Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.     

On Preparation of Non‐Disrupted Particles by Spray Pyrolysis

Using spray pyrolysis, solid fully‐filled zirconia particles were synthesized at relatively high reactor temperatures (～ 400 °C) by adding NaCl as impurities to zirconium hydroxychloride (ZHC) precursor that would have lead to the formation of hollow disrupted particles otherwise. FE‐SEM images show that at comparable concentration of NaCl and ZHC both cubic and spherical NaCl/ZrO₂ particles form. The particle characteristics were varied by varying solute concentration, type, and solvent content. Addition of NaCl caused the formation of both cubic and spherical particles which were non‐disrupted at even high temperatures. According to the EDS compositional analysis, the cubic particles had more Na content while the spherical ones had higher Zr content. It is concluded that growth mechanism of NaCl particles is different from that of zirconia particles. Drying of the former even at high temperatures leads to the formation of solid, fully‐filled, porous particles, whereas hollow, disrupted particles are formed using the latter.     

Formation of ZnO,MgO and NiO Nanoparticles from Aqueous Droplets in Flame Reactor

Nanoparticles of ZnO, MgO and NiO were produced from droplets of aqueous salt solution in the flame spray pyrolysis reactor. Conventional spray pyrolysis, in which electrical furnace reactor is used, is reported to produce nanoparticles only from acetate precursor. If the reactor pressure is low (60torr), nitrate salt precursor is also known to produce nanoparticles. In this paper, we report that nanoparticles are produced from nitrate as well as acetate salt precursor solution when propane–oxygen diffusion flame is used to decompose aqueous aerosol droplets. At low flame temperature, however, nanoparticles are not formed and the particle morphology is similar to the morphology produced by the conventional spray pyrolysis. At high flame temperature, nanoparticles are formed, regardless of the salt type. Nanoparticles are formed at lower flame temperature from acetate salts than from nitrate salts. All nanoparticle prepared in this work were fully crystallized and the size measured from transmission electron microscopy images was 30nm. This size agreed well with the particle size calculated from X-ray diffraction and specific surface area data.     

Synthesis of Single Crystalline ZnO Nanoparticles by Salt-Assisted Spray Pyrolysis

LiNO₃ was used as a shield in the preparation of single crystalline ZnO particles by a spray pyrolysis process in order to prevent agglomeration and enhance the crystallinity of the ZnO. LiNO₃ was added to a precursor solution of zinc acetate dihydrate prior to its atomization by means of an ultrasonic transducer. Agglomerate-free particles having a mean particle size of 26 nm were successfully obtained after washing the product. X-ray diffractometry, field-emission scanning electron micrograph and transmission electron micrograph data indicate that the size and morphology of ZnO were strongly influenced by the operating temperature used and the residence time of the particle in the reactor.     

喷雾热解法制备的SrWO4膜的阴极射线发光

利用超声喷雾热解法制备了钨酸锶SrWO₄多晶发光膜,并研究了制备条件及掺杂对其阴极射线发光特性的影响.生成的发光膜在300℃以上退火后具有白钨矿结构,其阴极射线发光为一宽带的蓝光,包括一个位于448nm的蓝色发光带和一个位于488.6nm的蓝绿色发光带,是由阴离子络合物WO₄^2-的电荷转移跃迁引起的.发光强度随着退火温度的升高而增强,而退火气氛对其影响不大.在SrWO₄膜中掺入银离子Ag⁺和镧离子La³⁺后,不影响其发光特性,但铕离子Eu³⁺的掺入对发光特性有影响.     

喷雾热解法制备发光材料研究进展

喷雾热解法是近年来新兴的合成无机功能材料的方法，使用这种方法制备的发光材料一般具有均匀的球形形貌，粒子的粒度分布窄，这不仅有利于提高材料的发光强度，还可以改善发光粉的涂敷性能并提高发光显示的分辨率。本文综述了喷雾热解法的基本过程及其制备的发光材料的特点，并对其未来发展趋势进行了展望。     

Synthesis of α‐Willemite Nanoparticles by Post‐calcination of Flame‐made Zinc Oxide/Silica Composites

Composite ZnO/SiO₂ nanoparticles were made by flame spray pyrolysis (FSP). Characteristics of the product powder and its crystallization behavior on post‐calcination were evaluated. Polyhedral aggregates of nano‐sized primary particles consisting of ZnO nano‐crystals 1–3 nm in size and amorphous SiO₂ were obtained by FSP. A short residence time in the flame can result in the co‐existence of the ZnO and SiO₂ clusters without substitution or reaction hindering each other's grain growth. There was almost no change in the XRD pattern by calcination at 600 °C for 2 h, suggesting a high thermal stability of the ZnO nano‐crystals in the composite particles. A pure α‐willemite phase was obtained at 900 °C. At this calcination temperature, d_C and d_BET of the powder were 63 and 44 nm, respectively. The nano‐composite structure of the FSP‐made particles can suppress crystalline growth of ZnO during calcination to maintain a high reactivity of ZnO with SiO₂, obtaining pure α‐willemite with high specific surface area at low calcination temperatures.     

