In situ TEM study of mechanical behaviour of twinned nanoparticles

There is strong interest in studying changes in mechanical properties with reducing grain size. The rational is that consequent dislocation glide cannot be sustained, resulting in an increase in material strength. However, this comes with the cost of a reduction in ductility. It has been shown that coherent twin boundaries in nanostructured Cu improve the ductility to 14% [Lu et al., Science 324 (2009) p. 349]. In this paper, we report for the first time the compression of individual nanoparticles using an in situ force probing holder in the transmission electron microscope. Four types of nanoparticles were tested, three with twin boundaries (decahedra, icosahedra and a single twin) and one free of defects (octahedral). Our results indicate the yield strength of the twinned nanoparticles is between 0.5 and 2.0 GPa. The total malleability for the twinned particles range from 80 to 100%. In addition, experimental results were reproduced by MD simulations of the compression phenomena and suggest that the outstanding mechanical properties are related with partial dislocation multiplication at twin boundaries.     

Glancing-incidence X-ray diffraction of Ag nanoparticles in gold lustre decoration of Italian Renaissance pottery

Lustre is known as one of the most significant decorative techniques of Medieval and Renaissance pottery in the Mediterranean basin, characterized by brilliant gold and red metallic reflections and iridescence effects. Previous studies by various techniques (SEM-EDS and TEM, UV-VIS, XRF, RBS and EXAFS) demonstrated that lustre consists of a heterogeneous metal-glass composite film, formed by Cu and Ag nanoparticles dispersed within the outer layer of a tin-opacified lead glaze. In the present work the investigation of an original gold lustre sample from Deruta has been carried out by means of glancing-incidence X-ray diffraction techniques (GIXRD). The study was aimed at providing information on structure and depth distribution of Ag nanoparticles. Exploiting the capability of controlling X-ray penetration in the glaze by changing the incidence angle, we used GIXRD measurements to estimate non-destructively thickness and depth of silver particles present in the first layers of the glaze. PACS 61.10.Nz; 61.10.Eq; 81.70.-q; 61.46.+w     

In situ TEM nanoindentation of nanoparticles

The deformation behavior of nanoparticles continues to be an exciting area for materials research. Typically, nanoparticles show a conspicuous lack of dislocations, even after significant deformation. Therefore, it has been suggested that dislocations cannot exist or/do not play a role on the deformation of nanoparticles. In situ TEM nanoindentation is a critical tool for addressing this issue because it allows for the deformation to be monitored in real time. In this article, we discuss some of the experimental needs and challenges for performing in situ nanoindentation TEM experiments on nanoparticles. In addition, we show both diffraction contrast and phase contrast in situ TEM nanoindentation experiments on silver nanoparticles with diameters below 50nm. Evidence of the presence of dislocations was observed during deformation, but upon unloading dislocations disappeared.     

XAFS study of copper and silver nanoparticles in glazes of medieval middle-east lustreware (10th–13th century)

It has recently been shown that lustre decoration of medieval and Renaissance pottery consists of silver and copper nanoparticles dispersed in the glassy matrix of the ceramic glaze. Here the findings of an X-ray absorption fine structure (XAFS) study on lustred glazes of shards belonging to 10th and 13rd century pottery from the National Museum of Iran are reported. Absorption spectra in the visible range have been also measured in order to investigate the relations between colour and glaze composition. Gold colour is mainly due to Ag nanoparticles, though Ag⁺, Cu⁺ and Cu²⁺ ions can be also dispersed within the glassy matrix, with different ratios. Red colour is mainly due to Cu nanoparticles, although some Ag nanoparticles, Ag⁺ and Cu⁺ ions can be present. The achievement of metallic Cu and the absence of Cu²⁺ indicate a higher reduction of copper in red lustre. These findings are in substantial agreement with previous results on Italian Renaissance pottery. In spite of the large heterogeneity of cases, the presence of copper and silver ions in the glaze confirms that lustre formation is mediated by a copper- and silver-alkali ion exchange, followed by nucleation and growth of metal nanoparticles.     

Initial oxidation of MgO-supported Rh nanoparticles studied by TEM

The formation of ultrathin oxide layers on the facets of MgO(0 0 1) supported Rh nanoparticles is revealed by high-resolution transmission electron microscopy (HRTEM) and spatially-resolved electron energy-loss spectroscopy (EELS). An O–Rh–O trilayer surface oxide has been observed on both {1 1 1} and (0 0 1) facets, which is confirmed by image simulation using the atomic model of a two-dimensional surface oxide obtained by density functional theory (DFT). The spacing between the oxide layer and the Rh {1 1 1} facet is however markedly smaller, indicating a variation of interface bonding in the case of nanoparticles. When the oxide layer is slightly thicker with two Rh planes, the structure of the surface oxide is different from corundum Rh₂O₃ bulk oxide, and the trilayer surface oxide persists as terminating layer. The spacing between the oxide layer and the Rh(1 1 1) facet is found to vary, being smaller in the middle of the oxide layer. It is also found that oxidation is more pronounced at the intersections of the nanoparticles’ facets.     

