相容剂对聚丙烯/聚酰胺体系界面张力的影响

采用断裂纤维丝线法和变形液滴回缩法两种方法相结合,在线观察聚酰胺6(PA6)液滴在聚丙烯(PP)中的回缩过程,研究不同相容剂对该体系界面张力的影响。结果表明,PA6液滴在剪切场下发生变形,然后在界面张力的作用下逐渐回缩成球形,并测得该体系的界面张力为7.16 mN/m。添加相容剂可以显著降低体系的界面张力。不同相容剂[聚丙烯接枝马来酸酐(PP-g-MA)、聚丙烯接枝丙烯酸(PP-g-AA)、氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)]对体系界面张力影响不同,满足以下关系:γ_(PP/PA6)>γ_(PP/SEBS/PA6)>γ_(PP/PP-g-AA/PA6)>γ_(PP/PP-g-MAH/PA6)。     

Inhibited transesterification and enhanced fibrillation of TLCP by nano-SiO2 in polycarbonate matrix

Hybrid composites composed of a thermotropic liquid crystalline polymer (TLCP), nano-SiO₂ and polycarbonate (PC) were prepared by melt blending in a twin-screw extruder. Infrared spectroscopy analysis indicated that the transesterification between PC and TLCP molecules during melt blending was significantly reduced in TLCP/PC blends filled with nano-SiO₂, compared to the unfilled TLCP/PC one. Scanning electron microscopy (SEM) observation showed that better compatibility and finer TLCP dispersion were reached in the unfilled blend, which made the fibrillation of TLCP difficult in capillary flow even at high shear rate. In contrast to this, well-developed TLCP fibrils were formed by capillary flow in nano-SiO₂ filled TLCP/PC blends. By increasing the nano-SiO₂ concentration and shear rate, the fibrillation of TLCP was significantly enhanced. Thermodynamically the interfacial tension between these components and dynamically the viscosity ratio of TLCP to PC were used to investigate the mechanism of nano-SiO₂ in inhibiting the transesterification and enhancing the fibrillation of TLCP droplets in these hybrid composites.     

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.     

Stability of blends of thermotropic liquid crystalline polymers with thermoplastic polymers

Breakup of fibers of a thermotropic liquid crystalline polymer (TLCP) above the melting temperature in various ordinary polymers has been studied by capillary instability experiments on single TLCP fibers and by annealing experiments on extruded TLCP/thermoplast blends. The TLCP was an aromatic copolyester, Vectra A900, the matrix polymers were PP, PS, PC, PEL PES, and PEBT. Both types of experiments show that the fiber/matrix morphology is, in general, highly unstable in the molten state. The TLCP fibers break up into droplets by a combination of Rayleigh distortions, end-pinching and retraction, depending on the system and shape of the fiber. Fibers of a thickness of ～1 μm can break up in a few seconds. Breakup times of fibrous blends and individual fibers are in agreement provided size effects are accounted for. Rayleigh distortions develop exponentially in time up to relative distortions of 0.5 to 0.6. Breakup occurs within a range of wave numbers rather than at one distinct dominant wave number, which is shown to be the consequence of relatively large initial distortions. Apparent values for the interfacial tensions calculated with Tomotika's theory turned out to be of the correct order of magnitude, ranging from 7 mN/m for Vectra/PES to 24 mN/m for Vectra/PP and to yield correct values of the interfacial tensions of PP/PS, PP/PC, and PS/PC using Antonow's rule.     

Thermotropic liquid‐crystalline copolyester/thermoplastic elastomer in situ composites. I. Rheology,morphology, and mechanical properties of extruded strands

