双微乳液法制备纳米硫酸钡颗粒

在水溶液/Triton X-100/正己醇/环己烷组成的反相微乳液中,以氯化钡和硫酸钠为原料,通过沉淀反应,制备出类球形BaSO_4纳米颗粒,并通过XRD、SEM、TEM、FTIR对其进行表征。考察了三种反应方式、水/Triton X-100摩尔比(R)、反应物浓度以及助表面活性剂/表面活性剂摩尔比(P)对纳米BaSO_4颗粒大小和形貌的影响。同时考察了R对微乳液液滴大小和粒径分布的影响,并通过动态光散射技术(DLS)对微乳液液滴进行测定。实验结果表明:室温条件下,采用双微乳液法,R=17.97,P在2.11~4.22之间是纳米BaSO_4颗粒合成的最佳反应条件,反应物浓度对BaSO_4颗粒的大小和形貌几乎没有影响。在该反应条件下,合成出的类球形BaSO_4粒径为18~22 nm,产率可达87.5%。     

微通道反应器合成纳米BaSO4颗粒及其在干片多功能层上的应用

以BaCl₂和Na₂SO₄为原料，采用微通道反应器制备得到立方形纳米BaSO₄颗粒，并通过SEM、XRD对其进行表征。考察了不同反应方式及微通道反应器结构、反应物体积流量、反应物浓度、反应温度、体积流量比对纳米BaSO₄颗粒大小和形貌的影响。实验结果表明：25℃下，体积流量为2.5 ml/min，反应物浓度为0.1 mol/L，体积流量比为5是应用于淀粉酶医用干片多功能层的纳米BaSO₄颗粒合成的最佳反应条件。与直接沉淀法相比，微通道反应器内制备出的纳米BaSO₄颗粒形貌规整，最终得到产物粒径为25～55 nm。将所制备的BaSO₄多功能层应用到淀粉酶医用干片中，颜色梯度明显，经反射光密度仪检测，信号值依次减小，且信号值变化曲线重复性、稳定性较好，说明制备的BaSO₄颗粒可应用于淀粉酶体外诊断试剂中多功能层上。     

微通道连续沉淀法制备球形BaTiO3颗粒及其在医学检测干片上的应用

以BaCl₂、TiCl₄、NaOH为原料，采用微通道连续沉淀法制备纳米级球形形貌的BaTiO₃颗粒。考察了钡浓度、体积流量、反应温度及两分支物料流量比等因素对产物形貌及粒径大小的影响，并将其与间歇沉淀法得到的产物进行了比较。实验结果表明：钡浓度0.15 mol/L，碱浓度3 mol/L，两分支物料体积流量均为2 ml/min，反应温度90℃条件下可制备得到具有规整球形形貌、粒径分布均匀的纳米级BaTiO₃颗粒，其粒径为80～150 nm。最后，将所得BaTiO₃扩散层应用到肌酸激酶干片中，重复性较好，且浓度梯度明显，光反射率值与浓度的关系与之对应。结果具有较高的可信度，说明微通道连续沉淀法得到的BaTiO₃颗粒在医用干片上应用是可行的。     

微通道反应器合成纳米BaSO_4颗粒及其在干片多功能层上的应用

以BaCl_2和Na_2SO_4为原料,采用微通道反应器制备得到立方形纳米BaSO_4颗粒,并通过SEM、XRD对其进行表征。考察了不同反应方式及微通道反应器结构、反应物体积流量、反应物浓度、反应温度、体积流量比对纳米BaSO_4颗粒大小和形貌的影响。实验结果表明:25℃下,体积流量为2.5 ml/min,反应物浓度为0.1 mol/L,体积流量比为5是应用于淀粉酶医用干片多功能层的纳米BaSO_4颗粒合成的最佳反应条件。与直接沉淀法相比,微通道反应器内制备出的纳米BaSO_4颗粒形貌规整,最终得到产物粒径为25～55 nm。将所制备的BaSO_4多功能层应用到淀粉酶医用干片中,颜色梯度明显,经反射光密度仪检测,信号值依次减小,且信号值变化曲线重复性、稳定性较好,说明制备的BaSO_4颗粒可应用于淀粉酶体外诊断试剂中多功能层上。关键词:微反应器;合成;纳米粒子;医用干片     

