Melt extrudate swell behavior of graphene nano-platelets filled-polypropylene composites

The extrudate swell ratios of polypropylene (PP) composite melts filled with graphene nano-platelets (GNPs) were measured using a capillary rheometer within a temperature range of 180–230 °C and apparent shear rate varying from 100 to 4000 s⁻¹ in order to identify the effects of the filler content and test conditions on the melt die-swell behavior. It was found that the values of the extrudate swell ratio of the composites increased with increasing apparent shear rate, with the correlation between them obeying a power law relationship, while the values of the extrudate swell ratio decreased almost linearly with rise in temperature. The values of the melt extrudate swell ratio increased approximately linearly with increasing shear stress, and decreased roughly linearly with an increase of the GNP weight fraction. In addition, the extrudate swell mechanisms are discussed from the observation of the fracture surface of the extrudate using scanning electronic microscopy. This study provides a basis for further development of graphene reinforced polymer composites with desirable mechanical performance and good damage resistance.     

Semicrystalline blends of polyethylene and isotactic polypropylene: Improving mechanical performance by enhancing the interfacial structure

The low‐temperature mechanical behavior of semicrystalline polymer blends is investigated. Isotactic polypropylene (iPP) is blended with both Zeigler–Natta polyethylene (PE) and metallocene PE. Transmission electron microscopy (TEM) on failed tensile bars reveals that the predominate failure mode in the Zeigler–Natta blend is interfacial, while that in the metallocene blend is failure of the iPP matrix. The observed change in failure mode is accompanied by a 40% increase in both tensile toughness and elongation at −10 °C. We argue that crystallite anchoring of interfacially entangled chains is responsible for this dramatic property improvement in the metallocene blend. The interfacial width between PE and iPP melts is approximately 40 Å, allowing significant interfacial entanglement in both blends. TEM micrographs illustrate that the segregation of low molecular weight amorphous material in the Zeigler–Natta blend reduces the number and quality of crystallite anchors as compared with the metallocene blend. The contribution of anchored interfacial structure was further explored by introducing a block copolymer at the PE/iPP interface in the metallocene blend. Small‐angle X‐ray scattering (SAXS) experiments show the block copolymer dilutes the number of crystalline anchors, decoupling the interface. Increasing the interfacial coverage of the block copolymer reduces the number of anchored interfacial chains. At 2% block copolymer loading, the low‐temperature failure mode of the metallocene blend changes from iPP failure to interfacial failure, reducing the blend toughness and elongation to that of the Zeigler–Natta blend. This work demonstrates that anchored interfacial entanglements are a critical factor in designing semicrystalline blends with improved low‐temperature properties. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 108–121, 2000     

What is the role of the interfacial interaction in the slow relaxation of nanometer-thick polymer melts on a solid surface?

At the nanoscale and interfaces, the relaxation behavior of polymer melts, which affects the polymer's long-term performance in many important applications, is very different from that in the bulk. The role of polymer-substrate interfacial interaction, which does not have a bulk counterpart, has not been fully understood to date. In this study, the relaxation of nanometer-thick perfluoropolyether melts on a silicon wafer has been investigated by water contact angle measurement. The polymer-substrate interactions have been systematically changed by tailoring the polymer structure to clarify the effect of the interfacial interaction. The experimental results show that (1) when there is attractive interaction at the interface, some polymers are anchored to the substrate and others are free, (2) the attractive interfacial interaction drives the free polymers to relax at the interface, and (3) the relaxation is much slower than in the bulk, which has been attributed to the low mobility of the anchored polymer chains and the motional cooperativity between anchored and free polymer chains in the nanometer-thick films.     

