纳米粒度测量方法浅析

本文介绍了多种纳米颗粒粒度的测量方法。主要讨论了X射线小角散射法、光子相关谱法和透射电镜-图像分析法的原理、适用范围及其优缺点。     

Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

The nanostructure of stretched and nonstretched PVDF samples was studied by small-angle X-ray scattering (SAXS). The crystallinity of the samples was determined by wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC), and crystalline phases by Fourier transform infrared spectroscopy (FTIR). The nanostructure can be described by a lamellar stacking of crystalline and amorphous layers, with a fairly well defined long period D and a diffuse-boundary in the interface between the crystalline and amorphous phases. The crystallinity of the stretched sample was found to be greater than that of the nonstretched sample. The long period D and the thicknesses of the crystalline lamellae T_c were found to be greater in the stretched sample than those in the nonstretched sample. The thickness of the diffuse-boundary was evaluated as being ∼ 1.4 nm in the nonstretched sample and 1.1 nm in the stretched sample. It was concluded that the growth of the thickness of the crystalline layer induced by the stretching process (stretch-induced crystallization) occurs partially at expense of the diffuse boundary and also by the coarsening of the structure with the stretching process, because of the diminution in the surface area to volume ratio observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characterisation and sintering studies of mechanically milled nano tungsten powder

Abstract

Elemental tungsten powder was mechanically milled by planetary mill for 100 h. Particles were thinned down to nanometre scale. The shape of the milled powders was flat cylindrical with average diameter and length 12˙5 and 46˙5 nm respectively. The corresponding crystallite size obtained by X-ray diffraction (XRD) was 26˙96 nm. The results obtained by XRD and small angle X-ray scattering were well supported by transmission electron microscopy and high resolution transmission electron microscopy results. The maximum shrinkage of the compact has been observed at ～1500 K, which has been used as a guideline for sintering experiments. The powders sintered at 1773 K have resulted in 96% relative density.     

Electrostatic Control of Structure in Self‐Assembled Membranes

Self‐assembling peptide amphiphiles (PAs) can form hierarchically ordered membranes when brought in contact with aqueous polyelectrolytes of the opposite charge by rapidly creating a diffusion barrier composed of filamentous nanostructures parallel to the plane of the incipient membrane. Following this event, osmotic forces and charge complexation template nanofiber growth perpendicular to the plane of the membrane in a dynamic self‐assembly process. In this work, we show that this hierarchical structure requires massive interfacial aggregation of PA molecules, suggesting the importance of rapid diffusion barrier formation. Strong PA aggregation is induced here through the use of heparin‐binding PAs with heparin and also with polyelectrolytes of varying charge density. Small angle X‐ray scattering shows that in the case of weak PA‐polyelectrolyte interaction, membranes formed display a cubic phase ordering on the nanoscale that likely results from clusters of PA nanostructures surrounded by polyelectrolyte chains.     

Oleogels from Glycerol‐Based Lyotropic Liquid Crystals: Phase Diagrams and Structural Characterization

In the course of our studies on structured reverse lyotropic liquid crystals (LLC) as oleogels, a system was designed with the desired physical and rheology properties for cosmetic and pharmaceutical applications. The aqueous phase was partially replaced by glycerol to minimize bacteriological problems and obtain specific rheology characteristics. The constructed phase diagrams are based on ternary mixtures of glycerol monooleate (GMO), decane, water, and glycerol. The main lyotropic mesophase obtained in this study was reverse hexagonal derived from dilution line 8:2 (72 wt% GMO and 18 wt% decane) and 10 wt% water; or water:glycerol (wt ratios 3:1 and 1:1) mixture. It was found that heat‐cool fluctuation caused formation of new pseudo‐equilibrium structures with mesomorphic transformations to more fluid and less ordered mesostructures. Replacing up to 50 wt% of the water by glycerol significantly increases the gel phase region in the phase diagram, meaning more structural compositional options. The structural parameters were determined using cross‐polarized light microscopy (CPLM), differential scanning calorimeter (DSC), powder X‐ray diffraction (PXRD), and small angle X‐ray scattering (SAXS). Rheological measurements revealed viscoelastic properties of lyotropic liquid crystals with a decrease in the elasticity (G′), plasticity (G″), and complex viscosity (η*), as a function of increasing the glycerol content.     

