Synthesis of heterocyclic metal complexes and their evaluation as marine antifoulants

4-Amino-3-thio-1,24-triazolidine (L₁) and 4-amino-5-thio-1,3,4-thiadiazole (L_II) as well as their metal complexes of the general formulae ML_I·2H₂O and ML_IICl (M; Pb(II), Cd(II) and Zn(II)) were prepared. With Sn(II), we obtained Sn(L_I)₂·2H₂O and SnL_IICl, respectively. The structures of the compounds were identified through elemental analysis, and IR and UV spectra measurements, in addition to thermal analysis in case of the metal complexes. The antifouling properties of the compounds were tested by their incorporation into paint formulations which were applied to PVC substrates and tested in water from Alexandria western harbour. When the compounds were added at 17·5% by volume, the coated panels were fouled after 3 months of immersion. The addition of 6·7% by volume of tributyltin oxide to 15·8% of the prepared compounds in one formulation elevated the paint efficiency and prevented fouling for 11 months. Paint containing solely tributyltin oxide at the same concentration was inactive against algae.     

Fractionation and characterisation for antioxidant activity of hydrolysed whey protein

Whey protein isolate (WPI) was hydrolysed for 1 h using Alcalase, Protamex and Flavourzyme. Native WPI, hydrolysed WPI and two commercial WPI hydrolysates were subjected to fractionation by size exclusion chromatography. Antioxidant activity of WPI fractions was measured with a liposome‐oxidising system (50 µM FeCl₃/0.1 µM ascorbate, pH 7.0). Lipid oxidation was measured as thiobarbituric acid‐reactive substances (TBARS). Gel electrophoresis and amino acid analysis were run to identify the peptide composition. The influence of amino acid composition on antioxidant activity was evaluated using multivariate analysis methods (correlation analysis, principal component analysis, multiple linear regression and discriminant analysis). TBARS assays indicated the presence of antioxidant activity in all protein fractions, including non‐hydrolysed WPI. For native and hydrolysed WPI samples the first fraction (> 45 kDa) showed a higher TBARS inhibition effect (24–27%) when compared with lower‐molecular‐weight fractions and hydrolysate mixtures. In contrast, for commercial WPI hydrolysates a higher inhibitory effect was found in most of the lower‐molecular‐weight fractions (30–55%). The ability of WPI fractions to delay lipid oxidation was found to be related to the prevalence of histidine and hydrophobic amino acids. Copyright © 2004 Society of Chemical Industry     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

Time-series primitive static states for detailing work state and flow of human-operated work machine

This paper proposes a quantification method for a comprehensive work flow in construction work for describing work states in more detail on the basis of analyzing state transitions of primitive static states (PSS), which consist of 16 symbolic work states defined by using on-off state of the lever operations and joint loads for the manipulator and end-effector. On the basis of the state transition rules derived from a transition-condition analysis, practical state transitions (PST), which are common and frequent transitions in arbitrary construction work, are defined. PST can be classified into essential state transition (EST) or nonessential state transitions (NST). EST extracts common phases of work progress and estimates positional relations between a manipulator and an object. NST reveals wasted movements that degrade the efficiency and quality of work. To evaluate comprehensive work flows modeled by combining EST and NST, work-analysis experiments using our instrumented setup were conducted. Results indicate that all the PSS definitely changes on the basis of PST under various work conditions, and work analysis using EST and NST easily reveals work characteristics and untrained tasks related to wasted movements.     

Gel-size dependence of temperature-induced microphase separation in weakly-charged polymer gels

The gel-size dependence of microphase separation in weakly-charged gels of N-isopropylacrylamide (NIPA) and 1-vinylimidazole (VI) copolymers has been investigated using swelling measurement, small-angle neutron scattering (SANS), and dynamic and static light scattering (DLS/SLS). It is known that weakly-charged polymer gels undergo microphase separation in a poor solvent as a result of competing interactions involving hydrophobic attraction versus electrostatic repulsion. The microphase separation is characterized by a scattering maximum in SANS intensity functions of which Bragg spacing, Λ, is around 20-30 nm. However, when gel size was reduced to the order of Λ, no microphase separation was observed. Instead, a typical scattering of isolated spherical particles was clearly observed. On the basis of the experimental evidence, we conclude that microphase separation has its own wavelength independent of gel size, and nanometer-order gels, i.e., nanogels, do not undergo microphase separation.     

Elastoplastic Finite Element Analysis and Strength Evaluation of Adhesive Butt Joints of Similar and Dissimilar Hollow Shafts Subjected to External Bending Moments

Stress distributions and deformation of adhesive butt joints are analyzed by an elastoplastic finite element method when the joints of similar and dissimilar shafts are subjected to external bending moments. The effects of the ratio of Young's modulus for the adherends to that for an adhesive and the effects of the adhesive thickness on the interface stress distribution are investigated. Joint strength is predicted by using the elastoplastic interface stress distributions. It is found that the singular stress at the edge of the interfaces increases with an increase of the ratio of Young's modulus. Measurement of strains in joints and experiments on joint strength were conducted. The numerical results are in fairly good agreement with the experimental results. It is observed that the joint strength for dissimilar shafts are smaller than those for similar shafts. A fracture of dissimilar adhesive up-bonded shafts occurred from the interface of the adherend with smaller Young's modulus. It is seen that joint strength increases as the adhesive thickness increases.     

