Photochromic properties of polyimide and polysiloxane azopolymers

BACKROUND: One of the most important properties of the azobenzene chromophores is the photochemical trans–cis isomerization induced by UV or visible light. In azopolymers, the photoisomerization induces conformational changes in the polymer chains, which in turn lead to macroscopic variations in the chemical and physical properties of the surroundings and media. RESULTS: This work reports the photochromic behaviour and surface structuring capacity of azopolymers having rigid polyimide and flexible polysiloxane structures, respectively. These polymers have good thermostabilities, with the degradation process starting above 315 °C. The glass transition temperature of the azopolyimide is 228 °C, while that of the azopolysiloxane modified with thymine is 34 °C. CONCLUSION: The experiments show that the azobenzene groups can isomerize even in the case of the rigid polyimide, but the maximum degree of conversion to the cis isomer is less than in the case of the flexible polysiloxane. This behaviour is reversed in solution, probably due to both the thymine and azo group interactions and for conformational reasons. The azopolymers show a good surface structuring capacity. The polysiloxane is more sensitive in the case of low irradiation energy and irradiation time. By increasing the irradiation time for both polymers, the modulation depth increases and has comparable values. Copyright © 2008 Society of Chemical Industry     

Inhibition effect of some aromatic amines on copper electrodeposition from acidic baths

To improve the quality requirements for copper deposits, the influence of some inhibition agents added to the acidic copper bath has been studied. Several aromatic nitrogen compounds have been tested as inhibition agents, such as aniline, N-methylaniline, N-ethylaniline, N,N-dimethylaniline (DMA), and N,N-diethylaniline (DEA). The electrochemical behavior of these organic additives and the most relevant aspects of the electrochemical behavior of copper in acid solutions have been analyzed by cyclic voltammetry. At the same time, a correlation between voltammetric data and molecular properties of protonated amines obtained by molecular modeling has been performed. The morphology of the copper deposits obtained in the absence and presence of organic compounds has been studied by scanning electron microscopy. An improvement of the roughness degree and crystallite size upon addition of aromatic amine has been found. Best results were obtained for DMA and DEA working at room temperature (25 ± 0.1 °C) and 200 A m⁻² current density, in 1 mol L⁻¹ sulfuric acid solution with 50 g L⁻¹ Cu²⁺.     

Aromatic amines as proton carriers for catalytic enhancement of hydrogen evolution reaction on copper in acid solutions

The catalytic effect of some aromatic amines towards hydrogen evolution reaction on copper in diluted sulfuric acid solution has been studied. Since amines facilitate the transport of protons from the solution bulk to the interface in the cathodic hydrogen evolution reaction, they are known as proton carriers. The catalytic effect of aniline, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,N-diethylaniline, o-toluidine, m-toluidine and p-toluidine has been highlighted by linear sweep voltammetry. The kinetic parameters for the hydrogen evolution reaction (cathodic transfer coefficient 1-α and exchange current density i_o) in the presence of the studied aromatic amines were derived from the Tafel plots. It has been found that the catalytic effect of amines is active even at low concentration. Thus, in 0.5 mol L⁻¹ H₂SO₄ solution the exchange current density increases by two orders of magnitude, from 2.01⋅10⁻⁵ A m⁻² in the absence of aniline to 2.85⋅10⁻³ A m⁻² in the presence of 10⁻⁴ mol L⁻¹ aniline. The influence of amines concentration on the catalytic effect is described in detail for the case of m-toluidine. The results obtained by voltammetry have been compared with electrochemical impedance spectroscopy data. Furthermore, the kinetic parameters for the hydrogen evolution reaction have been determined as a function of temperature and amines concentration.     

JuNoLo - Jülich nonlocal code for parallel post-processing evaluation of vdW-DF correlation energy

Nowadays the state of the art Density Functional Theory (DFT) codes are based on local (LDA) or semilocal (GGA) energy functionals. Recently the theory of a truly nonlocal energy functional has been developed. It has been used mostly as a post-DFT calculation approach, i.e. by applying the functional to the charge density calculated using any standard DFT code, thus obtaining a new improved value for the total energy of the system. Nonlocal calculation is computationally quite expensive and scales as N² where N is the number of points in which the density is defined, and a massively parallel calculation is welcome for a wider applicability of the new approach. In this article we present a code which accomplishes this goal.

