Molecular origin of shear thickening in transient polymer networks: A molecular dynamics study

This paper proposes a simple model of transient networks of telechelic associating polymers for molecular simulations and reports the main results obtained by molecular dynamics on the rheological properties of the transient networks. The steady shear viscosity obtained by the non-equilibrium molecular dynamics simulation exhibits shear thickening at moderate shear rates and shear thinning at larger shear rates. The behavior is similar to that observed in experiments of telechelic associating polymers. By analyzing the distribution function of the end-to-end vector of bridge chains as a function of the shear rate, we find that shear thickening is mainly caused by the stress from the bridge chains highly stretched by shear flow. We also find that fracture of the transient network occurs in the shear-thinning regime at high shear rates.     

Viscosity and lubricity of aqueous NaCl solution confined between mica surfaces studied by shear resonance measurement

We report the viscoelasticity of the thin film of aqueous NaCl solution confined between mica surfaces measured by shear resonance apparatus. The observed shear resonance curves at separations less than ca. 2 nm indicated that the solution exhibits the high lubrication effects under some loads. The effective viscosity (0.1-10 Pa s) obtained for the separations less than 1 nm from a mechanical model was 2-4 orders of magnitude larger than the bulk value. Our study employing a novel shear measurement provided a comprehensive picture for the dynamics of confined water thinner than a few nanometers.     

纳米级润滑膜分子排列取向的拉曼光谱表征技术

利用激光拉曼散射技术,对剪切作用下受限于钢球与石英盘之间的纳米级液晶5 CB的分子排列取向进行研究. 结果表明,在特定的实验条件下,可以得到高信噪比的纳米级润滑膜的拉曼散射信号(20∶1). 同时发现,当激光偏振方向与剪切运动方向平行(垂直)时,所得拉曼信号强度达到最大(小)值,表明纳米级液晶5 CB分子在剪切诱导作用下,沿剪切运动方向趋于定向排列. 另外,当钢球与石英盘之间的剪切速度逐渐增大时,受限的纳米级液晶5 CB的拉曼信号强度也逐渐增大. 最后,利用根据相对光强干涉原理研制的纳米膜厚测量仪对纳米级 关键词： 薄膜润滑 分子排列取向 拉曼散射     

Near-Field Birefringence Response of Liquid Crystal Molecules in Thickness Direction of Liquid Crystal Thin Film Orientated by Shear Force

Information of molecular orientation in nematic liquid crystal （LC） is attractive and important for applications in the field of display devices. We demonstrate a novel method using a birefringence scanning near-field optical microscope （Bi-SNOM） with a probe which is inserted into the LC thin film to detect the molecular orientation from its birefringence responses in the thickness direction of the LC thin film. The probe is laterally vibrated when going forward into the LC thin film, and the retardation and azimuth angle are recorded as the probe going down. Firstly, the thickness of the LC thin film is measured by the shear force detection. Since the shear force acts as a stimulation to reorientate the LC molecules above the substrate surface, we can detect the molecular orientation caused by a polyimide alignment substrate and the effect to molecular orientation caused by vibration of fibre probe. As a result, the orientation profiling of the LC film in depth direction is obtained in both the cases that the direction of probe vibrating is vertical/parallel to the rubbing direction of the alignment film. Furthermore, the thickness of completely orientated layers just above the substrate surface can also be obtained by either vibrating probe or no-vibrating probe. Ultimately, the LC thin film can be modelled in thickness direction from all the results using this method.     

Dynamics of capillary drying in water

We use atomistic simulations to address the question when capillary evaporation of water confined in a hydrocarbonlike slit is kinetically viable. Activation barriers and absolute rates of evaporation are estimated using open ensemble Monte Carlo-umbrella sampling and molecular dynamics simulations. At ambient conditions, the evaporation rate in a water film four molecular diameters thick is found to be of the order 10(5)(nm(2) s)(-1), meaning that water readily evaporates. Films more than a few nanometers thick will persist in a metastable liquid state. Dissolved atmospheric gas molecules do not significantly decrease the activation barrier.     

Frictional properties of confined polymers

We present molecular dynamics friction calculations for confined hydrocarbon solids with molecular lengths from 20 to 1400 carbon atoms. Two cases are considered: a) polymer sliding against a hard substrate, and b) polymer sliding on polymer. In the first setup the shear stresses are relatively independent of molecular length. For polymer sliding on polymer the friction is significantly larger, and dependent on the molecular chain length. In both cases, the shear stresses are proportional to the squeezing pressure and finite at zero load, indicating an adhesional contribution to the friction force. The friction decreases when the sliding distance is of the order of the molecular length indicating a strong influence of molecular alignment during run-in. The results of our calculations show good correlation with experimental work.     

