振动剪切作用下聚合物熔体的非仿射网络结构模型 Ⅱ．非仿射网络结构模型

假设聚合物熔体的缠结网络形变是非仿射的，运用瞬态网络结构原理，采用在本课题第一部分^[1]中所建立的动态速率方程，并对上随体Maxwell本构方程加以修正来建立一个非仿射网络结构模型，利用这一模型来研究振动剪切作用下LDPE熔体的流变行为，研究表明，随着应变振幅和频率的增加，LDPE熔体的剪切应力也增加，同时指出了非仿射网络结构模型的精确变比仿射结构模型有较大提高，这表明在振动力场作用下，网络形变发生了非仿射形变，因此在建立振动力场作用下聚烯烃熔体本构方程时，不能假设其网络是仿射形变的。     

注射成型中模腔内振动剪切流动的理论模型

采用Ｌｅｏｎｏｖ本构模型,首次研究了在注射成型中模腔内聚合物熔体的振动剪切流动时所产生的振动剪切应力。结果表明,振动剪切应力的振幅随着聚合物熔体的粘度,振动频率和应变振幅的增加而增加,随着熔体温度的增加而减小。     

A sliding plate normal thrust rheometer for molten plastics

A sliding plate rheometer has been developed to measure the normal thrust of a molten plastic in large amplitude oscillatory shear. The normal thrust of a molten plastic in large amplitude oscillatory shear is a significant nonlinear effect that has previously been unobtainable. Normal thrust measurements may now be used to help understand and characterize nonlinear viscoelastic behavior inherent in most molten plastics. The new rhemoeter incorporates a piezoelectric pressure transducer in a very stiff plate that minimizes compliance. Normal thrust measurements with cone and plate rheometers are made by measuring the total force on the plate (or cone) and are subject to error due to edge effects. The new rheometer measures the local pressure in the sample and is therefore unaffected by sample size or edge effects. Normal thrust measurements in large amplitude oscillatory shear are reported for both molten Phillips TR480 high density polyethylene pipe resin which contains 2% by weight of carbon black filler and IUPAC LDPE X. Crosstalk due to shear stress on the active face of the pressure transducer causes signal error which for oscillatory shear is filtered out using a discrete Fourier transform.     

Phase behaviors of diblock copolymer/nanorod composites under oscillatory shear flow

The phase behaviors of lamellar diblock copolymers (DBCPs) melts and lamellar DBCPs/nanorods (NRs) composites subjected to oscillatory shear flow, have been investigated using dissipative particle dynamics. The oscillatory shear is a quite common shearing mode used in experiments and manufacturing processes. The rich lamellar (LAM) reorientation and morphological transition of systems strongly depend on the shear amplitude and shear frequency. At very low frequency, the amplitude‐induced phase behaviors of DBCPs melts or DBCPs/NRs composites are quite similar to those subjected to a steady shear. For DBCPs/NRs case, we control NRs concentration low 15% to preserve LAM morphology in the nanocomposites, and simultaneously consider both types of selective and nonselective NRs. Our aim is to compare the different inductions on DBCPs melts or nanocomposites caused by shear amplitude and frequency, and observe how the NRs are oriented and dispersed in phase‐separated copolymers matrix while under oscillatory shear, and how the presence of selective/nonselective NRs affects the shear‐induced LAM reorientations and rheological properties of systems. Our results show the NRs orientation not only directly depend on the imposed shear flow but also is interfered by the alignment of shear‐stretched copolymer molecules. The shear viscosity decreases with the frequency decreases, also influenced by the NRs concentration and surface property. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A review of nonlinear oscillatory shear tests: Analysis and application of large amplitude oscillatory shear (LAOS)

