Encrustation Prevention in PVC Reactors

Poly(vinyl chloride) is one of the world's most important bulk thermoplastics. Approximately 15 million tons are produced annually. About 80% of this is made by the suspension process. Suspension polymerization of vinyl chloride is almost invariably accompanied by the formation of scale on the internal surfaces of the polymerization reactor, including moving surfaces such as those of the impeller. The formation of scale, or deposits of PVC, on the internal surfaces of reactors has always been a problem in the manufacture of PVC because of reduced heat transfer, large alteration of the agitation regime present in the reactor, and broken-off scale fragments that block transfer systems and contaminate the product. Therefore scale must be cleaned periodically. Until the early 1970s these deposits were removed manually; PVC workers were exposed to high levels of VCM and considerable production time was lost. The introduction of large reactors in 1975 made it practical to mechanize the cleaning. High-pressure water sprays are employed for this purpose. However, such devices remove only the slightly adherent sandy deposits. For strongly attached deposits, a thorough manual cleaning is necessary after a series of polymerization batches. Manual cleaning requires extensive safety measures to protect the workers from VCM vapor inside the reactor. In addition, such cleaning is costly and undesirable. In more recent years, methods have been developed to suppress or inhibit the formation of scale on the reactor walls. Proposed solutions in this field are sparese. The patient literature claims many chemical treatments to resuce reactor fouling. Many PVC producers have developed effective buildup-suppressant treatments, which significantly reduce the need for reactior cleaning. They vary from treatments to render the reactor wall hydrophilic and reduce the adsorption of VCM (e.g., application of a sulfonic acid polymer to the reactor surface [1]) to systems containing polymerization inhibitors and radical traps (e.g., organic dyes and phenolic resins). The most successful of these probably work by a combination of both mechanisms. In this paper the soultions are reviewed brifly and emphasis is given to suspension polymerization where the initiator is monomer soluble.     

Ab initio lattice dynamics of Ni2MnX (X = Sn, Sb) magnetic shape memory alloys

In this study, we present the results of first principles calculations of elastic constants and phonon properties of nickel-manganese based magnetic shape memory compounds Ni₂MnSn and Ni₂MnSb in stoichiometric composition. The plane wave basis sets and pseudopotential method within spin-polarized generalized gradient approximation (σ-GGA) scheme of the density functional theory is applied. In investigation of the phonon dispersion spectra, linear response technique of the Density Functional Perturbation Theory is used. Phonon softening is observed in dispersion spectra at the transverse acoustic mode (TA₂) in [ζ ζ 0] direction as an indication of the structural instability of these systems to shear deformation. The vibrational instability of Ni₂MnSb system is larger than that of Ni₂MnSn yielding negative phonon frequencies. This vibrational anomaly is also verified by the low shear modulus and large elastic anisotropy ratio. The minority spin Fermi surfaces of both systems exhibit strong nesting features.     

Electronic structure of antiferromagnetic PbCrO3 (0 0 1) surfaces

Surfaces of cubic perovksite PbCrO₃ in (0 0 1) plane are investigated through density functional theory. The plane wave pseudopotential method is applied with generalized gradient approximation scheme. Hubbard U correction (GGA + U) is included in all calculations in order to simulate on-site Coulomb interactions between Cr-d states. Two types of terminations, namely, PbO- and CrO₂-terminations are considered in construction of the surfaces. Surfaces of both terminations show convergence at 9-layer slab geometry. The density of states calculations on the converged slab geometry yield a metallic behavior for both PbO- and CrO₂-terminations. Both metal atoms, Pb and Cr, in the uppermost layer of the respective terminations, have inward atomic relaxations much larger in magnitude than the oxygen atoms of the respective layer. However, Cr atoms which are labeled as up and down according to their spin orientation show different relaxations. The interlayer distance between the uppermost layer and the first one next to it decreases in both PbO- and CrO₂-terminated surface geometries. The calculations of the relative movement of the oxygen atom with respect to the Pb or Cr atom in each terminations give a positive rumpling in the uppermost layer.     

A2-MAKE: An efficient anonymous and accountable mutual authentication and key agreement protocol for WMNs

Multi-hop hybrid wireless mesh networks (WMNs) have recently attracted increasing attention and deployment. For easy acceptance and wide deployment of WMNs, security, privacy, and accountability issues have to be addressed by providing efficient, reliable, and scalable protocols. The fact that regular users, which may be resource-constrained wireless devices, are involved in routing activities highlights the need for efficiency and compactness. However, the said objectives, i.e., security, privacy, accountability, efficiency etc., are, most of the time, not compatible. So far no previous work has adequately reconciled these conflicting objectives in a practical framework. In this paper, we design and implement such a framework named as A²-MAKE, which is a collection of protocols. The framework provides an anonymous mutual authentication protocol whereby legitimate users can connect to network from anywhere without being identified or tracked unwillingly. No single party (or authority, network operator, etc.) can violate the privacy of a user, which is provided in our framework in the strongest sense. Our framework utilizes group signatures, where the private keys and corresponding credentials of the users are generated in a secure three-party protocol. User accountability is implemented via user identification and revocation protocols that can be executed by two semi-trusted authorities, one of which is the network operator. The assumptions about the trust level of the network operator are relaxed with respect to similar protocols. Our framework makes use of more efficient signature generation and verification algorithms in terms of computational complexity than their counterparts in literature, where signature size is almost the same as the shortest signatures proposed for similar purposes so far.     