A thermotropic liquid‐crystalline polymer (TLCP), a copolyester with a 60/40 molar ratio of p‐hydroxy benzoic acid and poly(ethylene terephthalate), was blended with a styrene/ethylene butylene/styrene thermoplastic elastomer with a twin‐screw extruder. The rheological behavior, morphology, and mechanical properties of the extruded strands of the blends were investigated. The rheological measurements were performed on a capillary rheometer in the shear rate range of 5–2000 s^?1 and on a plate‐and‐plate rheometer in the frequency range of 0.6–200 rad s^?1. All the neat components and blends exhibited shear thinning behavior. Both the shear and complex viscosities of all the blends decreased with increasing TLCP contents, but the decrease in the shear viscosity was more pronounced. The best fibrillar morphology was observed in the extruded strands of a blend containing 30 wt % TLCP, and a lamellar structure started to form at 40 wt % TLCP. With an increasing concentration of TLCP, the tensile modulus of the blends was greatly enhanced, whereas the tensile strength was almost unchanged. The elongation at break of the blends first slightly decreased with the addition of TLCP and then sharply dropped at 40 wt % TLCP. The tension set measured at 200% deformation slightly increased with increasing TLCP contents up to 30 wt %, over which the set value was unacceptable for a thermoplastic elastomer. A remarkable improvement in the dynamic mechanical properties of the extruded strands was observed in the blends with increasing amounts of TLCP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2676–2685, 2003     

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 interfacial properties between a flexible‐chain polymer and a thermotropic liquid crystalline polymer investigated by an ellipsoidal drop retraction method

In this study, the dynamic interfacial properties between an isotropic polymer and a thermotropic liquid crystalline polymer (TLCP) were investigated by measuring the time‐dependent interfacial tension between them. As a TLCP drop retracts in a flexible polymer matrix, the evolution of its shape is recorded by microscopy. By fitting the ellipsoidal model of Maffettone and Minale, the model of Marrucci and Santo, and large deformation ellipsoidal models by Jackson–Tucker and Yu–Bousmina, the interfacial tension could then be determined. It was found that the retraction of a TLCP ellipsoidal drop in a flexible polymer cannot be described by these models as accurately as in Newtonian systems. The apparent interfacial tension obtained from these models evolves with time; the evolution is ascribed to the slow relaxation of domain orientation within the TLCP drop. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94:1404–1410, 2004     

Structure evolution in polymer blending using microfabricated samples

The transient rheological behavior and morphology evolution of polymethyl methacrylate (PMMA)/polystyrene (PS) binary polymer blends with well-defined initial structure were measured in simple shear flow under isothermal conditions. The size and distribution of the dispersed phase and the composition of the blends were designed and fabricated by Computer Numerical Controlling (CNC) machining, photolithography, and micro-embossing. Compatibilizer can easily be placed at the interface of the two components during sample preparation. The effects of initial dispersed domain size, blend composition, and interfacial tension on rheological behavior and morphology evolution were investigated. It was found that the transient shear stress and first normal stress difference are very sensitive to these parameters. The transient rheological responses up to the breakup point are compared with those predicted by both Doi-Ohta and Vinckier-Moldenaers-Mewis models.     

Study on morphology development for in situ fiber–reinforced composites by blending polyolefin and polycaprolactone

The morphology developments and interfacial properties of extruded polyethylene/polycaprolactone and polypropylene/polycaprolactone blends were investigated. The interfacial thicknesses of both polymer blends were thin and this was investigated by interfacial tension measurement in the melt state. The aspect of boundary area was observed by AFM, and a clear line could be observed at the interface area as a result of thin interfacial thickness. The in situ fiber formation of the dispersed phase was remarkably generated under elongational flow (between die exit and solidification) rather than under shear flow (in the cylinder and die). Drawing ratio was varied at three levels to study its effect on elongation of the dispersed phases. The dispersions dramatically changed from spherical to spheroidal and filament shapes depending on the drawing ratio. Reduced capillary number (Ca*) was used to characterize droplet deformation. The deformation mode under shear flow was classified as nondeformation mode due to the fact that the Ca* was almost 0. On the other hand, the deformation mode under elongational flow was classified into filament shape mode (Ca* > 4). This classification was in agreement with the SEM images. The tensile properties were increased at the border line where the Ca* was 4.0. The melt interfacial tensions of polyolefin/polycaprolactone were relatively large, and a clear line could be observed at the interface area as a result of little affinity of polymer interface. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 500–508, 2005     

Rheological properties of polystyrene and poly(methyl methacrylate) blends

Rheological properties of the polystyrene (PS) and poly(methyl methacrylate) (PMMA) blends were studied by Advanced Rheometric Expansion System (ARES). Storage modulus and loss modulus of the PS and PMMA blends were measured, and the interfacial tension of the PS and PMMA blends were obtained with various emulsion models by using the storage modulus and loss modulus of the blends. The value of interfacial tension estimated from the Palierne emulsion model was found to be 2.0 mN/m. Also, the interfacial tension between PS and PMMA was calculated by a theoretical model. The values of interfacial tension of the PS and PMMA blends obtained by the experiment and theoretical model were found to be in good agreement.     

