Growth kinetics of gold nanocrystals: a combined small-angle X-ray scattering and calorimetric study

The growth of gold nanocrystals prepared by the reduction of tetrachloroauric acid by tetrakis(hydroxymethyl)phosphonium chloride, which allows slow reduction, is investigated by small-angle X-ray scattering and isothermal titration calorimetry in combination with transmission electron microscopy. The growth of the nanocrystals does not follow the diffusion-limited Ostwald ripening but instead follows a sigmoidal rate curve. The activation energy obtained from the temperature-dependent growth study is very small. The heat change associated with the growth is determined for the first time as approximately 10 kcal mol(-1) per 1 nm increase in the nanocrystals' diameter.     

Study of Al2O3 effect on structural change and phase separation in Na2O-B2O3-SiO2 glass by NMR

The effect of Al₂O₃ on the structure change and the phase separation in Na₂O-B₂O₃-SiO₂ glass was investigated using ¹¹B nuclear magnetic resonance (NMR), ²⁹Si MAS NMR, and ²⁷Al MAS NMR together with infrared absorption spectroscopy and field emission scanning electron microscopy (FE-SEM). The results show that the structure change from the introduction of Al₂O₃ contributes greatly to the inhibition of phase separation. First, the introduction of Al₂O₃ imparts an ionic character to the boron-oxygen network, resulting in the formation of B-O-Al-O-Si bonds and thus increases the compatibility of the silicon network with the boron-oxygen network. Second, the addition of Al₂O₃ causes the sodium ion to transfer from the boron-oxygen network to AlO₄ tetradedra, changing a number of four-coordinated borons into three-coordinated borons. As the bond energy of the four-coordinated boron is weaker than that of the three-coordinated boron, the -B-O-Si- bond with the four-coordinated boron in Na₂O-B₂O₃-SiO₂ glasses is easily broken and results in severe phase separation during heat treatment. However, the -B-O-Al- bond with the three-coordinated boron formed in Na₂O-B₂O₃-SiO₂-Al₂O₃ glasses is difficult to be broken due to the high bond energy. In addition, the silicon network in Na₂O-B₂O₃-SiO₂-Al₂O₃ glasses is also strengthened by the addition of Al₂O₃, which prevents [BO] groups from further aggregation. As a result, the tendency of the glass towards phase separation is greatly suppressed in the Na₂O-B₂O₃-SiO₂-Al₂O₃ system.     

Analytical transmission electron microscopy of La2O3-doped Y2O3

Analytical electron microscopy has been used to study the precipitation reactions in sintered samples of 9 mol% La₂O₃-Y₂O₃ samples upquenched from the single phase cubic region into the cubic and hexagonal phase field. Samples annealed just inside the two-phase cubic-cubic and hexagonal solvus exhibited predominantly grain boundary precipitation. Small La₂O₃ rich second phases formed within the first ten minutes and developed into strained, facetted precipitates after 300 min. Intergranular and intragranular precipitation occurred in samples annealed further into the two-phase field. Strained, lathlike La₂O₃-rich monoclinic precipitates, exhibiting a preferrred orientation in the matrix, appeared as the dominant morphology for long times at temperature. Chemical microanalyses of the strained structures obtained in samples annealed for 300 min revealed La₂O₃ matrix concentrations in agreement with phase diagram predictions. However, the La₂O₃ concentrations in the second-phase precipitates were found to be far in excess of the cubic and hexagonal-hexagonal solvus. This discrepancy is believed to arise from a re-equilibration of the second phase in the cubic and monoclinic phase field during quenching.     

