铜及其氧化物薄膜的磁控溅射法制备及对AP的催化性能研究

【作者】 赵静；

【导师】 江晓红；

【作者基本信息】 南京理工大学 ， 材料学， 2012， 硕士

【摘要】 近年来,液相法制备过渡金属或过渡金属氧化物应用于催化高氯酸铵(AP)的热分解已被广泛研究,但用磁控溅射法等物理气相沉积方法制备过渡金属及氧化物薄膜应用于AP热分解反应的研究还几乎未见报道。本文以99.99%高纯无氧铜为靶材,采用磁控溅射法制备铜薄膜,随后对其进行氧化处理得到铜氧化物薄膜。采用X射线衍射仪(XRD)、拉曼光谱仪(Raman)、原子力显微镜(AFM)、场发射扫描电子显微镜(FESEM)和台阶仪等测试手段,分析讨论了基底材料、溅射功率、溅射压强、沉积时间和氧化温度对铜及氧化物薄膜结构、形貌、成分和厚度的影响；研究结果表明基底材料会影响薄膜表面晶粒结构的变化：沉积时间不仅影响薄膜镀层厚度,还可以看出薄膜表面颗粒结构由球形向正八面体结构转变；溅射压强和溅射功率影响薄膜沉积速率、薄膜表面晶粒粒径和粗糙度的大小；氧化处理温度的不同造成薄膜的成分、颗粒和粗糙度有明显差异。将制备的铜及氧化物薄膜以一定比例添加在高氯酸铵中,通过差示扫描量热仪(DSC)分析不同含量、不同制备条件及不同成分的铜及氧化物薄膜对高氯酸铵热分解性能的影响,研究表明,铜薄膜对AP的高低温分解阶段都有显著的催化效果,大幅度降低AP的高低温分解温度,低温分解温度最低降至270℃,高温分解温度最低降至350℃,特别是,添加铜薄膜时AP低温分解阶段的放热峰尖锐陡直；添加铜价氧化物薄膜也增加了AP的表观分解热,其中效果最好的达到1212.98J·g-1,而纯AP的只有563.74J·g-1。另外,用热质联用仪(TG-MS)检测添加或未添加铜薄膜时AP高低温分解阶段产生的气体产物,产物分别有H2O、NH3、O2、NO和N2O,进而初步探讨铜及氧化物薄膜对AP热分解的催化作用机理。更多还原

【Abstract】 Compared to the liquid method, which is widely used to prepare transition metals or transition metal oxides on the thermal decomposition of ammonium perchlorate (AP), Physical Vapor Deposition (eg.magnetron sputtering technology) has scarely been reported so far.In this paper, copper thin films were prepared form 99.99% high purity copper target by magnetron sputtering technology, and then calcined to CuxO(x=1,2) thin films. The structure, morphology and thickness of Cu thin films were characterized by X-ray diffraction (XRD), Raman spectrometer (Raman), Atomic force microscopy (AFM), Field emission scanning electron microscopy (FESEM) and Step devices, respectively. We discussed the substrate material, sputtering power, sputtering pressure, deposition time and calcining temperature on the effect of Cu films structure, morphology, grain size, ingredient and thickness. The results indicated that the substrate material influenced the crystal structure of Cu films; the deposition time not only affected the film coating thickness, but also the film microscopy structure was changed from spherical grains to octahedral grains; the sputtering pressure and the sputtering power exhibited the different film surface grain size, roughness and deposition rate; furthermore, the calcining temperature caused the difference film competition and surface roughness.Cu and CuxO(x=1,2) thin films with a certain proportion were mixed in the ammonium perchlorates. The different preparation condition, content and composition of Cu and CuxO(x=1,2) thin films on the AP thermal decomposition were studied via Differential scanning calorimeter (DSC). It was showed that the presence of copper films had obviously catalytic effect on the thermal decomposition of AP, decreased the best low and high temperature exothermic peaks to about 270℃and 350℃respectively, and increased the heat release of AP to 1212.98J·g-1 greatly compared with 563.74J·g-1 of pure AP. Addition of Cu thin films led to the low temperature stage exothermic peak of AP becoming steep significantly.In addition, Using Thermal gravity and Mass spectrometer (TG-MS), gaseous products of the high and low temperature decomposition stages of pure AP and adding Cu films to AP were measured separately, all including H2O, NH3, O2, NO and N2O; and the mechanism of AP thermal decomposition was studied preliminaryly.更多还原