空气在二甲基硅油和液压油中扩散系数的测量

A piston-cylinder apparatus was established to measure the solubility and diffusivity of air in dimethyl silicone oils and in hydraulic oils based on the PVT state equation of air and the solution of unsteady one-dimensional diffusion equation. The measured diffusivity-temperature relation can be well fitted by the Arrhenius equation for engineering applications. The correlation between the solute diffusivity D and solvent viscosity  is examined. In terms of Eyring’s activation theory, the activation in the air-silicone-oil diffusion process is quite different from that in the momentum transport of the silicone oil: the activation entropy of the former is positive while that of latter is negative. However, the activation enthalpies of the two processes are in the same order of magnitude, which leads to the observation that D/T is roughly constant.     

液体混合物粘度与过量热力学性质的关联(Ⅰ)

基于Eyring的速率过程理论,并考虑了提供分子从一个平衡位置向另一位置迁移所需新位置的频率,得到了二元混台物粘度与过量吉布斯活化自由能间的关联式: K发现过量吉布斯活化自由能(?)对于相应的过量吉布斯自由能(?)有一通用比值,新位置的提供频率是组成和温度的函数.对10对二元系统(其中3对是水溶液系统)的粘度计算值与相应的55套数据进行比较,结果较为满意,均方根差为0.002一0.009.     

Camphene as a novel solvent for polypropylene: Comparison study based on viscous behavior of solutions

Polypropylene solutions were prepared using three solvents: paraffin oil, decalin, and a novel solvent—camphene. The effects of these solvents were evaluated based on the activation energy of flow and on their melting‐point depression. Experimental results indicate that the values of the viscosity of the resulting solutions were close to Newtonian behavior in the shear rates below 34 s⁻¹. The Arrhenius–Frenkel–Eyring equation was used to describe the dependence of the viscosity on the temperature. In addition, the viscosity increased with the polymer concentration, which can be described by a power‐law correlation. The activation energy of the flow of the polypropylene/camphene solution was the lowest and that of the paraffin oil solution was the highest. Correspondingly, the melting‐point depression of polypropylene solutions in camphene and decalin were substantially lower than that in paraffin oil (71, 61, and 33°C, respectively). These results indicate that lower activation energies of flow correspond to higher values of melting‐point depression. Moreover, analysis of variance indicated that the primary factor affecting the viscous behavior is the concentration, followed by the solvent and the temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2068–2074, 2000     

FACTORS THAT INFLUENCE THE COALESCENCE OF BUBBLES IN OILS THAT CONTAIN SILICONE ANTIFOAMANTS

This paper deals with several factors that contribute to the dual nature of silicone antifoamants. For example, soluble silicones can concentrate at the air/oil interface to stabilize bubbles, while dispersed drops of silicone can accelerate the coalescence process by rapidly spreading at the gas/liquid interface of a bubble causing film thinning by surface transport. In this paper, experiments are described that show that the apparently low solubility of silicone in different oils is actually a slow rate of dissolution that depends on the viscosity of the oil and the concentration of dispersed drops. Furthermore, it is shown that there is a critical size for the coalescence of air bubbles in different oils and with different amounts of silicone. Insight into the mechanisms of the critical bubble size and the reason why significantly faster coalescence occurs at a lower concentration of silicone can be explained in terms of higher interfacial mobility (as determined by bubble rise velocities).     

Estimations of the viscosities of binary mixtures with different equations of state and mixing rules

In this study, the Eyring's kinematic viscosity model was applied with the consideration that the activation free energy of flow was related to the excess free energy of mixtures and estimated with the equation of state (EOS). The effects of the equation of state, mixing rule, and interaction parameter on the viscosity estimations were considered.     

