Low temperature nanoparticle sintering with continuous wave and pulse lasers

New manufacturing methods are being sought for electronics production. Printable electronics is a promising method for producing low cost and large-scale electronics. In printable electronics nanoparticle inks printed on the surface of substrate contain additives, such as dispersing agent and carrier fluids that provide good printing properties by changing the viscosity and separating the nanoparticles of the ink. In the sintering process ink particles are heated to a certain, ink-specific temperature. During the sintering process the carrier fluid and dispersing agents are evaporated from the ink. Additional heating after evaporation causes the nanoparticles to start to agglomerate. A small particle size allows the use of a considerably lower sintering temperature than with bulk silver, for example 220 °C. The sintering process is usually utilized with a convection oven, with a long sintering time, and the thermal load on the surrounding material can become too great as components and patterns are formed from layers of different type inks. Hence, alternative sintering methods are sought. This paper describes tests done with two different types of laser; pulsed and continuous wave lasers. Laser sintering enables short sintering times and selective sintering, making it possible for printed structures to contain fragile active components produced with other technologies.     

Up-Conversion Luminescence of the NaRF<Subscript>4</Subscript>-NaR′F<Subscript>4</Subscript> (R: Y,Yb, Er) Core-Shell Nanomaterials

Up-converting NaRF₄-NaR′F₄ (R: Y, Yb, Er) nanomaterials with different core-shell combinations were prepared with the co-precipitation method. The X-ray powder diffraction (XPD) measurements revealed the presence of both the cubic and hexagonal NaRF₄ phases. The crystallite sizes calculated with the Scherrer formula were 100 and 150 nm for the cubic and hexagonal phases, respectively. The FT-IR spectra showed water impurities. The up-conversion luminescence and luminescence decays were studied with NIR laser excitation at 970 nm. The up-conversion luminescence spectra showed strong red (640–685 nm) (⁴F_9/2 → ⁴I_15/2) and moderate green (515–560 nm) (²H_11/2, ⁴S_3/2 → ⁴I_15/2) Er³⁺ luminescence. The strongest up-conversion luminescence and longest red luminescence decay was obtained from the Na(Y,Yb)F₄-NaErF₄ core-shell combination.     

Aerosol characterization and lung deposition of synthesized TiO2 nanoparticles for murine inhalation studies

This study presents a novel exposure protocol for synthesized nanoparticles (NPs). NPs were synthesized in gas phase by thermal decomposition of metal alkoxide vapors in a laminar flow reactor. The exposure protocol was used to estimate the deposition fraction of titanium dioxide (TiO₂) NPs to mice lung. The experiments were conducted at aerosol mass concentrations of 0.8, 7.2, 10.0, and 28.5 mg m^?3. The means of aerosol geometric mobility diameter and aerodynamic diameter were 80 and 124 nm, and the geometric standard deviations were 1.8 and 1.7, respectively. The effective density of the particles was approximately from 1.5 to 1.7 g cm^?3. Particle concentration varied from 4 × 10⁵ cm^?3 at mass concentrations of 0.8 mg m^?3 to 12 × 10⁶ cm^?3 at 28.5 mg m^?3. Particle phase structures were 74% of anatase and 26% of brookite with respective crystallite sized of 41 and 6 nm. The brookite crystallites were approximately 100 times the size of the anatase crystallites. The TiO₂ particles were porous and highly agglomerated, with a mean primary particle size of 21 nm. The specific surface area of TiO₂ powder was 61 m² g^?1. We defined mice respiratory minute volume (RMV) value during exposure to TiO₂ aerosol. Both TiO₂ particulate matter and gaseous by-products affected respiratory parameters. The RMV values were used to quantify the deposition fraction of TiO₂ matter by using two different methods. According to individual samples, the deposition fraction was 8% on an average, and when defined from aerosol mass concentration series, it was 7%. These results show that the exposure protocol can be used to study toxicological effects of synthesized NPs.     

Broadband fluorescence reveals mechanistic differences in excited-state proton transfer to protic and aprotic solvents

Excited-state proton transfer (ESPT) to solvent is often explained according to the two-step Eigen–Weller model including a contact ion pair (CIP*) as an intermediate, but general applicability of the model has not been thoroughly examined. Furthermore, examples of the spectral identification of CIP* are scarce. Here, we report on a detailed investigation of ESPT to protic (H₂O, D₂O, MeOH and EtOH) and aprotic (DMSO) solvents utilizing a broadband fluorescence technique with sub-200 fs time resolution. The time-resolved spectra are decomposed into contributions from the protonated and deprotonated species and a clear signature of CIP* is identified in DMSO and MeOH. Interestingly, the CIP* intermediate is not observable in aqueous environment although the dynamics in all solvents are multi-exponential. Global analysis based on the Eigen–Weller model is satisfactory in all solvents, but the marked mechanistic differences between aqueous and organic solvents cast doubt on the physical validity of the rate constants obtained.

