張志東研究員申報2011年度遼寧省自然科學(xué)獎材料

PAGEPAGE15張志東研究員申報2011年度遼寧省自然科學(xué)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(xué)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(shù)十種新型磁性納米膠囊。

發(fā)明了控制反應(yīng)氣氛制備碳、硼包裹等磁性納米膠囊的方法。發(fā)現(xiàn)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(jié)構(gòu)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(jié)構(gòu)。還發(fā)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(jié)構(gòu)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(jié)構(gòu)、相轉(zhuǎn)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(fā)現(xiàn)在具有殼-核結(jié)構(gòu)的磁性納米顆粒中存在非傳統(tǒng)的交換偏置、超順磁性等效應(yīng)。報導(dǎo)了磁性納米膠囊具有優(yōu)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(fù)合材料的微波吸收機理。開辟了制備和應(yīng)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(xué)術(shù)刊物上發(fā)表論文94篇，被同行在國際學(xué)術(shù)刊物上1016余篇次引用（統(tǒng)計至2011年4月）。應(yīng)邀為國際專著Encyclopedia

of

Nanoscience

and

Nanotechnology撰寫納米膠囊章節(jié)、為J.

Mater.

Sci.

Tech.撰寫磁性納米膠囊的綜述報告。完成人及其學(xué)術(shù)貢獻張志東，負(fù)責(zé)項目的總體設(shè)計和運行，課題申請，國際合作項目的申請和執(zhí)行。提出一系列創(chuàng)新學(xué)術(shù)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(xì)研究了納米膠囊的形貌、平均尺寸、晶格常數(shù)、表面狀態(tài)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(jié)構(gòu)、相轉(zhuǎn)變過程和磁性進行了研究。分析相的相轉(zhuǎn)變機理和各類相之間的關(guān)系，找出影響其結(jié)構(gòu)熱穩(wěn)定性的關(guān)鍵因素。根據(jù)獲得的微觀結(jié)構(gòu)和成分的實驗觀察結(jié)果構(gòu)建納米膠囊殼-核結(jié)構(gòu)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(yīng)、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(fā)現(xiàn)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(jié)構(gòu)，從而增強了抗氧化性和磁性。在傳統(tǒng)氣-液-固（Vapour-Liquid-Solid，VLS）機制的基礎(chǔ)上，提出一種對傳統(tǒng)VLS機制的擴充概念??“定量氧輔助VLS”機制。制備和研究了數(shù)種“核/殼”型納米結(jié)構(gòu)，包括碳材料、異質(zhì)金屬氧化物、聚合物“殼”層包覆各類金屬合金“核”復(fù)合粒子，對其物理化學(xué)制備方法、形成規(guī)律、微結(jié)構(gòu)及特性進行系統(tǒng)研究。以“核/殼”型結(jié)構(gòu)作為磁性、介電損耗材料的復(fù)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(fā)明一種利用不同金屬的熔點和蒸汽壓不同制備異質(zhì)合金納米膠囊的技術(shù)，先后成功制備了Al2O3包覆Fe納米膠囊等,為發(fā)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(xué)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(qū)體為原料，蒸發(fā)、熱解形成原子（離子）態(tài)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(xiàn)出從鐵磁性到超順磁性的變化過程，并構(gòu)造出不同類型的殼/核結(jié)構(gòu)。在Co/C納米膠囊中發(fā)現(xiàn)CoC2納米粒子的存在，CoC2現(xiàn)在已經(jīng)發(fā)展成為一種新型不含稀土的永磁材料，成為國際學(xué)術(shù)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(zhì)納米膠囊。利用后續(xù)高溫反應(yīng)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(fā)現(xiàn)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(tǒng)的交換偏置現(xiàn)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(fā)表時間年月通訊作者/第一責(zé)任人SCI他引次數(shù)他引總次數(shù)是否國內(nèi)完成1Microwaveabsorptionpropertiesofthecarbon-coatednickelnanocapsules,Appl.Phys.Lett.

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