Drilling fluid shear stress overshoot behavior

Shear stress overshoot behavior was studied in four drilling fluid systems and ten bentonite dispersions. These overshoot properties, also described by the American Petroleum Institute as gel strengths, were measured after gelation times of 10 s to 24 h at temperatures of 20–80 °C. Two different rheometers were used to measure overshoot behavior. Gel strength development with time followed a first-order model. Gel development rates at 20 °C varied from 0.005 to 0.01 min^–1 for drilling fluid systems and from 0.0004 to 0.02 min^–1 for bentonite dispersions. Increasing the gelation temperature for each drilling fluid system caused an increase in the gelling rate constant. Comparison of gel strengths in bentonite dispersions were made using a Fann 35 A viscometer and a Weissenberg Rheogoniometer. Higher gel strength values observed using the Rheogoniometer were believed to be due to differences in instrument spring stiffness and fixture inertia.     

Stress-induced interfacial failure in filled polymer melts

We study a dynamic interfacial slip phenomenon in filled polymer melts. When a poly(dimethyl siloxane) melt of weight average molecular weight M _w = 93 700 is mixed with glass beads of diameter up to 45 m, the sample shows some evidence of breakdown of interfacial adhesion between the glass beads and the PDMS matrix at a level of oscillatory stress under which the pure PDMS melt exhibits no decay. The decay of viscoelastic properties with time is essentially independent of the amplitude of shear strain as long as the magnitude of the oscillating stress is sufficiently high. It is suggested that much higher local stress than the apparent applied stress may be generated between the narrowly spaced beads. The interfacial slip was observable because it was measured against a natural length scale d in the filled polymer melts which is the filler size or the inter-filler distance and is much smaller than the dimensions of the flow cell. The decay under high stress and healing of interfacial adhesion upon a large reduction in stress may be related to the de-bonding and reformation of hydrogen bonds between the PDMS chains and the glass bead surfaces.     

Influence of thermal aging on tensile and creep behavior of thermoplastic polyurethane

Changes in mechanical and physical properties of polyurethane thermoplastic during aging at 70 °C and 90 °C were investigated. The loss weight response was analyzed by gravimetric measurements under these temperatures. Changes in appearance and morphology of TPU after thermal aging were revealed by optical microscopy. The prolongation of the thermal exposure time, up to 270 days, leads to a progressive increase in tensile strength. In fact, elastic modulus and stress at 200% of strain were increased with thermal exposure time. These results can be explained by the increase of thermal stability due to the increase of material rigidity and the decrease in chain mobility. The evolution of the mechanical properties from tensile tests seems to be well correlated to the creep behavior. Finally, Scanning Electron Microscopy (SEM) revealed the modification of TPU morphology fracture surface after thermal aging.     

The peculiar rheo-optical behavior of bisphenol A-polycarbonate and polymethylmethacrylate

The rheological and stress-optical behavior of the melts of several grades ob bisphenol-A-polycarbonate (PC) and polymethylmethacrylate (PMMA) is investigated. Pertinent flow birefringence measurements are carried out in a remodelled cone-plate apparatus [1]. The shear stress in the polymer melt is calculated from the dynamic moduli, which are determined separately. It is shown that the linear stress optical rule is obeyed. In this way, the stress-optical coefficient C of the melt can be determined. The low-Mw polycarbonates all behave as Maxwellian fluids. The main stress direction does not deviate significantly from 45°. In the temperature range from 160° to 260°C the stress-optical coefficients of the different grades lie between 3 and 4×10^–9 Pa^–1 and show a weak temperature dependence. The stress-optical coefficient of PMMA is about a factor of 100 lower and shows a peculiar temperature-dependence, changing its sign at 144°C. The results are discussed in terms of the anisotropy of the polarizability of the polymer chain.     