Interfacial Properties of Asymmetric Polymer Mixtures

Using a Monte‐Carlo simulation of a continuous space Rod Bead Model the interface properties of systems of flexible polymer chains with different sizes of monomers are investigated. An immiscible polymer blend in the strong segregation state is modeled by a double sandwich system of chains differing by an factor of two in the size of the beads and the interfacial tension is calculated by a virial theorem method. The simulation data are compared to self‐consistent mean field and experimental data. The results show that the simulation data agree very satisfactory with mean‐field results. The interfacial tension decreases for asymmetric systems in comparison to symmetric systems with comparable volume contents of monomers and interaction strengths due to a decrease of the effective interaction. The parameters of the investigated systems are close to the properties of PS, PMMA and PI melts. A comparison with experimental results yields a very good agreement with data for PS/PMMA and less satisfactory for PS/PI. Additionally to the interfacial tension we have studied the interfacial width, the deformation of polymer chains near the interface, distributions of chain ends, monomer densities and distributions of centers of mass of chains.

Snapshot of a typical configuration for chains with different monomer sizes and equal number of monomers per chain.     

线型与支化聚烯烃熔体高速挤出时的不稳定扰动源

采用恒速型双毛细管流变仪对比研究线型与支化聚烯烃熔体在高速流场中的流动曲线、挤出畸变、挤出压力变化及粘弹性的特征,分析讨论了引发熔体不稳定流动的扰动源位置及扰动性质.结果表明,高速流场中的扰动源有:口模入口区的扰动、口模壁处的扰动、口模出口区的扰动.支化聚合物易受入口区的扰动干扰,造成挤出物无规破裂;线型聚合物易受口模壁处的扰动干扰,造成挤出压力振荡和挤出物有规畸变;鲨鱼皮畸变主要由于口模出口区的振荡扰动造成.     

Interfacial properties of compressible polymer solutions

A chemomechanical model for the interfacial concentration and density in compressible polymer solutions is formulated using variational principles. The nonlinear model with boundary conditions obtained from phase equilibrium calculations gives the coupled concentration and density profiles. The couplings between chemical and mechanical balances are identified and efficient ways to calculate the interfacial structure is identified. A specific model appropriate to high‐pressure processing of the polyolefins is developed using the modified Sanchez Lacombe equation of state. Bakker's formula for the interfacial tension is adapted to compressible polymer solutions. The structure and tension of a flat interface is characterized using the developed model and material properties of three molecular weight hydrogenated polybutadiene; the main variables of interest were the pressure, polymer molecular weight, and temperature. The relation between the pressure profile across the interface and the interfacial tension is characterized. Scaling power laws for interfacial tension and interfacial thickness as a function of pressure are obtained and contrasted with the corresponding laws observed and predicted for incompressible polymer solutions. It is found that the modified Sanchez Lacombe‐based power law prediction predictions for compressible solutions in terms of pressure quenches are similar to those from those obtained by the Flory‐Huggins incompressible model for temperature quenches. The present results provide the basis for the future study of the kinetics of pressure‐induced phase separation in compressible polymer solutions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 640–654, 2009     

Charge transport in melt-dispersed carbon nanotubes

We investigate the effect of interfacial stabilizer on charge transport in polymer-dispersed carbon nanotubes. Despite mechanical contact, samples with dispersant show poor conductivity, which we attribute to a robust interfacial layer between contacted nanotubes. In comparison, results obtained when nanotubes are mechanically mixed into polymer melts without dispersant show much better conductivity. The difference is striking; at comparable loading, neat melt composites have resistivities five orders of magnitude smaller than those containing interfacial stabilizer. Our results highlight a fundamental issue for the engineering of conducting carbon nanotube composites; dispersion stability will typically be achieved at the expense of conductivity.     

Effect of polymer surface morphology on adhesion and adhesive joint strength. II. FEP Teflon and nylon 6

Heterogeneous nucleation and crystallization of FEP Teflon and nylon 6 melts against high energy surfaces (i.e., gold) produce an interfacial region, in these polymers, of high mechanical strength. Dissolution of the metal substrate rather than removal by mechanical means results in a polymer surface which is amenable to conventional structural adhesive bonding. Nucleation and crystallization of the polymer melts in contact with phases of low surface energy (e.g., vapor) result in the generation of weak boundary layers.     

