Theory of nonlinear rheology and yielding of dense colloidal suspensions

A first-principles approach to the nonlinear flow of dense suspensions is presented which captures shear thinning of colloidal fluids and dynamical yielding of colloidal glasses. The advection of density fluctuations plays a central role, suppressing the caging of particles and speeding up structural relaxation. A mode coupling approach is developed to explore these effects.     

Slow dynamics of self-diffusion in metastable colloidal fluids

A simple theory for nonequilibrium density fluctuations in concentrated hard-sphere suspensions of interacting Brownian particles with both hydrodynamic and direct interactions is proposed. The correlation effects due to the many-body hydrodynamic interactions among particles are shown to cause a structural arrest in the relaxation of nonequilibrium density fluctuations. A volume fraction dependence of slow relaxation process in concentrated colloidal suspensions is thus explored from a new unifying point of view.     

Thermal Lens Phenomenon Studied by the Z-Scan Technique: Measurement of the Thermal Conductivity of Highly Absorbing Colloidal Solutions

We discuss the thermal lens phenomenon in high-absorbing colloidal systems, studied by using the Z-scan technique. The characteristics of the experimental setup to avoid undesirable effects are presented, in particular when pulsed laser beam is used. We show that a cumulative effect may appear in the experiment with chopped laser beams and compromise the results obtained with this technique. This artefact is more significative when colloidal suspensions are investigated. These materials have different characteristic times of heat and mass diffusion, which must be carefully considered to choose the appropriate time interval for the laser pulse and the time between pulses. Two experimental cases with a chopped laser beam, with and without a shutter, are discussed. The sample employed is a magnetic colloidal suspension (a ferrofluid). This sample has magnetic nanoparticles electrically charged in an aqueous solution with free ions and counter ions. Besides the thermal lens effect, charge and mass diffusion may take place when the sample is illuminated by the Gaussian beam, which imposes a thermal gradient on it. The results show that, with the experimental setup without a shutter, the sample does not achieve a complete relaxation between two laser pulses. This generates a measurable cumulative effect after the sample is illuminated during a relatively long period of time. A time modulation with longer time interval between chopped pulses allows the complete relaxation of the sample. This procedure is important for the correct analysis of the thermal lens effect. Reliable values of the thermal conductivity of the sample in different temperatures are obtained and discussed.     

Three-dimensional imaging of colloidal glasses under steady shear

Using fast confocal microscopy we image the three-dimensional dynamics of particles in a yielded hard-sphere colloidal glass under steady shear. The structural relaxation, observed in regions with uniform shear, is nearly isotropic but is distinctly different from that of quiescent metastable colloidal fluids. The inverse relaxation time tau(alpha)(-1) and diffusion constant D, as functions of the local shear rate gamma*, show marked shear thinning with tau(alpha)(-1) proportional to D proportional to gamma*(0.8) over more than two decades in gamma*. In contrast, the global rheology of the system displays Herschel-Bulkley behavior. We discuss the possible role of large scale shear localization and other mechanisms in generating this difference.     

Compression behavior of Zr_(41)Ti_(14)Cu_(12.5)Ni_(10)Be_(22.5) bulk metallic glass up to 24 GPa

With the development of multicomponent Zr-based glass bulk metallic glasses(BMGs) with a larger geometry by a conventional casting process with a low coolingrate[1—4], high pressure, which is the simplest way to vary the interatomic distance ofsubstance and thus change its physical properties, has been employed as an importantmeans to investigate structural relaxation and the crystallization of the BMGs[5]. Relativeto crystalline, metallic glasses have excess free volume, which will annihil…     

Rotational stretched exponential relaxation in random trap–barrier model

The relaxation behavior of complex-disordered systems, such as spin glasses, polymers, colloidal suspensions, structural glasses,and granular media, has not been clarified. Theoretical studies show that relaxation in these systems has a topological origin. In this paper, we focus on the rotational stretched exponential relaxation behavior in complex-disordered systems and introduce a simple phase space model to understand the mechanism of the non-exponential relaxation of these systems. By employing the Monte Carlo simulation method to the model, we obtain the rotational relaxation function as a function of temperature. We show that the relaxation function has a stretched exponential form under the critical temperature while it obeys the Debye law above the critical temperature.     

