CN108059193B - 一种埃洛石管内组装四氧化三铁纳米复合材料的制备方法 - Google Patents
一种埃洛石管内组装四氧化三铁纳米复合材料的制备方法 Download PDFInfo
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- CN108059193B CN108059193B CN201710540471.5A CN201710540471A CN108059193B CN 108059193 B CN108059193 B CN 108059193B CN 201710540471 A CN201710540471 A CN 201710540471A CN 108059193 B CN108059193 B CN 108059193B
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052621 halloysite Inorganic materials 0.000 title claims abstract description 55
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 45
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0018—Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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Abstract
本发明提供了一种埃洛石管内组装四氧化三铁制备纳米复合材料的方法,属于非金属矿物深加工技术领域。本发明制备方法包括四个步骤:(1)埃洛石矿物的预处理及扩管、提纯,(2)埃洛石管内改性,(3)以混合热液法制备Fe3O4纳米磁性颗粒,(4)真空浸渍得到埃洛石管内组装有纳米Fe3O4的复合材料。本发明所制备的埃洛石/Fe3O4复合材料没有剩余磁化强度和矫顽力,表现为典型的顺磁性能。该发明所制得的材料具有良好的生物相容性,产品开拓了矿物磁性材料在生物医药和复合磁性材料方面的应用前景。
Description
欧阳静,杨华明,穆大伟,郭斌斌,张毅
技术领域
本发明涉及一种矿物基复合功能材料的制备方法,尤其是以两步法在埃洛石管内组装纳米四氧化三铁颗粒的复合功能材料。
背景技术
埃洛石的化学组成为Al[Si2O5](OH)4·2H2O,属单斜晶系的含水层状结构硅酸盐矿物。呈直的管状形态,在透射电子显微镜(TEM)下呈天然的纳米中空管状形貌,管外径为50~100nm,内径为16~30nm,管长为几十到几百纳米不等。常用于制备高质量白色陶瓷材料,也有基于一些包括物理化学改性、表面以及结构修饰等方法使得埃洛石在复合聚合物填料、储氢基体和催化剂载体等方面有较好的应用前景,但在高新技术领域的应用技术还有待开发。埃洛石的表面和管内腔的性质有明显不同,所有的埃洛石管外部均是[SiO4]四面体,而内部则是[AlO6]八面体,决定了埃洛石具有生物相容性好、稳定性强和环境友好的特点,使得埃洛石在生物材料领域具有较大的开发潜力。
Fe3O4纳米粒子作为一种超顺磁性氧化物,具有可控的形状和尺寸,并且由于晶格内八面体位置的Fe2+和Fe3+之间发生电子传递,产生独特的电和磁特性,使用Fe3O4纳米粒子具有巨大的应用前景,广泛应用于铁磁流体、生物医学、磁共振成像(MRI)、磁分离等各个领域。但同时Fe3O4纳米粒子极易聚集,极大地阻碍了其应用,且在生物医用检测与分析领域,还需要以SiO2等表面包覆 Fe3O4纳米颗粒,以增强Fe3O4的生物相容性和表面吸附游离核酸的能力,但相关包覆材料的成本高、产品性能不稳定。
