Joint Experimental and Theoretical Study on Deposition Morphologies in Polymer Sessile Droplets.

Although past experimental and theoretical research has made substantial progress in understanding evaporation behaviors in various suspensions, the fundamental mechanism for polymer sessile droplets is still lacking. One critical effect is the molecular weight on the evaporation behaviors. Here, systematic experiments are carried out to investigate the evaporation behavior of polymer droplets under the effects of polymer concentration, evaporation rate, and especially molecular weight. We obtain polymer films with various morphologies with molecular weights ranging from 2 orders of magnitude to 4 orders of magnitude and polymer concentration across 4 orders of magnitude. We further develop a theoretical model based on the Onsager principle to explain the evaporation mechanism from a dynamic perspective. Analysis indicates that increasing molecular weight or polymer concentration enhances the contact angle hysteresis and slows down the evaporation, resulting in the transition from multiring to coffee ring and eventually to uniform films. The findings offer a guideline for achieving the desired deposition patterns via droplet processing techniques.

Liquid-liquid phase separation of immiscible polymers at double emulsion interfaces for configurable microcapsules.

Liquid-liquid phase separation at complex interfaces is a common phenomenon in biological systems and is also a fundamental basis to create synthetic materials in multicomponent mixtures. Understanding the liquid-liquid phase separation in well-defined macromolecular systems is anticipated to shed light on similar behaviors in cross-disciplinary areas. Here we study a series of immiscible polymers and reveal a generic phase diagram of liquid-liquid phase separation at double emulsion interfaces, which depicts the equilibrium structures by interfacial tension and polymer fraction. We further reveal that the interfacial tensions in various systems fall on a linear relationship with spreading coefficients. Based on this theoretical guideline, the liquid-liquid phase separation can be modulated by a low fraction of amphiphilic block copolymers, leading the double emulsion droplets configurable between compartments and anisotropic shapes. The solidified anisotropic microcapsules could provide unique orientation-sensitive optical properties and thermomechanical responses. The theoretical analysis and experimental protocol in this study yield a generalizable strategy to prepare multiphase double emulsions with controlled structures and desired properties.

Unraveling the Molar Mass Dependence of Shearing-Induced Aggregation Structure of a High-Mobility Polymer Semiconductor.

Aggregation-structure formation of conjugated polymers is a fundamental problem in the field of organic electronics and remains poorly understood. Herein, the molar mass dependence of the aggregation structure of a high-mobility conjugated copolymer (TDPP-Se) comprising thiophene-flanked diketopyrrolopyrrole and selenophene is thoroughly shown. Five batches of TDPP-Se are prepared with the number-average molecular weights (Mn ) varied greatly from 21 to 135 kg mol-1 . Small-angle neutron scattering and transmission electron microscopy are combined to probe the solution structure of these polymers, consistently using a deuterated solvent. All the polymers adopt 1D rod-like aggregation structures and the radius of the 1D rods is not sensitive to the Mn , while the length increases monotonically with Mn . By utilizing the ordered packing of the aggregated structure in solution, a highly aligned and ordered film is prepared and, thereafter, a reliable hole mobility of 13.8 cm2 V-1 s-1 is realized in organic thin-film transistors with the moderate Mn batch via bar coating. The hole mobility is among the highest values reported for diketopyrrolopyrrole-based polymers. This work paves the way to visualize the real aggregated structure of polymer semiconductors in solution and sheds light on the microstructure control of high-performance electronic devices.

Effects of Vimentin Intermediate Filaments on the Structure and Dynamics of In Vitro Multicomponent Interpenetrating Cytoskeletal Networks.

We investigate the rheological properties of interpenetrating networks reconstituted from the main cytoskeletal components: filamentous actin, microtubules, and vimentin intermediate filaments. The elastic modulus is determined largely by actin, with little contribution from either microtubules or vimentin. However, vimentin dramatically impacts the relaxation, with even small amounts significantly increasing the relaxation time of the interpenetrating network. This highly unusual decoupling between dissipation and elasticity may reflect weak attractive interactions between vimentin and actin networks.

Hydroacoustic and hydrodynamic investigation of bio-inspired leading-edge tubercles on marine-ducted thrusters.