籽晶层对喷雾热分解法生长ZnO薄膜结晶质量和光电性能的影响

通过脉冲激光沉积(PLD)方法在Si(100)衬底上沉积一层高质量的ZnO籽晶层,在籽晶层上进一步采用超声喷雾热分解(USP)法生长ZnO薄膜,研究了籽晶层对ZnO薄膜结晶质量和ZnO/Si异质结光电特性的影响。研究结果表明,在籽晶层的诱导作用下,USP法生长ZnO薄膜由多取向结构变为(002)单一取向,结晶性能得到了显著改善;籽晶层上生长的薄膜呈现出垂直于衬底生长的柱状晶结构,微观结构更加致密。通过研究紫外光照前后ZnO/Si异质结的整流特性,发现引入籽晶层后,反向偏压下异质结的光电响应显著增加,并且在开路状态下出现明显的光伏效应。     

A novel deposition method to grow ZnO nanorods: Spray pyrolysis

ZnO layers were deposited by chemical spray pyrolysis (CSP) using zinc chloride aqueous solutions onto indium tin oxide (ITO) glass substrates at growth temperatures in the region of 400–580 C. The layers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and low-temperature () photoluminescence (PL) measurements. The flat film of ZnO obtained at 400 C evolves to a structured layer by raising the temperature up to 500 C. Deposition around 550 C and above results in a layer comprising well-shaped hexagonal ZnO nanorods with diameter of 100–150 nm and length of up to 1 micron. XRD shows strong c-axis orientation of ZnO being in accordance with the SEM study. Deposition of nanorods was successful using ITO with grain size around 100 nm, whereas on fine-grained ITO (grain size < 50 nm) with smooth surface fat crystals with diameter up to 400 nm and length of about 300 nm were formed. Sharp near band edge (NBE) emission peaks centered at 3.360 and 3.356 eV dominated the PL spectra of ZnO at , originating from the exciton transition bound to neutral donors. PL and XRD results suggest that ZnO rods prepared by spray pyrolysis are of high optical and crystalline quality.     

Synthesis of Manganese Oxide Microspheres by Ultrasonic Spray Pyrolysis and Their Application as Supercapacitors

Manganese oxide (MnO₂) microspheres are prepared using an ultrasonic spray pyrolysis (USP) process. A mixed solution of potassium permanganate and hydrochloric acid is nebulized into microsized droplets, which are then carried by air flow through a furnace tube. Each microdroplet serves as one microreactor and produces one microsphere. Upon heating, KMnO₄ is decomposed into MnO₂ microspheres; this synthetic process can easily be scaled up. Characterization of the MnO₂ microspheres by scanning electron microscopy, transmission electron microscopy, powder X‐ray diffraction, Raman spectroscopy, and X‐ray photoelectron spectra is described. Different morphologies of MnO₂ microspheres can be controlled by tuning the precursor concentrations (and ratios) and furnace temperatures. Microspheres synthesized at 150 °C give amorphous MnO₂ while synthesis at 500 °C yields crystalline α‐MnO₂. The electrochemical properties investigated by cyclic voltammetry give specific capacitance as high as 320 F g^?1, demonstrating promising properties as supercapacitors. In addition, these microspheres can be directly sprayed on conductive substrates, such as carbon fiber paper, and may have useful applications as a supercapacitor electrode coating. The supercapacitive properties of MnO₂ microspheres at higher charge and discharge rates can be improved by increasing the surface area coverage or coating them with a thin layer of conductive polymer.     

Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

火焰喷雾法合成ZnO和MgxZn1－xO纳米颗粒的光学性能研究

利用火焰喷雾法成功制备了纳米级的ZnO和Mg_xZn_1-xO颗粒. 通过对样品的X射线衍射谱和场发射扫描电子显微镜照片分析，发现制备的颗粒大小较为均匀，直径在20nm左右；镁元素的掺入引起晶格常数变小. 通过透射光谱和光致发光谱的测量，发现Mg_xZn_1-xO颗粒的禁带宽度远大于ZnO颗粒的禁带宽度，同时对两组样品的紫外发光和可见发光的强度变化和发光机理进行了探讨. 关键词： 火焰喷雾 ZnO 禁带宽度 纳米颗粒     

Progress in Ultrasonic Spray Pyrolysis for Condensed Matter Sciences Developed From Ultrasonic Nebulization Theories Since Michael Faraday

This review outlines, in great detail, the history of the phenomenon of ultrasonic nebulization of liquids since the discovery of such an effect by Michael Faraday and the explanation of the phenomenon by capillary wave mechanism and “cavitation” hypothesis. Capillary waves described by the Kelvin equation are confirmed by Lang's experiment and more theoretical models by Peskin & Raco and Jokanovic. Cavitation bubbles have been elaborated by the Rayleigh-Plesset equation as well as the correlation equations between predicted and experimentally measured droplet diameter. Correlation equations such as one by Rajan & Pandit and Avvaru et al. have been considered. Ultrasonic spray pyrolysis for materials processing and the theories that predict the final particle size distribution are introduced. The popularity of the technique is shown by the rising number of research groups in the world processing various materials by this method due to its cost-effectiveness, purity of its products, and controllability of particle size as well as final properties.     