基于天然矿物(比如埃洛石、膨润土、海泡石等)具有较高的吸附能力、生物相容性好、但是没有磁性的特点,本发明利用矿物材料纳米结构的高吸附能力,结合Fe3O4纳米粒子的超顺磁性能特点,公开一种将磁性粒子负载在纳米管状矿物的内部管腔中的方法。本发明所获得的产品可以从根本上避免铁磁材料的团聚问题,同时,通过使用埃洛石矿物作为载体,有望同时解决吸附材料回收和磁性材料团聚的问题,极大降低材料的总体合成成本,获得具有高效、低毒的矿物基生物功能材料。
有关HNTs表面或内壁上组装磁性氧化物已有一定的报道。如郑鹏武等人 [Zheng,P.et al.Mater.Chem.Phys.,2015,151:14-17]利用带负电的尿酶负载到带电荷的HNTs内腔,尿酶催化尿素的水解,导致HNTs腔中的碱性环境,在HNTs 管内选择性合成了Fe3O4颗粒。Jia等[Jia,P.et al.Integ.Ferroelectr.,2011, 127(1):116-120]利用酸浸对HNTs进行扩孔,后在64℃氮气气氛下通过控制 FeCl3、Na2SO3和HNTs的重量比为4:0.13:1,连续搅拌并利用磁场分离重复纯化合成了Fe3O4/HNTs复合材料。其合成的Fe3O4颗粒尺寸为10~30nm,且大部分负载在HNTs外部。朱克诚等[Zhu,K.et al.Chem.Engineer.J.,2017, 311(3):236-246]通过浸渍和原位共沉淀在HNTs管内原位合成Fe3O4。但其反应时间较长,且颗粒尺寸不易控制。Ramin等[Ramin.R,et al.Appl.Clay Sci.,2017, 137:101-106]在N2气氛下将FeSO4·7H2O与注入放有埃洛石分散液的烧杯中,后将反应温度调节至60℃,逐滴加入稀释的氨水搅拌该溶液制备了Fe3O4,制备的埃洛石/Fe3O4复合材料中,Fe3O4主要负载在管外。基于以上文献调研,已公开的专利及文献中,涉及SiO2包覆Fe3O4、Fe3O4与埃洛石、蒙脱石等的复合材料已有报道,但主要是以Fe3O4在外表面的负载型为主,尚没有将全部的Fe3O4组装于矿物管内的成功例子。
本发明所公开的通过两步法在矿物管内组装Fe3O4磁性材料的合成技术,与现有资料报道的方法相比,具有明显的新颖性和原创性。本发明公开的新制备技术,有望扩宽矿物材料的应用领域,并提高磁性Fe3O4纳米材料的生物相容性、大幅降低包覆型Fe3O4纳米材料的合成成本。
发明内容
本发明涉及一种两步法实现埃洛石矿物管内负载Fe3O4纳米粒子的方法。首先将埃洛石原矿进行扩管径与管道内清洗,再选择性负载改性剂以便于纳米粒子的进入;通过简单的混合液相热高温分解方法制备单分散的均匀尺寸Fe3O4颗粒,并以适当改性剂将Fe3O4颗粒表面改性;最后通过真空浸渍的物理作用、以及电荷引导的化学作用,将单分散Fe3O4纳米粒子负载到改性的埃洛石纳米管中,一定温度下焙烧去除残留有机物,得到埃洛石管内负载Fe3O4的复合材料。其中的液相热分解方法与文献类似,主要以乙酰丙酮铁(Fe(acac)3)为铁源、油酸(OA)和油胺(OAm)为捕获剂、三辛基氧化磷(TOPO)为表面活性剂、十八烯(ODE)为溶剂,先合成平均粒径为4~5nm的单分散Fe3O4纳米粒子,通过添加保护剂的方法控制产物颗粒的粒径与形貌,并实现纳米粒子的表面改性;
本发明公开的一种以高温热分解辅助的两步法制备埃洛石管内组装Fe3O4纳米复合材料的方法,其具体制备步骤为:
步骤一、埃洛石矿物的预处理及提纯、扩管及管内接枝改性技术。先取一定埃洛石原矿分散在去离子水中,以混合酸溶液中搅拌并浸泡一定时间后,过滤、清洗至无离子残留,再离心收集,烘干。再以改性剂的溶液浸泡上述埃洛石粉末,离心收集、烘干后备用。
所述的混合酸为硝酸、磷酸、盐酸、醋酸等无机酸的混合溶液,浓度为0.6 mol/L,所述的浸泡时间为1~5h,烘干为60℃的烘箱中干燥。所述的改性剂为油酸钠、胺基硅烷、过硫酸胺、壳聚糖、磷酸二氢胺、多巴胺中的一种,所述的改性剂溶液浓度为0.1~1mol/L;
