Pyridazines. LXII. Tetrazolo-Azido Equilibria of Tetrazolo[1,5-b ]pyridazines

Tetrazolo[l,5-b]pyridazines exist in solution exclusively in the tetrazolo form. In solutions of strong acids an equilibrium of both forms, azido and tetrazolo, is established. The equilibrium constants in concentrated sulfuric acid or in trifluoromethanesulfonic acid were determined

Pyridazines. LXII. Tetrazolo-Azido Equilibria of Tetrazolo[1,5-b ]pyridazines

Tetrazolo[l,5-b]pyridazines exist in solution exclusively in the tetrazolo form. In solutions of strong acids an equilibrium of both forms, azido and tetrazolo, is established. The equilibrium constants in concentrated sulfuric acid or in trifluoromethanesulfonic acid were determined

3D BEM-based cooling-channel shape optimization for injection moulding processes

International audienceToday, around 30 % of manufactured plastic goods rely on injection moulding. The cooling time can represents more than 70 % of the injection cycle. Moreover, in order to avoid defects in the manufactured plastic parts, the temperature in the mould must be homogeneous. We propose in this paper a practical methodology to optimize both the position and the shape of the cooling channels in 3D injection moulding processes. For the evaluation of the temperature required both by the objective and the constraint functions, we must solve 3D heat-transfer problems via numerical simulation. We solve the heat-transfer problem using Boundary Element Method (BEM). This yields a reduction of the dimension of the computational space from 3D to 2D,avoiding full 3D remeshing: only the surface of the cooling channels needs to be remeshed at each evaluation required by the optimization algorithm. We propose a general optimization model that attempts at minimizing the desired overall low temperature of the plastic-part surface subject to constraints imposing homogeneity of the temperature. Encouraging preliminary results on two semi-industrial plastic parts show that our optimization methodology is viable

Tricritical Points in the Sherrington-Kirkpatrick Model in the Presence of Discrete Random Fields

The infinite-range-interaction Ising spin glass is considered in the presence of an external random magnetic field following a trimodal (three-peak) distribution. The model is studied through the replica method and phase diagrams are obtained within the replica-symmetry approximation. It is shown that the border of the ferromagnetic phase may present first-order phase transitions, as well as tricritical points at finite temperatures. Analogous to what happens for the Ising ferromagnet under a trimodal random field, it is verified that the first-order phase transitions are directly related to the dilution in the fields (represented by $p_{0}$). The ferromagnetic boundary at zero temperature also exhibits an interesting behavior: for $0<p_{0}<p_{0}^{*} \approx 0.30856$, a single tricritical point occurs, whereas if $p_{0}>p_{0}^{*}$ the critical frontier is completely continuous; however, for $p_{0}=p_{0}^{*}$, a fourth-order critical point appears. The stability analysis of the replica-symmetric solution is performed and the regions of validity of such a solution are identified; in particular, the Almeida-Thouless line in the plane field versus temperature is shown to depend on the weight $p_{0}$.Comment: 23pages, 7 ps figure

Random Field Models for Relaxor Ferroelectric Behavior

Heat bath Monte Carlo simulations have been used to study a four-state clock model with a type of random field on simple cubic lattices. The model has the standard nonrandom two-spin exchange term with coupling energy $J$ and a random field which consists of adding an energy $D$ to one of the four spin states, chosen randomly at each site. This Ashkin-Teller-like model does not separate; the two random-field Ising model components are coupled. When $D / J = 3$, the ground states of the model remain fully aligned. When $D / J \ge 4$, a different type of ground state is found, in which the occupation of two of the four spin states is close to 50%, and the other two are nearly absent. This means that one of the Ising components is almost completely ordered, while the other one has only short-range correlations. A large peak in the structure factor $S (k)$ appears at small $k$ for temperatures well above the transition to long-range order, and the appearance of this peak is associated with slow, "glassy" dynamics. The phase transition into the state where one Ising component is long-range ordered appears to be first order, but the latent heat is very small.Comment: 7 pages + 12 eps figures, to appear in Phys Rev

Optimization of 3D Cooling Channels in Injection Molding using DRBEM and Model Reduction

Issu de : ESAFORM 2009 - 12th ESAFORM Conference on material forming, Enschede, THE NETHERLANDS, 27-29 April 2009International audienceToday, around 30% of manufactured plastic goods rely on injection moulding. The cooling time can represent more than 70% of the injection cycle. In this process, heat transfer during the cooling step has a great influence both on the quality of the final parts that are produced, and on the moulding cycle time. In the numerical solution of three-dimensional boundary value problems, the matrix size can be so large that it is beyond a computer capacity to solve it. To overcome this difficulty, we develop an iterative dual reciprocity boundary element method (DRBEM) to solve Poisson’s equation without the need of assembling a matrix. This yields a reduction of the computational space dimension from 3D to 2D, avoiding full 3D remeshing. Only the surface of the cooling channels needs to be remeshed at each evaluation required by the optimisation algorithm. For more efficiency, DRBEM computing results are extracted stored and exploited in order to construct a model with very few degrees of freedom. This approach is based on a model reduction technique known as proper orthogonal (POD) or Karhunen-Loève decompositions. We introduce in this paper a practical methodology to optimise both the position and the shape of the cooling channels in 3D injection moulding processes. First, we propose an implementation of the model reduction in the 3D transient BEM solver. This reduction permits to reduce considerably the computing time required by each direct computation. Secondly, we present an optimisation methodology applied to different injection cooling problems. For example, we can minimize the maximal temperature on the cavity surface subject to a temperature uniformityconstraint. Thirdly, we compare our results obtained by our approach with experimental results to show that our optimisation methodology is viable

Classical transverse Ising spin glass with short- range interaction beyond the mean field approximation

The classical transverse field Ising spin- glass model with short-range interactions is investigated beyond the mean- field approximation for a real d- dimensional lattice. We use an appropriate nontrivial modification of the Bethe- Peierls method recently formulated for the Ising spin- glass. The zero- temperature critical value of the transverse field and the linear susceptibility in the paramagnetic phase are obtained analytically as functions of dimensionality d. The phase diagram is also calculated numerically for different values of d. In the limit d -> infinity, known mean- field results are consistently reproduced.Comment: LaTex, 11 pages, 2 figure

Molecular basis for functional diversity among microbial Nep1-like proteins

Necrosis and ethylene-inducing peptide 1 (Nep1)-like proteins (NLPs) are secreted by several phytopathogenic microorganisms. They trigger necrosis in various eudicot plants upon binding to plant sphingolipid glycosylinositol phosphorylceramides (GIPC). Interestingly, HaNLP3 from the obligate biotroph oomycete Hyaloperonospora arabidopsidis does not induce necrosis. We determined the crystal structure of HaNLP3 and showed that it adopts the NLP fold. However, the conformations of the loops surrounding the GIPC headgroup-binding cavity differ from those of cytotoxic Pythium aphanidermatum NLPPya. Essential dynamics extracted from \u3bcs-long molecular dynamics (MD) simulations reveals a limited conformational plasticity of the GIPC-binding cavity in HaNLP3 relative to toxic NLPs. This likely precludes HaNLP3 binding to GIPCs, which is the underlying reason for the lack of toxicity. This study reveals that mutations at key protein regions cause a switch between nontoxic and toxic phenotypes within the same protein scaffold. Altogether, these data provide evidence that protein flexibility is a distinguishing trait of toxic NLPs and highlight structural determinants for a potential functional diversification of non-toxic NLPs utilized by biotrophic plant pathogens