The thermal properties of water-n,n-dimethylformamide solutions at 278–323.15 K and 0.1–100 MPa

The isothermal compressibility coefficients κ _T , volumetric thermal expansion coefficients α, and pressure coefficients (?p/?T) _v were calculated for water-N,N-dimethylformamide (DMFA) mixtures of 12 compositions over the temperature and pressure ranges 278–323.15 K and 0.1–100 MPa. The composition dependences of κ _T passed minima, and the corresponding α and (?p/?T) _v dependences passed maxima. The structural features of water and hydrophobic hydration effects were found to play a determining role in changes in the thermodynamic properties of water-DMFA solutions.     

Diffusion and Relaxation Dynamics of Supercooled Polymer Melts

The dynamic properties of polymer melts are investigated in the range of normal liquid regime to the supercooled liquid regime. The polymer is modeled as a coarse-grained bead-spring model with chain length ranging from 5 to 160. The mean squared displacement and non-Gaussian parameter are used to describe the self diffusion of polymer beads. We find slow dynamics with decreasing temperature and increasing chain length. The time evolution of non-Gaussian parameters shows two peaks(or one peak one shoulder) in the α-relaxation time, τα, regime and sub-diffusion time regime, respectively, where the first primary peak indicates the dynamic heterogeneity stemmed from the motion of beads, and the secondary peak is the result of correlated motion along a polymer chain. Moreover, the relaxation of polymer beads shows clear two-step decay in supercooled melts and the dynamics shows growing heterogeneity with decreasing temperature. As chain length is increased, a peak of the dynamic susceptibility occurs, and the peak height,χ*4, increases and then reaches a plateau. The curves of the height of the first peak of α_2, α _2~*, versus τ and the curves of χ_4~*α versus τα follow two master curves for different chain lengths. Our results indicate the similarity of dynamic heterogeneity dominated by the motion of single bead even the chain length is different. It is interesting to find that the Stokes-Einstein(SE) relation between τα and diffusion coefficient D, D~τ-1 q, is highly length-scale dependent. The SE relation breaks down in both normal melts regime and supercooled regime at large magnitude of wave vectors, attributed to the non-Brownian motion arising from the chain connectivity and growing heterogeneity due to supercooling. However, the SE relation is reconstructed when the probing length scale is large(at small magnitude of wave vectors). Our results show a hierarchical physical picture of the supercooled polymeric dynamics.     

Thermoresponsive behavior of water-salt solutions of a graft copolymer with a main polyimide chain and side poly(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylamino-2-ethyl methacrylate) side chains

The water-salt solutions of the graft copolymer bearing a polyimide main chain and poly(N,N-dimethylamino-2-ethyl methacrylate) side chains (M = 4.7 × 10⁵, the density of grafting with side chains z = 0.44) are studied by static and dynamic light scattering and turbidimetry. The solutions are investigated in a tenfold range of NaCl concentrations (from 0.015 to 0.15 mol/L) at the polymer concentration from 0.002 to 0.015 g/cm³ and pH from 8 to 12. The temperature dependences of the intensity of scattered light, optical transmission, hydrodynamic radius of scattering objects, and their concentrations in solutions are derived. The temperatures of phase separation onset T ₁ and end T ₂ are determined. It is shown that an increase in the salt content in solution leads to reduction in the polymer solubility and in temperatures T ₁ and T ₂. The watersalt solutions retain all the regularities of phase-separation temperature variation observed for aqueous solutions with change in the concentration of solution and pH of a medium: the values of T ₁ and T ₂ increase upon dilution and growth of acidity.     

Slow Down Dewetting in Polymer Films by Isocyanate-treated Graphite Oxide

Isocyanate-treated graphite oxides(i GOs) were well-dispersed into the polystyrene(PS) thin films and formed a novel network structure. With control in fabrication, an i GOs-web layer was horizontally embedded near the surface of the films and thus formed a composite slightly doped by i GOs. This work demonstrated that the i GOs network can remarkably depress the dewetting process in the polymer matrix of the composite, while dewetting often leads to rupture of polymer films and is considered as a major practical limit in using polymeric materials above their glass transition temperatures(Tg). Via annealing the 50–120 nm thick composite and associated neat PS films at temperatures ranging from 35 °C to 70 °C above Tg, surface morphology evolution of the films was monitored by atomic force microscopy(AFM). The i GOs-doped PS exhibited excellent thermal stability, i.e., the number of dewetting holes was greatly reduced and the long-term hole growth was fairly restricted. In contrast, the neat PS film showed serious surface fluctuation and a final rupture induced by ordinary dewetting. The method developed in this work may pave a road to reinforce thin polymer films and enhance their thermal stability, in order to meet requirements by technological advances.     

