Dependence of Crystallization Behavior of Interacting Telechelic Poly(butylene succinate) Oligomer on Molecular Weight

A large spherulite structure deteriorates the mechanical properties of crystalline polymers, and therefore various methods have been explored to increase primary nucleation density. Recently, chain-end modification has been proposed as an effective approach for regulating polymer crystal nucleation. However, the relevant nucleation mechanism still requires investigation. Therefore, in this work, 2-ureido-4[1H]-pyrimidinone (UPy) units, which can form stacks via quadruple hydrogen bonds with each other, are introduced as end groups for the preparation of interacting telechelic poly(butylene succinate) (PBS-UPy) oligomers with different molecular weights (Mns). The crystallization, especially the nucleation behavior of PBS-UPy, is studied in detail by comparing with the corresponding pre-polymer, the hydroxyl-terminal PBS (PBS-OH). The thermal properties of PBS-UPy exhibit similar Mn-dependent tendency to those of PBS-OH, but with weaker total crystallization rate. The spherulite growth rate is significantly reduced, whereas the primary nucleation density is highly promoted, after introducing UPy groups. Further investigation reveals that the mechanism of UPy stacks’ influence on nucleation ability changes from inhibition to promotion with respect to Mn. Even under an inhibition of nucleation ability, the final nucleation density is obviously increased because of a significant decline of the growth rate. In addition, the change in the impact of UPy stacks on nucleation ability is speculated to originate from the memory expression feasibility of ordered conformation in the melt during crystallization.

Efficient Ag-Doped Perovskite Solar Cells Fabricated in Ambient Air

So far, it is still a great challenge to prepare high efficiency organic–inorganic perovskite solar cells in ambient air. Specifically, moisture is easily combined with the perovskite material during the spin-coating process, which result in porous perovskite films with poor surface morphology. In this study, we investigated crystalline Ag-doped perovskite films by a one-step spin-coating method in air with 30–40% relative humidity (RH), in which ethyl acetate (EA) was used as antisolvent can absorb moisture in air to reduced nucleation density. More significantly, EA is a feasible and environmentally friendly solvent to replace highly toxic solvent. Moreover, 1.0% Ag-doped device shows a highest power conversion efficiency (PCE) of 14.36%. The improved performance is not only ascribed to the superior CH3NH3PbI3 film with high crystallinity but to the versatile tunability of energy band structure.

Model Catalysis with HOPG-Supported Pd Nanoparticles and Pd Foil: XPS, STM and C2H4 Hydrogenation

A surface science based approach was applied to model carbon supported Pd nanoparticle catalysts. Employing physical vapour deposition of Pd on sputtered surfaces of highly oriented pyrolytic graphite (HOPG), model catalysts were prepared that are well-suited for characterization by X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). Analysis of the HOPG substrate before and after ion-bombardment, and of Pd/HOPG before and after annealing, revealed the number of “nominal” HOPG defects (~ 1014 cm−2) as well as the nucleation density (~ 1012 cm−2) and structural characteristics of the Pd nanoparticles (mean size/height/distribution). Two model systems were stabilized by UHV annealing to 300 °C, with mean Pd particles sizes of 4.3 and 6.8 nm and size/height aspect ratio up to ~ 10. A UHV-compatible flow microreactor and gas chromatography were used to determine the catalytic performance of Pd/HOPG in ethylene (C2H4) hydrogenation up to 150 °C under atmospheric pressure, yielding temperature-dependent conversion values, turnover frequencies (TOFs) and activation energies. The performance of Pd nanocatalysts is compared to that of polycrystalline Pd foil and contrasted to Pt/HOPG and Pt foil, pointing to a beneficial effect of the metal/carbon phase boundary, reflected by up to 10 kJ mol−1 lower activation energies for supported nanoparticles. Graphical Abstract

Impact of basement thrust faults on low-angle normal faults and rift basin evolution: a case study in the Enping sag, Pearl River Basin