Dynamic viscoelastic behavior of polypropylene/polybutene-1 blends and its correlation with morphology

In this study the rheology, morphology, and interfacial interaction of polypropylene (PP)/polybutene-1 (PB-1) blends in different percentages of PB-1 are investigated. The morphology of cryo-fractured surfaces of samples was studied by scanning electron microscopy (SEM). The SEM images showed a droplet-matrix structure in all range of compositions and the size of dispersed phase increased proportionally with PB-1 content. The miscibility of blends at various compositions is evaluated by viscoelastic parameters determined by dynamic oscillation rheometry in the linear viscoelastic region. A distinct Newtonian plateau at low frequencies is observed and the variations of complex viscosity (η*) against angular frequency (ω) for all blends are in agreement with Cross model. The complex viscosity of samples at various percentages of PB-1 showed the log-additivity mixing rule behavior in low frequencies and positive-negative deviation behavior (PNDB) at high shear rates. The phenomena such as decrease in the sensitivity of storage modulus to shear rate in the terminal region, the deviation of Cole–Cole plots from the semi-circular shape, and the tail in relaxation spectrums at high relaxation times are the evidences of two phase heterogenous morphology. The effect of time–temperature on the phase behavior is studied and the interfacial tension between matrix and dispersed phase was evaluated by using emulsion theoretical models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of temperature on the interfacial tension of polycarbonate/polyethylene blends

Controlling interfacial tension during the processing of blends is critical to developing morphologies that will yield consistent and acceptable mechanical properties. Determination of the interfacial tension is important in developing a predictive understanding of the effects of processing conditions on the morphology and the physical properties of multicomponent systems. The focus of the research reported herein was to investigate the temperature dependence of the interfacial tension for blends composed of polycarbonate (PC) and polyethylene (PE). The effects of temperature were characterized by direct measurements of the interfacial tension using the imbedded fiber retraction (IFR) method. The interfacial tensions of PC/PE were measured at 210, 220, 230, and 240°C. The temperature dependence of the interfacial tension was found to be ?0.018 ± 0.006 dyn/cm-°C. In general, the interfacial tension, evaluated for low-viscosity simple fluids, is commonly a weak function of temperature (on the order of 0.01 dyn/cm-°C). The results found in this study are in accord with those findings.     

热致性液晶聚芳酯纤维表面的化学修饰

采用环氧氯丙烷作为处理试剂,通过傅-克化学反应来修饰热致性液晶聚芳酯(TLCP)纤维的表面,并通过傅里叶变换红外光谱仪(FTIR)、万能电子强力仪、单丝拔出试验(SFP)与扫描电子显微镜(SEM)系统研究了化学修饰对纤维表面的化学结构、纤维力学性能、复合材料的界面剪切强度及纤维的表面形态的影响。研究结果表明:通过傅-克化学反应修饰TLCP纤维的表面,可以有效地提高TLCP单纤维-环氧树脂复合材料的界面剪切强度,相对于未修饰的纤维约提高了52%,表面化学修饰的最佳反应时间为40 min。此外,经修饰的TLCP单纤维表面没有明显的刻蚀或受损现象,且纤维的力学性能不会受到明显影响。傅-克化学反应修饰TLCP纤维可有效提高TLCP纤维-环氧树脂复合材料的界面性能。     

Determination of interfacial tension between PA/PP and LCP/PP by IFR method and effect of compatibilization on interfacial tension

The dynamic imbedded fiber retraction (IFR) method was used to measure the interfacial tension between two molten polymers. The aim was to evaluate the applicability of this method for polypropylene (PP) used as matrix, and two polyamide (PA6, PA66) and thermotropic main-chain liquid crystalline polymer fibers. The effect on the interfacial properties of modifying the PP matrix with compatibilizers was studied as well. The IFR method was found to be suitable for evaluating the interfacial properties of these polymer blends. The measured interfacial tensions correlated well with the morphology and mechanical properties of the blends and values calculated from the harmonic mean equation. Although the measured interfacial tensions were generally lower than the theoretical ones, the order of the values for the different polymer pairs was similar. © 1995 John Wiley & Sons, Inc.     

