Mesoscale modeling of microgel mechanics and kinetics through the swelling transition

The mechanics and swelling kinetics of polymeric microgels are simulated using a mesoscale computational model based on dissipative particle dynamics. Microgels are represented by a random elastic network submerged in an explicit viscous solvent. The model is used to probe the effect of different solvent conditions on the bulk modulus of the microgels. Comparison of the simulation results through the volume phase transition reveals favorable agreement with Flory-Rehner’s theory for polymeric gels. The model is also used to examine the microgel swelling kinetics, and is found to be in good agreement with Tanaka’s theory for spherical gels. The simulations show that, during the swelling process, the microgel maintains a nearly homogeneous structure, whereas deswelling is characterized by the formation of chain bundles and network coarsening.     

Tracking the interfacial dynamics of PNiPAM soft microgels particles adsorbed at the air–water interface and in thin liquid films

We report the behavior of thermosensitive soft microgel particles adsorbed at the air–water interface. We study the effect of temperature on the adsorption, interfacial diffusion, and surface rheology of pure N-isopropylacrylamide (NiPAM) microgel particles at the air–water interface. We find that the surface tensions of the solutions are the same as those of polyNiPAM solution; hence, their adsorption properties are dominated by the surface activity of the NiPAM repeat units of the particles. Particle-tracking experiments show that the particles adsorb irreversibly at the interface and form stable clusters at very low concentrations, e.g., 5.10^-3 wt%. We suggest that attractions between dangling arms or capillary interaction may be responsible for the formation of these clusters. For concentrations above 10^-2 wt%, the interface is filled with particles, and their Brownian diffusivity is arrested. The compression elastic moduli—measured using the pendant drop method—are one or two orders of magnitude below those obtained for hard particles and NiPAM chains, and their value is probably dominated by the intrinsic compressibility of the particles. The thin liquid films made from microgels exhibit a symmetric drainage, consistent with a high surface viscosity, but their lifetime is surprisingly short, illustrating the fragility of the films. We observed the formation of a monolayer of microgels bridging the two interfaces of the film outside the dimple. This zone grows and thins over time to a point where the microgels are highly compressed and stretched, resulting in the rupture of the film.     

Interparticle interaction and gel characterization of PE microgels using small- and large-strain viscoelastic response

PE microgels were prepared from mechanical fragmentation and from immiscible blends of PS and PE. The surface topology of microgels obtained from mechanical fragmentation was hypothesized to consist of long linear PE chains that are capable of interparticle co-crystallization as suggested by low-strain oscillatory shear experiment results. To investigate this hypothesis, PE microgels with a smooth surface and a PS corona were prepared using immiscible blends of PE and PS, followed by removal of the PS matrix. The rheological response of suspensions of PE microgels with a PS corona in squalane was similar to suspensions of PE microgels with crystallizable surface chains whereby the system would gel and exhibit hysteresis upon a cooling and heating cycle. Suspensions of PE microgels without any surface chains, however, were reversible over multiple cooling and heating cycles. It was determined that the PS corona and the cross-link density of the microgels had an effect (p < 0.01) on the reversibility whereas the microgel concentration in the suspension did not (p = 0.82).     

碳酸钙纳米颗粒复合超分子凝胶润滑剂的摩擦学性能研究

采用碳酸钙纳米颗粒与全氟聚醚型超分子凝胶复合得到了一种新型的纳米颗粒复合超分子凝胶润滑剂. 超分子凝胶具有错综复杂的网络结构,有效地提高了碳酸钙纳米颗粒在全氟聚醚润滑油中的分散稳定性. 此外,碳酸钙纳米颗粒作为添加剂极大地提高了超分子凝胶的润滑性能,使其表现出较好的耐高温性能,以及较高的承载力. 采用差式扫描量热仪、热重分析仪和流变分析仪对该复合润滑剂的热力学性能进行表征,结果显示该复合润滑剂具有很好的热稳定性以及较好的力学性能. 最后,通过X射线光电子能谱(XPS)对其摩擦机理进行表征,结果表明碳酸钙纳米颗粒复合超分子凝胶润滑剂优异的摩擦学性能可归因于碳酸钙纳米颗粒在摩擦副表面形成了易剪切的薄膜,以及小尺寸的纳米粒子在摩擦过程中对摩擦表面进行的自修复效应.      

