Precision Chain‐Walking Polymerization of trans‐4‐Octene Catalyzed by α‐Diimine Nickel(II) Catalysts Bearing ortho‐sec‐Phenethyl Groups

α‐Diimine nickel complexes bearing bulky ortho‐sec‐phenethyl groups (bis{[N,N′‐(4‐methyl‐2,6‐di‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 1 ), bis{[N,N′‐(4,6‐dimethyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 2 ), bis{[N,N′‐(4‐methyl‐2‐sec‐phenethylphenyl)imino]‐1,2‐dimethylethane}dibromonickel ( 3 )) and {bis[N,N′‐(2,4,6‐trimethylphenyl)imino]‐1,2‐dimethylethane}dibromidonickel ( 4 ) are used as a precatalyst for the polymerization of trans‐4‐octene upon activation with modified methylaluminoxane. These catalysts conduct chain‐walking polymerization of trans‐4‐octene to give polymers possessing propyl and butyl branches with high molecular weight and narrow molecular weight distribution. The branching structure depends on the nickel complex as well as the polymerization temperature, and the ratio of propyl branch was increased with increasing the bulkiness of the ligand and decreasing the polymerization temperature. Consequently, the most bulky 1 among the complexes used is found to polymerize trans‐4‐octene with high 1,5‐regioselectivity at −20 °C to give poly(1‐propylpentan‐1,5‐diyl).

     

A new micromechanical formulation of martensite kinetics driven by temperature and/or stress

Summary Martensitic transformation behavior of alloys is studied under the arbitrary action of a thermal and/or a triaxial mechanical load-stress state by solving a transformation kinetic equation presented recently by the same authors. Numerical and analytical solutions reveal that the transformation behavior is almost path-independent. Lines of constant volume fraction of martensite are nearly parallel in the stress-temperature plane. Some new analytical formulae for martensitic transformation kinetics are presented.

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Eine neue mikromechanische Formulierung der Martensit-Kinetik unter Temperatur- und/order Spannungsbelastung

Übersicht Es wird das Verhalten der martensitischen Umwandlung von Legierungen unter beliebiger thermischer und/oder dreiachsiger mechanischer Spannungsbelastung untersucht, indem eine neue Gleichung der Umwandlungskinetik gelöst wird. Diese Gleichung wurde vor kurzem von denselben Autoren vorgestellt. Die numerischen und die analytischen Lösungen zeigen, daß das Transformationsverhalten nahezu pfadunabhängig ist. Die Linien gleicher Volumsfraktion von Martensit sind nahezu parallel im Spannungs-Temperatur-Diagramm. Es werden auch einige neue analytische Formeln für die Umwandlungskinetik von Martensit präsentiert.

     

Meshless method for nonlinear heat conduction analysis of nano-composites

Carbon nanotubes (CNTs) may become ideal reinforcing materials for high-performance nano-composites due their exceptional properties. Still, much work is needed to be done before the potentials of CNT based composites can be fully realized. The evaluation of effective material properties of nano-composites is one of many difficult tasks. Simulations using continuum mechanics approach can play a significant role in the analysis of these composites. In the present work, nonlinear heat conduction analysis of CNT based composites has been carried out using continuum mechanics approach. Element free Galerkin method has been applied as a numerical tool. Thermal conductivities of nanotube and polymer matrix are assumed to vary quadratically with temperature. Picard and quasi-linearization schemes have been utilized to obtain the solution of a system of nonlinear equations. Cylindrical representative volume element has been used to evaluate the thermal properties of nano-composites. Present simulations show that the temperature dependent matrix thermal conductivity has a significant effect on the equivalent thermal conductivity of the composite, whereas temperature dependent nanotube thermal conductivity has a small effect on the equivalent thermal conductivity of the composite. The results obtained by Picard method have been found almost similar with those obtained by quasi-linearization approach.     

Effects of strain path shapes on non-proportional cyclic plasticity

The title problem was discussed to facilitate the formulation of constitutive models of cyclic plasticity under general states of loading. A series of plastic strain controlled cyclic tests was performed by applying combined axial force and torque to thin-walled tubular specimens of Type 316 stainless steel at room temperature. These tests consist of cyclic loading along uniaxial, torsional, cruciform, stellate in eight directions, square and circular plastic strain paths with a constant amplitude of equivalent plastic strain.The results of these tests showed that the strain-hardening depends markedly on the shape of the plastic strain path, and that the strain-hardening (measured by equivalent stress amplitudes) in the saturated state is significant in the order of circular, square, stellate, cruciform and proportional paths. It was also observed that these saturated values were independent of the less significant plastic strain cycles experienced in the past. Finally, the characteristic features of strain-hardening mechanisms under non-proportional loadings were discussed in some detail on the basis of the present results.     