Chain entanglement in thin freestanding polymer films

When a thin glassy film is strained uniaxially, a shear deformation zone (SDZ) can be observed. The ratio of the thickness of the SDZ to that of the undeformed film is related to the maximum extension ratio, lambda, which depends on the entanglement molecular weight, M(e). We have measured lambda as a function of film thickness in strained freestanding films of polystyrene as a probe of M(e) in confinement. It is found that thin films stretch further than thick films before failure, consistent with the interpretation that polymers in thin films are less entangled than bulk polymers, thus the effective value of M(e) in thin films is significantly larger than that of the bulk. Our results are well described by a conceptually simple model based on the probability of finding intermolecular entanglements near an interface.     

Correlation dimension of the sheared hard-disk Lorentz gas

The correlation dimension for the isokinetic Lorentz gas is calculated for hard disks using nonequilibrium molecular dynamics simulation. The trajectories are confined to a strange attractor embedded in a four-dimensional phase space—the additional degree of freedom having not been included properly until this work. This degree of freedom accounts for the explicit time dependence of the system (as quantified by the moving periodic cells under shear) and is significant because the collisions tend to synchronize with the periodic change of symmetry of the lattice at high shear rates.     

Effective viscosity of confined hydrocarbons

We present molecular dynamics friction calculations for confined hydrocarbon films with molecular lengths from 20 to 1400 carbon atoms. We find that the logarithm of the effective viscosity η(eff) for nanometer-thin films depends linearly on the logarithm of the shear rate: log η(eff)=C-nlog ?γ, where n varies from 1 (solidlike friction) at very low temperatures to 0 (Newtonian liquid) at very high temperatures, following an inverse sigmoidal curve. Only the shortest chain molecules melt, whereas the longer ones only show a softening in the studied temperature interval 0相似文献   

The mica slit-pore as a tool to control the orientation and distortion of simple liquid monolayers

Grand canonical ensemble Monte Carlo computer simulations have been used to study mono-layer octamethylcyclotetrasiloxane (OMCTS) and cyclohexane films confined between mica-like surfaces to determine the effect of the mica surfaces on the orientation and distortion of the films at different surface alignments. The film molecules are packed as a highly ordered lattice. The orientation of the lattice is fixed relative to the mica surfaces and depends on the size of the film molecule. Registry shifts distort the film lattice by effectively stretching it along a particular direction that depends on the size of the film molecule. For a particular registry, OMCTS and cyclohexane monolayers are stretched in perpendicular directions. Coupling between the monolayers and the mica surfaces generates a nonzero shear stress when the surfaces are out of alignment, but the film does not become disordered or melt. It is possible that precisely controlled solid surfaces could be used to create packed arrays of film molecules with desired orientation and degree of distortion that may be useful in nanotechnological applications.     

Shear localization in a model glass

Using molecular dynamics simulations, we show that a simple model of a glassy material exhibits the shear localization phenomenon observed in many complex fluids. At low shear rates, the system separates into a fluidized shear band and an unsheared part. The two bands are characterized by a very different dynamics probed by a local intermediate scattering function. Furthermore, a stick-slip motion is observed at very small shear rates. Our results, which open the possibility of exploring complex rheological behavior using simulations, are compared to recent experiments on various soft glasses.     

Fluidity of hydration layers nanoconfined between mica surfaces

We perform molecular dynamics simulations to investigate the shear dynamics of hydration water nanoconfined between two mica surfaces at 1 bar pressure and 298 K. Newtonian plateaus of shear viscosity comparable to the bulk value for different hydration layers D=0.92-2.44 nm are obtained. The origin of this persistent fluidity of the confined aqueous system is found to be closely associated with the rotational dynamics of water molecules, accompanied by fast translational diffusion under this confinement.     

Numerical simulation of flow in a screw-type blood pump

This study presents a numerical investigation of the flow field in a screw pump designed to circulate biological fluid such as blood. A simplified channel flow model is used to allow analysis using a Cartesian set of coordinates. Finite analytic (FA) numerical simulation of the flow field inside the channel was performed to study the influence of Reynolds number and pressure gradient on velocity distribution and shear stresses across the channel cross-section. Simulation results were used to predict flow rates, circulatory flow and the shear stresses, which are known to be related to the level of red blood cell damage (hemolysis) caused by the pump. The study shows that high shear levels are confined to small regions within the channel cross-section, but the circulatory nature of the flow causes an increased percentage of blood elements to pass through the high shear regions, and increases the likelihood of cell damage.     

Viscoelastic properties of confined molecular layers

We study the viscoelastic properties of a film of n layers of spherical molecules confined between two walls. We find that the dynamic response arises from two competing contributions: the effective stiffness of n + 1 springs in series and softening due to strain fluctuations. In particular, the latter are the origin of the oscillatory behavior of the stiffness and the damping coefficient. The dissipation is strongest at the minima of the stiffness; the inverse behavior may occur for a modulated relaxation time. As a corollary we show that confined molecular layers cannot be described as Maxwell fluids.     