Mechanics and chemical thermodynamics of phase transition in temperature-sensitive hydrogels

This paper uses the thermodynamic data of aqueous solutions of uncrosslinked poly(N-isopropylacrylamide) (PNIPAM) to study the phase transition of PNIPAM hydrogels. At a low temperature, uncrosslinked PNIPAM can be dissolved in water and form a homogenous liquid solution. When the temperature is increased, the solution separates into two liquid phases with different concentrations of the polymer. Covalently crosslinked PNIPAM, however, does not dissolve in water, but can imbibe water and form a hydrogel. When the temperature is changed, the hydrogel undergoes a phase transition: the amount of water in the hydrogel in equilibrium changes with temperature discontinuously. While the aqueous solution is a liquid and cannot sustain any nonhydrostatic stress in equilibrium, the hydrogel is a solid and can sustain nonhydrostatic stress in equilibrium. The nonhydrostatic stress can markedly affect various aspects of the phase transition in the hydrogel. We adopt the Flory-Rehner model, and show that the interaction parameter as a function of temperature and concentration obtained from the PNIPAM-water solution can be used to analyze diverse phenomena associated with the phase transition of the PNIPAM hydrogel. We analyze free swelling, uniaxially and biaxially constrained swelling of a hydrogel, swelling of a core-shell structure, and coexistent phases in a rod. The analysis is related to available experimental observations. Also outlined is a general theory of coexistent phases undergoing inhomogeneous deformation.     

Linear viscoelasticity of thermoassociative chitosan-g-poly(N-isopropylacrylamide) copolymer

Chitosan-g-poly(N-isopropylacrylamide) (chitosan-g-PNIPAM) was synthesized and characterized rheologically in aqueous solutions. The copolymer solution exhibits a thermoassociative behavior in which its elastic response dramatically increases when temperature is above the critical temperature or the association temperature, T _assoc. The copolymer at low concentration shows typical solution property. When the temperature is increased up to the critical temperature, the copolymer exhibits a gel-like characteristic due to the formation of physical cross-links between chitosan backbones through the self-aggregation of PNIPAM side chains. At high concentration, the system exhibits a weak elastic response due to the entanglement of the copolymer at 25°C. As temperature is raised above T _assoc, the system shows a strong elastic behavior due to the formation of additional physical cross-links via the aggregation of PNIPAM side chains. Chitosan-g-PNIPAM offers an attractive associating behavior in aqueous solution at temperature close to the body temperature, thus providing potential applications in pharmaceutical and medical industries.     

Relaxation and viscoelastic properties of complex polymer systems

Dynamic behavior of various polymer melts is studied on the basis of a comparison of viscoelastic properties with the information obtained from dielectric spectroscopy. The experimental observations are compared with results of computer simulation of corresponding systems. The studies include simple melts of linear chains, block copolymer systems of miscible components, as well as the behavior of melts with molecular objects of complex topology-like stars or microgels. In the case of polyisoprene linear chain melts an equivalence of terminal relaxation times determined from mechanical and dielectric measurements is demonstrated. Using linear block copolymers of isoprene and butadiene, relaxation times of chain fragments (isoprene blocks) in relation to relaxation times of whole copolymer chains are determined and compared with theory and simulation. Both the experimentally determined block relaxation times and relaxation times of chain fragments in simulated linear chain melts show a disagreement with predictions of the reptation theory. In the case of multiarm star polymers and microgel melts, the slow relaxation modes observed in viscoelastic spectra are assigned to cooperative translational motions detected in corresponding simulated systems in which an ordering of such molecules is demonstrated. This suggests that the terminal relaxation in multiarm star or microgel melts is governed by another relaxation mechanism than in linear chain melts. High efficiency of the Cooperative Motion Algorithm in simulation of dense systems of complex molecules is demonstrated.Dedicated to the memory of Professor Tasos C. Papanastasiou     

功能梯度界面相对周期分布纤维增强复合材料反平面剪切的影响

基于复变函数理论和边界配点法,探索了功能梯度界面相在周期均匀分布纤维增强复合材料反平面剪切问题中所起的作用。由于纤维在复合材料基体中的周期分布是均匀的,将其简化成含一功能梯度界面相夹杂的方形单胞。采用分层均匀化方法,将功能梯度界面相离散成K层界面层。当K足够大时,每个界面层可视为匀质材料,同时计算得到的复合材料宏观性能趋于定值。根据单胞内的基体、界面相和夹杂的几何外形特点,分别给出复势函数的级数形式,这些复势函数在各组分的相邻界面应满足连续性条件,在单胞的外边界应满足周期性边界条件和远场加载条件,从而确定复势函数中的待定系数,进而根据平均场理论确定复合材料有效模量。主要探讨了夹杂体积分数、各组分模量、功能梯度界面相的模量渐变形式等因素对纤维增强复合材料性能的影响。结果表明：不管基体模量相对于夹杂模量是大还是小,都有对应的界面相模量渐变形式可使夹杂周围的等效应力集中系数减小;另外还发现仅当夹杂模量较大时,功能梯度界面相模量的变化方式对复合材料有效模量产生不可忽视的影响。     

