超微镍粉的微乳液法制备研究

采用水（溶液）／二甲苯／SDS／正戊醇反相微乳液体系,用水合肼还原硫酸镍制备了纳米级（15－100nm)镍微粒,采用XRD、TEM等法对产物进行了鉴定与表征,考察了微乳液体系诸构成因素对纳米级镍制备的影响规律。     

Synthesis of Spin‐Crossover Nano‐ and Micro‐objects in Homogeneous Media

New methods are proposed for the synthesis of spin‐crossover nano‐ and micro‐objects. Several nano‐objects that are based upon the spin‐crossover complex [Fe(hptrz)₃](OTs)₂ (hptrz=4‐heptyl‐1,2,4‐triazole, Ts=para‐toluenesulfonyl) were prepared in homogeneous media. The use of various reagents (Triton X‐100, PVP, TOPO, and PEGs of different molecular weights) as stabilizing agents yielded materials of different size (6 nm–2 μm) and morphology (nanorods, nanoplates, small spherical particles, and nano‐ and micro‐crystals). In particular, when Triton X‐100 was used, a variation in the morphology from nanorods to nanoplates was observed by changing the nature of the solvent. Interestingly, the preparation of the nanorods and nanoplates was always accompanied by the formation of small spherical particles. Alternatively, when PEG was used, 200–400 nm crystals of the complex were obtained. In addition, a very promising polymer‐free synthetic method is discussed that was based on the preparation of relatively stable Fe^II–triazole oligomers in CHCl₃. Their specific treatment led to micro‐crystals, small nanoparticles, or gels. The size and morphology of all of these objects were characterized by TEM and by dynamic light scattering (DLS) where possible. Their spin‐crossover behavior was studied by optical and magnetic measurements. The spin‐transition features for large particles (>100 nm) were very similar to that of the bulk material, that is, close to room temperature with a hysteresis width of up to 8 K. The effects of the matrix and/or size‐reduction led to modification of the transition temperature and an abruptness of the spin transition for oligomeric solutions and small nanoparticles of 6 nm in size.     

聚(N-异丙基丙烯酰胺)水凝胶微球体积相变的研究

窄分散的聚（Ｎ 异丙基丙烯酰胺）水凝胶微球用乳液聚合方法制备，并用动态和静态光散射对其体积相变进行了研究．与水中聚（Ｎ 异丙基丙烯酰胺）线性单链比较，水中凝胶微球的体积相变温度较高，对温度的响应比较平缓．相变是连续的，有别于大块凝胶非连续的体积变化．在体积相变过程中，凝胶微球始终是密度均一的热力学稳定球体．从相变过程网络密度的变化可以确定，绝大部分的水在收缩过程被排了出来，但在紧缩的凝胶微球中仍含有约７０％的水．     

Synthesis of Spherical Titanium Dioxide Particles by Homogeneous Precipitation in Acetone Solution

Titania powders were synthesized by thermal hydrolysis of titanium tetrachloride in a mixed solvent was studied. The dielectric constant was tuned by regulating the acetone/water volume ratio (R/H ratio) and temperature of the solvent. Hydroxypropyl cellulose (HPC) was used as a steric dispersant. The synthesis were carried out at R/H ratios of 0–4, temperatures of 70–90°C, TiCl₄ concentrations of 0.05–0.2 M, HPC concentrations of 0–5 × 10^–3 g/cm³, and synthesis times of 15–60 min. The TiO₂ particles obtained at an R/H ratio of 0, i.e., pure water system, were fine and agglomerated. In contrast, the TiO₂ particles prepared at an R/H ratio of 3 were uniform and spherical. The TiO₂ particle size increased with increasing TiCl₄ concentration. The synthesis temperature did not influence the particle size, but greatly influenced the morphologyof the TiO₂. Adding HPC to the solution yielded more uniform and spherical particles. In addition, the synthesis time should be longer than 30 min to obtain the most uniform and spherical particles. The dielectric constant of the acetone-water mixed solvent at 28 gave the most uniform and spherical TiO₂ particles. The powders prepared at the condition of 0.1 M TiCl₄, R/H ratio of 3, HPC concentration of 0.001 g/cm³, temperature of 70°C, and synthesis time of 1 h exhibited the most uniform and spherical morphology. The as-synthesized powder was anatase and retained the phase below 400°C. It transformed to the rutile phase after calcination at 700°C.     

