Interfacial tension between demixed symmetrical polymer solutions: Polystyrene-poly(dimethylsiloxane)-propylbenzene system

Interfacial tension between demixed symmetrical polymer solutions of polystyrene-poly(dimethylsiloxane)-propylbenzene was measured as a function of temperature near the critical point at a fixed critical temperature (60.0°C) for molecular weights from 9000 to 1.0 × 10⁵. The interfacial tension increased as the molecular weight was lowered. The order of magnitudes of the interfacial tension was in good agreement with the theoretical prediction proposed previously by Nose. The critical exponents β and μ were estimated as near the values found for ordinary binary mixtures or liquids. Cloud point curves and coexistence curves were also obtained and properties related to incompatibility were also briefly discussed.     

Interfacial tension of demixed polymer solutions over a wide range of reduced temperature

Interfacial tensions were measured for solutions of polystyrene-methylcyclohexane, polystyrene-heptamethylnonane and poly(dimethyl siloxane)-phenylethyl ether to investigate the behaviour of the interfacial tension from the critical point to a region far away from it. In the polystyrene-heptamethylnonane system, measurements were performed until the concentration of the polymer rich phase became about 70～80%. The molecular weight dependence of the interfacial tension was stronger away from the critical temperature than near to it. Data for polystyrene solutions with different solvents were connected by a scaling law. Recent scaling theories were compared with the results for poly(dimethyl siloxane) solution.     

Influence of temperature,molecular weight,and polydispersity of polystyrene on interfacial tension between low‐density polyethylene and polystyrene

In this work, the influence of temperature, molecular weight, and polydispersity of polystyrene on interfacial tension between low‐density polyethylene (LDPE) and polystyrene (PS) was evaluated using the pendant drop method. It was shown that interfacial tension between LDPE and PS decreases with increasing temperature for all LDPE–PS pairs studied. The temperature coefficient (∂γ/∂T) (where λ is interfacial tension and T is temperature) was higher for lower molecular weight and larger polydispersity of PS. The interfacial tension between LDPE and PS at a temperature of 202°C increased when the molecular weight of polystyrene was varied from 13,000 to 30,000. When the molecular weight of PS was further increased, the interfacial tension was shown to level off. The effect of polydispersity on interfacial tension between PS and LDPE, at a temperature of 202°C, was studied using PS with a constant‐number average molecular weight and varying polydispersity. The interfacial tension was shown to decrease with increasing polydispersity. However, the influence of polydispersity was lower for PS of higher molecular weight. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2423–2431, 1999     

Interfacial tension of polycaprolactone/polystyrene blends by the imbedded fiber retraction method

Polycaprolactone (PCL) is a biodegradable polyester that is widely used in blends with synthetic and natural polymers for various applications. PCL is blended with biopolymers such as starch to improve its wet mechanical properties without impairing the biodegradability and other useful properties of starch. In spite of its importance, little is known about the interfacial tension of PCL blends. Indirect estimates of the room‐temperature interfacial tension of PCL blends using wettability methods have been reported. However, direct measurements of the interfacial tension of PCL blends have not been achieved until now, mainly because of the unsuitability of existing equilibrium methods for measuring the interfacial tension of high viscosity blends. We have measured the interfacial tension of PCL/PS blends using the imbedded fiber retraction (IFR) method. The IFR is a dynamic method that allows for the measurement of interfacial tension of high viscosity polymer blends in a relatively short period of time. The interfacial tension of PCL/PS blends was measured from 160 to 200°C. In this temperature range, the interfacial tension of PCL/PS blends is independent of temperature and has a value of 7.6 ± 1.8 dyn/cm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3145–3151, 2002; DOI 10.1002/app.10178     

Interfacial tension between coexisting polymer solutions in mixed solvents and its correlation with bulk thermodynamics: phase equilibria (liquid/gas and liquid/liquid) for the system toluene/ethanol/PDMS