Rheology of oil in water emulsions with added solids

The effect of added solids on the rheology of oil in water emulsions was investigated. The range of the oil concentration, solids free basis, was (0-70%) and the solids volume fraction was (0-0.16). The solids mean diameter was 45 μm and it was about four times larger than the oil droplets. In the absence of added solids, non-Newtonian behaviour was observed for oil concentrations above 40%. The added solids increased the emulsion viscosity in a manner similar to the addition of solids to a homogeneous fluid. The rheological data of all the emulsion-solids mixtures investigated were correlated as relative viscosity versus solids volume fraction, where the relative viscosity is defined as the ratio of the emulsion-solids mixture viscosity to the solids-free emulsion viscosity. In the case of non-Newtonian systems, the emulsion-solids mixture viscosity and the solids-free emulsion viscosity were calculated at the same shear stress. The Barnea and Mizrahi viscosity correlation was found to fit the data well.     

On the linear approximation of mixture internal energies of departure

Direct Monte Carlo simulation of internal energies of departure for binary mixtures of geological interest are gathered and compared to those calculated using a linear mixing rule. Simulation results for gas–oil, oil–oil, and oil–water mixtures show that the linear mixing rule used in the Gibbs–Helmholtz Constrained (GHC) equation of state framework gives accurate approximations of binary mixture internal energies of departure. A flowchart for computing internal energies of departure using Monte Carlo simulation is included along with a sensitivity analysis for the GHC mixture energy parameter with respect to uncertainty in internal energies of departure.     

A STUDY OF SILICONE OIL-IN-WATER EMULSIONS

Emulsions of silicone oil-in water were formed using a Brinkmann Polytron homogenizer with Igepal CO-530 as an emulsifier. Silicone viscosities ranged from 10 to 33,000 mPa.s at 25°C. Rheological characteristics and particle size analyses of silicone oil-in-water emulsions were studied. At high volume fraction of the dispersed phase (70%-75%), silicone oil-in-water emulsions were stable. At lower volume fractions (50%-60%), emulsions formed were less stable and the two phases easily separated in a few days. The emulsions formed with high volume fraction silicone oil show highly non-Newtonian behavior (shear thinning). Emulsions made with low viscosity oils had lower viscosities than those made from high viscosity oils. Relative viscosity-concentration data could be correlated by the Frankel and Acrivos Equation. Increasing the emulsifier concentration of 70% oil-in-water emulsions resulted in a decrease in mean droplet size and an increase in emulsion viscosity. Increasing the intensity of agitation also resulted in higher viscosity and smaller droplet size until a critical energy input above which droplet size increased. Emulsification with low shear mixing provides more control in decreasing mean droplet size with time.     

STUDIES OF IRANIAN HEAVY OILS PERTINENT TO RESERVOIR CONDITIONS FOR THEIR AUTO-IGNITION TO INITIATE FIRE FLOODING

In this work, the potential for the auto-ignition of Iranian heavy oil during in situ combustion (ISC) process conditions was studied. Kinetic studies were carried out using thermal analysis techniques. Effects of oxygen partial pressure, reservoir pressure, and clay on the auto-ignition condition were investigated. Based on the experimental results obtained, a kinetic equation was derived for each of the different oil samples in the presence of different sands. The effect of partial pressure of oxygen in the injected air showed that at atmospheric pressure, low temperature combustion (LTC) was initiated at 275°C. Also, enriching the injected air by oxygen lowers the initial LTC temperature by up to 50°C. ARC experiments were undertaken to extend the studies to reservoir pressure conditions (1300 psi). It was found that activation energy in the LTC region was lowered as a consequence. As a result, initiation of LTC commenced at 115°C when air was injected. The effect of clay as a catalyst was also studied, and it was found that the activation energy decreases considerably when clay is present in the system. Experiments in a high-pressure combustion tube showed that LTC was initiated in the temperature range 120°–150°C, which is in line with the results obtained in the ARC. Fire flooding was sustained during the combustion tube test.     

