Characterization of silver nanoparticle products using asymmetric flow field flow fractionation with a multidetector approach--a comparison to transmission electron microscopy and batch dynamic light scattering

Due to the already prevalent and increasing use of silver-nanoparticle (Ag-NP) products and the raised concerns in particular for the aquatic environment, analytical techniques for the characterization of such products are of need. However, because Ag-NP products are of different compositions and polydispersities, analysis especially of the size distribution is challenging. In this work, an asymmetric flow field flow fractionation (A4F) multidetector system (UV/vis, light scattering, inductively coupled plasma mass spectrometry - ICPMS), in combination with a method to distinguish and quantify the particle and dissolved Ag fractions (ICPMS after ultracentrifugation), for the characterization of Ag-NP products with different degrees of polydispersities is presented. For validation and to outline benefits and limitations, results obtained from batch dynamic light scattering (batch-DLS) and transmission electron microscopy (TEM) were compared. With the developed method a comprehensive understanding in terms of dissolved Ag and Ag-NP concentration as well as an element selective, mass- and number particle size distribution (PSD) was obtained. In relation to batch-DLS, the reliability of the data was improved significantly. In comparison to TEM, faster measurement times and the ability to determine the samples directly in dispersions are clearly advantageous. The proposed setup shows potential for a rapid- and reliable characterization method of virtually any polydisperse metallic NP dispersion, many of them available on the market already.     

Microstructural examination of layered coatings by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy

The structure of r.f. sputtered multilayer Ti-BN coatings was investigated by low-voltage scanning electron microscopy, energy-dispersive X-ray spectrometry, transmission electron microscopy, and atomic force microscopy. Appropriate specimen preparation methods are described for each technique; these included fracture of the substrate, masking the growing film to produce a taper section, and ion-beam milling of embedded cross sections. Correlation of scanning electron micrographs with atomic force images was facilitated by the presence of similar composition contrast in both cases. Quantitative X-ray microanalysis of the layers was performed using the φ(z) approach. The crystal structures of nanocrystalline grains nucleated as a result of interdiffusion reactions during thermal annealing were identified by selected-area electron diffraction and convergent-beam microdiffraction as -titanium and f.c.c. titanium nitride.     

Microtexture and structure of boron nitride fibres by transmission electron microscopy, X-ray diffraction, photoelectron spectroscopy and Raman scattering

Continuous boron nitride fibres have been fabricated by melt spinning and pyrolysis of poly[2,4,6-tris(methylamino)borazine]. The longitudinal mechanical properties depend on mechanical stress and temperature applied during the conversion process. High-performance and low-performance fibres were characterized in order to find relationship between structure and physical properties. In all the cases, photoelectron spectroscopy (XPS) analysis proves that the chemical composition of the fibre is close to stoichiometric BN. The crystallite sizes were measured by means of X-ray diffraction (XRD) and Raman techniques. Cross-sections of separated fibres were investigated by high-resolution electron microscopy (HREM) and transmission electron microscopy (TEM). All the BN fibres have a hexagonal turbostratic structure. With increasing stress and temperature, the tensile strength and the elastic modulus increase. In the high-performance fibres, the 002 layers with an increased distance (about 0.35 nm) showed a mean stacking sequence near to graphite and a preferred orientation of the 002 layers parallel to the fibre axis.     

Characterisation of dislocations, nanopipes and inversion domains in GaN by transmission electron microscopy

Transmission electron microscopy is used to analyse a range of defects observed in hexagonal GaN films grown on sapphire and GaN substrates by metalorganic chemical vapour deposition. Large angle convergent beam electron diffraction is used to analyse the Burgers vectors of dislocations and to show that hollow tubes, or nanopipes, are associated with screw dislocations having Burgers vectors±c. Weak-beam electron microscopy shows that dislocations are dissociated into partials in the (0001) basal plane, but that threading segments are generally undissociated. The presence of high densities of inversion domains in GaN/sapphire films is confirmed using convergent beam electron diffraction and the atomic structure of the {

Full-size image

} inversion domain boundary is determined by an analysis of displacement fringes seen in inclined domains.     

