The glass temperature of polymer blends

The entropy theory of glasses is used to derive the glass temperature, T_g, of a binary polymer blend in terms of the glass temperatures of the two substituents. The formula is T_g = B₁T_g1 + B₂T_g2, where B_i is the fraction of flexible bonds of substituent i. A bond is flexible if rotation about it changes the shape of the molecule. Bonds in side groups as well as in the backbone are to be counted. This formula assumes that the free volume, taken here to be the volume fraction of empty lattice sites, is the same for each of the three materials. It has no parameters. The above equation expressed in weight fractions, W_i, is (T_g − T_g1)W₁(γ₁/ω₁) + (T_g − T_g2)W₂(γ₂/ω₂) = 0, where ω_i is the weight of a monomer unit and gg_i is the number of flexible bonds per monomer unit. A more general treatment is given. One variation of the more general treatment which expresses the properties of the blend in purely additive terms gives T_g = B₁T_g1 + B₂T_g2 + KB₁B₂(T_g1 − T_g2)(V₀₁ − V₀₂), where V_0i are the free volume fractions of the homopolymers at their glass temperatures and K is a constant. The added term is usually small. The most general form of the equation requires the energy of interaction between the two unlike molecules, which can be estimated by volume measurements on the blend.     

温度对氨基酸同系物在盐酸二甲双胍水溶液中体积和黏度特性的影响(英文)

Density(ρ)and viscosity(η)are measured for glycine,DL-α-alanine DL-α-valine,and DL-α-leucine in 0.05,0.10,0.15 and 0.20 mol·L-1aqueous metformin hydrochloride at 308.15,313.15 and 318.15 K.The measured values are used to estimate some important parameters,such as partial molal volume Vφ,standard partial molal volume0Vφ,transfer volume 0 ΔVφ,hydration number nH,the second derivative of infinite dilution of partial molal volume with respect to temperature,viz.,2 0 2 Vφ /T,viscosity B-coefficient,variation of B with temperature,viz., dB/dT,free energy of activation per mole of solvent0 * 1 Δμand solute 0* 2 Δμof the amino acids.These parameters are interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.In addition,0Vφ, 0 ΔVφ,viscosity B-coefficient,ΔB and 0* 2 Δμare split into group contributions(3NH COO +-)and CH2 of the amino acids using their linear correlation and their behavior is discussed.     

Effect of macromolecular length on anisotropic scattering of light in an electric field

Light scattering by monodisperse solutions of rigid rod-like anisotropic macromolecules, with linear dimensions l of the order of incident wavelength λ, oriented in an external d.c. electric field, →E has been analysed. The relative variations δV^E_v, δH^E_v, δV^E_h, δH^E_h of the scattered light components are discussed for the three values [l/λ] = 1, 0·5, 2, and various reorientation parameters, p = [μE/kT] of the permanent dipole moment μ and q = [(₃ − ₁)E²/2kT] of the moment induced by the principal polarizabilities ₁ = ₂ ≠ ₃. The saturation orientation field strength has been calculated for certain macromolecules with the aim of determining their optical anisotropy numerically.     

Molar volumes of multicharged electrolytes in water and aqueous sulphuric acid

The apparent molar volumes, φ_v, of aluminium ammonium sulphate and potassium aluminium sulphate in water and aqueous sulphuric acid (0.01, 0.05, 0.10 and 0.15 N) at different concentrations and temperatures have been estimated from the densities of the solutions measured by hydrostatic balance. The φ_v values vary linearly with square root of concentrations. The limiting apparent molar volume, φ⁰_v, and the experimental slope S_v, have been interpreted in terms of solute-solvent and solute-solute interactions, respectively. The φ⁰_v values vary with temperature and can be represented in the power series of temperature. Structure making/breaking capacity of the electrolyte is inferred from the sign of [?φ⁰_v/?T²] values. Both the electrolytes behave as structure breakers in water but structure makers in aqueous sulphuric acid. The molar expansibility, at infinite dilution have been found to be the same for both electrolytes at 290.5 K.     