Fabrication of hollow glass microspheres in the Na2O-B2O3-SiO2 system from metal alkoxides

Hollow glass microspheres (HGS) for laser fusion targets were fabricated in the system Na₂O-B₂O₃-SiO₂ from NaOCH₃, B(OCH₃)₃ and Si(OC₂H₅)₄. Gel powders prepared from metal alkoxides and urea liberate H₂O, CO₂ and NH₃ gases, evolution of which takes place completely at about 500° C. The precursor of HGS is formed by the encapsulation of these gas components in the glass layer formed at the surface of the powder. HGS are produced from the gel powders having both a melting temperature lower than about 1000° C and a viscosity at that temperature lower than 10⁵ P. In the Na₂O-B₂O₃-SiO₂ system, the compositions from which HGS are produced are those containing 55–75 wt% SiO₂ and 0–20 wt% B₂O₃. HGS ranging from 100–500m diameter and 0.5–7.0m wall thickness are obtained by change of urea content.     

The nature of the lamellar overgrowth in polyethylene shish-kebab fibres as revealed by small-angle X-ray scattering and electron microscopy

The melting, dissolution and crystallization behaviour of the lamellar overgrowth in polyethylene shish-kebab fibres have been studied by small-angle X-ray scattering and electron microscopy. SAXS experiments in which fibres were heatedin situ demonstrated the irreversible reorganization of the lamellar overgrowth already at 60° C. Reorganization continued in an inhomogeneous manner until the fibre lost its porosity around 140° C. The morphology that developed upon cooling depended on the crystallization temperature as well as on the maximum temperature attained before crystallization. Transmission electron microscopy observations showed the influence of molecular weight on aggregation. The SAXS patterns obtained duringin situ dissolution experiments disclosed that the lamellae dissolved in dodecane above 115° C. Recrystallization of the lamellae on to the backbones was almost complete within 10 min at 110° C. These high temperatures, as compared with single-crystal behaviour, indicate that the cilia nucleated with exceptionally high stem lengths on to the backbones. SAXS of fibres elongated to a maximum ratio of 1.5 at 90° C demonstrated the role of the lamellar overgrowth as a matrix between the elementary fibrils. The shish-kebab morphology could be restored after elongation by selective dissolution of the lamellae and recrystallization.     

Characterization and sintering of a porous glass-ceramic in the system Na2O-B2O3-Ta2O5

Substitution of SiO₂ in the ternary sodium borosilicate system with Ta₂O₅ was found to produce glasses, which after heat treatment separated into immiscible microphases, one of which was water soluble. The structure of the leached material after heat treatment was a well developed low temperature form of Ta₂O₅. After firing at temperatures between 1100 and 1550°C X-ray diffraction analysis showed the presence of low and high temperature forms of Ta₂O₅ and of orthorhombic Na₂Ta₅O₂₁. The high solubility of up to 40 wt% Ta₂O₅ in the sodium-borate matrix resulting in clear glasses is of practical interest. The specific surface areas of the leached materials ranged between 5.54 and 35.57 m²g⁻¹ while in an additionally Al₂O₃ doped material the value of 307 m²g⁻¹ was measured. Mean pore radii of interconnected pores were calculated to be between 18.63 to 41.12 nm in the Ta₂O₅-rich materials while the additional Al₂O₃ doping decreased the value to 2.71 nm. A sintering temperature between 1500 and 1550°C is estimated from void volume measurements after a series of firing steps at temperatures between 1100 and 1550°C were undertaken.     

EPR and optical absorption of Cr3+ in binary Na2O-B2O3 glasses

The optical absorption and EPR spectra of Cr³⁺ in binary sodium borate glasses have been studied as functions of chromium concentration and Na₂O/B₂O₃ ratio in the glass; the ligand field and EPR parameters have been calculated and were found to be independent of Cr₃₊ concentration in any particular glass. In low-alkali borate glasses (Na₂O = 11 or 14 mol %) a single symmetrical EPR line was observed with g _¦=g =1.984±0.001 corresponding to perfect octahedral symmetry of the Cr³⁺ ion in these glasses. With increasing Na₂O content of the glass, the EPR line becomes more asymmetric (characteristic two-peaked pattern); this has been explained as being due to axial elongation of the six co-ordinated Cr³⁺-complex in these glasses.     

