Reverse Monte Carlo simulations and Raman scattering of an amorphous GeSe4 alloy produced by mechanical alloying

The short and intermediate range order of an amorphous GeSe₄ alloy produced by Mechanical Alloying were studied by Reverse Monte Carlo simulations of its X-ray total structure factor and Raman scattering. The simulations were used to compute the , and partial distribution functions and the , and partial structure factors. We calculated the coordination numbers and interatomic distances for the first and second neighbors. The data obtained indicate that the structure of the alloy has important differences when compared to alloys prepared by other techniques. There are a high number of Se-Se pairs in the first shell, and some of the tetrahedral units formed seemed to be connected by Se-Se bridges.     

Electrochemical,morphological, and spectroscopic study of poly(aniline-co-<Emphasis Type="Italic">o</Emphasis>-bromoaniline) (PA-co-<Emphasis Type="Italic">o</Emphasis>-BrA) conducting copolymer

A series of moderately conducting and soluble copolymers of poly(aniline-co-o-bromoaniline) (PA-co-o-BrA) having different compositions was obtained by in the situ copolymerization method using different concentrations of monomer units of aniline and o-bromoaniline in the feed. The physio-chemical properties of the copolymers have been studied with sophisticated instrumental techniques. The electrochemical study of the copolymers was conducted by cyclic voltammetry. The band gap of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of the copolymers was evaluated by UV-vis spectroscopy. The morphological study was conducted by scanning electron microscopy and transmission electron microscopy at high magnification which shows non-uniform tubular to globular morphology of the copolymers. Surface profiles of the polymers were studied by AFM analyses, and it has confirmed the smooth surface of the copolymers while the homopolymers possesses non-uniform surfaces. The particle size distribution curve indicates that the particle sizes vary in the range of 5 to 9000 nm, and a small fraction of particles possess a size in the range of 5–10 nm.     

The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock copolymer or a comb copolymer. Due to the presence of the large-scale structure, the chains are stretched. The aim of this paper is to investigate the influence of this chain stretching on the formation of the small-scale structure. To gain insight we study infinite melts of infinitely long copolymer chains that are subjected to a stretching force. For melts of monodisperse multiblock copolymers we find that the stretching destabilizes the homogeneous phase. If the stretching is strong, the lamellar structure is the only stable structure. The periodicity increases with the degree of stretching. For melts of monodisperse comb copolymers the chain stretching has no influence on the stability of the homogeneous phase. If the stretching is strong, the lamellar structure and the hexagonal structure are the only stable structures. The periodicity is independent of the degree of stretching. For the multiblock copolymer we investigated the influence of block length polydispersity. For small polydispersity the period of the structure increases monotonically with the degree of stretching. For intermediate polydispersity, the period initially decreases before it starts to increase. For large polydispersity, the mean-field period at the spinodal is infinite, becoming finite once the stretching force exceeds some critical value. For very large polydispersity the mean-field period at the spinodal remains infinite for any value of the stretching force. Received: 14 February 2002 / Accepted: 24 March 2003 / Published online: 29 April 2003 RID="a" ID="a"e-mail: hindrik.angerman@abp.nl     

Miscibility in poly(L-lactide)- b -poly( $ \upvarepsilon$ -caprolactone) double crystalline diblock copolymers

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T_g contrast.     

The Composition,Sequence Analysis,and Crystallization Characterization of Poly(Trimethylene‐co‐Butylene Terephthalate) Copolymer

A series of poly(trimethylene‐co‐butylene terephthalate) (PTBT) copolymers were prepared by direct esterification followed by polycondensation. The composition and sequence distribution of the copolymers were investigated by nuclear magnetic resonance (NMR). The results demonstrate that the synthesized PTBT copolymers are block copolymers and the content of poly(butylene terephthalate) (PBT) units incorporated into the copolymers is always less than that in the polymerization feed. The 1,4‐butanediol consumption by a side reaction leads to a relatively lower content of PBT units in the resultant copolymers. At the same time, the PBT and poly(trimethylene terephthalate) (PTT) sequence length distributions in the copolymers are different. The PBT segments favor a longer sequence length than do the PTT segments in their corresponding enriched copolymers. The crystallization rate of the copolymers becomes lower than the homopolymers, especially for PTT‐enriched copolymers. Compared with the PTT segment, the presence of PBT segments in the copolymers seems to accelerate crystallization. A wide‐angle X‐ray diffraction (WAXD) analysis indicates PTT and PBT units do not co‐crystallize. The reduced melting temperatures of the copolymers may be attributed to a smaller lamellar thickness and lateral size due to short sequence lengths.     

