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.     

Influence of temperature,molecular weight,and molecular weight dispersity on the surface tension of PS,PP, and PE. I. Experimental

In this work, the influence of temperature, molecular weight (M?_n), and molecular weight dispersity (MWD) on the surface tension of polystyrene (PS) was evaluated using the pendant drop method. The influence of temperature on the surface tension of isotatic polypropylene (i‐PP) and of linear low‐density polyethylene (LLDPE) was also studied here. It was shown that surface tension decreases linearly with increasing temperature for all the polymers studied. The temperature coefficient ?dγ/dT (where γ is the surface tension, and T, the temperature) was shown to decrease with increasing molecular weight and to increase with increasing MWD. The surface tension of PS increased when the molecular weight was varied from 3400 to 41,200 g/mol. When the molecular weight of PS was further increased, the surface tension was shown to level off. The surface tension was shown to decrease with increasing molecular weight distribution. Contact angles formed by drops of diiomethane and water on films of PS with different molecular weights were measured at 20°C. The surface energies of those polymers were then evaluated using the values of the different pairs of contact angles obtained here using two different models: the harmonic mean equation and the geometric mean equation. It was shown that the values of the surface energy obtained are slightly less than are the ones extrapolated from surface‐tension measurements in the rubbery state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1907–1920, 2001     

Rheological evaluation of polystyrene/polyethylene blends

The dynamic shear behavior at 200°C of low density polyethylene, LDPE, polystyrene, PS, and their blends was studied. Two series of blends were prepared containing LDPE:PS = 1:2, 2:1 and 17:3; the first series contained 0, the second 5 wt% of the compatibilizing, partially hydro-genated poly(styrene-b-isoprene) di-block copolymer, SEB. From the Casson plot the relative values of apparent yield stress were found to be G′_y > G″_y the addition of SEB decreased both these functions, but the inequality remained valid. After subtracting the yield stress values the frequency relaxation spectrum was computed from the relation G″ = G″(ω). The linear viscoelastic functions determined from the spectrum were found to agree with experimental values within a range of error below 5%. The blends were found to be thermorheologically complex with the time-temperature shift factors depending on both temperature and frequency. A compositional dissymmetry of blend morphology was observed: PS dispersed in LDPE formed spheres, while at corresponding concentration LDPE in PS formed fibers. A difference in surface tension of the two polymers, leading to different spreading coefficients (S_PE/PS≠S_PS/PE), or dissymmetry of the interfacial tension coefficient, could provide a possible explanation.     

Surface Tension in Polymer Blends of Isotactic Poly(propylene) and Atactic Polystyrene

The surface tension of atactic polystyrene (PS), isotactic poly(propylene) (PP) and PS/PP‐blends, and additionally the interfacial tension between PP/PS have been measured in the temperature range between 200 and 280°C using the pendant drop method. Within the temperature range studied, the surface tension decreased linearly with increasing temperature for all systems whereas the surface tension of neat PP is approximately 7 mN/m smaller than the value of PS. The interfacial tension between PS and PP is in the range of approximately 4 mN/m and this indicates a strong incompatibility. It results a heterogeneous PP/PS blend morphology. A significant increase of the surface tension of the blends as a function of composition is observed only when the PS content exceeds 60 wt.‐%. Furthermore, microscopic observations indicate that even if the bulk matrix material is PS, a thin layer of PP can be detected by atomic force microscopy on the droplet surface used for surface tension measurements.     

Interfacial tension of polypropylene/polystyrene: Degradation of polypropylene

The coefficient of the decrease of the interfacial tension of polypropylene/polystyrene with temperature is considerably higher than the value of other polymer pairs. This coefficient can be estimated by considering the change of the interaction parameters with temperature, but this approach fails for polypropylene/polystyrene, and other mechanisms are expected to play a role. In this paper it is shown that polypropylene starts to degrade at higher temperatures, leading to smaller polymer chains, which decrease the interfacial tension. Besides the change of the interaction parameters with temperature, these smaller molecules also contribute to the temperature coefficient, leading to an apparently high coefficient. The smaller molecules, however, lead to a permanent lower interfacial tension, e.g. the interfacial tension of polypropylene/polystyrene at 200°C is 4.9, 3.9, and 3.0 mN/m, if the polypropylene is first processed at 200, 250, and 300°C, respectively.     