The thermochemical characteristics of solution of DL-α-alanylglycine and DL-α-alanyl-DL-α-alanine in water-organic solvent mixtures at 298.15 K

The integral enthalpies of solution of DL-α-alanylglycine and DL-α-alanyl-DL-α-alanine in water-organic solvent (acetonitrile, 1,4-dioxane, acetone, N,N-dimethylformamide, and N,N-dimethylsulfoxide) mixtures were measured at organic component concentrations x ₂ = 0–0.4 mole fractions and T = 298.15 K. The standard enthalpies of solution (Δ_sol H°) and transfer (Δ_tr H°) of the peptides from water into mixed solvents were calculated. The influence of the structure and properties of solutes and mixture composition on the thermochemical characteristics of the peptides was considered. The enthalpy coefficients of pair interactions (h _xy ) of DL-α-alanylglycine and DL-α-alanyl-DL-α-alanine with organic solvent molecules were calculated. The h _xy values were correlated with the properties of organic solvents using the Kamlet-Taft equation.     

Characterization of a novel <Emphasis Type="Italic">Aspergillus niger</Emphasis> beta-glucosidase tolerant to saccharification of lignocellulosic biomass products and fermentation inhibitors

Properties of beta-glucosidase produced by Aspergillus niger URM 6642 recently isolated from the Atlantic rainforest biome and its potential tolerance to saccharification of lignocellulosic biomass products and fermentation inhibitors was evaluated. The fungus was cultivated under solid state culture conditions at 37°C with different agro-industrial wastes. High levels of beta-glucosidase (3778.9 U g^?1)from A. niger were obtained with rice meal as substrate under solid state culture conditions after ten days. Optimum pH for this particular beta-glucosidase activity was 4.0 although it was stable in the range of 4.0 to 7.0. The half-life (T_½) of beta-glucosidase at 55°C is 3 h. However, at the optimum temperature of the enzyme, 65°C, T_½ is 20 min. The enzyme showed tolerance to various compounds such as glucose, xylose, 5-hydroxymethyl furfural, furfural, coumarin, ethanol and acetic acid. Therefore, beta-glucosidase from the novel A. niger species may be of potential use in the saccharification of lignocellulosic biomass, as well as an additional enzyme supplement in cellulase cocktails used to increase the yield of fermentable sugars.     

Transport and physicochemical parameters of polypentenamer

Physicochemical properties of a cis-polypentenamer—a hydrocarbon polymer with a low glass transition temperature (T _g = 168.8 K)—have been studied. Measurements of permeability coefficients P in rubbery material for a wide range of gases (He, H₂, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈, and n-C₄H₁₀) indicate a high permeability of this polymer for which the values of P are only slightly lower than those of the most permeable rubber—poly(dimethylsiloxane). The method of inverse gas chromatography has been employed to estimate solubility coefficients S for n alkanes C₃–C₁₀ and cycloalkanes in cis-polypentenamer in the range from 25 to 150°C. It has been shown that the solubility coefficients linearly increase in lnS-T _cr ² coordinates, where T _cr is the critical temperature of a solute. In terms of the above correlation, the solubility coefficients of light gases have been estimated and the diffusion coefficients D of gases in the same polymer have been calculated via the formula P=DS. The free volume in cis-polypentenamer has been studied by positron annihilation lifetime spectroscopy. The temperature dependence of the positronium lifetime τ ₃ that characterizes the size of the free volume element in a polymer demonstrates saturation at temperatures above 250 K. This effect is probably related to a rapid migration of fluctuation holes in the rubbery polymer at temperatures remote enough from its glass transition temperature.     