Program summary

Program title: JuNoLoCatalogue identifier: AEFM_v1_0Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFM_v1_0.htmlProgram obtainable from: CPC Program Library, Queen's University, Belfast, N. IrelandLicensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.htmlNo. of lines in distributed program, including test data, etc.: 176 980No. of bytes in distributed program, including test data, etc.: 2 126 072Distribution format: tar.gzProgramming language: Fortran 90Computer: any architecture with a Fortran 90 compilerOperating system: Linux, AIXHas the code been vectorised or parallelized?: Yes, from 1 to 65536 processors may be used.RAM: depends strongly on the problem's size.Classification: 7.3External routines:• FFTW (http://www.tw.org/)• MPI (http://www.mcs.anl.gov/research/projects/mpich2/ or http://www.lam-mpi.org/)Nature of problem: Obtaining the value of the nonlocal vdW-DF energy based on the charge density distribution obtained from some Density Functional Theory code.Solution method: Numerical calculation of the double sum is implemented in a parallel F90 code. Calculation of this sum yields the required nonlocal vdW-DF energy.Unusual features: Binds to virtually any DFT program.Additional comments: Excellent parallelization features.Running time: Depends strongly on the size of the problem and the number of CPUs used.     

BlobCR: Virtual disk based checkpoint-restart for HPC applications on IaaS clouds

Infrastructure-as-a-Service (IaaS) cloud computing is gaining significant interest in industry and academia as an alternative platform for running HPC applications. Given the need to provide fault tolerance, support for suspend–resume and offline migration, an efficient Checkpoint-Restart mechanism becomes paramount in this context. We propose BlobCR, a dedicated checkpoint repository that is able to take live incremental snapshots of the whole disk attached to the virtual machine (VM) instances. BlobCR aims to minimize the performance overhead of checkpointing by persisting VM disk snapshots asynchronously in the background using a low overhead technique we call selective copy-on-write. It includes support for both application-level and process-level checkpointing, as well as support to roll back filesystem changes. Experiments at large scale demonstrate the benefits of our proposal both in synthetic settings and for a real-life HPC application.     

Online help-seeking in communities of practice: Modeling the acceptance of conceptual artifacts

Interactive online help systems are considered to be a fruitful supplement to traditional IT helpdesks, which are often overloaded. They often comprise user-generated FAQ collections playing the role of technology-based conceptual artifacts. Two main questions arise: how the conceptual artifacts should be used, and which factors influence their acceptance in a community of practice (CoP). Firstly, this paper offers a theoretical frame and a usage scenario for technology-based conceptual artifacts against the theoretical background of the academic help-seeking and CoP approach. Each of the two approaches is extensively covered by psychological and educational research literature, however their combination is not yet sufficiently investigated. Secondly, the paper proposes a research model explaining the acceptance of conceptual artifacts. The model includes users' expectations toward the artifact, perceived social influence and users' roles in the CoP as predictors of artifact use intention and actual usage. A correlational study conducted in an academic software users' CoP and involving structural equations modeling validates the model, suggesting thus a research line that is worth further pursuing. For educational practice, the study suggests three ways of supporting knowledge sharing in CoPs, i.e. use of technology-based conceptual artifacts, roles and division of labor, and purposeful communication in CoPs.     

Two-axis flexure hinges with axially-collocated and symmetric notches

The paper introduces a new class of two-axis flexure hinges with axially-collocated and symmetric notches as an alternative to the existing flexure designs with serially-disposed notches. A generic formulation is developed in terms of the geometric curves defining the two notches which includes assessing the capacity of rotation, precision of rotation, sensitivity to parasitic effects, stress values, motion efficiency and shearing effects by means of compliance factors. Closed-form compliance equations are derived for a two-axis flexure hinge that is defined by two non-identical parabolic profiles. The analytical model predictions are confirmed by finite element data. A numerical comparison is made of the parabolic flexure with a constant rectangular cross-section flexure hinge in terms of several performance criteria.     

