Effect of Sinusoidal Surface Roughness and Energy on the Orientation of Cylinder-Forming Block Copolymer Thin Films

We explore the relative stability of three possible orientations of cylinder-forming di-block copolymer on a sinusoidally corrugated substrate. The cylinders can be aligned either parallel to the substrate, with their long axis being oriented along or orthogonal to the corrugation trenches, or perpendicular to the substrate. Using self-consistent field theory, we investigate the influence of substrate roughness and surface preference on the phase transition between the three orientations. When the substrate preference, $u$, towards one of components is small, increasing the substrate roughness induces a phase transition from parallel to perpendicular cylindrical phase. However, when $u$ is large, the parallel orientation is more stable than the perpendicular one. Within this parallel phase, increasing the substrate roughness leads to a transition of cylinder orientation changing from being orthogonal to parallel to the trench long axis. Increasing the substrate preference leads to an opposite transition from parallel to orthogonal to the trenches. Furthermore, we predict that the perpendicular cylinder phase is easier to be obtained when the unidirectional corrugation is along the longer unit vector of the hexagonal packing than when it is along the shorter unit vector. Our results qualitatively agree with previous experiments, and contribute towards applications of the cylinder-forming block copolymer in nanotechnology.Comment: 9 pages, 7 figure

The Chain Flexibility Effects on the Self-assembly of Diblock Copolymer in Thin Film

We investigate the effects of chain flexibility on the self-assembly behavior of symmetric diblock copolymers (BCPs) when they are confined as a thin film between two surfaces. Employing worm-like chain (WLC) self-consistent field theory, we study the relative stability of parallel (L$_{\parallel}$) and perpendicular (L$_{\perp}$) orientations of BCP lamellar phases, ranging in chain flexibility from flexible Gaussian chains to semi-flexible and rigid chains. For flat and neutral bounding surfaces (no surface preference for one of the two BCP components), the stability of the L$_{\perp}$ lamellae increases with chain rigidity. When the top surface is flat and the bottom substrate is corrugated, increasing the surface roughness enhances the stability of the L$_{\perp}$ lamellae for flexible Gaussian chains. However, an opposite behavior is observed for rigid chains, where the L$_{\perp}$ stability decreases as the substrate roughness increases. We further show that as the substrate roughness increases, the critical value of the substrate preference, $u^{*}$, corresponding to an L$_{\perp}$-to-L$_{\parallel}$ transition, decreases for rigid chains, while it increases for flexible Gaussian chains. Our results highlight the physical mechanism of tailoring the orientation of lamellar phases in thin-film setups. This is of importance, in particular, for short (semi-flexible or rigid) chains that are in high demand in emerging nanolithography and other industrial applications

Kinetic Paths of Block Copolymer Particles: Dynamic Self-Consistent Field Theory Studies

We explore the kinetic paths of structural evolution and formation of block copolymer (BCP) particles using dynamic self-consistent field theory (DSCFT). We show that the process-directed self-assembly of BCP immersed in a poor solvent leads to the formation of striped ellipsoids, onion-like particles and double-spiral lamellar particles. The theory predicts a reversible path of shape transition between onion-like particles and striped ellipsoidal ones by regulating the temperature (related to the Flory-Huggins parameter between the two components of BCP, $\chi_{\rm{AB}}$) and the selectivity of solvent towards one of the two BCP components. Furthermore, a kinetic path of shape transition from onion-like particles to double-spiral lamellar particles, and then back to onion-like particles is demonstrated. By investigating the inner-structural evolution of a BCP particle, we identify that changing the intermediate bi-continuous structure into a layered one is crucial for the formation of striped ellipsoidal particles. Another interesting finding is that the formation of onion-like particles is characterized by a two-stage microphase separation. The first is induced by the solvent preference, and the second is controlled by the thermodynamics. Our findings lead to an effective way of tailoring nanostructure of BCP particles for various industrial applications, ranging from sensors to smart coating to drug delivery

Formation of Diblock Copolymer Nanoparticles: Theoretical Aspects

We explore the shape and internal structure of diblock copolymer (di-BCP) nanoparticles (NPs) by using the Ginzburg-Landau free-energy expansion. The self-assembly of di-BCP lamellae confined in emulsion droplets can form either ellipsoidal or onion-like NPs. The corresponding inner structure is a lamellar phase that is either perpendicular to the long axis of the ellipsoids (L$_\perp$) or forms a multi-layer concentric shell (C$_\parallel$), respectively. We focus on the effects of the interaction parameter between the A/B monomers $\tau$, and the polymer/solvent $\chi$, as well as the NP size on the nanoparticle shape and internal morphology. The aspect ratio ($l_{\rm AR}$) defined as the length ratio between the long and short axes is used to characterize the overall NP shape. Our results show that for the solvent that is neutral towards the two blocks, as $\tau$ increases, the $l_{\rm AR}$ of the NP first increases and then decreases, indicating that the NP becomes more elongated and then changes to a spherical NP. Likewise, decreasing $\chi$ or increasing the NP size can result in a more elongated NP. However, when the solvent has a preference towards the A or B blocks, the NP shape changes from striped ellipsoid to onion-like sphere by increasing the A/B preference parameter strength. The critical condition of the transition from an L$_\perp$ to C$_\parallel$ phase has been identified. Our results are in good agreement with previous experiments, and some of our predictions could be tested in future experiments