W/O型微乳法制备超细球形碳酸钙

本文采用Triton X-100/环已烷/正辛醇W/O型微乳液体系,制备出了粒径分布均匀、尺寸在70～100nm范围内的球形CaCO3颗粒.对不同水表比(体系中水与表面活性剂摩尔比)ω、反应物浓度等因素的影响进行了研究,获得了较佳的反应条件.所得产物利用扫描电子显微镜(SEM)进行了表征.     

微乳液法制备无定形纳米二氧化硅

采用Triton X-100／正己醇／环己烷／氨水体系配制反相微乳液，在碱性条件下正硅酸乙酯在反相微乳液中发生受控水解，合成了具有无定形结构的球形二氧化硅纳米粒子。通过红外光谱（FT-IR）、X衍射（XRD）、透射电镜（TEM）分别对样品的结构及形貌尺寸进行了表征和分析。结果表明：改变表面活性剂加入量可以得到不同粒径（50～110nm）、不同粒度分布及不同分散程度的球形二氧化硅纳米粒子。随着表面活性剂在微乳液中体积分数的增大，二氧化硅纳米粒子的粒径先减小后增大，团聚程度也呈现先减小后增大的趋势。当表面活性剂在微乳液体系中的体积分数为20％时，所合成的二氧化硅纳米粒子粒径最小（50nm），粒度均匀且呈现出良好的分散性。     

非离子反相微乳液体系制备单分散可控粒径纳米二氧化硅微球

本文以TritonX-100为表面活性剂,正辛醇为助表面活性剂,环己烷为油相,氨水为水相,正硅酸乙酯为硅源,采用反相微乳液法制备单分散纳米SiO2.通过系统地改变R[n(H2O):n(TritonX-100)]值、h[n(H2O):n(TEOS)]值和氨水浓度,运用电镜、动态光散射仪等表征方法研究各种反应条件对粒径和分散度的影响规律,探索制备一定粒径的纳米SiO2颗粒的优化工艺条件.     

CaO-P2O5-SiO2系统生物活性纳米粒子形貌和粒径分布影响因素探讨

制备了TritonX-100／正辛醇／环己烷／水微乳液,并研究了该微乳液系统稳定相行为与制备条件的关系。在稳定的微乳液系统中制备出CaO-P2O5-SiO2系统生物玻璃纳米粒子。采用X射线衍射、透射电子显微镜(TEM)和氮气吸附-解吸(BET)技术并结合测量统计法对样品的晶相、形貌、粒度进行表征。研究表明：粒子尺寸与工艺参数σ(表面活性剂与助表面活性剂的质量比)、ω(水与表面活性剂的摩摩尔比)、γ(水与醇盐的摩尔比)等有关。在σ为1．2,ω为6,7为8条件下可制得平均粒径为25nm的球形无定形态生物玻璃粒子。     

微乳液法制备超细Ni-Ce-B非晶态合金及表征

以OP-10-SDS/正丁醇/环己烷/水四元复配微乳液体系为反应介质、以KBH4为还原剂,在50℃还原氯化镍和硝酸铈制备了超细Ni-Ce-B非晶态合金,利用TEM、SEM、TG-DSC、XRD等手段对产物的形貌、结构、热稳定性和晶化性质进行了研究,并通过改变水相的组成来考察水核大小对合成产物平均粒径的影响.结果表明:在微乳液中可得到平均粒径30 nm左右的超细Ni-Ce-B非晶态合金,其颗粒大小均匀,分散性良好;超细Ni-Ce-B非晶态合金的平均粒径随着ψ值(水和复配表面活性剂的摩尔比)及水核半径的增大而增大;超细Ni-Ce-B非晶态合金的晶化温度较Ni-B非晶态合金的晶化温度升高了近360℃.     