聚合物熔体界面扩散理论与研究方法

本文结合与聚合物加工过程密切相关的界面扩散问题,从动力学和热力学两方面综述了与聚合物界面互扩散相关的基础理论.结合在聚合物界面扩散方面的研究进展,系统介绍了聚合物熔体界面扩散的常用研究方法.对其中的流变学方法的原理及进展作了重点论述,该方法不仅可以有效表征聚合物熔体界面扩散的动力学过程,进一步从分子动力学角度发展并完善聚合物扩散理论,而且对于聚合物加工成型过程的界面结构设计和性能优化起到关键的指导作用.本文最后提出了聚合物熔体界面扩散研究中存在的问题并对其前景进行了展望.     

Welding immiscible polymers with a supercritical fluid

Polymer adhesion between two immiscible polymers is usually poor because there is little interpenetration of one polymer into the other at the interface. Increasing the width of the interfacial zone can enhance adhesion and mechanical properties. In principle, this can be accomplished by exposing heterogeneous polymer materials to a high-pressure fluid. The fluid can act as a common solvent and promote interpenetration. It also increases chain mobility at the interface, which helps to promote "welding" of the two polymers. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state was used to investigate this phenomenon, especially the effect of the high compressibility of supercritical (SC) fluid on the compatibilization of two incompatible polymers. We calculate the interfacial density profile, interfacial thickness, and interfacial tension between the two polymers with and without the SC fluid. We find that the interfacial tension is decreased and the interfacial thickness is increased with high-pressure SC fluid for the ternary systems we have investigated. As the critical point is approached and the SC compressibility becomes large, no enhancement or deleterious effects on compatibilization were observed.     

Role of the interface in multicomponent materials

Studies of the relationship between interfacial structure and mechanical properties in multicomponent materials are reviewed in this article. The following categories are considered for role of the interface in multicomponent systems: Interpenetrating polymer network(IPN), catalytic effect of silane coupling agent, morphological differences of filler surface, particle-particle interaction and particle size of the filler. The interfacial role in terms of the reinforcement mechanism of the composite and the behavior in the melt state is also discussed in the multicomponent system.     

Relations entre les caracteristiques physico-chimiques des charges et les proprietes mecaniques des polymeres (PVC) plastifies et charges

Some rheological and mechanical properties of polyvinyl chloride filled with up to 80 phr CaCO₃ have been evaluated with a view to rationalizing results in terms of polymer/filler interfacial interactions. These interactions have been characterized by inverse chromatography using a series of acid-base vapour probes selected from literature classifications. Both pure and industrially pretreated CaCO₃ samples were employed; in addition, one of the pure materials was surface-modified by exposure to selected vapours in a microwave plasma apparatus. Though the data are not adequate to develop exact correlations linking interaction parameters and the physical properties of the filled systems, it is clear that favourable interaction (wetting, adhesion) states at the polymer-filler interface promote ease of dispersion of solids in the molten polymer, enhance mechanical properties (such as elongation at break and the yield stress in the stress/strain curve of the materials) and reduce the rates at which these properties deteriorate when compounds are exposed to weathering. This preliminary work therefore confirms the apparent importance of interfacial effects to property development in filled polymers, suggests the usefulness of acid-base concepts as an index of these effects, and shows inverse chromatography data to be convenient for their quantification. Plasma treatment appears to be a particularly flexible approach to the tailoring of diverse surface properties in filler particles. Detailed development of the various concepts is indicated.     

On modifying properties of polymeric melts by nanoscopic particles

We study geometric and energetic factors that partake in modifying properties of polymeric melts via inserting well‐dispersed nanoscopic particles (NP). Model systems are cis‐1,4‐polybutadiene melts including a single atomic clusters of size varied in the range 10–150 atoms (3–7 Å in radius; 0.1–1.5% v/v). We modify the interactions between the chains and the particle by tuning attractive van der Waals interactions. Using molecular dynamics, we study equilibrium fluctuations and dynamical properties at the interface. The NPs move in the polymer matrix in two different regimes corresponding to trapped and free diffusion, depending on the NP size. Furthermore, degree of crowding around the NP by the polymer chains is quantified. Effect of NP size and interaction strength both on volume and volumetric fluctuations is manifested in mechanical properties, quantified here by bulk modulus, K. Tuning NP size and nonbonded interactions results in ～15% enhancement in K by addition of a maximum of 1.5% v/v NP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Interactions between Hydrophobically Modified Associating Polyacrylamide and Cationic Surfactant at the Water‐Octane Interface: Interfacial Dilational Viscoelasticity and Relaxation Processes