Time-resolved broadband fluorescence facilitates direct observation of reaction intermediates in excited-state proton transfer to solvent in protic and aprotic solvents.     

Lattice Boltzmann Simulation of Flow-Induced Wall Shear Stress in Porous Media

The lattice Boltzmann method is increasingly utilized in the simulation of flow-induced wall shear stress needed in various applications. In image-based flow simulations, the simulation geometry is usually based on a three-dimensional reconstruction of the true structure of the pore space obtained, for example, by X-ray tomography. The geometry is then given in a voxel-based representation, which complicates an accurate determination of the surface-normal vectors that are necessary in the computation of the wall shear stress. To avoid this problem, we introduce here a method for the determination of surface-normal vectors directly from a greyscale image instead of its segmented binary image version. The proposed method is fast and automatic, and it can be used for an arbitrary pore space geometry provided in a greyscale form by any imaging modality. We show that this method can produce accurate surface-normal vectors even for binary images and that their accuracy is further increased when the original greyscale images are used instead. We compute wall shear stresses for generated benchmark geometries and then demonstrate the utility of the method for soil samples with ‘random’ pores imaged by X-ray tomography.     

Probing lattice defects in Sr2MgSi2O7:Eu2+,Dy3+

The Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ materials were prepared with a solid state reaction and their microscopic structure (at 295 K only) and luminescence were studied at selected temperatures between 150 and 295 K. Undisturbed Sr crystal planes were common in the TEM images of the undoped Sr₂MgSi₂O₇ material, whereas with Eu²⁺ doping more disturbed planes were observed even in the nanometer scale. With Dy³⁺ co-doping, a large number of small lattice domains created by the discontinuities in the crystal structure was observed. The domains with different orientations seem to be centered around point defects. The decay curves of Sr₂MgSi₂O₇:Eu²⁺,Dy³⁺ showed fast (ms scale) persistent luminescence. The intensity of persistent luminescence increased considerably between 200 and 250 K while remaining constant in the ranges of 150–200 and 250–295 K. The changes were used to study the depth of the traps. In general, Dy³⁺ co-doping was found to deepen the traps.     

Characterization of a potato reference material for major, minor and trace elements

Summary A potato reference material (RM) was prepared for the analytical quality control program to be employed by the Sub-network on Trace Elements in Food of the FAO European Co-operative Network on Trace Elements. Approximately 50 kg of commercially available potato granules prepared from baked, mashed and roller-dried potatoes, containing 2.8% ash and 3 mg/kg added butylhydroxyanisole was purchased. The granules were carefully homogenised in large glass cylinders followed by division into 50 g portions into numbered acid-washed bottles. The bottled material was tested for homogeneity by taking ten bottles throughout the bottling line and determining by validated atomic absorption spectrometric methods 1.0 g samples for seven mineral elements. Homogeneity for Mg, Ca, Zn, Fe, Mo, Ni and Cd was better than 5%. An international network on experienced, high-quality reference laboratories was established to conduct an interlaboratory comparison study on the determination of 14 mineral elements in the RM. A total of seven methods based on independent analytical principles were employed by the reference laboratories. After excluding outlying analytical results, the criteria defined by the IAEA were used for classification of the overall medians obtained through the interlaboratory comparison study. The relative standard deviations for the 95% confidence limits of the medians were as follows: P=4.2%, K=0.7%, Na=4.7%, Ca=5.5%, Mg=2.4%, Fe=9.3%, Mn=4.0%, Zn=3.6%, Cu=4.7%, Mo=23%, Ni=22%, Cr=19%, Pb=11% and Cd=4.6%. With the exception of Cr, all of the recommended concentration values obtained for the above indicated elements fell into category A, i.e. values recommended with a high degree of confidence according to the classification criteria of the IAEA. The present RM is the only certified potato RM currently available for mineral elements.

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Charakterisierung eines Kartoffel-Referenzmaterials für Haupt-, Neben- und Spurenelemente

     

Conformational analysis: IX–a 300 MHz study of 4-vinylbutyrolactone

The 300 MHz ¹H NMR spectrum of 4-vinylbutyrolactone has been recorded and analysed. The results showed that the compound is a mixture of two rapidly interconverting envelope forms in which (C-3) is the flap atom. The vinyl group favours the pseudo-equatorial orientation by 1·9 ± 0.3 kJ mol^?1, as shown by the dependence of the vicinal coupling constants on temperature.     

Determination of chromium in human milk and urine by graphite-furnace atomic absorption spectrometry

Low-temperature ashing and dry ashing at 500°C are compared for the analysis of urine and human milk. Dry ashing gives superior accuracy. The importance of contamination control, background correction and temperature control are stressed. Both urine and human milk contain about 1 ng Cr ml^-1.