反相微乳液法合成纳米钛酸钡球形颗粒

0引言BaTiO3陶瓷是一种具有高介电常数及优良的铁电、压电和绝缘性能的电子陶瓷材料。不仅是重要的电子陶瓷、PTC陶瓷原料[1],而且也是制备多层陶瓷电容器(M LC C)的必要组分[2,3]。随着现代科学技术的发展,人们更注重材料颗粒的大小和形貌,当材料的粒径达到纳米级时,材料的性能将发生很大的变化。另外,这种具有纳米尺度、球形颗粒的电子陶瓷材料,可能还具有一些新的物理作用,具有潜在的应用价值。B aTiO3粉体的制备方法有:固相煅烧法、化学共沉淀法、溶胶-凝胶法、水热法[4￣11]等。固相法反应温度高(一般1000￣1200℃)、反应活性差…     

Electrical properties of sulfonated polyether ether ketone/polyetherimide blend membranes doped with inorganic acids

The influence of blending with polyetherimide (PEI) and doping with HCl and H₃PO₄ on the properties of sulfonated polyether ether ketone (SPEEK) was studied. Blending with PEI first results in an increase and then in a decrease in membrane swelling at PEI concentrations greater than 5%. The electrical conductivity of blend membranes follows the same trend. Doping with the acids enhances the conductivity several times, and the effect of doping with HCl is more significant. PEI forms spherical particles dispersed in the SPEEK matrix and, at the same time, partially dissolves in SPEEK, which reduces the swelling of the matrix at higher PEI concentrations. The increase in the membrane capacity to absorb water at small PEI contents is due to the formation of new water adsorption sites along the interface between the particles and the matrix. A modified effective medium model yielded calculated results in good agreement with the measured conductivity values, when the experimental absorption data were used in the simulation. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1386–1395, 2000     

Solid-liquid phase transition of tin particles observed by UHV high resolution transmission electron microscopy: pseudo-crystalline phase

Solid-liquid transition of fine tin particles having diameter of 2–10 nm is studied in-situ by high-resolution transmission electron microscopy under a ultra-high vacuum condition. Melting temperature is confirmed to decrease with the decrease of particle diameter. The particles less than the critical size, 2r _c?5 nm, are found to have a specific phase between the solid and the liquid phase. The particle in this “pseudo-crystalline” phase contains crystalline embryos in it. Particles larger than the critical size have sharp liquid-solid transition, which completed within the time resolution of our microscope observation, 33 ms upon heating or cooling process. Large solid particles have Wulff's polyhedron, while particles around the critical diameter have rather spherical shape. Structural anomaly at the critical size occurs all over the outer most surface layer slightly below the melting temperature. Origin of the “pseudo-crystalline” phase and surface pre-melting phenomena are discussed.     

Effect of the structures of microemulsions on chemical reactions

Two kinds of chemical reactions were studied in two different microemulsion systems: cetyltrimethylammonium bromide/1-butanol/10 and 25% n-octane/water and sodium dodecyl sulfonate/1-butanol/20% styrene/water. One reaction is a hydrolysis reaction, in which aspirin and 2,4-dinitrochlorobenzene were used as the hydrolysis substrates. The second reaction is the polymerization of styrene, which was initiated by using two initiators, water-soluble K₂S₂O₈ and oil-soluble 2,2′-azobis(isobutyronitrile), and, at the same time, the polymerization of acrylamide, which was initiated by NaHSO₃, was also studied. All the hydrolysis reaction experimental results show that the hydrolysis is greatly affected by the structures and the structural transitions of microemulsions. The hydrolysis rates are higher in water-in-oil (W/O) microemulsion media and decrease with the addition of water. The rates increase in bicontinuous (BC) microemulsions and decrease in oil-in-water (O/W) microemulsions. The transition points of the hydrolysis rates occurred at the two microemulsion structural transition points from W/O to BC and from BC to O/W. The polymerization relationships between the conversions of styrene, the molecular weights of polystyrene and the water contents of the microemulsion system were obtained. The effects of microemulsion structures on the sizes of the polystyrene particles and on the molecular weights of the polymers are discussed. Polystyrene particles with diameters of 10–60 nm were observed by microscopy. Our experimental polymerization results show that microemulsions are suitable as media for the production of polymers, the molecular weights and the particle sizes of which can be controlled and predicted by variations in microemulsion structures. Received: 11 July 1999/Accepted: 26 July 1999     

