Insight into shear‐induced modification for improving processability of polymers: Effect of shear rate on the evolution of entanglement state

Many experimental results have revealed that the re‐entanglement kinetics of disentangled polymers is much slower than that predicted by tube theory. This retarded recovery of fully entangled state is of practical significance that shear‐induced modification may offer a way to improve processability for a polymer by reducing viscosity. This work tried to figure out the shear‐rate dependence variation of viscosity in the view of evolution of entanglement state through disentanglement and re‐entanglement, aiming to provide fundamental insights into application prospect of shear‐induced modification in preparing “in‐pellet” disentangled polymers prior to final processing. High‐density polyethylene was sheared on a parallel‐plate rotational rheometer with a linearly increased shear rate. Results showed that higher shear rate could induce further disentanglement, resulting in a lower viscosity with a reduction rate up to 93.7%, larger molecular weight between entanglements M_e , and longer re‐entanglement time. Additionally, less entanglement would give a larger lamellar thickness of sheared samples after nonisothermal crystallization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 598–606     

Catalytic Chemosensing Assay for Selective Detection of Methyl Parathion Organophosphate Pesticide

Herein, a catalytic chemosensing assay (CCA), based on a bimetallic complex, [Ru^II(bpy)₂(CN)₂]₂(Cu^II)₂ (bpy=2,2′-bipyridine), is described. This complex integrates a task-specific catalyst (Cu^I-catalyst) and a signaling unit ([Ru^II(bpy)₂(CN)₂]) to specifically hydrolyze methyl parathion, a highly toxic organophosphate (OP) pesticide. The bimetallic complex catalyzed the hydrolysis of the phosphate ester to generate o,o-dimethyl thiophosphate (DTP) anion and 4-nitrophenolate. Intrinsically, 4-nitrophenolate absorbed UV/Vis light at λ_max=400 nm, creating the first level of the chemosensing signal. DTP interacted with the original complex to displace the chromophore, [Ru^II(bpy)₂(CN)₂], which was monitored by spectrofluorometry; this was classified as the second level of chemosensing signal. By integrating both spectroscopic and spectrofluorometric signals with a simple AND logic gate, only methyl parathion was able to provide a positive response. Other aromatic and aliphatic OP pesticides (diazinon, fenthion, meviphos, terbufos, and phosalone) and 4-nitrophenyl acetate provided negative responses. Furthermore, owing to the metal-catalyzed hydrolysis of methyl parathion, the CCA system led to the detoxification of the pesticide. The CCA system also demonstrated its catalytic chemosensing properties in the detection of methyl parathion in real samples, including tap water, river water, and underground water.     

An automated vane shear test tool for environmental monitoring with unmanned ground vehicles

The present work describes the development of a novel robotic vane shear test tool for characterization of soil parameters with high precision and accuracy. The tool automates industrial standards for testing procedures. The proposed system is capable of performing high resolution torque measurements, which are then used to estimate the shear strength of the soil. The design of the instrument and its advantages over traditional manual instruments are discussed, after which error sources, calibration, and test procedures are described. The developed tool was successfully validated against high-end commercial equipment. The built unit was employed for characterizing mine waste in a laboratory setting and also deployed in the field on board an Unmanned Ground Vehicle for remote soil characterization.     

Wall shear stress modified by bubbles in a horizontal channel flow of silicone oil in the transition region

We performed laboratory experiments on bubbly channel flows using silicone oil, which has a low surface tension and clean interface to bubbles, as a test fluid to evaluate the wall shear stress modification for different regimes of bubble migration status. The channel Reynolds numbers of the flow ranged from 1000 to 5000, covering laminar, transition and turbulent flow regimes. The bubble deformation and swarms were classified as packing, film, foam, dispersed, and stretched states based on visualization of bubbles as a bulk void fraction changed. In the dispersed and film states, the wall shear stress reduced by 9% from that in the single-phase condition; by contrast, the wall shear stress increased in the stretched, packing, and foam states. We carried out statistical analysis of the time-series of the wall shear stress in the transition and turbulent-flow regimes. Variations of the PDF of the shear stress and the higher order moments in the statistic indicated that the injection of bubbles generated pseudo-turbulence in the transition regime and suppressed drag-inducing events in the turbulent regime. Bubble images and measurements of shear stress revealed a correlated wave with a time lag, for which we discuss associated to the bubble dynamics and effective viscosity of the bubble mixture in wall proximity.     