Underwater radiated noise (URN) has a negative impact on the marine acoustic environment where it can disrupt marine creature's basic living functions such as navigation and communication. To control the ambient ocean noise levels due to human activities, international governing bodies such as the International Maritime Organization (IMO) have issued non-mandatory guidelines to address this issue. Under such framework, the hydroacoustic performance of marine vehicles has become a critical factor to be evaluated and controlled throughout the vehicles' service life in order to mitigate the URN level and the role humankind plays in the ocean. This study aims to apply leading-edge (LE) tubercles of the humpback whales' pectoral fins to a benchmark ducted propeller to investigate its potential in noise mitigation. This was conducted using CFD, where the high-fidelity improved delayed detached eddy simulations (IDDES) in combination with the porous Ffowcs-Williams Hawkings (FW-H) acoustic analogy was used to solve the hydrodynamic flow field and propagate the generated noise to the far-field. It has been found that the LE tubercles have shown promising noise mitigation capabilities in the far-field, where the OASPL at J = 0.1 was reduced to a maximum of 3.4 dB with a maximum of 11 dB reduction in certain frequency ranges at other operating conditions. Based on detailed flow analysis researching the fundamental vortex dynamics, this noise reduction is shown to be due to the disruption of the coherent turbulent wake structure in the propeller slipstream causing the acceleration in the dissipation of turbulence and vorticity-induced noise.

Understanding of remora's "hitchhiking" behaviour from a hydrodynamic point of view.

Symbiotic relationships have developed through natural evolution. For example, that of the remora fish attached to the body of a shark. From the remora's perspective, this could be associated to an increased hydrodynamic efficiency in swimming and this needs to be investigated. To understand the remora's swimming strategy in the attachment state, a systematic study has been conducted using the commercial Computational Fluid Dynamics (CFD) software, STAR-CCM + to analyse and compare the resistance characteristics of the remora in attached swimming conditions. Two fundamental questions are addressed: what is the effect of the developed boundary layer flow and the effect of the adverse pressure gradient on the remora's hydrodynamic characteristics? According to the results, the resistance of the remora can generally be halved when attached. Besides, the results have also demonstrated that the drag reduction rate increases with the developed boundary layer thickness and can be estimated using the boundary layer thickness ratio and velocity deficit. The paper demonstrates that the most frequent attachment locations are also the areas that provide the maximum drag reduction rate.

Characterization of Machined Surface Topography Based on the Normal Declination Angle of Microfacets.

It is important to characterize surface topography in order to study machined surface characteristics. Due to the features of periodicity and randomness of machined surface topography, the existing topographical parameters may not describe its features accurately. A novel characterization method called the normal declination angle of microfacet-based surface topography is thus proposed for this task. The topography of machined surfaces is measured and the data on the normal declination angle are obtained. Then, surface topography is analyzed via the distribution of the normal declination angle. The lognormal distribution characterization model of machined surface topography is established, and the accuracy of the model is verified by error analysis. The results show that the calculated results of the present characterization model are generally consistent with the distribution of the normal declination angle, where the maximal root mean square errors (RMSE) is 4.5%. Therefore, this study may serve as an effective and novel way to describe the characteristics of the machined surface topography.

Role of Defects in Achieving Highly Asymmetric Lamellar Self-Assembly in Block Copolymer/Homopolymer Blends.

Lamellar structure is a prominent state in soft condensed matter. Swelling lamellar layers to highly asymmetric structures by a second component is a facile, cost-effective strategy to impart materials with adaptive size and tunable properties. One key question that remains unsolved is how defects form and affect the asymmetric lamellar order. This study unravels the role of defects by swelling a miktoarm block copolymer with a homopolymer. Ordered lamellae first lose translational order by a significant increase in the number of dislocations and then lose orientational order by the generation of disclinations. The homopolymers are not uniformly distributed in defective lamellae and primarily segregate in the vicinity of disclination cores. The free energy of defects is mainly contributed by molecular splay and significantly alleviated by an increased radius of local curvature. This study provides direct evidence to reveal the role of defects and lamellar order in block copolymer/homopolymer blends and also sheds light on understanding analogous structural transitions in other soft systems, including lyotropic liquid crystals, phospholipid membranes, and polymer nanocomposites.

Laser Ranging-Assisted Binocular Visual Sensor Tracking System.

Aimed at improving the low measurement accuracy of the binocular vision sensor along the optical axis in the process of target tracking, we proposed a method for auxiliary correction using a laser-ranging sensor in this paper. In the process of system measurement, limited to the mechanical performance of the two-dimensional turntable, the measurement value of a laser-ranging sensor is lagged. In this paper, the lag information is updated directly to solve the time delay. Moreover, in order to give full play to the advantages of binocular vision sensors and laser-ranging sensors in target tracking, federated filtering is used to improve the information utilization and measurement accuracy and to solve the estimated correlation. The experimental results show that the real-time and measurement accuracy of the laser ranging-assisted binocular visual-tracking system is improved by the direct update algorithm and the federal filtering algorithm. The results of this paper are significant for binocular vision sensors and laser-ranging sensors in engineering applications involving target tracking systems.

