流态化气相沉积过程中稀释气体流量对颗粒表面SiO2沉积的影响

利用Fe(Si)合金球形粉末为沉积基底,正硅酸乙酯为SiO2气相介质前驱体,采用引入流化环节的化学气相沉积工艺合成了Fe(Si)/SiO2复合粉末。考察了沉积过程中Ar稀释气体流量对Fe(Si)基底粉末表面SiO2绝缘介质沉积过程的影响规律及形成完整核壳异质结构的稀释气体流量范围。实验结果表明,随着流态化气相沉积过程中Ar稀释气体流量的逐渐增大,SiO2绝缘介质在Fe(Si)粉末基底表面的微观形貌从亚微米级团簇转变为完整薄膜再向多孔薄膜转变,沉积速率先减小后增大再降低,在250 sccm时SiO2绝缘介质均匀性最好,沉积速率为0.069 nm/s。此外,形成完整Fe(Si)/SiO2核壳异质结构的Ar稀释气体流量范围为200~300 sccm。     

均相沉淀-燃烧法合成单分散球形SiO2/CaMoO4:Eu3+,Li+红色荧光粉的发光性能

采用均相沉淀和燃烧合成相结合的方法合成了单分散球形核壳结构SiO2/CaMoO4:Eu3+,Li+荧光粉。用X射线衍射仪、扫描电子显微镜、透射电子显微镜和荧光光谱对样品的物相、结构、显微形貌和发光性能进行了表征。结果表明:产品物相由四方晶系CaMoO4和非晶态SiO2组成;CaMoO4:Eu3+,Li+荧光粉微粒在球形SiO2表面结晶良好,所形成的核壳结构微球粒径均匀;该荧光粉能在近紫外光(395nm)激发下,发出波长为617nm的红光。     

SiO_2@C核壳结构复合材料的制备及表征

以SiO_2气凝胶粉末和乙炔气体为原料,通过化学气相沉积的方法,在SiO_2气凝胶的表面包覆碳层形成SiO_2@C核壳结构复合材料。采用扫描电子显微镜观察了SiO_2包覆碳前后的微观结构和形貌,采用X射线能谱证明了碳的成功包覆,采用热重分析法计算了碳包覆层的含量,采用X射线衍射分析了SiO_2包覆碳前后的晶体结构,采用N_2静态吸附脱附法测试了SiO_2包覆碳前后的比表面积和孔隙结构。另外,结合该核壳结构复合材料的特点,分析了其作为保温隔热材料的可能性。     

Fe,N共掺杂TiO_2/SiO_2复合材料的制备及光催化性能

采用溶胶—凝胶法制备了掺杂不同量Fe,N的TiO2/SiO2复合纳米粒子。通过红外光谱、X射线衍射、透射电子显微镜等对制备的样品的结构和形貌进行表征。以甲基橙水溶液的光催化降解为模拟反应,在紫外光照射下评价了样品的光催化活性。结果表明:Fe,N共掺杂TiO2/SiO2为核壳结构,SiO2核与TiO2壳间形成了Ti—O—Si键。由于金属Fe3+离子抑制光生载流子的复合,非金属N降低了TiO2/SiO2的带隙能,Fe,N共掺杂的协同作用使复合TiO2/SiO2具有更好的光催化性能。共掺杂0.05%Fe及0.05%N的TiO2/SiO2复合光催化粒子的催化活性最高,光照1h后对甲基橙的降解率提高到52%。     

磁性核壳Fe3O4/Ag纳米复合粒子的制备及性能

以硅烷偶联剂巯基丙基三甲氧基硅烷作为添加剂,甲醛作为还原剂,在Ag[(NH3)2] 溶液中制备出具有核壳结构的Fe3O4/Ag纳米复合粒子.用X射线衍射、场发射扫描电镜、差热分析、振动样品磁强计和Hall效应测试系统对样品进行了表征.结果表明:Fe3O4/Ag核壳复合粒子粒径为40～60 nm,Ag壳层厚度为10～15 nm,体积电阻率为7.757 3×10-4 Ω·cm,饱和磁化强度为26.37 A·m2/kg.     