采用铁基催化剂在V型热解火焰中合成碳纳米管的实验研究

催化剂的选取对于V型热解火焰合成碳纳米管具有重要的影响.实验中分别采用五羰基铁、二茂铁、纳米铁粉等作为催化剂,取样时间为10 min,温度约为1150 K,催化剂的引入方式为喷雾热解方法,利用扫描电镜和透射电镜对合成的碳纳米管进行形态和结构表征分析.实验结果表明:利用V型热解火焰合成碳纳米管时的关键物质是纳米氧化铁颗粒...     

收集方式对喷雾热分解Bi-2223 前驱粉末的影响

采用国产喷雾热分解设备制备了Bi-2223 前驱粉末, 分别选用一步收集和分级收集热分解后的粉末, 对不同方式收集的粉末进行了XRD 分析、SEM 观察以及ICP-AES 分析, 对比了粉末在相成份以及含量、 外观形貌、 粒径大小和元素原子配比等方面的差别, 最终发现采用一步收集方式采集的粉末在相组成、 成分均匀度以及原子配比方面均优于分级收集粉末, 一步收集方式更适合于收集Bi-2223 喷雾热分解粉末.     

Variable Frequency Microwave Synthesis of Silver Nanoparticles

Synthesis of silver nanoparticles based on a polyol process and variable frequency microwave (VFM) was investigated. Comparing to a thermal method, the reaction by VFM radiation was much faster. The effects of silver nitrate concentration, poly(N-vinylpyrrolidone) (PVP) concentration, reaction time and reaction temperature were studied. It was found that the higher concentration of silver nitrate, longer reaction time and higher temperature increased the particle size while the higher concentration of PVP decreased the particle size.     

Safety Issue of Changed Nanotoxicity of Zinc Oxide Nanoparticles in the Multicomponent System

When nanomaterials are exposed to complex systems, such as food, they may cause significant changes in physical and chemical properties and even toxicity. The toxicity evaluation of complex systems is urgent. Unfortunately, so far, there is no database established about the toxicity changes of nanoparticles in composite systems. In this paper, the changes and toxicity mechanism of zinc oxide nanoparticles (ZnO NPs) in a composite system are studied. The results show that the dissolution of zinc ions (Zn²⁺) in acidic systems (vitamin C, tartaric acid, or citric acid) increases the toxicity of ZnO NPs. However, the toxicity of ZnO NPs is reduced by the complexation effect with Zn²⁺ in phosphoric acid, phosphate, and glutathione systems. The influence of titanium dioxide nanoparticles (TiO₂ NPs) on the toxicity of ZnO NPs depends on size and surface properties. In brief, the intracellular Zn²⁺ homeostasis level is the decisive factor in determining the toxicity change in complex systems. The results indicate that the toxicity changes are very different in combined systems, which may have potential food safety issues, especially for unstable nanoparticles.     

Photo- and cathodoluminescence of the cetylpyridinium chloride: ZnO nanocomposites

The cathodoluminescence and photoluminescence (PL) spectra of ZnO nanoparticles (NPs) embedded into the cetylpyridinium chloride (CPCL) matrix were studied. The composites were obtained by drying an aqueous suspension of CPCL and ZnO NPs, with NaCl and with NaOH additives. We observed that only NaOH addition lead to a significant increase in the PL intensity which we attribute to the surface chemistry of the ZnO NPs. We propose that thin ZnOH₂ and Na₂ZnO₂ layers form on the surface of the NPs; these layers present an increased number of oxygen vacancies, which act as emitting centres.     

Research in Korea on Gas Phase Synthesis and Control of Nanoparticles

Research activity into the gas phase synthesis of nanoparticles has witnessed rapid growth on a worldwide basis, which is also reflected by Korean research efforts. Nanoparticle research is inherently a multi-disciplinary activity involving both science and engineering. In this paper, the recent studies undertaken in Korea on the gas phase synthesis and control of nanoparticles are reviewed. Studies on the synthesis of various kinds of nanoparticles are first discussed with a focus on the different types of reactors used. Recent experimental and theoretical studies and newly developed methods of measuring and modeling nanoparticle growth are also reviewed.