The Interplay of Modulus,Strength, and Ductility in Adhesive Design Using Biomimetic Polymer Chemistry

High‐performance adhesives require mechanical properties tuned to demands of the surroundings. A mismatch in stiffness between substrate and adhesive leads to stress concentrations and fracture when the bonding is subjected to mechanical load. Balancing material strength versus ductility, as well as considering the relationship between adhesive modulus and substrate modulus, creates stronger joints. However, a detailed understanding of how these properties interplay is lacking. Here, a biomimetic terpolymer is altered systematically to identify regions of optimal bonding. Mechanical properties of these terpolymers are tailored by controlling the amount of a methyl methacrylate stiff monomer versus a similar monomer containing flexible poly(ethylene glycol) chains. Dopamine methacrylamide, the cross‐linking monomer, is a catechol moiety analogous to 3,4‐dihydroxyphenylalanine, a key component in the adhesive proteins of marine mussels. Bulk adhesion of this family of terpolymers is tested on metal and plastic substrates. Incorporating higher amounts of poly(ethylene glycol) into the terpolymer introduces flexibility and ductility. By taking a systematic approach to polymer design, the region in which material strength and ductility are balanced in relation to the substrate modulus is found, thereby yielding the most robust joints.     

Design criterion for fatigue strengthening of riveted beams in a 120-year-old railway metallic bridge using pre-stressed CFRP plates

This study presents a design criterion developed for fatigue strengthening of a 120-year-old metallic railway bridge in Switzerland and presents a pre-stressed un-bonded reinforcement (PUR) system developed to apply the strengthening. The PUR system uses carbon fiber reinforced polymer (CFRP) plates; however, unlike conventional pre-stressed CFRP reinforcement methods, preparation of the existing metallic bridge surface is not required. This decreases the time required for on-site strengthening procedures. The principle of the constant life diagram (CLD) and two fatigue failure criteria (Johnson and Goodman) are described. Analytical formulations are developed based on the CLD method to determine the minimum CFRP pre-stress level required to prevent fatigue crack initiation. The PUR system uses an applied pre-stress force to reduce the mean stress level (and stress ratio) to shift an existing fatigue-susceptible metallic detail from the ‘at risk’ finite life regime to the ‘safe’ infinite life regime. The applied CLD method is particularly valuable when the stress history of the detail is not known and it is difficult to assess the remaining fatigue life. Moreover, it is shown that the currently adopted approach in many structural codes which emphasizes stress range as the dominant parameter influencing fatigue life are non-conservative for tension–tension stress patterns (i.e., stress ratios of 0 < R < 1). Analyses show that the modified Johnson formula accurately reflects the combined effect of stress range, mean stress level, and material properties, and offers a relatively easy design procedure. Details of a retrofit field application on members of a riveted wrought iron railway bridge are given. A wireless sensor network (WSN) system is used for long-term monitoring of the on-site CFRP stress levels and temperature of the retrofitted details. WSN measurements indicate that increases in ambient temperature result in increased CFRP pre-stress levels.     

Lipase‐catalyzed synthesis of aliphatic poly(β‐thioether ester) with various methylene group contents: thermal properties,crystallization and degradation

A series of novel aliphatic poly(β‐thioether ester)s with various methylene group contents were prepared by direct lipase‐catalyzed polycondensation of the monomer with an acid‐labile β‐thiopropionate group. The polycondensation reaction using immobilized lipase B from Candida antarctica was carried out in diphenyl ether at 90 °C. Poly(β‐thioether ester)s with high molecular weights of 20 500–57 000 Da and narrow polydispersities in the range 1.40–1.48 were obtained. Thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction were used to investigate the thermal properties and crystal structures of these polyesters. All the poly(β‐thioether ester)s were semicrystalline polymers and thermally stable up to at least 200 °C. In vitro degradation studies showed that they can rapidly degrade under acidic conditions by the hydrolysis of the β‐thiopropionate groups, suggesting their potential as acid‐degradable polymeric materials. © 2019 Society of Chemical Industry     

Toward optimization of a robust low-cost sulfonated-polyethersulfone containing layered double hydroxide for PEM fuel cells

Polyethersulphone (PES) is an aromatic thermoplastic, at low environmental impact, evaluated in this work as a promising candidate for new polymer electrolytes in the PEMFCs technology. A sulfonation procedure has been tuned in order to graft sulfonic acid groups on the polymer chains (sPES) and to make it hydrophilic. Homogeneous membranes with different polymer's sulfonation degrees (SD%) have demonstrated excellent mechanical properties and very low permeability toward methanol (important in the DMFCs), even if low proton conductivity. Nanocomposite sPES membranes were prepared by dispersion of highly hydrophilic lamellar particles such as layered double hydroxide (LDH) in the polymer. Deep investigations performed by a combination of PFG-NMR, EIS, XRD, DMA, and scanning electron microscopy have evidenced the exfoliation of the lamellae in polymer matrix. However, a certain anisotropy was evidenced both in the morphology and molecular diffusion, favored in the longitudinal direction (parallel to surface), while completely inhibited in the cross-section. This finding is most likely induced by the polymer structure, therefore particular attention must be paid to the choice of the filler and preparation of the composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47884.     

