The melt elastic behavior of polypropylene/glass bead composites in capillary flow

The melt extrudate swell and entry pressure losses are important characteristics of elastic properties during die extrusion of polymeric fluids. They are usually expressed with die-swell ratio (B) and entry pressure drop (ΔP_o). In the present paper, the die-swell behavior and entrance pressure drop of a polypropylene (PP) filled with A-glass beads were investigated by using a Rosand capillary rheometer to identify the effects of the filler contents and extrusion rate on the elastic behavior of the sample melts. The experiments were carried out under the conditions with an apparent shear rate range of 50–10⁴ s⁻¹ and a temperature of 190 °C. The results showed that B increased nonlinearly with increasing shear rate at the wall (γ_w), and increased linearly with the increase of shear stress at the wall (τ_w). With the increase of the volume fraction of the fillers B decreased nonlinearly. Similarly, the entry pressure drop increased linearly with the increase of τ_w, whereas the influence of the filler concentration on ΔP_o was insignificant in this case. Furthermore, B increased as a linear function of ΔP_o, and extension stress (σ_e) increased nonlinearly with increasing γ_w.     

多个时间常数线性体系恒电量响应的频谱分析

从线性条件出发,利用拉普拉斯变换及其逆运算推导多个时间常数体系在恒电量激励条件下线性响应暂态方程,并推导出恒电量激励下Rs(C₁(R₁(C₂(R₂(C₃R₃)))))电路模型的极化电位响应式. 通过线性响应方程的理论验证以及与实际腐蚀体系的EIS进行对比,结果表明：对恒电量瞬态响应进行频谱分析,可以促进恒电量测量结果与EIS进行更加细致的对比验证. 对含有多时间常数的电极过程,利用阻抗拟合软件进行局部拟合,可以确定初始值的设置,以避免时域的曲线拟合时出现多种结果的局面,大大地提高了恒电量瞬态响应数据解析的准确性.     

Amphiphile bilayer films from DPPC: bilayer lipid membranes and Newton black films

Amphiphile bilayer films are obtained from 1,2 dipalmitoyl-glycero-3-phosphocholine (DPPC): bilayer lipid membranes (BLM) and Newton black films (NBF), through thinning of the respective thin liquid films, thus allowing for a very precise determination of the moment of their formation. Stability (or rupture) and formation of BLM and NBF are considered from a unified point of view with the microscopic theory of Kashchiev–Exerowa [J. Colloid Interface Sci., 77 (1980) 501–511], based on the formation of nanoscopic holes in them. BLM and NBF are obtained and studied with the microinterferometric method of Scheludko–Exerowa in its contemporary version. The equivalent thickness of both BLM (in benzene solution between two water phases with 0.1 M NaCl) and NBF in aqueous DPPC solution (in the presence of 0.1 M NaCl) is determined as being h_w = 7.0 nm for BLM and h_w = 7.8 nm for NBF. By means of the dependences: BLM lifetime versus DPPC concentration and probability for BLM formation versus DPPC concentration, it is established that there exist metastable BLM and stable NBF. The good fit between the experimental results of τ(C) dependence and theory in the case of BLM allow to determine the three constants: pre-exponential factor A = 1.5 × 10⁻³ s, related to the process kinetics; constant B = 20.2 ± 0.2, related to the specific hole energy γ = 1.7 × 10⁻¹¹ J/m and the equilibrium concentration C_e = 6 × 10⁻⁴ ± 7.2 × 10⁻⁶ m/l. The specific hole linear energy γ = 1.7 × 10⁻¹¹ J/m determined as well as the binding energy Q between first neighbor molecules in the bilayers Q = 1.48 × 10⁻¹⁹ J (36 kT) are lower than the ones determined for DPPC foam bilayer in gel state γ = 9.1 × 10⁻¹¹ J/m and Q = 55 kT. This means that interaction is weaker in the case of BLM. The critical concentration C_c at which bilayer formation starts is: for BLM C_c = 30 μg/ml and for NBF C_c = 70 μg/ml. This concentration characterizes quantitatively the formation of the amphiphile bilayer and is a very useful parameter that can be used for various purposes.     