A New Method for the Preparation of Co3O4 Nanoparticles

In this study, a novel method was used to prepare well-separated and spherical tricobalt tetraoxide (Co₃O₄) nanosized particles. The overall process involves three steps: preparation of insoluble carboxyl-containing grafted starch copolymer (ISC), formation of precursor (ISC-Co), decomposition of ISC-Co, and phase transition of Co₃O₄ nanoparticles. The Infrared spectra used for ISC and ISC-Co are discussed. The decomposition of the precursor was studied by thermogravimetric-differential thermal analysis, the crystalline phase was characterized by x-ray diffraction, and the size distribution and shape of particles were observed by transmission electron microscopy. Translated from Journal of Northwest Normal University (Natural Science Edition), 2005, 5(5) (in Chinese)     

Conformational change of adsorbed and desorbed bovine serum albumin on nano-sized magnetic particles

Adsorptions of bovine serum albumin (BSA) on nano-sized magnetic particles with and without the presence of carbodiimide were studied. Desorption of BSA from magnetic particles were carried out in either NaOH or Na₂HPO₄ solutions. The structures of native BSA, adsorbed BSA on magnetic particles, and desorbed BSA were studied by several methods, circular dichroism (CD), fluorescence spectroscopy and differential scanning calorimetry (DSC). The magnitude of conformational changes of protein was determined by calculating the α-helix content from the circular dichroism (CD) spectra and by evaluating fluorescence spectrum and DSC thermograms. Adsorbed BSA on magnetic particles shows no thermal transition with respect to the native BSA. The structural change of BSA when desorbed by Na₂HPO₄ solution is much smaller in comparison to that when desorbed by NaOH solution. Hence, this indicates that BSA could be desorbed from nano-sized magnetic particles using Na₂HPO₄ without much conformational change.     

中空球状Fe3O4颗粒的合成及对刚果红溶液吸附-脱附能力的研究

通过简单的水热过程合成具有优良磁学性能的中空Fe3O4单晶颗粒。空心球状颗粒外部直径约500 nm,内径约200 nm,是由粒径为50 nm的颗粒团聚而成。随着反应时间的增加,相邻的Fe3O4纳米晶沿着(311)晶面取向团聚,经过奥斯瓦尔德熟化过程最终形成中空的球状颗粒。实验合成的Fe3O4粒子表现出特殊的磁学性能,具有相对较低的饱和磁化强度和较高的矫顽力。通过对刚果红溶液的吸附-脱附实验证明,中空结构Fe3O4颗粒对刚果红溶液有更高的吸附和脱附能力,在废水处理过程中,采用Fe3O4作为吸附剂,可以更高效的去除溶解的有机污染物,同时可以回收再利用,提高废水净化率,也进一步扩展了磁性材料的应用领域。     

The effect of different monocarboxylic acids on the gelation behaviour of Cu ethoxide

Cu ethoxide becomes soluble in methoxyethanol when formic, acetic, or acrylic acid is added. For the complete dissolution, the minimum molar ratio of an acid to Cu ethoxide is two for formic acid (HOFA), and one for acetic (HOAC) or acrylic (HOAA) acid. The solutions of Cu ethoxide with any amounts of formic acid are incapable of forming gels. Those with acetic or acrylic acid/Cu ratio of 1 are able to convert to gels. For the range of the water concentration from 1.5 to 10 M, the gelation time is strongly dependent on [H₂O] for the solution with HOAC/Cu ratio of 1, while it is almost independent for the solution with HOAA. It is suggested that the differences in the behaviour of soluble Cu species derived from the three acids are attributed to different coordination forms and the bonding strength between ligands and copper ions.     