Quantum chemical molecular dynamical investigation of alkyl nitrite photo-dissociated on copper surfaces

An accelerated quantum chemical molecular dynamical code “Colors-Excite” was used to investigate the photolysis of alkyl nitrites series, RONO (RCH₃ and C(CH₃)₃) on copper surfaces. Our calculations showed that the photo-dissociated processes are associated with the alkyl substituents of RONO when adsorbed on copper surfaces. For RCH₃, a two-step photolysis reaction occurred, yielding diverse intermediate products including RO radical, NO, and HNO, consistent with those reported in gas phase. While for RC(CH₃)₃, only one-step photolysis reaction occurred and gave intermediate products of RO radical and NO. Consequently, pure RO species were achieved to adsorb on metal surfaces by removing the NO species in photolysis reaction. The detailed photo-dissociated behaviors of RONO on copper surfaces with different alkyl substituents which are uncovered by the present simulation can be extended to explain the diverse dissociative mechanism experimentally observed. The quantum chemical molecular dynamical code “Colors-Excite” is proved to be highly applicable to the photo-dissociations on metal surfaces.     

Stability of dense hydrophobic-polar copolymer globules: Regular,random and designed sequences

Stability of dense globular structures formed by amphiphilic copolymers consisting of hydrophobic (insoluble) units and a small fraction of single polar (soluble) monomer units is considered in the mean-field approximation for different types of unit distributions along the chain. Polar (P) units are located in a relatively thin surface layer due to their strong repulsion from hydrophobic (H) monomer units. We compared globules formed by different copolymer sequences with the same gross numbers of P- and H-units: regular HP-sequences (P-units separated by equal H-blocks), random copolymers (uncorrelated positions of P-units, i.e. Flory distribution of H-block lengths), proteinlike (PL) sequences (designed sequences involving both long H-blocks dominating by total mass, and short blocks dominating by number). We showed that PL-globules are more stable (lower free energy) and are characterized by a higher temperature of the coil-to-globule transition when compared with the other sequences mentioned above. We also considered HP-H-copolymers consisting of one long and many short hydrophobic blocks; we showed that it is these sequences that yield the dense globules corresponding to the lowest free energy.Received: 3 July 2003, Published online: 11 November 2003PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling     

Theoretical study of local lattice structure of Mn in perovskite fluorides A2MF4 (A=K, Rb; M=Mg, Zn, Cd) series

A theoretical method for investigating the inter-relation between the molecular structure and electronic structure has been established on the basis of the 252×252 complete energy matrices for a 3d⁵ configuration ion in a tetragonal ligand field. By means of this method, which is independent of the X-ray diffraction, the local structure of the paramagnetic Mn²⁺ ion in perovskite fluorides A₂MF₄ (A=K, Rb; M=Zn, Mg, Cd) are determined directly by analyzing the EPR spectrum of octahedral Mn²⁺ center in A₂MF₄ crystals and the optical absorption spectrum of the (MnF₆)⁴⁻ cluster. It is shown that, comparing with the octahedral cubic structure, the local micro-structure in the vicinity of Mn²⁺ displays an elongated distortion when and a compressed distortion when , and ΔR vs. as well as ΔR vs. in the distortion region is, respectively, approximately linear. Simultaneously, the theoretical zero-field-splitting parameters , and are in good agreement with the experimental values.     

