Anisotropic Packing Research Articles

Evaluation of performance improvements through application of anisotropic foam packings in rotating packed beds

Constantly increasing interest in HIGEE technology and rotating packed beds require detailed investigations of the mass transfer and hydrodynamic performance. Classical isotropic single block packings constitute the most applied and investigated packings for absorption and stripping processes. Yet, the large geometric surface area which is offered by these packings can hardly be exploited to the full extent due to the constant change in gas and liquid loads along the radius of the annular packings. In order to overcome these limitations and extend the operating range and mass transfer performance of foam packings, the current study presents a detailed comparison of isotropic and anisotropic packings. The conducted pressure drop and mass transfer experiments, based on chemical absorption of CO2 with aqueous sodium hydroxide, illustrate the improved performance that can be expected from anisotropic packings, while dedicated gamma-ray computed tomography provides further insight into the improved liquid distribution for this kind of packings.

Anisotropic Vapor-Deposited Glasses: Hybrid Organic Solids

The term "organic solids" encompasses both crystals and glasses. Organic crystals are commonly grown for purification and structure determination and are being extensively explored for applications in organic electronics including field effect transistors. The ability to control the packing of one molecule relative to its neighbors is of critical importance for most uses of organic crystals. Often, anisotropic packing is also highly desirable as it enhances charge transport and optimizes light absorption/emission. When compared to crystals, the local packing in organic glasses is highly disordered and often isotropic. Glasses, however, offer two key advantages with respect to crystals. First, glasses typically lack grain boundaries and thus exhibit better macroscopic homogeneity. Second, glass composition can often be varied over a wide range while maintaining homogeneity. Besides electronic materials, many modern plastics used in a wide range of technologies are organic glasses, and the glassy state is being increasingly utilized to deliver pharmaceuticals because of higher bioavailability. In this article, we introduce vapor-deposited organic glasses as hybrid materials that combine some of the useful features of crystals and traditional liquid-cooled glasses. Physical vapor deposition produces glasses by directly condensing molecules from the gas phase onto a temperature-controlled substrate and allows film thickness to be controlled with nanometer precision. Just as liquid-cooled glasses, vapor-deposited glasses have smooth surfaces and lack grain boundaries. These attributes are critical for applications such as organic light emitting diodes (OLEDs), in which vapor-deposited glasses of organic semiconductors form the active layers. In common with crystals, vapor-deposited glasses can exhibit anisotropic packing, and the extent of anisotropy can be comparable to that of the typical organic crystal. For vapor-deposited glasses, in contrast to crystals, anisotropic packing can generally be controlled as a continuous variable. Deposition conditions can be chosen to produce glasses with significant molecular orientation (molecules "standing up" or "lying down" relative to the substrate), and π-stacking can be directed along different directions relative to the substrate. Over the last five years, we have gained a fundamental understanding of the mechanism that controls the anisotropy of vapor-deposited glasses and learned how to control many aspects of anisotropic packing. Two key elements that enable such control are the high mobility present at the surface of an organic glass and the tendency of the surface to promote anisotropic packing of molecules. In contrast to traditional epitaxial growth, for vapor-deposited glasses, the free surface (not the substrate) acts as a template that controls the structure of a growing film. The structure of any given layer is decoupled from those beneath it, thereby providing considerable freedom in producing layered glassy structures.

Origin of Anisotropic Molecular Packing in Vapor-Deposited Alq3 Glasses.

Anisotropic molecular packing is a key feature that makes glasses prepared by physical vapor deposition (PVD) unique materials, warranting a mechanistic understanding of how a PVD glass attains its structure. To this end, we use X-ray scattering and ellipsometry to characterize the structure of PVD glasses of tris(8-hydroxyquinoline) aluminum (Alq3), a molecule used in organic electronics, and compare our results to simulations of its supercooled liquid. X-ray scattering reveals a tendency for molecular layering in Alq3 glasses that depends upon the substrate temperature during deposition and the deposition rate. Simulations reveal that the Alq3 supercooled liquid, like liquid metals, exhibits surface layering. We propose that the layering in Alq3 glasses observed here as well as the previously reported bulk dipole orientation are inherited from the surface structure of the supercooled liquid. This work significantly advances our understanding of the mechanism governing the formation of anisotropic structure in PVD glasses.

2D Organic Photonics: An Asymmetric Optical Waveguide in Self-Assembled Halogen-Bonded Cocrystals.

Anisotropic organic molecular construction and packing are crucial for the optoelectronic properties of organic crystals. Two-dimensional (2D) organic crystals with regular morphology and good photon confinement are potentially suitable for a chip-scale planar photonics system. Herein, through the bottom-up process, 2D halogen-bonded DPEpe-F4 DIB cocrystals were fabricated that exhibit an asymmetric optical waveguide with the optical-loss coefficients of RBackward =0.0346 dB μm-1 and RForward =0.0894 dB μm-1 along the [010] crystal direction, which can be attributed to the unidirectional total internal reflection caused by the anisotropic molecular packing mode. Based on this crystal direction-oriented asymmetric photon transport, these as-prepared 2D cocrystals have been demonstrated as a microscale optical logic gate with multiple input/out channels, which will offer potential applications as the 2D optical component for the integrated organic photonics.

