Synthesis of diblock copolymers by combination of organocatalyzed ring‐opening polymerization and atom transfer radical polymerization using trichloroethanol as a bifunctional initiator

This study reports an application of trichloroethanol (TCE) as a bifunctional initiator for the synthesis of block copolymers (BCPs) by organocatalyzed ring‐opening polymerization (OROP) and atom transfer radical polymerization (ATRP). TCE was employed to synthesize a low dispersity poly (valerolactone) macroinitiator, which was subsequently used for the ATRP of tert‐butyl methacrylate. While it is known that TCE can serve as an initiator in ATRP, the ability to induce polymerization under OROP is reported for the first time. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and ¹H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 563–569     

A Dual Threat: Redox-Activity and Electronic Structures of Well-Defined Donor–Acceptor Fulleretic Covalent-Organic Materials

The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.     

Iridium catalyzed alkylation of 2′-hydroxyacetophenone with alcohols under thermal or microwave conditions

2′-Hydroxyacetophenone was alkylated with a range of substituted benzyl and heteroaryl alcohols to afford the corresponding C-alkylated products in good yields under microwave irradiation. The C-alkylated products were reacted with bromoacetonitrile to afford 2-amino-3-benzyl 1,4-naphthoquinone derivatives in moderate yields.     

Asymptotic analysis of growing plane strain tensile cracks in elastic-ideally plastic solids

An exact asymptotic analysis is presented of the stress and deformation fields near the tip of a quasistatically advancing plane strain tensile crack in an elastic-ideally plastic solid. In contrast to previous approximate analyses, no assumptions which reduce the yield condition, a priori, to the form of constant in-plane principal shear stress near the crack tip are made, and the analysis is valid for general Poisson ratio ν. Specific results are given for ν = 0.3 and 0.5, the latter duplicating solutions in previous work by L.I. Slepyan, Y.-C. Gao and the present authors. The crack tip field is shown to divide into five angular sectors of four different types ; in the order in which these sweep across a point in the vicinity of the advancing crack, they are : two plastic sectors which can be described asymptotically (i.e., as r → 0, where r is distance from the crack tip) in slip-line terminology as ‘constant stress’ and ‘centered fan’ sectors, respectively ; a plastic sector of non-constant stress which cannot be described asymptotically in terms of slip lines; an elastic unloading sector; and a trailing plastic sector of the same type as that directly preceding the elastic sector. Further, these four different sector types constitute the full set of asymptotically possible solutions at the crack tip. As is known from prior work, the plastic strain accumulated by a material point passing through such a moving ‘centered fan’ sector is O(ln r) as r → 0 ; it is proved in the present work that the plastic strain accumulated by a material point passing through the ‘constant stress’ sector ahead of a growing crack must be less singular than In r as r → 0. As suggested also in earlier studies, the rate of increase of opening gap δ at a point currently at a distance r behind, but very near, the crack tip is given for crack advance under contained yielding by

$\text{δ}\text{?}\text{=}\text{α}\text{J}\text{?}\text{σ}{}_0\text{+β(}\text{σ}{}_0\text{E}\text{)}\text{a}\text{?}\text{ln(}\text{R}\text{r}\text{)}$

where a is crack length, σ0 is tensile yield strength, E is Young's modulus, J is the value of the J-integral taken in surrounding elastic material, and the parameters α and R are undetermined by the asymptotic analysis. The exact solution for ν = 0.3 gives β = 5.462, which agrees very closely with estimates obtained from finite element solutions. An approximate analysis based on use of slip line representations in all plastic sectors is outlined in the Appendix.     

Strain localization in ductile single crystals

This paper is concerned with an analysis of strain localization in ductile crystals deforming by single slip. The plastic flow is modelled as rate-insensitive, and localization, viewed as a bifurcation from a homogeneous deformation mode to one which is concentrated in a narrow ‘shear band’, is found to be possible only when the plastic hardening modulus for the slip system has fallen to a certain critical value h_cr, sensitive to the precise form of the constitutive law governing incremental shear. We develop the general form of this constitutive law, incorporating within it the possibility of deviations from the Schmid rule of a critical resolved shear stress, and we show that h_cr may in fact be positive when there are deviations from the Schmid rule. It is suggested that micromechanical processes such as ‘cross-slip’ in crystals provide specific cases for which stresses other than the Schmid stress may influence plastic response and, further, there is an experimental association of localization with the onset of large amounts of cross-slip. Thus, we give the specific form of h_cr for a constitutive model that corresponds to non-Schmid effects in cross-slip, and we develop a dislocation model of the process from which we estimate the magnitude of the parameters involved. The work supports the notion that localization can occur with positive strain-hardening, h_cr > 0, and the often invoked notions of the attainment of an ideally-plastic or strain-softening state for localization may be unnecessary.     

Mode spectra of natural disturbances in a circular jet and the effect of acoustic forcing

A modal spectrum technique was used to study coherent instability modes (both axisymmetric and azimuthal) triggered by naturally occurring disturbances in a circular jet. This technique was applied to a high Reynolds number (400,000) jet for both untripped (transitional) and tripped (turbulent) nozzle exit boundary layers, with both cases having a core turbulence level of 0.15%. The region up to the end of the potential core was dominated by the axisymmetric mode, with the azimuthal modes dominating further downstream. The growth of the azimuthal modes was observed closer to the nozzle exit for the jet with a transitional boundary layer. Whether for locally parallel flow or slowly diverging flow, even at low levels of acoustic forcing, the inviscid linear theory is seen to be inadequate for predicting the amplitude of the forced mode. In contrast, the energy integral approach reasonably predicts the evolution of the forced mode.     

Study on the Collapse of Pin-Reinforced Foam Sandwich Panel Cores

New fabrication technologies now allow for hybrid sandwich structures, known as X-core, to be manufactured. The X-core panels consist of a pin reinforced polymer foam core with carbon fiber face sheets. Carbon fiber or metallic (Titanium/Steel) pins are inserted into the foam core in the out-of-plane direction and extend from face sheet to face sheet. The through thickness three-point simply supported bending behavior of these panels is used to evaluate the collapse characteristics of the panels. Explicit experimental observations are used to calibrate analytical energy balance models describing the panel collapse as a function of geometry and properties. The mechanical response of X-core sandwich panels is compared to current sandwich materials for material selection.     

Absorption of shocked benzene

Abstract

We used absorption spectroscopy to observe decomposition of benzene (C₆H₆) subjected to the passage of strong shock waves generated by projectile impact. These measurements were made using a recently developed double-beam, double-pass, fiber-optic-coupled apparatus. Near 13 GPa, we observe absorption throughout most of the visible region, with strong absorption occurring for wavelengths below 400 nm. The absorption is most likely due to a combination of molecular absorption and Mie scattering from carbon particles formed as a result of shock decomposition.