Atomistic insights into solvation dynamics and conformational transformation in thermo-sensitive and non-thermo-sensitive oligomers

Solvation dynamics and conformational transformation in oligomers with varying degree of temperature sensitivity is studied using molecular dynamics (MD) simulations. Conformational transformation in three model systems namely poly(N-isopropylacrylamide) (PNIPAM), poly(acrylamide) (PAA), and poly(ethylene glycol) (PEG) are compared and contrasted to understand the origin of a coil-to-globule transformations across the lower critical solution temperature (LCST) in thermo-sensitive oligomers. PNIPAM, PAA, and PEG are water-soluble oligomers. However, for the temperature range used in these simulations, PNIPAM shows an LCST whereas PAA and PEG are non-thermo-sensitive. Oligomers of PNIPAM, PAA, and PEG consisting of 30 monomer units (30-mer) each were simulated at 5 °C (278 K) and 37 °C (310 K). Conformational transformations in the oligomers are evaluated using structural and dynamical correlation functions such as radius of gyration, radial distribution function, residence time probabilities and hydrogen-bonding life-times. Our simulations suggest that the solubility, solvation dynamics, and conformation of the oligomers are dictated by two factors: (a) the local structure of proximal water and (b) the diffusion and exchange kinetics of proximal water with bulk water. In thermo-sensitive oligomer such as PNIPAM, we find that the coil-to-globule transition is closely related to the local ordering and solvation dynamics of PNIPAM. We have identified stable configurations of proximal water molecules for an oligomer undergoing conformational transition. The slow diffusional properties of proximal water molecules near PNIPAM oligomers suggests that water forms a stable network near hydrophilic groups of PNIPAM as compared to the hydrophilic groups of PAA and PEG. Thermal perturbation of this solvated structure results in significant reduction in local ordering of water, which contributes to the globular collapse and the reduced solubility of PNIPAM above its LCST. On the other hand, non-thermo-sensitive oligomers such as PAA and PEG are characterized by much faster diffusion and exchange kinetics of proximal water at the two simulated temperatures compared to PNIPAM. This faster exchange kinetics helps in maintaining higher hydration level of the oligomers and is responsible for the apparent hydrophilic character and thereby the observed solubility at the two simulated temperatures.     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Processing and Properties of TiB2 with MoSi2 Sinter-additive: A First Report

The densification of non-oxide ceramics like titanium boride (TiB₂) has always been a major challenge. The use of metallic binders to obtain a high density in liquid phase-sintered borides is investigated and reported. However, a non-metallic sintering additive needs to be used to obtain dense borides for high-temperature applications. This contribution, for the first time, reports the sintering, microstructure, and properties of TiB₂ materials densified using a MoSi₂ sinter-additive. The densification experiments were carried out using a hot-pressing and pressureless sintering route. The binderless densification of monolithic TiB₂ to 98% theoretical density with 2–5 μm grain size was achieved by hot pressing at 1800°C for 1 h in vacuum. The addition of 10–20 wt% MoSi₂ enables us to achieve 97%–99%ρ_th in the composites at 1700°C under similar hot-pressing conditions. The densification mechanism is dominated by liquid-phase sintering in the presence of TiSi₂. In the pressureless sintering route, a maximum of 90%ρ_th is achieved after sintering at 1900°C for 2 h in an (Ar+H₂) atmosphere. The hot-pressed TiB₂–10 wt% MoSi₂ composites exhibit high Vickers hardness (∼26–27 GPa) and modest indentation toughness (∼4–5 MPa·m^1/2).     

Vortex characteristics due to nozzle clogging in water caster mould: modelling and validation

In continuous slab casting, clogging in the submerged entry nozzle (SEN) ports leads to flow asymmetry and vortex formation in the mould. Knowledge of vortexing and its influence on product quality is fundamental for defect-free production. In this study, the interconnected effects of nozzle clogging and SEN submergence depth, variation on flow asymmetry and vortex characteristics in a 0.4 scale water caster have been characterised by CFD investigation and validated with experimental results from the authors’ previous work. Mean flow velocities at the sub-meniscus and near the port exit predicted by the computational model are compared with the time-averaged values of the impeller probe velocity measurements and found to be in reasonable agreement. Three different clogging conditions (0, 33 and 66% in the left port of the SEN) for SEN submergence depth of 60?mm are studied and the 66% clogging produced vortices having largest diameter, which is consistent with the experimental observations. The effects of SEN submergence depth on flow asymmetry and vortexing are investigated with three different conditions – 40, 60 and 80?mm. It is found that the shallow SEN submergence depth (40?mm) produces vortices of largest diameter and the flow is most stable for a SEN submergence depth of 60?mm among the three cases. Vortex bending towards the SEN as noticed in the experimental observations is also observed in the computational study. This work illustrates the possibility of capturing features of vortexing using validated CFD model.     

