The role of the amorphous fraction for the equilibrium shape of polymer single crystals

The equilibrium state of polymer single crystals is considered by explicitly taking into account the amorphous fraction formed by loops and tails of the chains using a statistical model introduced by Muthukumar (Philos. Trans. R. Soc. London, Ser. A 361, 539 (2003)). We show that under realistic conditions below the equilibrium melting temperature, tight loops and close re-entries are favored, and that the amorphous fraction can be mapped into an excess surface free energy. The model is extended to many-chain crystals where it is shown that the lamellar thickness increases with the number of chains in the crystal and extended-chain conformations are thermodynamically favored if the number of chains in the crystal is sufficiently large. The number of chains necessary to form an extended-chain crystal in thermodynamic equilibrium scales with the square of the degree of polymerization of the chains. We discuss the temperature behavior of the equilibrium crystal thickness in the under-cooled state.     

Hierarchical Cu precipitation in lamellated steel after multistage heat treatment

Abstract

The hierarchical distribution of Cu-rich precipitates (CRPs) and related partitioning and segregation behaviours of solute atoms were investigated in a 1.54 Cu-3.51 Ni (wt.%) low-carbon high-strength low-alloy (HSLA) steel after multistage heat treatment by using the combination of electron backscatter diffraction (EBSD), transmission electron microscopy (TEM) and atom probe tomography (APT). Intercritical tempering at 725 °C of as-quenched lathlike martensitic structure leads to the coprecipitation of CRPs at the periphery of a carbide precipitate which is possibly in its paraequilibrium state due to distinct solute segregation at the interface. The alloyed carbide and CRPs provide constituent elements for each other and make the coprecipitation thermodynamically favourable. Meanwhile, austenite reversion occurs to form fresh secondary martensite (FSM) zone where is rich in Cu and pertinent Ni and Mn atoms, which gives rise to a different distributional morphology of CRPs with large size and high density. In addition, conventional tempering at 500 °C leads to the formation of nanoscale Cu-rich clusters in α-Fe matrix. As a consequence, three populations of CRPs are hierarchically formed around carbide precipitate, at FSM zone and in α-Fe matrix. The formation of different precipitated features can be turned by controlling diffusion pathways of related solute atoms and further to tailor mechanical properties via proper multistage heat treatments.     

Characterization of mechanochemically synthesized imidazolates of Ag, Zn, Cd, and Hg: Solid state reactivity of nd cations

Silver, zinc, cadmium, and mercury imidazolates have been synthesized mechanochemically by milling imidazole and the metal oxides in an agate mortar. The reaction products were characterized by FTIR and XRPD techniques. The results obtained for the mechanochemical imidazolates have been compared with those obtained by precipitation reported in the literature. The mechanochemical Ag imidazolate has the same orthorhombic crystal structure as the precipitated one. The mechanochemical Zn imidazolate has a tetragonal structure with similar crystal parameters to those of Zn(Imz)₂H₂O, but no water molecules are present in the structure. This new anhydrous form is a polymorph of the one obtained by precipitation. The mechanochemical Cd imidazolate has a monoclinic structure which is the polymorph of the precipited orthorombic form. The mechanochemical Hg imidazolate presents a hexagonal structure which is a polymorph of the orthorombic structure obtained by precipitation. The influence of the nd¹⁰ electronic configuration of the cations on the mechanochemical reaction is discussed.     

Turbulence temperature spectra: Scaling theory

Grand canonical Monte Carlo, histogram reweighting and finite-size scaling methods are used to determine the phase transitions of bulk (three-dimensional) and confined (quasi-two-dimensional) neutral colloid–polymer systems. The colloids are modeled as hard spheres and the polymer molecules as hard chains, and the only attractive forces are effective ones induced by depletion effects. In contrast to the predictions of mean field and other approximate theories, the nature of the coexistence phases is found to not depend solely on the polymer-to-colloid size ratio, q, but on the colloid diameter, the polymer radius of gyration, and the polymer monomer size. The threshold values of q for the onset of liquid–liquid phase separation differ significantly from earlier predictions, and depend strongly on the dimensionality of space. Extrapolation to the “protein limit” of very small colloid and very long polymer indicates that immiscibility persists at this limit in three dimensions, while it does not always do so for confined systems.     

LEED and STM studies of the stability of the MoO2(100) surface

Atomic scale images and low energy electron diffraction pattern of a MoO₂(100) single crystal surface are presented, which show different structural modifications depending on surface preparation. A short in-situ heat treatment of the as-grown single crystal results in an atomically ordered surface whose diffraction pattern and STM images are consistent with those expected from the bulk structure. The symmetry of the STM images suggests an oxygen termination of the surface. A significantly longer heat treatment causes a thermodynamically stable (4 × 1) reconstruction which is interpreted to be due to a loss of oxygen chains. The (4 × 1) reconstruction vanishes after Ar-ion-sputtering and subsequent annealing. Additional long sputtering cycles result in a (2 × 1) reconstruction. The observed surface reconstructions can be transformed into each other by heating or sputtering cycles.     