Dynamic oscillatory shear tests are common in rheology and have been used to investigate a wide range of soft matter and complex fluids including polymer melts and solutions, block copolymers, biological macromolecules, polyelectrolytes, surfactants, suspensions, emulsions and beyond. More specifically, small amplitude oscillatory shear (SAOS) tests have become the canonical method for probing the linear viscoelastic properties of these complex fluids because of the firm theoretical background [1], [2], [3] and [4] and the ease of implementing suitable test protocols. However, in most processing operations the deformations can be large and rapid: it is therefore the nonlinear material properties that control the system response. A full sample characterization thus requires well-defined nonlinear test protocols. Consequently there has been a recent renewal of interest in exploiting large amplitude oscillatory shear (LAOS) tests to investigate and quantify the nonlinear viscoelastic behavior of complex fluids. In terms of the experimental input, both LAOS and SAOS require the user to select appropriate ranges of strain amplitude (γ₀) and frequency (ω). However, there is a distinct difference in the analysis of experimental output, i.e. the material response. At sufficiently large strain amplitude, the material response will become nonlinear in LAOS tests and the familiar material functions used to quantify the linear behavior in SAOS tests are no longer sufficient. For example, the definitions of the linear viscoelastic moduli G′(ω) and G″(ω) are based inherently on the assumption that the stress response is purely sinusoidal (linear). However, a nonlinear stress response is not a perfect sinusoid and therefore the viscoelastic moduli are not uniquely defined; other methods are needed for quantifying the nonlinear material response under LAOS deformation. In the present review article, we first summarize the typical nonlinear responses observed with complex fluids under LAOS deformations. We then introduce and critically compare several methods that quantify the nonlinear oscillatory stress response. We illustrate the utility and sensitivity of these protocols by investigating the nonlinear response of various complex fluids over a wide range of frequency and amplitude of deformation, and show that LAOS characterization is a rigorous test for rheological models and advanced quality control.     

Effects of small‐amplitude oscillatory shear on polymeric reaction

The effects of small‐amplitude oscillatory shear on the polymeric reaction between poly(butylene terephthalate) (PBT) and epoxy in melts were studied. Two kinds of samples, sandwich sample and blending sample, were prepared for reaction kinetics by using a new rheological method which correlates the change of the rheological property of reactive system with the conversion of the in situ formed copolymers. The results indicated that the reaction between PBT and epoxy was hardly affected by the small‐amplitude oscillatory shear. The increase of apparent reaction rate in sandwich sample was due to the increase of molecular diffusion by oscillatory shear. POLYM. COMPOS., 29:72–76, 2008. © 2007 Society of Plastics Engineers     

小振幅振荡剪切法测量PP/(E/VAC)共混物的界面张力

借助于动态流变学中小振幅振荡剪切法测得聚丙烯(PP)与两种不同牌号(乙烯/乙酸乙烯酯)共聚物(E/VAC)共混物的动态模量,通过扫描电子显微镜对共混物中分散相粒径及分布进行表征,将实际测得的共混物动态模量与用Palierne乳液模型计算得到的共混物动态模量进行数据拟合,得到PP与两种不同牌号E/VAC共混物的界面张力分别为0.44 mN/m和1.39 mN/m。     

Effect of large amplitude oscillatory shear (LAOS) on the dielectric response of 1,4-cis-polyisoprene

The dielectric response of 1,4-cis-polyisoprene under applied mechanical oscillatory shear with various shear amplitudes was investigated. For this purpose, a special setup was constructed which enables to measure dielectric spectra under the influence of large amplitude oscillatory shear (LAOS); the setup is explained in detail. A strong influence of the shear amplitude on the dielectric relaxation strength was observed if the dielectric normal mode was mechanically affected. With increasing amplitude the relaxation strength decreased while the mean relaxation time, the width and asymmetry basically remained unchanged. We interpret this process as an orientational phenomenon of the end-to-end-vectors which results in a decreasing fluctuation amplitude of the polarization fluctuations.     

High shear strain rate rheometry of polymer melts

The rheology of a range of polymer melts has been measured at strain rates above those attained during conventional rheometry using an instrumented injection molding machine. Deviations from shear thinning behavior were observed at high rates, and previously unreported shear thickening behavior occurred for some of the polymers examined. Measured pressure and volumetric throughputs were used to calculate shear and extensional viscosity at wall shear strain rates up to 10⁷ s^?1. Parallel plate rheometry and twin bore capillary rheometry were used to provide comparative rheological data at low and medium shear strain rates, respectively. Commercial grades of polyethylene, polypropylene, polystyrene, and PMMA were studied. Measured shear viscosity was found to follow Newtonian behavior at low rates and shear thinning power law behavior at intermediate strain rates. At shear strain rates approaching or above 10⁶ s^?1, shear viscosity reached a rate‐independent plateau, and in some cases shear thickened with further increase in strain rate. A relationship between the measured high strain rate rheological behavior and molecular structure was noted, with polymers containing larger side groups reaching the rate‐independent plateau at lower strain rates than those with simpler structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The rheology of filled polymers

