The spread of perfluoropolyether （PFPE） droplets on solid surfaces has been measured from the top-down view through a microscope system. Effects of substrates, molecular weight and end-group functionality on spreadi...The spread of perfluoropolyether （PFPE） droplets on solid surfaces has been measured from the top-down view through a microscope system. Effects of substrates, molecular weight and end-group functionality on spreading of the PFPE droplets have been studied experimentally and the results were compared with those by molecular dynamics （MD） simulations. Silicon wafer and diamond-like carbon （DLC） substrates were used to study the effect of substrates on spreading. Two types of PFPE, Z-dol and Z-tetraol, with the same chain structure and various molecular weights （2000 and 4000 g/mol） were employed in experiments. Effect of molecular weight has been investigated through comparing the spreading of Z-dol 2000 and Z-dol 4000, and it is found that the increase of molecular weight will decrease the mobility of PFPE. Comparison between spreading of Z-dol and Z-tetraol of the same molecular weight proved that functional end group plays a significant role on the spreading of PFPE, which confirmed the MD simulation results.展开更多
The geometries of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2 radicals were investigated by density functional theory（DFT） method. The calculated results indicate that all the three radicals have pyramidal shapes at their cen...The geometries of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2 radicals were investigated by density functional theory（DFT） method. The calculated results indicate that all the three radicals have pyramidal shapes at their centers, and the aC is one top of the pyramids. Based on the DFT optimized geometries, the hyperfine coupling constants（hfec＇s） of the 19F atoms of the three radicals were calculated by B3LYP, MP2（full） and QCISD（full） methods. The calculated values agree with the experimental values, especially for the a values of Fa, the a values are 125.6× 10 -4, 104.2× 10 - 4, and 83.2×10 -4 T of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2, respectively. These results better explain the experimental observation.展开更多
The Z-type ferrites of nominal composition Ba3Co2 Fe24O41+x wt% Bi2O3, where x=0.25, 0.5, 1.0, 1.5, 2.0, were prepared by conventional ceramic processes. The influence of Bi2O3 content on the bulk densities, microstru...The Z-type ferrites of nominal composition Ba3Co2 Fe24O41+x wt% Bi2O3, where x=0.25, 0.5, 1.0, 1.5, 2.0, were prepared by conventional ceramic processes. The influence of Bi2O3 content on the bulk densities, microstructures, magnetic and dielectric properties of Z-type ferrite samples were systematically examined so as to obtain materials with low magnetic and dielectric loss tangent over a frequency ranging from 600 to 800 MHz. The experimental results showed that addition of Bi2O3 lowered the sintering temperature(1 020 ℃) and then reduced the average grain size(<2 μm) and enhanced the resistivity(>2.68×10^8 Ω·cm) dramatically, which consequently decreased the magnetic and dielectric loss. Additionally, the low loss factors were observed at the Bi2O3 content x = 1.0, i e, tan δμ/μ’=0.013 and tan δε/ε’= 0.001 at 800 MHz, and such materials could be used for antennas miniaturization from 600 to 800 MHz.展开更多
Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resu...Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resulting in a large amount of radioactive waste PFPE lubricants annually.Moreover,radioactive waste PFPE lubricants are difficult to be effectively treated due to their high stability,the risk of possible leakage of radionuclides,and hypertoxic fluorine-containing by-products.In this study,without any precedent,a strategy of Mn O_(2)-catalyzed decomposition and Na_(2)CO_(3)-immobilized conversion was proposed for PFPE lubricant decomposition and fluorine immobilization simultaneously based on the Lewis acid-base and oxygen vacancies concept.A high fluorine conversion efficiency of 95.4%was achieved.Meanwhile,the mechanism of decomposition suggested that Mn O_(2)mainly provided Lewis acid sites and attacked the(basic)fluorine or oxygen atoms in PFPE molecules.The decomposition of PFPE chains was proceed down and volatile fluorine-containing gas was released by partial electron transfer,intramolecular disproportionation reaction,and unzipping fashion.Subsequently,gas by-products could be further oxidized and then immobilized into fluoride salts by carbonate solid absorbents.Overall,this study provides a simple,safe,and potentially practical strategy for the harmless conversion of refractory fluorinated organic wastes,especially perfluoropolymers.展开更多
基金Project supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No20060003025)the State Key Development Program for Basic Research of China(Grant No2003CB716201)
文摘The spread of perfluoropolyether （PFPE） droplets on solid surfaces has been measured from the top-down view through a microscope system. Effects of substrates, molecular weight and end-group functionality on spreading of the PFPE droplets have been studied experimentally and the results were compared with those by molecular dynamics （MD） simulations. Silicon wafer and diamond-like carbon （DLC） substrates were used to study the effect of substrates on spreading. Two types of PFPE, Z-dol and Z-tetraol, with the same chain structure and various molecular weights （2000 and 4000 g/mol） were employed in experiments. Effect of molecular weight has been investigated through comparing the spreading of Z-dol 2000 and Z-dol 4000, and it is found that the increase of molecular weight will decrease the mobility of PFPE. Comparison between spreading of Z-dol and Z-tetraol of the same molecular weight proved that functional end group plays a significant role on the spreading of PFPE, which confirmed the MD simulation results.