On the combined use of discrete solvent models and continuum descriptions of solvent effects in ligand exchange reactions: a case study of the uranyl(VI) aquo ion

Modeling of the solvent is important when using quantum chemical methods for the assignment of mechanisms from experimental studies of the exchange of water between metal aquo ions and the bulk solvent. In the present study, we have investigated if and how the mechanisms for water exchange in the UO₂(OH₂) ₅ ²⁺ –H₂O system is affected by the choice of chemical models for the second coordination sphere and physical models for describing the cavity in conductor-like polarizable continuum (CPCM) models. In the first case, we have compared models with one and five waters in the second coordination sphere. For both models, we have compared cavities in which each atom is assigned one spherical cavity and one in which the water molecules are described by a single spherical cavity (the United Atom model). There are significant differences in the relative energy of dissociative and associative intermediates; however, they are not large enough to affect the conclusion that the water exchange proceeds through an associative/interchange mechanism.     

The Electrochemical Oxidation of Sulphite on Gold Electrodes

The electro‐oxidation of sulphite is studied in acid media on gold macroelectrodes and Au particle array modified boron doped diamond electrodes. The sulphite oxidation proceeds through a one‐electron transfer process followed by a chemical step of second order (EC₂ mechanism), as evidenced by experimental voltammetry and digital simulation for both gold macroelectrodes and gold particle modified substrates. The diffusion coefficient of sulphite is calculated consistently for both cases at about 4×10^?9 m² s^?1, with the reverse peak behaviour concentration dependent. The arrays are made by electrodeposition and show a morphological transition from a quasi‐spherical to a star shape as the growth time of the particles increases. Kinetic parameters inferred from the electro‐oxidation at the macroelectrode can be successfully applied to model the gold particle modified electrode data to confirm the EC₂ mechanism, whilst recognising the overlapping diffusion layers of adjacent gold particles.     

Effect of tetraethoxysilane pretreatment on synthesis of colloidal particles of amorphous silicon dioxide

The effect of the time passed after tetraethoxysilane treatment with ammonia on the diameter of particles produced by tetraethoxysilane hydrolysis in alcohol-water-ammonia media is studied. The regulation the time passed after of tetraethoxysilane treatment results in the synthesis of submicron monodisperse spherical silica particles with diameters differing by a factor of two. The difference is explained by the formation of SiO₂ particles with sizes of 10–100 nm in tetraethoxysilane during 10–30 h after treatment with ammonia. These particles enhance the concentration of nucleation centers in a reaction mixture, thus decreasing the final size of monodisperse silica spheres. Opal films with a high structural perfection and pronounced photonic crystal properties are grown based on the obtained monodisperse SiO₂ particles.     

Preparation and characterization of calcium hydroxyapatite and balloon-like calcium phosphate particles from forced hydrolysis of Ca(OH)2–triphosphate solution

Calcium phosphate particles were prepared by aging a solution of dissolved Ca(OH)₂ and sodium triphosphate (sodium tripolyphosphate, Natpp: Na₅P₃O₁₀) at 100–150 °C for 18 h in a Teflon-lined screw-capped Pyrex test tube. Large spherical and/or small aggregated spherical particles were precipitated with an extremely fast rate of reaction under 100 °C. The large spherical particles were amorphous and the small aggregated ones were α-CaNa₂P₂O₇^.4H₂O. The former amorphous ones crystallized to β-Ca₂P₂O₇ after being calcined above 600 °C. Calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, Hap), with rod-like and ellipsoidal or spherical aggregated shapes, was successfully produced using polyphosphates as a source of orthophosphate ions. Time resolved TEM measurement revealed that the crystallization of Hap particles takes place on the surface of tiny amorphous particles precipitated before aging. The tiny particles played the role of nuclei for Hap crystallization. The aging temperature drastically varied the particle shape under conditions for producing uniform amorphous spherical particles; solid spherical particles were produced with an aging temperature of up to 120 °C, whilst transparent balloon-like hollow spheres were precipitated at 125 °C. Finally, fully transparent balloon-like hollow spheres were produced with mere trace amounts of small rod-like particles after aging the solution above 127 °C. The time resolved TEM observation and ICP-AES measurements revealed that the balloon-like hollow spheres were produced by dissolving the interior of solid spherical particles after reinforcing their shell by the adsorption of unhydrolyzed tpp and/or pyrophosphate (pp) ions, which are the hydrolysis product of tpp. The balloon-like hollow spheres of calcium phosphate may have the potential use as drug delivery vehicles and have biocompatibility advantages.     