A study on effects of size and structure on hygroscopicity of nanoparticles using a tandem differential mobility analyzer and TEM

A hygroscopicity tandem differential mobility analyzer (HTDMA) technique is used to determine size-effect of nanoparticles (NaCl, (NH₄)₂SO₄, KCl, NH₄NO₃, MgCl₂, CaCl₂) on their hygroscopic properties (deliquescence relative humidity (DRH) and hygroscopic growth factor (GF)). The HTDMA system uses a combination of two nano DMAs and two regular DMAs to measure particle size change in a wide dynamic particle size range. Particles are subsequently analyzed with a transmission electron microscopy to investigate the potential effect of particle structure or morphology on the hygroscopic properties. We found that structural properties of NaCl and (NH₄)₂SO₄ particles also play an important role in determination of the DRH and GF and are more pronounced at smaller diameters. Data show that the DRH of NaCl nanoparticles increased from ~75% up to ~83% RH at 8 nm and that their GF decreased with decreasing size. The extent to which the GF of NaCl nanoparticles decreased with decreasing size was greater than theoretically predicted with the Kelvin correction. The GF of furnace-generated NaCl nanoparticles that have pores and aggregate shape was found to be smaller than that of atomizer-generated particles that are close to perfectly cubic. For the case of atomizer-generated (NH₄)₂SO₄ nanoparticles, we observed no significant size-effect on their DRH, and the measured GF agreed well with predicted values using the Kelvin correction. For furnace-generated (NH₄)₂SO₄ nanoparticles, a gradual growth at moderate RH without noticeable deliquescence behavior occurred. Their TEM images showed that contrary to atomizer-generated (NH₄)₂SO₄ nanoparticles the furnace-generated (NH₄)₂SO₄ nanoparticles are not perfectly spherical and are often aggregates having pores and holes, which may favor holding residual water even in the dried condition. For atomizer-generated KCl, MgCl₂, and CaCl₂ nanoparticles, we observed no significant size-effects on their DRH and GF for the mobility size as small as 20 nm.     

Calcium in ancient glazes and glasses: a XAFS study

Ceramic tiles used to manufacture artistic panels during the XVI to the XVIII centuries were decorated with high-lead soda-lime glazes, incorporating a diversity of chromophore cations, as ascertained by SRXRF (synchrotron radiation X-ray fluorescence). Previous X-ray absorption spectroscopy (XAS) studies have shown that sodium and lead are hosted by the glassy matrix in those glazes. However, the possible role of calcium as a modifier of the tetrahedral silica network is not fully clarified, despite being recognized that calcium cations alter some fundamental properties of glazes, namely transparency. An X-ray absorption fine structure (XAFS) study of glazes with varied colorings was therefore undertaken at Ca K- and L-edges. Well crystallized oxide minerals were used to model distinct coordination environments by oxygen atoms – close to octahedral geometry in calcite and dodecahedral in gypsum – while fluorite was chosen to mimic ideal cubic coordination. A first XAS approach suggested a minor variation in the energy separation between L₂–L₃ absorption edges when comparing blue and yellow glazes, irrespective of the period of manufacture. A further study on the X-ray absorption near-edge structure (XANES) carried out at the K-edge corroborated this difference and, along with the theoretical spectra modeling performed with the FEFF code, allowed interpreting of the Ca 1s absorption spectra of glazes as arising from a non-regular high-coordination environment within the silica matrix. PACS  61.43.Fs; 41.60.Ap; 61.10.Ht     

Luminescence properties of lustre decorated majolica

Luminescence measurements have been performed on several Italian Renaissance ceramic shards produced in central Italy, as well as on some others from Hispano–Moresque and Fatimid periods. The aim of this study was the characterisation of the raw materials used to manufacture lustre decorated majolica. At first, the thermoluminescence (TL) dating of all ceramic bodies was performed, because the shards lacked sure chronological attribution, having been provided by private collectors, or found during emergency restoration works or archaeological surveys. To characterise the defects and the recombination centers of the different components of the ceramics (ceramic body, glaze, glaze, and lustre), radioluminescence (RL) measurements have been performed on samples representative of each historical period. The dating results are reported, as well as the preliminary RL results. PACS 78.66Jg; 87.66Sq; 81.05.Mh     

TEM study on hollow and prepared from porous Cu20 nanoparticles solution phase

In this paper, hollow and porous Cu2O nanoparticles were prepared by adjusting the cationic surfactant cetyltrimethylammonium （CTAB） concentration in the solution-phase reaction. Structural investigations reveal that Cu2Onanoparticles can be either well-defined hollow nanoboxes or porous nanocubes depending on the synthesis conditions. The transmission electron microscopy （TEM） observations demonstrated that the nanoparticles in general are composed of small grains coherently growing along certain preferred orientations.     

