物理老化对玻璃态高聚物非线性蠕变行为的影响

在不同应力水平下对经历不同老化时间的有机玻璃(PMMA)进行常温蠕变测试,分析物理老化和应力对材料蠕变柔量函数的影响.分析表明,老化时间对PMMA蠕变行为的影响满足流变简单性规律,即不同老化时间的蠕变柔量曲线可以沿对数时间轴平移而叠加到参考曲线上.取最长的老化时间为参考状态,依时间-老化时间等效原理,得到了各应力水平下的蠕变柔量主曲线.老化移位因子与老化时间在双对数坐标图上呈现线性关系,其负斜率就是老化移位率.结果表明,老化移位率随应力的增高而减小.     

An empirical constitutive model for complex glass-forming liquids using bitumen as a model material

While extensive research efforts have been devoted to understand the dynamics of chemically and structurally simple glass-forming liquids (SGFLs), the viscoelasticity of chemically and structurally complex glass-forming liquids (CGFLs) has received only little attention. This study explores the rheological properties of CGFLs in the vicinity of the glass transition. Bitumen is selected as the model material for CGFLs due to its extremely complex chemical composition and microstructure, fast physical aging and thermorheological simplicity, and abundant availability. A comprehensive rheological analysis reveals a significant broadening of the glass transition dynamics in bitumen as compared to SGFLs. In particular, the relaxation time spectrum of bitumen is characterized by a broad distribution of long relaxation modes. This observation leads to the development of a new constitutive equation, named the broadened power-law spectrum model. In this model, the wide distribution of long relaxation times is described by a power-law with positive exponent and a stretched exponential cut-off, with parameter β serving as a measure of the broadness of the distribution. This characteristic shape of the bitumen spectrum is attributed to the heterogeneous freezing of different molecular components of bitumen, i.e., to the coexistence of liquid and glassy micro-phases. Furthermore, as this type of heterogeneous glass transition behavior can be considered as a general feature of complex glass-forming systems, the broadened power-law spectrum model is expected to be valid for all types of CGFLs. Examples of the applicability of this model in various complex glass-forming systems are given.     

Small-diameter parallel plate rheometry: a simple technique for measuring rheological properties of glass-forming liquids in shear

The rheological characterization of glass-forming liquids is challenging due to their extreme temperature dependence and high stiffness at low temperatures. This study focuses on the special precautions that need to be taken to accommodate high sample stiffness and torsional instrument compliance in shear rheological experiments. The measurement errors due to the instrument compliance can be avoided by employing small-diameter parallel plate (SDPP) rheometry in combination of numerical instrument compliance corrections. Measurements of that type demonstrate that accurate and reliable rheological data can be obtained by SDPP rheometry despite unusually small diameter-to-gap (d/h) ratios. Specimen preparation for SDPP requires special attention, but then experiments show excellent repeatability. Advantages and some current applications of SDPP rheometry are briefly reviewed. SDPP rheometry is seen as a simple and versatile way to measure rheological properties of glass-forming liquids especially near their glass transition temperature.     

Rheological changes in the bitumen caused by heating and interaction with rubber during asphalt–rubber production

The demand for more safe and durable roads, combined with the need to preserve the environment, led to the production and application of asphalt–rubber (AR) on roads. Nevertheless, this complex material needs further study in order to better distinguish among the phenomena that take place during AR production, as they impact on the final product characteristics. Here, we effectively quantify the rheological changes related to bitumen aging due to diffusion of small molecules of bitumen into the rubber particles and to the release of fillers from rubber into the bitumen during AR production. “A sphere AR production simulator” was developed to assess AR aging independently. The comparison of the characteristic relaxation times of both AR and simulated AR shows that the aging alone cannot explain the rheological changes during AR production. The extent of the changes related to the combined effects of aging and filler release increases as the bitumen used to produce AR is softer.     