Characterisation of nano-structured titanium and aluminium nitride coatings by indentation, transmission electron microscopy and electron energy loss spectroscopy

Titanium and aluminium nitride Ti_1 − xAl_xN films deposited by radiofrequency magnetron reactive sputtering onto steel substrate are examined by transmission electron microscopy over all the range of composition (x = 0, 0.5, 0.68, 0.86, 1). The deposition parameters are optimised in order to grow nitride films with low stress over all the composition range. Transmission electron microscopy cross-section images of Vickers indentation prints performed on that set of coatings show the evolution of their damage behaviour as increasing x Al content. Cubic Ti-rich nitrides consist of small grains clustered in rather large columns sliding along each other during indentation. Hexagonal Al-rich films grow in thinner columns which can be bent under the Vickers tip. Indentation tests carried out on TiN and AlN films are simulated using finite element modelling. Particular aspects of shear stresses and displacements in the coating/substrate are investigated. The growth mode and the nanostructure of two typical films, TiN and Ti_0.14Al_0.86N, are studied in detail by combining transmission electron microscopy cross-sections and plan views. Electron energy loss spectrum taken across Ti_0.14Al_0.86N film suggests that a part of nitrogen atoms is in cubic-like local environment though the lattice symmetry of Al-rich coatings is hexagonal. The poorly crystallised domains containing Ti and N atoms in cubic-like environment are obviously located in grain boundaries and afford protection of the coating against cracking.     

Analysis of brittle–ductile transition of polypropylene/ethylene-octene copolymer blends by scanning electron microscopy and small angle laser light scattering

Blends of polypropylene (PP)/ethylene-octene copolymer (EOC) were studied. The influences of blend composition and mixing time on phase morphology development of the blends were investigated by scanning electron microscopy (SEM) and on-line small-angle light scattering (SALS) in detail. The toughness of the PP/EOC blends was investigated over wide ranges of EOC content and determined from the impact fracture energy of the side-edge notched samples. The concept of interparticle distance (ID) and the surface-to-surface interparticle distance (τ) were introduced into this study to probe the size effect on the brittle–ductile transition (BDT) of PP/EOC blends. The results showed that ID based on the SEM photograph and the surface-to-surface interparticle distance (τ) getting from SALS have similar effects on charactering the toughness of the PP/EOC blends. But the surface-to-surface interparticle distance (τ) is more prone to character the BDT of PP/EOC blends than the ID value. On-line SALS can be applied to the research of BDT of PP/EOC blends.     

纳米TiO2粉末的结构表征:X射线衍射、透射电镜及高温Raman光谱分析

采用沉淀-胶溶-絮凝法，以偏钛酸为反应物．制备出锐钛矿型纳米TiO2粉末．用X射线衍射(XRD)、透射电镜(TEM)和高温Raman光谱对其结构进行表征。并采用高温Raman光谱仪对所制备的纳米TiO2从25～1200℃进行了原住Raman光谱研究。温度较低时，锐钛矿相的Raman谱峰明显可见．由于高温下Raman信号减弱，随着温度升高，Raman特征谱峰逐渐减弱以至于全部消失，仅显示出几个宽宽的凸起。同时，高温Raman光谱存在明显的温度效应，因而导致了随温度升高144cm^-1和196cm^-1谱峰的蓝移,640cm^-1谱峰的红移以及谱峰宽化。     

Growth kinetics of silver chloride precipitation in a Na2O-B2O3 glass investigated by means of small-angle X-ray scattering and transmission electron microscopy

The kinetics of silver chloride cluster formation in a sodium borate glass heat treated isothermally at different temperatures above the glass transition temperature has been studied with small-angle X-ray scattering (SAXS). It is established that the size distributions of particle number and particle volume have bimodal shapes, i.e. the system of AgCl droplets consists of two populations with significantly different mean radii. The bimodality of the size distribution functions is confirmed by results of transmission electron microscopy (TEM) even if different techniques of sample preparation are used. The resolution limits of the TEM techniques applied amount to 2 nm and are comparable with the smallest particle diameters detectable by the SAXS method. The evolution of the size distributions is discussed in the framework of the theories of nucleation, growth and Ostwald ripening.     

