Cis-trans isomerization of [9]-annulenanion（1） and its 2-fluoro-,2-chloro-and 2-bromo-derivatives（2,3 and 4,respectively） were investigated at the HF/6-31G＊ and B3LYP/6-311＋＋G＊＊ levels of theory.Cis,cis,cis,c...Cis-trans isomerization of [9]-annulenanion（1） and its 2-fluoro-,2-chloro-and 2-bromo-derivatives（2,3 and 4,respectively） were investigated at the HF/6-31G＊ and B3LYP/6-311＋＋G＊＊ levels of theory.Cis,cis,cis,cis structures appear more stable than their corresponding cis,cis,cis,trans-isomers.The relative height of energy barriers for cis-trans isomerization is：2cis 〉1cis 〉3cis〉 4cis.This trend for the reverse trans-cis isomerization follows the electronegativity of the substituent at C-2（2trans 3trans 4trans 1trans）.展开更多
To shield TiAl alloy from hot corrosion attack,a compact protective coating was fabricated by the combination of aluminizing,anodization and pre-oxidation.The hot corrosion behavior of the coated-TiAl specimen was inv...To shield TiAl alloy from hot corrosion attack,a compact protective coating was fabricated by the combination of aluminizing,anodization and pre-oxidation.The hot corrosion behavior of the coated-TiAl specimen was investigated in the mixture salt consisting of 75 wt.%Na2SO4 and 25 wt.%NaCl at 700°C.Results indicated that the anodization and pre-oxidation were beneficial to the generation of Al2O3 layer,which could act as a diffusion barrier to prevent the molten salts and oxygen from diffusing into the alloy during exposure to a hot corrosion environment while the aluminizing coating could provide sufficient aluminum source to support the continuous formation of Al2O3 layer.Moreover,the internal stress of the coating was reduced due to the formation of a gradient coating consisting of TiAl3 and TiAl2.展开更多
The hot corrosion behavior of Ti45 A18.5 Nb alloy was studied in the salt of Na_(2)SO_(4)and/or NaCl at 700℃.To improve the hot corrosion resistance,Ti45 A18.5 Nb alloy was anodized in fluorine-containing solution an...The hot corrosion behavior of Ti45 A18.5 Nb alloy was studied in the salt of Na_(2)SO_(4)and/or NaCl at 700℃.To improve the hot corrosion resistance,Ti45 A18.5 Nb alloy was anodized in fluorine-containing solution and pre-oxidized in air.Results showed that the combination of anodization and pre-oxidation can efficiently enhance the hot corrosion resistance of Ti45 A18.5 Nb alloy contaminated with Na_(2)SO_(4)or Na_(2)SO_(4)+NaCl deposits.This is because anodization and pre-oxidation result in the formation of compact AlOlayer which can act as a diffusion barrier to prevent sulfur,chlorine,and oxygen from attacking the alloy,therefore providing good resistance against hot corrosion.When exposed to NaCl deposit,however,no obvious improvement was achieved on the hot corrosion behavior no matter the alloy was anodized or further pre-oxidized in air.展开更多
The iodine-catalyzed nucleophilic addition reactions of pyrrole, furan, or thiophene with acetone were studied in gas and solvent by the density functional theory at the level of Lanl2DZ^＊. It was seen that the halog...The iodine-catalyzed nucleophilic addition reactions of pyrrole, furan, or thiophene with acetone were studied in gas and solvent by the density functional theory at the level of Lanl2DZ^＊. It was seen that the halogen bond between iodine and carbonyl oxygen appeared to have an important catalytic effect on such reactions, and the first iodine molecule maximally diminished the barrier height by 41 kJ/mol, while the second iodine molecule could not improve such reactions largely. It was concluded that the C2-addition was generally more favorable than the C3-addition for the three heterocycles; however, iodine considerably more effectively catalyzed the C3-addition than the C2-addition for pyrrole. It was also revealed by PCM calculation that the iodine-catalyzed nucleophilic additions occurred more easily in solvent than in gas, which explained the experiment performed by Bandgar et al..展开更多
文摘Cis-trans isomerization of [9]-annulenanion（1） and its 2-fluoro-,2-chloro-and 2-bromo-derivatives（2,3 and 4,respectively） were investigated at the HF/6-31G＊ and B3LYP/6-311＋＋G＊＊ levels of theory.Cis,cis,cis,cis structures appear more stable than their corresponding cis,cis,cis,trans-isomers.The relative height of energy barriers for cis-trans isomerization is：2cis 〉1cis 〉3cis〉 4cis.This trend for the reverse trans-cis isomerization follows the electronegativity of the substituent at C-2（2trans 3trans 4trans 1trans）.
基金The authors are grateful for the financial supports from the National Natural Science Foundation of China(51971205)Shenzhen Science and Technology Innovation Program,China(JCYJ20190807154005593)the Fundamental Research Funds for the Central Universities,China(19lgpy20).
文摘To shield TiAl alloy from hot corrosion attack,a compact protective coating was fabricated by the combination of aluminizing,anodization and pre-oxidation.The hot corrosion behavior of the coated-TiAl specimen was investigated in the mixture salt consisting of 75 wt.%Na2SO4 and 25 wt.%NaCl at 700°C.Results indicated that the anodization and pre-oxidation were beneficial to the generation of Al2O3 layer,which could act as a diffusion barrier to prevent the molten salts and oxygen from diffusing into the alloy during exposure to a hot corrosion environment while the aluminizing coating could provide sufficient aluminum source to support the continuous formation of Al2O3 layer.Moreover,the internal stress of the coating was reduced due to the formation of a gradient coating consisting of TiAl3 and TiAl2.
基金supported by the National Natural Science Foundation of China(No.51971205)the Guangdong Basic and Applied Basic Research Foundation(No.2021B1515020056)the Basic Research Project of Shenzhen Science and Technology Innovation Program(No.JCYJ20190807154005593)。
文摘The hot corrosion behavior of Ti45 A18.5 Nb alloy was studied in the salt of Na_(2)SO_(4)and/or NaCl at 700℃.To improve the hot corrosion resistance,Ti45 A18.5 Nb alloy was anodized in fluorine-containing solution and pre-oxidized in air.Results showed that the combination of anodization and pre-oxidation can efficiently enhance the hot corrosion resistance of Ti45 A18.5 Nb alloy contaminated with Na_(2)SO_(4)or Na_(2)SO_(4)+NaCl deposits.This is because anodization and pre-oxidation result in the formation of compact AlOlayer which can act as a diffusion barrier to prevent sulfur,chlorine,and oxygen from attacking the alloy,therefore providing good resistance against hot corrosion.When exposed to NaCl deposit,however,no obvious improvement was achieved on the hot corrosion behavior no matter the alloy was anodized or further pre-oxidized in air.
基金the Natural Science Foundation of Zhejiang Province,China(No.Y406374)
文摘The iodine-catalyzed nucleophilic addition reactions of pyrrole, furan, or thiophene with acetone were studied in gas and solvent by the density functional theory at the level of Lanl2DZ^＊. It was seen that the halogen bond between iodine and carbonyl oxygen appeared to have an important catalytic effect on such reactions, and the first iodine molecule maximally diminished the barrier height by 41 kJ/mol, while the second iodine molecule could not improve such reactions largely. It was concluded that the C2-addition was generally more favorable than the C3-addition for the three heterocycles; however, iodine considerably more effectively catalyzed the C3-addition than the C2-addition for pyrrole. It was also revealed by PCM calculation that the iodine-catalyzed nucleophilic additions occurred more easily in solvent than in gas, which explained the experiment performed by Bandgar et al..