Vapor pressures, phase equilibria and interfacial tensions σ were measured for solutions of poly(dimethylsiloxane) (PDMS, M_w[equals]75 kg/mol and M_n[equals]50 kg/mol) in mixed solvents of toluene (TL) and ethanol (EtOH) at 30, 40, 50 and 60 °C. The experimental ternary phase diagrams can be modeled quantitatively from the determined concentration and temperature dependent binary interaction parameters χ_ij if the experimentally inaccessible composition dependence of χ_EtOH/PDMS is adjusted. The relations between σ and the equation of state of the system differ from that applying to single solvents. The exponents as well as the amplitude prefactors of the corresponding scaling laws (e.g. the dependencies of σ on the length of the tie lines or on the hump energy, i.e. on the intrusion into the two phase regime quantified in terms of Gibbs energies) change considerably with temperature. However, this variation can be reduced significantly by normalizing the independent variables. Dividing the length of the tie lines by the length for the corresponding binary subsystem proves more efficient than the distance of these tie lines from the critical point of the ternary system relative to the maximum distance of the binary subsystem. A combined normalization does not improve the situation.     

聚合物结构对界面张力与相对分子质量关系的影响

以3组分子结构不同的聚合物为研究体系,采用熔融体悬滴测量装置系统地测量了不同相对分子质量的聚合物之间的界面张力,讨论了聚合物分子结构对其界面张力与相对分子质量关系的影响,通过对实验数据的分析推导出聚合物之间的界面张力与相对分子质量的关系式,并对传统的关系式作了改进。改进后的关系式考虑了聚合物分子结构的影响,具有更广泛的适用性。     

Interfacial tension of compatibilized blends of LDPE and PA6: the breaking thread method

The interfacial tension of the uncompatibilized and compatibilized blends of low density polyethylene (LDPE) and polyamide 6 (PA6) has been measured by the breaking thread method. Different types of compatibilizer precursors have been used: poly(ethylene-co-acrylic acid) (Escor 5001, by Exxon) having 6 wt% concentration of acrylic acid; an ethylene-acrylic acid zinc ionomer (Iotek 4200); a triblock copolymer with polystyrene end blocks and a rubbery poly(ethylene–butylene mid block (SEBS) (Kraton G 1652); and SEBS-g-MA (Kraton FG 1901X) with 2 wt% maleic anhydride. The compatibilizing efficiency of the different types of the compatibilizer precursors towards the blends has been evaluated quantitatively by the values of the interfacial tension obtained. It has been shown that Iotek and SEBS-g-MA posses the highest compatibilizing efficiency, demonstrated by the strongest decrease of the interfacial tension and the dimension of the droplets of the dispersed phase. Contrary, SEBS almost does not influence the interfacial tension and the size of the particles. Hence, it possesses the lowest compatibilizing activity towards the blends. The compatibilizer Escor displays an activity lower than that of Iotek and SEBS-g-MA, but it is higher than that of SEBS.     

Effects of molecular weight distribution on the spinodal temperature of polymer mixtures

The effects of molecular weight distribution on the phase stability of polymer mixtures were explored theoretically and experimentally. Based on the lattice‐fluid theory and volume‐fluctuation thermodynamics, the spinodal conditions for a lattice‐fluid mixture of two polymers with molecular weight distribution were derived. The results indicated that the phase stability of a polymer mixture decreases by increasing the molecular weight distribution of polymers in the blend. To confirm the theoretical results with experiments, the changes in the spinodal temperatures of poly(ethyl methacrylate)/polystyrene (PEMA/PS) blends and tetramethyl polycarbonate/polystyrene (TMPC/PS) blends were examined when each component has a different molecular weight distribution. When the weight‐average molecular weight of each component is the same, a blend composed of polymers having broad molecular weight distribution always exhibited lower phase separation than that composed of polymers having narrow molecular weight distribution at the same blend composition. Copyright © 2004 Society of Chemical Industry     