Spontaneous Creation of Anisotropic Polymer Crystals with Orientation-Sensitive Birefringence in Liquid Drops.

It remains a grand challenge to prepare anisotropic crystal superstructures with sensitive optical properties in polymer science and materials field. This study demonstrates that semicrystalline polymers develop into anisotropic hollow spherulitic crystals spontaneously at interfaces of liquid drops. In contrast to conventional spherulites with centrosymmetric optics and grain boundaries, these anisotropic spherulitic crystals have vanished boundary defects, tunable aspect ratios, and noncentrosymmetric, orientation-sensitive birefringence. The experimental finding is elaborated in poly(l-lactic acid) crystals and is further verified in a broad class of semicrystalline polymers, irrespective of molecular chirality, chemical constitution, or interfacial modification. The facile methods and general mechanism revealed in this study shed light on developing new types of optical microdevices and synthesis of anisotropic semicrystalline particles from liquid emulsions.

Collective Shape Actuation of Polymer Double Emulsions by Solvent Evaporation.

We demonstrate that the shape actuation of water-in-oil-in-water double emulsion droplets can be achieved by controlling solvent evaporation in a model system, where the oil phase consists of hydrophobic homopolymer/amphiphilic block copolymer/solvent. A gradient of interfacial tension is created in the polymer shell, which drives significant deformation of the droplets in constant volume. The deformed droplets recover to their initial shape spontaneously, and shape actuation of droplets can be further tuned by osmotic pressure. Our model system provides a new prototype for developing shape-responsive droplets in a solvent environment.

Block Co-PolyMOCs by Stepwise Self-Assembly.

We report a stepwise assembly strategy for the integration of metal-organic cages (MOCs) into block copolymers (BCPs). This approach creates "block co-polyMOC" (BCPMOC) materials whose microscopic structures and mechanical properties are readily tunable by adjusting the size and geometry of the MOCs and the composition of the BCPs. In the first assembly step, BCPs functionalized with a pyridyl ligand on the chain end form star-shaped polymers triggered by metal-coordination-induced MOC assembly. The type of MOC junction employed precisely determines the number of arms for the star polymer. In the second step, microphase separation of the BCP is induced, physically cross-linking the star polymers and producing the desired BCPMOC networks in the bulk or gel state. We demonstrate that large spherical M12L24 MOCs, small paddlewheel M2L4 MOCs, or a mixture of both can be incorporated into BCPMOCs to provide materials with tailored branch functionality, phase separation, microdomain spacing, and mechanical properties. Given the synthetic and functional diversity of MOCs and BCPs, our method should enable access to BCPMOCs for a wide range of applications.

Biosynthesis of poly(glycolate-co-lactate-co-3-hydroxybutyrate) from glucose by metabolically engineered Escherichia coli.

Metabolically engineered Escherichia coli strains were constructed to effectively produce novel glycolate-containing biopolymers from glucose. First, the glyoxylate bypass pathway and glyoxylate reductase were engineered such as to generate glycolate. Second, glycolate and lactate were activated by the Megasphaera elsdenii propionyl-CoA transferase to synthesize glycolyl-CoA and lactyl-CoA, respectively. Third, ß-ketothiolase and acetoacetyl-CoA reductase from Ralstonia eutropha were introduced to synthesize 3-hydroxybutyryl-CoA from acetyl-CoA. At last, the Ser325Thr/Gln481Lys mutant of polyhydroxyalkanoate (PHA) synthase from Pseudomonas sp. 61-3 was over-expressed to polymerize glycolyl-CoA, lactyl-CoA and 3-hydroxybutyryl-CoA to produce poly(glycolate-co-lactate-co-3-hydroxybutyrate). The recombinant E. coli was able to accumulate the novel terpolymer with a titer of 3.90g/l in shake flask cultures. The structure of the resulting polymer was chemically characterized by proton NMR analysis. Assessment of thermal and mechanical properties demonstrated that the produced terpolymer possessed decreased crystallinity and improved toughness, in comparison to poly(3-hydroxybutyrate) homopolymer. This is the first study reporting efficient microbial production of poly(glycolate-co-lactate-co-3-hydroxybutyrate) from glucose.

Mechanics of an Asymmetric Hard-Soft Lamellar Nanomaterial.

