Speckle correlation for the analysis of random processes at rough surfaces

The importance of technological processes like corrosion, ablation or deposition causes interest in the quantitative monitoring of changes at rough surfaces. Thus, there is a need for effective methods to measure the statistical parameters characterizing changes in the profile or the material composition of such objects. The speckle field scattered from the surface is used as information carrier and its change is measured by correlation. This is realized by sophisticated data acquisition and digital processing techniques. An important issue is the interpretation of the correlation output in terms of statistical parameters describing the surface change. For many random surfaces a geometrical relation between surface profile and optical phase proves satisfactory. This allows to determine the standard deviation of the profile change. For a verification, speckle decorrelation in model surfaces of known deviation is measured. The paper introduces the speckle correlation concept, outlines some history and current setups and describes methods for data evaluation. The reliability of the quantitative interpretation of the speckle decorrelation is demonstrated. The method is illustrated by studies of metal corrosion and material removal in the cleaning of historical objects by laser ablation.     

Thermal Back‐Isomerization of Spirocyclic Naphtho‐oxazine and Phenanthro‐oxazine Derivatives in Alcohols,Nitriles, and Poly(alkyl methacrylates)

The thermal back‐isomerization of spiro[indole‐naphtho‐oxazine] 1 and spiro[indole‐phenanthro‐oxazine] 2 was studied in a series of primary alcohols, nitriles, and poly(methylmethacrylate), poly(ethylmethacrylate), and poly(isobutyl methacrylate) films by laser‐flash photolysis in the temperature range of 0 – 70°. The decay is monoexponential in fluid solution, but deviates strongly from this behavior in polymeric environments even above the glass transition temperature of the polymers (Tg). In liquids, a very small solvent effect is observed on the isomerization rate constants (k_iso) for 1 , which is attributed mostly to the solvent viscosity η. The values of k_iso for 2 show influence of solvent viscosity and polarity, which were studied by application of a semiempirical relationship that accounts for non‐Markovian processes. The decay kinetics in polymers was described by a Gaussian distribution of the activation energy and by a kinetic model that takes into account the simultaneous relaxation of the probe and the environment. For 1 and 2 , the rate constant at the center of the Gaussian distribution is very similar to the first‐order rate constant in nonpolar solvents. The Gaussian width of the distribution (σ) decreases with temperature and is very similar in all polymers under Tg, and, above Tg, σ decreases more abruptly. We make comparisons of the parameters derived from analysis of both 1 and 2 in polymers, as well as of their behaviors in solution and in polymers.     

A Novel Method for the Demetalation of Tricarbonyliron–Diene Complexes by a Photolytically Induced Ligand Exchange Reaction with Acetonitrile

The photochemical exchange of all three carbonyl ligands with acetonitrile converts tricarbonyliron–diene complexes into the very labile triacetonitrile-iron–diene complexes. These easily demetalate in high yields to the corresponding free ligands on injection of air at −30°C [Eq. (1)]. The novel demetalation procedure is applied to the tricarbonyliron complexes of cyclopentadienones, cyclohexa-1,3-dienes, and buta-1,3-dienes.     

Quantitative modeling of laser speckle imaging

We have analyzed the image formation and dynamic properties in laser speckle imaging (LSI) both experimentally and with Monte Carlo simulation. We show for the case of a liquid inclusion that the spatial resolution and the signal itself are both significantly affected by scattering from the turbid environment. Multiple scattering leads to blurring of the dynamic inhomogeneity as detected by LSI. The presence of a nonfluctuating component of scattered light results in the significant increase in the measured image contrast and complicates the estimation of the relaxation time. We present a refined processing scheme that allows a correct estimation of the relaxation time from LSI data.     

Snapshot of the palladium(II)-catalyzed oxidative biaryl bond formation by X-ray analysis of the intermediate diaryl palladium(II) complex

Pd(II) caught in the act: The diaryl Pd(II) intermediate of a Pd(II)-catalyzed oxidative biaryl bond formation proceeding via a double C-H bond activation has been isolated and fully characterized, including an X-ray crystal structure analysis. Stabilization due to chelation by adjacent pivaloyloxy and acetyl groups has allowed the isolation of this long-sought crucial intermediate. On gentle warming, the complex is transformed into a carbazole product, and the catalytically active Pd(II) species is regenerated by oxidation with Cu(II).     

Stereoselective synthesis and hormonal activity of novel dafachronic acids and naturally occurring steroids isolated from corals

A stereoselective synthesis of (25S)-Δ(1)-, (25S)-Δ(1,4)-, (25S)-Δ(1,7)-, (25S)-Δ(8(14))-, (25S)-Δ(4,6,8(14))-dafachronic acid, methyl (25S)-Δ(1,4)-dafachronate and (25S)-5α-hydroxy-3,6-dioxocholest-7-en-26-oic acid is described. (25S)-Δ(1,4)-Dafachronic acid and its methyl ester are natural products isolated from corals and have been obtained by synthesis for the first time. (25S)-5α-Hydroxy-3,6-dioxocholest-7-en-26-oic acid represents a promising synthetic precursor for cytotoxic marine steroids.     

Hybrid heuristics for the capacitated lot sizing and loading problem with setup times and overtime decisions

The capacitated lot sizing and loading problem (CLSLP) deals with the issue of determining the lot sizes of product families/end items and loading them on parallel facilities to satisfy dynamic demand over a given planning horizon. The capacity restrictions in the CLSLP are imposed by constraints specific to the production environment considered. When a lot size is positive in a specific period, it is loaded on a facility without exceeding the sum of the regular and overtime capacity limits. Each family may have a different process time on each facility and furthermore, it may be technologically feasible to load a family only on a subset of existing facilities. So, in the most general case, the loading problem may involve unrelated parallel facilities of different classes. Once loaded on a facility, a family may consume capacity during setup time. Inventory holding and overtime costs are minimized in the objective function. Setup costs can be included if setups incur costs other than lost production capacity. The CLSLP is relevant in many industrial applications and may be generalized to multi-stage production planning and loading models. The CLSLP is a synthesis of three different planning and loading problems, i.e., the capacitated lot sizing problem (CLSP) with overtime decisions and setup times, minimizing total tardiness on unrelated parallel processors, and, the class scheduling problem, each of which is NP in the feasibility and optimality problems. Consequently, we develop hybrid heuristics involving powerful search techniques such as simulated annealing (SA), tabu search (TS) and genetic algorithms (GA) to deal with the CLSLP. Results are compared with optimal solutions for 108 randomly generated small test problems. The procedures developed here are also compared against each other in 36 larger size problems.     

Bose-einstein correlations of soft pions in ultrarelativistic nucleus-nucleus collisions

A detailed analysis of pair correlations of positive pions in the target fragmentation region is presented. Data on nuclear collisions at 200 GeV per nucleon were measured with the Plastic Ball in the WA80 experiment at the CERN SPS. The correlation functions are compared with analytical functions and with simulations incorporating Bose-Einstein symmetrization, final-state interactions and detector resolution. Source radii are shown to increase with increasing target size and with centrality. For central collisions the radii are larger than the geometrical sizes of the involved nuclei.