Unsupervised SAR Despeckling by Combining Online Speckle Generation and Unpaired Training

Speckle suppression is a crucial preliminary step for synthetic aperture radar (SAR) image processing. Supervised despeckling approaches trained on synthetic datasets usually perform poorly in practice due to the unavailability of clean SAR images. Besides, the spatial correlation of speckle is rarely considered in many methods based on the fully developed speckle assumption. In this article, we propose an unsupervised despeckling method to address these issues by combining online speckle generation and unpaired training. The method consists of two branches: the stop-gradient branch and the unpaired branch. First, the stop-gradient branch learns to generate the spatially correlated speckle. Then, the unpaired branch combines the generated speckle with the unpaired optical image to form pairs of training data for network parameter updates. More specifically, in order to generate the more realistic speckle in the stop-gradient branch, we design a speckle correction module with three SAR speckle priors: the threshold prior, the unit mean prior, and the correlation prior coupled with the weighted patch-shuffle. In the unpaired training, a hybrid loss function is employed, which takes spatial smoothness and detail protection into consideration. Afterward, we combine the stop-gradient branch with the unpaired branch by the Siamese network to achieve alternate optimization of speckle generation and speckle removal. Finally, the optimization process in our method is analyzed theoretically. Qualitative and quantitative experiments demonstrate that the proposed method is comparable to the supervised despeckling approaches on synthetic datasets and outperforms several state-of-the-art unsupervised methods on real SAR datasets

Formation of diblock copolymer nanoparticles: Theoretical aspects

We explore the shape and internal structure of diblock copolymer (di-BCP) nanoparticles (NPs) by using the Ginzburg-Landau free-energy expansion and the dynamic self-consistent field theory (DSCFT). The self-assembly of di-BCP lamellae confined in emulsion droplets can form either ellipsoidal or onion-like NPs. The corresponding inner structure is a lamellar phase that is either perpendicular to the ellipsoid long axis (L⊥) or forms a multi-layer concentric shell (C∥), respectively. We focus on the effects of the interaction parameters between the A and B monomers χ, and polymer/solvent χPS, as well as the NP size on the nanoparticle shape and internal morphology. The aspect ratio (lAR), defined as the length ratio between the long and short axes, is used to characterize the overall NP shape. Our results show that when the solvent is neutral towards the two blocks, the ratio lAR increases as χ increases, indicating that the NP becomes more elongated. Likewise, decreasing χPS or increasing the NP size also results in a more elongated NP. Furthermore, as the solvent preference towards one of the A or B blocks increases, the NP undergoes a shape transition from a striped ellipsoid (L⊥) to onion-like sphere (C∥). Our results are in good agreement with previous experiments, and some of the predictions could be tested in future experiments

Optimum O2:CH4 Ratio Promotes the Synergy between Aerobic Methanotrophs and Denitrifiers to Enhance Nitrogen Removal

The O2:CH4 ratio significantly effects nitrogen removal in mixed cultures where aerobic methane oxidation is coupled with denitrification (AME-D). The goal of this study was to investigate nitrogen removal of the AME-D process at four different O2:CH4 ratios [0, 0.05, 0.25, and 1 (v/v)]. In batch tests, the highest denitrifying activity was observed when the O2:CH4 ratio was 0.25. At this ratio, the methanotrophs produced sufficient carbon sources for denitrifiers and the oxygen level did not inhibit nitrite removal. The results indicated that the synergy between methanotrophs and denitrifiers was significantly improved, thereby achieving a greater capacity of nitrogen removal. Based on thermodynamic and chemical analyses, methanol, butyrate, and formaldehyde could be the main trophic links of AME-D process in our study. Our research provides valuable information for improving the practical application of the AME-D systems

Multifunctional Single-Site Catalysts for Alkoxycarbonylation of Terminal Alkynes

A multifunctional copolymer (PyPPh2-SO3H@porous organic polymers, POPs) was prepared by combining acidic groups and heterogeneous P,N ligands through the copolymerization of vinyl-functionalized 2-pyridyldiphenylphosphine (2-PyPPh2) and p-styrene sulfonic acid under solvothermal conditions. The morphology and chemical structure of the copolymer were evaluated using a series of characterization techniques. Compared with traditional homogeneous Pd(OAc)(2)/2-PyPPh2/ p-toluenesulfonic acid catalyst, the copolymer supported palladium catalyst (Pd-PyPPh2-SO3H@POPs) exhibited higher activity for alkoxycarbonylation of terminal alkynes under the same conditions. This phenomenon could be attributed to the synergistic effect between the single-site Pd centers, 2-PyPPh2 ligands, and SO3H groups, the outstanding swelling properties as well as the high enrichment of the reactant concentration by the porous catalyst. In addition, the catalyst could be reused at least 4times without any apparent loss of activity. The excellent catalytic reactivity and good recycling properties make it an attractive catalyst for industrial applications. This work paves the way for advanced multifunctional porous organic polymers as a new type of platform for heterogeneous catalysis in the future