩擦磨损试验机和电化学工作站对渗氮层及复合改性层的硬度、耐磨性和耐蚀性进行评价。结果表明,渗氮层表面主要由ε-Fe_(23)N、γ'-Fe_(4)N和α_N相组成,经不同时间的氧化处理后,渗氮层表面生成Fe_(3)O_(4)相和Fe_(2)O_(3)相;随着氧化时间的延长,氧化物的含量增大,表面硬度增大,最大可达1012 HV_(0.05),改性层的有效硬化层厚度约为200μm;在防腐耐磨方面,渗氮层和渗氮-氧化复合改性层的耐磨性和耐蚀性均显著提高,且短时间氧化的复合改性层具有更好的耐磨性和耐蚀性。
文摘The utilization of graded Al powders offers the possibility to adjust the combustion performance of Al powders,while simultaneously safeguarding their energy properties.In this paper,a series of graded Al powder have been incorporated into the typical Al@AP composites through the spray drying technique.The thermal behavior,ignition and combustion characteristics were comprehensively evaluated and compared.The experimental results showed that with the varying inclusion of the graded Al,the heat of reaction exhibited a significant change,ranging from 9090 J·g^(-1) to 11036 J·g^(-1),which was strongly dependent on the particle size of Al.The combination of Al with diverse range of particle sizes in graded configuration serves to significantly enhance the decomposition of AP,resulting in the disappearance of the LTD stage and a conspicuous decrease of at least 11.7℃ in the peak temperature of the HTD.Furthermore,the maximum burning rate achieved by the Al-3@AP composite was 33.6 mm·s^(-1),which was exactly twice as high as that of the graded Al-1@AP composite with the lowest burning rate.Diffraction peaks corresponding to unburned Al were detected in the condensed combustion products of Al-1@AP,and the combustion images clearly indicated an incomplete combustion tendency for this sample.In contrast,a well-designed gradation of Al powders,such as a combination of fine Al powders with a particle size below 5μm,has proven to be the most conducive to enhancing the combustion efficiency of the composites.