Elongational and shear flow in polymer-clay nanocomposites measured by on-line extensional and off-line shear rheometry

Rheological behaviour of polymer nanocomposites has been usually characterized by rotational as well as capillary rheometry, which are both time and cost consuming. We have already published that reinforcement in polymer-clay nanocomposites can be estimated very fast using extensional rheometer in combination with a capillary rheometer. It has been proven that the magnitude of melt strength can be correlated with that of tensile strength, i.e. 3D physical network made of layered silicate and polymer matrix, which is responsible for material reinforcement, can be monitored directly using extensional rheometry. Therefore, additional time for samples preparation by press or injection moulding as well for long measurements by tensile testing is not required any more. In this contribution, results of extensional rheometry measured directly during compounding process are presented. In this manner, further reduction in time required for material characterization has been achieved. The samples have been prepared by advanced compounding using a melt pump and special screw geometries. With the use of on-line extensional rheometry and off-line rotational rheometry, different nanocomposites have been tested and the effect of processing conditions (screw speed and geometry in the twin-screw extruder) on elongational and viscoelastic properties has been investigated. It has been found that the level of melt strength measured by extensional rheometry correlates with a high accuracy with dynamic rheological data measured by rotational rheometry. It was hereby confirmed that the network structure made of silicate platelets in polymer melt is reflected in both elongational and shear flow in the same way.     

Process rheokinetics and microstructure of recycled EVA/LDPE-modified bitumen

Knowledge of the kinetics of the manufacturing process of polymer–bitumen blends is of great interest because it provides information on the behaviour of the binder at different stages of the mixing operation, which is useful for the establishment of the optimum processing conditions, involving temperature and operation time. The purpose of this research was to study the evolution of the rheological properties and microstructure of a polymer-modified bitumen during its processing. A 60/70-penetration grade bitumen and recycled EVA/LDPE were mixed under different processing conditions. Measurements of the evolution of viscosity with time, at different temperatures and agitation speeds, were carried out with an experimental device known as ‘rheomixer’, that is, a helical ribbon impeller inside a mixing vessel coupled with the transducer and motor of a conventional rheometer. Under the experimental conditions selected (within the laminar region, Re<10), temperature is the most important processing variable. Hence, low agitation speeds and a processing temperature of around 180°C should be chosen for bitumen modification with the polymer used.     

Rheological behavior in the transient state of PP/EPDM blends with carbon nanofillers

The rheological properties in the transient state of PP/EPDM blends with carbon nanofillers had been studied. The carbon nanofillers were incorporated into molten EPDM in an internal mixer at 150 °C. The rheological variables were determined in rotational rheometry at constant temperature of 200 °C. The results suggest that the magnitude of the difference of the normal stress differences (N₁-N₂) of PP/EPDM blends through the time, with and without nanofillers, and has a transition cycle from positive to negative values and vice versa, at constant and at zero shear rate in previously sheared samples. At constant shear rate, the transition cycle is random; meanwhile, it is constant at zero shear rate. This behavior is attributed to the polymeric chain movement, considering that the sheared samples have two molecular reorder processes: an immediate mechanism and another one slower. The fastest reorder process is attributed to the polymeric chains entanglement forming non-stable and stressed molecular structures. In the other hand, the second process is referred to the molecular mobility that takes place inside the stressed entangled polymer, in such a way that its structure tends to molecular stability as the rest time increases.     

Rheological properties of polyacrylates used as synthetic road binders

Most adhesives and binders, including bitumen for asphalt mixture production, are presently produced from petrochemicals after the refining of crude oil. The fact that crude oil reserves are a finite resource means that in the future, it may become necessary to produce these materials from alternative and probably renewable sources. Suitable resources of this kind may include polysaccharides, plant oils and proteins. This paper deals with the synthesis of polymer binders from monomers that could, in future, be derived from renewable resources. These binders consist of polyethyl acrylate (PEA) of different molecular weight, polymethyl acrylate (PMA) and polybutyl acrylate (PBA), which were synthesised from ethyl acrylate, methyl acrylate and butyl acrylate, respectively, by atom transfer radical polymerisation. The rheological properties of these binders were determined by means of oscillatory testing using a dynamic shear rheometer and combinations of stress/strain, temperature and frequency sweeps. The results indicate that PEA can be produced to have rheological properties similar to that of ‘soft’ 100/150 penetration grade bitumen, PMA with similar rheological properties to that of ‘hard’ 10/20 penetration grade bitumen, while PBA, due to its highly viscous nature and low dynamic moduli, cannot be used on its own as a binder. The synthetic polymers were found to be thermo-rheologically simple, and the shift factors, used to produce the dynamic moduli master curves, were found to fit an Arrhenius function.     