步骤二、以混合热液法制备Fe3O4纳米磁性颗粒。称量设计量的Fe(acac)3、量取高沸点溶剂分别装入三颈烧瓶中,放置在恒温加热套上恒速搅拌,使乙酰丙酮铁充分溶解在溶剂当中,再加入适量的保护剂。在氩气气氛下,将整个反应体系密封,加热至120℃,将装有三辛基氧化磷/油胺混合溶液和油酸溶液的注射器分别注入至三颈烧瓶中,继续将混合溶液加热至200℃~260℃,在此温度下保温2h~4h后,冷却至室温。得到均匀的单分散Fe3O4纳米颗粒的悬浊液。
所述的原料配比为Fe(acac)3:油胺:油酸:三辛基氧化磷的摩尔比,以 Fe(acac)3的量为基准,比例为1:4~16:4:0.1~1.0;所述的改性剂是聚乙二胺、聚乙醚、聚甲酸乙酯、十二烷基磺酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)、聚乙二醇(PEG)、聚乙烯吡咯烷酮(PVP)和油酸钠中的一种。所述的保护剂是十八烯、油胺和三甘醇中的一种;
步骤三、将步骤二制备的单分散Fe3O4分散液转移到真空烧瓶中,同时加入适量的经扩管、改性后的埃洛石粉体,使用磁力搅拌器搅拌0.5h后,使用真空泵抽真空30min,整个抽空过程重复三次。产物经离心分离后,再用酒精和丙酮混合液清洗,收集后烘干,得到埃洛石管内组装有纳米Fe3O4的复合材料;
步骤四、将步骤三制备的产物在一定温度的空气和氩气气氛炉中煅烧,最后获得埃洛石纳米管内组装有Fe3O4纳米粒子的复合磁性材料。
所述的气氛制度为:先在含5%空气的氩气气氛中焙烧30min以氧化有机物,再在氩气气氛中焙烧2h以保护Fe3O4不再被氧化,温度为280~350℃,升温速率为5℃/min,保温时间为1~2h。
本发明的有益效果是:
1、本发明通过典型的高温热分解方法,预先合成平均粒径为4~5nm的单分散Fe3O4纳米粒子。再通过真空浸渍法,将单分散Fe3O4负载到管径被扩大、管内表面被修饰改性的埃洛石纳米管中,得到埃洛石/Fe3O4复合材料。这是其它方法及文献中未有报道的思路。单分散Fe3O4纳米粒子可以被成功的组装在埃洛石管内,而在埃洛石的管外壁则由于未被改性,将没有Fe3O4纳米粒子沉积,因而极大提升了矿物基磁性材料的生物相容性。
2、本发明所制备的埃洛石/Fe3O4复合材料的磁饱和强度为2~20emu/g,没有剩余磁化强度和矫顽力,表现为典型的顺磁性能,在浅色复合磁性材料、生物医药领域具有较强的应用优势。
附图说明
图1是本发明实施例1所获得的埃洛石原矿、埃洛石/Fe3O4复合材料产品的 TEM图。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步说明本发明的内容,但本发明并不局限于以下实施例,有关技术领域的技术人员,在不脱离本发明精神和范围的情况下,还可以做出各种变化。因此,所有等同的技术方案也应该属于本发明的范畴,应由各权利要求限定。
实施例1
一种以高温热分解制备埃洛石管内组装Fe3O4纳米复合材料的方法,其具体制备步骤为:
步骤一、取10g埃洛石分散在500mL的去离子水中,在室温下磁力搅拌3 小时后得到混浊液,将其进行抽滤,对抽滤所得固体产物进行多次洗涤后,60℃的温度下烘干8小时,获得粗选埃洛石;
步骤二、将22mL的浓硝酸、14mL的浓硫酸、4g氯化铵以及2g氯化钠放入烧杯,往烧杯中加入714mL的去离子水,使用磁力搅拌器在60℃下搅拌 0.5h后,获得混合酸、强离子性盐等混合溶液备用;
步骤三、分别取750mL步骤三所制备的混合酸、强离子性盐等混合溶液和10g步骤一所得粗选埃洛石,放入烧杯中。在室温下磁力搅拌3h后得到混浊液,再抽滤后收集、清洗固体,60℃的温度下烘干,最终得到扩孔的白色埃洛石固体样品(A-HNTs),使用研钵研磨至过200目筛的粉末待用;
步骤四、称取3g壳聚糖加入到300mL的乙酸溶液(2wt%)中并搅拌直到壳聚糖完全溶解,然后将3g上述获得的A-HNTs粉末加入到壳聚糖溶液中,超声30min以得到均匀的混合液。60℃下连续搅拌2小时,之后离心收集固体,将固体加入到碳酸钠溶液(1M)中1小时,随后在300mL硼氢化钠溶液(0.2M) 中浸泡5小时。最后,通过离心收集,获得壳聚糖改性的埃洛石纳米管(CHNTs),并用去离子水洗涤三次。然后将CHNTS在60℃下干燥48小时,并在玛瑙研钵中研磨过200目筛;