Novel properties of nanoscale organic–inorganic systems and photonic crystals — conducting polymers in nanoscale periodic structures,microcavities and photonic crystals

Conducting polymer/C₆₀and C₆₀doped conducting polymer/C₆₀heterojunctions have been fabricated and found to exhibit remarkably enhanced photoresponse due to the highly effective photoinduced charge transfer at the interface. In conducting polymer/C₆₀alkali metal nanoscale composite systems, multiphase superconductivity has been clarified and explained by taking the coupling of nanoscale grains by Josephson junctions into consideration. As examples of intramolecular organic-inorganic combined systems, unique electrical and optical characteristics have been revealed in oligosilanylene oligophenylene polymers. Electroluminescence has been demonstrated in organic-inorganic junction devices such as conducting polymer/porous Si and conducting polymer/diamond junctions. Conducting, polymer-based nanoscale multilayer systems have been studied utilizing molecular self-assembly method and novel photosensitive characteristics have been revealed. \indent Novel optical and electrical properties of conducting polymers infiltrated in a photonic crystal, synthetic opal made of SiO₂spheres of several hundred nm in diameter, and also a conducting polymer replica have been revealed. A clear diffraction pattern was observed in a photonic crystal infiltrated with conducting polymers, and transmission spectra are dependent on various ambient conditions. Their photoluminescence (PL) spectra, spectral narrowing of PL and lasing characteristics at relatively low optical excitation have also been clarified. Novel conducting characteristics of conducting polymers in a photonic crystal that was prepared by pyrolysis of a polymer replica of opal have also been observed.     

Properties of nanocrystalline TiO2 synthesized in premixed flames stabilized on a rotating surface

The properties of TiO₂ nanoparticles synthesized using the flame stabilized on a rotating surface method (FSRS) are investigated. The method uses a laminar, premixed, stagnation flame, combining particle synthesis and film deposition in a single step. The current study examines the effects of flame properties on particle characteristics. Synthesized particles were characterized using X-ray diffractometry, Transmission Electron Microscopy and UV–vis spectrometry in order to quantify the effects of equivalence ratio and precursor loading on particle size, crystallinity and optical band-gap. Results show that flame stoichiometry significantly affects crystal phase, but it has little to no effect on particle size and light absorption band edge. In addition, precursor loading impacts both the particle size and the crystal phase. The study demonstrates the potential of the FSRS method for producing tailored nanoscale TiO₂ particles for a variety of applications.     

Photo-orientation at liquid crystal—polymer interfaces

It is suggested that liquid crystal—polymer interfaces are coupled systems, in which the components mutually influence the orientational state of each other. The photo-orientation process at liquid crystal-polymer interfaces provides a striking example of such a coupling. Experiments show that the anisotropic structure generated by polarised light at a polymer surface is strongly affected by the phase of the liquid crystal covering the polymer. Photo-orientation is significantly more efficient when the liquid crystal is in the isotropic phase than when it exhibits orientational order. The observations are interpreted by assuming that in the smectic and nematic phases the liquid crystal stabilises to a large extent polymer chain-segments aligned parallel to the director, while it blocks the photo-induced formation of chain-segments in the perpendicular direction. Other situations, in which the coupling between the liquid crystal and the polymer can be important, are also discussed briefly.     

Energetics of 2D colloids in free-standing smectic-C films

The formation of regular colloid patterns in free-standing smectic films at the transition from the smectic-C to the isotropic or nematic phase is well known experimentally. The self-organization of isotropic or nematic droplets is caused by their mutual interaction, mediated by elastic distortions of the local director in the surrounding liquid crystal. These distortions are related to the anchoring conditions of the director at the droplet border. We describe analytically the energetics of the liquid crystal environment of a single droplet in one-constant approximation. A method of complex analysis, Conformal Mapping, is employed. Following a suggestion of Dolganov et al. (Phys. Rev. E. 73, 041706 (2006)), energetics of chain and grid patterns built from the colloids are investigated numerically in order to explain experimentally observed formations and their director fields.     

Single long-polymer translocation through a long pore

This paper theoretically studies the free energy and conformational entropy of a long polymer threading a long nanopore (n₀/N \ge 0.1) on external electric field. The polymer expanded model is built in this paper, that is, a single long polymer chain with N monomers (each of size a) threading a pore with n₀ monomers can be regarded as polymer with N+n_{0} monomers translocating a 2-dimension hole embedded in membrane. A theoretical approach is presented which explicitly takes into account the nucleation theory. Our calculations imply that, the structure of polymer changes more acutely than other situation, while its leading monomer reaches the second vacuum and its end monomer escapes the first vacuum. And it is also shown that the length scale of polymer and pore play a very important role for polymer translocation dynamics. The present model predicts that the translocation time depends on the chemical potential gradient and the property of the solvent on sides of pore to some extent.     