Liquid crystalline polymers, 9. Synthesis and thermal behavior of some oligomers containing a diethyletheric spacer

Polyethers based on bis(2-chloroethyl) ether and various bisphenols were obtained using a phase transfer catalysis technique in a liquid/liquid system. 4,4′-Dihydroxyazobenzene, 4,4′-dihydroxybiphenyl, bisphenol A, 2,7-dihydroxynaphthalene and 4,4′-dihydroxydiphenyl) sulfide were used. Only the polymers with azobenzene and biphenyl units exhibited mesophases, since the others have semi-crystalline or amorphous structures. The polymers were characterized by ¹H NMR, DSC and optical microscopy in polarized light. The molecular weights of the samples were low, situated in the oligomeric domain. The various transfer rates of the bisphenols from the aqueous to the organic phase, in some cases, led to very different copolymerization ratios as compared to the feed ratios. The LC polymers exhibited monotropic mesophases, probably for conformational reasons. A comparison between similar polyether structures containing the diethyletheric spacer and an oxetanic one was effectuated.     

The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐ b‐styrene] on dielectric,thermal, and morphological characteristics of polypropylene/silica nanocomposites

The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) copolymer on the thermal and dielectric properties of polypropylene (PP)—nanosilica (NS) composites in relation with morphological aspects revealed by atomic force microscopy (AFM) was investigated in this article. SEBS hindered the crystallization process of PP in PP/NS composites, leading to a smaller degree of crystallinity and lower perfection of crystalline structure. Broader lamellar thickness distribution was obtained in nanocomposites containing SEBS. Almost two times higher dielectric loss as compared to PP reference and two relaxation processes were detected in ε_r ^′′(f) curves of nanocomposites. The first peak, in the same frequency domain as for the references, was assigned to α‐relaxation of polymer components together with interfacial polarization. The relaxation time follows the Arrhenius law with an activation energy of 80–90 kJ/mol. For the second process, the temperature dependence of the relaxation times obeyed the VFT equation. The dielectric changes following the incorporation of SEBS support its tendency to hinder the motional processes in PP, in accordance with DSC results. A smooth transition from a phase rich in SEBS to one containing mainly PP was detected in the AFM image of the composite with the larger amount of SEBS, emphasizing the good compatibility at the PP/SEBS interface. POLYM. ENG. SCI., 53:2081–2092, 2013. © 2013 Society of Plastics Engineers     

Assessment of the availability of agricultural and forest residues for bioenergy production in Romania

This paper provides a resource-based assessment of availability of biomass resources for energy production in Romania, at NUTS-3 level. The estimation of available biomass includes the residues generated from crop production, pruning of vineyards and orchards, forestry operations and wood processing. The estimation of crop residue availability considers several site-specific factors such as crop yields, multi-annual yield variation, environmental constraints and competitive uses. The evaluation of agricultural residues was based on specific residue to product ratios, depending on crop type and crop yield. An estimate of pruning residues is proposed, based on current orchard and vineyard areas and specific ratios of residues. Woody biomass considers forest and forestry residues (including firewood) and wood processing by-products, taking into account the type and share of the unused part of the tree biomass and technical and economic aspects, including availability and competitive use. The amount of agricultural and forest residues available for bioenergy in Romania was estimated at 228.1 PJ on average, of which 137.1 PJ was from annual crop residues, 17.3 PJ residues from permanent crops and 73.7 PJ/year from forestry residues, firewood and wood processing by-products. The biomass availability shows large annual and spatial variations, between 135.6 and 320.0 PJ, due to the variation in crop production and forestry operations. This variation, which is even larger at the NUTS-3 level, if not properly considered may result in shortages in biomass supply in some years, when biomass is available in a lower amount than the average.