金纳米颗粒的微反应连续合成

金纳米颗粒具有特征性紫外-可见吸收光谱,在分析检测领域被广泛应用。为了突破间歇搅拌反应制备金纳米颗粒的技术局限,提出了一种连续流微反应方法。该方法在酸性条件下借助螺纹管实施HAuCl₄和Na₃Ct水溶液的快速均匀混合,引入惰性溶剂避免颗粒在反应器内沉积,利用膜分相装置完成油水在线相分离,实现了金纳米颗粒的连续稳定制备。探索了反应物摩尔比、浓度、停留时间、水油体积比、pH等因素对于颗粒粒径分布和吸收光谱的影响规律,成功制备了平均粒径20~24 nm、分散因子小于10%的窄分布金纳米颗粒。     

聚乙二醇4000对硫酸钡微粒形貌的调控作用

以水溶性高聚物聚乙二醇4000（PEG4000）为分散剂,研究了反应方式、聚乙二醇浓度、钡离子与硫酸根物质的量比等因素对硫酸钡微粒形貌和晶体结构的影响,通过扫描电镜（SEM）、透射电镜（TEM）、X射线粉末衍射（XRD）等手段对合成样品的形貌和结构进行了表征。结果表明,反应体系经陈化和回流过程,均有利于硫酸钡微粒“溶解与再生长过程”的发生,易于得到较大尺寸的硫酸钡微粒;随着聚乙二醇浓度的增加,所得硫酸钡晶体的形貌呈现从十字花形经片状向棒状结构的显著变化,且在合适聚乙二醇浓度时可以得到具有良好光泽性能的片状硫酸钡单晶结构。钡离子与硫酸根物质的量比的改变也能影响硫酸钡微粒的形貌而得到新颖的“鱼骨刺”形的纳米结构。     

Numerical study on particle size distribution in the process of preparing ultrafine particles by reactive precipitation

Based on the population balance and mass balance in a reactive precipitation process, a numerical simulation model was developed to predict the particle size distribution (PSD) in the reactive precipitation process. The precipitation system of BaCl₂ with Na₂SO₄ to prepare BaSO₄ in aqueous solution was adopted to obtain ultrafine particles in a stirred precipitation reactor and the particle size distribution and the morphology of the particle were observed under transmission electron microscope. It was illustrated by the experimental observation of the micrographs of BaSO₄ particles obtained that apparent agglomeration occurred between the particles, which phenomenon must be taken into consideration in PSD modeling. The population balance equation was calculated by discretization method to obtain particle number and particle size distribution. By implementing the model, the reactive precipitation process in a batch reactor including reaction, nucleation, growth and agglomeration was simulated. The simulation results were validated by the experimental data of BaSO₄ precipitation. Further analysis was endeavored to explore the effects of some important factors such as the supersaturation degree and agglomeration on the evolution of the volume-based characteristic particle size and the variance of volume-based characteristic size of the particles. It was depicted that particle size and particle size distribution are controlled by the supersaturation degree and agglomeration between the particles. Stemming from the analysis in the context, the disciplinarian of the influences of these factors and the method for controlling particle size distribution were presented for the reactive precipitation process.     

Preparation of transparent BaSO4 nanodispersions by high-gravity reactive precipitation combined with surface modification for transparent X-ray shielding nanocomposite films

BaSO₄ nanoparticles as important functional materials have attracted considerable research interests, due to their X-rays barrier and absorption properties. However, most of BaSO₄ nanoparticles prepared by traditional technology are nanopowders with broad size distribution and poor dispersibility, which may greatly limit their applications. To the best of our knowledge, the synthesis of transparent BaSO₄ nanodispersions was rarely reported. Here, we firstly present a novel and efficient method to prepare transparent and stable BaSO₄ nanodispersions with a relatively small particle size around 10 to 17 nm using a precipitation method in a rotating packed bed (RPB), followed by a modification treatment using stearic acid. Compared with the BaSO₄ prepared in a traditional stirred tank, the product prepared using an RPB has much smaller particle size and narrower size distribution. More importantly, by using RPB, the reaction time can be significantly decreased from 20 min to 18 s. Furthermore, the transparent BaSO₄-polyvinyl butyral nanocomposite films with good X-ray shielding performance can be easily fabricated. We believe that the stable BaSO₄ nanodispersions may have a wide range of applications for transparent composite materials and coatings with X-ray shielding performance for future research.     

