Promoting effect of potassium on catalytic and surface properties and phase commposition of catalysts for synthesis of alcohols

The dependence between catalytic and surface acid-base properties of Zn–Cr–K catalysts has been established. Modification by potassium and an increase in potassium concentration promotes Zn–Cr–K reduction and raises the yield of higher alcohols. The spinel structure of catalysts is preserved.

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Zn–Cr–K . Zn–Cr–K , .

     

Numerical analysis of TOF measurements in pulsed laser ablation

The results of numerical simulation of pulsed laser ablation both in vacuum and into a background gas are presented. The influences of different processes, such as time evolution of the surface temperature, interspecies interactions (elastic collisions, recombination-dissociation reaction), interaction with an ambient gas, and excitations-relaxation processes on time-of-flight (TOF) distributions are examined. Experimentally obtained time-of-flight distributions are further analyzed, based on the results of numerical simulation. It is found that with the aid of numerical results one can explain not only the shape of the TOF distribution, but also the distance dependency of its maximum position (mean delay time). In addition, the mechanisms leading to the appearance of bimodal time-of-flight distribution are revealed. The study presents particular interest for the analysis of experimental results obtained during pulsed laser ablation.     

Femtosecond laser interactions with dielectric materials: insights of a detailed modeling of electronic excitation and relaxation processes

Electronic excitation–relaxation processes induced by ultra-short laser pulses are studied numerically for dielectric targets. A detailed kinetic approach is used in the calculations accounting for the absence of equilibrium in the electronic subsystem. Such processes as electron–photon–phonon, electron–phonon and electron–electron scatterings are considered in the model. In addition, both laser field ionization ranging from multi-photon to tunneling one, and electron impact (avalanche) ionization processes are included in the model. The calculation results provide electron energy distribution. Based on the time-evolution of the energy distribution function, we estimate the electron thermalization time as a function of laser parameters. The effect of the density of conduction band electrons on this time is examined. By using the average electron energy, a new criterion is proposed based on determined damage threshold in agreement with recent experiments (Sanner et al. in Appl. Phys. Lett. 96:071111, 2010).     

Nanoparticle formation by laser ablation in air and by spark discharges at atmospheric pressure

Recent promising methods of nanoparticle fabrication include laser ablation and spark discharge. Despite different experimental conditions, a striking similarity is often observed in the sizes of the obtained particles. To explain this result, we elucidate physical mechanisms involved in the formation of metallic nanoparticles. In particular, we compare supersaturation degree and sizes of critical nucleus obtained under laser ablation conditions with that obtained for spark discharge in air. For this, the dynamics of the expansion of either ablated or eroded products is described by using a three-dimensional blast wave model. Firstly, we consider nanosecond laser ablation in air. In the presence of a background gas, the plume expansion is limited by the gas pressure. Nanoparticles are mostly formed by nucleation and condensation taking place in the supersaturated vapor. Secondly, we investigate nanoparticles formation by spark discharge at atmospheric pressure. After efficient photoionization and streamer expansion, the cathode material suffers erosion and NPs appear. The calculation results allow us to examine the sizes of critical nuclei as function of the experimental parameters and to reveal the conditions favorable for the size reduction and for the increase in the nanoparticle yield.     

Investigation of nanoparticle generation during femtosecond laser ablation of metals

The production of nanoparticles via femtosecond laser ablation of gold and copper is investigated experimentally involving measurements of the ablated mass, plasma diagnostics, and analysis of the nanoparticle size distribution. The targets were irradiated under vacuum with a spot of uniform energy distribution. Only a few laser pulses were applied to each irradiation site to make sure that the plume expansion dynamics were not altered by the depth of the laser-produced crater. Under these conditions, the size distribution of nanoparticles does not exhibit a maximum and the particle abundance monotonously decreases with size. Furthermore, the results indicate that two populations of nanoparticles exist within the plume: small clusters that are more abundant in the fast frontal plume component and larger particles that are located mostly at the back. It is shown that the ablation efficiency is strongly related to the presence of nanoparticles in the plume.     

Modelling the formation of nanostructures on metal surface induced by femtosecond laser ablation

We employ the particle-in-cell method to simulate the mechanisms of femtosecond (fs) laser interactions with a metallic target. The theoretical approach considers the solid as a gas of free electrons in a lattice of immobile ions and the laser fluences close to the ablation threshold. At first moments of the interaction, our simulations mapped out different nanostructures. We carefully characterized the rippling phase and found that its morphology is dependent on the distribution of the electron density and the period of the ripples depends on the laser intensity. The simulation method provides new insights into the mechanisms that are responsible for surface grating formation.     

Numerical study of ultra-short laser ablation of metals and of laser plume dynamics

Numerical modeling is used to investigate the physical mechanisms of the interaction of ultra-short (sub-picosecond) laser pulses with metallic targets. The laser–target interaction is modeled by using a one-dimensional hydrodynamic code that includes the absorption of laser radiation, the electronic heat conduction, the electron-phonon or electron–ion energy exchange, as well as a realistic equation of state. Laser fluences typical for micromachining are considered. The results of the 1D modeling are then used as the initial conditions for a 2D plasma expansion model. The dynamics of laser plume expansion in femtosecond regime is investigated. Calculations show that the plasma plume is strongly forward directed. In addition, a two-peaked axial density profile is obtained for 400 nm laser wavelength. The calculation results agree with the experimental observations. PACS 52.38.Mf; 02.60.Cb     

Electronic excitation in femtosecond laser interactions with wide-band-gap materials

Effects of the ultrashort laser excitations of wide-band-gap materials are investigated. Single-, double-, and multiple-shot cases are considered with a particular focus on the control over the transient reflectivity changes and the energy deposition rate. We show that the history of laser excitations affects not only the ionization process and the final number of the conduction-band electrons, but also determines the reflectivity time evolution and the rate of laser energy deposition into the target. Based on the obtained calculation results, both thermal effects and structural modifications can be better controlled.     

Correlation between ablation efficiency and nanoparticle generation during the short-pulse laser ablation of metals

The mechanisms of material ablation and nanoparticle generation from metal samples exposed to intense short laser pulses are experimentally investigated. We performed measurements of the ablated volume using optical microscopy and the analysis of the ablation plume by fast imaging. The results confirm the existence of two distinguished ablation regimes as a function of the laser fluence, and give a deeper insight in the involved physical mechanisms. Thus, both regimes are found to be related to the relative amount of atoms and nanoparticles within the plume. Comparing the results obtained for copper and gold, it is possible to determine the influence of electron-lattice coupling on the sample heat regime and the resulting plume properties.     

Rippled area formed by surface plasmon polaritons upon femtosecond laser double-pulse irradiation of silicon: the role of carrier generation and relaxation processes

The formation of laser-induced periodic surface structures (LIPSS, ripples) upon irradiation of silicon with multiple irradiation sequences consisting of femtosecond laser pulse pairs (pulse duration 150 fs, central wavelength 800 nm) is studied numerically using a rate equation system along with a two-temperature model accounting for one- and two-photon absorption and subsequent carrier diffusion and Auger recombination processes. The temporal delay between the individual equal-energy fs-laser pulses was varied between 0 and ～4 ps for quantification of the transient carrier densities in the conduction band of the laser-excited silicon. The results of the numerical analysis reveal the importance of carrier generation and relaxation processes in fs-LIPSS formation on silicon and quantitatively explain the two time constants of the delay-dependent decrease of the low spatial frequency LIPSS (LSFL) area observed experimentally. The role of carrier generation, diffusion and recombination is quantified individually.