Thermodynamics of ionic-association in aqueous solutions of Ca and Mg organic salts using ion-selective electrode technique—I. Formates, acetates, propionates and butyrates

The divalent selective electrode together with high precision solid state, digital pH -mv -meter makes broader application of potentiometry in physical and inorganic chemistry a certainty. The above set-up is used to determine the stoichiometric constants, K, for Ca and Mg ions association with formates, acetates, propionates and butyrates at 25°, 35° and 45°C in aqueous media. The K-values were converted to infinite dilution K_A values were found to be 8.4 LM⁻¹, 10.4 LM⁻¹, 19.1 LM⁻¹ and 19.3 LM⁻¹ for calcium salts of formate, acetate, propionate and butyrate respectively. Also K_A values for Mg salts of formate, acetate, propionate and butyrate were found to be 7.8 LM⁻¹, 9.5 LM⁻¹, 13.1 LM⁻¹ and 13.1 LM⁻¹ respectively. Other thermodynamic parameters such as ΔG°, ΔH° and ΔS° are also obtained from the variation of K_A with temperature for each salt. The data are interpreted relative to each other on basis of pK_a of the corresponding organic acid. Their temperature behaviour is similar to those salts derived from strong acids such as sulphates, rather than weak acids.     

Mass transfer at cylindrical gas evolving electrodes

Mass transfer coefficients at cylindrical, H₂ evolving electrodes, were measured by determining the reduction rate of K₃Fe(CN)₆. The variables studied were: gas discharge rate V, diameter of the cylinder D, height and position of the cylinder. The diameters ranged from 0·2–2·5 cm, the cd from 25-380 mA/cm². For horizontal cylinders, the following correlation was found: log K = a + 2·17 log(V^0·11/D^0·08). The application of gas evolving cylindrical electrodes in industrial electrolysis is discussed in comparison with rotating electrodes.     

Mathematical modeling of gas evolution from flowing electrolytes on stable porous anodes of finite matrix phase conductivity

A mathematical model was developed to simulate the effects of the matrix phase conductivity on the behavior of flow-through porous anode operating for gas evolution reaction. The anode material was assumed to be stable and has a finite conductivity. The model accounts for the conductivities of the solution and the matrix phases, the electrode kinetics, hydrodynamics and gas bubble formation. The different ratios and values of the matrix conductivity group, K_σ (a measure of the matrix conductivity) and the electrolyte conductivity group, K_κ (a measure of the electrolyte conductivity) were found to have significant effects on the distributions of current, potential and gas void fraction. When K_σ was a finite value the reaction was pushed towards the back of the electrode and when K_κ was finite the reaction was pushed towards the front face. The effects of the bubble group, χ on the potential and current distributions were investigated under different impacts of K_σ and K_κ. When K_σ was limited the gas bubbles formed at the back of the electrode were forced to travel within the whole bed with the electrolyte streams, causing larger accumulation of the bubbles and hence higher polarization within the bed. The gas bubble formation limited the conductivity of the pore electrolyte resulting in potential and current distributions similar to the case of finite electrolyte conductivity.     

Mechanical behaviour of partially stabilized zirconia crystals with terbia and ceria additives

Mechanical behaviour of partially stabilized zirconia crystals (PSZC) with terbia and ceria additives was investigated under bending and indentation conditions. Test specimens were oriented along the [010] direction and along the axis of crystal growth. The PSZC bending strength (σ_b) was dependent on the crystallographic orientation of the specimens. The specimen volume subjected to stress influenced the PSZC strength. The highest mechanical characteristics were measured for ceria-doped crystals (σ_b = 1.9 GPa, K_lc = 11.4 MPa m^1/2, E_d = 366 GPa). The failure process was studied on the Vickers indentation, with special emphasis put on the development and propagation of lateral cracks. Anisotropy of lateral cracks in the (100) plane associated with that of the elastic moduli was revealed. At the same time anisotropy of radial cracks and hardness was not found. A new version of the equation to evaluate the fracture toughness (K_c^v) on the Vickers indentation was derived. The K_c^v values calculated by this equation correspond to those (K_lc) obtained by an SENB method.     

Grain growth in TiO2-added ZnO–Bi2O3–CoO–MnO ceramics prepared by chemical processing

The effect of TiO₂ on the grain growth of the ZnO–Bi₂O₃–CoO–MnO ceramic system prepared by chemical coprecipitation, was studied between 1150 and 1300 °C in air. Bi₂O₃ melts during firing, and then TiO₂ dissolves into Bi₂O₃-rich liquid. TiO₂ initially reacts with Bi₂O₃ to form Bi₄Ti₃O₁₂. Above ≈1050 °C, Bi₄Ti₃O₁₂ reacts with ZnO to form Zn₂TiO₄ spinel phase. The kinetic study of grain growth carried out using the expression Gⁿ–G_oⁿ=K_o·t·exp(−Q/RT) gave grain exponent (n) value as 6 and the apparent activation energy (Q) as 226.46 kJ/mol. 1.00 mol% TiO₂ addition increased the grain growth exponent value from 6 to 7 and apparent activation energy with 1.00 mol% TiO₂ addition was found to be 197.10 kJ/mol. The ZnO grain size gradually increases with increasing TiO₂ content. Addition of TiO₂ may increase the reactivity of the Bi₂O₃-rich liquid towards the ZnO grain, thus affecting the ZnO grain growth.     

