A new kinetic model for bulk polymerization of vinyl chloride based on two-phase hypothesis

A kinetic model has been developed for the bulk polymerization of vinyl chloride using Talamini's hypothesis of two-phase polymerization and a new concept of kinetic solubility which assumes that rapidly growing polymer chains have considerably greater solubility than the thermodynamic solubility of preformed polymer molecules of the same size and so can remain in solution even under thermodynamically unfavourable conditions. It is further assumed that this kinetic solubility is a function of chain length. The model yields a rate expression consistent with the experimental data for vinyl chloride bulk polymerization and moreover is able to explain several characteristic kinetic features of this system. Application of the model rate expression to the available rate data has yielded 2.36 × 108l mol−1 sec−1 for the termination rate constant in the polymer-rich phase; as expected, this value is smaller than that reported for homogenous polymerization by a factor of 10–30.

Mixed ligand complexes in vinyl polymerization-II: [NN′-ethylenebis(salicylideneiminato)] (benzoylacetonato)cobalt(III) as an initiator

The polymerization of methyl methacrylate initiated by a mixed ligand complex. [NN′-ethylenebis(salicylideneiminato)](benzoylacetonato)cobalt(III) has been studied in bulk and in benzene at 70° and 80°. The rate of polymerization is proportional to (concentration of the chelate)1/2 and the monomer exponent is close to 1.5. The activation energy and the kinetic and transfer constants are evaluated. A free radical mechanism has been proposed.

Mixed ligand complexes in vinyl polymerization. I. [N,N-ethylenebis (salicylideneiminato)](acetylacetonato)cobalt(III) as an initiator

Polymerization of methyl methacrylate in the presence of a mixed ligand complex, [N,N-ethylenebis(salicylideneiminato)](acetylacetonato)cobalt(III) in benzene was studied. The rate of polymerization was proportional to the square root of the concentration of the chelate and the monomer exponent was 1.67 and 1.69 at 60 and 70°C, respectively. The activation energy and the kinetic and transfer constants were evaluated. A free-radical mechanism has been proposed.

Metal chelates in vinyl polymerization. I. Ferric dipivaloylmethide as an initiator

The behavior of the chelate, ferric dipivaloylmethide, Fe(DPM)3, in vinyl polymerization systems was investigated. The polymerization was found to be of free-radical nature. The rate of polymerization was proportional to the square root of the concentration of the chelate. The monomer exponent was close to 1.5 for the Fe(DPM)3-initiated polymerization of styrene and methyl methacrylate. The kinetic and transfer constants and activation energies for these systems have been evaluated. Spectral studies revealed the possibility of a complex formation between the chelate and the monomer. A kinetic scheme for the Fe(DPM)3-initiated polymerization is derived based on this initial complex formation.

Metal chelates in vinyl polymerization. II. Mechanism of initiation by Fe(DPM)3

The nature of the interaction between the unsaturated monomer and the chelate, Fe(DPM)3, is studied in detail. The interaction is found to occur only in solution. The stoichiometry of interaction and the equilibrium constant are evaluated. With the help of spectral evidence, attempts are made to point out the specific sites of interaction.

Enhancement of (BH)(max) in a hard-soft-ferrite nanocomposite using exchange spring mechanism

We have observed the exchange spring behavior in the soft (Fe3O4)-hard (BaCa2Fe16O27)-ferrite composite by tailoring the particle size of the individual phases and by suitable thermal treatment of the composite. The magnetization curve for the nanocomposite heated at 800 degrees C shows a single loop hysteresis showing the existence of the exchange spring phenomena in the composite and an enhancement of 13% in (BH)(max) compared to the parent hard ferrite (BaCa2Fe16O27). The Henkel plot provides the proof of the presence of the exchange interaction between the soft and hard grains as well as its dominance over the dipolar interaction in the nanocomposite.

Soft matter lithium salt electrolytes: ion conduction and application to rechargeable batteries

Soft matter provides diverse opportunities for the development of electrolytes for all solid state lithium batteries. Here we review soft matter solid electrolytes for lithium batteriesthat are primarily obtained starting from liquid electrolytic systems. This concept of solid electrolyte synthesis from liquid is significantly different from prevalent approaches. The novelty of our approach is discussed in the light of various fundamental issues and in relation to its application to rechargeable lithium batteries.