Generalized Maxwell model for the viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading

The linear viscoelastic behavior of a soda-lime-silica glass under low frequency shear loading is investigated in the glass transition range. Using the time-temperature superposition technique, the master curves of the shear dynamic relaxation moduli are obtained at a reference temperature of 566°C. A method to determine the viscoelastic constants from dynamic relaxation moduli is proposed. However, some viscoelastic constants cannot be directly measured from the experimental curves and others cannot be precisely obtained due to non-linearity effects at very low frequencies. The generalized Maxwell model is investigated from the experimental dynamic moduli without fixing the viscoelastic constants. A set of parameters is shown to be in good agreement with the experimental dynamic relaxation moduli, but does not give the correct values of the viscoelastic constants of the investigated glass. The soda-lime-silica glass exhibits a non-linear viscoelastic behavior at very low stress level which is usually observed for organic glasses. This non-linear behavior is questioned.     

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.     

Sulfur modified bitumen: A new binder

Summary Bitumen is modified after a treatment with 2% sulfur, at 160°C. It is more plastic consecutive to a variation of the nature of the interactions between asphaltene molecules.Composites prepared with this bitumen and silica present dynamic viscoelastic properties obeying the time-temperature-interfacial parameter equivalence principles, evidenced previously. However, the domains of applicability of these principles are more restricted.With 11 figures     

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.     

Fluctuation regime in the viscoelastic properties of block copolymer solutions

We report measurements of the dynamic shear moduli for solutions of three symmetric styrene isoprene diblock copolymers in the neutral solvent di-octyl phthalate. For each sample the concentration range was selected to extend from the disordered regime to the (lamellar) ordered state, with the emphasis placed on the intermediate regime, where large amplitude composition fluctuations are clearly evident. Temperatures from 0° to nearly 100°C were employed. The fluctuations were most clearly revealed when the data were plotted as phase angle versus reduced frequency, where the frequency axis was scaled by the longest relaxation time in the absence of fluctuations. The dynamic shear moduli and the apparent longest relaxation times, all normalized to their respective values in the absence of fluctuations, increased markedly as the order-disorder transition was approached. The rate of increase was consistent with recent theoretical predictions of Fredrickson, Larson, and Helfand, but the magnitude of the effect is larger than anticipated by theory. The onset of visible fluctuation effects depends on molecular weight in a manner that suggests that entanglements play an important role in determining the coupling of the fluctuations to the viscoelastic properties. This is consistent with previous measurements of translational diffusion, which demonstrated that entanglements severely diminish the mobility of lamellar-forming block copolymers along the interfaces between microdomains.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Large-deformation properties of wheat dough in uni- and biaxial extension. Part II. Gluten dough

Glutens were isolated from flour of three European wheat cultivars which perform differently in cereal products. The rheological and fracture properties of gluten-water doughs were determined in uniaxial and biaxial extension at large deformations and small angle sinusoidal oscillation tests and compared with the mechanical properties of the parental flour doughs. At 25 °C the linear region was in the same range as that of flour dough, while at a higher temperature (45 °C) the linear region was more than an order of magnitude higher. At 45 °C the storage modulus and tan were lower than at 25 °C. Variation in moduli between cultivars was much more pronounced for gluten than for flour doughs.Similarly to flour dough in both uniaxial and biaxial extension the stress () increased more than proportionally with the strain, a phenomenon called strain hardening. The stress at a set strain and strain hardening depended much more strongly on the type of deformation for gluten than for flour dough: was higher in biaxial extension for gluten than for flour dough, but was much higher in uniaxial extension. This indicates that orientational effects in elongational flow are of even larger importance for the mechanical properties of gluten than of flour dough. It is likely that it is the glutenin fraction that, because of its large size, confers these direction dependent properties to gluten and flour doughs. Fracture stresses were much higher for gluten than for flour dough, while fracture strains were in the same range or higher. For gluten dough fracture strains increased less strongly with increasing strain rate than for flour dough. Glutens exhibiting a higher stress at a certain strain had a smaller fracture strain.Our findings confirm the conviction that the large deformation properties of flour dough are mainly governed by the gluten fraction. However, there are also differences. Compared to flour dough gluten dough exhibits (i) a stronger strain hardening, (ii) a larger difference in between uniaxial and biaxial extension and (iii) a smaller strain rate dependency of the fracture strain.     