Silver and copper nanoclusters in the lustre decoration of Italian Renaissance pottery: an EXAFS study

Lustre is one of the most important decorative techniques of the Medieval and Renaissance pottery of the Mediterranean basin, capable of producing brilliant metallic reflections and iridescence. Following the recent finding that the colour of lustre decorations is mainly determined by copper and silver nanoclusters dispersed in the glaze layer, the local environment of copper and silver atoms has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy on original samples of gold and red lustre. It has been found that, in gold lustre, whose colour is attributed mainly to the silver nanocluster dispersion, silver is only partially present in the metallic form and copper is almost completely oxidised. In the red lustre, whose colour is attributed mainly to the copper nanocluster dispersion, only a fraction of copper is present in the metallic form. EXAFS measurements on red lustre, carried out in the total electron yield mode to probe only the first 150 nm of the glaze layer, indicated that in some cases lustre nanoclusters may be confined in a very thin layer close to the surface. PACS 61.46.+w; 81.05.Kf; 61.10.Ht     

Ag离子注入非晶SiO2的光学吸收、拉曼谱和透射电镜研究

能量为200keV的Ag离子,以1×1016,5×1016,1×1017cm-2的剂量分别注入到非晶SiO2玻璃,光学吸收谱显示:注入剂量为1×1016 cm-2的样品的光吸收谱为洛伦兹曲线,与Mie理论模拟的曲线形状一致;注入剂量较大的5×1016,1×1017 cm-2的谱线共振吸收增强,峰位红移并出现伴峰.透射电镜观察分析表明,注入剂量不同的样品中形成的纳米颗粒的大小、形状、分布都不同,注入剂量较大的还会产生明显的表面溅射效应,这些因素都会影响共振吸收的峰形、峰位和峰强.当注入剂量达到1×1017 cm-2时,Ag纳米颗粒内部可能还形成了杂质团簇.     

XRF mapping and TEM analysis of coated and uncoated silica nanoparticles in A549 cells and human monocytes

The evaluation of nanomaterials intracellular distribution still remains a challenge in nanomedicine applications and toxicological studies. Synchrotron radiation X-ray microscopy combined with X-ray fluorescence (XRF) microspectroscopy provides unique information that has pushed the frontiers of biological research, particularly when investigating intracellular mechanisms. In this work, the presence of silica nanoparticles in in vitro cultured human lung epithelial cell line and freshly extract human monocytes has been investigated. For the uptake and intracellular distribution of NPs, cells were cultured on polymeric substrates (Mylar). The SiO₂–NPs have been synthesized at JRC and characterized by dynamic light scattering, centrifugal liquid sedimentation, and transmission electron microscopy (TEM), whereas their interaction with cells was investigated with TEM and XRF. For the latter, we used TwinMic in scanning transmission mode coupled with low-energy XRF spectroscopy, paying particular attention to the distribution of different elements, namely, Fe, O, C, Si, and Mg. Si XRF signals recorded on cells exposed to uncoated silica and epoxy-coated silica nanoparticles are comparable, indicating low difference in cellular uptake and suggesting a similar interaction between nanoparticles and cells. However, the TEM analysis indicates a better affinity of the coated nanoparticles for the cell membrane. Moreover, the TEM analysis shows also the presence of nanoparticles in endosomes.     

TEM study of NbC heterogeneous precipitation in ferrite

The heterogeneous precipitation of NbC in ferrite has been quantitatively characterized by transmission electron microscopy in a Fe–C–Nb model alloy for different isothermal heat treatments. The elongation and size distribution of precipitates were derived using dark field imaging. For each precipitation state, the precipitation of NbC occurs on dislocations due to the as-quenched state. This precipitation mechanism leads to characteristic arrays of precipitates in which precipitates grow in a self-similar manner. A detailed study of these arrays has shown that most dislocations decorated by these arrays are edge dislocations with ?112? type line vectors. There is only one variant on a given dislocation. This selection can be interpreted by the interaction between dislocation and precipitate strain fields.     