Release properties on gelatin-gum arabic microcapsules containing camphor oil with added polystyrene

In this study, gelatin blended with arabic gum microcapsules containing camphor oil with added polystyrene were fabricated by a compound coacervation method. The parameters of oil/wall volume ratio, emulsification stirring speed, concentration of cross-linking agent, treated time and oil release properties were investigated. In order to improve the constant release effect of camphor oil, oil-soluble polystyrene (PS) was used as a sustained release agent. The camphor oil release curves were expressed by the exponential equation: ψ(t) = C_eq(1–e^−t/τ), where ψ(t) represent the variant of camphor oil concentration in the operation environment, C_eq as the equilibrium state, t as the release time and τ as time constant. C_eq and τ are significant factors pertaining to the camphor oil release properties. The results indicated that, for the microcapsules, the optimal oil/wall volume ratio was 0.75 to achieve the encapsulation efficiency of 99.6 wt.%. The average particle size were 294.7 ± 14.2 μm, 167.2 ± 11.2 μm, 85.7 ± 8.7 μm at the homogenization stirring speed of 500, 1000, and 2000 rpm, respectively. The effect of sustained oil release will increase whereas the stirring speed decreases and the concentration of glutaraldehyde (GA) and treated time increases. Along with the increasing of quantity of polystyrene added, C_eq decreased and τ increased, indicating that the sustained oil release amount and the release rate depend on the quantity of PS considerably.     

Emulsification using micro porous glass (MPG): surface behaviour of milk proteins

To investigate the emulsifying properties and adsorption behaviour of high molecular amphiphilic substances such as proteins, it is important to maintain the native status of the used samples. The new method of micro porous glass (MPG) emulsification could offer an opportunity to do this because of the low shear forces. The oil-in-water emulsions were produced by dispersing the hydrophobic phase (liquid butter fat or sunflower oil) through the MPG of different average pore diameters (d_p=0.2 or 0.5 μm) into the flowing continuous phase containing the milk proteins (from reconstituted skim milk and buttermilk). The emulsions were characterised by particle size distribution, creaming behaviour and protein adsorption at the hydrophobic phase. The particle size distribution of protein-stabilised MPG emulsions is determined by the pore size of MPG, the velocity of continuous phase (or wall shear stress σ_w) and the transmembrane pressure. A high velocity of =2 m s⁻¹ (σ_w=13.4 Pa) and low pressure (pressure of disperse phase slightly exceeded the critical pressure Δp_TM=4.5 bar of 0.2 μm-MPG) led to the smallest droplet diameter. As a consequence of average droplet diameters of d₄₃>3.5 μm creaming was observed without centrifugation in all MPG emulsions after 24 h, but no coalescence of the oil droplets occurred. The study of protein adsorption showed that the MPG emulsification at low shear forces resulted in lower protein load values (2.5±0.5 mg m⁻²) than pressure emulsification (11.5±1.0 mg m⁻²). In addition, the various emulsification conditions (MPG or pressure homogenization) led to differences in the relative proportions of casein fractions, whey proteins and milk fat globule membranes (MFGM) at the fat globule surfaces.     

Dibenzo[b, e]-7,7,8,8-tetraneopentyl- and dibenzo[b, e]-7,7,8,8-tetraisopropyl-7,8-disilabicyclo[2.2.2]octa-2,5-dienes: interaction with tetracyanoethylene and transition metal chlorides

Dibenzo[b,e]-7,7,8,8-tetraalkyl-7,8-disilabicyclo[2.2.2]octa-2,5-dienes (1: R = ^tBuCH₂; 2: R = ⁱPr) were prepared by the reaction of ClR₂SiSiR₂Cl with lithium anthracenide in 1,2-dimethoxyethane (DME) at room temperature. The structure of 1 was determined by X-ray crystallography. Crystal data for 1: monoclinic, rC2/c, A = 12.941(2), B = 14.601(1), C = 35.109(6) Å, β = 94.957(7)°, V = 6609(2) ų, Z= 8, R = 0.048, R_w = 0.053 for 4037 reflections. Compounds 1 and 2 show the bathochromic shift of ¹L_a and ¹L_b bands in UV spectra and exhibit considerably low oxidation potentials due to effective σ-π conjugation. Compounds 1 and 2 form charge-transfer complexes with tetracyanoethylene (TCNE). In the case of 1, the charge-transfer complex (1: TCNE = 2: 1) could be isolated as crystals and the structure was determined by X-ray crystallography. Crystal data for the 1-TCNE complex: monoclinic, C2/c, A= 10.267(2), b = 36.077(4), C = 20.022(4) Å, β = 100.680(8)°, V = 7288(2) ų, Z = 4, R = 0.045, R_w = 0.077 for 4120 reflections. The action of transition metal chlorides on 2 resulted in [4+2] cycloreversion to form ClⁱPr₂SiSiⁱPr₂Cl and anthracene.     