Linear viscoelastic analysis using frequency-domain algorithm on oscillating circular shear flows for bubble suspensions

To achieve a stable evaluation of the linear viscoelasticity of bubble suspensions, which have difficulties for conventional rheometers from spatial distributions of rheological properties with bubble deformations, we proposed a novel rheometry based on spatio-temporal velocity data obtained by ultrasonic velocity profiling (UVP). A frequency-domain algorithm was adopted to overcome a critical influence of measurement noise on the rheological assessment, which is inferred from error propagation characteristics through the equations of motion in discretized form. Applicability and advantage of the present rheometry with the frequency-domain algorithm were verified by two kinds of fluids: high viscous oil as a Newtonian fluid and polyacrylamide aqueous solution as a shear thinning, viscoelastic fluid. The rheometry was finally adopted for bubble suspensions subject to high oscillatory shear, and it could validly extract elasticity-originated momentum transfer as a function of space.     

Bitumen/polyethylene blends: using m-LLDPEs to improve stability and viscoelastic properties

The stability and the rheological properties of blends of a 60/70 penetration-grade bitumen with conventional HDPEs and metallocene catalysed LLDPEs (m-LLDPE) are investigated. Considerably better stability results are obtained using m-LLDPEs instead of conventional polyethylenes, allowing one to avoid phase separation of the emulsion-like system during storage at high temperature. Thermodynamical interaction between bitumen and polyethylene is discarded as a cause of the observed difference, because the solubility parameter is practically the same for all the investigated polyethylenes. The result is explained on the basis of the lower melt elasticity of m-LLDPEs (attributed to their narrow molecular weight distribution), which facilitates the drop breakup during mixing process. The modification of bitumen with any of the m-LLDPEs considered in this work gives a new material with considerably improved viscoelastic properties.     

The influence of flow confinement on the rheological properties of complex fluids

The rheological properties of plastic and viscoplastic complex fluids have been investigated using constant velocity squeeze flow rheometry at small gaps in order to examine the influence of the resulting flow confinement. The fluids investigated were aqueous carbopol suspensions and three commercial products (Tesco English mustard, Tesco value lemon curd and Heinz tomato ketchup (HTK)). The bulk rheological properties were measured using parallel plate rheometry. Rough plates were used to eliminate wall slip in both rheometric configurations. The commercial products are Herschel–Bulkley fluids and, for gaps less than a critical value of ~200 μm, the yield stresses tended to large values. There was a corresponding trend to small values for the flow consistencies except for HTK, which has a negligibly small bulk value. A possible explanation is that the micro-structural correlation lengths of these fluids are of the order of that of the critical separation. The yield stresses of the carbopol suspensions also increased sharply at the critical gap but then decreased gradually with decreasing gap separation. The transition may correspond to the formation of a jammed state with the subsequent plastic flow at smaller gap separations arising from localised shearing.     

Large frequency bands viscoelastic properties of honey

Honey is a viscoelastic material which presents a crystallization phase transition at low temperatures. This phase transition limits the studies of dynamic behavior at high frequencies from the classical rheometry using time–temperature superposition (TTS). In order to characterize the viscoelastic properties of honey at high frequencies, we have developed a multiple ultrasonic reflection device (MUR). The viscoelastic properties of honey were measured by MUR and classical rheometry at high and low frequencies, respectively, between 13.1 and 31.3 °$°$C. Matching both results, we built the master curve over a frequency range covering nine decades, from which we determined the main rheological parameters of honey. Finally, from an inverse approach, we extracted from this master curve, the acoustical parameters for frequencies inaccessible by the ultrasonic methods.     