Dielectric properties of films of Ag-ED20 epoxy nanocomposite synthesized in situ. Temperature dependence of direct current conductivity

The influence of silver myristate used as a precursor of silver nanoparticles on the direct current conductivity σ _dc of epoxy polymer within the concentration range of ≤0.8 wt % was investigated. The value of direct current conductivity was determined on the basis of analysis of the frequency dependence of complex permittivity within the frequency range of 10^?2–10⁵ Hz. The temperature dependence of σ _dc is composed of two regions. The dependence corresponds to the Vogel-Fulcher-Tammann empirical law σ _dc = σ _dc0exp{?DT ₀/(T-T ₀)} (where T ₀ is the Vogel temperature and D is the strength parameter) at temperatures higher than the glass transition temperature T _g. At the same time, T ₀ does not depend on the concentration of nanoparticles. The Arrhenius temperature dependence characterized by activation energy about 1.2 eV is observed at temperatures lower than T _g. The observed shape of the temperature dependence is related to the change in the mechanism of conductivity after “freezing” of ionic mobility at temperatures lower than T _g. The value of σ _dc is increased as the concentration of nanoparticles is raised within the temperature range of T > T _g. The obtained dependence of σ _dc on silver myristate concentration is similar to the root one, indicating the absence of percolation within the studied range of concentrations.     

Characterization of neutron spectrum at Es-Salam Research Reactor using Høgdahl convention and Westcott formalism for the k<Subscript>0</Subscript>-based neutron activation analysis

For the general applicability of the k ₀-NAA method two formalisms were carried out to deal with “1/ν and non-l/ν ((n,γ)” reaction nuclides, respectively. In the Høgdahl-formalism the reactor neutron spectrum parameters, such as α and f were measured using three methods: Cd-ratio, Cdcovered and bare triple monitors. In addition, bare bi-isotopic method using Zr is also utilized for the calculation of f. According to the Westcottformalism the modified spectral index r(α)√T _n /T ₀ and g(T _n ) factor for monitoring neutron temperature T _n , were measured employing Lu as non “1/v” monitor and ¹⁹⁷Au, ⁹⁶Zr and ⁹⁴Zr as “1/v” monitors. The reduced resonance integral of lutetium s _0,Lu was also calculated. To evaluate the applicability of k ₀-NAA in our analytical system, the analysis of two kinds of SRMs was executed. The analytical results showed that the relative error of most of the elements was less than 10%.     

The enthalpies of solution of L-α-alanyl-L-α-alanine in water-organic solvent mixtures at 298.15 K

The integral enthalpies of solution (T = 298.15 K) of L-α-alanyl-L-α-alanine in aqueous-organic solvents (acetonitrile, 1,4-dioxane, acetone, formamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylsulfoxide) were measured at organic component concentrations x ₂ = 0–0.3 mole fractions. The standard enthalpies of solution (Δ_sol H ^o) and transfer (Δ_tr H ^o) of the peptide from water into mixed solvents were calculated. The influence of the structure and properties of solutes and mixture composition on solute thermochemical characteristics is considered. The enthalpy pair interaction coefficients h _xy between L-α-alanyl-L-α-alanine and organic solvent molecules were calculated. The linear Kamlet-Taft four-parameter equation was used to reveal correlation between the h _xy values and the properties of organic solvents.     

Dehydroxylation of high-energy ball-milled diasporic bauxite

The review consists of four parts. Part I is about the thermal transformation in clay minerals under firing and about the properties of fired clay. The transformations in the clay are expressed quantitatively with the extent of conversion, α, which is the function of two parameters of firing process, time t and temperature T: α?=?f(t, T). Part II is about the estimation of firing temperature after the analysis of the products of firing clays. All the estimations are speculative, without mathematical equations. It is impossible to derive the value of only one variable T from α?=?f(t,T), the function of two variables. Part III is about the long-term inverse transformation in fired ceramic paste under ambient conditions. The mass gain as a function of time is used for the evaluation of the time elapsed from the ancient firing, t. Part IV is about the visualization of the extent of conversion of the clay in the paste after all direct and reverse reactions, i.e., α.     

Effect of cooling rate and Al content on solidification characteristics of AZ magnesium alloys using cooling curve thermal analysis

The solidification behavior of AZ Magnesium alloys in various cooling conditions was investigated using a computer-aided cooling curve thermal analysis method. In each case, the cooling curve and its first and second derivative curves have been plotted using accurate thermal analysis equipment and solidification characteristics were recognized from these curves. The cooling rates used in the present study range from 0.22 to 8.13 °C s^?1. The results of thermal analysis show that the solidification parameters of AZ alloys such as nucleation temperature (T _N,α), nucleation undercooling (?T _N,α), recalescence undercooling (?T _R,α), range of solidification temperature (?T _S) and total solidification time (t _f) are influenced by variation of cooling rate. Also, the effect of Al content on these parameters was studied. Microstructural evaluation was carried out to determine the correlation between the cooling rate and secondary dendrite arm spacing.     