Time characteristics of electromotive force in single-membrane cell for stable and unstable conditions of reconstructing of concentration boundary layers

The stability of concentration boundary layers near membrane (CBLs), arising after turning off mechanical stirring of KCl solutions in single-membrane cell with polymer membrane placed in horizontal plane, was studied by measurement of time changes of electromotive force of single-membrane cell (EMF). In the case when solution with low concentration and low density (C_l) was over the membrane and the solution with higher concentration and higher density (C_h) was under the membrane (configuration A) the stable recreation of CBLs by diffusion was observed, which was manifested by gradual and monotonous decrease of EMF after turning off mechanical stirring. The results of the carried out experiment show that character of time changes of EMF for A configuration depends on the quotient of concentrations on the membrane C_h/C_l at the initial moment. Besides, for configuration A the pulsations of EMF were not observed in the whole studied range of concentrations. In the case of opposite location of solutions in relation to the membrane (configuration B) it was stated that for C_h/C_l ≤ 10 time changes of EMF were similar to time changes of EMF in configuration A. For C_h/C_l > 10 time characteristics of EMF for A and B configurations were different. For B configuration and C_h/C_l ≥ 100 the pulsations of EMF, arising in a short time after turning off mechanical stirring, were observed. The pulsations of EMF can be connected with hydrodynamic instability in CBLs. Increase of C_h/C_l caused increase of amplitude and decrease of period of EMF pulsations. Besides, for C_h/C_l > 1000 damping of EMF pulsation was observed, greater for higher C_h/C_l. The interpretation of experimental data was made by means of the Kedem–Katchalsky model, diffusion equation and concentration Rayleigh number.     

Studies on potentiometric stripping analysis

Theoretical and experimental investigations have been made on the method of potentiometric stripping analysis. By solving Fick's second law of diffusion for the metal in the amalgam, it was found that τ = C⁰_Rl/k[Ox], where τ is the elapsed time, l is the thickness of the mercury film, C⁰_R is the concentration of the metal in the amalgam, [Ox] is the concentration of the oxidant in the solution and k is a constant. Since C⁰_R is proportional to the concentration of that particular ion in the solution under given pre-electrolysis conditions, the relations given by the equation above can all be verified experimentally. The equation of the potential—time curve and the effect of complex formation on the elapsed time were also investigated and discussed. In the absence of complexation reactions in the solution and with proper control of the concentration of the oxidant, the lowest limit of detection for Pb was found to be 10⁻¹²M for a 4-min pre-electrolysis, with dissolved oxygen as oxidant.     

Investigation on the relationship between leaf water use efficiency and physio-biochemical traits of winter wheat under rained condition

Different statistical methods and path analysis were used to study the relationship between leaf water use efficiency (WUE) and physio-biochemical traits for 19 wheat genotypes, including photosynthesis rate (P_n), stomatal conductance (g_s), transpiration rate (T_r), intercellular concentration of carbon oxide (C_i), leaf water potential (Ψ_w), leaf temperature, wax content, leaf relative water content (RWC), rate of water loss from excised-leaf (RWL), peroxidase (POD) and superoxide dismutase (SOD) activities. The results showed that photosynthesis rate, stomatal conductance and transpiration rate were the most important leaf WUE variables under rainfed conditions. Based on the results of five statistical analyses, it is reasonable to assume that high leaf WUE wheat under the rained could be obtained by selecting breeding materials with high photosynthesis rate, low transpiration rate and stomatal conductance.     