Experimental and numerical study of stratified viscous oil–water flow

Stratified two-phase flows of oil and water are important to the energy industry, and models capable of predicting this type of flow are primordial. Many studies focus on fluids with low viscosity, but a high viscosity oil in the mixture significantly changes its behavior. We gathered experimental data of pressure drop, volumetric fractions, and flow-pattern data of a stratified liquid–liquid flow with high viscosity ratio. In addition, a wire-mesh sensor provided tomographic views of the flow. The data were compared with computational fluid dynamics (CFD) models using OpenFOAM and a one-dimensional model. CFD simulations used an interface capturing method, and turbulence damping was introduced to avoid high eddy viscosity at the interface region. Reynolds Average Navier–Stokes and large eddy simulations were used to account for turbulence, and they showed significant differences. The comparisons showed good overall results for pressure drop, volumetric fractions, and phase distributions between CFD and experiments.     

A bubbling fluidization model using kinetic theory of rough spheres

Collisional motion of inelastic rough spheres is analyzed on the basis of the kinetic theory for flow of dense, slightly inelastic, slightly rough sphere with the consideration of gas–solid interactions. The fluctuation kinetic energy of particles is introduced to characterize the random motion of particles as a measure of the translational and rotational velocities fluctuations. The kinetic energy transport equation is proposed with the consideration of the redistribution of particle kinetic energy between the rotational and translational modes and kinetic energy dissipation by collisions. The solid pressure and viscosity are obtained in terms of the particle roughness and restitution coefficient. The partition of the random‐motion kinetic energy of inelastic rough particles between rotational and translational modes is shown to be strongly affected by the particle restitution coefficient and roughness. Hydrodynamics of gas–solid bubbling fluidized beds are numerically simulated on the basis of the kinetic theory for flow of rough spheres. Computed profiles of particles are in agreement with the experimental measurements in a bubbling fluidized bed. The effect of roughness on the distribution of energy dissipation, kinetic energy, and viscosity of particles is analyzed. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

N,N-二甲基甲酰胺+醇二元混合物的黏度测定与关联

在288.15~313.15 K和常压下,利用乌氏黏度计测定了N,N-二甲基甲酰胺（DMF）分别与乙醇、丙醇、乙二醇和1,2-丙二醇组成的二元系全浓度范围内的黏度,计算了过量黏度△η和过量流动活化自由能△G^*E。用Redlich-Kister方程对过量黏度进行了关联;用黏度模型如Frenkel方程,Grunberg-Nissan方程,Katti-Chaudhari方程和McAllister方程对实验黏度数据进行了关联和预测,并利用Eyring理论方法计算了流动活化自由能、活化焓和活化熵等热力学函数。结果表明,4个二元系的过量黏度和过量流动活化自由能均为负值,且都随温度降低而偏差增大。过量黏度最低值均发生在DMF摩尔分数约为0.3处。McAllister模型对黏度数据的关联结果最好,预测值与实验值的平均相对偏差最小。比较并分析了DMF与一元醇和二元醇之间分子相互作用的差异。。     

乳化硅油的制备研究

以1 000 mPa.s硅油为主要原料,选用非离子型表面活性剂（span-60和tween-60的质量比为0.43：0.57）为复合乳化剂,复配乳化剂含量为硅油的50%,采用转相乳化法,乳化温度80℃,乳化时间60 min,制备了硅油含量为30%的二甲基乳化硅油,其外观为均匀、细腻的乳白色黏性液体。     