First-principles constitutive equation for suspension rheology

Using mode-coupling theory, we derive a constitutive equation for the nonlinear rheology of dense colloidal suspensions under arbitrary time-dependent homogeneous flow. Generalizing previous results for simple shear, this allows the full tensorial structure of the theory to be identified. Macroscopic deformation measures, such as the Cauchy-Green tensors, thereby emerge. So does a direct relation between the stress and the distorted microstructure, illuminating the interplay of slow structural relaxation and arbitrary imposed flow. We present flow curves for steady planar and uniaxial elongation and compare these to simple shear. The resulting nonlinear Trouton ratios point to a tensorially nontrivial dynamic yield condition for colloidal glasses.     

Universal nature of particle displacements close to glass and jamming transitions

We examine the structure of the distribution of single particle displacements (van Hove function) in a broad class of materials close to glass and jamming transitions. In a wide time window comprising structural relaxation, van Hove functions reflect the coexistence of slow and fast particles (dynamic heterogeneity). The tails of the distributions exhibit exponential, rather than Gaussian, decay. We argue that this behavior is universal in glassy materials and should be considered the analog, in space, of the stretched exponential decay of time correlation functions. We introduce a dynamical model that describes quantitatively numerical and experimental data in supercooled liquids, colloidal hard spheres, and granular materials. The tails of the distributions directly explain the decoupling between translational diffusion and structural relaxation observed in glassy materials.     

平板电极间胶体晶体在电场作用下的各向同性压缩

用直径 300 nm的聚苯乙烯微球配制不同浓度的胶体晶体溶液, 将其快速注入内表面镀有导电薄膜的玻璃样品池中, 形成 (111) 晶面平行于玻璃表面的面心立方单晶结构. 通过激光衍射Kossel线方法, 研究了不同体积分数的胶体晶体样品 及它们在均匀电场作用下晶体结构的变化. 实验发现, 随着电场强度的增加, 胶体晶体表现为各向同性的压缩. 胶体晶体在恒定电场下始终保持面心立方结构, 晶格常数随着电场强度的增加逐渐减小. 实验结果可用电场力、电流体力学作用力及颗粒间静电斥力共同解释: 电场力使带电微球克服静电斥力并沿电场反方向运动导致晶体压缩, 而由电场力作用引起的电流体力学液流产生的持续推力使垂直于电场平面上的胶体微球相互靠近. 本实验为天宫一号搭载科学实验的地基实验. 关键词： 胶体晶体 Kossel衍射 结构变化     

Improvement of duty-cycle heating compensation in NMR spin relaxation experiments

To reliably measure NMR relaxation properties of macromolecules is a prerequisite for precise experiments that identify subtle variations in relaxation rates, as required for the determination of rotational diffusion anisotropy, CSA tensor determination, advanced motional modeling or entropy difference estimations. An underlying problem with current NMR relaxation measurement protocols is maintaining constant sample temperature throughout the execution of the relaxation series especially when rapid data acquisition is required. Here, it is proposed to use a combination of a heating compensation and a proton saturation sequence at the beginning of the NMR relaxation pulse scheme. This simple extension allows reproducible, robust and rapid acquisition of NMR spin relaxation data sets. The method is verified with (15)N spin relaxation measurements for human ubiquitin.     

Compression behavior of Zr<Subscript>41</Subscript>Ti<Subscript>14</Subscript>Cu<Subscript>12.5</Subscript>Ni<Subscript>10</Subscript>Be<Subscript>22.5</Subscript> bulk metallic glass up to 24 GPa

The compression of a Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass (BMG) is investigated at room temperature up to 24 GPa using in-situ high pressure energy dispersive X-ray diffraction with a synchrotron radiation source. The pressure-induced structural relaxation is exhibited. It is found that below about 8 GPa, the existence of excess free volume contributes to the rapid structural relaxation, which gives rise to the rapid volumetric change, and the structural relaxation results in the structural stiffness under higher pressure.     

Small angle X-ray scattering of the colloidal crystal

The monodisperse polystyrene spheres are assembled into the colloidal crystal on the glass substrate by vertical deposition method, which is aimed at the so-called photonic crystal applications. The structural information of the bulk colloidal crystal is crucial for understanding the crystal growth mechanism and developing the various applications of colloidal crystal. Small-angle X-ray scattering (SAXS) technique was used to obtain the bulk structure of the colloidal crystal at Beamline 1W2A of BSRF. It is found that the SAXS pattern is sensitive to the relative orientation between the colloidal sample and the incident X-ray direction. The crystal lattice was well distinguished and determined by the SAXS data.     

Subdiffusion and cage effect in a sheared granular material

We investigate experimentally the diffusion properties of a bidimensional bidisperse dry granular material under quasistatic cyclic shear. The comparison of these properties with results obtained both in computer simulations of hard spheres systems and Lennard-Jones liquids and experiments on colloidal systems near the glass transition demonstrates a strong analogy between the statistical behavior of granular matter and these systems, despite their intrinsic microscopic differences (thermal vs athermal). More specifically, we study in detail the cage dynamics responsible for the subdiffusion in the slow relaxation regime, and obtain the values of relevant time and length scales.     