Electrons and photons in mesoscopic structures: Quantum dots in a photonic crystal

The synthesis and properties of a photonic crystal doped with quantum dots are reported. The structure exhibits a two-stage self-organization of silica nanoparticles along with quantum confinement effects in semiconductor colloids. The interplay of electron and photon confinement results in controllable spontaneous emission from the mesoscopic structure. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 2, 131–135 (25 July 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Director-configurational transitions around microbubbles of hydrostatically regulated size in liquid crystals

A high-pressure technique is introduced which allows a continuous variation of the inclusion size in liquid crystal colloids. We use a nematic liquid crystal host into which micrometer-sized gas bubbles are injected. By applying hydrostatic pressures, the diameter of these gas bubbles can be continuously decreased via compression and absorption of gas into the host liquid crystal, so that the director configurations around a single bubble can be investigated as a function of the bubble size. The theoretically predicted transition from a hyperbolic hedgehog to a Saturn-ring configuration, on reduction of the particle size below a certain threshold, is confirmed to occur at the radius of a few micrometers.     

结晶紫在混合正、负电性银胶上的表面增强拉曼散射

利用化学还原的方法分别制备了具有正、负电性的纳米银胶 ,通过测定结晶紫分子在正、负电性银胶以及混合银胶体系的表面增强拉曼光谱的变化 ,探讨了不同电性银胶基底对结晶紫分子表面增强拉曼活性的影响。结果表明 ,混合银胶体系能有效的改进单银胶体系的表面增强拉曼活性。     

Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains

We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and θ -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a θ -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a θ -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction.     

Mechanical properties of bulk and nanoscale TiO2 phases

The mechanical properties of bulk and nanoscale TiO₂ phases are examined with a view to assess the available bulk modulus and hardness data, and to understand the size-dependent behaviors. The bulk modulus values of thermodynamically stable bulk TiO₂ phases show a general correlation with Ti-O coordination number. As with the cotunnite-structured (OII) phase, it is likely that the seven-coordinated OI and eight-coordinated fluorite forms of TiO₂ are ultrahard substances. Of the nanoscale phases investigated thus far, nanocrystalline anatase displays the strongest size dependence of bulk modulus values, with possible stiffening behavior effected by incipient grain boundary amorphization under pressure. Nanocrystalline rutile and baddeleyite phases do not show appreciable size dependence in their compression behaviors.     

The Shape Memory Effect in Structurally Heterogeneous Polymer Systems

The kinematics of shape recovery for the mixtures of thermodynamically incompatible polymers and polymer composites filled with thermoexpanded graphite has been investigated. It is shown that in these systems the shape recovery is accompanied by an increase in volume. The latter is attained at the expense of formation of microdiscontinuities at the interfaces (the polymer mixtures) or of recovery of filler porosity.     

Solution Lithography for Colloidal Crystal Patterning: Revisiting Flory–Huggins Interaction Parameters and Co-Nonsolvent Systems

For fundamental studies and practical applications, colloidal crystal patterns on substrates are typically fabricated through etching and conventional lithography. However, a wet-chemical based method is necessary for simplifying the procedure, preserving the substrate structure, and reproducibly fabricating the colloidal crystal patterns. The present study demonstrates that colloidal crystal patterns can be conveniently generated using thermodynamic relationships between a polymer colloid and surrounding solvents. Close-packed colloidal monolayers in good solvents that cause colloidal swelling spontaneously transform into non–close-packed crystal patterns when non-solvents that cause their shrinkage replace the good solvents. The colloid diameter in the close-packed monolayer decreases significantly when the polymer in the colloid is passing thermodynamic theta conditions (when Flory–Huggins interaction parameters increase to higher than ≈0.5). The close-packed monolayers also transform into the patterns in co-nonsolvent conditions. The “solution lithography” might be particularly useful for patterning colloids on curved microstructures and plastic/flexible films. The colloidal shapes in the patterns vary with the solvent pairs and substrates. The method does not require special facilities to reproducibly fabricate the patterns. The study further suggests methods simultaneously fixing the patterns. The patterns exhibit anti-reflection properties. Therefore, the solution lithography is applicable to optics, electronics, analytical science, and energy systems.     

Effect of low-symmetry mechanical stresses on the magnetic properties of iron borate

Low-(C ₃) symmetry mechanical stresses are used to induce an additional crystalline magnetic anisotropy in the basal plane of a FeBO₃ single crystal. The effect of the stress-induced anisotropy on the main magnetic properties of this weak ferromagnet is studied by a magnetooptic method. This additional anisotropy is shown to transform the initial 180° domain structure of iron borate into a structure with domain walls making an angle of ～ 120° with each other in the basal plane of the crystal. However, unlike in the ordinary 120° DW structure, the azimuthal angle of the spontaneous magnetization vectors in the arising domains varies along domain walls. It is found that the stress-induced transformation of the crystal’s domain structure significantly affects the shape of hysteresis loops recorded at quasi-static magnetization, increases the initial magnetooptic susceptibility, and makes the coercive force anisotropic.