Rheological characterization of highly branched poly(ethyleneterephthalate)

Linear and highly branched poly(ethyleneterephthalate) samples were synthesized and characterized in terms of intrinsic viscosity, molecular weight and melt viscosity over a wide range of shear rates at several temperatures, in the range from 265° to 295 °C. Linear samples exhibited Newtonian behavior over a wide range of shear rates, while the branched ones became shear thinning at relatively low shear rates. Our experimental data, as well as data previously reported, were found to be described by a proposed correlation between the melt viscosity ratio and a branching index. Moreover, the activation energy for melt flow was found for the highly branched samples to be a little higher than that of the linear samples.     

The dynamic performance of the Weissenberg Rheogoniometer

The dynamic performance of a standard Model R18 Weissenberg Rheogoniometer has been studied in detail. The Rheogoniometer was carefully calibrated and used to measure accurately the rheological behaviour of a highly nonlinear viscoelastic polymer solution (1% polyacrylamide in 50% glycerol/water).In this paper the elaborate procedures that were used to calibrate the electronic signal processing equipment are described. The various static and dynamic calibration/correction factors are defined and incorporated into a computer implemented calculation scheme for evaluating the linear dynamic properties from the raw digital transfer function analyser readings.The linear dynamic properties of the polymer solution are presented together with the corresponding steady shearing properties. Both cone and plate and parallel plates geometries were used and good agreement was obtained over the wide range (six decades) of frequencies and shear rates employed.Fluid inertia effects were found to become important when the modified Reynolds number,Re _c ² orRe(H/R)², exceeded a value of about 0.1. These effects had a strong influence on the phase angle() which could readily be detected by varying the gap angle/width. The Walters-Kemp equations were found to give consistently accurate values for the linear dynamic properties for modified Reynolds numbers up to 11.6 which was the highest reached.     

The effect of liquid crystal structure on the rheological properties of nitrocellulose-dimethylacetamide solutions

Solutions of Pyro grade nitrocellulose (NC) in dimethyl acetamide (DMA), containing between 42.5% and 60% NC (w/w), have been studied by differential scanning calorimetry and polarised light microscopy. The results showed that NC forms a lyotropic liquid crystal structure in DMA. A transition from the liquid crystal phase to an isotropic phase occurred over the temperature range 27 °C to 67 °C, and the enthalpy of transition increased with NC concentration. Rheological properties were determined using an extrusion rheometer with a slit die. The solutions were shown to have a yield stress for flow which increased with increasing NC concentration. The solutions were also found to be thixotropic.     

Thermo-mechanical response of Al 6061 with and without equal channel angular pressing (ECAP)

The thermo-mechanical responses of Al 6061 before and after equal channel angular pressing (ECAP) at different strain rates and temperatures were measured. Al 6061 was solution heat treated before ECAP pressing at room temperature and subjected to up to three passes. After pressing, the billets were aged at 100 °C for 2 days. An as-received Al 6061-T651 was studied similarly to investigate the differences between processed and non-processed specimens. The responses of ECAP material were determined at −30, 22, 125 and 250 °C, and at strain rates from 10⁻⁵ to 2530 s⁻¹; the 6061-T651 specimens were subjected to uniaxial compressive loading at −31, 22, 85, 150, 230 and 315 °C, and strain rates ranging from 10⁻⁵ to 2200 s⁻¹. It was found that, the ECAP process increases the strength versus the T651 condition. Additionally, the Al 6061 ECAP is not sensitive to strain rate at room and lower temperatures, but the sensitivity increases as the number of passes and/or temperature are increased and this is the same for the non-processed material. Increasing the number of passes increases the flow stress at room and lower temperatures, has almost no effect at 125 °C and decreases at 250 °C. For both materials, the dynamic flow stress is higher than the stress at quasi-static strain rates even when the quasi-static strain rate regime is insensitive to strain rate. The Al 6061 has strong texture after one pass but steadily increases as the number of passes are increased. This is the first study that reports on the thermo-mechanical responses of ECAP and non-ECAP Al 6061 at such a wide range of strain rates, including dynamic, and temperatures.     