X‐ray photon correlation spectroscopy under flow

X‐ray photon correlation spectroscopy was used to probe the diffusive dynamics of colloidal particles in a shear flow. Combining X‐ray techniques with microfluidics is an experimental strategy that reduces the risk of X‐ray‐induced beam damage and also allows time‐resolved studies of processes taking place in flow cells. The experimental results and theoretical predictions presented here show that in the low shear limit for a `transverse flow' scattering geometry (scattering wavevector q perpendicular to the direction of flow) the measured relaxation times are independent of the flow rate and determined only by the diffusive motion of the particles. This is not generally valid and, in particular, for a `longitudinal flow' ( q ∥ flow) scattering geometry the relaxation times are strongly affected by the flow‐induced motion of the particles. The results here show that the Brownian diffusion of colloidal particles can be measured in a flowing sample and that, up to flux limitations, the experimental conditions under which this is possible are easier to achieve at higher values of q.     

Crystallization of glassy metal surfaces in Mg–Zn alloy determined by resonant photoacoustic detection

Amorphous layers in a Mg-based alloy are studied by a resonant photoacoustic technique. The technique is shown to provide information on the crystallization temperature of a thin amorphous layer when the sample is heated. This determination provides crucial information regarding thermal stability of the treated surface, not accessible by standard calorimetric techniques. The layer analyzed is tens of micrometers thick, produced by rapid melting by a pulsed electron gun and subsequent rapid cooling towards the substrate. It is shown that the signal from the photoacoustic detection arises mainly from the volume change during crystallization at about 390 K. The volume change due to the structural relaxation of the glass before crystallization is also detected. PACS 64.70.Pf; 78.20.Nv; 81.70.Cv     

Dielectric relaxation of samarium aluminate

A ceramic SmAlO₃ (SAO) sample is synthesized by the solid-state reaction technique. The Rietveld refinement of the X-ray diffraction pattern has been done to find the crystal symmetry of the sample at room temperature. An impedance spectroscopy study of the sample has been performed in the frequency range from 50 Hz to 1 MHz and in the temperature range from 313 K to 573 K. Dielectric relaxation peaks are observed in the imaginary parts of the spectra. The Cole–Cole model is used to analyze the dielectric relaxation mechanism in SAO. The temperature-dependent relaxation times are found to obey the Arrhenius law having an activation energy of 0.29 eV, which indicates that polaron hopping is responsible for conduction or dielectric relaxation in this material. The complex impedance plane plot of the sample indicates the presence of both grain and grain-boundary effects and is analyzed by an electrical equivalent circuit consisting of a resistance and a constant-phase element. The frequency-dependent conductivity spectra follow a double-power law due to the presence of two plateaus.     

Time and amplitude dependences of the damping decrement and shear modulus upon irreversible structural relaxation in a Zr-Cu-Ni-Al-Ti bulk metallic glass

The time dependences of the irreversible relaxation of the damping decrement and the shear modulus of a Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ bulk metallic glass are investigated using an inverse torsion pendulum in the range from room temperature to ～650 K. The spectrum of activation energies of irreversible structural relaxation is evaluated from the results obtained. Analysis of the amplitude dependences of the damping decrement and the shear modulus allows the conclusion that the relaxation centers responsible for the amplitude dependence differ from those associated with the irreversible structural relaxation at temperatures below and in the vicinity of the glass transition point.     

Crystallization evolution and relaxation behavior of high entropy bulk metallic glasses using microalloying process

The role of the microalloying process in relaxation behavior and crystallization evolution of Zr_(20) Cu_(20) Ni_(20) Ti_(20) Hf_(20) high entropy bulk metallic glass(HEBMG) was investigated. We selected Al and Nb elements as minor elements, which led to the negative and positive effects on the heat of mixing in the master HEBMG composition, respectively. According to the results, both elements intensified β relaxation in the structure; however, α relaxation remained stable. By using different frequencies in dynamic mechanical analysis, it was revealed that the activation energy of β relaxation for the Nb-added sample was much higher, which was due to the creation of significant structural heterogeneity under the microalloying process. Moreover, it was found that Nb addition led to a diversity in crystallization stages at the supercooled liquid region.It was suggested that the severe structural heterogeneity in the Nb-added sample provided multiple energy-level sites in the structure for enhancing the crystallization stages.