Structure development during crystallization of polycaprolactone

In this paper, the quiescent crystallization of polycaprolactone (PCL) melts is studied by rheological measurements coupled to calorimetry and optical microscopy. Based on a comparison between the different techniques, we find that the increase in viscoelastic properties during crystallization starts only when a relatively high degree of crystallinity is reached, which corresponds to a much developed crystalline microstructure. Like other semicrystalline thermoplastic polymers, the crystallization of PCL can be seen as a gelation process. In this case, however, we find a peculiar critical gel behavior, as the liquid-to-solid transition takes place at a very high (~20%) relative crystallinity, and this value is independent of temperature. These facts, and the comparison with optical microscopy observations, suggest that the microstructure at the gel point is controlled by the interactions between the growing crystallites. The gel time (from rheometry) and the half-crystallization time [from differential scanning calorimetry (DSC)] both show an Arrhenius-like behavior and have the same pseudoactivation energy. A practical implication of this parallel behavior of t _gel and t _0.5 is that the rheological measurements can be used to extend to higher temperatures the study of crystallization kinetics where DSC is not sufficiently sensitive.This paper was presented at the second Annual European Rheology Conference (AERC) held in Grenoble, France, 21–23 April 2005.     

Rheological properties of service weathered road bitumens

A study was carried out of the rheological properties of service weathered bitumens and their properties were compared with road performance. Bitumen from 39 test sites was recovered from the uppermost layer of stone particles covering the road surfacing and tested under dynamic and transient loading. Dynamic testing was carried out under forced sinusoidal loading. Testing under transient loading was mainly with a viscosity test conducted at 45°C, but some creep testing in compression was conducted at 0°C. From the results of dynamic testing, master curves of modulus and loss angle were constructed, spanning over ten decades in loading frequency. The hyperbolic expressions of Dickinson and Witt successfully described the frequency dependence of bitumen modulus and loss angle. The Williams, Landel and Ferry (WLF) equation, with newly derived coefficients, described the temperature dependence of the shift factor (or Newtonian viscosity) for the temperature range –10 to 60°C. Attempts were made to compare the measured transient response with that calculated from dynamic results. The result of the viscosity test conducted at 45°C as an indicator of modulus at low temperatures was assessed. Surfacing distress increased as the bitumen viscosity or modulus increased, however service performance of the bitumens was best correlated with the modulus calculated at conditions representative of traffic stressing and lowest site temperature. The changes in the rheological properties of bitumens induced by weathering is discussed.     

Viscous dissipation with fluid inertia in oscillatory shear flow

For liquids with high viscosity and low thermal conductivity, viscous dissipation can cause appreciable errors in rheological property measurements. Here, the influences of both viscous dissipation and fluid inertia on the property measurements in oscillatory sliding plate rheometry are investigated. For Newtonian fluids, Bird (1965) solved the combined problem analytically, but only for high frequencies. Here his solution is extended to any frequencies. Also, the equations of motion and energy are solved for linear viscoelastic fluids, and new analytical solutions for the velocity and temperature profiles are given. In both Newtonian and linear viscoelastic fluids, the temperature rise in the gap increases with frequency. The location of the maximum temperature shifts from the mid-plane at low frequency towards the moving wall at high frequency. The fluid inertia increases the viscous dissipation in both fluids. By solving the combined problem, this paper simplifies rheometer design by providing one unified criterion for avoiding measurement errors. Operating limits are presented graphically for minimizing the effects of both fluid inertia and viscous dissipation in oscillatory sliding plate rheometry.     