Dynamic shearing resistance of molten metal films under high pressures and extremely high shearing rates

In the present study plate-impact pressureshear experiments have been conducted to study the dynamic shearing resistance of molten metal films at shearing rates of approximately 10⁷ s⁻¹. These molten films are generated by pressure-shear impact of relatively low melt-point metals such as 7075-T6 Al alloy with high hardness and high flow-strength tool-steel plates. By employing high impact speeds and relatively smooth impacting surfaces, normal interfacial pressures ranging from 1–3 GPa and slip speeds of over 100 m/s are generated during the pressure-shear loading. The resulting friction stress (∼100 to 400 MPa) combined with the high slip speeds generate conditions conductive to interfacial temperatures approaching the fully melt temperature regime of the lower melt-point metal (7075-T6 aluminum alloy) comprising the tribo-pair. During pressure-shear loading, laser interferometry is employed to measure normal and transverse motion at the rear surface of the target plate. The normal component of the particle velocity provides the interfacial normal traction while the transverse component provides the shearing resistance of the interface as it passes through melt. In order to extract the critical interfacial parameters, such as the interfacial slip-speed and interfacial temperatures, a Lagrangian finiteelement code is developed. The computational procedure accounts for dynamic effects, heat conduction, contact with friction, and full thermo-mechanical coupling. At temperatures below melt the flyer and target materials are described as an isotropic thermally softening elastic-viscoplastic solid. For material elements with temperatures in excess of the melt point, a purely Newtonian fluid constitutive model is employed. The results of this hybrid experimental-computational study provide insights into the dynamic shearing resistance of molten metal films at high pressures and extremely high shearing rates.     

Dynamic-mechanical properties of interfacially modified glass sphere filled polyethylene

Model composites of spherical glass particles dispersed in a matrix of high density polyethylene were prepared both with and without interfacial modification by an azidofunctional trialkoxysilane. Dynamic mechanical measurements of the composites in the melt state were recorded. The unmodified composites behave as theoretically predicted and the effect of particle—particle interaction at high volume fractions can be measured. The composites with a modified interfacial region have greater shear moduli due to the effect of a region surrounding the particle modified by the silane. The material in this region is largely bound to the glass surface and was examined by Fourier transform infrared spectroscopy after extraction of the bulk matrix. Theoretical calculations are shown to be useful in calculating the mechanical properties and volume fraction of the interfacial region.     

Deformation of silicon – Insights from microcompression testing at 25–500 °C

The plastic deformation of silicon and other brittle materials near room temperature has conventionally been studied under high confining pressures, although it has been suggested that these may modify the dislocation core structure. Here, the possibility of using microcompression has been studied. Using this method the yield stress of silicon micropillars was measured for different pillar diameters and between 25 and 500 °C for a constant diameter of 2 μm. No pronounced effect of size on the yield stress was found, but the transition from failure by cracking to predominately plastic deformation was shown to be consistent with a previously proposed simple model for axial splitting. Deformed specimens were analysed by transmission electron microscopy to elucidate the operative dislocation mechanisms. This showed that at 500 °C deformation occurs by twinning and formation of partial dislocations, whereas at 100 °C it is associated with micro-cracking and only weakly dissociated dislocations.     