Rheokinetic modeling of HTPB–TDI and HTPB–DOA–TDI systems

A study of the effect of temperature on a mixture of polymer and curative in the processing of rocket propellants is reported. Experimental viscosity of a hydroxyl‐terminated polybutadiene–toluene diisocyanate (HTPB–TDI) system was measured using a Brookfield viscometer model DV III. Viscosity showed dependence on temperature as well as time. The viscosity data of the HTPB–TDI system showed a linear relationship with temperature, with a change in slope at 45°C. The time dependence model showed a fourth‐order curve fit, which gave better results over the exponential model fit. The activation energy required for flow of the HTPB–TDI system was found to be 15.5 kJ/mol. Experimental viscosity measurements at various temperatures was also carried out on a hydroxyl‐terminated polybutadiene–dioctyl adipate –toluene diisocyanate (HTPB–DOA–TDI) system. The temperature dependence showed a decrease in viscosity with an increase in temperature up to 60 min, beyond which the viscosity increased. Viscosity showed a linear relation with temperature, with a change in the slope at 50°C instead of at 45°C for HTPB–TDI system. Beyond 50°C the data followed a polynomial model similar to that of the HTPB–TDI system, and the results matched well with the experimental data. The activation energy of the HTPB–DOA–TDI system increased with an increase in the binder weight ratio. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1331–1335, 2003     

Prediction of Droplet Velocities and Rain Out in Horizontal Isothermal Free Jet Flows of Air and Viscous Liquid in Stagnant Ambient Air

Two‐dimensional phase Doppler anemometer measurements of droplet size and velocity conducted under several nozzle conditions and a systematic variation of the air mass flow quality and liquid phase viscosity show that the air entrainment process is enhanced when keeping all test conditions constant except for increasing the Newtonian liquid viscosity above of that of water. A two‐zone entrainment model based on a variable two‐phase entrainment coefficient is proposed with the normalized axial distance allowing for a change in the jet angle. Thus, the jet perimeter is lower and the breakup length is longer in the case of air/relatively higher viscosity liquid phase. It provides the most accurate reproduction of the experimental droplet velocity in comparison with that of other models in the literature and, hence, is recommended for the prediction of the droplet velocity in the case of two‐phase air/liquid phase free jet flow in stagnant ambient air. A model for predicting the droplet rain out, considering the droplet trajectories in the free jet flow, allows also for an adequate reproduction of the experimental data.     

Kinetic study of the degradation of acrylonitrile–acrylamide copolymers

Differential scanning calorimetry was used to investigate the degradation of acrylonitrile–acrylamide copolymers in air. The apparent activation energy of degradation of the copolymers was calculated with the Kissinger method. The effects of the copolymerization conditions on the apparent activation energy of the copolymers were studied. Increasing the dimethylformamide concentration in the solvent mixture led to a rapid increase in the apparent activation energy of degradation of the acrylonitrile–acrylamide copolymers. The apparent activation energy decreased quickly as the comonomer acrylamide concentration increased, and this change became less prominent as the acrylamide/acrylonitrile weight ratio increased beyond 5/95. The apparent activation energy increased as the copolymerization temperature increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1017–1020, 2005     

油气工况下提升管出口旋流快分系统性能的数值研究

为促进旋流快分(SVQS)系统的工业应用、准确评估其性能,参照国家标准设计了一系列不同密度、黏度的油气模型,并采用商用软件FLUENT 2019 R3对一套Φ600 mm×3150 mm的SVQS系统进行了流动模拟和可行性验证。用单因素变量法分别研究了油气性质对系统无量纲切向速度和压降的影响;用标量输运方程分析了油气在系统内的停留时间分布规律。结果表明,无量纲切向速度随油气密度增加或黏度降低而变大;无量纲最大切向速度随油气密度增加或黏度减小而呈对数递增,最大为0.912;密度越大、黏度越小的油气在SVQS系统内的平均停留时间越短,最短可达6.279 s;压降、阻力系数不仅与系统的结构参数相关,也与油气黏度呈对数关系。拟合得到了与油气参数相关的无量纲切向速度、压降和阻力系数函数式,具有较好的普适性,可为SVQS系统的结构优化提供参考。     

Wettability of polytetrafluoroethylene and polymethyl methacrylate by aqueous solutions of TX-100 and TX-165 mixture with propanol