蚕丝蛋白对魔芋葡甘聚糖结构与溶胶性能的影响

本文研究了蚕丝蛋白对魔芋葡甘聚糖(KGM)结构与溶胶性质的影响。通过溶胀平衡的数学分析方法,计算出偏摩尔自由能的变化,从而预测溶胀平衡参数。与此同时,利用红外光谱、扫描电镜和流变技术,分析了蚕丝蛋白-KGM复配体系的结构特征和流变性质。结果表明:蚕丝蛋白对KGM结构与溶胶性质有显著影响。随着蚕丝蛋白组分比例的增加,KGM分子内的氢键破坏程度增加,其凝胶的粘度及弹性模量下降,凝胶稳定性降低。     

A simple finite-difference frequency-domain (FDFD) algorithm for analysis of switching noise in printed circuit boards and packages

Simultaneous switching noise (SSN) compromises the integrity of the power distribution structure on multilayer printed circuit boards (PCB). Several methods have been used to investigate SSN. These methods ranged from simple lumped circuit models to full-wave (dynamic) three-dimensional Maxwell equations simulators. In this work, we present an efficient and simple finite-difference frequency-domain (FDFD) based algorithm that can simulate, with high accuracy, the capacity of a PCB board to introduce SSN. The FDFD code developed here also allows for simulation of real-world decoupling capacitors that are typically used to mitigate SSN effects at sub 1 GHz frequencies. Furthermore, the algorithm is capable of including lumped circuit elements having user-specified complex impedance. Numerical results are presented for several test boards and packages, with and without decoupling capacitors. Validation of the FDFD code is demonstrated through comparison with other algorithms and laboratory measurements.     

Failure analysis of left barrel of an aircraft engine

This investigation analyses the failure of left barrel used in engine of an aircraft. The barrel was subjected to detailed examination using standard non-destructive and destructive testing methods in order to identify the cause of failure of left barrel. The experimental results include fractography, chemical analysis, coating analysis and optical microstructure. The investigation concludes that failure is caused by the formation of corrosion pits which act as stress raiser and fatigue has assisted in propagation of the crack.     

Magnetoelectric properties of Ni/PZT/Ni layered composite for low field applications

A composite material when placed under the external magnetic/electric fields exhibits voltage/induced magnetization is known as magnetoelectric (ME) composite. Such composite materials should have ferroelectric and ferro/ferri magnetic phases as constituents. The magnetoelectric output is exhibited as a product property. Magnetoelectric composites are being used for variety of applications including resonators, filters, phase shifters, optical isolators, actuators and magnetic field sensors. Metal/ferroelectric/metal magnetoelectric composite using Ni and PZT as constituent phases has been fabricated in 2-2 composite pattern to study its product property. The paper presents magnetoelectric studies of Ni/PZT/Ni composite using low dc magnetic field magnetoelectric set-up. Using this ME set-up ME output of Ni/PZT/Ni composite is studied as a function of dc magnetic field. The results were analyzed to identify the useful magnetic field (dc and ac) range in which Ni/PZT/Ni sensor can be utilized for applications.     

Structural,optical and magnetic properties of nanocrystalline Zn0.9Co0.1O-based diluted magnetic semiconductors

With a view to understand the influence of nano size on various properties of cobalt-doped ZnO-based diluted magnetic semiconductors, a series of materials were prepared by the citrate gel route. The phase and morphology studies have been carried out by X-ray diffraction and transmission electron microscopy, respectively. All the samples of the present investigation are found to have hexagonal wurtzite structure and crystallite sizes are found to vary from 25 nm to 65 nm. From the optical absorption measurements it has been observed that upon doping with cobalt, the energy band gap is found to shift towards lower energy side (red shift) while it shifts towards higher energy side (blue shift) when the crystallite size is increased continuously. It has been observed from the XPS results that oxidation state of Cobalt is +2 and that the difference in binding energies of Co 2p_3/2 and Co 2p_1/2 is found to increase continuously with increasing crystallite size. Finally, all the samples are found to exhibit room temperature ferromagnetism and the specific magnetization decreases with increasing crystallite size.