The interfacial dilational viscoelastic properties of hydrophobically associating block copolymer composed of acrylamide (AM) and a low amount of 2‐ethylhexyl acrylate (EHA) (<1.0 mol%) with a hydrolyzed degree of about 1.5–2.0% at the octane‐water interfaces were investigated by means of two methods: the interfacial tension response to sinusoidal area variations (oscillating barriers method) and the relaxation of an applied stress (interfacial tension relaxation method) respectively. The influence of cationic surfactant cetyl trimethylammonium bromide (CTAB) on the dilational viscoelastic properties was studied. The results obtained by oscillating barriers method showed that dilational modulus decreased moderately with the increase of CTAB concentration. The results obtained by interfacial tension relaxation measurements showed that two main relaxation processes exist in the interface at 7,000 ppm polymer concentration: one is the fast process involving the exchange of hydrophobic blocks between the proximal region and distal region in the interface; the other is the slow relaxation process involving conformational changes of polymer chain in the interface. By adding CTAB, the slow process changed obviously due to the strong electrostatic interaction between oppositely charged surfactant and hydrolyzed part of polymer chain. Only when the CTAB concentration was close to the “equal charge point,” the associations formed mainly by the hydrophobic interaction like that in SDS/polymer system appeared and the characteristic time of fast process decreased obviously. The information of relaxation processes obtained from interfacial tension relaxation measurements can explain the results from dilational viscoelasticity measurements very well.     

Rheological properties and the interface in polycarbonate/impact modifier blends: Effect of modifier shell molecular weight

Core-shell impact modifiers are used to enhance the impact strength of thermoplastics such as polycarbonate. The shell of the modifier is designed specifically to interact with the matrix polymer because interfacial adhesion between the modifier and matrix is important in improving the impact strength. Several methods have been proposed to study the interactions at the modifier/matrix interface. One measure of this interaction is the strength of lap joints. The degree of interactions at the interface can be characterized as the thickness of the interfacial region where the chains of the two polymers mix. Yet another aspect is related to the effect of interfacial interactions on the dynamic mechanical properties of the blend. Previous studies have shown that the viscoelastic properties of these blends deviate from the emulsion models that have been proposed for such blends. The deviation of the measured viscoelastic behavior of these blends compared to that predicted by the models has been attributed to the formation of network structure of particles in the blend. The formation of the network structure is a consequence of larger effective volumes of the particles due to interactions at the interface with the matrix. This study provides a means of using rheological properties and the emulsion models to estimate the extent of interaction at the modifier/matrix interface. In blends used in this study it can be shown that the interactions between the modifier and matrix extend far beyond the boundary between the two and the estimated effective volume fraction of modifier is much larger than the actual modifier content in the blend. The effective volume fraction is frequency dependent and decreases with increasing frequency. The data suggest that beyond certain frequencies the modifier no longer interacts with the matrix and the system has properties similar to the matrix with holes. The data are presented which indicate that, within the range studied, lower modifier shell molecular weight results in a higher level of interaction with polycarbonate. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1095–1105, 1998     

线型聚乙烯及其共聚物的挤出畸变与熔体粘弹性的关系

采用恒速型双筒毛细管流变仪研究了一类线型聚乙烯熔体的挤出畸变与熔体非线性粘弹性的关系。实验研究了发生畸变时挤出压力的振荡规律,发现线型大分子或带小侧基的大分子熔体,容易发生壁滑和挤出压力振荡;而有较大侧基、或分子量分布宽、或带大量短支链的熔体,挤出畸变现象较轻。挤出畸变与熔体的弹性及熔体．壁面吸附状态紧密相关。容易发生壁滑和挤出压力振荡的熔体,弹性较大(入口压力降大);在壁面的吸附作用强(壁面临界剪切应力大)。稳态剪切粘度大小与挤出畸变和压力振荡的关系不大;而拉伸应力和拉伸粘度大的熔体较易发生壁滑和挤出压力振荡。     