Two-dimensional optical coherence tomography for real-time structural dynamical characterization

We present a two-dimensional optical coherence vibration tomography (2DOCVT) system with an ultra-precision displacement resolution of ~0.1 nm that is capable of in site real-time absolute displacement measurement of structural line vibrations. Experimental results of sinusoidal, sweep and impulse vibrations were reported. The key figures of merit such as the 2DOCVT system could obtain fast line vibration measurement without scanning and it also could be used to capture structural modal parameters in one single impulse excitation measurement without any vibration excitation input information, making it attractive for the application in low-frequency vibration measurement and response-only modal analysis.     

Hexametaphosphate‐Capped Silica Mesoporous Nanoparticles Containing CuII Complexes for the Selective and Sensitive Optical Detection of Hydrogen Sulfide in Water

Cu^II‐macrocycle functionalized hexametaphosphate‐capped silica mesoporous nanoparticles have been prepared and used for the selective and sensitive detection of hydrogen sulfide in aqueous environments. The possibility of using different metal complexes combined with different capping anions and choice of different dyes or other sensing molecules as indicators makes this new protocol highly appealing for the preparation of new sensing systems for sulfide detection in different environments.     

Length scale effects in epoxy: The dependence of elastic moduli measurements on spherical indenter tip radius

Significant increases in the measured elastic moduli with decreasing indentation depth have been previously found in various polymers by indentation tests with a Berkovich tip at micro-to nanometer length scales. These increases in the determined elastic moduli were related to second order displacement gradients which increase with decreasing depth when a conical tip is applied. When a spherical tip is applied, such depth dependence should not be present as the second order displacement gradients remain essentially unchanged with indentation depth. However, these gradients should be proportional to the radius of the spherical tip. To examine the notion of second order displacement gradient dependence in measurements of elastic moduli, indentation experiments are conducted on epoxy with spherical tips of different nominal radii. Accounting for tip imperfections, an increase in the determined elastic moduli is found with decreasing tip radius, which corroborates the notion of second order displacement gradient dependence.     

基于八面体理论的岩石循环加-卸载本构模型及修正

探究岩石的受力特点及破坏特性是研究岩石地下工程安全性的关键,诸多学者都期望能在岩石本构模型的研究上取得突破性进展。在此背景下,提出了一种能够描述循环加-卸载条件下岩石的本构模型。首先,假设岩石的微元强度服从八面体剪应力理论并且微元破坏服从Weibull概率公式,将岩石本构中的损伤变量以及岩石微元强度表达式里包含的损伤因子进行本构变换,得到关于应力、应变等其他表现加-卸载下岩石损伤本构模型的参数,表示出岩石微元强度和损伤变量,再将得到的岩石微元强度和损伤变量代入所提出的岩石本构模型中,并进行等式变换得到一个函数表达式。通过将其与实验数据进行拟合对比分析,得出修正后的拟合参数,将其代入函数式中,得到损伤本构模型的修正式。最后将拟合参数进行必要的敏感性分析,得出各拟合参数的实际物理意义。     

自由活塞斯特林发动机活塞位移测量

自由活塞斯特林发动机活塞往复振动位移对研究发动机特性具有重要意义,然而该类发动机活塞位于高压封闭腔体内且结构较为紧凑,其活塞往复振动位移难于直接进行测量。加速度传感器具有尺寸小、安装方便和工作稳定等特点,提出了采用加速度传感器测量活塞位移的方法。根据加速度传感器测量位移的原理,建立了一套加速度传感器测量自由活塞斯特林发动机活塞位移的标定试验系统,以位移传感器为基准测试并分析了不同活塞振幅和不同振动频率下加速度传感器测量位移的误差大小。实验结果表明,在活塞振幅小于8 mm,振动频率大于20 Hz条件下,加速度传感器测量位移的误差小于5%。因此加速度传感器可以用于测量自由活塞斯特林发动机的活塞往复运动位移。最后成功把加速度传感器测量的自由活塞斯特林发动机活塞振动位移用于发动机循环指示功的实验研究。     

Biocatalytic Feedback‐Controlled Non‐Newtonian Fluids

Non‐Newtonian fluids are ubiquitous in daily life and industrial applications. Herein, we report an intelligent fluidic system integrating two distinct non‐Newtonian rheological properties mediated by an autocatalytic enzyme reaction. Associative polyelectrolytes bearing a small amount of ionic and alkyl groups are engineered: by carefully balancing the charge density and the hydrophobic effect, the polymer solutions demonstrate a unique shear thickening property at low pH while shear thinning at high pH. The urea‐urease clock reaction is utilized to program a feedback‐induced pH change, leading to a strong upturn of the nonlinear viscoelastic properties. As long as the chemical fuel is supplied, two distinct non‐Newtonian states can be achieved with a tunable lifetime span. As a proof of concept, we demonstrate how the physical energy‐driven nonequilibrium properties can be manipulated by a chemical‐fueled process.