Mechanism of Producing Metallic Nanoparticles,with an Emphasis on Silver and Gold Nanoparticles,Using Bottom-Up Methods

Bottom-up nanoparticle (NP) formation is assumed to begin with the reduction of the precursor metallic ions to form zero-valent atoms. Studies in which this assumption was made are reviewed. The standard reduction potential for the formation of aqueous metallic atoms—E⁰(Mⁿ⁺_aq/M⁰_aq)—is significantly lower than the usual standard reduction potential for reducing metallic ions Mⁿ⁺ in aqueous solution to a metal in solid state. E⁰(Mⁿ⁺_aq/M⁰_solid). E⁰(Mⁿ⁺_aq/M⁰_aq) values are negative for many typical metals, including Ag and Au, for which E⁰(Mⁿ⁺_aq/M⁰_solid) is positive. Therefore, many common moderate reduction agents that do not have significantly high negative reduction standard potentials (e.g., hydrogen, carbon monoxide, citrate, hydroxylamine, formaldehyde, ascorbate, squartic acid, and BH₄⁻), and cannot reduce the metallic cations to zero-valent atoms, indicating that the mechanism of NP production should be reconsidered. Both AgNP and AuNP formations were found to be multi-step processes that begin with the formation of clusters constructed from a skeleton of M⁺-M⁺ (M = Ag or Au) bonds that is followed by the reduction of a cation M⁺ in the cluster to M⁰, to form M_n⁰ via the formation of NPs. The plausibility of M⁺-M⁺ formation is reviewed. Studies that suggest a revised mechanism for the formation of AgNPs and AuNPs are also reviewed.     

Morphological stability,interfacial tension,and dual-phase continuity in polystyrene-polyethylene blends

The morphological stability of polystyrene high-density polyethylene (PS/PE) blend is investigated in the region of dual-phase continuity. The effect of the addition of a triblock SEBS copolymer to the blends on the stability of these morphologies, is examined. The results show that the morphology of the unmodified blends changes from co-continuous to droplet matrix for PS-rich blends whereas the morphology of a 50/50 blend maintains continuity but coarsened significantly upon annealing at 200°C. In the presence of the copolymer, these morphologies are much more stable. Selective solvent extraction of polystyrene in di-ethyl ether reveals that the level of PS continuity in the 50/50 blend is higher for the unmodified system than for the modified one. Upon annealing, the level of PS continuity significantly increases for the unmodified 50/50 PS/PE blend. The effect of the copolymer content in the blend on the interfacial tension between the two components is also investigated using the breaking thread method. The interfacial tension is found to be reduced from 5.6 to 1.1 mN/m by the addition of 20 parts of the copolymer to the blend. © 1997 John Wiley & Sons, Inc.     

The relative role of coalescence and interfacial tension in controlling dispersed phase size reduction during the compatibilization of polyethylene terephthalate/polypropylene blends

The breaking thread and the sessile drop methods have been used to evaluate the interfacial tension between a polypropylene (PP) and a polyethylene-terephthalate (PET). An excellent correlation was found between the two. The breaking thread technique was then used to evaluate the interfacial tension of these blends at various levels of a styrene-ethylene butylene-styrene grafted with maleic anhydride (SEBS-g-MA) compatibilizer. In order to evaluate the relative roles of coalescence and interfacial tension in controlling dispersed phase size reduction during compatibilization, the morphology of PP/PET 1/99 and 10/90 blends compatibilized by a SEBS-g-MA were studied and compared. The samples were prepared in a Brabender mixer. For the 10/90 blend, the addition of the compatibilizer leads to a typical emulsification curve, and a decrease in dispersed phase size of 3.4 times is observed. For the 1/99 blend, a 1.7 times reduction in particle size is observed. In the latter case, this decrease can only be attributed to the decrease of the interfacial tension. It is evident from these results that the drop in particle size for the 10/90 PP/PET blend after compatibilization is almost equally due to diminished coalescence and interfacial tension reduction. These results were corroborated with the interfacial tension data in the presence of the copolymer. A direct relationship between the drop in dispersed phase size for the 1/99 PP/PET blend and the interfacial tension reduction was found for this predominantly shear mixing device. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2271–2280, 1997     

D-leaping: Accelerating stochastic simulation algorithms for reactions with delays

We propose a novel, accelerated algorithm for the approximate stochastic simulation of biochemical systems with delays. The present work extends existing accelerated algorithms by distributing, in a time adaptive fashion, the delayed reactions so as to minimize the computational effort while preserving their accuracy. The accuracy of the present algorithm is assessed by comparing its results to those of the corresponding delay differential equations for a representative biochemical system. In addition, the fluctuations produced from the present algorithm are comparable to those from an exact stochastic simulation with delays. The algorithm is used to simulate biochemical systems that model oscillatory gene expression. The results indicate that the present algorithm is competitive with existing works for several benchmark problems while it is orders of magnitude faster for certain systems of biochemical reactions.     

A cutoff phenomenon in accelerated stochastic simulations of chemical kinetics via flow averaging (FLAVOR-SSA)

We present a simple algorithm for the simulation of stiff, discrete-space, continuous-time Markov processes. The algorithm is based on the concept of flow averaging for the integration of stiff ordinary and stochastic differential equations and ultimately leads to a straightforward variation of the the well-known stochastic simulation algorithm (SSA). The speedup that can be achieved by the present algorithm [flow averaging integrator SSA (FLAVOR-SSA)] over the classical SSA comes naturally at the expense of its accuracy. The error of the proposed method exhibits a cutoff phenomenon as a function of its speed-up, allowing for optimal tuning. Two numerical examples from chemical kinetics are provided to illustrate the efficiency of the method.     

Parameterless discrete Painlevé equations and their Miura relations

We present a study of discrete Painlevé equations which do not have any parameter, apart from those that can be removed by the appropriate scaling. We find four basic equations of this type as well as several more related to the basic ones by Miura transformations, which we derive explicitly. We obtain also the continuous limits of the basic parameterless equations and show that two of them are the discrete analogues of both the continuous Painlevé I and the zero-parameter Painlevé III.     

Decoupling of reactions in reactive polymer blending for nanoscale morphology control

In this study, a dynamic vulcanized alloy of brominated poly(isobutylene‐co‐p‐methylstyrene) (BIMSM) and polyamide (PA) has been investigated. An interfacial reaction between BIMSM and PA and a crosslinking reaction between BIMSM molecules is carried out simultaneously during melt blending. To form a vulcanized, nanoscale elastomer dispersion, the timing of these reactions is key and the interfacial reaction should be well advanced before the vulcanization reaction initiates. At a blending temperature of 205 °C, independent of the processing conditions, it is found that the interfacial reaction dominates the phase morphology development. Increasing the melt processing temperature, however, begins to favor the vulcanization reaction over the interfacial reaction. In nonplasticized blends, it is found that increasing the temperature above 235 °C increases the speed of the vulcanization reaction to a level that it dominates the phase morphology development. As a result, the phase size increases by 2.5‐fold because the system is vulcanized before the interfacial modification step is complete. Adding plasticizer to the PA matrix increases the overall phase size, but shows a similar behavior with increase in temperature from 205 to 255 °C. The critical temperature where the vulcanization reaction starts dominating phase morphology in the plasticized systems is at 225 °C. Once the processing temperature is above the critical temperature, it is found that the mixing sequence can be used to time and decouple the reactions. The work demonstrates that a close control over the temperature and processing conditions can be used to decouple the interfacial and vulcanization reactions resulting in vulcanized, nanoscale dispersions for the BIMSM and PA system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012