Triphenylphosphonium (TPP)-Based Antioxidants: A New Perspective on Antioxidant Design

Mitochondrial oxidative damage and dysfunction contribute to a wide range of human diseases. Considering the limitation of conventional antioxidants and that mitochondria are the main source of reactive oxygen species (ROS) which induce oxidative damage, mitochondria-targeted antioxidants which can selectively block mitochondrial oxidative damage and prevent various types of cell death have been widely developed. As a lipophilic cation, triphenylphosphonium (TPP) has been commonly used in designing mitochondria-targeted antioxidants. Conjugated with the TPP moiety, antioxidants can achieve more than 1000-fold higher mitochondrial concentration depending on cell membrane potentials and mitochondrial membrane potentials. Herein we discuss the deficiencies of conventional antioxidants and the advantages of mitochondrial targeting, and review various types of TPP-based mitochondria-targeted antioxidants. These provide theoretical and background support for the design of new anti-oxidant.     

Effect of hyperbranched poly(citric polyethylene glycol) with various polyethylene glycol chain lengths on starch plasticization and retrogradation

A series of hyperbranched poly(citric polyethylene glycol) (PCPEG) materials with varied polyethylene glycol (PEG) chain lengths as plasticizers were mixed with maize starch (MS) via cooking and film‐forming. The structure, pasting property, plasticization, aging property, moisture absorption and compatibility of plasticized starches were studied by means of Fourier transform infrared spectroscopy, X‐ray diffraction, rapid viscosity analysis, tension testing, moisture absorption measurements and scanning electron microscopy. Compared with PEG and citric acid, PCPEG was more effective in promoting starch chain movement and inhibiting the retrogradation of starch film. Also, PCPEG/MS had smaller moisture content. The longer the plasticizer chain, the better were the aging resistance and moisture resistance of starch. But with an increase of PEG chain length, mechanical properties of PCPEG/MS deteriorated and the compatibility between PCPEG and MS decreased. The hyperbranched derivative of PEG with longer chain exhibited improved plasticization and compatibility with starch. © 2019 Society of Chemical Industry     

浅谈氯碱氢的一种深度脱水工艺

概述了氢的主要工业生产方法和实际应用,详细介绍了氯碱氢三级脱水工艺过程,并运用在线分析手段,准确显示了干燥过程中的氯碱氢水分含量变化规律。     

High-resolution ISAR imaging of fast rotating targets based on pattern-coupled Bayesian strategy for multiple measurement vectors

Very high resolution inverse synthetic aperture radar (ISAR) imaging of fast rotating targets is a complicated task. There may be insufficient pulses or may introduce migration through range cells (MTRC) during the coherent processing interval (CPI) when we use the conventional range Doppler (RD) ISAR technique. With compressed sensing (CS) technique, we can achieve the high-resolution ISAR imaging of a target with limited number of pulses. Sparse representation based method can achieve the super resolution ISAR imaging of a target with a short CPI, during which the target rotates only a small angle and the range migration of the scatterers is small. However, traditional CS-based ISAR imaging method generally faced with the problem of basis mismatch, which may degrade the ISAR image. To achieve the high resolution ISAR imaging of fast rotating targets, this paper proposed a pattern-coupled sparse Bayesian learning method for multiple measurement vectors, i.e. the PC-MSBL algorithm. A multi-channel pattern-coupled hierarchical Gaussian prior is proposed to model the pattern dependencies among neighboring range cells and correct the MTRC problem. The expectation-maximization (EM) algorithm is used to infer the maximum a posterior (MAP) estimate of the hyperparameters. Simulation results validate the effectiveness and superiority of the proposed algorithm.     

Entry into force of the UN Watercourses Convention: why should it matter?

The United Nations Watercourses Convention entered into force on 17 August 2014, following a long and complex journey that dates back to 1970 when the UN referred the matter to its legal arm, the International Law Commission. This article follows the Convention through that long and turbulent road, examines its main provisions and analyses the reasons for the delay of its entry into force. It concludes by answering the question of why entry into force of the Convention should indeed matter.