Interfacial slip‐stick transition induced by reactive compatibilization in ethylene‐co‐butyl acrylate elastomer dispersed polyamide 6 blend subjected to high shear flow and extensional flow

The effect of phase interaction induced by reactive compatibilization during high shear and extensional flow in polyamide (PA6) and ethylene‐co‐butyl acrylate (EBA) blends was studied using advanced dual bore capillary rheometer. The viscosity‐composition behavior of the uncompatibilized PA6/EBA blends exhibited negative deviation behavior from log‐additivity rule. The interfacial slip mechanism, operative between the matrix PA6 and dispersed EBA during shear flow was studied by the use of Lin's and Bousmina‐Palierne‐Utracki (BPU) model for viscosity for the blends under the processing conditions. On the other hand, the compatibilized PA6/EBA‐g‐MAH^0.49/EBA blends with varying dispersed phase volume fraction show positive deviation behavior. The reactive compatibilizers EBA‐g‐MAH^0.49 and EBA‐g‐MAH^0.96 increased the phase interaction with adequate reduction in the dynamic interfacial tension, which favored the particle break‐up and stabilized the morphology in the compatibilized blends. The extensional viscosity of the blends has enhanced because of the inclusion of EBA in all the uncompatibilized and compatibilized blends. The melt elasticity and elasticity function were systematically studied from first normal stress coefficient functions (ψ₁). The variation in the recoverable shear strain (γ_R), shear rate dependent relaxation time (λ) and shear compliance (J_c) under various shear rates were thoroughly analyzed for all the blend compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Compatibilizers for thermotropic liquid crystalline polymer/polyethylene blends prepared by reactive mixing

This paper describes the effects of composition and processing conditions on the efficiency of the compatibilizer prepared from a thermotropic liquid crystalline polymer (TLCP) and the sodium salt of a poly(ethylene‐co‐r‐acrylic acid) ionomer (EAA‐Na) in TLCP/low‐density polyethylene (LDPE) blends and TLCP/high‐density polyethylene (HDPE) blends. The TLCP‐ionomer graft copolymer formed by a melt acidolysis reaction effectively reduced the interfacial tension between TLCP and polyethylene, which improved impact strength and toughness of the compatibilized blends. Higher processing temperatures for the reactive extrusion produced a more efficient compatibilizer, presumably due to increased graft‐copolymer formation, but the reaction temperature had little effect on the impact strength of compatibilized blends for temperatures above 300°C. The addition of the compatibilizer to TLCP/LDPE blends significantly increased the melt viscosity due to increased interfacial adhesion. The TLCP/EAA‐Na ratio used to prepare the compatibilizer had little effect on the performance of the compatibilizer. Although the compatibilizer can be prepared in situ by blending and extruding a ternary blend of TLCP/EAA‐Na/polyethylene, pre‐reacting the compatibilizer resulted in blends with improved toughness and elongation.     

Shear-induced interactions in blends of HMMPE containing a small amount of thermotropic copolyester HBA/HQ/SA

Shear-induced interactions between high molecular mass polyethylene (HMMPE) melt and a thermotropic liquid crystalline copolyester, HBA/HQ/SA (TLCP) were investigated using large amplitude oscillatory shear and capillary shear. Polarized optical microscopy (POM) observations show that the mono-domain nematic TLCP droplets embedded inside a HMMPE melt may be readily elongated using large amplitude oscillatory shear. The HMMPE melt adjacent to the elongated TLCP filament was observed to crystallize faster than that in the matrix away from the interface. TEM analysis on the 1 wt% TLCP/HMMPE blend quenched after capillary shear shows that there are strong interfacial interactions between the elongated TLCP filament and the HMMPE matrix. Long range PE lamellae orientational order up to 2 μm away from the TLCP filament surface were observed, with all the lamellae surface normal parallel to the TLCP fiber. Additionally, a strong interfacial compatibility between the TLCP filament and the HMMPE matrix with an interfacial thickness of ∼30 nm has also been observed. The enhanced interfacial compatibility is attributed to the -CH₂- group interactions due to chain alignment in both components at their interface. These results provide a fundamental insight to other TLCP containing thermoplastics where compatibilities may be present due to segmental interactions.     