Structure and reactions of halo nuclei: An entangled approach

Halo nuclei are characterised by their weak binding, large spatial extent and hence a quite pronounced, yet highly correlated, few-body structure. This is typically in terms of a well-defined core plus one or more valence nucleons. Over the past decade the properties of halo nuclei have been studied theoretically using a range of reaction models, many of which having served us well for half a century or more in the study of less exotic, “mean-field”, nuclei. However, it is now clear that for many reactions with halo nuclei, it is not appropriate to disentangle (factorise out) the structure information from the reaction information. That is, the few-body nature of these systems requires few-body reaction models in which the nuclear structure and reaction mechanisms are necessarily entangled. This talk will briefly review the physical assumptions made by various reaction models, and point to areas where progress is being made to extend their range of applicability in order to provide further insights into halo structure. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: j.al-khalili@surrey.ac.uk     

Measurement of photo-fission yields and photo-neutron cross-sections in 209Bi with 50 and 65 MeV bremsstrahlung

The photo-fission yields and photo-neutron cross-sections of ( $ \gamma$ , 3n) and ( $ \gamma$ , 4n) on ²⁰⁹Bi induced by 50 and 65MeV bremsstrahlung have been measured by using a recoil catcher and an off-line $ \gamma$ -ray spectrometric technique. The mass-yield distribution of fission products in ²⁰⁹Bi induced by bremsstrahlung photons from the present work and literature data in the energy range 28-85MeV is symmetric around 103 mass units. However, the full width at half maximum of the yields distribution increases from 19 mass units at 28-40MeV to 23 mass units at 85MeV. The ( $ \gamma$ , 3n) reaction cross-section in the 50MeV and the ( $ \gamma$ , 4n) reaction cross-section in the 50 and 65MeV bremsstrahlung-induced reaction of ²⁰⁹Bi were determined for the first time.     

Experimental and theoretical studies on the magnetic property of carbon-doped ZnO

Intrinsic room-temperature ferromagnetism was detected over n-type carbon-doped ZnO prepared through solid-state reaction. Our results of first-principle calculations based on density functional theory revealed that the CZn₄O₁₂ unit is the origin of magnetic moment in the carbon-doped ZnO system. The carbon component has a significant contribution to the net magnetic moment, and any oxygen vacancy present in CZn₄O₁₂ has a negative effect on the magnetic properties of the system. Moreover, both antiferromagnetic and ferromagnetic interactions are predicted among carbon atoms located at different CC distances. The result suggests that the defect density influenced by the distribution of carbon has a significant effect on the magnetic properties of the carbon-doped ZnO system.     

Statistical properties of trading volume of Chinese stocks

The cumulative distribution of trading volume is investigated for Chinese stocks. Different from the power-law scaling of mature markets, the distribution is well fitted by a stretched exponential function . With the autocorrelation function and the detrended fluctuation analysis, the long-range autocorrelation of trading volume is revealed. The conditional dependence of volume on volatility and the volume-volatility cross-correlation are studied, and a positive long-range correlation between volume and volatility is observed.     

A study of the mechanical and structural properties of polonium

We have performed an ab initio study of the structure of polonium. By calculating total energies in a number of tetragonal lattice configurations, we have shown that the simple cubic structure is preferred by the system. The other two zero-stress structures, bcc and fcc, correspond to inflection points along this path. These calculations agree with experimental evidence that polonium is the only known element to assume the simple cubic structure at room temperature. We have found an LDA lattice constant of 3.28 Å, and we have obtained two of the elastic constants: and      

On the size distribution of Poisson Voronoi cells

Poisson Voronoi diagrams are useful for modeling and describing various natural patterns and for generating random lattices. Although this particular space tessellation is intensively studied by mathematicians, in two- and three-dimensional (3D) spaces there is no exact result known for the size distribution of Voronoi cells. Motivated by the simple form of the distribution function in the 1D case, a simple and compact analytical formula is proposed for approximating the Voronoi cell's size-distribution function in the practically important 2D and 3D cases as well. Denoting the dimensionality of the space by d (d=1,2,3) the compact form is suggested for the normalized cell-size distribution function. By using large-scale computer simulations the viability of the proposed distribution function is studied and critically discussed.     

Room temperature ferromagnetism in Zn-Mn-O

Zn-Mn-O semiconductor crystallites with nominal manganese concentration x=0.01, 0.04 and 0.10 were synthesized by a solid state reaction method using oxalate precursors. A sintering procedure was carried out in air at 500 and 900  ^°C. The samples were investigated by X-ray diffraction, magnetization measurements and electron paramagnetic resonance. X-ray diffraction spectra reveal that the dominant crystal phase in the Zn-Mn-O system corresponds to the wurtzite structure of ZnO. Room temperature ferromagnetism is observed in Zn-Mn-O samples with manganese concentrations x=0.01 and 0.04 sintered at low temperature (500  ^°C). Saturation magnetization in the x=0.01 sample is found to be at . The ferromagnetic phase seems to be developed by Zn diffusion into Mn-oxide grains.     