Three-phase extraction study of cyanex 923-n-heptane/H(2)SO(4) system

Phase behavior of the extraction system, Cyanex 923–heptane/H₂SO₄–H₂O has been studied. The third phase appeared at different aqueous H₂SO₄ concentration with varying initial Cyanex 923 concentration and temperature affects its appearance. Almost all of H₂SO₄ and H₂O are extracted into the middle phase. The H₂SO₄ concentration in the third phase increases with the increasing aqueous acid concentration (C_H2SO4,b) while the water content first increases and then reaches a constant value at C_H2SO4,b=11.3 mol l⁻¹. In the region of C_H2SO4,b higher than 5.2 mol l⁻¹, the composition of the middle phase is only related to the equilibrium concentration of H₂SO₄ in the bottom phase. H₂SO₄ and H₂O are transferred into the middle phase mainly by their coordination with Cyanex 923 when C_H2SO4,b is less than 11.3 mol l⁻¹. When C_H2SO4,b is higher than 11.3 mol l⁻¹, excess H₂SO₄ is solubilized into the polar layer of the aggregates. In the region considered, the extracted complex changes from C923 · H₂SO₄ to C923 · H₂SO₄ · H₂O and then to C923 · (H₂SO₄)₂ · H₂O.     

Action of Humicola lanuginosa lipase on long-chain lipid substrates: 1. Hydrolysis of monoolein monolayers

The hydrolysis of 1-monoolein (MO) monomolecular films by Humicola lanuginosa lipase (HLL) was followed by measuring the simultaneous decrease with time in the film area and the surface potential using a ‘zero order trough’ at constant surface pressure (Verger and de Haas, Chem. Phys. Lipids 10 (1973) 127). The decrease with time in the film area reflects both the reduction in the area per molecule as well as the solubilization of the substrate and the product molecules during the transformation of the substrate MO into product of oleic acid (OA). The surface potential changes were interpreted as the results of the accumulation at the interface of negatively charged OA. The surface concentration of OA transiently present at the interface was determined by the surface pressure and the surface potential measurements on the basis of a developed kinetic model. In the proposed model we have taken into account the product and substrate solubilization rates in the presence of β-cyclodextrin (β-CD) as well as the flux supplied progressively by the moving barrier from the reservoir to the reaction compartment in order to keep the constant surface pressure. Values of the global kinetic constant Q_m were obtained. The selective lipolytic product acceptor, β-CD, accelerated considerably the hydrolytic process.     

Effect of sulphur on both thermal and dielectric properties of pre-compressed FEF black-loaded SBR vulcanizates

The thermal properties (thermal conductivity λ, thermal diffusivity a, and specific heat C_p) as well as the dielectric constant ε′ and dielectric loss ε′ of conductive styrene butadiene rubber loaded with different concentrations of sulphur were measured. It was found that both λ and C_p increase gradually at around 1 phr of sulphur content. Meanwhile, the dielectric constant ε′, showed a pronounced peak at 2 phr of sulphur content. Moreover, the effect of hydrostatic pressure on the dielectric constant ε′ and dielectric loss ε′ was found to rise with pre-compression.     

Causes and remediation of reduced efficiency in micellar liquid chromatography

Broad peaks are obtained when purely aqueous micellar phases are used in micellar liquid chromatography (MLC). The causes of reduced efficiency in MLC are investigated. Slow solute mass-transfer kinetics between micelles, the aqueous phase and the surfactant covered stationary phase are the origins of the efficiency loss. Knox plots show that the reduced efficiency comes from A term increase and, for lipophilic solutes, A and C terms increases. Surfactant adsorption reduces the pore volume and surface area of the stationary phase changing the flow anisotropy (A term). The surfactant adsorbed layer slows down the mass transfer (C term). Three ways for efficiency loss remediation are known: flow-rate reduction, temperature increase and alcohol addition. Alcohols are known to change the micelle structure and to increase the kinetics of micelle formation-destruction. It is shown that the ratio of the alcohol chain length to surfactant alkyl chain length, C_{n, OH}/C_{nm surf}, should be equal or higher than 1/3 to produce the best efficiency enhancements in MLC. Also, the volume of alcohol to be added is not absolute but relative to the surfactant concentration. The alcohol to surfactant concentration ratio should be kept constant. Temperature increases and especially alcohol additions reduce the retention factors. Thermodynamic and kinetics of the micellar exchanges in MLC cannot be dissociated.     