Microscopic and macroscopic atomization characteristics of a pressure-swirl atomizer,injecting a viscous fuel oil

Combustion of heavy fuels is one of the main sources of greenhouse gases, particulate emissions, ashes, NOxand SOx. Gasification is an advanced and environmentally friendly process that generates combustible and clean gas products such as hydrogen. Some entrained flow gasifiers operate with Heavy Fuel Oil(HFO) feedstock. In this application, HFO atomization is very important in determining the performance and efficiency of the gasifiers.The atomization characteristics of HFO(Mazut) discharging from a pressure-swirl atomizer(PSA) are studied for different pressures difference(Δp) and temperatures in the atmospheric ambient. The investigated parameters include atomizer mass flow rate( _m), discharge coefficient(CD), spray cone angle(θ), breakup length(Lb), the unstable wavelength of undulations on the liquid sheet(λs), global and local SMD(sauter mean diameter) and size distribution of droplets. The characteristics of Mazut sheet breakup are deduced from the shadowgraph technique. The experiments on Mazut film breakup were compared with the predictions obtained from the liquid film breakup model. Validity of the theory for predicting maximum unstable wavelength was investigated for HFO(as a highly viscous liquid). A modification on the formulation of maximum unstable wavelength was presented for HFO. SMD decreases by getting far from the atomizer. The measurement for SMD and θ were compared with the available correlations. The comparisons of the available correlations with the measurements of SMD andθ show a good agreement for Ballester and Varde correlations, respectively. The results show that the experimental sizing data could be presented by Rosin-Rammler distributions very well at different pressure difference and temperatures.     

Plasma-electrochemical synthesis of europium doped cerium oxide nanoparticles

In the present study,a plasma-electrochemical method was demonstrated for the synthesis of europium doped ceria nanoparticles.Ce(NO3)3· 6H2O and Eu(NO3)3·5H2O were used as the starting materials and being dissolved in the distilled water as the electrolyte solution.The plasma-liquid interaction process was in-situ investigated by an optical emission spectroscopy,and the obtained products were characterized by complementary analytical methods.Results showed that crystalline cubic CeO2:Eu3+ nanoparticles were successfully obtained,with a particle size in the range from 30 to 60 nm.The crystal structure didn't change during the calcination at a temperature from 400℃ to 1000℃,with the average erystallite size being estimated to be 52 nm at 1000℃.Eu3+ ions were shown to be effectively and uniformly doped into the CeO2 lattices.As a result,the obtained nanophosphors emit apparent red color under the UV irradiation,which can be easily observed by naked eye.The photoluminescence spectrum further proves the downshift behavior of the obtained products,where characteristic 5Do → 7F1,2,3 transitions of Eu3+ ions had been detected.Due to the simple,flexible and environmental friendly process,this plasma-electrochemical method should have great potential for the synthesis of a series of nanophosphors,especially for bio-application purpose.     

发泡浆体流变特性对轻质混凝土匀质性的影响

为改善轻质混凝土匀质性,提升轻质混凝土力学性能,本文通过建立Herschel-Bulkley(H-B)塑性黏度计算模型,探究了发泡浆体流变特性对泡沫沉降和浆体中陶粒分布的影响。结果表明：随增稠剂掺量的增加,轻质混凝土发泡浆体的屈服应力和基于非线性H-B模型η_H-B=0.016 67K(80ⁿ-20ⁿ)(η_H-B为H-B模型得出的发泡浆体塑性黏度;K为一致性系数;n为流动指数)得到的塑性黏度增大,导致发泡浆体沉降距下降,陶粒在浆体中的分形维数提高;当发泡浆体塑性黏度大于1.74 Pa·s、屈服应力大于92.87 Pa时,可制备抗压强度大于10 MPa的轻质混凝土。由此可见,优化发泡浆体流变特性是克服陶粒在发泡浆体中易上浮问题的关键,可有效改善轻质混凝土匀质性,提升轻质混凝土力学性能。     