Emulsion polymerization of tetrafluoroethylene: effects of reaction conditions on the polymerization rate and polymer molecular weight

The emulsion polymerization of tetrafluoroethylene (TFE) was carried out in a semibatch reactor using a chemical initiator (ammonium persulfate) and a fluorinated surfactant (FC-143). The effects of the reaction condition were investigated though the polymerization rate, molecular weight of polytetrafluoroethylene (PTFE), and stability of the dispersion. The emulsion polymerization of TFE was different from conventional emulsion polymerization. The polymerization rate was suppressed when the polymer particles were significantly coagulated. The polymerization rate increased with operating temperature, surfactant concentration, and agitation speed, due to the enhanced stability of the polymer particles. However, once the parameter value was reached, the rate decreased due to the coagulation of the particles. Stable PTFE dispersion particles were obtained when the surfactant concentration was in the range between 3.48 × 10⁻³ and 32.48 × 10⁻³ mol/liter, which is below critical micelle concentration (CMC). The molecular weight of the PTFE obtained was a function of the surfactant and initiator concentrations, and the polymerization temperature. The molecular weight increased as each parameter decreased. This is against the phenomena observed in a conventional emulsion polymerization. A stable PTFE dispersion polymer having a high molecular weight was obtained by optimizing the reaction conditions. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 777–793, 1999     

pH值对硝酸铵水溶液临界爆炸温度的影响

研究了氯离子含量一定时pH值对硝酸铵水溶液临界爆温的影响。结果表明,氯离子质量分数为1．0×10^-4时,pH值越小,硝酸铵水溶液的临界爆温越低,且pH值与临界爆温值呈线性关系。本研究结果对硝酸铵的安全生产有重要的参考价值。     

Lower critical solution temperature of linear PNIPA obtained from a Yukawa potential of polymer chains

The lower critical solution temperature (LCST) behavior of a linear poly(N‐isopropylacrylamide) (PNIPA) in water is thought to result from the polymer–polymer attractive interaction. This polymer–polymer attraction is modeled by a temperature‐dependent Yukawa attractive potential, with Yukawa parameters determined by fitting the theoretical phase diagram for a pure Yukawa fluid to the experimental lower consolute boundary for a PNIPA–water solution. The predicted coexistence curve for the PNIPA–water mixtures in the temperature‐polymer volume fraction plane is reasonably close to the experimental cloud point data for the PNIPA–water system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1971–1976, 2000     

Surface tension prediction and thermodynamic analysis of the surface for binary solutions

The surface tensions of 100 aqueous and 200 non-aqueous binary solutions are correlated by Shereshefsky model and excellent results are obtained. The average percent deviations are about ∼1.8% for aqueous and ∼0.56% for non-aqueous binary solutions. The free energy change in the surface region is calculated and is used to obtain the excess number of molecular layers in the surface region. Furthermore, the model is used to derive an equation for the standard Gibbs energy of adsorption. Where experimental data is available for the standard Gibbs energy of adsorption, the agreement between the calculated and the experimental data is found to be very good.     

Molecular thermodynamics of binary polymer solutions using modified double lattice model: Chain length dependence of primary lattice

In a previous study we modified a double lattice model by introducing a new interaction parameter, which improved the mathematical approximation defect, and gave a new expression for the Helmholtz energy of mixing. In the model the universal constants C_β and C_γ in the primary lattice were determined by comparing them with literature Monte Carlo simulation data, which is the only case for r₁ = 1 and r₂ = 100 (case I). In this study we introduce new universal constants, C_β and C_γ, as a function of the chain length of a polymer in a solvent (case II) by comparing them with other literature simulation data for various polymer chain lengths. The proposed model is compared with polymer–solvent systems. In an upper critical solution temperature phase behavior the theoretical results of case II were improved over those of case I. However, in a lower critical solution temperature phase behavior those of case I were not very sensitive to C_β and C_γ. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2627–2633, 1999     

Liquid‐Liquid Equilibrium and Interfacial Properties of the System Water + Hexylacetate + 1‐Hexanol

Experimental and theoretical investigations of the phase diagram and the interfacial tension are presented. The theoretical framework was able to predict the phase behavior and the interfacial tension with a high accuracy, where only binary experimental data enter the model parameter. The theory permits the calculation of the concentration profiles across the interface. The profiles show that 1‐hexanol will be enriched, which was expected. In same circumstances a competition between hexylacetate and 1‐hexanol was figured out leading to slight minima in the profile of 1‐hexanol.     