Modified forward-backward overdetermined Prony method and itsapplication in modelling heart sounds

Prony's method is found to be a very effective method for the analysis-synthesis of transient data. However, straightforward application of this method can lead to poor performance, especially for short and noisy data records. The authors present a new over-determined forward-backward Prony method (MFBPM) and its application to the analysis of the first and second heart sounds. The accuracy of the method is measured using both cross-correlation and the normalised-mean-square-error (NMRSE) between a real signal and a synthetic one. Results from more than 80 different subjects show that the MFBPM is highly stable and gives very good performance with an average cross-correlation coefficient of 99.62%. Comparison of the results based on the NMRSE criterion show that the MFBPM is more precise than the modified backward Prony method (MBPM) with an accuracy improvement of upto 10%, and upto 20%, when compared with the conventional forward-backward Prony method (FBPM). Furthermore, a new method for dynamic estimation of model order is proposed for the case of heart sounds based on a subset of synthesised heart sounds which best approximates the observed data using NMRSE     

Improved parameters for the prediction of RNA hairpin stability

Thermodynamic parameters are reported for hairpin formation in 1 M NaCl by RNA sequences of the type GGXANmAYCC, where XY is the set of four Watson-Crick base pairs and the underlined loop sequences are three to nine nucleotides. A nearest neighbor analysis of the data indicates the free energy of loop formation at 37 degrees C is dependent upon loop size and closing base pair. The model previously developed to predict the stability for RNA hairpin loops (n > 3) includes contributions from the size of the loop, the identity of the closing base pair, the free energy increment (deltaGo(37mm)) for the interaction of the closing base pair with the first mismatch and an additional stabilization term for GA and UU first mismatches [Serra, M. J., Axenson, T. J., & Turner, D. H. (1994) Biochemistry 33, 14289]. The results presented here allow improvements in the parameters used to predict RNA hairpin stability. For hairpin loops of n = 4-9, deltaGo(37iL)(n) is 4.9, 5.0, 5.0, 5.0, 4.9, and 5.5 kcal/mol, respectively, and the penalty for hairpin closure by AU or UA is +0.6 kcal/mol. deltaGo(37iL)(n) is the free energy for initiating a loop of n nucleotides. The model for predicting hairpin loop stability for loops larger than three becomes deltaGo(37L)(n) = deltaGo(37iL)(n) + deltaGo(37mm) + 0.6(if closed by AU or UA) - 0.7(if first mismatch is GA or UU). Hairpin loops of three are modeled as independent of loop sequence with deltaGo(37iL)(3) = 4.8 and the penalty for AU closure of +0.6 kcal/mol. Thermodynamic parameters for hairpin formation in 1 M NaCl for 11 naturally occurring RNA hairpin sequences are reported. The model provides good agreement with the measured values for both T(M) (within 10 degrees C of the measured value) and deltaGo(37) (within 0.8 kcal/mol of the measured value) for hairpin formation. In general, the nearest neighbor model allows prediction of RNA hairpin stability to within 5-10% of the experimentally measured values.     

The quadratic minimum spanning tree problem: A lower bounding procedure and an efficient search algorithm

In this paper we consider the quadratic minimum spanning tree problem (QMSTP) which is known to be NP-hard. Given a complete graph, the QMSTP consists of finding a minimum spanning tree (MST) where interaction costs between pairs of edges are prescribed. A Lagrangian relaxation procedure is devised and an efficient local search algorithm with tabu thresholding is developed. Computational experiments are reported on standard test instances, randomly generated test instances and quadratic assignment problem (QAP) instances from the QAPLIB by using a transformation scheme. The local search heuristic yields very good performance and the Lagrangian relaxation procedure gives the tightest lower bounds for all instances when compared to previous lower bounding approaches.     

Beam search heuristics for the single and multi-commodity capacitated Multi-facility Weber Problems

The Multi-facility Weber Problem (MWP) is concerned with locating I uncapacitated facilities in the plane to satisfy the demand of J customers with the minimum total transportation cost of a single commodity. It is a non-convex optimization problem and difficult to solve. In this work, we focus on the capacitated extensions of the MWP which are Capacitated MWP (CMWP) and multi-commodity CMWP (MCMWP). Both the CMWP and MCMWP impose capacity restrictions on facilities. Indeed, the MCMWP is a natural extension of the CMWP and considers the situation where K distinct commodities are shipped subject to limitations on the total amount of goods sent from facilities to the customers. Customer locations, demands and capacities for each commodity are known a priori. The transportation costs, which depend on the commodity type, are proportional to the distance between customers and facilities. We first introduce branch and bound algorithms for both the CMWP and the MCMWP then we propose beam search heuristics for these problems. According to our computational experiments on standard and randomly generated test instances, we can say that the new heuristics perform very well.     

Non-identical parallel machine scheduling using genetic algorithm

Most of the scheduling problems are NP-hard. In the literature, several heuristics and dispatching rules are proposed to solve such hard combinatorial optimization problems and genetic algorithm (GA) ranks among the most preferred ones in view of its characteristics such as high adaptability, near optimization and easy realization. But, even though it is a common problem in the industry, only a small number of studies deal with non-identical parallel machines. In this paper, the authors propose a new “crossover operator” and a new “optimality criterion” in order to adapt the GA to non-identical parallel machine scheduling problem. New algorithm is tested on a numerical example by implementing it in a simulation software and computational results are compared to those obtained with LPT (Longest Processing Time) dispatching rule; results were promising. Findings show that, in addition to its high computational speed for larger scale problem, the GA proposed here fits the non-identical parallel machine scheduling problem of minimizing the maximum completion time (makespan).