Density,Viscosity, and Glass Transition of an Ethylenediamine–Ethylene Glycol Binary System

Densities ρ and viscosities η were measured for the binary mixtures of ethylenediamine (EDA) and ethylene glycol (EG) in the temperature range 288.15–323.15 K for ρ and at 273.15–323.15 K for η, both of which are broader temperature ranges than those reported previously. The value of ρ monotonously decreases against the mole fraction of EDA, x _EDA, and increasing temperature. The concentration dependence of η exhibits a maximum in the intermediate concentration range at all temperatures measured. The glass transition temperature, T _g, for samples with x _EDA < 0.7 was measured using differential scanning calorimetry. The measured T _g values show a peak in the intermediate concentration range, which is a behavior similar to that of η; however, the peak concentrations for η and T _g did not precisely align because of a deviation in the maximum hydrogen-bond density. The partial molar volumes for EDA and EG and the thermal expansivities, α, were obtained from ρ. Results in the present study are discussed in terms of the extensively increasing hydrogen-bond density for polyamine–polyhydric alcohol systems.     

Transition from two-to three-dimensional behavior in anisotropic polymer layers

Two types of anisotropic polymer systems were studied in the spherical approximation used in the classical theory of ferromagnetism. These were a three-dimensional system composed of weakly interacting layers with isotropic interactions between chain segments in the layer planes and thin quasi-two-dimensional polymer films possessing intra-and interchain interaction anisotropy, whose behavior is close to that of two-dimensional systems. Laws that govern a change in the temperature T _cr of phase transition from the long-range order state to a disordered state depending on the magnitude of anisotropy and the size of the layers were established. For systems of the former type in which interlayer interactions is weakened, T _cr tends to zero, being inversely proportional to lng, where g is the ratio of the interaction constant between the layers to that of inplane interaction in a layer. For systems of the latter type, the transition temperature T _cr → 0 according to the T _cr ～ √? law, where ? is the parameter that characterizes the anisotropy of intra-and interchain interactions. The number of layers required for the systems to be considered three-dimensional was estimated. Regardless of the type of boundary conditions for finite systems, the number of layers increases with enhancement of interaction anisotropy (a decrease in g and ?) and an increase in the number of chains in the layers, especially for systems of the former type. Transverse orientational correlations of chain segments with respect to the arrangement of the layers decrease according to a power law, as in the case of infinite two-dimensional systems. There are fluctuations of three-dimensional long-range orientation order in the plane of the layers, the fluctuations are enhanced with an increase in the anisotropy of interactions in the system.     

Thermodynamics of the sorption of organic vapors in a carbosilane dendrimer and a hyperbranched polymer

Fluorinated derivatives of the carbosilane G6 dendrimer and the hyperbranched polymer of the same chemical structure are synthesized and characterized via the method of inverse gas chromatography. For various organic compounds (n-alkanes, aromatic hydrocarbons, partially fluorinated and perfluorinated organic compounds), the following thermodynamic parameters of their interaction with the above polymers are defined: solubility coefficient S, the sorption enthalpy, the partial molar enthalpy of mixing, the Flory-Huggins parameter, and the solubility parameter. The thermodynamic behavior of vapors in the dendrimer is similar to that in the hyperbranched polymer. For a dendrimer and a hyperbranched polymer, a linear correlation between the logarithm of S and T _cr ² is established, where T _cr is the critical temperature of a probe. For both polymers, the partial enthalpy of mixing of n-alkanes is shown to be independent of the dimensions of the probe molecules. This behavior is typical of the vapor sorption in linear polymers at temperatures above the glass transition temperature.     

Analysis and characterization of the transition from the Arrhenius to non-Arrhenius structural relaxation in fragile glass-forming liquids

We have studied the transition from an Arrhenius-like to a non-Arrhenius-like structural relaxation behavior in fragile glass-forming liquids. This transition is denoted by the temperature T_A that usually occurs above the melting point T_m and the dynamic crossover temperature T_B. Recent studies reveal that T_A is a characteristic temperature related with the dynamical properties of the system. However, its unambiguous determination is not easy. In this work, a method to obtain the temperature T_A from the experimental data of α-relaxation time is presented. The obtained T_A is compared with the cooperativity onset temperature T_x extracted from the bond strength–coordination number fluctuation model. The result reveals that T_A is close to T_x for fragile liquids. From the result of the present analyses combined with the linear relation T_x \(\propto\) T₀, where T₀ is the Vogel temperature, the Arrhenius crossover phenomenon in fragile liquids is linked to the low-temperature structural relaxation dynamics.     