Nanolayered lamellae are common structures in nanoscience and nanotechnology, but most are nearly symmetric in layer thickness. Here, we report on the structure and mechanics of highly asymmetric and thermodynamically stable soft-hard lamellar structures self-assembled from optimally designed PS1-(PI-b-PS2)3 miktoarm star block copolymers. The remarkable mechanical properties of these strong and ductile PS (polystyrene)-based nanomaterials can be tuned over a broad range by varying the hard layer thickness while maintaining the soft layer thickness constant at 13 nm. Upon deformation, thin PS lamellae (<100 nm) exhibited kinks and predamaged/damaged grains, as well as cavitation in the soft layers. In contrast, deformation of thick lamellae (>100 nm) manifests cavitation in both soft and hard nanolayers. In situ tensile-SAXS experiments revealed the evolution of cavities during deformation and confirmed that the damage in such systems reflects both plastic deformation by shear and residual cavities. The aspects of the mechanics should point to universal deformation behavior in broader classes of asymmetric hard-soft lamellar materials, whose properties are just being revealed for versatile applications.

Synthetic Strategy for Preparing Chiral Double-semicrystalline Polyether Block Copolymers.

We report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic (R or S) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [mm]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small angle x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties.

Creating Extremely Asymmetric Lamellar Structures via Fluctuation-Assisted Unbinding of Miktoarm Star Block Copolymer Alloys.

We report the creation of highly asymmetric lamellar structures with a well-designed miktoarm star block copolymer of the S(IS')3 type, where S and S' are polystyrenes of different lengths and I is poly(isoprene). The domain spacing can be tuned continuously from 37 nm to over 300 nm when the miktoarm star block copolymer is blended with suitable molecular weight polystyrene homopolymers. Beyond the unbinding transition of the lamellar phase, extremely asymmetric lamellar structures were obtained with up to 97 wt % polystyrene, remarkably leaving the poly(isoprene) layers intact at only 3 wt %!

Producing Small Domain Features Using Miktoarm Block Copolymers with Large Interaction Parameters.

We demonstrate that small domain features (∼13 nm) can be obtained in a series of polystyrene (PS) and poly(lactic acid) (PLA) block copolymers, PS-(PLA)2 and (PS)2-(PLA)2, that combine miktoarm molecular architectures with large interaction parameters. To supplement the experimental work, we used self-consistent field theory in tandem with the random phase approximation to explore and contrast the phase behavior of ABn and AnBn types of miktoarm block copolymers. Specifically, AB2 and A2B2 were found to be effective molecular architectures for inducing strong shifts in phase boundaries with copolymer composition and to simultaneously tune domain feature sizes. The performance of these systems is markedly different from the corresponding linear diblock copolymers and indicates the potential of macromolecular architecture control for future applications in lithography.

Hierarchical coarsening in the late stage of viscoelastic phase separation.

Coarsening is a general phenomenon in phase separating mixtures. In this study, we report a hierarchical coarsening at different length scales. Dispersed domains grew by direct combination of two/three small ones while some small domains can survive for a long time. The small angle laser light scattering showed that the scattered intensity exhibited multiple "decay-growth" transitions in the coarsening process. The evolution of the main peak gave a characteristic power law index of about -3/4, which is much faster than the -1/3 relationship from the traditional theories. We propose that relaxation and hydrodynamic flow play important roles in this process.

Viscoelastic Phase Separation and Interface Assisted Crystallization in a Highly Immiscible iPP/PMMA Blend.

Polymer blends with dynamic asymmetry have attracted much interest recently. In this study, we report a more typical case where the dynamically asymmetric system is highly immiscible. We find that there is a transient network growth and phase inversion for the slow minor component. The network structure shows a hierarchical growth behavior, which is the result of competition between a slow relaxation-controlled concentration growth on local scale and a fast hydrodynamic growth on large scale. When phase separation couples with a subsequent crystallization, the interfacial boundary may assist lateral crystallization and irregular spherulites would grow epitaxially around the amorphous component-rich domains. The interface may play the role of substrates for heterogeneous nucleation. These phenomena may help us with morphological control in material processing.

Concentric ring pattern formation in a competing crystallization and phase separation process.

Spherulitic patterns usually form in the single process of crystallization in polymer blends. But when phase separation intervenes under deep quench, the radial growth of the initial spherulitic patterns tends to invert into concentric alternating crystalline-/amorphous-rich ring structures. Within crystalline-rich regions, lateral lamellae orient in the tangential direction rather than in the usual radial direction. We demonstrate the determining factor for this first observed phenomenon is the concentration deviation enhanced phase separation dynamics at the growth interface of crystals.