(1. 集美大學(xué) 輪機(jī)工程學(xué)院 福建省船舶與海洋工程重點(diǎn)實(shí)驗(yàn)室，廈門 361021；
2. 船舶檢測(cè)與再制造福建省高校工程研究中心，廈門 361021；
3. 大連理工大學(xué) 材料改性教育部重點(diǎn)實(shí)驗(yàn)室，大連 116024)
摘 要: 對(duì)鋁(Al)和二氨基馬來腈(C4H4N4)的混合物分別進(jìn)行等離子體輔助球磨和普通球磨，研究等離子體輔助球磨活化對(duì)合成AlN的作用機(jī)制。結(jié)果表明：相對(duì)于普通球磨，等離子體輔助球磨更有利于Al粉的晶粒細(xì)化和晶格畸變，并有利于形成Al-C4H4N4納米級(jí)的復(fù)合結(jié)構(gòu)。輔助球磨中的等離子體促進(jìn)C4H4N4的脫胺，使C4H4N4分解出更多的游離含N基團(tuán)，加速與活化的Al合成AlN，輔助球磨14 h后AlN的轉(zhuǎn)化率達(dá)到91%，遠(yuǎn)高于普通球磨合成AlN的產(chǎn)率83%。等離子體輔助球磨8 h的Al+C4H4N4前驅(qū)體發(fā)生氮化反應(yīng)的激活能為353.46 kJ/mol，在Ar中于800 ℃保溫1 h可以通過固-固反應(yīng)機(jī)制全部轉(zhuǎn)化為超細(xì)AlN，而普通球磨8 h的前驅(qū)體反應(yīng)激活能高達(dá)441.21 kJ/mol，Al需熔化后才能進(jìn)行氮化反應(yīng)，導(dǎo)致部分C4H4N4先行受熱分解蒸發(fā)，AlN產(chǎn)率僅為86%。輔助球磨促進(jìn)AlN合成的主要原因是等離子體放電的高頻脈沖轟擊和瞬態(tài)“電火花”對(duì)粉體產(chǎn)生協(xié)同球磨作用。
關(guān)鍵字: 二氨基馬來腈；AlN；等離子輔助球磨；固-固反應(yīng)；活化
（1. Fujian Provincial Key Laboratory of Naval Architecture and Ocean Engineering, Institute of Marine Engineering, Jimei University, Xiamen 361021, China;
2. Fujian Engineering Research Center of Ship Detecting and Remanufacturing, Xiamen 361021, China;
3. Key Lab of Materials Modification, Ministry of Education, Dalian University of Technology, Dalian 116024, China）
Abstract:The synthesis mechanism of AlN from diaminomaleonitrile (C4H4N4) and aluminum (Al) by using plasma assisted ball milling (PM) was investigated, in which the conventional ball milling (CM) was also used under the same conditions for comparison. The results indicate that PM is much more favorable for the grain refinement and lattice distortion of Al, as compared with that of CM, which promotes the synthesis of nanocomposite structure between Al and C4H4N4. During the process, the plasma formed in PM can promote the deammoniation of C4H4N4 to decompose much more free N-containing groups than that of the CM, which accelerates to react with the activated Al powders. After 14 h milling, the conversion rate of AlN by using PM method is up to 91%, which is much higher than the value of 83% in CM process. Furthermore, a lower nitriding reaction activation energy (353.46 kJ/mol) was obtained in the Al+C4H4N4 precursors by 8 h-PM process, which could achieve a full conversion temperature is about 800 ℃, but for the 8 h-CM process, a higher nitriding reaction activation energy (441.21 kJ/mol) needs a higher nitriding temperature in the Al+C4H4N4 precursors, leading to the melting of Al phase and evaporation of part of C4H4N4, and obviously reducing the conversion rate to 86%. The main synthesis mechanisms of AlN through the plasma assisted ball milling is a synergistic effect between high frequency pulse bombardment and transient “spark” on the powders by plasma discharge.
Key words: diaminomaleonitrile; AlN; plasma assisted ball milling; solid-solid reaction; activation