Soft gluon k(t)-resummation and the Froissart bound

We study soft gluon k(t)-resurnmation and the relevance of InfraRed (IR) gluons for the energy dependence of total hadronic cross-sections. In our model, consistency with the Froissart bound is directly related to the ansatz that the IR behaviour of the QCD coupling constant follows an inverse power law.

Mycobacterium tuberculosis FtsZ requires at least one arginine residue at the C-terminal end for polymerization in vitro

We examined whether C-terminal residues of soluble recombinant FtsZ of Mycobacterium tuberculosis (MtFtsZ) have any role in MtFtsZ polymerization in vitro. MtFtsZ-delta C1, which lacks C-terminal extreme Arg residue (underlined in the C-terminal extreme stretch of 13 residues, DDDDVDVPPFMRR), but retaining the penultimate Arg residue (DDDDVDVPPFMR), polymerizes like full-length MtFtsZ in vitro. However, MtFtsZ-delta C2 that lacks both the Arg residues at the C-terminus (DDDDVDVPPFM), neither polymerizes at pH 6.5 nor forms even single- or double-stranded filaments at pH 7.7 in the presence of 10 mM CaCl2. Neither replacement of the penultimate Arg residue, in the C-terminal Arg deletion mutant DDDDVDVPPFMR, with Lys or His or Ala or Asp (DDDDVDVPPFMK/H/A/D) enabled polymerization. Although MtFtsZ-delta C2 showed secondary and tertiary structural changes, which might have affected polymerization, GTPase activity of MtFtsZ-delta C2 was comparable to that of MtFtsZ. These data suggest that MtFtsZ requires an Arg residue as the extreme C-terminal residue for polymerization in vitro. The polypeptide segment containing C-terminal 67 residues, whose coordinates were absent from MtFtsZ crystal structure, was modeled on tubulin and MtFtsZ dimers. Possibilities for the influence of the C-terminal Arg residues on the stability of the dimer and thereby on MtFtsZ polymerization have been discussed.

False Error Study of On-line Soft Error Detection Mechanisms

With technology scaling, vulnerability to soft errors in random logic is increasing. There is a need for on-line error detection and protection for logic gates even at sea level. The error checker is the key element for an on-line detection mechanism. We compare three different checkers for error detection from the point of view of area, power and false error detection rates. We find that the double sampling checker (used in Razor), is the simplest and most area and power efficient, but suffers from very high false detection rates of 1.15 times the actual error rates. We also find that the alternate approaches of triple sampling and integrate and sample method (I&S) can be designed to have zero false detection rates, but at an increased area, power and implementation complexity. The triple sampling method has about 1.74 times the area and twice the power as compared to the Double Sampling method and also needs a complex clock generation scheme. The I&S method needs about 16% more power with 0.58 times the area as double sampling, but comes with more stringent implementation constraints as it requires detection of small voltage swings.

Total cross-section at LHC from minijets and soft gluon resummation in the infrared region

A model for total cross-sections incorporating QCD jet cross-sections and soft gluon resummation is described and compared with present data on pp and pp cross-sections. Predictions for LHC are presented for different parameter sets. It is shown that they differ according to the small x-behaviour of available parton density functions.

Synthesis and characterization of polyaniline salts with phenoxy acetic acids by emulsion polymerization

Polyaniline salts have been synthesized by chemical oxidative polymerization of aniline in the presence of phenoxy acetic acid and its two derivatives using emulsion method at room temperature and characterized by different techniques such as infrared, H-1 and C-13 NMR, UV-visible spectroscopy, SEM, wide angle X-ray diffractograms and conductivity measurements. These polyaniline salts have the desirable property of high solubility for processibility in solvents such as DNIF, DMSO and a mixture of CHCl3 and acetone and they exhibit fairly good conductivity of similar to 3.0 x 10(-3) S cm(-1). The variations in solubility, conductivity and morphology with the protonating strength of the dopants are examined.

Influence lines for bending under a ring load of a free shell, a shell embedded in a soft medium and a shell containing a soft core

Theoretical expressions for stresses and displacements have been derived for bending under a ring load of a free shell, a shell embedded in a soft medium, and a shell containing a soft core. Numerical work has been done for typical cases with an Elliot 803 Digital Computer and influence lines are drawn therefrom.