Morphology,thermal, and mechanical properties of vinylester resin nanocomposites with various organo‐modified montmorillonites

New nanocomposites based on a vinylester resin (VER) and the organo‐montmorillonites (ODA‐M, BHL‐M, DEM‐M, BHLV‐M) modified with octadecylammonium, bis(2‐hydroxyethyl)lauryl ammonium, diethyl[2‐(methacryloyloxyl)ethyl]ammonium, and bis(2‐hydroxyethyl)lauryl(vinylbenzyl)‐ammonium chlorides, respectively, were prepared by dispersing the organoclays in VER, and subsequent crosslinking at finally 120°C. X‐ray diffraction studies and morphological studies using transmission electron microscopy revealed that exfoliation occurs for the VER/ODA‐M and BHL‐M composites, intercalation occurs for the VER/BHLV‐M composite, and neither intercalation nor exfoliation occur for the VER/DEM‐M and unmodified montmorillonite composites. On the whole, although the enhancement in flexural modulus was observed for the exfoliated ODA‐M and BHL‐M composites, the flexural strength was rather lowered. Dynamic viscoelastic measurement revealed that the ODA‐M, BHL‐M, and BHLV‐M nanocomposites have significantly higher storage modulus at the rubbery state than the other composites. Polym. Eng. Sci. 44:2041–2046, 2004. © 2004 Society of Plastics Engineers.     

Biodegradability and improved mechanical performance of polyhydroxyalkanoates/agave fiber biocomposites compatibilized by different strategies

In this work, biocomposites made of polyhydroxyalkanoates (PHA) with natural fibers were produced via compression molding. In particular, polyhydroxybutyrate (PHB) and polyhydroxybutyrate-co-hydroxyvalerate (PHBV) were reinforced with 20 wt% of agave fibers. Different compatibilization strategies were investigated to improve the fiber-matrix interaction: fiber surface treatment in PHA solution, fiber surface treatment in maleated PHA solution, fiber propionylation, and extrusion with maleated PHA. The biocomposites were characterized in terms of morphology, mechanical properties, water absorption, and biodegradability by CO₂ production tracking. In general, fiber propionylation was the best strategy for mechanical properties enhancement and water uptake decreasing. Biocomposites with propionylated fibers showed improved flexural strength (170% for PHB and 84% for PHBV). The flexural modulus was also enhanced with propionylated fibers up to 19% and 18% compared to uncompatibilized biocomposites (PHB and PHBV, respectively). Tensile strength increased by 16% (PHB) and 14% (PHBV), and the water absorption was reduced using propionylated fibers going from 6.6% to 4.4% compared with biocomposites with untreated fibers. Most importantly, the impact strength was also improved for all biocomposites by up to 96% compared with the neat PHA matrices. Finally, it was found that the compatibilization did not negatively modify the PHA biodegradability.     

Dependency-based security risk assessment for cyber-physical systems

A cyber-physical attack is a security breach in cyber space that impacts on the physical environment. The number and diversity of such attacks against Cyber-Physical Systems (CPSs) are increasing at impressive rates. In times of Industry 4.0 and Cyber-Physical Systems, providing security against cyber-physical attacks is a serious challenge which calls for cybersecurity risk assessment methods capable of investigating the tight interactions and interdependencies between the cyber and the physical components in such systems. However, existing risk assessment methods do not consider this specific characteristic of CPSs. In this paper, we propose a dependency-based, domain-agnostic cybersecurity risk assessment method that leverages a model of the CPS under study that captures dependencies among the system components. The proposed method identifies possible attack paths against critical components of a CPS by taking an attacker’s viewpoint and prioritizes these paths according to their risk to materialize, thus allowing the defenders to define efficient security controls. We illustrate the workings of the proposed method by applying it to a case study of a CPS in the energy domain, and we highlight the advantages that the proposed method offers when used to assess cybersecurity risks in CPSs.

     

Ontology-driven web-based semantic similarity

Estimation of the degree of semantic similarity/distance between concepts is a very common problem in research areas such as natural language processing, knowledge acquisition, information retrieval or data mining. In the past, many similarity measures have been proposed, exploiting explicit knowledge—such as the structure of a taxonomy—or implicit knowledge—such as information distribution. In the former case, taxonomies and/or ontologies are used to introduce additional semantics; in the latter case, frequencies of term appearances in a corpus are considered. Classical measures based on those premises suffer from some problems: in the first case, their excessive dependency of the taxonomical/ontological structure; in the second case, the lack of semantics of a pure statistical analysis of occurrences and/or the ambiguity of estimating concept statistical distribution from term appearances. Measures based on Information Content (IC) of taxonomical concepts combine both approaches. However, they heavily depend on a properly pre-tagged and disambiguated corpus according to the ontological entities in order to compute accurate concept appearance probabilities. This limits the applicability of those measures to other ontologies –like specific domain ontologies- and massive corpus –like the Web-. In this paper, several of the presented issues are analyzed. Modifications of classical similarity measures are also proposed. They are based on a contextualized and scalable version of IC computation in the Web by exploiting taxonomical knowledge. The goal is to avoid the measures’ dependency on the corpus pre-processing to achieve reliable results and minimize language ambiguity. Our proposals are able to outperform classical approaches when using the Web for estimating concept probabilities.