The effect of the architecture and concentration of styrene–butadiene compatibilizers on the morphology of polystyrene/low‐density polyethylene blends

The effect of styrene–butadiene block copolymers (SB) with varying number of blocks and length of styrene blocks on the morphology, rheology, and impact strength of 4/1 polystyrene/low‐density polyethylene (PS/LDPE) blends was studied. The scanning and transmission electron microscopy and X‐ray scattering were used for determination of the size of LDPE particles and the localization and structure of SB copolymers in blends. It is shown that the dependence of the LDPE particle size on the amount of added SB and localization of SB copolymers in blends is predominantly controlled by the length of their styrene blocks. It follows from thermodynamic considerations that the reason is the difference in composition asymmetry between SB with short and long styrene blocks. Coalescence of particles of SB having short styrene blocks at the surface of LDPE droplets and movement of SB with long styrene blocks to the PS–LDPE interface were observed during annealing of PS/LDPE/SB blends. Pronounced migration of SB copolymer during annealing shows that their localizations in blends in steady state on long steady mixing and at thermodynamic equilibrium are different. The values of tensile impact strength of PS/LDPE/SB blends correlate well with the size of LDPE particles and the amount of SB at the interface. Viscosity of PS/LDPE/SB depends on molecular structure of SB copolymers by a manner different from that of tensile impact strength. The results of this study and literature data lead to the conclusion that the compatibilization efficiency of SB copolymers for a certain polystyrene‐polyolefin pair is a function of not only molecular parameters of SB but also of the polystyrene/polyolefin ratio, the amount of SB in a blend, and mixing and processing conditions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2803–2816, 2006     

Dynamic rheological properties of high‐density polyethylene/polystyrene blends extruded in the presence of ultrasonic oscillations

The linear rheological properties of high‐density polyethylene (HDPE), polystyrene (PS), and HDPE/PS (80/20) blends were used to characterize their structural development during extrusion in the presence of ultrasonic oscillations. The master curves of the storage shear modulus (G′) and loss shear modulus (G″) at 200°C for HDPE, PS, and HDPE/PS (80/20) blends were constructed with time–temperature superposition, and their zero shear viscosity was determined from Cole–Cole plots of the out‐of‐phase viscous component of the dynamic complex viscosity (η″) versus the dynamic shear viscosity. The experimental results showed that ultrasonic oscillations during extrusion reduced G′ and G″ as well as the zero shear viscosity of HDPE and PS because of their mechanochemical degradation in the presence of ultrasonic oscillations; this was confirmed by molecular weight measurements. Ultrasonic oscillations increased the slopes of log G′ versus log G″ for HDPE and PS in the low‐frequency terminal zone because of the increase in their molecular weight distributions. The slopes of log G′ versus log G″ for HDPE/PS (80/20) blends and an emulsion model were used to characterize the ultrasonic enhancement of the compatibility of the blends. The results showed that ultrasonic oscillations could reduce the interfacial tension and enhance the compatibility of the blends, and this was consistent with our previous work. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3153–3158, 2004     

Effect of composition on the linear viscoelastic behavior and morphology of PMMA/PS and PMMA/PP blends

Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.     