Fe_3O_4/SiO_2核壳复合磁性微球的制备和表征

以溶剂热法制备的高磁饱和强度Fe3O4纳米颗粒为核,正硅酸乙酯(TEOS)为前驱体,采用Stber方法,在乙醇/水溶液中,通过氨水催化水解硅醇盐,制得核壳结构的Fe3O4/SiO2复合磁性微球。对制备的样品的物相结构、形貌和磁性能进行了测试表征。结果表明:制备的Fe3O4/SiO2磁性微球呈球形,粒径分布均一,SiO2壳层圆整光滑,厚度为40~70nm。X射线衍射分析显示,Fe3O4/SiO2磁性微球具有尖锐的Fe3O4特征衍射峰,表明包覆过程没有破坏Fe3O4的晶体结构,其室温下的磁滞回线呈顺磁性,且比饱和磁化强度为30A·m2/kg。此外,对SiO2壳层的包覆机理进行了探究。     

单分散核壳结构SiO2磁性微球的制备及性能

采用溶胶-凝胶法、酸碱两步催化法和乳液成球法制备单分散核壳结构的SiO2磁性微球,利用Leitz光学显微镜、场发射扫描电镜、X射线衍射仪、能谱仪和振动样品磁强计分别对微球的形貌、粒度分布、物相组成、化学成分和磁性能进行了表征.结果显示:采用酸碱二步催化乳液成球法制备的SiO2磁性微球显示出良好的核壳结构,粒径分布在20 μm左右,主要物相是无定形的SiO2和尖晶石型的FegO4,保持了Fe3O4磁性粒子的超顺磁性,是一种优异的生物磁性材料.     

二氧化硅/二氧化锆核壳复合材料的制备及性能

合成了一种新型的二氧化硅/二氧化锆(SiO2/ZrO2)核壳型复合材料。利用异丙醇锆的水解缩合在SiO2微球表面沉积ZrO2层,得到二氧化锆包覆的SiO2/ZrO2核壳型复合氧化物。采用SEM、EDX、XRD等对复合材料的形貌及性质进行表征。利用IR-1红外发射率测量仪测定复合粒子在8～14μm波段的红外发射率。结果显示:该复合物具有明显的核壳结构。随着沉积次数的增加,ZrO2在SiO2表面的含量增加。ZrO2层经高温热处理可分别形成四方和单斜两种晶型。ZrO2层沉积在SiO2表面后,得到的SiO2/ZrO2核壳复合粒子的红外发射率较基底SiO2的有所降低。ZrO2的晶型也影响着复合材料的红外发射性能。ZrO2层为单斜晶的SiO2/ZrO2核壳复合物在8～14μm波段的红外发射率值比ZrO2层为四方晶时的更小。ZrO2层和SiO2球之间的界面作用解释了该复合材料红外发射率降低的原因。     

CVD法制备碳/高活性铝复合材料

采用化学气相沉积技术(CVD),在乙炔气氛、500℃条件下制备了碳/高活性铝复合材料.通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)对复合材料的物相、形貌、组成进行了表征.结果表明,碳/高活性铝复合材料具有特殊的核壳结构及良好的耐水能力.     

等离子体增强化学气相沉积技术制备锗反蛋白石三维光子晶体

采用溶剂蒸发对流自组装法将单分散二氧化硅(SiO2)微球组装形成三维有序胶体晶体模板,以锗烷(GeH4)为先驱体气用等离子增强化学气相沉积法在350℃填充高折射率材料锗.获得了锗反蛋白石光子晶体.通过扫描电镜、X射线衍射仪对锗反蛋白石的形貌、成分、结构进行了表征.结果表明:锗在SiO2微球空隙内填充均匀,得到的锗为多晶态.锗反蛋白石光子晶体为三维有序多孔结构.等离子体增强化学气相沉积的潜在优势在于可实现材料的低温填充,从而以高分子材料为模板进行复型,得到多种结构的三维光子晶体.     