Viscoelastic interfacial properties of compatibilized poly(ε‐caprolactone)/polylactide blend

Poly(ε‐caprolactone)/polylactide blend (PCL/PLA) is an interesting biomaterial because the two component polymers show good complementarity in their physical properties. However, PCL and PLA are incompatible thermodynamically and hence the interfacial properties act as the important roles controlling the final properties of their blends. Thus, in this work, the PCL/PLA blends were prepared by melt mixing using the block copolymers as compatibilizer for the studies of interfacial properties. Several rheological methods and viscoelastic models were used to establish the relations between improved phase morphologies and interfacial properties. The results show that the interfacial behaviors of the PCL/PLA blends highly depend on the interface‐located copolymers. The presence of copolymers reduces the interfacial tension and emulsified the phase interface, leading to stabilization of the interface and retarding both the shape relaxation and the elastic interface relaxation. As a result, besides the relaxation of matrices (τ_m) and the shape relaxation of the dispersed PLA phase (τ_F), a new relaxation behavior (τ_β), which is attribute to the relaxation of Marangoni stresses tangential to the interface between dispersed PLA phase and matrix PCL, is observed on the compatibilized blends. In contrast to that of the diblock copolymers, the triblock copolymers show higher emulsifying level. However, both can improve the overall interfacial properties and enhance the mechanical strength of the PCL/PLA blends as a result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 756–765, 2010     

粒子-聚合物相互作用与粒子-粒子相互作用对聚合物基纳米复合物力学性能的影响

聚合物基纳米复合物(PNCs)具有比传统高分子材料更加优异的光学、力学、热力学等性能,广泛应用于各个工程领域.而纳米粒子(NPs)对材料性能提高的机理则是当前聚合物纳米复合物领域研究的重要问题,聚合物纳米复合体系相互作用的影响因素众多,至今尚未明确并完整建立复合体系相互作用与性能增强之间的关系.本文总结了近年来关于纳米粒子填充聚合物基体力学性能的研究,从粒子-聚合物相互作用和粒子-粒子相互作用角度阐述了聚合物纳米复合体系力学性能的增强机理,并根据体系中不同的结构关系分别总结了聚合物/未改性纳米粒子复合体系和聚合物/聚合物接枝纳米粒子复合体系中影响力学性能的因素.该部分内容具有重要的理论和实践意义,有助于构建复合体系微观结构与宏观性能之间的关系,进而对微观层面调控PNCs的力学性能提供指导.     

聚合物熔体挤出胀大的三维数值模拟

采用粘弹性PTT模型对聚合物熔体的矩形口模挤出胀大进行了三维等温数值模拟,得出了不同条件下的口模外流动速度和挤出胀大率沿挤出方向的分布规律.模拟时利用罚函数有限元法和把动量方程转化成椭圆类方程的去耦算法以降低模拟对计算机内存的要求和增加计算收敛的稳定性,采用用路线法对挤出胀大自由表面进行更新迭代.模拟结果表明:We数越大,则挤出胀大率越大,而且对于矩形口模挤出而言,高度方向的挤出胀大率比宽度方向的挤出胀大率大.     

Macromolecules at surfaces: Research challenges and opportunities from tribology to biology

A comprehensive review of ongoing and recommended research directions concerning the structure, dynamics, and interfacial activity of synthetic and naturally occurring macromolecules at the solid–liquid interface is presented. Many new developments stem from the ability to target new size regimes of 1–100 nm. These rapid developments are reviewed critically with respect to chemical synthesis, processing, structural characterization, dynamic processes, and theoretical and computational analysis. The common problems shared by flat and particulate surfaces are emphasized. A broad spectrum of material properties are discussed, from the control of interfacial friction between surfaces in moving contact, to the mechanical strength and durability of the interfaces in hybrid materials, to optical and electronic properties. Future research opportunities are identified that involve (1) the emergence of nanoscale material properties, (2) polymer‐assisted nanostructures, and (3) the crossroads between interfacial science and biological and bioinspired applications. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2755–2793, 2003