Optical and esr spectra of titanium (III) in Na2O-B2O3 and Na2O-P2O5 glasses

The optical absorption and the esr spectra of titanium(III) in binary Na₂O-B₂O₃ and Na₂O-P₂O₅ glasses have been studied. Titanium(III) produces two optical absorption bands around 20 000 and 14 000 cm^–1 which are assigned to the²B_2g ²B_1g and²B_2g ²A_1g transitions respectively of Ti³⁺ in a tetragonally distorted octahedral environment. The absorption bands in phosphate glasses are narrower and absorption coefficients higher than those in borate glasses. The esr spectrum of titanium(III) in all the glasses consists of a broad asymmetric line withg 1.94 in borate glasses, andg 1.92 in phosphate glasses; no hyperfine structure has been observed.     

Crystallization in glass: elucidating a realm of diversity by transmission electron microscopy

Glass ceramics, i.e. intentionally devitrified glasses, are used in manifold applications. This is due to the capability to precisely control the precipitation of crystalline phases possessing useful properties related to optics, mechanics, biocompatibility, piezoelectricity, machinability, etc. In order to control the nano and microstructure, transmission electron microscope imaging proves particularly useful. Illustrated by numerous examples, the diverse precipitate shapes and mechanisms at work upon crystallization of glasses are discussed. In addition, it is shown how useful cutting-edge transmission electron microscopy is in the field of nanoanalytics. The investigation of nanoscale processes controlling the precipitation of functional crystals evidences the need for more sophisticated theories describing the changes of composition accompanying crystallization in non-isochemical systems (precipitates possess compositions different from those of the host glasses).     

Characterization and study of Na2O-B2O3-SiO2 glasses prepared by the sol-gel method

The sol-gel procedure has been used to prepare vitreous materials whose compositions are situated in the liquid-liquid immiscibility area of the Na₂O-B₂O₃ SiO₂ phase equilibrium diagram. Gels were prepared from different precursors and under different experimental conditions. After determining optimum conditions for gelling and heat-treatment, the gels were characterized with the aid of thermal analysis, X-ray diffraction, density and specific surface area measurements, as well as infrared and near-infrared spectroscopy. The textures of the samples and their microstructures were studied by means of scanning electron microscopy and transmission electron microscopy, respectively. The phase separation in the gels was compared to the same phenomenon in one of the glasses of identical composition, but prepared by conventional melting.     

Hot stage transmission electron microscopy of crystallisation in a lithia-silica glass

Hot stage transmission electron microscopy has allowed the nucleation sequence in a 30 mole % Li₂O-70 mole % SiO₂ glass to be monitored in situ. This result agrees with previous work, in that the sequence of phases observed is identical but small temperature changes give rise to pronounced morphology changes. Hot stage electron microscopy has been proven to be a very useful technique for observing glass crystallisation processes, but the results must be carefully interpreted because of possible surface effects.Commercial masking lacquer.     

Thermal activation energy of silver in ion-exchanged soda–lime glass investigated by X-ray photoelectron spectroscopy

The thermal effect on silver in ion-exchanged glasses was investigated in situ by X-ray photoelectron spectroscopy (XPS) in an ultra-high vacuum environment. Each XPS signal of Ag 3d_3/2 and 3d_5/2 consists of two components, the metallic state (Ag⁰) and the oxidized state (Ag⁺), resolved after curve fitting. The toward-surface diffusion of silver was observed by monitoring the changes in concentration on the surface during sample annealing between 20 and 450°C. Judging from the variations in line shape and binding energy and from the enhancement of surface silver under annealing, both metallic and oxidized silver are accumulated on the surface. By applying the diffusion theory in a semi-infinite system to the experimental data, the thermal activation energy of the oxidized silver in ion-exchanged glass, 0.16 eV, was estimated. The activation energy of metallic Ag precipitated during heating, 0.23 eV, was estimated as well.     