The measurements of the contact angle of the aqueous solutions of TX-100 and TX-165 mixture with propanol on polytetrafluoroethylene (PTFE) and polymethyl methacrylate (PMMA) were carried out. On the basis of the obtained results, the dependence between the cosine of contact angle and surface tension as well as between the adhesion and surface tension of the solutions in the light of the work of adhesion of the solutions to the PTFE and PMMA surface was discussed. The dependence between the adhesion and surface tension for PMMA was correlated to the surface concentration of propanol as well as TX-100 and TX-165 mixture concentration determined from the Frumkin equation at the PMMA-air, PMMA-solution and solution–air interfaces. For this purpose, the surface tension of PMMA covered by a surface active agent film was determined using the Neumann et al. equation and next the PMMA–solution interface tension was evaluated from the Young equation. The values of the surface tension of PMMA covered by propanol and surfactants mixture layer were applied to describe the changes of the adhesion work of solutions to PMMA surface as a function of propanol and surfactants mixture concentration. The adhesion work of the aqueous solutions of TX-100 and TX-165 mixture with propanol to the PTFE and PMMA surfaces was discussed in the light of the adhesion work of particular components of the solutions. On the basis of the results obtained from the contact angle measurements, the standard Gibbs free energy of adsorption of particular components of solution was also considered.     

Extrudate swell during the melt spinning of fibers—influence of rheological properties and take-up force

A theoretical and experimental study has been carried out on extrudate swell B, especially the influence of rheological properties and applied take-up force on the emerging melt. The problem is analyzed in terms of (1) dimensional analysis, (2) force–momentum balances, (3) partially constrained elastic recovery. Analyses in terms of force–momentum balances are only able to give extrudate swell B in the asymptote of high Reynolds numbers. For low Reynolds numbers, they simply relate the take-up force to the pressure field in the spinneret. Increasing the take-up force predicts a decrease in the exit pressure. The partially constrained elastic recovery theory yields an expression for B as a decreasing function of applied take-up force. Specifically, this is where B(0) is the extrudate swell in the absence of applied forces, λ_eff is the effective relaxation time, μ is viscosity (both evaluated at the capillary wall), and D is the spinneret capillary diameter. An experimental study of extrudate swell of several rheologically characterized melts (high density polyethylene, low-density polyethylene, polypropylene, polystyrene) has been carried out at 180°C by four different methods (frozen, annealed in hot silicone oil, photographed emerging into air, photographed emerging through 180°C silicone oil) in the absence of applied take-up forces. Extrudate swell for a melt emerging from dies with differing diameters correlates with capillary-wall shear rate. A comparison of extrudate swell with normal stress–shear stress ratio shows the best agreement for frozen extrudates and photographs of melts emerging into air. The data is compared to the Tanner theory of extrudate swell. B has been determined during melt spinning and shown to be a function of take-up force for both a high-density polyethylene and polypropylene melt. B decreases rapidly with applied take-up stresses. The results are compared to the predictions of the partially constrained elastic recovery theory.     

Rheological kinetics of acrylonitrile–acrylamide copolymer solutions in dimethyl formamide

Viscosity behavior of dimethyl formamide solutions of acrylonitrile–acrylamide copolymer is discussed. The rheological kinetics of the solutions was studied for contrast. It is shown that the solutions behave the same as Newtonian flow as the rotor speed goes beyond 6 revolutions min⁻¹. With an increase of temperature, the apparent viscosity of acrylonitrile–acrylamide copolymer solutions shows a decreasing trend. The changes of the apparent flow–activation energy of solutions calculated by Arrhenius equation become less prominent along with the changes of the molecular weight of acrylonitrile–acrylamide copolymers. The apparent flow–activation energy of the copolymer solutions increases continuously with an increase of copolymer concentration. The viscosity of copolymer solutions decreases continuously at concentrations of KCl and NaCl up to 0.02 mol L⁻¹ and then increases. The apparent flow–activation energy of acrylonitrile–acrylamide copolymer solutions shows an obvious trend of decrease with addition of alkali salts and the changes of the apparent flow–activation energy of solutions containing NaCl are more prominent than those of solutions containing KCl. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 527–531, 2005