PAGEPAGE15張志東研究員申報2011年度遼寧省自然科學獎材料項目名稱磁性納米膠囊的制備、磁性和電磁性能研究推薦單位（或推薦專家）中科院金屬研究所（都有為院士,葉恒強院士,李依依院士）項目簡介本項目用直流電弧等離子體法、化學氣相冷凝法等在不同氣氛中制備出Fe-Ni(C)、Fe-Co(C)、Fe(B)@BO、B@BN、Dy@C、α-Fe@Al2O3、Mn@MnO、WS2、Dy@Dy2O3、GdAl2@Al2O3、Fe@BN等數十種新型磁性納米膠囊。

發明了控制反應氣氛制備碳、硼包裹等磁性納米膠囊的方法。發現甲烷中的碳分解在過渡金屬超微顆粒的表面形成保護層從而形成了具有核－殼層結構的納米膠囊，從而增強了超微顆粒的抗氧化性和磁性。乙硼烷中的硼分解在過渡金屬超微顆粒的表面形成氧化硼殼層結構。還發明了利用不同元素熔點、定量氧輔助氣-液-固機制制備合金納米膠囊的方法，特別是成功合成稀土-過渡金屬化合物的納米膠囊。用高分辨電鏡對各種納米膠囊的殼－核結構進行表征和對比，研究其生長機制以及形成機理。成功地將無序的納米膠囊自組裝成新型三維珊瑚狀的宏觀聚集體。對形成的納米膠囊中的不同的相結構、相轉變過程和介觀磁性進行了研究。研究各種納米膠囊的磁性交換耦合、交換各向異性、超順磁性、自旋排列等介觀磁性。發現在具有殼-核結構的磁性納米顆粒中存在非傳統的交換偏置、超順磁性等效應。報導了磁性納米膠囊具有優秀的電磁吸收和磁致冷性能。研究“核/殼”型納米膠囊及其改性納米復合材料的微波吸收機理。開辟了制備和應用各種新型納米膠囊的新方法和新途徑。

納米膠囊的工作在國際學術刊物上發表論文94篇，被同行在國際學術刊物上1016余篇次引用（統計至2011年4月）。應邀為國際專著Encyclopedia

of

Nanoscience

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Nanotechnology撰寫納米膠囊章節、為J.

Mater.

Sci.

Tech.撰寫磁性納米膠囊的綜述報告。完成人及其學術貢獻張志東，負責項目的總體設計和運行，課題申請，國際合作項目的申請和執行。提出一系列創新學術思想。采用氣體硼源（乙硼烷）制備出氧化硼包覆金屬納米膠囊，用X射線衍射、電子能譜儀、X射線光電子譜儀、高分辨電子顯微鏡詳細研究了納米膠囊的形貌、平均尺寸、晶格常數、表面狀態等。用穆斯堡爾譜等手段分析了納米膠囊中存在的不同相組成。對形成的納米膠囊中的不同的相的結構、相轉變過程和磁性進行了研究。分析相的相轉變機理和各類相之間的關系，找出影響其結構熱穩定性的關鍵因素。根據獲得的微觀結構和成分的實驗觀察結果構建納米膠囊殼-核結構的模型。分析在不同氣氛條件下制備的金屬納米膠囊的形成機制。研究納米膠囊的超順磁性、交換耦合、磁熵變效應、電磁波吸收等。董星龍，直接利用甲烷、乙硼烷等氣體中的原子合成了過渡金屬和合金的磁性納米膠囊。發現甲烷中的碳在過渡金屬超微顆粒的表面形成一層保護層從而形成了一種特殊的核－殼層結構，從而增強了抗氧化性和磁性。在傳統氣-液-固（Vapour-Liquid-Solid，VLS）機制的基礎上，提出一種對傳統VLS機制的擴充概念??“定量氧輔助VLS”機制。制備和研究了數種“核/殼”型納米結構，包括碳材料、異質金屬氧化物、聚合物“殼”層包覆各類金屬合金“核”復合粒子，對其物理化學制備方法、形成規律、微結構及特性進行系統研究。以“核/殼”型結構作為磁性、介電損耗材料的復合形式，研究微波損耗特性，開拓新型納米微波吸收劑的新途徑。耿殿雨，發明一種利用不同金屬的熔點和蒸汽壓不同制備異質合金納米膠囊的技術，先后成功制備了Al2O3包覆Fe納米膠囊等,為發展其它類型的Al2O3包覆過渡金屬納米膠囊,Al2O3包覆稀土過渡金屬化合物納米膠囊以及ZnO包覆過渡金屬納米膠囊等開辟了道路.

參與利用乙醇等制備出碳包覆過渡金屬納米膠囊、碳包覆稀土金屬納米膠囊等工作。參與磁性納米膠囊的電磁性能研究。王振華，將化學氣相冷凝法用于制備Fe/C、FeCo/C、Co/C金屬納米粒子/膠囊，即以有機金屬前驅體為原料，蒸發、熱解形成原子（離子）態金屬，液氮冷凝后形成小顆粒金屬納米粒子。通過不同制備工藝制備出不同平均尺寸磁性金屬納米粒子，展現出從鐵磁性到超順磁性的變化過程，并構造出不同類型的殼/核結構。在Co/C納米膠囊中發現CoC2納米粒子的存在，CoC2現在已經發展成為一種新型不含稀土的永磁材料，成為國際學術界的熱點。司平占，用酒精制備碳包覆金屬納米膠囊，并合成稀土單質納米膠囊。利用后續高溫反應制備出氮化硼納米膠囊、WS2包裹W的納米膠囊、MoS2包裹Mo/MoO2和WS2包裹CoS/CoO的納米膠囊等。發現在反鐵磁相的奈爾溫度高于鐵磁相的居里溫度的殼核Mn/

MnO/

Mn3O4納米顆粒體系中存在非傳統的交換偏置現象。論文、論著目錄序號論文名稱/刊名/作者影響因子年卷頁碼發表時間年月通訊作者/第一責任人SCI他引次數他引總次數是否國內完成1Microwaveabsorptionpropertiesofthecarbon-coatednickelnanocapsules,Appl.Phys.Lett.

ZhangXF,DongXL,HuangH,LiuYY,WangWN,ZhuXG,LvB,LeiJP,andLeeCG3.552006,

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