The flow properties of polymer melts containing fillers of various shapes and sizes have been examined. If there is no failure of either the filler or polymer in the solid state, then the modulus enhancement for randomly distributed filler is equal to the melt viscosity enhancement under medium shear stress conditions (10⁴ Nm^?2) in simple shear flow or in oscillatory shear flow. Submicron-size fillers, in particular, can form weak structures in the melt that greatly increase the low shear rate viscosity without changing the modulus of the solid proportionately. The highly pseudo-plastic nature of polymer melts at shear stresses of 10⁶ Nm^?2 means that, even without orientation of filler particles toward the flow direction, the viscosity enhancement is less than at lower shear stresses.     

Rheological behavior of highly filled polymer melts

The rheological behavior of highly filled polymer melts has been examined. At concentrations near the maximum packing fraction, strain-dependent behavior was observed at strains as low as 1 percent. Selected surface treatments were shown to reduce particle agglomeration. This produced composite melts with lower viscosities and higher maximum loadings. While η* – ω plots provide information on the shear strength of the interparticle network, G′ – ω plots show evidence of phase separation.     

Using multiple‐mode models for fitting and predicting the rheological properties of polymeric melts. II. Single and double step‐strain flows

Several classes of multiple‐mode rheological constitutive equations are examined for predicting the viscoelastic flow properties of a typical polymer melt in single and double step‐strain flows. The phenomenological parameters appearing in these models have been obtained by the fitting of experimental data taken in small‐amplitude oscillatory shear and steady shear flows. The performance of the models for predicting the experimental data in the step‐strain experiments is examined in detail. Specifically, we examine whether or not mode coupling is necessary to describe the experimental behavior under step‐strain flows. Furthermore, it is demonstrated that the reversing double step‐strain experiment is a very powerful tool for testing viscoelastic constitutive equations. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Shear dependence of thermal conductivity in polyethylene melts

Thermal conductivity measurements with a modified Couette flow cell were obtained as a function of shear rate for two linear polyethylene melts of weight-average molecular weights 27,300 and 56,700, respectively. The lower-molecular-weight polyethylene revealed a maximum decrease in thermal conductivity of 55 percent at 150 s^?1. After shearing at 400 s^?1, approximately 90 minutes was required to recover the value corresponding to the zero shear condition. This was considered consistent with molecular orientation into the flow direction during shear with a subsequent relaxation upon the removal of stress. The higher-molecular-weight polyethylene gave a similar decrease in thermal conductivity at 50 s^?1. Unlike the lower-molecular-weight melt, an increase was observed at higher shear rates. Enhancement of energy transport via cluster flow mechanism was presented as a possible interpretation of these results. A theory of molecular orientation of liquid poly(dimethylsiloxane) (PDMS) under shear flow was previously developed from thermal conductivity and birefringence data of this material. An attempt to clarify the difference in behavior between the two melts examined in this work, and between the polyethylene melts and the PDMS previously studied is presented.     

Polarization-optical investigation of polymers in fluid and high-elastic states under oscillatory deformation

The relationship was investigated between birefringence and oscillatory shear deformation of linear high molecular mass polymers exemplified by narrow- and broad-distribution polybutadienes and polyisoprenes. Polymer deformation at different frequencies and amplitudes was carried out in an annular gap. The stress field uniformity was not below 95%. It was shown that in oscillatory deformation of polymers in the fluid and high-elastic states, birefringence contains a time-independent steady component and an oscillatory component with a frequency equal to that of the assigned oscillation. A linear interrelation was found to exist between the amplitude of the oscillatory component of birefringence and that of the shear stresses, with a proportionality factor equal to the stress-optical coefficient of the polymers. The phase of the oscillatory component of birefringence coincides with that of the shear stresses. Measurements of the steady component of the birefringence make it possible to find the steady component of the first normal stress difference resulting from the assignment of shear oscillations to the polymer. On the basis of the experimental data obtained for polybutadienes and polyisoprenes, and the literature data for polystyrene solutions, a master curve was constructed that generalizes the dependence of the steady component of the first normal stress difference in the linear and nonlinear deformation regimes on the product of the square of the deformation amplitude and the storage modulus measured at low amplitudes. This dependence is valid in the linear and nonlinear deformation regimes. It is invariant with frequency, amplitude deformation, molecular mass, and molecular mass distribution of the polymers. It is shown by visual observation of deformation that the abrupt drop in resistance of polymer to shear in large-amplitude deformation is due to polymer rupture near the surface of the inner cylinder and is accompanied by a slip-stick process. This is the phenomenon of spurt early observed in capillary viscometers at high shear stresses and recently investigated in coaxial cylinder devices at large amplitude deformation.     