Textural features of highly ordered Al-MCM-41 molecular sieve studied by X-ray diffraction,nitrogen adsorption and transmission electron microscopy

The preparation of a Al-MCM-41 mesoporous materials has been carried out using silica-gel and pseudoboehmite as silica and aluminum sources, respectively, and surfactant cetyltrimethylammonium bromide as structure template. The textural properties of the calcined Al-MCM-41 were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and N₂ isothermal adsorption measurements. The hexagonal structure parameter a_o was calculated based on d₍₁₀₀₎ XRD reflection as 4.75 nm. TEM images revealed the formation of a well-ordered Al-MCM-41. Accordingly, nitrogen adsorption measurements (BJH) showed a material with very narrow distribution and medium pore diameter of 3.14 nm. Mesopore volume based on adsorbed nitrogen was 0.51 cm³ g^− 1. Through a combination of XRD and N₂ adsorption data, the thickness of the channel walls of 1.61 nm could be calculated.     

Complete on-line determination of biopolymer molecular weight via high-performance liquid chromatography coupled to low-angle laser light scattering, ultraviolet, and differential refractive index detection

An optically modified high-performance liquid chromatography refractive index detector was developed to allow complete on-line determinations for biopolymer molecular weights. On-line concentration, refractive index, specific refractive index increment (dn/dc2)mu, and Rayleigh factor were determined under flow injection analysis (FIA) and size exclusion chromatography (SEC) conditions using low-angle laser light scattering, ultraviolet, and modified refractive index detection. This instrumental system is capable of determining absolute on-line molecular weights. The error and time requirements involved in conventional methodologies for proteins have been reduced. Sample quantities have been reduced from 150 to 200 mg, in conventional off-line methods, to less than 2 mg for on-line FIA and 0.5 mg for on-line SEC, if mass absorptivities (a) are known. Otherwise, the determination of a will be the most sample-demanding step, requiring about 3 mg of the pure protein. On-line measurements of (dn/dc2)mu are in good agreement with traditional off-line values established at Donnan equilibrium (usually within 5%). In addition, this technique provides true injected mass as determined by the UV detector, after chromatographic exposure where losses may occur, which is then used in the calculation of biopolymer molecular weight.     

Least-mean-squares algorithm to determine submicrometer particle diameter,volume fraction,and size distribution width by elastic light scattering

A computationally fast method to determine values and their uncertainty for particulate system volume median diameter, volume fraction, and size distribution width is presented. These properties cannot be obtained for submicrometer particulate by diffraction-based methods. The technique relies on a least-mean-squares method applied over a prespecified size range and distribution width. Prespecifying the range significantly reduces the number of calculations required to determine the particulate parameters from experimental data, allowing the practical evaluation of large data sets. The solution method that was developed has significant advantages over ratio-style calculations that are more commonly performed, the primary of which is a simple method to determine errors in the measurement parameters. We evaluated the predicted performance for a specific experimental system for various levels of noise, with monodisperse and log-normal distributions, by analyzing synthetic data with the algorithm. Results were a quantitative statement of system accuracy. In addition, synthetic log-normal data evaluated with monodisperse models revealed significant and systematic errors in the predicted volume median diameter. These errors indicate that, in general, systems with a significant size distribution width must be analyzed with a model that includes this size distribution. Finally, calibrated polystyrene spheres were measured with an experimental system that used four simultaneous scattering measurements, and all diameters were within the reported uncertainty.     