Surface wettability and flow properties of non-metallic pipes in laminar flow

In this paper, three liquids flowing in five pipes with the same inner diameter of 14 mm were studied to determine the relationship between the surface wettability and flow properties in laminar flow(Re b 2000). This was motivated by oilfield observations of increased pressure drops in non-metallic pipes compared to those in metal pipes,which was contrary to expectations. A new expression for the frictional coefficient that considers the Reynolds number and contact angle θ in laminar flow for non-metallic pipes was proposed based on the experimental results of single-phase flow using dimension and regression analyses. The solutions of the anomalous phenomenon were proposed from the perspectives of the pipe diameter, contact-angle difference, and the compatibility between flexible composite pipe and JLHW105 oil according to the new formula. The surprising finding was that the surface wettability could control the frictional resistance by the critical contact angle(39.9°) obtained at the same Reynolds number. If 0° b θ≤ 39.9°, the frictional coefficient increased as the contact angle increased. In contrast, if 39.9° b θ b 180°,the frictional coefficient decreased with increasing contact angle. The influences of the pipe diameter and contactangle difference on the pressure drop difference of JLHW105 oil showed an inversely proportional relation. A series of materials and liquids were tested. The selection of pipe material for transporting a given fluid can be based on the contact angle, surface tension, and critical limit of the contact angle obtained. The research results are expected to provide some guidelines for the selection of the appropriate pipe material for a given set of fluids.     

Influence of surface modified mixed metal oxide nanoparticles on the electrochemical and mechanical properties of polyurethane matrix

Newly synthesized functional nanoparticles, 3-amino-1,2,4-triazole (ATA)/SiO₂–TiO₂ were introduced to the polyurethane (PU) matrix. Electrochemical techniques were used to investigate the barrier properties of the synthesized PU–ATA/SiO₂–TiO₂ nanocomposite coated steel specimen. In natural seawater, electrochemical impedance spectroscopy experiments indicated outstanding protective behaviour for the PU–ATA/SiO₂–TiO₂ coated steel. The coating resistance (R_coat) of PU–ATA/SiO₂–TiO₂ was determined to be 2956.90 kΩ·cm^–2. The R_coat of the PU–ATA/SiO₂–TiO₂ nanocomposite coating was found to be over 50% higher than the PU coating. The current measured along the scratched surface of the PU–ATA/SiO₂–TiO₂ coating was found to be very low (1.65 nA). The enhanced ATA/SiO₂–TiO₂ nanoparticles inhibited the entry of electrolytes into the coating interface, as revealed by scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray diffraction analysis of the degradation products. Water contact angle testing validated the hydrophobic nature of the PU–ATA/SiO₂–TiO₂ coating (θ = 115.4°). When the concentration of ATA/SiO₂−TiO₂ nanoparticles was 2 wt %, dynamic mechanical analysis revealed better mechanical properties. Therefore, the newly synthesised PU–ATA/SiO₂–TiO₂ nanocomposite provided excellent barrier and mechanical properties due to the addition of ATA/SiO₂–TiO₂ nanoparticles to the polyurethane, which inhibited material degradation and aided in the prolongation of the coated steel’s life.     

Solubilization of Phenanthrene and Fluorene in Equimolar Binary Mixtures of Gemini/Conventional Surfactants

abstract This study deals with the enhanced solubilization of polycyclic aromatic hydrocarbons (PAHs) such as phenan-threne (PHE) and fluorene (FLR) in a pure cationic gemini (G6) and three conventiona...     

Simultaneous desulfurization and denitrification of sintering flue gas via composite absorbent

Experiments on simultaneous absorption of SO_2 and NO_X from sintering flue gas via a composite absorbent NaClO_2/NaClO were carried out. The effects of various operating parameters such as NaClO_2 concentration(ms), NaClO concentration(mp), molar ratio of NaClO_2/NaClO(M), solution temperature(TR), initial solution pH, gas flow(Vg) and inlet concentration of SO_2(CS) and NO(CN) on the removal efficiencies of SO_2 and NO were discussed. The optimal experimental conditions were determined to be initial solution pH = 6, TR=55 °C and M = 1.3 under which the average efficiencies of desulfurization and denitrification could reach99.7% and 90.8%, respectively. Moreover, according to the analysis of reaction products, it was found that adding NaClO to NaClO_2 aqueous solution is favorable for the generation of ClO_2 and Cl_2 which have significant effect on desulfurization and denitrification. Finally, engineering experiments were performed and obtained good results demonstrating that this method is practicable and promising.     