Electrohydrodynamic controlled assembly and fracturing of thin colloidal particle films confined at drop interfaces

Particles can adsorb strongly at liquid interfaces due to capillary forces, which in practice can confine the particles to the interface. Here we investigate the electrohydrodynamic flow driven packing and deformation of colloidal particle layers confined at the surface of liquid drops. The electrohydrodynamic flow has a stagnation point at the drop equator, leading to assembly of particles in a ribbon shaped film. The flow is entirely controlled by the electric field, and we demonstrate that AC fields can be used to induce hydrodynamic “shaking” of the colloidal particle film. We find that the mechanical properties of the film is highly dependent on the particles: monodisperse polystyrene beads form packed granular monolayers which “liquefies” upon shaking, whereas clay mineral particles form cohesive films that fracture upon shaking. The results are expected to be relevant for understanding the mechanics and rheology of particle stabilized emulsions.     

Cluster crystals under shear

We show that a distinct class of colloidal crystals, which consist of mutually overlapping particles, has a novel and universal response to steady shear. After a shear-banding regime at low shear rates, strings parallel to the flow direction form as shear grows, which order on a hexagonal crystal in the gradient-vorticity plane. At even higher shear, lateral fluctuations of the strings, enhanced by hydrodynamics, lead to a disordered, fluid state. Our results are based on appropriate simulation techniques that correctly account for hydrodynamics. We also find that shear vastly accelerates the nucleation rates of supercooled fluids into the cluster crystals.     

Study of Friction between Liquid Crystals and Crystalline Surfaces by Molecular Dynamic Simulations

The lubrication characteristics of liquid crystal (LC) molecules sheared between two crystalline surfaces obtained from molecular dynamics (MD) simulations are reported in this article. We consider a coarse-grained rigid bead-necklace model of the LC molecules confined between two atomic surfaces subject to different shearing velocities. A systematic study shows that the slip length of LC lubrication changes significantly as a function of the LC-surface interaction energy, which can be well described though a theoretical curve. The slip length increases as shear rate increases at high LC-surface interaction energy. However, this trend can not be observed for low interaction energy. The orientation of the LC molecules near the surface is found to be guided by the atomics surfaces. The influence of temperature on the lubrication characteristics is also discussed in this article.     

Boundary lubrication properties of materials with expansive freezing

We have performed molecular dynamics simulations of solid-solid contacts lubricated by a model fluid displaying many of the properties of water, particularly its expansive freezing. Near the region where expansive freezing occurs, the lubricating film remains fluid, and the friction force decreases linearly as the shear velocity is reduced. No sign of stick-slip motion is observed, even at the lowest velocities. We give a simple interpretation of these results, and suggest that, in general, good boundary lubrication properties will be found in the family of materials with expansive freezing.     

Measurement of diffusion in the presence of shear flow

We demonstrate here a method whereby molecular diffusion coefficients may be measured in the presence of the deformational flow field of a rheo-NMR cell. The method, which uses a repetitive CPMG train of rf pulses interspersed with magnetic field gradient pulses, allows the anisotropic diffusion spectrum to be directly probed. We focus on the cylindrical Couette cell, for which the radial, tangential, and axial directions correspond to the hydrodynamic velocity gradient, velocity, and vorticity directions. While ideal Couette flow does not perturb the vorticity direction, it does perturb diffusion measurements for the velocity gradient direction, and to a lesser extent, the velocity direction. We show that with closely spaced gradient pulses operating in a flow-compensating mode, there exists a diffusion limit below which one cannot measure, that scales as T(2)gamma(4), where gamma is the shear rate and T the gradient pulse repetition period. For a typical rheo-NMR cell, and for the more challenging velocity gradient direction, diffusion rates above 10(-12) m(2) s(-1) can be accurately measured (to 1% error) at shear rates up to 3s(-1). We demonstrate the use of the method in measuring the diffusion spectrum of a lyotropic lamellar phase under shear.     

Log-rolling micelles in sheared amphiphilic thin films

Using molecular dynamics simulations, we show that sheared solutions of cylindrical micelle-forming amphiphiles behave very differently under extreme confinement as compared to the bulk. When confined to ultrathin films, the self-assembled cylindrical micelles roll along the shearing direction and align parallel to each other with their axes along the vorticity direction, as opposed to aligning parallel to the shearing direction in the bulk. It is shown that this new "log-rolling" phase arises due to a strong coupling between the rotational degree of freedom of the micelles and the steady sliding motion of the confining surfaces. We examine the microscopic mechanism of the log-rolling phenomenon and also discuss its dependence on the segregation strength and length of the amphiphile, the shear rate, and the film thickness.