Direct visualization of the nanoscopic three‐phase structure and stiffness of NBR/PVC blends by AFM nanomechanical mapping

The PeakForce Quantitative Nanomechanical Mapping based on atomic force microscope (AFM) is employed to first visualize and then quantify the elastic properties of a model nitrile rubber/poly(vinyl chloride) (NBR/PVC) blend at the nanoscale. This method allows us to consistently observe the changes in mechanical properties of each phase in polymer blends. Beyond measuring and discriminating elastic modulus and adhesion forces of each phase, we tune the AFM tips and the peak force parameters in order to reliably image samples. In view of viscoelastic difference in each phase, a three‐phase coexistence of an unmixed NBR phase, the mixed phase, and PVC microcrystallites is directly visualized in NBR/PVC blends. The nanomechanical investigation is also capable of recognizing the crosslinked rubber phase in cured rubber. The contribution of the mixed phase was quantified and it was found that the mechanical properties of blends are mainly determined by the homogeneity and stiffness of the mixed phase. This study furthers our understanding the structure–mechanical property relationship of thermoplastic elastomers, which is important for their potential design and applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 662–669     

A unified theory for brittle and ductile shear mode fracture

A unified theory captures both brittle and ductile fracture. The fracture toughness is proportional to the applied stress squared and the length of the crack. For purely brittle solids, this criterion is equivalent to Griffith's theory. In other cases, it provides a theoretical basis for the Irwin-Orowan formula. For purely ductile solids, the theory makes direct contact with the Bilby-Cottrell-Swinden model. The toughness is highest in ductile materials because the shielding dislocations in the plastic zone provide additional resistance to crack growth. This resistance is the force opposing dislocation motion, and the Peach-Koehler force overcomes it. A dislocation-free zone separates the plastic zone from and the tip of the crack. The dislocation-free zone is finite because molecular forces responsible for the cohesion of the surfaces near the crack tip are not negligible. At the point of crack growth, the length of the dislocation-free zone is constant and the shielding dislocations advance in concert. As in Griffith's theory, the crack is in unstable equilibrium. The theory shows that a dimensionless variable controls the elastoplastic behaviour. A relationship for the size of the dislocation-free zone is derived in terms of the macroscopic and microscopic parameters that govern the fracture.     

Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties

A new kind of nanocomposite (NC) hydrogel with Na‐montmorillonite (MMT) is presented in this article. The NC hydrogels were synthesized by free radical copolymerization of acrylamide and (3‐acrylamidopropyl) trimethylammonium chloride (ATC) in the presence of MMT and N,N′‐methylene‐bis‐acrylamide used as chemical cross‐linker. Due to the cation‐exchange reaction between MMT and ATC (cationic monomer) during the synthesis of NC hydrogels, MMT platelets were considered chemical “plane” cross‐linkers, different from “point” cross‐linkers. With increasing amount of MMT, the crosslinking degree enhanced, causing a decrease of the swelling degree at equilibrium. Investigations of mechanical properties indicated that NC hydrogels exhibited enhanced strength and toughness, which resulted from chemical interaction between exfoliated MMT platelets and polymer chains in hydrogels. Dynamic shear measurements showed that both storage modulus and loss modulus increased with increasing MMT content. The idea described here provided a new route to prepare hydrogels with high mechanical properties by using alternative natural Na‐MMT. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1020–1026     

Achieving Rich and Active Alkaline Hydrogen Evolution Heterostructures via Interface Engineering on 2D 1T‐MoS2 Quantum Sheets

Large‐scale production of hydrogen from water‐alkali electrolyzers is impeded by the sluggish kinetics of hydrogen evolution reaction (HER) electrocatalysts. The hybridization of an acid‐active HER catalyst with a cocatalyst at the nanoscale helps boost HER kinetics in alkaline media. Here, it is demonstrated that 1T–MoS₂ nanosheet edges (instead of basal planes) decorated by metal hydroxides form highly active ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ heterostructures, which significantly enhance HER performance in alkaline media. Featured with rich ${\text{edge}}_{{\text{1T‐MoS}}_{\text{2}}}$/ ${\text{edge}}_{\text{Ni}{(\text{OH})}_{\text{2}}}$ sites, the fabricated 1T–MoS₂ QS/Ni(OH)₂ hybrid (quantum sized 1T–MoS₂ sheets decorated with Ni(OH)₂ via interface engineering) only requires overpotentials of 57 and 112 mV to drive HER current densities of 10 and 100 mA cm^?2, respectively, and has a low Tafel slope of 30 mV dec^?1 in 1 m KOH. So far, this is the best performance for MoS₂‐based electrocatalysts and the 1T–MoS₂ QS/Ni(OH)₂ hybrid is among the best‐performing non‐Pt alkaline HER electrocatalysts known. The HER process is durable for 100 h at current densities up to 500 mA cm^?2. This work not only provides an active, cost‐effective, and robust alkaline HER electrocatalyst, but also demonstrates a design strategy for preparing high‐performance catalysts based on edge‐rich 2D quantum sheets for other catalytic reactions.     

Residual strain in cadmium telluride/gallium arsenide (001) heterostructures as a function of temperature

Optical studies of residual strain in cadmium telluride (CdTe) films grown using molecular beam epitaxy on gallium arsenide (GaAs) substrate have been performed using photoreflectance techniques. Measurements have been conducted to determine the fundamental transition energy, heavy-hole and light-hole transition energy critical-point parameters in a range of temperatures between 12 and 300 K. There are problems inherent in the fabrication of optoelectronic devices using high-quality CdTe films, due to strain effects resulting from both the lattice mismatch (CdTe: 14.6%) and the thermal expansion coefficient difference. The CdTe film exhibits compressive stress causing valence-band splitting for light and heavy holes. We have used different models to fit the obtained experimental data and, although the critical thickness for the CdTe has been surpassed, the strain due to the lattice mismatch is still significant. However, the strain due to the thermal expansion is dominant. We have found that the fundamental transition energy, E₀, is affected by the compressive strain and the characteristic values are smaller than those reported. In addition, the total strain is compressive for the full measured range, since the strain due to the lattice mismatch is one order of magnitude higher than that calculated from the thermal expansion.     

Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating

In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g^?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging.     

Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling

Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements.     

介绍一个与材料相关的研究型综合化学实验——壳聚糖的制备与表征

在中国科学技术大学夏季学期的研究型实验课程"化学科研基础训练"中开设"壳聚糖的制备与表征"综合实验,以龙虾壳为原料,通过除蛋白、脱盐、脱色、脱乙酰等一系列反应,制备得到目标产物壳聚糖。运用红外光谱、核磁共振仪、黏度法、滴定等对产品的结构及性能进行表征。