基金Supported by the Major State Basic Research Development Programs of China(No2007CB815206)the National Natural Science Foundation of China(Nos20873010, 20720102038)the Fundamental Research Funds for the Central Universities of China
文摘The geometries of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2 radicals were investigated by density functional theory（DFT） method. The calculated results indicate that all the three radicals have pyramidal shapes at their centers, and the aC is one top of the pyramids. Based on the DFT optimized geometries, the hyperfine coupling constants（hfec＇s） of the 19F atoms of the three radicals were calculated by B3LYP, MP2（full） and QCISD（full） methods. The calculated values agree with the experimental values, especially for the a values of Fa, the a values are 125.6× 10 -4, 104.2× 10 - 4, and 83.2×10 -4 T of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2, respectively. These results better explain the experimental observation.
基金Funded by the National Natural Science Foundation of China(No.U1435209)Wuhan Science and Technology Program(No.2014010101010018)Fundamental Research Funds for the Central Universities(No.2015ZZGH007)
文摘The Z-type ferrites of nominal composition Ba3Co2 Fe24O41+x wt% Bi2O3, where x=0.25, 0.5, 1.0, 1.5, 2.0, were prepared by conventional ceramic processes. The influence of Bi2O3 content on the bulk densities, microstructures, magnetic and dielectric properties of Z-type ferrite samples were systematically examined so as to obtain materials with low magnetic and dielectric loss tangent over a frequency ranging from 600 to 800 MHz. The experimental results showed that addition of Bi2O3 lowered the sintering temperature(1 020 ℃) and then reduced the average grain size(<2 μm) and enhanced the resistivity(>2.68×10^8 Ω·cm) dramatically, which consequently decreased the magnetic and dielectric loss. Additionally, the low loss factors were observed at the Bi2O3 content x = 1.0, i e, tan δμ/μ’=0.013 and tan δε/ε’= 0.001 at 800 MHz, and such materials could be used for antennas miniaturization from 600 to 800 MHz.
基金Sichuan Science and Technology Program (No.2021YJ0482)the Fundamental Research Funds for the Central Universities (No.2021SCU12087)。
文摘Perfluoropolyether(PFPE)lubricants are a kind of high-molecular polymer with many excellent properties.However,the use of PFPEs in the nuclear industry can lead to partial decomposition and carrying radionuclides,resulting in a large amount of radioactive waste PFPE lubricants annually.Moreover,radioactive waste PFPE lubricants are difficult to be effectively treated due to their high stability,the risk of possible leakage of radionuclides,and hypertoxic fluorine-containing by-products.In this study,without any precedent,a strategy of Mn O_(2)-catalyzed decomposition and Na_(2)CO_(3)-immobilized conversion was proposed for PFPE lubricant decomposition and fluorine immobilization simultaneously based on the Lewis acid-base and oxygen vacancies concept.A high fluorine conversion efficiency of 95.4%was achieved.Meanwhile,the mechanism of decomposition suggested that Mn O_(2)mainly provided Lewis acid sites and attacked the(basic)fluorine or oxygen atoms in PFPE molecules.The decomposition of PFPE chains was proceed down and volatile fluorine-containing gas was released by partial electron transfer,intramolecular disproportionation reaction,and unzipping fashion.Subsequently,gas by-products could be further oxidized and then immobilized into fluoride salts by carbonate solid absorbents.Overall,this study provides a simple,safe,and potentially practical strategy for the harmless conversion of refractory fluorinated organic wastes,especially perfluoropolymers.