Modelling the clarification of lactic acid fermentation broths by cross-flow microfiltration

This work is focused on modelling microfiltration for clarifying fermentation broths for the production of lactic acid. The hydraulic resistance-in-series model was used with membrane resistance, bacterial cell cake resistance, adsorption resistance and solute concentration polarisation resistance. Most of the model parameters were determined from independent experiments. This model was applied for microfiltrations operated either under constant transmembrane pressure or under constant permeate flux. Resistances due to adsorption and to solute concentration polarisation dominated. Bacterial cake resistance was found to be very low or equal to zero when microfiltration was below the critical flux.     

Isothermal curing of an epoxy resin by alternating differential scanning calorimetry

The quasi-isothermal curing of a diepoxide resin with a triamine of polyoxypropylene was studied by alternating differential scanning calorimetry (ADSC), which is a temperature modulated DSC technique. The complex heat capacity measurements allows to analyse the vitrification process at curing temperatures (T_c) below the maximum glass transition of the fully cured epoxy (T_g∞=85.8°C). Initially, the modulus of the complex heat capacity, |C^*_p|, increases until a maximum (conversion between 0.42 and 0.56) and then decreases. This step is followed by an abrupt decay of |C^*_p|, due to the vitrification of the system, which allows the determination of the vitrification time. This value agrees well with that determined by the partial curing method. The phase angle and out-of-phase heat capacity show an asymmetric wide peak during the vitrification process. The change in |C^*_p| at vitrification decreases with the increase of T_c becoming zero at temperature T_g∞. This epoxy-triamine system shows a delay of the vitrification process respect to other model epoxy systems probably due to the presence of polyoxypropylene chains in the network.

The decay of |C^*_p| during vitrification may be normalised between unity and zero by defining a mobility factor. This mobility factor has been used to simulate the reaction rate during the stage where the reaction is controlled by diffusion. The observed reaction rate is simulated by the product of the kinetic reaction rate, determined by the autocatalytic model, and the mobility factor.     

A constant flux based mathematical model for predicting permeate flux decline in constant pressure protein ultrafiltration

This paper discusses a novel approach for predicting permeate flux decline in constant pressure ultrafiltration of protein solutions. A constant pressure process is assumed to be made up of a large number of small, sequential, constant flux ultrafiltration steps: the flux decreasing due to fouling and other related factors at the end of each step. The advantage of this approach is that constant flux ultrafiltration is easier to study, characterize, and model than constant pressure ultrafiltration. Consequently model parameters can be obtained in reliable and reproducible manner. Constant pressure ultrafiltration is dynamic in nature since both the magnitude of osmotic back-pressure and the extent of membrane fouling decrease as the permeate flux decreases with time. The proposed model takes into consideration the interplay between permeate flux, concentration polarization, and membrane fouling. The model demonstrates that the initial rapid flux decline is due to a combination of concentration polarization and membrane fouling while during the remaining part of the process, the effect of concentration polarization becomes negligible. The model also shows that concentration polarization affects the initial flux decline only at higher transmembrane pressures. This model which was validated using experimental data is conceptually simpler than other available models and easy to use. In addition to its value as a predictive tool it would particularly be useful for deciding appropriate start-up conditions in ultrafiltration processes.     

A novel method for determining the viscosity of polymer solution

The relative viscosity η_r and, thus, the reduced viscosity η_sp/C of polymer solution could be obtained by recording the flow times of the polymer solution and the pure solvent in a capillary viscometer. Our experimental results indicated that the measurement of the flow time of the pure solvent was unnecessary. In particular, if the recorded flow time of the pure solvent was used to determine the viscosity of polymer solution, the reduced viscosity η_sp/C exhibited either a drastic increase or a significant decrease in an extremely dilute solution, depending upon the properties of the polymer solution investigated. In this research work, a new method for determining the viscosity of polymer solutions is reported. In the proposed method, the flow time of polymer solution at zero concentration, t₀^*, instead of the measured flow time of the pure solvent, was used to determine the viscosity of polymer solution. The reduced viscosity η_sp/C determined by the new method is proportional to concentration C even in an extremely dilute solution. The relative viscosity η_r vs. C plot also indicated clearly that t₀^*, instead of the measured flow time of the pure solvent, should be used for determining the viscosity of polymer solution. At low concentrations, the flow time of the polymer solution was proportional to C. As a result, t₀^* could be determined by extrapolating the flow time of the polymer solution to C=0.     