Three-dimensional phase morphologies in HDPE/EVA blends obtained via dynamic injection packing molding

The formation of phase morphology of injection molded HDPE/EVA blends, under the effect of shear stress, has been investigated in detail. The shear stress was induced by dynamic packing injection molding, by which a specimen is forced to move repeatedly in the model by two pistons that move reversibly with the same frequency during cooling. Two kinds of EVA with VA content 16 wt% (16EVA) and 33 wt% (33EVA) were used to investigate the effect of interfacial tension. The phase morphology was viewed both parallel and perpendicular to the shear flow direction, so one can get an overall three-dimensional phase morphology. Low shear stress provided by the pistons has a substantial effect on the phase morphology along the flow direction but is insignificant in the direction perpendicular to the flow direction. Generally, a much elongated and layer-like structure is formed along the flow direction, and spherical droplet-like morphology is formed perpendicular to the flow direction, and the degree of deformation of rubber particles also depends upon their size and elasticity as well as on the interfacial properties between matrix and dispersed phase. For static samples of HDPE/16EVA blends (without shearing), only droplet morphology is formed as 16EVA content increases from10 to 40 wt%. However, under the effect of shear stress (dynamic samples), both droplet and cylinder morphologies can be formed depending on the volume ratio. For static samples of HDPE/33EVA blends, not only droplet, but also cylinder and co-continuous morphology (perpendicular to flow direction) can be formed depending on the volume ratio. For dynamic samples of HDPE/33EVA blends, droplet, cylinder and co-continuous network (co-continuous in both parallel and perpendicular to flow direction) can be formed under the effect of shear stress. The formation of phase morphology is discussed based on interfacial interaction, viscosity ratio, shear stress, and phase inversion.     

Self‐reinforcing elastomer composites based on polyolefinic thermoplastic elastomer and thermotropic liquid crystalline polymer

In situ reinforcing elastomer composites based on Santoprene thermoplastic elastomer, a polymerized polyolefin compound of ethylene–propylene–diene monomer/polypropylene, and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a single‐screw extruder. The rheological behavior, morphology, mechanical, and thermal properties of the blends containing various LC3000 contents were investigated. All neat components and their blends exhibited shear thinning behavior. With increasing TLCP content, processability became easier because of the decrease in melt viscosity of the blends. Despite the viscosity ratio of dispersed phase to the matrix phase for the blend system is lower than 0.14, most of TLCP domains in the blends containing 5–10 wt % LC3000 appeared as droplets. At 20 wt % LC3000 or more, the domain size of TLCP became larger because of the coalescence of liquid TLCP threads that occurred during extrusion. The addition of LC3000 into the elastomer matrix enhanced the initial tensile modulus considerably whereas the extensibility of the blends remarkably decreased with addition of high TLCP level (>.20 wt %). The incorporation of LC3000 into Santoprene slightly improved the thermal resistance both in nitrogen and in air. Dynamic mechanical analysis results clearly showed an enhancement in dynamic moduli for the blends with 20–30 wt % LC3000. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of composition on the linear viscoelastic behavior and morphology of PP/HDPE blends

In this paper the influence of temperature and composition on the dynamic behavior and morphology of polypropylene (PP)/high-density polyethylene (HDPE) blends were studied. The blend composition ranged from 5 to 30 wt% of dispersed phase (HDPE) and the temperatures ranged from 180 to 220 °C. The interfacial tension between PP and HDPE at temperatures of 180, 200 and 220 °C was obtained from fitting Palierne's emulsion model [1] to the experimental data of PP/HDPE blends with different compositions and from the weighted relaxation spectra of PP/HDPE blends with different compositions, following Gramespacher and Meissner [2] analysis. The interfacial tension between PP and HDPE as inferred from the rheological measurements was shown to depend on PP/HDPE blend composition. However, the results indicated that there is a range of PP/HDPE blend composition for which interfacial tension between PP and HDPE is constant. Considering these values, it was shown that interfacial tension between PP and HDPE decreases linearly with increasing temperature.