Interfacial tension in polymer melts. Part II: Effects of temperature and molecular weight on interfacial tension

Interfacial tension is one of the most important parameters that govern the morphology of polymer blends and the quality of adhesion between polymers. However, few data are available on interfacial tension due to experimental difficulties. A pendant drop apparatus was used for the determination of the interfacial tension for the polymer pair polypropylene/polystyrene (PP/PS). The effects of temperature and molecular weight were evaluated. The range of temperatures used was from 178° to 250°C, and the range of molecular weights used was from 1590 to 400,000. The interfacial tension decreased linearly with increasing temperature. With only one exception, higher molecular weight systems showed weaker dependence of interfacial tension on temperature than lower molecular weight systems. Also, polydisperse systems showed a stronger dependency on temperature than the monodisperse systems. The value of the interfacial tension, which increases with molecular weight, appears to level off at molecular weights above the entanglement chain length. For the polymer pair PP/PS, the dependency of the interfacial tension on the number average molecular weight appears to follow the well-known semi-empirical (?2/3) power rule over most of the range of molecular weights. Comparable correlations were obtained with values of the power between ?1/2 and ?1.0.     

Interfacial tension measurement between immiscible polymers: improved deformed drop retraction method

This paper describes an improvement of the technique to measure interfacial tension in immiscible polymer blends. Our method is based on the droplet retraction method, in which one relates the kinetics of relaxation of a deformed droplet to the interfacial tension between the matrix and droplet. Previously, the problem with this technique has been the difficulty in preparing axisymmetric ellipsoidal droplets. In our work, we demonstrate that perfect axisymmetric ellipsoidal droplets are produced at a later stage of relaxation of short imbedded fibers. With this technique, we utilize the strengths of both the deformed droplet method and the imbedded fiber retraction method while overcoming their shortcomings. The interfacial tension value thus obtained was compared to that by conventional methods. Additionally, the effect of confinement by external walls on the interfacial tension measurement was studied. Confinement affects interfacial tension measurement when the gap between the walls is less than two times the equilibrium drop size.     

Interfacial tension of poly(p-phenylene sulfide) with other polymer melts

The interfacial tension of poly(p-phenylene sulfide) (PPS) with various thermoplastics of different compostion and polarity has been carried out using the breaking thread and pendent drop methods. The value of the polyethylene (PE)/PPS interfacial tension is found to be intermediate between PE/polysulfone and PE/polycarbonate. The highest interfacial tension for PPS found in the systems studied was with polyamide-6 followed by PE. The lowest values were with polysulfone followed by polystyrene. The effects of small additions of polysulfone and polystyrene in PPS on interfacial tension is studied with various thermoplastics. © 1994 John Wiley & Sons, Inc.     

Dynamic interfacial tension in melts of fibre-forming polymer blends

The dynamic interfacial tension was determined in melts of fibre-forming polymer blends: PPr-HDPE, PPr-LDPE, P4MP1-HDPE, P4MP1-PPr, PCA-PPr, PCA-HDPE, PCA-LDPE. It was determined by the method of capillary decomposition of liquid polymer jets. Translated from Khimicheskie Volokna, No. 1, pp. 19–22, January–February, 1998.     

时间效应在悬滴法测定表面张力中的影响

表面张力是流体重要的物理性质,测定表面张力的方法通常包括毛细管上升法、最大气泡压力法、拉环法、旋滴法和悬滴法等。目前,最普遍的表面张力的测定方法为国家标准推荐的平板法或拉环法。然而,悬滴法作为一项成熟的表面张力测定方法且具备静态表面张力及动态表面张力测定功能,目前使用该法测定的较少。文章使用悬滴法测定较低含量的表面活性剂溶液静态表面张力时发现结果与拉环法差异较大,而测定单组分液体及含量较大的表面活性剂溶液,悬滴法与拉环法的测定数据差异较小,这种情况的相关报道较少。另外,使用动态表面张力测定探索了静态测定时出现差异的原因,并对应用悬滴法进行表面张力测定的适用范围进行了总结。使用悬滴法测定表面张力时,应注意时间效应的影响。     