2D Organic Photonics: An Asymmetric Optical Waveguide in Self‐Assembled Halogen‐Bonded Cocrystals

AbstractAnisotropic organic molecular construction and packing are crucial for the optoelectronic properties of organic crystals. Two‐dimensional (2D) organic crystals with regular morphology and good photon confinement are potentially suitable for a chip‐scale planar photonics system. Herein, through the bottom‐up process, 2D halogen‐bonded DPEpe‐F4DIB cocrystals were fabricated that exhibit an asymmetric optical waveguide with the optical‐loss coefficients of RBackward=0.0346 dB μm−1and RForward=0.0894 dB μm−1along the [010] crystal direction, which can be attributed to the unidirectional total internal reflection caused by the anisotropic molecular packing mode. Based on this crystal direction‐oriented asymmetric photon transport, these as‐prepared 2D cocrystals have been demonstrated as a microscale optical logic gate with multiple input/out channels, which will offer potential applications as the 2D optical component for the integrated organic photonics.

Characterization of maximally random jammed sphere packings. III. Transport and electromagnetic properties via correlation functions.

In the first two papers of this series, we characterized the structure of maximally random jammed (MRJ) sphere packings across length scales by computing a variety of different correlation functions, spectral functions, hole probabilities, and local density fluctuations. From the remarkable structural features of the MRJ packings, especially its disordered hyperuniformity, exceptional physical properties can be expected. Here we employ these structural descriptors to estimate effective transport and electromagnetic properties via rigorous bounds, exact expansions, and accurate analytical approximation formulas. These property formulas include interfacial bounds as well as universal scaling laws for the mean survival time and the fluid permeability. We also estimate the principal relaxation time associated with Brownian motion among perfectly absorbing traps. For the propagation of electromagnetic waves in the long-wavelength limit, we show that a dispersion of dielectric MRJ spheres within a matrix of another dielectric material forms, to a very good approximation, a dissipationless disordered and isotropic two-phase medium for any phase dielectric contrast ratio. We compare the effective properties of the MRJ sphere packings to those of overlapping spheres, equilibrium hard-sphere packings, and lattices of hard spheres. Moreover, we generalize results to micro- and macroscopically anisotropic packings of spheroids with tensorial effective properties. The analytic bounds predict the qualitative trend in the physical properties associated with these structures, which provides guidance to more time-consuming simulations and experiments. They especially provide impetus for experiments to design materials with unique bulk properties resulting from hyperuniformity, including structural-color and color-sensing applications.

Anisotropic particles strengthen granular pillars under compression.

We probe the effects of particle shape on the global and local behavior of a two-dimensional granular pillar, acting as a proxy for a disordered solid, under uniaxial compression. This geometry allows for direct measurement of global material response, as well as tracking of all individual particle trajectories. In general, drawing connections between local structure and local dynamics can be challenging in amorphous materials due to lower precision of atomic positions, so this study aims to elucidate such connections. We vary local interactions by using three different particle shapes: discrete circular grains (monomers), pairs of grains bonded together (dimers), and groups of three bonded in a triangle (trimers). We find that dimers substantially strengthen the pillar and the degree of this effect is determined by orientational order in the initial condition. In addition, while the three particle shapes form void regions at distinct rates, we find that anisotropies in the local amorphous structure remain robust through the definition of a metric that quantifies packing anisotropy. Finally, we highlight connections between local deformation rates and local structure.

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition. The structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.

Molecular-scale shear response of the organic semiconductor β -DBDCS (100) surface

In this work we present friction-force microscopy (FFM) lattice-resolved images acquired on the (100) facet of the semiconductor organic oligomer (2Z,2'Z) − 3,3'-(1,4-phenylene)bis(2-(4-butoxyphenyl)acrylonitrile) (β-DBDCS) crystal in water at room temperature. Stick-slip contrast, lateral contact stiffness, and friction forces are found to depend strongly on the sliding direction due to the anisotropic packing of the molecular chains forming the crystal surface along the [010] and [001] directions. The anisotropy also causes the maximum value of the normal force applicable before wearing to increase by a factor of 3 when the scan is performed along the [001] direction on the (100) face. Altogether, our results contribute to achieving a better understanding of the molecular origin of friction anisotropy on soft crystalline surfaces, which has been often hypothesized but rarely investigated in the literature.

Influence of Hydrogen Bonding on the Kinetic Stability of Vapor-Deposited Glasses of Triazine Derivatives.

