Disentangling the Orientations of Spectrally Overlapping Transition Dipoles in Dense Dye Layers.

The transition dipole orientations of dye assemblies in heterostructures have a crucial impact on the efficiency of novel optoelectronic devices such as organic thin-film transistors and light-emitting diodes. These devices are frequently based on heterojunctions and tandem structures featuring multiple optical transitions. Precise knowledge of preferred orientations, spatial order, and spatial variations is highly relevant. We present a fast and universal large-area screening method to determine the transition dipole orientations in dye assemblies with diffraction-limited spatial resolution. Moreover, our hyperspectral imaging approach disentangles the orientations of different chromophores. As a demonstration, we apply our technique to dye monolayers with two optical transitions sandwiched between two ultrathin silicate nanosheets. A comprehensive model for dipole orientation distributions in monolayers reveals a long-range orientational order and a strong correlation between the two transitions.

The Effect of Sodium Bentonite in the Thermo-Catalytic Reduction of Viscosity of Heavy Oils.

To study the synergistic catalysis of an ex situ catalyst and in situ clay in the aquathermolysis of heavy oil, in this paper, a series of bentonite-supported catechol-metal complexes were prepared, and the catalytic viscosity reduction performance in the aquathermolysis of heavy oil was investigated. Under the optimized conditions, the viscosity can be reduced by 73%, and the pour point can be lowered by 15.0 °C at most, showing the synergistic catalysis of the ex situ catalyst and in situ clay in this aquathermolytic reaction. Thermogravimetry, physical adsorption-desorption, and scanning electron microscopy were conducted to characterize the thermal stability and microstructure of the ex situ catalyst. The components of the heavy oil before and after the reaction were fully characterized. Six model compounds were used to simulate the aquathermolysis reaction process. In order to study the mechanism of viscosity reduction after the catalytic aquathermolysis reaction, the compounds were analyzed by GC-MS. It is believed that these results will be beneficial in the future for related research in this field.

Delamination by Repulsive Osmotic Swelling of Synthetic Na-Hectorite with Variable Charge in Binary Dimethyl Sulfoxide-Water Mixtures.

Swelling of clays is hampered by increasing layer charge. With vermiculite-type layer charge densities, crystalline swelling is limited to the two-layer hydrate, while osmotic swelling requires ion exchange with bulky and hydrophilic organic molecules or with Li+ cations to trigger repulsive osmotic swelling. Here, we report on surprising and counterintuitive osmotic swelling behavior of a vermiculite-type synthetic clay [Na0.7]inter[Mg2.3Li0.7]oct[Si4]tetO10F2 in mixtures of water and dimethyl sulfoxide (DMSO). Although swelling in pure water is restricted to crystalline swelling, with the addition of DMSO, osmotic swelling sets in at some threshold composition. Finally, when the DMSO concentration is increased further to 75 vol %, swelling is restricted again to crystalline swelling as expected. Repulsive osmotic swelling thus is observed in a narrow composition range of the binary water-DMSO mixture, where a freezing point suppression is observed. This suppression is related to DMSO and water molecules exhibiting strong interactions leading to stable molecular clusters. Based on this phenomenological observation, we hypothesize that the unexpected swelling behavior might be related to the formation of different complexes of interlayer cations being formed at different compositions. Powder X-ray diffraction and 23Na magic angle spinning-NMR evidence is presented that supports this hypothesis. We propose that the synergistic solvation of the interlayer sodium at favorable compositions exerts a steric pressure by the complexes formed in the interlayer. Concomitantly, the basal spacing is increased to a level, where entropic contributions of interlayer species lead to a spontaneous thermodynamically allowed one-dimensional dissolution of the clay stack.

Multi-Mixed Metal Hydroxide as a Strong Stratigraphic Nanoclay Inhibitor in Solid-Free Drilling Fluid.

Solid-free drilling fluid has more advantages as a new type of drilling fluid compared with traditional drilling fluid, such as improving drilling efficiency, protecting oil and not having clay particles clog the oil and gas layer. In this study, Zn/Cu/Fe-doped magnesium-aluminum hydroxide (Mg-Al MMH) was prepared using the co-precipitation method and evaluated in solid-free drilling fluid. The inhibition mechanism of synthesized hydroxide was analyzed by X-ray diffraction, laser particle-size analysis and thermogravimetric analysis. The samples were directly used as drilling fluid base muds for performance evaluation. The results showed that the linear expansion rate of 4% M6-Fe was only 12.32% at room temperature within 2 h, that the linear expansion rate was 20.28% at 90 °C and that the anti-swelling rate was 81.16% at room temperature, indicating that it has a strong inhibition ability at both room temperature and at high temperatures. Meanwhile, the possibility of multi-mixed metal hydroxide as a drilling fluid base mud is discussed in this study. We found that 4% M6-Fe exhibited low viscosity, a high YP/PV ratio and high temperature resistance, and its apparent viscosity retention rate reached 100% rolled at 200 °C for 16 h, with a YP/PV ratio of 2.33.

Light-steered locomotion of muscle-like hydrogel by self-coordinated shape change and friction modulation.

Many creatures have the ability to traverse challenging environments by using their active muscles with anisotropic structures as the motors in a highly coordinated fashion. However, most artificial robots require multiple independently activated actuators to achieve similar purposes. Here we report a hydrogel-based, biomimetic soft robot capable of multimodal locomotion fueled and steered by light irradiation. A muscle-like poly(N-isopropylacrylamide) nanocomposite hydrogel is prepared by electrical orientation of nanosheets and subsequent gelation. Patterned anisotropic hydrogels are fabricated by multi-step electrical orientation and photolithographic polymerization, affording programmed deformations. Under light irradiation, the gold-nanoparticle-incorporated hydrogels undergo concurrent fast isochoric deformation and rapid increase in friction against a hydrophobic substrate. Versatile motion gaits including crawling, walking, and turning with controllable directions are realized in the soft robots by dynamic synergy of localized shape-changing and friction manipulation under spatiotemporal light stimuli. The principle and strategy should merit designing of continuum soft robots with biomimetic mechanisms.