Evaluation of the interfacial state in high impact polystyrene through dynamic mechanical analysis as a function of the synthesis conditions

High impact polystyrene was synthesized using two series of styrene/butadiene (SB) tapered block copolymers with a polystyrene (PS)/polybutadiene (PB) composition of 30/70 and 10/90 wt%. During the synthesis, concentration of initiator, SB and transfer agent were varied. From dynamic mechanical analysis, the corresponding α relaxation of the rubber phase was detected at low temperature (near ?100°C) and that of the glassy PS phase at high temperature (near 100°C). Also, another relaxation at temperature near 40°C was identified, which was associated to the β relaxation of the glassy PS phase. The variations found in the α relaxation of the rubber phase, were attributed to changes in the morphological structure as a consequence of variation in initiator, SB or transfer agent concentrations and in SB composition. β relaxation showed a strong dependency with the interfacial state between the rubber and the glassy phase, where an increase in the amount of graft PS at the interface, which promotes the interfacial adhesion between phases, causes an increase in the magnitude of β relaxation of the PS phase. The results were attributed to variations in the interfacial area as a result of the change in the particle size and to the contribution of molecular chains of each phase in participating in the relaxation process. POLYM. ENG. SCI., 47:1827–1838, 2007. © 2007 Society of Plastics Engineers     

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     

Dynamic mechanical properties of polystyrene‐block‐poly[ethylene‐co‐(ethylene‐propylene)]‐block‐polystyrene triblock copolymer/hydrocarbon oil blends

Blend systems of polystyrene‐block‐poly(ethylene‐co‐(ethylene‐propylene))‐block‐polystyrene (SEEPS) triblock copolymer with three types of hydrocarbon oil of different molecular weight were prepared. The E″ curves as a function of temperature exhibited two peaks; one peak at low temperature (? ?50°C), arising from the glass transition of the poly[ethylene‐co‐(ethylene‐propylene)] (PEEP) phase and a high temperature peak (? 100°C), arising from the glass transition of the polystyrene (PS) phase. The glass transition temperature (T_g) of the PEEP phase shifted to lower temperature with increasing oil content. The shifted T_g depended on the types of oil and was lower for the low molecular weight oil. The T_g of PS phase of the present blend system, were found to be constant and independent of the oil content, when molecular weight of the oil is high. However, for the lower molecular weight oil, the T_g of the PS phase also shifted to lower temperatures. This fact indicates that the oil of high molecular weight is merely dissolved in the PS phase. The E′ at (75°C, at which temperature both of PEEP and PS phases are in glassy state, was found to be independent of oil content. In contrast, at 25°C, at which temperature the PEEP phase is in rubbery state, the E′ decreased sharply with increasing oil content. This result indicates that the hydrocarbon oil was a selective solvent in the PEEP phase. It mainly dissolved in the PEEP phase, although slightly dissolved into the PS phase as well, when molecular weight of oil is low. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Phase behavior and kinetics of polystyrene degradation in supercritical toluene

The phase behavior of polystyrene (PS) degradation in toluene was investigated in a visual high‐pressure reactor. The system of PS and toluene was heated from room temperature and atmospheric pressure to 350°C and 5.0 MPa. It was observed that during this process, PS dissolved quickly, and then, the system appeared to be a homogeneous phase, and PS degradation occurred in this system. With another high‐pressure batch reactor, PS degradation was studied in the temperature range 275–360°C and the pressure ranges 4.5–10.5 MPa. The drop‐in molecular weights in the temperature ranges and the amount of PS converted into volatile products were observed. Moreover, the effects of the temperature, pressure, and ratio of toluene to PS on the rate of PS degradation are discussed. The kinetic studies showed that the rate of PS degradation in supercritical toluene increased substantially because the degradation occurred in a homogeneous phase. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The synthesis of fulvic acid–thiourea amide derivates grafted polystyrene and its effect on the crystallization and performance of poly(lactic acid)