Compared imbibitions of ordinary and high performance concrete with null or positive water pressure head

A method to simultaneously measure the moisture diffusion coefficient, D_θ, of unsaturated concrete, and the saturated concrete hydraulic conductivity, K_l, was developed for cylindrical specimens placed on a container filled with water that could be maintained at a given hydraulic pressure. Ordinary Portland cement Concrete (OPC) with a moderate and High Performance Concrete (HPC) with a low water to cement ratio were tested. The time dependent distribution of water content in the specimens was measured using a non-intrusive method based on gamma-ray attenuation. The measurements were conducted with varying hydraulic head (positive or null). Boltzmann's transformation was used to analyze the experimental results obtained at different hydraulic pressures and the difference between the null (or atmospheric) and positive pressure results is used to accurately determine K_l and also D_θ . This paper will present the results obtained using this original method, possible interpretations and future research.     

Structural and Thermal Expansions in Alkali Silicate Binary Glasses

Two volume-changing processes that should be considered in detail are (1) distention of networks by added oxides which may swell glass volumes in proportion to the added oxide volumes and (2) angular change in intertetrahedral bonding which may take place at and above annealing temperatures in proportion to the number of metal ions introduced by the modifications. Accordingly, the partial molar volumes of modifiers, ν _R , are assumed as those of their crystal or liquid states and the partial molar volumes of silica are computed from (1/ν_S) = 2.20 + 0.00057 ( r_m – 0.12) (1723 – t ). Tentative glass volumes are then computed as V_g= S_mν_S+ r_mν_R by use of the mole fractions S_m and r_m for silica and nonsilica, respectively. The excess of computed glass volumes, V₀ , over V as derived from observed densities is taken as a measure of the penetration of modifiers into the network cavities without corresponding distention of the network. By using the computed density of 1.95 for vitron, the value 2.20 for silica glass, and 2.30 as reported for irradiated silica, one can estimate that silica glass consists of 28% vitron and 72% disordered silica in the intervitron tissues. The values of V_g , – V mentioned are found to be in fair accord with expectations computable from the vitron theory.     

Characterization and activity of Mo supported catalysts for diesel deep hydrodesulphurization

Various highly dispersed Mo supported catalysts with various carriers were prepared for deep hydrodesulphurization of diesel. The carriers included a high surface area and large pore volume γ-Al₂O₃, two types of meso-microporous composite molecular sieves prepared by incipient-wetness impregnation method. A new mesoporous MoSiO_x catalyst synthesized with in situ composite method was also studied. The hydrodesulphurization experiments were carried out in a micro-reactor over different catalysts including Mo supported series and a commercial catalyst. Spectroscopic techniques (FT-IR and UV–vis DRS) were utilized to determine the structure of MoO_x species. The catalyst characterizations of BET, XRD, FT-IR, UV–vis DRS and FTIR pyridine adsorption indicated that the existences of metal active component of Mo in the catalysts were highly dispersed nano MoO₃ clusters and the Mo series catalysts had high surface areas and plenty of large pores which were propitious to the diffusions of reactant and product molecules. Cat_NiMo exhibited the highest B/L acidity ratio and higher total concentration of Brønsted acid sites and Lewis acid sites, and its HDS activity also gave the highest in this study to produce a sulphur-free diesel, which was verified by the sulphur content in products analyzed by GC–MS methods.     

离子液体[Mmim][DMP]与DMSO/乙腈二元体系的密度和黏度

离子液体因其特殊的内在结构及性能,使得其在纤维素预处理应用过程中展现出良好的效果,其相关体系的物性研究是推进工业化进程的基础必要数据。因此选用甲基咪唑和磷酸三甲酯合成了离子液体1,3-二甲基咪唑磷酸二甲酯([Mmim][DMP]),并测定了[Mmim][DMP] (1) + DMSO (2) 和 [Mmim][DMP] (1) + 乙腈 (2) 两个二元体系,在293.15~323.15 K时,全组成范围内的密度和黏度。计算了体积性质和超额性质数据。通过比较分析二元体系的超额摩尔体积(V ^E)、表观摩尔体积( V_{?} )、无限稀释表观摩尔体积( V_{?}^{\mathrm{\infty }} )和偏摩尔体积( \stackrel{\text{?}}{V} )数据,以及分子模拟手段讨论了离子液体与溶剂之间的作用形式,包括离子液体与溶剂之间形成的氢键对溶液性质的影响。