Development of freeze flow apparatus to study filled polymer melts

A novel method to study the distribution of filler particles and polymer orientation of a polymer melt within a capillary die has been developed. Material within the die is quench‐cooled and then removed to provide information about the flow regime at the instant it was frozen. The equipment has been used to examine calcium carbonate‐filled high density polyethylene under high shear. The samples were examined using Energy Dispersive X‐ray Spectrometry (EDS) as well as being studied using X‐ray Diffraction (XRD). The distribution of filler particles across the radius of the capillary has been studied at high and low wall shear rates using EDS. A constant particle distribution across the radius of the die was observed for both flow regimes. The arrangement of crystalline structures within the specimens was examined by XRD. An increase in crystalline order was noticed with increasing wall shear rate. POLYM. ENG. SCI., 47:1937–1942, 2007. © 2007 Society of Plastics Engineers     

Stress relaxation of polymer melts subjected to large uniaxial tension

The stress relaxation behaviour of two molten amorphous polymers (PMMA and PS), has been investigated. The range of draw ratios extends to about 3.5 for PMMA and 7 for PS. The results have been compared with a modification of the original reptation model. The experimental results are fitted rather well by the theoretical predictions in all the range of tested draw ratios for both the materials used.     

Suspension stabilizers for PVC production I: Interfacial tension measurements

The effect of commonly used suspension stabilizers on the interfacial tension of the vinyl chloride (VCM)/water interface was studied at 50°C, using the drop volume method. The measurements covered drop times from a few seconds to about 1000 s. The interfacial tension between VCM and pure water was found to be 32 mN/m. In the presence of additives, the interfacial tension varied with drop time. An equilibrium situation was probably not reached in any of these experiments. The surface activity of the poly(vinyl alcohol) increased with increasing acetate content. The interfacial tension decreased much more slowly with time in the presence of the poly(vinyl alcohol)s than with the cellulose ether tested. However, this polymer, Methocel F50, on adsorption at the interface formed a solid, mechanically strong surface film. The formation of such films was delayed by addition of ammonium laurate and/or Span 20.     

The marangoni effect and enhanced oil recovery Part 2. Interfacial tension and drop instability

A computer-based method is described for the determination of the interfacial tension between pendant and sessile drops in a surrounding continuous phase. This has been used to determine the effect on interfacial tension of increasing amounts of aliphatic alcohols, from methanol up to n-octanol, equilibrated between a hydrocarbon solvent (Shellsol) and water. The results indicated large decreases in interfacial tension, with n-butanol, followed by n-propanol giving the greatest reduction. Measurements were also made of the rate of change of interfacial tension during the mass transfer of 2.5% of the alcohols between phases. Changes were observed for all alcohols from ethanol to n-pentanol, the effect being greatest for transfer into water drops and out of solvent drops. Application of the linear stability theory of Sørensen to these results failed to predict the observed instability for transfer into solvent drops.     

Interfacial tension measurements and evidence of order in high‐density polyethylene melts

Polyethylene (PE) is a widely used product commercially. However, our knowledge is incomplete about the properties of high‐density polyethylene (HDPE) at temperatures above its melting point, where solid crystals disappear. Recently, there has been increasing evidence from rheological, differential scanning calorimetry, and NMR studies that suggests the presence of microstructural order in the bulk of PE melts. In this study, the interfacial tension of HDPE melts in contact with silicone oil was measured with a spinning drop tensiometer in the same temperature range in which phase transitions have been observed in the bulk HDPE. Anomalous temperature dependence of interfacial tension was found between 200 and 230°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4061–4067, 2003     

Crystallization of polymer melts under fast cooling. I: Nucleated polyamide 6

Samples of nucleated polyamide 6 were quenched from the melt so as to monitor cooling histories. Their morphology and crystal structures were discussed in relation to sample thermal history; cooling history relevant to quenched sample morphology was recognized as being confined in the interval 110 to 160°C. In particular, samples were essentially amorphous for cooling rates larger than 200°C/s. The γ-crystalline form was observed for cooling rates in the interval 70 to 200°C/s, whereas α crystalline structure was found dominant for yet lower cooling rates. Crystallinities evaluated from densities of quenched samples were compared with predictions of an isokinetic form of the Avrami model for polymer crystallization kinetics.     