反应器内流场分布对球形氢氧化镍生长结晶的影响

在相同停留时间、不同搅拌桨线速度条件下,利用化学沉淀法制备球形氢氧化镍样品并运用SEM技术考察制得样品的形貌。研究表明:在相同的停留时间和化学条件下,随着搅拌桨线速度的提高样品的微观形貌由无定型状晶体变为大颗粒类球状晶体再变为较规则的球状晶体。利用PIV物理模拟技术模拟反应器内流场分布情况并结合XRD表征结果分析得出:在相同的停留时间和化学条件下,反应器内流场分布越均匀、速度矢量越大氢氧化镍晶体的生长越完整,结晶性、球形度和相对结晶度越高,并从流场分布的角度描述了球形氢氧化镍生长结晶的过程。     

Sequestration of CO2 using Cu nanoparticles supported on spherical and rod-shape mesoporous silica

The CO₂ sequestration is one of the most promising solutions to tackle global warming. In this study, spherical mesoporous silica particles (MPS-S) and rod-shaped mesoporous silica particles (MPS-R) loaded with Cu nanoparticles were selectively prepared and employed for CO₂ adsorption. For the first time uniform Cu nanoparticles were incorporated into the rod-shaped mesoporous silica particles by post-synthesis modification using both N-[3-(trimethoxysilyl)propyl]ethylenediamine (PEDA) and ethylenediamine (EDA) as coupling agents. The physiochemical properties of the mesoporous and copper grifted silica composites were investigated by CHN elemental analysis, FTIR spectroscopy, thermogravimetric analysis, X-ray diffraction, energy dispersive X-ray spectroscopy (EDX), surface area analysis, scanning, transmission electron microscopy and gas analysis system (GSD 320, TERMO). The mesoporous silica shows highly ordered mesoporous structures, with the rod-shaped particles having a higher surface area than the spherical ones. Copper nanoparticles with an average diameter of 6.0 nm were uniformly incorporated into the MPS-S and MPS-R. Moreover, Cu-loaded mesoporous silica exhibits up to 40% higher CO₂ adsorption capacity than the bare MPS. The MPS-R modified with Cu nanoparticles showed a maximum CO₂ adsorption capacity of 0.62 mmol/g and the humidity showed a slight negative effect on CO₂ uptake process. The enhancement of CO₂ adsorption onto transition metal/mesoporous substrates provides basis for imminent CO₂ sequestration.     

反应器内流场分布对球形氢氧化镍生长结晶的影响

在相同停留时间、不同搅拌桨线速度条件下,利用化学沉淀法制备球形氢氧化镍样品并运用SEM技术考察制得样品的形貌。研究表明：在相同的停留时间和化学条件下,随着搅拌桨线速度的提高样品的微观形貌由无定型状晶体变为大颗粒类球状晶体再变为较规则的球状晶体。利用PIV物理模拟技术模拟反应器内流场分布情况并结合XRD表征结果分析得出：在相同的停留时间和化学条件下,反应器内流场分布越均匀、速度矢量越大氢氧化镍晶体的生长越完整,结晶性、球形度和相对结晶度越高,并从流场分布的角度描述了球形氢氧化镍生长结晶的过程。     

Kinetics of the Growth of Supramolecular Crystals in a Suspension of Monodisperse Spherical Silica Particles

Kinetics of the supramolecular crystallization of monodisperse spherical silica particles (MSSP) suspended in diethyl ether with a concentration of structural units close to the phase transition point has been studied for the first time. It was found that the linear crystal growth rate depends on temperature and the process activation energy is 25 kcal/mol. The linear law of crystal growth is associated with diffusion of the structural units on the interface.