步骤五、按Fe(acac)3:油胺:油酸和三辛基氧化磷的摩尔比为1:10:4:0.1。称量0.7064g的Fe(acac)3和量取40mL的十八烯分别加入容积为250mL的三颈烧瓶中,外接电子恒速搅拌机使Fe(acac)3充分溶解在十八烯溶液当中,整个装置放置在恒温加热套上;
步骤六、取0.0774g的三辛基氧化磷放入烧杯中,往烧杯中加入6.6mL的油胺,将其放置超声分散仪中5min,使三辛基氧化磷完全溶于油胺得到混合溶液,再往混合液中加入0.1mL聚乙烯吡咯烷酮粉末,溶解并搅拌30min后,使用注射器吸取混合溶液备用。另使用注射器取2.4mL的油酸备用;
步骤七、将反应混合物在室温下通入氩气30min,检验三颈烧瓶的回流管中无空气排出,再使用气球密封整个反应体系,同时使用恒温加热套加热至 120℃,在该温度点,将步骤四的三辛基氧化磷/油胺混合溶液的注射器和油酸溶液的注射器分别注入至三颈烧瓶中,同时可以观察到黄色的烟雾。之后继续将混合溶液加热至260℃,在此温度下保温2h后,冷却至室温。最后得到均匀的单分散Fe3O4纳米颗粒的溶液;
步骤八、将步骤五制备的单分散Fe3O4溶液转移到真空烧瓶中,同时称量 2.22g的CHNTs加入装有单分散Fe3O4纳米颗粒溶液的真空烧瓶中,使用磁力搅拌器搅拌0.5h后,使用真空泵抽真空30min,此过程停止后搅拌10min,再重复三次。使用酒精溶液离心清洗三遍,之后再使用2/3的酒精和1/3的丙酮混合溶液离心清洗,以除去过量的Fe3O4纳米颗粒和有机物。60℃下干燥约2h,得到HNTs/Fe3O4复合材料的前驱体;
步骤九、将步骤八制备的前驱体先在含5%空气的氩气气氛中焙烧30min 以氧化有机物,再在氩气气氛中焙烧2h以保护Fe3O4不再被氧化,温度为 280~350℃,升温速率为5℃/min,保温时间为1~2h。最终获得HNTs/Fe3O4复合材料产品。
实施例2
一种以高温热分解制备埃洛石管内组装Fe3O4纳米复合材料的方法,其具体制备步骤为:
步骤一、与实施例1类似的方法,获得提纯并扩管的埃洛石粉末;
步骤二、称取1.5g油酸钠加入到300mL的柠檬酸溶液(2wt%)中并搅拌直到油酸钠完全溶解。然后将3g扩管的HNTs粉末加入上述到油酸钠溶液中超声30min以得到均匀的混合液。60℃下连续搅拌2小时,之后离心收集,获得油酸根改性的埃洛石纳米管(BHNTs),并用去离子水洗涤三次。然后将BHNTs 在60℃下干燥12小时,并在玛瑙研钵中研磨过200目筛;
步骤三、按实施例1的方法,按Fe(acac)3:油胺:油酸和三辛基氧化磷的摩尔比为1:10:4:0.2。以聚乙烯醇为表面改性剂,使用相同的步骤制备均匀的单分散、表面改性的Fe3O4纳米颗粒的悬浊液;
步骤四、将步骤三制备的单分散Fe3O4溶液转移到真空烧瓶中,同时称量 2.22g的A-CHNTs加入装有单分散Fe3O4纳米颗粒溶液的真空烧瓶中,使用磁力搅拌器搅拌0.5h后,使用真空泵抽真空30min,整个抽真空过程重复三次。使用酒精溶液离心清洗三遍,之后再使用2/3的酒精和1/3的丙酮混合溶液离心清洗,以除去过量的Fe3O4纳米颗粒和有机物。60℃下干燥2h,得到HNTs/Fe3O4复合材料的前驱体;
步骤五、将步骤四制备的前驱体按实施例1的方案焙烧,获得埃洛石纳米管内负载Fe3O4纳米粒子的复合材料(HNTs/Fe3O4)。
实施例3
一种以高温热分解制备埃洛石管内组装Fe3O4纳米复合材料的方法,其具体制备步骤为:
步骤一、与实施例1类似的方法,获得提纯并扩管的埃洛石粉末;