On the formulation of D = 11 supergravity and the composite nature of its three-form gauge field

The underlying gauge group structure of the D = 11 Cremmer-Julia-Scherk supergravity becomes manifest when its three-form field A₃ is expressed through a set of one-form gauge fields, , , η_1α, and E^a, ψ^α. These are associated with the generators of the elements of a family of enlarged supersymmetry algebras parametrized by a real number s. We study in detail the composite structure of A₃ extending previous results by D’Auria and Fré, stress the equivalence of the above problem to the trivialization of a standard supersymmetry algebra E^(11|32) cohomology four-cocycle on the enlarged superalgebras, and discuss its possible dynamical consequences. To this aim we consider the properties of the first order supergravity action with a composite A₃ field and find the set of extra gauge symmetries that guarantee that the field theoretical degrees of freedom of the theory remain the same as with a fundamental A₃. The extra gauge symmetries are also present in the so-called rheonomic treatment of the first order D = 11 supergravity action when A₃ is composite. Our considerations on the composite structure of A₃ provide one more application of the idea that there exists an extended superspace coordinates/fields correspondence. They also suggest that there is a possible embedding of D = 11 supergravity into a theory defined on the enlarged superspace .     

Diffusion-induced growth of compositional heterogeneity in polymer blends containing random copolymers

The compositional relaxation in random copolymer systems on a macroscopic scale is considered in theory. A set of diffusion equations is derived that describes the motion of chains of different composition and then converted into coupled equations for statistical moments of the compositional distribution. Several ways to solve the closure problem for these equations are discussed. The simplest is the situation when the shape of the transient compositional distribution can be predicted a priori, for example, a bimodal distribution is kept during interdiffusion of two copolymers that are not very close in composition. For a general case, it is shown that the cumulant-neglect closure based on the truncation of high-order cumulants is an effective method to get an approximate solution in terms of the time-dependent local mean composition and its dispersion. This method is applied to non-homogeneous compatible polymer systems, such as a random copolymer AB of a composition varying in space, a bilayer of Bernoullian copolymers AB of different composition, and a bilayer of homopolymers A and B, in which an autocatalytic polymer-analogous reaction A → B takes place, with possibility of the neighbor group effect. It is found that the interdiffusion can lead to a substantial broadening of the local compositional distribution, which, in turn, accelerates the system dynamics and promotes chemical reactions.     

Classical Limit of Quantum Dissipative Systems

We discuss the Lindblad equation for the density matrix where the dissipation is linear in the position operator. We consider a potential which is a bounded perturbation of the harmonic oscillator. We show that the perturbation of the potential leads to an analytic perturbation of the Wigner distribution. Then the Wigner distribution of the quantum dissipative system tends (uniformly in time) to the classical phase space distribution of the classical dissipative system (if the initial distribution converges when 0).     

Information theory link between MaxEnt and a key thermodynamic relation

We focus attention on the particular thermodynamic relation . Using information theory concepts we show that, for a reversible process in which intensive variables change, microscopic considerations related to this thermodynamic relation make the informational contents of, respectively, and MaxEnt equivalent. The pertinent demonstration is obtained when trying to ascertain the corresponding equilibrium microscopic probability distribution.     

Melt brushes of diblock copolymer

Using self-consistent field theory (SCFT), we investigate the morphologies formed by a melt brush of AB diblock copolymers grafted to a flat substrate by their B ends. In addition to a laterally uniform morphology, SCFT predicts three ordered morphologies exhibiting different periodic patterns at the air surface: a hexagonal array of A-rich dots, an alternating sequence of A- and B-rich stripes, and a hexagonal pattern of B-rich dots. When the phase diagram of the tethered film is plotted as a function of A/B incompatibility, N , and diblock composition, f , it resembles the bulk phase diagram with the periodic phases converging to a mean-field critical point at weak segregation. The periodic-phase region in the phase diagram shrinks with increasing grafting density and expands when the air surface acquires an affinity for the grafted B blocks.