Prediction of nonlinear viscoelastic behavior of polymeric composites using an artificial neural network

Creep tests at constant stress are performed for the carbon-fiber reinforced epoxy composite at various temperatures and initial stresses. A nonlinear viscoelastic constitutive model is developed, and its material parameters are determined by fitting it to creep test data. Model results are found to agree very well with the experimental data at low temperature and low stress conditions. However, the agreement deteriorates at high temperatures, particularly in the vicinity of the glass transition temperature.An alternative model based on an artificial neural network (ANN) is developed to predict the stress relaxation of the polymer matrix composite. The ANN model is trained and validated with 9000 experimental data sets obtained from stress relaxation tests performed at various constant strain (initial stress) and constant temperature conditions. Training of the ANN employs a scaled conjugate gradient method. The optimal brain surgeon algorithm is employed to optimize the topology. The optimal ANN configuration has 88 processing elements (3 in the input layer, 45 in the first hidden layer, 39 in the second hidden layer, and 1 in the output layer) and 410 links. The predictions of the ANN model are found to be more accurate over a wider range of stress and temperature conditions than those of the explicit nonlinear viscoelastic model, in particular near the glass transition temperature.     

摩擦温度对Ni—P基复合刷镀层摩擦学性能的影响

为了考察摩擦温度对Ni-P基复合镀层摩擦学性能的影响,作者按球-盘接触形式推导出了计算摩擦温度的数学表达式,其对Ni-P/WC和Ni-P/BN及Ni-P/MoS_2等几种复合镀层摩擦温度的计算结果与试样表面层的硬度分布显示了良好的对应性。磨损试验结果表明,特别在高PV值的情况下,Ni-P基复合镀层的摩擦学性能主要受摩擦温度的影响。这是因为Ni-P基复合镀层在镀态下呈非晶态组织,受热发生晶化反应后会使硬度上升,但温度过高时硬度却又下降。因此,镀层硬度是依摩擦温度的高低及其在镀层中的梯度分布而呈现出不同的分布特征,从而揭示了Ni-P/WC复合镀层在高PV值条件下显示良好固体润滑性能的原因。     

A finite-deformation constitutive model for bulk metallic glass composites

The focus of this study is the development of an elastic-viscoplastic, three-dimensional, finite-deformation constitutive model to describe the large deformation behavior of bulk metallic glass (BMG) composite. A macroscopic theoretical formulation is proposed based on thermodynamic considerations to describe the response at ambient temperature and pressure, as well as at different strain rates. A constitutive equation is derived using the principle of thermodynamics and the augmenting of free energy. This is done by assuming that deformation within the constituent phases of the composite is affine; kinetic equations defining plastic shear and evolution of free volume concentration are then derived. The constitutive model is subsequently implemented in a finite-element program (Abaqus/Explicit) via a user-defined material subroutine. Numerical predictions are compared with experimental results from tests on La-based in situ BMG composite (La–Al–Cu–Ni) specimens cast in-house; this demonstrates that the model is able to describe the material behavior observed.     

Investigating the transient response of a shear thickening fluid using the split Hopkinson pressure bar technique

The split Hopkinson pressure bar (SHPB) technique is implemented to evaluate the transient response of a colloidal suspension exhibiting shear thickening at strain rates and timescales never before explored in a laboratory instrument. These suspensions are shown to exhibit a discontinuous transition from fluid-like (shear thinning) to solid-like (shear thickening) behavior when evaluated using rotational rheometry. The effect of loading rate on this transition time is studied for a particle volume fraction of 0.54 using the SHPB technique. It is shown that the time required for transition to occur decreases logarithmically with loading rate. From these results, we conclude that transition is not triggered by a characteristic shear rate, but rather a critical shear strain is required. Results from SHPB experiments performed up to Peclet numbers of order 10⁷ are presented and discussed for 0.50, 0.52, and 0.54 particle volume fraction suspensions.     