Fulvic acid–thiourea amide derivates (FA‐T) was synthesized via amidation with FA and thiourea, and its optimum reaction conditions were 7 h of reaction time, 1 wt% of sodium methylate, 130°C of reaction temperature, and 2 g of thiourea. Then, FA‐T grafted polystyrene (FA‐T‐PS) was synthesized by activators generated by electron transfer for atom transfer radical polymerization. Fourier transform infrared spectroscopy, static contact angle analysis, and X‐ray photoelectron spectroscopy confirmed that the synthesis of FA‐T‐PS. Then, poly(lactic acid)/FA‐T‐PS(PLA/FA‐T‐PS) composites were prepared by the melt blending with FA‐T‐PS as fillers. Mechanical test demonstrated that FA‐T‐PS increased the flexibility and ductility of PLA composites. Dynamic mechanical analysis revealed that FA‐T‐PS reduced friction and loss between PLA chain and filler, and further reformed had higher interfacial compatibility with PLA. Differential scanning calorimetric results and polarized optical microscopy analysis displayed that FA‐T‐PS had strong heterogeneous nucleation effect, which effectively enhanced the crystallization rate and the crystallinity of PLA. Friedman thermal decomposition kinetics presented that E _a of PLA/FA‐T‐PS (0.3 wt%) was increased by 52.94% compared with PLA, which demonstrated that FA‐T‐PS significantly enhanced the thermal stability of PLA. Therefore, FA‐T‐PS effectively improved the comprehensive performance of PLA. POLYM. ENG. SCI., 59:1787–1798, 2019. © 2019 Society of Plastics Engineers     

γ‐Irradiated poly(tetrafluoroethylene) particle‐filled low‐density polyethylene. I. Effect of silane coupling agents on mechanical,thermal, and morphological properties

Poly(tetrafluoroethylene) (PTFE) scraps were recovered as a filler material for low‐density polyethylene (LDPE) after they were degraded by Co‐60 γ‐rays under atmospheric conditions to make small‐size powder. The powder PTFE, which was called secondary PTFE (2°‐PTFE), was melt mixed with LDPE and then extruded to obtain 200 µm films. The mechanical and thermal properties and also the morphology of the fractured surface of these 2°‐PTFE–filled LDPE were studied. It was found that the addition of 2°‐PTFE resulted in thermofilm property of LDPE but it slightly decreased the thermal oxidative temperature of LDPE. The tensile strength and ultimate elongation of LDPE were found to decrease with the addition of 2°‐PTFE. However, when it is compared to the addition of virgin PTFE into LDPE, 2°‐PTFE shows better mechanical properties due to the presence of oxy groups which are capable of interacting with the main matrix. A further improvement in mechanical properties was achieved by silane coupling agent treatment of 2°‐PTFE. Silane coupling agents were found to enhance the interfacial adhesion between 2°‐PTFE and LDPE. The study on the fractured surfaces by scanning electron microscope revealed this adhesion between these two polymers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 866–876, 1999     

Thermodynamic analysis of phase separation in an epoxy/polystyrene mixture

The phase separation process of an epoxy prepolymer based on diglycidyl ether of bisphenol A (DGEBA) with a thermoplastic polystyrene (PS) was thermodynamically studied in the frame of the Flory-Huggins theory. The thermodynamic treatment was carried out in two steps: first analysing the phase separation in cloud point conditions, and second analysing the advance of the phase separation for two compositions of 2 and 10% in volume of PS. The effect of the polydispersity of thermoplastic on phase separation was also studied. The polydispersity of PS produces a displacement of the threshold temperature to lower thermoplastic volume fraction (between 2 and 3%) and higher temperature value and the fact that the shadow curve and coexistence curves do not superimpose with the cloud point curve. Theoretical calculations of molecular weight distributions of PS at different degrees of phase separation were realized and different average molecular properties were obtained in each separated phase.     