Influence of molecular weight distribution on the elasticity and processing properties of polypropylene melts

In a study of the flow behavior of polymer melts a semi-empirical viscometric equation has been used which contains an elasticity parameter relating the shear dependence of the viscosity to the normal-stress effect. The way in which both these effects are influenced by the molecular weight distribution of the polymers investigated is shown, and the influence of melt elasticity on polymer processing behavior is discussed. From previously published viscosity data the elasticity parameter has been determined for a number of polypropylene grades, and the possibility of classifying these grades according to a characteristic time constant is indicated.     

不同代数端羟基超支化聚酯及其二元共混物的流变行为

系统研究了消除热历史后的G1~G5端羟基超支化聚酯熔体及组分质量比为1∶1的二元共混物的流变行为。结果表明,无论是稳态剪切测试还是振荡测试,消除热历史后的G2~G5端羟基超支化聚酯熔体均表现为牛顿流体的流变行为。G3~G5端羟基超支化聚酯的流变行为均遵循Cox-Merz方程。G2端羟基超支化聚酯在振荡测试的高频区出现了剪切增稠现象。对于组分质量比为1∶1的低代/高代端羟基超支化聚酯二元共混物,无论是稳态剪切还是振荡剪切,只要一种组分是牛顿流体,那么二元共混体系也是牛顿流体。高代数组分决定了二元共混物的流变特性,而低代数组分主要影响二元共混物的黏度。     

Relating blow moldability to large amplitude oscillatory shear behavior

The large amplitude oscillatory shear test has been used to discriminate subtle differences in nonlinear viscoelasticity between two high density polyethyene blow molding resins with different processability. Structural network theory was used to explain the subtle differences in terms of entanglement kinetics with remarkable accuracy. The resin with better shape retention characteristics in programmed parison blow molding was found to have a higher kinetic rate constant for molecular re-entanglement.     

Auto-oscillatory processes in aerodynamic spinning of yarns from polymer melts

Conclusions A new class of auto-oscillatory processes has been examined; they arise in aerodynamic yarn spinning from polymer melts.Mathematical modeling of the oscillatory processes has been performed, and an experimental check of the results obtained by calculation has been carried out. The mechanism for the generation and growth of auto-oscillations has been shown.Translated from Khimicheskie Volokna, No. 6, pp. 13–15, November–December, 1989.     

Measurement of dynamic viscoelastic properties of polymer melts and liquids by the modified rheovibron

A new technique is presented which permits the quantitative characterization of the dynamic viscoelastic properties of polymer melts and liquids. A new sample holding system with oscillatory shear platen and modification of the amplifier and oscillating unit made it possible to measure rheological properties of the viscous liquids using the Rheovibron. The dynamic shear modulus, viscosity, and internal friction of acrylic dope, and silicone fluids are obtained by using the new procedure and developed mathematical expressions. This technique will be useful in studies on the rheological properties characterization of polymer melts and liquids in conjunction with process parameters.     

Morphology development during shearing of poly(ethylene oxide) melts

A parallel glass-plate rotary shearing device has been constructed. This device allows direct observation of the crystallization of polymeric melts being subjected to a constant rate of shear under controlled temperature conditions. Polarized light microscopy and small-angle light-scattering techniques were employed to study the kinetics and morphology of poly(ethylene oxide) melts as they crystallized under various combinations of supercooling and shear rate. The techniques of epimicroscopy, differential scanning calorimetry, and wide-angle x-ray diffraction were used to study the already crystallized material. Crystalline aggregates developing from sheared melts showed a sheaf-like lamellar morphology. The long axes of the sheaf-like structures oriented perpendicular to the flow direction when crystallized under shear. This behavior can be explained in terms of hydrodynamic theory.