磷铁渣制备电池级纳米磷酸铁

以磷铁废渣为原料提供磷源和铁源,用硝酸和硫酸混合溶液浸出磷铁渣中的铁和磷元素,并通过沉淀法制备电池级纳米磷酸铁。探究了硝酸浓度、反应时间、反应温度对磷铁渣溶解率的影响,并研究了反应过程中铁磷比、温度和pH对制备的磷酸铁性能影响。利用X衍射分析仪、扫描电子显微镜、热重分析仪、红外光谱仪和电感耦合等离子体发射光谱仪等分析手段对磷酸铁的形貌、晶体结构与化学成分进行了表征。实验结果表明,磷铁渣浸出最佳的实验条件为：硝酸浓度1.5mol/L,反应时间4h,反应温度90℃,此条件下磷铁的溶解率为95.11%;磷酸铁制备过程中的最佳实验条件为：铁磷比1∶1,反应温度60℃,反应pH=1.0,所制备的FePO₄结晶度高,颗粒形貌规整,分散均匀,一次颗粒粒径为100～200nm,铁磷摩尔比为0.97,杂质元素含量符合电池级磷酸铁的要求。     

Synthesis of aluminophosphate molecular sieve AlPO4-11 nanocrystals

AlPO₄-11 nanocrystals, 0.05×0.08 μm in size, were synthesized by optimizing the following chemical parameters: the crystallization temperature and time, the H₂O content, the molar ratio of phosphorus to organic template (P₂O₅/R), and the HF content. The products were characterized by powder X-ray diffraction and scanning electron microscope. AlPO₄-11 nanocrystals could not be obtained by optimizing only the crystallization temperature, time and the water content, but obtained by optimizing the molar ratio of P₂O₅/R, the organic template, and the HF content.     

TiO2-ZrO2聚合溶胶形成过程的小角X射线散射研究

由金属醇盐（M（OR）₄）水解制备溶胶的方法已广泛应用于溶胶-凝胶法制备纳米孔无机膜。通过控制异丙醇钛[Ti（i-OC₃H₇）₄]和正丙醇锆[Zr（n-OC₃H₇）₄]的混合物在异丙醇（i-C₃H₇OH）中水解制备聚合型TiO₂-ZrO₂溶胶,利用小角X射线散射方法（SAXS）研究了初始反应混合物Ti（i-OC₃H₇）₄：Zr（n-OC₃H₇）₄：H₂O：i-C₃H₇OH=0.9：0.1：m：30（摩尔比,m=1.8,2.0,2.2）形成TiO₂-ZrO₂溶胶的过程,探讨了水与醇盐摩尔比H₂O/M（OR）₄（M=Ti+Zr）、反应温度和正丙醇锆对TiO₂-ZrO₂溶胶形成的影响。研究结果表明,H₂O/M（OR）₄=1.8时,只有少量胶粒形成;H₂O/M（OR）₄=2.0～2.2时,TiO₂-ZrO₂溶胶中胶粒具有质量分形结构,分形维数1.2 ≤ D_m < 1.4;随着H₂O/M（OR）₄增加,胶粒的形成时间缩短,胶粒大小和分形维数均增大,溶胶的稳定性显著下降。升高反应温度有利于胶粒形成。[Ti（i-OC₃H₇）₄+Zr（n-OC₃H₇）₄]混合物比Ti（i-OC₃H₇）₄水解快,H₂O/M（OR）₄相同时,TiO₂-ZrO₂溶胶比TiO₂溶胶稳定性差。     