Interfacial microstructure and defect analysis in Cu(In,Ga)Se([sub]2)-based multilayered film by analytical transmission electron microscopy and focused ion beam

Interfacial microstructures of Cu(In,Ga)Se₂(CIGS)-based multilayered film are closely characterized by TEM (transmission electron microscopy), SEM (scanning electron microscopy) and FIB (focused ion beam). A cross-sectional TEM, energy dispersive X-ray spectroscopy and energy-filtered TEM reveal that a pronounced Cu diffusion occurs across the interface of the CdS/CIGS, which leads to a large amount of Cu rich in the CdS layer and a Cu-deficient sub-surface in the CIGS layer as well as a rough interfacial structure. TEM studies further reveal that the interface microstructures in the multilayered film are dissimilar, both ZnO/CdS and CdS/CIGS interfaces are strongly bonded whereas the CIGS/Mo interface is weakly bonded and interface separation occasionally occurs. Mo back contact layer shows a well adhesion to glass substrate.Detailed observation on defects in the CIGS-based multilayered film is carried out by 3D (3-dimensional) FIB and SEM techniques. Sequential 2D (2-demensional) cross-sectioning shows that dominant growth-defects in the CIGS and top SiO₂ layers are micro-scale crack, appearing as diversified morphologies. The micro-scale crack in the CIGS layer is possibly released by propagating into the adjacent layer while the crack in the SiO₂ layer is relieved usually by forming a small particle behind. It is noted that in the multilayered film the interface frequently acts as crack initiation sites due to distinct thermal expansion coefficients.     

The modification of MoO<Subscript>3</Subscript> nanoparticles supported on mesoporous SBA-15: characterization using X-ray scattering,N<Subscript>2</Subscript> physisorption,transmission electron microscopy,high-angle annular darkfield technique,Raman and XAFS spectroscopy

Abstract MoO₃ was dispersed onto mesoporous SBA-15 by using ammonium heptamolybdate as MoO₃ source. The formation of MoO₃ was carried out by heating the loaded material to 500 °C for 3 h in air. Below 13 wt% Mo loading, no reflections of MoO₃ occur in the X-ray powder patterns and even for high MoO₃ contents, the intensities of the reflections are much lower than expected for fully crystalline material. A detailed XAFS analysis reveals that at low Mo contents, the metastable hexagonal modification of MoO₃ is formed despite the high calcination temperature of 500 °C. It is highly likely that the nanosize of the particles and the interaction between MoO₃ and SBA-15 stabilize the metastable modification of the material. Nitrogen physisorption experiments show the typical type-IV isotherms indicating that the mesoporosity of the materials is preserved despite the large amount of MoO₃. Transmission electron micrographs demonstrate the presence of MoO₃ inside the SBA-15 support. The Raman spectra display a remarkable size-dependent intensity loss and several features give evidences for a bond formation between nano-sized MoO₃ particles and the silica support. Moreover, the spectroscopic details suggest the formation of (MoO₃)_n oligomers. Graphical Abstract MoO₃ nanoparticles are successfully introduced into the pores of mesoporous SBA-15. Up to about 13 wt% Mo the material is amorphous and even for higher loadings a large amount of MoO₃ is still not crystalline. Nitrogen physisorption and transmission electron microscopy evidences that the mesoporosity of the material is retained. At low Mo loading, the metastable hexagonal modification of MoO₃ appears to be stabilized by the interaction with the SBA-15 support material (XAFS).      

Structural studies on Si:H network by Raman, micro-photoluminescence, electron microscopy and ultraviolet ellipsometry: effect of Ar dilution to the SiH4-plasma

Structural characterization of the material has been performed using micro-Raman spectroscopy, ultraviolet (UV) ellipsometry, electron microscopy and micro-photoluminescence (PL) studies on Si:H films prepared at a wide range of Ar dilution to the SiH₄ plasma, defined by R(Ar)=Ar/SiH₄ and varying from 10 to 400. Microcrystallization in Si:H network was easily obtained introducing Ar as a diluent, however, increasing Ar dilution revealed a continuous transformation of the network from microcrystalline to amorphous dominated structure. An overall amorphization of the network and its initiation by the presence of an enormously high void density (∼81 vol.%) in an extended incubation layer (∼163 nm) is the result of extremely high Ar dilution (R(Ar)∼400), on the formation of Si:H films. Increasing porosity in the amorphous dominated matrix resulted in a significant increase in the photoluminescence intensity, contributing to a photoluminescent Si:H material available from extremely high Ar dilution to the SiH₄ plasma in rf glow discharge. Effect of Ar dilution inducing the growth morphology by controlling both the gas phase reactions and solid phase network modifications in Si:H network has been discussed.