Computation of a two-dimensional stress intensity factor by the boundary element method

Summary This paper presents a boundary element formulation for elastostatic problems. The formulation is expressed in terms of the matrix notation, so that it is easily applicable to an available system of matrix structural analysis. A computer program developed is used to calculate the stress intensity factor K _I for some example problems in plane elasticity. Comparison is made between the boundary element calculations and other solutions, whereby the effectiveness of the boundary element method is demonstrated.

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Berechnung eines zweidimensionalen Spannungsintensitätsfaktors mit der Methode der Bandelemente

Übersicht Dieser Aufsatz bietet eine Formulierung elastostatischer Probleme durch die Methode der Randelemente an. Die Formulierung benutzt eine Darstellung in Matrizenbezeichnung, so daß sie auf ein verfügbares System für Matrizenstrukturberechnung einfach anwendbar ist. Ein ausgebautes Computerprogramm wird auf die Berechnung des Spannungsintensitätsfaktors K _i für einige Beispiele in der ebenen Elastizität angewendet. Die mittels der Randelemente erhaltenen Ergebnisse werden mit anderen Lösungen verglichen. Dadurch zeigt sich die Wirksamkeit der Methode der Randelemente.

     

Turning characteristics of multi-axle vehicles

This paper presents a mathematical model for multi-axle vehicles operating on level ground. Considering possible factors related to turning motion such as vehicle configuration and tire slip velocities, equations of motion were constructed to predict steerability and driving efficiency of such vehicles. Turning radius, slip angle at the mass center, and each wheel velocity were obtained by numerically solving the equations with steering angles and average wheel velocity as numerical inputs. To elucidate the turning characteristics of multi-axle vehicles, the effect of fundamental parameters such as vehicle speed, steering angles and type of driving system were examined for a sample of multi-axle vehicles. Additionally, field tests using full-scale vehicles were carried out to evaluate the basic turning characteristics on level ground.     

N-Doping of Polyaromatic Capsules: Small Cavity Modification Leads to Large Change in Host–Guest Interactions

To gain insight into the host functions of a nanocavity encircled by both polyaromatic panels and heteroatoms, nitrogen-doped polyaromatic capsules were successfully synthesized from metal ions and pyridine-embedded, bent anthracene-based ligands. The new capsules display unique host–guest interactions in the isolated cavities, which are distinct from those of the undoped analogues. Besides the inclusion of Ag⁺ ions, the large absorption change of fullerene C₆₀ and altered emission of a BODIPY dimer are observed upon encapsulation by the present hosts. Moreover, the N-doped capsule exhibits specific binding ability toward progesterone and methyltestosterone, known as a natural female and synthetic male hormone, respectively, in water.     

Mechanochromic Delayed Fluorescence Switching in Propeller-Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli-Responsive Intramolecular Charge-Transfer Excited States

Herein, the universal design of high-efficiency stimuli-responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli-triggered TADF switching for a series of carbazole–isophthalonitrile-based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X-ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited-state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light-emitting diodes using a single TADF emitter.     

Alloyed Tetranuclear Metal Chains of Pd4−nPtn (n=0–3) Scaffolded by a New Linear Tetraphosphine Containing a PNP Bridge

A new linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd_4−nPt_n(μ-rac-dpmppan)₂(XylNC)₂](PF₆)₂ (XylNC=xylyl isocyanide; n=0: Pd₄ ( 1 ), 1: PtPd₃ ( 2 ), 2: PtPd₂Pt ( 3 ), 2: Pt₂Pd₂ ( 4 ), 3: Pt₂PdPt ( 5 )), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The ³¹P{¹H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1 – 5 exhibited characteristic bands at 635–510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dσ*σσ*) to LUMO (dσ*σ*σ*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd₄ chain.     

An evaluation method for measuring SPL and mode shape of tire cavity resonance by using multi-microphone system

This paper presents an evaluation method for measuring the sound pressure level and mode shapes of tire cavity resonance by using a multi-microphone system. Two commercial tires were evaluated to compare abilities of noise suppression by means of this method in the range of the first resonance from 200 to 260 Hz. One tire was a special tire that suppresses tire cavity resonance with polyurethane foam mounted on the tire’s inner liner. The other tire was a normal tire with no polyurethane foam. The mode shape change from vertical to horizontal direction in both tires. However, the sound pressure level of the special tire was lower than the normal tire at all frequencies.