Compatibilizing agents in polymer blends: Interfacial tension,phase morphology,and mechanical properties

The interfacial tension, phase morphology, and phase growth was determined for four polymer blend systems: polyethylene/polystyrene, polyethylene/polyamide-6, polystyrene/polyamide-6, and polystyrene/poly(ethylene terephthalate). Generally, high interfacial tension correlates with coarse phase morphology and rapid phase coalescence. The addition of various potential compatibilizing agents to these binary blend systems results in lowered interfacial tension, finer and stabilized phase morphologies. The characteristics of different compatibilizing agents were compared for several of the blend systems. We also look at the influences of compatibilizing agents on mechanical properties of the blend systems. Some compatibilizing agents are able to produce substantial improvements in ultimate properties.     

Study on the surface tensions of polymer melts using axisymmetric drop shape analysis

It is shown that Axisymmetric Drop Shape Analysis (ADSA) is well-suited for the study of polymer melt surface tensions. The technique is not restricted to equilibrium surface (interfacial) tensions; it is also suitable for measuring the time dependence (or kinetics) of surface tension of polymer melts. Results for three polymers, polypropylene, polyethylene, and polystyrene, at temperatures above 170°C are reported. Contrary to the well-known decrease of surface tension in low molecular weight surfactant solutions as a result of equilibration, an increase in the melt surface tension is observed under isothermal conditions.     

Interfacial tension of demixed polymer solutions near the critical temperature: polystyrene + methylcyclohexane

Interfacial tension between demixed solutions of polystyrene + methylcyclohexane has been measured near the critical temperature as a function of temperature using polystyrenes with molecular weights 9000 ～ 1.26 × 10⁶. The critical exponent for the interfacial tension was determined to be about 1.30 for the lower molecular weight systems. However, for higher molecular weights the exponent could not be obtained because the system departed from critical behaviour. Magnitudes of the interfacial tension were proportional to about N^?0.44, where N is the polymerization index. Experimental results were compared with the recently-proposed theories and found to be in qualitative agreement. The tricritical theory of polymer solutions was also compared with the experimental results.     

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 from height and diameter of a single sessile drop or captive bubble

The silhouette of a sessile drop submerged in a transparent bulk phase appears to possess a contact angle of 180° with a plane solid support, when the drop is separated from the solid surface by a thin film of surrounding fluid. A computer-aided analysis of the generalized sessile drop form leads to an explicit equation for interfacial tension dependent only on drop height (from apex to solid support) and the magnitude of the drop equatorial diameter. The equation is valid for a wide range of physically realizable drops. Measurements of drop profile coordinates or the location of the drop equator are not required for the use of the method, leading to improvements in accuracy relative to current practice.     

Chemical analysis in a drop: a dynamic surface tension detector for polymer and protein characterization

A dynamic surface tension detector (DSTD) for the multidimensional analysis of polymers and proteins in aqueous solutions is reviewed. The DSTD is briefly compared with other instrumental methods for the measurement and evaluation of time‐dependent surface tension assessment. The dynamic nature of the surface tension signal is shown to provide unique selectivity and useful chemical information. The benefits of multidimensional detection using the DSTD for flow injection analysis and high performance liquid chromatography providing selective and sensitive surface activity analysis are discussed. © 2013 Society of Chemical Industry     

Transitions in polymer melts

It is shown that the liquid-liquid transition T_ll in polymer melts need not be a true polymer transition but can be an artifact of the torsional braid analysis technique. The shift in T_ll with molecular weight then is due to the variation of viscosity with molecular weight.     

An improved apparatus for oxygen bomb testing

An improved oxygen bomb apparatus has been developed. The increased precision and readability of the continuous pressure recording allows a new method of end-point measurement. It was possible to use smaller test samples than any previously reported. Sample size and oxygen pressure were shown to be relatively unimportant variables. Temperature is the most useful variable for controlling test time. This is preferable over sample dispersion or addition of catalysts in terms of simplifying the procedure. Peroxide formation at the oxygen bomb test end point is three to four times the value at the end point of the Active Oxygen Method. Presented at the AOCS meeting, New Orleans, April 1976. Part I of a series on Evaluation of Antioxidant Performance.