Toughening of epoxies via craze-like damage

The fracture behavior of a core-shell rubber (CSR) modified epoxy is investigated using both fracture mechanics and microscopy tools. The CSR-modified epoxy is found to be toughened via numerous line-array cavitations of the CSR particles, followed by plastic flow of the epoxy matrix. The toughening effect via the above craze-like damage process is found to be as effective as that of the well-known widespread rubber cavitation/matrix shear yielding mechanisms. The conditions for triggering the craze-like damage appear to be both stress state and rubber concentration dependent. The type of rubber tougheners utilized also plays a critical role in triggering this rather unusual craze-like damage in epoxy systems. © 1993 John Wiley & Sons, Inc.     

Silver nitrate-acetonitrile and iodine-benzene complexes as studied by NMR in thermotropic liquid crystals

Silver nitrate-acetonitrile and π iodine-benzene complexes in thermotropic liquid crystals have been studied by ¹H, ²H, and ¹³C NMR spectroscopy and by optical microscopy. Evidence for at least two silver complexes in each liquid crystal is presented.     

On practical metrology and chemical analysis: etalons and traceability systems

 National measurement systems are infrastructures to ensure, for each nation, a consistent and internationally recognised basis for measurement. Such complex systems have historical, technical, legal, organisational and institutional aspects to connect scientific metrology with practical measurements. Underlying any valid measurement is a chain of comparisons linking the measurement to an accepted standard. The ways the links are forged and the etalons (measurement standards) to which they connect are defining characteristics of all measurement systems. This is often referred to as traceability which aims at basing measurements in common measurement units – a key issue for the integration of quantitative chemical analysis with the evolving physical and engineering measurement systems. Adequate traceability and metrological control make possible new technical capabilities and new levels of quality assurance and confidence by users in the accuracy and integrity of quantitative analytical results. Traceability for chemical measurements is difficult to achieve and harder to demonstrate. The supply of appropriate etalons is critical to the development of metrology systems for chemical analysis. An approach is suggested that involves the development of networks of specialised reference laboratories able to make matrix-independent reference measurements on submitted samples, which may then be used as reference materials by an originating laboratory using its practical measurement procedures. Received: 31 July 1995 Accepted: 19 August 1995     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,dynamic light scattering,and luminescence properties of copolymers containing iridium(III) bisterpyridine in the side chain

Supramolecular block‐random copolymers containing [Ir(terpy)₂]³⁺ in the side chain were synthesized via postfunctionalization of a P(S‐b‐AC_terpy) block copolymer. Absorbance and emission spectra compared to a model compound show that the polymer backbone has a minor effect on the polymer absorbance but produces a larger shift for the phosphorescence signals to higher wavelength. Dynamic light scattering of the metal complex containing copolymer studied in various solvents showed monomodal aggregation with decreasing aggregate size as the solvent dielectric constant increased. The copolymer precursor P(S‐b‐AC_terpy) shows multimodal aggregation in different solvents with the major population consisting of single chains. This difference in behavior between the two polymers is attributed to the electrolytic nature of the complex and the amphiphilicity induced by the charged metal complex. Supramolecular copolymers like these will continue to have interesting self‐organizational properties and may find applications in multicomponent systems for photoinduced charge separation processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1109–1121, 2007     

Microstructural evolution of decagonal quasicrystal in the undercooled Al72Ni12Co16 alloy melts

The microstructure evolution of decagonal quasicrystals in Al₇₂Ni₁₂Co₁₆ alloy was investigated by the electromagnetic melting and cyclic superheating method. Single-phase decagonal quasicrystals have been obtained when the undercoolings were larger than 60 K. The decagonal quasicrystals formed at various undercoolings show different microstructural morphologies. Furthermore, grain refinement was found near the undercooling of 120 K. Based on current thermodynamic and dendrite growth theories, a dimensionless superheating parameter was adopted to explain the effect of processing conditions on the microstructure of Al₇₂Ni₁₂Co₁₆ alloy. The result indicate that the fine equiaxied microstructure of decagonal quasicrystal (D-phase) formed near on undercooling of 120 K originates from the break-up of dendrites.     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.