BaFe2O4/BaSO4复合光催化剂的制备及降解罗丹明B废水的活性研究

采用化学法、传统溶胶凝胶法和低温烧结技术合成了BaSO₄、BaFe₂O₄和BaSO₄/BaFe₂O₄复合物光催化剂。X射线粉末衍射和傅里叶红外光谱分析表明,BaSO₄和BaFe₂O₄复合后未改变主晶格相的结构。表面形貌分析发现,BaSO₄颗粒细小均匀,BaFe₂O₄颗粒较大且形貌不规则;当二者复合后颗粒尺寸变化较为明显。紫外可见吸收谱分析表明,5%BaSO₄/BaFe₂O₄复合物光催化剂具有强的紫外可见光吸收能力;BaSO₄、BaFe₂O₄、5%BaSO₄/BaFe₂O₄和10%BaSO₄/BaFe₂O₄复合物光催化剂的E_g值分别为3.23、2.89、2.74、2.26 eV。光催化结果表明,5%BaSO₄/BaFe₂O₄光催化剂在降解罗丹明B染料方面比其他几种催化剂显示出了更高的光催化活性。光催化机理分析发现,空穴、羟基自由基和超氧自由基在染料降解过程中扮演了至关重要的角色。     

Preparation of Ultrafine Silicon Nitride, and Silicon Nitride and Silicon Carbide Mixed Powders in a Hybrid Plasma

Ultrafine Si₃N₄ and Si₃N₄+ SiC mixed powders were synthesized through thermal plasma chemical vapor deposition (CVD) using a hybrid plasma which was characterized by the superposition of a radio-frequency plasma and an arc jet. The reactant, SiCl₄, was injected into an arc jet and completely decomposed in a hybrid plasma, and the second reactant, CH₄ and/or NH₃, was injected into the tail flame through multistage ring slits. In the case of ultrafine Si₃N₄ powder synthesis, reaction effieciency increased significantly by multistage injection compared to single-stage injection. The most striking result is that amorphous Si₃N₄ with a nitrogen content of about 37 wt% and a particle size of 10 to 30 nm could be prepared successfully even at the theoretical NH₃/SiCl₄ molar ratio of ∼ 1.33, although the crystallinity depended on the NH₃/SiCl₄ molar ratio and the injection method. For the preparation of Si₃N₄+ SiC mixed powders, the N/C composition ratio and particle size could be controlled not only by regulating the flow rate of the NH₃ and CH₄ reactant gases and the H₂ quenching gas, but also by adjusting the reaction space. The results of this study provide sufficient evidence to suggest that multistage injection is very effective for regulating the condensation process of fine particles in a plasma tail flame.     

A study on the characteristics of the SO2 reduction using coal gas over SnO2-ZrO2 catalysts

SO₂, which is an air pollutant causing acid rain and smog, can be converted into elemental sulfur in direct sulfur recovery process (DSRP). SO₂ reduction was performed over catalyst in DSRP. In this study, SnO₂-ZrO₂ catalysts were prepared by a co-precipitation method, and CO and coal gas, which contains H₂, CO, CO₂ and H₂O, were used as reductants. The reactivity profile of the SO₂ reduction over the catalysts was investigated at the various reaction conditions as follows: reaction temperature of 300–550 °C, space velocity of 5000–30,000 cm³/g_-cat. h, [reductant]/[SO₂] molar ratio of 1.0–4.0 and Sn/Zr molar ratio of SnO₂-ZrO₂ catalysts 0/1, 2/8, 3/5, 5/5, 2/1, 3/1, 4/1 and 1/0. SnO₂-ZrO₂ (Sn/Zr = 2/1) catalyst showed the best performance for the SO₂ reduction in DSRP on the basis of our experimental results. The optimized reaction temperature and space velocity were 325 °C and 10,000 cm³/g_-cat. h, respectively. The optimal molar ratio of [reductant]/[SO₂] varied with the reductants, that is, 2.0 for CO and 2.5 for coal gas. SO₂ conversion of 98% and sulfur yield of 78% were achieved with the coal gas.