Interface and defects engineering for multilayer laser coatings

High-reflective multilayer laser coatings are widely used in advanced optical systems from high power laser facilities to high precision metrology systems. However, the real interface quality and defects will significantly affect absorption/scattering losses and laser induced damage thresholds of multilayer coatings. With the recent advances in the control of coating design and deposition processes, these coating properties can be significantly improved when properly engineered the interface and defects. This paper reviews the recent progress in the physics of laser damage, optical losses and environmental stability involved in multilayer reflective coatings for high power nanosecond near-infrared lasers. We first provide an overview of the layer growth mechanisms, ways to control the microstructures and reduce layer roughness, as well as the nature of defects which are critical to the optical loss and laser induced damage. Then an overview of interface engineering based on the design of coating structure and the regulation of deposition materials reveals their ability to improve the laser induced damage threshold, reduce the backscattering, and realize the desirable properties of environmental stability and exceptional multifunctionality. Moreover, we describe the recent progress in the laser damage and scattering mechanism of nodule defects and give the approaches to suppress the defect-induced damage and scattering of the multilayer laser coatings. Finally, the present challenges and limitations of high-performance multilayer laser coatings are highlighted, along with the comments on likely trends in future.     

Orientation dependent size effects in thermal buckling and post-buckling of nanoplates with cubic anisotropy

In this work, a continuum model is presented for size and orientation dependent thermal buckling and post-buckling of anisotropic nanoplates considering surface and bulk residual stresses. The model with von-Karman nonlinear strains and material cubic anisotropy of single crystals contains two parameters that reflect the orientation effects. Using Ritz method, closed form solutions are given for buckling temperature and post-buckling deflections. Regarding self-instability states of nanoplates and their recovering at higher temperatures, an experiment is discussed based on low pressurized membranes to verify the predictions. For simply supported nanoplates, the size effects are lowest when they are aligned in [100] direction. When the edges get clamped, the orientation dependence is ignorable and the behavior becomes symmetric about [510] axis. The surface residual stress makes drastic increase in buckling temperature of thinner nanoplates for which a minimum thickness is pointed to stay far from material softening at higher temperatures. Deflection of [100]-oriented buckled nanoplates is higher than [110] ones but this reverses at higher temperatures. The results for long nanoplates show that the buckling mode numbers are changed by orientation which is verified by FEM.     

Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study

We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent.     

Strain induced strengthening of soft thermoplastic polyurethanes under cyclic deformation

We investigate the cyclic mechanical behavior in uniaxial tension of three different commercial thermoplastic polyurethane elastomers (TPU) often considered as a sustainable replacement for common filled elastomers. All TPU have similar hard segment contents and linear moduli but sensibly different large strain properties as shown by X-ray analysis. Despite these differences, we found a stiffening effect after conditioning in step cyclic loading which greatly differs from the common softening (also referred as Mullins effect) observed in chemically crosslinked filled rubbers. We propose that this self-reinforcement is related to the fragmentation of hard domains, naturally present in TPU, in smaller but more numerous sub-units that may act as new physical crosslinking points. The proposed stiffening mechanism is not dissimilar to the strain-induced crystallization observed in stretched natural rubber, but it presents a persistent nature. In particular, it may cause a local reinforcement where an inhomogeneous strain field is present, as is the case of a crack propagating in cyclic fatigue, providing a potential explanation for the well-known toughness and wear resistance of TPU.     

Chain transfer to solvent in BN 2-vinylnaphthalene radical polymerization

The synthesis of vinyl alcohol copolymers is limited due to the poor radical reactivity of vinyl acetate (VAc), the traditional precursor to polyvinyl alcohol (PVA). Main group monomers such as BN 2-vinylnaphthalene (BN2VN) have attracted attention as alternatives to VAc to form side chain hydroxyls via oxidation, but outstanding questions of molecular weight control remain. Herein we report systematic investigation of solvent, temperature, and initiator concentration as factors influencing BN2VN degree of polymerization. We find increased chain transfer to toluene, hypothesized to arise from differences in radical stabilization and reactivity by aromatic and BN aromatic rings. As a result of these combined efforts, high molecular weight (M_w ~ 10⁵ g mol⁻¹) BN2VN homopolymers and BN2VN-styrene copolymers were obtained.     

Transformation of malonic acid adsorbed on a clay-mineral by gamma irradiation

The effect of clay on the radiolysis of malonic acid solutions was studied. The results showed an enhanced of decarboxylation rather than condensation reactions.     

Linearization of column responses by correlation chromatography. Separation improvement and reduction of undesired adsorption effects

Summary Experiments and simulations prove that correlation chromatography can greatly reduce the disadvantage of a non-linear response of the chromatographic column. A factor that has been accepted as being an important source of error in correlation or multiplex chromatography, has been shown not to be. Separations affected, improve dramatically when correlation chromatography is used, and a substantial amount of correlation noise only arises when there is a large difference in separation between a conventional chromatogram and a correlogram.A model has been developed for simulating these nonlinearities. It is shown that, especially for correlation chromatography, the simulation results match the practical measurements very well.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.