流化床-化学气相沉积技术在先进核燃料制备中的应用进展

流化床-化学气相沉积（FB-CVD）技术是化工流化床技术和材料化学气相沉积制备技术的交叉耦合,兼有流化床处理量大、传热快、温度均匀以及化学气相沉积温度调节范围广、产物丰富多样等优点,其在先进核燃料制备中有着重要的应用,但随着先进核燃料“质”和“量”的不断发展要求,现有的FB-CVD技术有许多方面亟待完善。本文回顾了作者课题组利用流化床-化学气相沉积在高温气冷堆TRISO核燃料颗粒、先进核燃料包覆颗粒、核燃料示踪颗粒、基体SiC纳米颗粒、SiC@Al₂O₃复合纳米颗粒等方面的研究进展,阐述了基本方法、实验过程和典型研究结果,并分析了流化床-化学气相沉积过程中遇到的实际问题。指出了FB-CVD技术未来发展方向,主要涉及反应器规模化放大和连续性生产、孔口沉积消除及温区控制、粉体制备中的纳米颗粒连续收集、新型反应器及工艺设计等方面,具体包括高密度颗粒稳定流化放大准则、床层局部温区控制以及分区流化床结构设计等。     

采用二步法合成核-壳型二氧化硅/二氧化铈复合微粒

以正硅酸已酯为硅源,以氨水为催化剂,无水乙醇为溶剂,采用溶胶-凝胶法并经500℃煅烧1 h后制备了SiO2微粒,运用激光粒度分析方法研究了各原料配比对SiO2粒子大小和粒径分布的影响;再以硝酸铈为铈源,碳酸铵为沉淀剂,十二烷基苯磺酸钠为分散剂,加入SiO2微粒,用化学沉淀法,通过控制反应和焙烧条件,经300℃煅烧1 h后成功合成了核-壳型单分散球状SiO2/CeO2复合微粒.并用差示扫描量热仪/热重分析仪、X射线衍射仪、红外光谱仪、扫描电子显微镜、透射电子显微镜和X射线能谱仪等手段以及zeta电位测定对SiO2/CeO2复合微粒的结构、组成和性能进行了表征.结果表明:SiO2/CeO2复合微粒呈规则球状,粒子分布非常均匀,粒径约300～350 nm;CeO2基本上为膜包覆,伴有少量的CeO2沉积,CeO2包覆层厚度约为30nm;SiO2包覆CeO2后所得复合微粒的表面电性质发生变化,其等电点对应的pH值从2.2增大至5.5.     

A novel core-shell structured ultra-coarse WC-Co composite powders prepared by fluidized bed chemical vapor deposition

The ultra-coarse WC-Co composite powders with a core-shell structure were effectively prepared by fluidized bed chemical vapor deposition (FBCVD) using CoCl₂ precursor. An excellent interfacial bonding was formed between WC and the deposited Co. Defluidization was the major barrier to depositing high-Co-content composite powders, which was caused by the adhesion of the deposited Co particles. Decreasing the deposition temperature reduced the cohesion force of the deposited Co particles, which was thus beneficial to preventing the defluidization. Increasing the WC particle size and the gas velocity increased the collision force and benefited the fluidization. The final Co contents were largely dependent on the deposition and fluidization behaviors. For the conditions tested, the optimal deposition temperature was 800°C while the minimum WC particle size suitable for FBCVD was 25 μm.     

Controllable synthesis of SiC@Graphene core-shell nanoparticles via fluidized bed chemical vapor deposition

SiC@Graphene (SiC@G) core-shell nanoparticles were successfully prepared by a facile fluidized bed (FB) chemical vapor deposition (CVD) method. SiC@G core-shell nanoparticles with an average size of 10 nm and graphene from 1 to 5 layers with a controllable thickness were obtained by finely adjusting the experimental temperatures. The formation of SiC nanoparticles and graphene layers was confirmed by the results of X-ray diffraction (XRD) and Raman Spectroscopy. The graphene content in SiC@G core-shell nanoparticles prepared at different temperatures was measured from thermogravimetric analysis (TG), which varied from 5.89% to 11.88 mass%. From X-ray photoelectron spectroscopy (XPS) results, no absorption assigned to Si-O band was detected, indicating the effective protection of the SiC nanoparticles against oxidation by the graphene shell to resist oxidation of SiC nanoparticles. This novel method of preparation of SiC@G core-shell nanoparticles could be applied to large-scale production and find diverse applications in related fields.     