溶液聚合制备油溶性减阻剂中溶剂的选择和聚合产物性能的表征

依据溶度参数理论预测溶剂和聚合物的相容性,为合成具有更高分子量的减阻聚合物提供理论指导。实验结果表明,使用脂肪烃溶剂（正己烷、正辛烷和环己烷）和芳香烃溶剂（甲苯、苯和氯苯）合成减阻剂黏均分子量的大小顺序与依据溶度参数理论预测不同溶剂合成减阻剂的分子量大小顺序吻合。脂肪烃溶剂是α-烯烃聚合的良溶剂,芳香烃溶剂是α-烯烃聚合的不良溶剂。良溶剂中环己烷是α-烯烃聚合的最佳溶剂,易合成分子量较大的减阻剂。同时,通过室内环道评价装置及XRD和1H-NMR测试手段对聚合产物的结构和性能进行了表征。     

基于基团拓扑的遗传神经网络工质临界温度预测

用遗传神经网络预测工质的临界温度,网络的输入参数为分子基团和拓扑指数,输出参数为临界温度。所划分的16个分子基团涵盖了制冷、热泵及有机朗肯循环系统中的大部分工质,所选拓扑指数能够分辨工质中所有的同分异构体。通过遗传算法优化得到网络结构及初始参数后,由神经网络对工质临界温度进行预测,同时为了提高网络对临界温度预测的泛化能力,将200种工质划分成训练集、验证集及测试集。所得网络能够区分所有的同分异构体,且与实验值相比,各数据集临界温度的平均相对误差分别为1.18%、1.69%、1.28%,表明该网络对工质临界温度具有很好的预测能力。     

Study on polymer solutions in solvent mixtures in the vicinity of the critical point of the solvents: 4. Saturation phenomena

Turbidimetric results have been obtained with the ternary system N,N-dimethylformamide/cyclohexane/polystyrene. The displacement of the heterogeneous region depends on the molecular weight of the polystyrene sample and for each polystyrene sample the displacement changes with the concentration of the polymer. Above a certain molecular weight of the polymer, with a given concentration, the displacement reaches a plateau region. A plateau is also obtained when we change the concentration of the polymer of a given molecular weight. The crossover region, which is determined by the appearance of the plateau region, obeys the scaling laws and is probably the region where the distance between the macromolecular coils is comparable to their diameters.     

Dual lower critical solution temperature polymer networks based on block,laminate, and interpenetrating network structures composed of N‐alkylacrylamides and N,N‐dialkylaminoethyl methacrylates

Novel materials that display two lower critical solution temperatures (LCSTs) were developed by forming block copolymers, laminate structures, and interpenetrating networks of crosslinked polymer systems that displayed temperature sensitivity independently. A number of LCST polymers and copolymers were investigated, including those based on N‐isopropylacrylamide, N,N‐diethylacrylamide, N,N‐diethylaminoethyl methacrylate, and N,N‐dimethylaminoethyl methacrylate. The polymer structure was found to profoundly influence the thermal sensitivity, as polymer formulation techniques led to materials with varying degrees of temperature sensitivity. Random and block copolymerization, along with interpenetrating networks and laminate systems, were studied, with only the structures having the greatest physical separation between pendent chains of different types having the ability to separate temperature transitions. Experiments were conducted to characterize the equilibrium swelling behavior and thermal transitions in the polymer systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2974–2981, 2003