步骤二、将3g步骤一获得的扩管HNTs样品分散在600mL去离子水中,得到HNTs悬浮液(5mg/mL)。超声0.5小时后通过三羟基氨基甲烷调节悬浮液的pH到8.5。然后将1.2mg多巴胺粉末加入到HNTs悬浮液中,30℃下搅拌。最终混合物搅拌3h后获得灰色DHNTs产物。通过离心分离灰色产物并用蒸馏水反复洗涤直至滤液变成无色透明;
步骤三、按实施例1的方法,按Fe(acac)3:油胺:油酸和聚乙烯吡咯烷酮的摩尔比为1:10:4:0.5配制原料,以聚乙烯醇为表面改性剂,使用相同的步骤制备均匀的单分散、表面改性的Fe3O4纳米颗粒的悬浊液;
步骤四、将步骤三制备的单分散Fe3O4溶液转移到真空烧瓶中,同时称量 2.22g步骤二获得的DHNTs加入装有单分散Fe3O4纳米颗粒溶液的真空烧瓶中,使用磁力搅拌器搅拌0.5h后,使用真空泵抽真空30min,此过程停止后搅拌 10min,再重复三次。使用酒精溶液离心清洗三遍,之后再使用2/3的酒精和1/3 的丙酮混合溶液离心清洗一次,以除去过量的Fe3O4纳米颗粒和有机物。60℃下干燥约2h,得到HNTs/Fe3O4复合材料的前驱体;
步骤五、将步骤四制备的前驱体按实施例1的方案焙烧,获得埃洛石纳米管内负载Fe3O4纳米粒子的复合材料(HNTs/Fe3O4)。
Claims (5)
1.一种埃洛石管内组装四氧化三铁纳米复合材料的制备方法,其具体制备步骤为:
步骤一、埃洛石矿物的预处理及扩管、提纯及管内接枝技术:先取一定埃洛石原矿分散在去离子水中,在混合酸溶液中搅拌并浸泡一定时间后,过滤、清洗至无离子残留,离心收集,烘干;再以一定浓度的改性剂溶液浸泡,再离心收集、烘干后备用;
所述的改性剂为油酸钠、胺基硅烷、过硫酸铵、壳聚糖、磷酸二氢铵、多巴胺中的一种,改性剂浓度为1.0~3.0g/L;
步骤二、以混合热液法制备Fe3O4纳米磁性颗粒:称量设计量的乙酰丙酮铁,量取高沸点溶剂分别装入放置在恒温加热套的三颈烧瓶中,恒速搅拌使乙酰丙酮铁充分溶解在溶剂中,再加入适量的保护剂;在氩气气氛下,将整个反应体系密封,加热至120℃,用注射器将三辛基氧化磷/油胺混合溶液和油酸溶液分别注入至三颈烧瓶中,继续将混合溶液加热至200℃~260℃,在此温度下保温2h~4h后,冷却至室温;得表面改性的、单分散Fe3O4纳米颗粒的悬浊液;
步骤三、将步骤二制备的表面改性的、单分散Fe3O4分散液转移到真空烧瓶中,同时加入适量的步骤一获得的埃洛石粉体,搅拌0.5h后,使用真空泵抽真空30min,整个抽空过程重复2~3次;产物经离心分离后,再用酒精清洗,收集后烘干,得到埃洛石管内组装有纳米Fe3O4的复合材料;
步骤四、将步骤三制备的产物在一定温度的氩气气氛炉中煅烧,最后获得埃洛石纳米管内组装有Fe3O4纳米粒子的复合磁性材料;
步骤四中所述的气氛制度为:先在含5%空气的氩气气氛中焙烧30min,再在氩气气氛中焙烧2~4h,温度为280~350℃,升温速率为5℃/min,保温时间为1~2h。
2.根据权利要求1所述的方法,其特征在于:步骤一中所述的混合酸为硝酸、磷酸、盐酸、醋酸的混合溶液,浓度为0.6~1.0mol/L,浸泡时间为1~5h,烘干为60℃的烘箱中干燥。
3.根据权利要求1所述的方法,其特征在于:步骤二中的原料配比为乙酰丙酮铁:油胺:油酸:三辛基氧化磷的摩尔比,以乙酰丙酮铁的量为基准,比例为1:4~16:4:0.1~1.0;
所述的保护剂是聚乙二胺、聚乙醚、聚甲酸乙酯、十二烷基磺酸钠、十六烷基三甲基溴化铵、聚乙二醇、聚乙烯吡咯烷酮和油酸钠中的一种,浓度为0.1~0.5g/L;所述的溶剂是十八烯、油胺和三甘醇中的一种。
4.根据权利要求1所述的方法,其特征在于:步骤二中加入三辛基氧化磷/油胺混合溶液和油酸溶液后,继续将混合溶液加热至260℃,在此温度下保温2h。
5.根据权利要求1所述的方法,其特征在于:所制备的埃洛石/Fe3O4复合材料,Fe3O4主要组装于埃洛石管的内腔中,管外壁没有磁性颗粒;产品没有剩余磁化强度和矫顽力,表现为典型的顺磁性能。
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