Enabling the low-cost preparation of core-shell WC–Ni powder by developing a non-noble metal-based catalytic

A novel method of incorporating fluidized bed chemical vapor deposition (FBCVD) with electroless plating was developed to effectively prepare the core-shell structured high-Ni-content WC–Ni composite powders. FBCVD offered a unique approach to decorating Ni particles on WC particles. The small Ni particle acted as an active catalyst to effectively produce high-Ni-content composite powders in the subsequent electroless plating process. The particle size and quantity of decorated Ni particle determined the electroless plating rate. FBCVD pretreatment temperature and time had a conflicting influence on obtaining both the fine size and large quantity of deposited Ni particles. For the conditions tested, the maximum electroless plating rate of 2.93 mg / g/min was obtained using an optimal FBCVD pretreatment at 750°C for 5 minutes, corresponding to a 0.11 wt. % Ni deposition and 50 nm particle size.     

Coating Fine Nickel Particles with Al2O3 Utilizing an Atomic Layer Deposition-Fluidized Bed Reactor (ALD–FBR)

An atomic layer deposition–fluidized bed reactor (ALD–FBR) method has been developed to deposit ultrathin and conformal coatings on fine particles. Experiments of Al₂O₃ deposition on 150-μm-diameter nickel particles were conducted. The fluidized bed was constructed to operate under vacuum, and the fluidizing gas used was nitrogen. Trimethylaluminum and water were used as dosing reagents. The reactions were conducted at 450 K. Successful deposition of alumina films, with thickness controllable at the nanometer level, was observed based on transmission electron microscopy imaging, inductively coupled plasma atomic emission spectrometry, X-ray photoemission spectroscopy, particle-size distributions, and wavelength-dispersive spectrometry imaging.     

Utilizing the autocatalysis of Co to prepare low-cost WC-Co powder for high-performance atmospheric plasma spraying

A novel method of incorporating fluidized bed chemical vapor deposition (FBCVD) with electroless plating was developed to effectively prepare the core-shell structured WC-Co composite powders. The Co nanoparticles decorated on the surface of WC particles by FBCVD acted as active catalysts for the subsequent electroless plating process. The particle size and quantity of the decorated Co particles determined the electroless plating rate but the particle size played more important role. For the conditions tested, the maximum electroless plating rate of 2.34 mg/g/min was obtained by using an optimal FBCVD pretreatment at 750°C for 3 minutes. WC-12Co composite powders with a commercial composition widely used for atmospheric plasma spraying (APS) were efficiently prepared. The composite powders exhibited excellent suitability for APS by forming a homogenous Co-W-C ternary liquid stream. The APS coating is not only well-bonded with the substrate but also consisted of hard nonequilibrium Co₃W₃C and W₂C phases with a uniform distribution. Both remarkably improved the hardness and tribological properties of the APS coating.     

Manufacture of Granular Polysilicon from Trichlorosilane in a Fluidized‐Bed Reactor

Manufacturing of polysilicon by chemical vapor deposition from SiHCl₃ in a fluidized‐bed reactor was studied. The effects of reaction temperature, H₂/SiHCl₃ ratio, gas velocity, and seed particle loading were evaluated. The outlet gas composition was analyzed by gas chromatography. The physical features of the product particles were determined by scanning electron microscopy and laser particle size analyzer. Well‐grown product particles were obtained. The temperature and H₂/SiHCl₃ ratio significantly affected conversion, yield, and selectivity, which were less affected by gas velocity and seed particle loading at higher temperatures. The surface reaction kinetics determined the product yield only at lower temperatures, and thermodynamic equilibrium was approached at temperatures above 900 °C.     

流化床CVD法原位合成CNTs-Ni-TiO2及其光催化性能

采用柠檬酸修饰溶胶-凝胶法制备NiO-TiO₂催化剂,然后于流化床反应器中直接在NiO-TiO₂表面原位生长多壁碳纳米管,制备出CNTs-Ni-TiO₂复合光催化剂。采用XRD、SEM、TG、BET、PL荧光光谱等方法对制备的样品进行了表征,以亚甲基蓝降解为模型反应,考察了复合催化剂在紫外线下的光催化性能。结果表明,在NiO含量为5%的NiO-TiO₂催化剂上生长CNTs后得到的CNTs-Ni-TiO₂复合材料具有较高的光催化活性。