Melt shear rheology of carbon nanofiber/polystyrene composites

The rheological behavior and morphology of carbon nanofiber/polystyrene (CNF/PS) composites in their melt phase have been characterized both through experimental measurements and modeling. Composites prepared in the two different processes of solvent casting and melt blending are contrasted; melt-blended and solvent-cast composites were each prepared with CNF loadings of 2, 5, and 10 wt%. A morphological study revealed that the melt blending process results in composites with shorter CNFs than in the solvent-cast composites, due to damage caused by the higher stresses the CNFs encounter in melt blending, and that both processes retain the diameter of the as-received CNFs. The addition of carbon nanofiber to the polystyrene through either melt blending or solvent casting increases the linear viscoelastic moduli, G′ and G″, and steady-state viscosity, η, in the melt phase monotonically with CNF concentration, more so in solvent cast composites with their longer CNFs. The melt phase of solvent-cast composites with higher CNF concentrations exhibit a plateau of the elastic modulus, G′, at low frequencies, an apparent yield stress, and large first normal stress difference, N ₁, at low strain rates, which can be attributed to contact-based network nanostructure formed by the long CNFs. A nanostructurally-based model for CNF/PS composites in their melt phase is presented which considers the composite system as rigid rods in a viscoelastic fluid matrix. Except for two coupling parameters, all material constants in the model for the composite systems are deduced from morphological and shear flow measurements of its separate nanofiber and polymer melt constituents of the composite. These two coupling parameters are polymer–fiber interaction parameter, σ, and interfiber interaction parameter, C _I. Through comparison with our experimental measurements of the composite systems, we deduce that σ is effectively 1 (corresponding to no polymer–fiber interaction) for all CNF/PS nanocomposites studied. The dependence of CNF orientation on strain rate which we observe in our experiments is captured in the model by considering the interfiber interaction parameter, C _I, as a function of strain rate. Applied to shear flows, the model predicts the melt-phase, steady-state viscosities, and normal stress differences of the CNF/PS composites as functions of shear rate, polymer matrix properties, fiber length, and mass concentration consistent with our experimental measurements.     

ATP改性UHMWPE水润滑轴承材料的摩擦学特性研究

超高分子量聚乙烯(UHMWPE)轴承材料在低速重载工况下常发生严重磨损,通过添加改性填料能够显著提升其摩擦学性能. 凹凸棒土(ATP)作为一种改性填料能够增强基体材料的机械性能进而改善其摩擦特性,但是ATP作为填料往往会因为团聚效应而降低材料的补强效果. 通过对ATP进行表面改性处理可克服团聚效应,实现ATP与基体间的均匀共混. 通过表面化学包覆改性法制备由硅烷偶联剂KH570改性处理的ATP与UHMWPE共混制成复合材料,并与纯UHMWPE材料作对照试验. 利用RTEC摩擦试验机研究复合材料在水润滑条件下摩擦系数随载荷和转速的变化,以及材料填充含量对复合材料在低速重载(v=0.55 m/s、F_z=55 N)工况下磨损性能的影响. 利用傅里叶变换红外光谱仪(FTIR)、X射线衍射仪(XRD)、差示扫描量热仪(DSC)与电子万能材料试验机分别对ATP改性效果、熔融结晶行为及复合材料的重要力学性能进行表征测试. 试验结束后,利用表面轮廓仪与激光共聚焦显微镜观察复合材料表面形貌并分析其磨损机理. 结果表明:硅烷偶联剂KH570对ATP的改性效果良好,填充改性ATP能提高材料的邵氏硬度,且材料的拉伸性能随填充含量的提高呈下降趋势;对比纯UHMWP材料,复合材料的摩擦系数更低,适量的ATP填充能改善材料磨损性能,减小体积磨损率;试验中改性ATP质量分数为1%的复合材料其摩擦学性能最优,在低速重载时的摩擦系数及体积磨损率与纯UHMWPE相比分别降低了52.45%和37.58%.      

Rheological properties of carbon black-filled blends of liquid-crystalline copolyester with thermoplastic polysulfone

Rheological properties of a two-phase polymeric blend containing LCCPE of poly(ethylene terephthalate) and p-hydroxybenzoic acid and thermoplastic polysulfone with varying concentrations of polymeric components and particulate filler have been studied. The theological behavior of such blends at different temperatures is governed by variation of the degree of ordering of LC-CPE macromolecules associated with the phase transition in the CPE at 260°C. Experimental results are discussed on the basis of concepts of compatibility of polymeric components in the melt or, if the system is incompatible, of the degree of interphase interaction between the components, as well as the impact of the filler and of the shear straining conditions on structurization in the system and compatibility. The filler exerts a compatibilizing effect on blend components, while the shear stress encourages the phase separation in the system. An extremal variation of viscosity of the LC-CPE/carbon black, silica and talk blends with the filler concentration on both at the flow in a uniform shear stress field and at the capillary flow has been found. Normalization of the filler concentration with respect to its specific surface yields a unified concentration dependence of the relative viscosity of LC-CPE filled with solid particles of various natures and specific surfaces.