缓冲盐类型和离子对试剂非对离子对强离解酸性化合物离子对反相液相色谱保留行为的影响

在离子对反相液相色谱(IP-RPLC)分析中,溶质保留受对离子(counter ion)的影响比较受人关注,但鲜有研究流动相中缓冲盐类型和离子对试剂中非对离子(non-counter ion)对溶质保留行为的影响。鉴于此,该文以14种磺酸化合物为研究对象,甲醇为有机调节剂,分别考察了3种缓冲盐体系(磷酸二氢铵、氯化铵和乙酸铵)和5种离子对试剂体系(四丁基溴化铵、四丁基磷酸二氢铵、四丁基硫酸氢铵、四丁基硝酸铵和四丁基乙酸铵)下强离解酸性化合物的IP-RPLC保留行为,通过比较不同流动相条件下得到的溶质log k_w(100%水相作流动相时的保留因子)、S(线型溶剂强度模型线性回归得到的常数),以及CHI(色谱疏水指数,log k_w/S),寻找保留行为规律。研究表明,流动相中的缓冲盐类型和离子对试剂非对离子均会影响化合物的log k_w和S值,所有化合物在氯化铵缓冲盐体系下具有最大的log k_w值。相对于无机阴离子,离子对试剂中弱离解性有机阴离子(乙酸根)的存在有利于增加磺酸化合物的S值。通过对比不同条件下的保留行为,推测磺酸化合物的IP-RPLC保留机理中同时存在着离子对模型和动态离子交换模型。与log k_w和S值不同,化合物的CHI值受缓冲盐类型以及离子对试剂非对离子的影响较弱。此外,研究发现化合物的表观正辛醇/水分配系数(log D)与log k_w、S、CHI之间均具有良好的线性相关性。不同缓冲溶液和不同离子对试剂非对离子条件下获得的log k_w和S值存在着一定的差异,而CHI值相对稳定,因此,CHI更适用于IP-RPLC中定量结构-保留行为关系模型的建立。     

Ab initio molecular orbital study of potential energy surface for the H2NO(B1)→NO(Π)+H2 reaction

The mechanism of the H₂NO(²B₁)→NO(²Π)+H₂ reaction has been examined using ab initio molecular orbital methods. Ground-state and first-excited-state potential surfaces were plotted at the FOCI/cc-pVTZ level of theory as functions of two appropriate internal degrees of freedom. A conical intersection was found on the C_s pathway that is symmetric with respect to the plane perpendicular to the molecular plane of C_2v H₂NO(²B₁). It is therefore considered that trajectories that start from H₂NO(²B₁) towards the product region detour around the conical intersection, pass through the neighborhood of the transition state that is located at the saddle point on the C_s pathway, and finally reach the products, NO(²Π)+H₂. Thus we can explain the mechanism of the H₂NO(²B₁)→NO(²Π)+H₂ reaction, which has remained unclear to date.     

C94 IPR isomeric set: large-scale computations of relative stabilities based on the Gibbs function

At present C₉₄ is one of the highest sets of isomeric fullerenes that has been characterized by ¹³C NMR spectra. This contribution reports quantum-chemical computations on the C₉₄ system. The complete set of 134 isolated-pentagon-rule isomers of C₉₄ is described by four semiempirical quantum-chemical methods (MNDO, AM1, PM3, and SAM1). The C₉₄ energetics is also checked with Hartree–Fock SCF calculations in the standard 4-31G basis set (HF/4-31G). The calculations point out a C₂ structure as the system ground state. As energetics itself cannot produce reliable relative stabilities at high temperatures, entropy terms are also computed and the relative-stability problem is entirely treated in terms of the Gibbs function. The lowest-energy structure remains the most populated isomer at higher temperatures. However, several other structures show significant populations at higher temperatures. The six most populated species at the AM1 computational level read: C₂, C₂, C₁, C₁, C_s, and C₂. This selected six-membered isomeric set indeed contains the four symmetries observed in the available experiment (C₂, C_s, C₂, and C₂). This incidence represents a good agreement with the experiment and can be viewed as another evidence that the supposed inter-isomeric thermodynamic equilibrium does exist in experiments.