Thermodynamic Properties of Zincate-Manganites of LaM<Subscript>2</Subscript> <Superscript>II</Superscript>ZnMnO<Subscript>6</Subscript> (М<Superscript>II</Superscript> = Mg,Ca, Sr,Ba) Composition

Temperature dependences of the heat capacity of new zincate-manganites of LaM₂^IIZnMnO₆ (M^II = Mg, Ca, Sr, Ba) composition are studied via experimental calorimetry in the interval of 298.15–673 K. It is found that all compounds have λ-shape effects on the curve of dependence C_p° ~ ?(T) with respect to phase transitions of the second kind. Equations for the temperature dependence of the heat capacity are derived with allowance for phase transition temperatures, and thermodynamic functions H°(T) ? H°(298.15), S°(T) and Φ^xx(T) are calculated on the basis of experimental data on C_p°(T) and the calculated S°(298.15) value.     

Molecular orientation ordering in surface layers of polymer films

The spontaneous ordering of fragments of chain molecules near the surface in polymer films is described in terms of the multichain model that allows for local intra-and interchain orientational interactions of chain segments and for transverse fluctuation of their orientation in the approximation of strong planar-orientation order in the layers. Chain packing in the plane-ordered state is impossible unless the interchain interaction parameter has a value of b = 2K ₂/k _B T > b _c. The value of b _c decreases with a growth in chain rigidity (parameter a = 2K ₁/k _B T). The calculated dependence of the limiting values of the quadrupole orientation order parameter S ₀ on the length of the Kuhn statistical segment A = 2a reasonably well describes the experimental data obtained in a study of polymer-homolog (polysaccharide) films by means of the tilted polarized-beam technique at an interchain interaction parameter of b = 1.75. The monolayer thickness (d ? 10 mn) is films of some polysaccharides was calculated from the fit of the theoretical to the experimental dependences of the orientational order parameter and the birefringence on the number of layers.     

A novel 3D energetic coordination polymer containing Co(II) atoms in a pentanuclear cluster

A novel coordination polymer [Co₅(OH)₂(dnbpdc)₄(H₂O)₆]·16H₂O (1) (dnbpdc = 6,6′-dinitro-4,4′-biphenyldicarboxylic acid) is obtained from a hydrothermal reaction. The structure of complex 1 is characterized by elemental analysis, IR spectroscopy, and single crystal X-ray diffraction analysis. The title compound (C₅₆H₇₀Co₅N₈O₅₆, M _r = 2045.85) crystallizes in the triclinic space group P-1 with a = 11.9349(2) Å, b = 12.1895(2) Å, c = 15.420(2) Å, α = 109.390(7)°, β = 94.786(1)°, γ = 108.027(9)°, V = 1968.4(4) ų, Z = 1, D _c = 1.726 g/cm³, F(000) = 1045, μ(MoK _α) = 1.154 mm^–1, T = 133(2) K, the final R = 0.0316 and wR = 0.0692 for 7032 observed reflections with I > 2σ(I). The coordination polymer is built of a pentanuclear Co(II) cluster, four dnbpdc ligands, two hydroxyl groups, six coordination water and sixteen crystal water molecules. Ligand oxygen atoms exhibit three types of coordination modes (monodentate, syn-syn bridging bidentate and bridging tridentate). Moreover, the infinite three-dimensional supramolecular network is generated by coordination and hydrogen bonds. The thermal stability of complex 1 is evaluated by differential scanning calorimetry and thermogravimetric analysis.     

Apparent Molar Volumes of Aqueous Solutions of Magnesium Tetraborate from 283.15 to 363.15 K and 0.1 MPa

Densities for aqueous solutions of magnesium tetraborate MgB₄O₇(aq) at the molalities of (0.00556–0.03341) mol·kg^?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V _? ) of MgB₄O₇(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB₄O₇(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a₀?+?a₁?×?T?+?a₂?×?T ²?+?a₃/T?+?a₄?×?ln(T)?+?a₅?×?T ³ (where T is temperature in Kelvin, a _i are model parameters) for MgB₄O₇ were obtained for the first time.