A TEM study of the stability of intermetallic precipitates in Zircaloy nuclear reactor components

Transmission electron microscopy (TEM) has been used to characterise the radiation-induced changes in Zr(Cr,Fe)₂ intermetallic precipitates present in Zircaloy-2 and -4 nuclear reactor components. The results show that the precipitates become completely amorphous at low fluences (<1 × 10²⁴ n·m⁻²) during low temperature neutron irradiation (about 330 K) with no associated chemical composition change. At higher temperatures (about 573 K), a duplex amorphous-crystalline structure is produced. The precipitates retain a crystalline core surrounded by a peripheral amorphous layer that advances inwards with increasing fluence. The amorphous outer layer is coincident with a depletion of Fe that is dispersed into the surrounding hcp -phase matrix. Subsequent post-irradiation heat-treatment below the amorphous phase recrystallisation temperature results in the back-diffusion of Fe into the precipitates.     

A TEM and XRD study of the SbNbSe3 misfit layer structures

Two new misfit layer structures have been synthesized within the Sb-Nb-Se system. Powder X-ray diffraction and electron microscopy techniques (electron diffraction, HREM, XEDS) have been used to determine the nature of their structure. According to TEM and XEDS data (for more than 15 crystals studied) both phases are monolayer type, i.e. (SbSe)1+delta (NbSe2). Electron microscopy reveals a composite modulated structure that consists of the periodical intergrowth of a pseudotetragonal SbSe layer, denominated as Q, and a pseudohexagonal layer NbSe2, denominated as H. Both layers fit along b, stack along c and do not fit along a (misfit) giving rise to an incommensurate modulation along this direction. The two phases differ in the symmetry of the Q layers being in one case orthorhombic (for delta = 0.17) and monoclinic in the other (for delta = 0.19). After the characterization of the sample by electron microscopy the unit cells of the basic layers could be refined for both phases by powder X-ray diffraction: aQ = 5.824(2) A, bQ = 5.962(5) A, cQ = 23.927(6) A, alpha = 90 degrees, beta = 90 degrees and gamma = 90 degrees and aH = 3.415(5) A, bH = 5.962(6) A,, cH = 11.962(1) A, alpha = 90 degrees, beta = 90 degrees and gamma = 90 degrees for the orthorhombic phase; aQ = 5.844(2) A, bQ = 5.981(1) A, cQ = 23.919(5) A, alpha = 90 degrees, beta = 90 degrees and gamma = 96.00(3)degrees and aH = 3.439(1) A, bH = 5.994(2) A, cH = 11.956(3) A, alpha = 90 degrees, beta = 90 degrees and gamma = 90 degrees for the monoclinic phase. The phase with the monoclinic Q-sublattice often appears as twinned crystals. The more abundant crystals are disordered intergrowths of both monolayer phases.     

In situ TEM observation of the nucleation and growth of silver oxide nanoparticles

The nucleation, growth, and coalescence of silver oxide nanoparticles have been investigated dynamically and at high spatial resolution by using the electron beam of a transmission electron microscope to stimulate and to observe the processes. Under the assumption the particles are hemispherical, the growth rate was found to be proportional to the square root of the electron irradiation time. This result suggests that the rate-limiting step is the attachment of atoms to the nanoparticles. Growth of the nanoparticles occurred by the addition of columns of atoms on {111} planes. Particle impingement resulted in interpenetration of the particles and, ultimately, the formation of a grain boundary.     

TEM monitoring of silver nanoparticles formation on the surface of lead crystal glass

Silver nanoparticles have been formed on the surface of lead crystal glass by means of (i) ion-exchange of alkaline ions from the glass by Ag⁺ ions from a molten salts bath, and (ii) silica based sol-gel coatings containing silver. All experimental variables concerning both ion-exchange process and sol-gel coatings application were combined and studied as main parameters governing the reduction of Ag⁺ ions to Ag⁰ atoms and further aggregation to form nanosized colloids. The content of thermoreducing agents (arsenic or antimony oxides) in the lead crystal glass was essential to favour the reduction of silver ions to form nanoparticles. Optimal experimental conditions to be used for the obtaining of surface silver nanoparticles were determined. TEM was used as the principal characterisation technique for direct observation of the nanoparticles generated. The size of silver colloids varied in the 20-300 nm range for ion-exchanged samples and in the 10-80 nm range for sol-gel coated samples.     

A TEM study of precipitation in Al–Mg–Si alloys

A set of extrusion samples of Al–Si–Mg alloys (0.5 wt%Mg and 0.3–0.8 wt%Si) were, respectively, T1- and T4-heat-treated. Differential scanning calorimetry (DSC) was used to heat the samples to particular temperatures to promote the formation of precipitates for study by transmission electron microscopy (TEM). It was found that, apart from β″, β′, and B′, there were many precipitates showing rectangular lattices when viewed along the long axes of the precipitates. It is considered that the residual stresses (or dislocations) in the extrusion after the T1-treatment facilitated the nucleation and growth of the precipitates during the heating in the DSC.