Synthesis and characterization of polystyrene initiated using polymeric peroxide

Polymer peroxides were synthesized by copolymerizing tert‐butyl‐3‐isopropenylcumylperoxide (D‐120) with styrene (St). Exothermic peak at 192.7°C in DSC thermogram indicated that peroxy bonds in D‐120 remained intact during the copolymerizing process. The polymeric peroxide was used to initiate polymerization of St. GPC results showed that polystyrene (PS) initiated by the polymeric peroxides was composed of both linear and branched molecules. In addition, the rheology test showed that PS samples initiated by polymeric peroxide contained branched structure and had lower shear viscosities. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 197–202, 2006     

Measurement of interfacial tension in PS/LDPE melts saturated with supercritical CO2

The effect of supercritical carbon dioxide (scCO₂) on the interfacial tension between a polymer melt pair—polystyrene (PS) and low density polyethylene (LDPE)—was studied using the pendant drop method at temperatures varying from 200 to 240°C and CO₂ pressures up to 18 MPa. The LDPE melt was prepared in a high pressure optical cell and the PS pendant drop was injected into the LDPE melt with a special high pressure syringe. For measurements with scCO₂, the optical cell was first pressurized with scCO₂ and measurements were taken after the saturation of scCO₂ into both polymer melts. Excellent agreement was found with literature data for the same system without using scCO₂. For the polymer pair saturated with scCO₂, it was found that the interfacial tension decreases significantly with increasing CO₂ pressure and appears to level off at higher CO₂ pressures.     

Synthesis of polystyrene oligomers by nitroxide‐mediated radical polymerization using diethylketone triperoxide as a multifunctional radical initiator

Styrene oligomers (M_n, 2500–3000 g/mol) with low polydispersity index and containing peroxidic groups within their structure were synthesized using a novel trifunctional cyclic radical initiator, diethylketone triperoxide (DEKTP), through nitroxide‐mediated radical polymerization (NMRP), using OH‐TEMPO. During the synthesis of the polystyrene (PS) oligomers, camphorsulfonic acid (CSA) was used to inhibit the thermal autoinitiation of styrene at the evaluated temperatures (T = 120–130°C). The polymerization rate, which can be related to the slope of the plot of monomer conversion with reaction time, was monitored as a function of OH‐TEMPO, DEKTP, and CSA concentrations. The experimental results showed that all the synthesized polymers presented narrow molecular weight distributions, and the monomer conversion and the molecular weight of the polymers increased as a function of reaction time. Under the experimental conditions, T = 130°C, [DEKTP] = 10 mM, and [DEKTP]/[OH‐TEMPO] = 6.5, PS oligomers containing unreacted O? O sites in their inner structure were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Selective pyrolysis of polystyrene to that with a desired low polymeric degree

To obtain low polymeric polystyrene (PS), pyrolysis of high polymeric PS in solution was studied in the temperature range from 290 to 400°C by using additives or acid catalysts. The low polymeric PS targeted here was that with average molecular weight of 10⁴. When the feed PS was pyrolyzed in tetralin by adding sulfur or diphenyl disulfide, the molecular weight of PS decreased greatly, even at lower temperatures, and the desired low polymeric PS was formed in a relatively large amount at the temperatures below 350°C. The degradation behavior was able to be explained in terms of a random polymer chain scission mechanism initiated by sulfur radicals formed from the additives. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2299–2305, 1998     

Nonaqueous emulsion copolymerization of ethyl methacrylate/lauryl methacrylate in propylene glycol. I. Evaluation of stabilizing efficiency for PEO‐PS‐PEO triblock copolymers

Sixteen poly(ethylene oxide)–polystyrene–poly(ethylene oxide) (PEO‐PS‐PEO) triblock copolymers were synthesized by anionic polymerization. They were characterized by gel permeation chromatography and proton NMR. The molecular weight of these 16 PEO‐PS‐PEO triblock copolymers ranged from 5100 to 13,300. The polystyrene (PS) block length was between 13 and 41. The PEO block length was between 41 and 106. The polydispersity index for these PEO‐PS‐PEO triblock copolymers were 1.05 ± 0.02. When using these stabilizers in the emulsion copolymerization of ethyl methacrylate and lauryl methacylate in propylene glycol, only a narrow window of stability was observed. Stable latexes were formed only when the molecular weights of the PEO blocks were within the range of 5300–7700 and the molecular weights of the PS blocks were 2000–4000. The stabilizer ability for these triblock copolymers was correlated with their molecular weight and conformation in propylene glycol. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1951–1962, 2001