Microstructure of sol–gel synthesized Al2O3–ZrO2(Y2O3) nano-composites studied by transmission electron microscopy

The Al₂O₃–ZrO₂(Y₂O₃) composite powder was synthesized through a sol–gel process using aluminum sec-butoxide and zirconium butoxide as precursors. The as-received powders in an amorphous phase were crystallized with c-ZrO₂ at around 980 °C. As the calcination temperature increased, the c-ZrO₂ crystalline phase was transformed to t-ZrO₂ at about 1200 °C. However, the Al₂O₃ phase in the Al₂O₃–ZrO₂(Y₂O₃) composite powders still existed in an amorphous phase up to 1050 °C. In the sintered body using the calcined powders at 400 °C, the Al₂O₃ phase was crystallized in an α-phase at 1200 °C during the sintering for 2 h. Using the sol–gel Al₂O₃–ZrO₂(Y₂O₃) powder, a typical nano-composite having a nano-crystalline phase (less than 20 nm) can be successfully obtained by a pressureless-sintering process even at 1200 °C for 2 h.Using the sol–gel Al₂O₃–ZrO₂(Y₂O₃) powder, a typical nano-composite having a nano-crystalline phase (less than 20 nm) can be successfully obtained by a pressureless-sintering process even at 1200 °C for 2 h. The values of relative density and Vickers hardness were comparatively high value with about 96.2% and 1100 Hv, respectively, even though it was made at low temperature. In the composite sintered at 1400 °C, the hardness value was saturated with 1570 Hv and the values of fracture toughness were almost same with about 6 MPa m^1/2.     

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.     

Optical absorption and electron spin resonance studies of Cu2+ in Li2O-Na2O-B2O3-As2O3 glasses

The local structure around Cu²⁺ ion has been examined by means of electron spin resonance and optical absorption measurements in xLi₂O-(40-x)Na₂O-50B₂O₃-10As₂O₃ glasses. The site symmetry around Cu²⁺ ions is tetragonally distorted octahedral. The ground state of Cu²⁺ isd _x ²−y ².The glass exhibited broad absorption band near infrared region and small absorption band around 548 nm, which was assigned to the ²B_1g →²E_g transition.     

Comparison of glass hydration layer thickness measured by transmission electron microscopy and nanoindentation

The thicknesses of the hydration layers on the surfaces of 2 silicate glasses have been assessed using a) a combination of focused ion beam milling and transmission electron microscopy and b) nanoindentation; the two approaches give consistent layer thicknesses. Lighter contrast of the hydrated layers in TEM suggests that the layers have reduced density when compared to the bulk glasses; this is consistent with the reduced near surface modulus and hardness of hydrated glasses observed in nanoindentation.     

Electron microscopy and EDX-microanalysis of photochromic silver halide glasses of the composition systems Al2O3-B2O3-SiO2 and Na2O-CaO-SiO2

The microstructure and microanalysis study of two glasses containing AgCl precipitated particles have been carried out by transmission electron microscopy (TEM, replica method), scanning electron microscopy (SEM) and SEM/EDX (energy dispersive X-ray spectrometry). The composition of these glasses doped with silver halide and CuO was formulated from the Al₂O₃-B₂O₃-SiO₂ and Na₂O-CaO-SiO₂ systems respectively. In both glasses the seeds, nuclei, crystals and matrix were analysed, and the mean size and number of crystals were evaluated from the TEM and SEM observations. The microstructure in both glasses is different because of the different shape of the silver halide particles; the particles of the Al₂O₃-B₂O₃-SiO₂ glass are rounded while Na₂O-CaO-SiO₂ shows square precipitated particles. Likewise, the darkening behaviour is basically different; the Al₂O₃-B₂O₃-SiO₂ glass shows a higher darkening velocity than the Na₂O-CaO-SiO₂ glass, showing for this glass a very small slope value.