Reactivation of pre-existing structures and their influence on subsequent rift evolution have been extensively analysed in previous research on rifts that experienced multiple phases of rifting, where pre-existing structures were deemed to affect nucleation, density, strike orientation, and displacement of newly formed normal faults during later rifting stages. However, previous studies paid less attention to the extensional structures superimposing onto an earlier compressional background, leading to a lack of understanding of, e.g. the reactivation and growth pattern of pre-existing thrust faults as low-angle normal faults and the impact of pre-existing thrust faults on newly formed high-angle faults and subsequent rift structures. This study investigating the spatial relationship between intra-basement thrust and rift-related faults in the Enping sag, in the northern South China Sea, indicates that the rift system is built on the previously deformed basement with pervasive thrusting structures and that the low-angle major fault of the study area results from reactivation of intra-basement thrust faults. It also implies that the reactivation mode of basement thrust faults is dependent on the overall strain distribution across rifts, the scale of basement thrust faults, and the strain shadow zone. In addition, reactivated basement thrust faults influence the nucleation, dip, and displacement of nearby new faults, causing them to nucleate at or merge into downwards it, which is representative of the coupled and decoupled growth models of reactivated thrust faults and nearby new faults. This work not only provides insights into the growth pattern of rift-related faults interacting with reactivated low-angle faults but also has broader implications for how basement thrust faults influence rift structures, normal fault evolution, and syn-rift stratigraphy.

Synthesis of Single-Crystal Graphene on Copper Foils Using a Low-Nucleation-Density Region in a Quartz Boat

The nucleation of graphene at different locations in the quartz boat was studied, and the lowest nucleation density of graphene in the quartz boat was found. The nucleation density of graphene is the lowest at the bottom of the quartz boat near the gas inlet side. Based on the above results, a simple and reproducible way is proposed to significantly suppress the nucleation density of graphene on the copper foil during the chemical vapor deposition process. Placing the copper foil with an area of 1.3 cm × 1 cm in the middle of the bottom of the quartz boat or further back, and placing two copper pockets in front of the copper foil, an ultra-low nucleation density of ~42 nucleus/cm2 was achieved on the back of the copper foil. Single-crystal monolayer graphene with a lateral size of 800 μm can be grown on the back of copper foils after 60 min of growth. Raman spectroscopy revealed the single-crystal graphene to be in uniform monolayers with a low D-band intensity.

Analysis of the Foaming Window for Thermoplastic Polyurethane with Different Hard Segment Contents

A series of thermoplastic polyurethanes (TPUs) with different amounts of hard segments (HS) (40, 50 and 60 wt.%) are synthesized by a pre-polymer method. These synthesized TPUs are characterized by Shore hardness, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), dynamic mechanical thermal analysis (DMTA), and rheology. Then, these materials are foamed by a one-step gas dissolution foaming process and the processing window that allows producing homogeneous foams is analyzed. The effect of foaming temperature from 140 to 180 °C on the cellular structure and on density is evaluated, fixing a saturation pressure of 20 MPa and a saturation time of 1 h. Among the TPUs studied, only that with 50 wt.% HS allows obtaining a stable foam, whose better features are reached after foaming at 170 °C. Finally, the foaming of TPU with 50 wt.% HS is optimized by varying the saturation pressure from 10 to 25 MPa at 170 °C. The optimum saturation and foaming conditions are 25 MPa and 170 °C for 1 h, which gives foams with the lowest relative density of 0.74, the smallest average cell size of 4 μm, and the higher cell nucleation density of 8.0 × 109 nuclei/cm3. As a final conclusion of this investigation, the TPU with 50 wt.% HS is the only one that can be foamed under the saturation and foaming conditions used in this study. TPU foams containing 50 wt.% HS with a cell size below 15 microns and porosity of 1.4–18.6% can be obtained using foaming temperatures from 140 to 180 °C, saturation pressure of 20 MPa, and saturation time of 1 h. Varying the saturation pressure from 10 to 25 MPa and fixing the foaming temperature of 170 °C and saturation pressure of 1 h results in TPU foams with a cell size of below 37 microns and porosity of 1.7–21.2%.