Cavitation during deformation of semicrystalline polymers

Cavitation phenomenon is observed during deformation in many semicrystalline polymers above their glass transition temperature. Numerous voids (cavities) both nanometer and micrometer size are formed inside amorphous phase between lamellae during deformation of a polymer. The cavitation is observed only in tension, never during compression or shearing. Most often used methods of voids detection are: microscopies (SEM, TEM, AFM and light microscopy), small angle X-ray scattering and measurements of density. Usually the voids are detected close to yielding or at yielding, strongly suggesting that yielding is often caused by cavitation. However, there is a competition between two processes: breaking of amorphous phase leading to cavitation and plastic deformation of lamellar crystals. Which process occurs first depends on the relation between compliances of those two phases. If the crystals are weak and defected their deformation occurs (mostly by chain slips mechanism) without cavitation. If the crystals in a polymer are thick and more perfect then the barrier for their deformation, represented by shear yielding stress, is increased and the cavitation sets in first and yielding is determined by the stress needed for cavitation. Further deformation involves deformation of crystals due to rapid local change of stress around voids. The influence of different morphological factors: crystal thickness, crystallinity degree, arrangement of crystalline elements (e.g. in spherulites), morphology of amorphous phase (free volume, entanglements, tie molecules) were analyzed. Experimental factors, such as temperature of deformation and rate of deformation influence remarkably the formation of cavities. Cavitation is generated at points where a high local triaxial state of stress is developed. Triaxiality of stress can be amplified by a notch, even very mild notch with large radius of curvature stimulates generation of cavities. Evolution of nano-cavities into micro-cavities and change of their shapes with increasing deformation were evidenced by SAXS. Initially voids are oriented perpendicularly to deformation direction, however, with increasing elongation they become oriented along deformation direction. Stress whitening is visual sign of cavitation and is caused be light scattering either by microvoids or by assemblies of nanovoids.     

Dendrimer as nanocarrier for drug delivery

Dendrimers are novel three dimensional, hyperbranched globular nanopolymeric architectures. Attractive features like nanoscopic size, narrow polydispersity index, excellent control over molecular structure, availability of multiple functional groups at the periphery and cavities in the interior distinguish them amongst the available polymers. Applications of dendrimers in a large variety of fields have been explored. Drug delivery scientists are especially enthusiastic about possible utility of dendrimers as drug delivery tool. Terminal functionalities provide a platform for conjugation of the drug and targeting moieties. In addition, these peripheral functional groups can be employed to tailor-make the properties of dendrimers, enhancing their versatility. The present review highlights the contribution of dendrimers in the field of nanotechnology with intent to aid the researchers in exploring dendrimers in the field of drug delivery.     

降感RDX微观结构的X射线小角散射分析

应用同步辐射X射线小角散射技术研究了降感RDX材料的微观结构,分析了RDX微孔数量、尺寸以及数量分布信息。结果表明降感RDX微孔尺度随样品颗粒变化不明显,数据显示微孔平均半径只有1~2 nm的微弱变化。对比不同分析方法得到的微结构信息表明RDX内部除了微孔结构还存在裂缝微结构。     

Linking Simultaneous In Situ WAXS/SAXS/Raman with Raman/ATR/UV–vis Spectroscopy: Comprehensive Insight into the Synthesis of Molybdate Catalyst Precursors

A new setup is presented which enables simultaneous wide- and small-angle X-ray scattering (WAXS/SAXS) and Raman spectroscopic experiments during the synthesis of Mo-based mixed oxide catalyst precursors at the μ-spot beamline at the Berliner Elektronenspeicherring-Gesellschaft für Synchrotronstrahlung (BESSY). Furthermore, we report about the separate monitoring of the same reactions under comparable conditions by simultaneous combined ATR/UV–vis/Raman spectroscopic measurements. For testing the performance of both experimental setups two syntheses were described comprising the precipitation of metal molybdates by mixing solutions of metal nitrates and ammonium heptamolybdate. Additionally, the effect of H₃PO₄ admixture on precipitation was investigated. The combined evaluation of spectroscopic and WAXS/SAXS data allows the discrimination between different molybdate species appearing in solution and precipitate. Furthermore, these molybdate species could be assigned to separate phases of different crystallinity.