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为了提高酚醛树脂的残炭率并优化热解炭的结构和性能,将 Ni(NO3)2·6H2 O 按1∶100的质量比掺入热固性酚醛树脂中制备 Ni 掺杂酚醛树脂,经200℃固化后,分别在不同气氛(埋炭和 Ar 气氛)和不同温度(600、800、1000和1200℃)下保温3 h 炭化,然后检测其残炭率,并借助差示扫描量热仪、X 射线衍射仪、能谱仪、扫描电镜、透射电镜表征其热分解特征及其热解炭的抗氧化性、物相组成和显微结构。结果表明:1)Ni 掺杂酚醛树脂在800和1000℃的残炭率均比未掺杂酚醛树脂的提高较多;2)随炭化温度的升高,Ni 掺杂酚醛树脂热解炭逐渐向石墨化碳结构方向演化;3)Ni 掺杂酚醛树脂经1000℃炭化形成的热解炭中有大量直径50~100 nm、长度可达几十微米的多壁碳纳米管;4)在 Ar 气氛中炭化更有利于碳纳米管的生成,并且热解炭具有更高的残炭率和结晶度;5)1200℃炭化形成的热解炭的抗氧化性显著提高,氧化峰值温度比未掺杂酚醛树脂的提高约84℃。

Ni-doped phenol resin was prepared with 1 100 mass ratio of Ni(NO3 )2 ·6H2 O to thermosetting phenol resin to optimize the structure and properties of pyrolytic carbon derived from phenol resin and in-crease its carbon yield.The specimens were cured at 200 ℃ and coked under different atmospheres (car-bon-embedded atmosphere and Ar atmosphere)and at different temperatures (600,800,1 000 and 1 200℃)for 3 h,respectively.The carbon yield was measured.Thermal decomposition characteristics of Ni-doped phenol resin,and the oxidation resistance,phase composition and microstructure of pyrolytic carbon were characterized by differential scanning calorimetry,X-ray diffraction,energy dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy.The results show that the carbon yield of Ni-doped phenol resin coked at 800 or 1 000 ℃ is increased significantly,compared with that without any dopants.The graphitization degree of pyrolytic carbon structure derived from Ni-doped phenol resin increa-ses with the increase of carbonization temperature.The massive multi-wall carbon nanotubes of 50 -100 nm in diameter and of micrometre scale in length are generated at 1 000 ℃.Compared with the carbon-em-bedded atmosphere,carbon nanotubes can be more easily generated under Ar atmosphere,resulting in higher carbon yield and degree of crystallinity of the pyrolytic carbon derived from Ni-doped phenol resin. The oxidation resistance of the pyrolytic carbon derived from Ni-doped phenol resin at 1 200 ℃ is improved significantly and its highest oxidation temperature is increased by about 84 ℃,compared with that from Ni free phenol resin.

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