Effect of the Molecular Structure of TPU on the Cellular Structure of Nanocellular Polymers Based on PMMA/TPU Blends

In this work, the effects of thermoplastic polyurethane (TPU) chemistry and concentration on the cellular structure of nanocellular polymers based on poly(methyl-methacrylate) (PMMA) are presented. Three grades of TPU with different fractions of hard segments (HS) (60%, 70%, and 80%) have been synthesized by the prepolymer method. Nanocellular polymers based on PMMA have been produced by gas dissolution foaming using TPU as a nucleating agent in different contents (0.5 wt%, 2 wt%, and 5 wt%). TPU characterization shows that as the content of HS increases, the density, hardness, and molecular weight of the TPU are higher. PMMA/TPU cellular materials show a gradient cell size distribution from the edge of the sample towards the nanocellular core. In the core region, the addition of TPU has a strong nucleating effect in PMMA. Core structure depends on the HS content and the TPU content. As the HS or TPU content increases, the cell nucleation density increases, and the cell size is reduced. Then, the use of TPUs with different characteristics allows controlling the cellular structure. Nanocellular polymers have been obtained with a core relative density between 0.15 and 0.20 and cell sizes between 220 and 640 nm.

Nanoparticles Addition in PU Foams: The Dramatic Effect of Trapped-Air on Nucleation

To determine the effect of nanoclays and trapped air on the formation of rigid polyurethane foams, three different production procedures were used. To study the influence of mixing at atmospheric pressure, two approaches were carried out employing either an electric or a magnetic stirrer. The third approach was executed by mixing under vacuum conditions with magnetic stirring. The samples thus obtained were characterized, and the effect of trapped air into the reactive mixtures was evaluated by analyzing the cellular structures. Different levels of trapped air were achieved when employing each manufacturing method. A correlation between the trapped air and the increase in the nucleation density when nanoclays were added was found: the cell nucleation density increased by 1.54 and 1.25 times under atmospheric conditions with electric and magnetic stirring, respectively. Nevertheless, samples fabricated without the presence of air did not show any nucleating effect despite the nanoclay addition (ratio of 1.09). This result suggests that the inclusion of air into the components is key for improving nucleation and that this effect is more pronounced when the polyol viscosity increases due to nanoclay addition. This is the most important feature determining the nucleating effect and, therefore, the corresponding cell size decreases.

Study on Local Sub-Cooling Boiling in the Vertical Upward Pipe

In the heat transfer pipes of nuclear reactors with complex mass and heat exchange, there exists phenomenon of local sub-cooling boiling. Based on the Eulerian two-fluid model, this paper studied the local sub-cooling boiling phenomenon in the vertical upward pipe at a pressure of 4.5MPa. Firstly, a closed sub-cooling boiling model was built to make comparison with the existing experimental results of Bartolomei, the result of which is in great agreement with the experimental data. What’s more, the parameters of the experimental working conditions were expanded, it helped to analyze data that could not be directly measured in the experiment. The physical mechanism behind data distribution law mainly included the influence of the wall bubble departure diameter, the wall bubble departure frequency, and nucleation density. It is found that the RPI model has a good predictive ability for the liquid temperature field. The nucleation density model corresponding to KI combined with the wall departure diameter model KI can well predict the distribution of the void fractions in the pipe. Finally, the influence on heat and mass transfer of heating power along the pipe was analyzed. This paper put forward suggestions for the modification of the sub-cooling boiling model to help it predict the distribution of bubbles in the main flow region more precise.

Effect of Different Deposition Pressure on Diamond Films Deposited by Hot Filament Chemical Vapor Deposition

A hot filament chemical vapor deposition (HFCVD) method was adopted to deposit diamond films at deposition pressures ranging from 2–6 kPa. The effects of deposition pressure on the deposition rate, phase structure, and microstructure of diamond films were investigated. The surface morphology, grain size, micro-structure, and growth rate of the diamond films were analyzed using scanning electron microscopy, X-ray diffraction (XRD), and Raman spectrometry. The experimental results showed that granules on the surface exhibited increasingly compact structure with increasing deposition pressure. The diamond films deposited at various pressures have good compactness, and the particles on the film surfaces are arranged in an ordered manner. All films exhibited orientation along the (111) plane, which was the significant characteristic XRD peak of each diamond film. The (111) peak intensity was the strongest for the film prepared at 2 kPa deposition pressure. Overall, the deposition rate and grain size decreased with increasing deposition pressure, provided other deposition conditions remained unchanged. However, the densification of the microstructure and the nucleation density increased with increasing deposition pressure. Secondary nucleation became more pronounced as deposition pressure increased, and grain size decreased as nucleation density increased.