Thermal effects on interfacial stress transfer characteristics of carbon nanotubes/polymer composites

The paper presents an analytical method to investigate thermal effects on interfacial stress transfer characteristics of single/multi-walled carbon nanotubes/polymer composites system under thermal loading by means of thermoelastic theory and conventional fiber pullout models. In example calculations, the mechanical properties and the thermal expansion coefficients of carbon nanotubes and polymer matrix are, respectively, treated as the functions of temperature change. Numerical examples show that the interfacial shear stress transfer behavior can be described and affected by several parameters such as the temperature field, volume fraction of CNT, and numbers of wall layer and the outermost radius of carbon nanotubes. From the results carried out it is found that mismatch of thermal expansion coefficients between the carbon nanotubes and polymer matrix may be more important in governing interfacial stress transfer characteristics of carbon nanotubes/polymer composite system.     

Buckling and Postbuckling of Laminated Thin Cylindrical Shells under Hygrothermal Environments

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Physical gelation under shear for gelatin gels

Physical gelation is the process of crosslinking which reversibly transforms a solution of polymers into a gel. The crosslinks of the network have a physical origin (hydrogen bonding, Van der Waals forces... ) and therefore are sensitive to variations of temperature, pH, ionic content, etc. (non-permanent crosslinks). Physical and chemical gelation have been extensively studied in quiescent conditions, where rheology experiments have been performed to follow the network formation without disturbing the process. In this study we consider gelation of a well known physical, thermoreversible, gel (gelatin gel), which proceeds under flowing conditions. The gelling solution is submitted to a shearing, with imposed, permanent shear stresses or imposed, permanent, shear rates. Under flow, a competition arises between the formation of clusters by physical crosslinking and their disruption by the shear forces. This investigation defines the flowing conditions which either allow or impede gel formation. In particular, a critical shear rate , related to the gelation temperature and gelatin concentration, is identified which separates the two regimes. A microscopic model is proposed, based on the analysis of flow curves and dynamic measurements, which describes the structure of the gelling solution: microgel particles grow to a maximum size which depends on the flow. When the volume fraction of particles is high enough, percolation between particles occurs suddenly and a yield stress fluid is formed (particulate gel). The differences between gels made in quiescent conditions and gels made under flow are underlined.     

Influences of reinforcing particle and interface bonding strength on material properties of Mg/nano-particle composites

In the present study, an effective model is proposed to predict the effective elastic behavior of the three-phase composite containing spherical inclusions, each of which is surrounded by an interphase layer. The constitutive equations are derived for the stress and strain of each phase of the composite subjected to a far-field tension. Based on these constitutive laws, the effective bulk, shear and Young’s modulus are obtained. A statistical debonding criterion is adopted to characterize the varying probability of the evolution of interphase debonding. Influences of debonding damage, particle volume fraction, interphase properties and bonding strength on overall mechanical behavior of composites are also discussed. Numerical analyses are carried out on particle-reinforced composites and the predictions have a good agreement with the experimental results.     

Thermomechanical transitions in doubly-clamped micro-oscillators

The small size and low damping of MEMS oscillators give rise to phenomena that are not observed routinely at the macroscopic scale. In this work we document and explain an experimentally observed transition in the response of a doubly clamped micromechanical oscillator with pretension. The transition from softening to hardening is repeatedly observed upon increasing the power of an incident sensing laser beam, a procedure routinely used to improve signal strength during optical detection of resonant motion of microstructures. At intermediate laser power, a novel resonant response that displays characteristics of both softening and hardening in the same sweep, is observed experimentally. Increased laser heating of a structure in tension may be expected to increase softening behavior. Using tools from non-linear dynamics and continuum mechanics, we show that the observed counter-intuitive behavior can be explained by a competition between the opposing responses of linear and non-linear stiffnesses to a change in temperature.     

A comparison of nonlocal continuum and discrete dislocation plasticity predictions

Discrete dislocation simulations of two boundary value problems are used as numerical experiments to explore the extent to which the nonlocal crystal plasticity theory of Gurtin (J. Mech. Phys. Solids 50 (2002) 5) can reproduce their predictions. In one problem simple shear of a constrained strip is analyzed, while the other problem concerns a two-dimensional model composite with elastic reinforcements in a crystalline matrix subject to macroscopic shear. In the constrained layer problem, boundary layers develop that give rise to size effects. In the composite problem, the discrete dislocation solutions exhibit composite hardening that depends on the reinforcement morphology, a size dependence of the overall stress-strain response for some morphologies, and a strong Bauschinger effect on unloading. In neither problem are the qualitative features of the discrete dislocation results represented by conventional continuum crystal plasticity. The nonlocal plasticity calculations here reproduce the behavior seen in the discrete dislocation simulations in remarkable detail.