Rheological characterization of complex fluids in electro-magnetic fields

The paper is focused on the experimental investigations and rheological characterisations in magnetic and electric fields of liquids based on water in crude oils emulsions, added with ferrofluids (two types of crude oils are used in experiments: asphaltic and paraffinic, respectively). The final samples disclose weakly effects in the presence of magnetic field (saturated magnetization: M_n < 300 [G]) and behave almost as isolators in electric field (conductivity: σ < 10⁻⁵ [S/m]). The main goal of the study is to explore to what extent rheometry of complex fluids in electric and magnetic fields is able to offer value information about the internal structure of the samples. The experimental results prove that anomalous rheological behaviour (thixotropy, non-monotonic flow curve or viscosity function) of a complex fluid (in our case, emulsions based on paraffinic oil) generate also thixotropic properties and non-monotonic answers in the presence ferrofluids, under low magnetic and/or electric fields intensity. Our prospective study suggests that novel experimental procedures based on interaction: electro-magnetic field–complex fluids can be developed, in order to determine indirectly some relevant rheological properties of the complex fluids with internal network structure.     

Time-resolved rheometry

Applicability and limits of time-resolved rheometry have been analyzed for polymers which undergo change during a theological measurement. Processes such as gelation, phase transition, polymerization or decomposition affect the molecular mobility in these polymers and therefore the rheological experiment. We propose to choose the well known effect of heating (or cooling) during the relaxation and analyze it as a paradigm for rheometry on samples with changing molecular mobility. The temperature change does not cause permanent changes in sample structure, but it affects the molecular mobility and it significantly interferes with the measurement if the temperature changes occur too fast. In this study, time-resolved mechanical spectroscopy (TRMS) was used to experimentally investigate the effect of heating on the relaxation behavior of a typical polycarbonate sample. Each data point in a cyclic frequency sweep (CFS) was taken at a different state of the material; the data were interpolated using an interactive computer program. In this fashion, a single TRMS experiment yielded a master curve over eight decades. A model for relaxation under non-isothermal conditions showed the limitations of TRMS. It could be demonstrated that TRMS worked well for sufficiently small mutation numbers, i.e., for sufficiently small changes during the measurement. A critical mutation number of 0.9 was determined for the non-isothermal case beyond which the material response became non-linear. This corresponds to a calculated relative change of the shear stress amplitude of about 90%.Dedicated to Prof. Ken Walters on the occasion of his 60th birthday.     

Leveling and thixotropic characteristics of concentrated zirconia inks for screen-printing

Screen-printing is a cost-effective method for the mass manufacture of zirconia-based solid oxide fuel cells (SOFCs) and oxygen separation membranes. The present work outlines an investigation into the leveling, thixotropic, and screen-printing characteristics of concentrated zirconia inks by a variety of rheological and imaging methods. A combination of viscosity, shear rate jump experiments, creep and recovery analysis, and yield stress measurements were used to assess ink thixotropy. Oscillatory rheometry and scanning electron microscopy/optical microscopy revealed a consistent effect of ethyl cellulose (binder) content upon the thixotropic and leveling characteristics of zirconia inks. While the yield stress (τ ₀), extent of recovery R(%), and rate of recovery (K) increase with increasing binder content, so did the surface roughness and thickness of the screen-printed films. Increasing the binder content not only increases the network strength of the thick films but also leads to increased leveling time. As a result, rheological modifiers are proposed to be necessary to improve the leveling characteristics of zirconia inks without losing the green strength of the thick films.     

Rheological and morphological properties of PA6/ECO nanocomposites

Polyamide-6/poly(epichlorohydrin - co - ethylene oxide) (PA6/ECO) nanocomposites were prepared with 6 wt.% organoclay and different ECO content from 5 to 40 wt.%, via two-step melt blending process. The effects of organoclay and rubber content on the morphological and rheological properties of samples have been studied. Samples have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and rheometry in small amplitude oscillatory shear. XRD results indicate that the nanoclay platelets are partially exfoliated in both PA6 and ECO phases. The higher rubber content of nanocomposite samples results in higher exfoliation degree of the nanoclay layers. SEM photomicrographs of samples show that the size of rubber droplets increases by the introducing of nanoclay. Oscillatory shear measurements show that the storage modulus of nanocomposite samples significantly increases in comparison with unfilled blends. The formation of physical network is the prime cause of such increase. Moreover, presence of nanoclay dramatically increases melt yield stress of the samples. Palierne emulsion model has been applied to predict the rheological behavior of unfilled blends. A quantitative agreement between Palierne model and those of experimental data is found for low ECO content samples.