It has recently been established that physical vapor deposition (PVD) can produce organic glasses with enhanced kinetic stability, high density, and anisotropic packing, with the substrate temperature during deposition (Tsubstrate) as the key control parameter. The influence of hydrogen bonding on the formation of PVD glasses has not been fully explored. Herein, we use a high-throughput preparation method to vapor-deposit three triazine derivatives over a wide range of Tsubstrate, from 0.69 to 1.08Tg, where Tg is the glass transition temperature. These model systems are structural analogues containing a functional group with different H-bonding capability at the 2-position of a triazine ring: (1) 2-methylamino-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (NHMe) (H-bond donor), (2) 2-methoxy-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (OMe) (H-bond acceptor), and (3) 2-ethyl-4,6-bis(3,5-dimethyl-phenylamino)-1,3,5-triazine (Et) (none). Using spectroscopic ellipsometry, we find that the Et and OMe compounds form PVD glasses with relatively high kinetic stability, with the transformation time (scaled by the α-relaxation time) on the order of 103, comparable to other highly stable glasses formed by PVD. In contrast, PVD glasses of NHMe are only slightly more stable than the corresponding liquid-cooled glass. Using IR spectroscopy, we find that both the supercooled liquid and the PVD glasses of the NHMe derivative show a higher average number of bonded NH per molecule than that in the other two compounds. These results suggest that H-bonds hinder the formation of stable glasses, perhaps by limiting the surface mobility. Interestingly, despite this difference in kinetic stability, all three compounds show properties typically observed in highly stable glasses prepared by PVD, including a higher density and anisotropic molecular packing (as characterized by IR and wide-angle X-ray scattering).

Toughening of syndiotactic polypropylene with chalk

ABSTRACTWe hypothesized that polymer crystal anisotropy is advantageous for toughening of polymer composites involving easy slip network of oriented crystalline layers around filler particles. To this end, composites of syndiotactic polypropylene (sPP) with high concentration of submicrometer calcium carbonate particles were prepared and examined because usual sPP crystals exhibit high packing anisotropy. The specific orientation of sPP lamellae around chalk grains was found, which is supposed to facilitate the plastic deformation of polymer matrices. The compression molded bars of the composite exhibited markedly higher Izod impact strength than those of neat sPP. Toughening was even enhanced in the injection molded composite, for which 4.5‐fold increase in the impact strength was achieved. Injection‐induced orientation of the disordered form I sPP crystals was enhanced in the composite. The injection molded tensile specimens exhibited also a good drawability. Debonding at chalk–sPP interface occurred both during the impact and tensile tests facilitating the plastic deformation of sPP matrix. Chalk did not have any significant influence on the thermal properties of the composites but it affected the rheological behavior, increasing the loss and storage moduli, and the viscosity. Highly filled sPP composite exhibited solid‐like behavior in a molten state with the storage modulus exceeding the loss modulus in the entire frequency range. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43651.

Disentangling the role of structure and friction in shear jamming

Amorphous packings of spheres have been intensely investigated in order to understand the mechanical and flow behaviour of dense granular matter, and to explore universal aspects of the transition from fluid to structurally arrested or jammed states. Considerable attention has recently been focussed on anisotropic packings of frictional grains generated by shear deformation leading to shear jamming, which occurs below the jamming density for isotropic packings of frictionless grains. With the aim of disentangling the role of shear deformation induced structures and friction in generating shear jamming, we study sheared assemblies of frictionless spheres computationally, over a wide range of densities, extending far below the isotropic jamming point. We demonstrate the emergence of a variety of geometric features characteristic of jammed packings with the increase of shear strain. The average contact number and the distributions of contact forces suggest the presence of a threshold density, well below the isotropic jamming point, above which a qualitative change occurs in the jamming behaviour of sheared configurations. We show that above this threshold density, friction stabilizes the sheared configurations we generate. Our results thus reveal the emergence of geometric features characteristic of jammed states as a result of shear deformation alone, while friction is instrumental in stabilising packings over a range of densities below the isotropic jamming point.

Unambiguous characterization of anisotropic foldamer packing in a foldecture with an elongated hexagonal plate shape.

Herein we correlate secondary structure perturbation with changes in the solid-state molecular architectures of an elongated hexagonal plate-shaped foldecture derived from the self-assembly of rigid 12-helical β-peptide foldamers to which a flexible C-terminus α-leucine moiety has been appended. This study provides the first complete characterization of the directional molecular packing patterns of individual foldamer components within a foldecture, from which a 3D molecular-level picture of the entire foldecture was unambiguously constructed.

Anomalous Anisotropic Thermal Expansion in a One-Dimensional Coordination Polymer Driven by Conformational Flexibility.

A one-dimensional lithium(I) coordination polymer has been characterized by variable-temperature single-crystal X-ray diffraction and differential scanning calorimetry. This compound possesses an anisotropic packing arrangement that, along with a scissor-like or hingelike movement of the pyridyl ligand side arms, results in an extremely rare combination of positive, negative, and zero thermal expansion. Designing such types of materials and understanding the mechanistic details can facilitate the design of new thermoresponsive materials.

Structural Characterization of Vapor-Deposited Glasses of an Organic Hole Transport Material with X-ray Scattering

Vapor-deposited organic glasses can be produced with enhanced thermal stability and tunable molecular orientation by controlling the substrate temperature during deposition. Recent work has also shown improved charge carrier mobility associated with anisotropic molecular packing in organic electronics. Here grazing-incidence wide-angle X-ray scattering (GIWAXS) is used to characterize the structural anisotropy in glasses of a hole transport material, N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine, commonly referred to as TPD. The TPD glasses were prepared by physical vapor deposition at substrate temperatures between 0.79 Tg and 0.98 Tg, where Tg is the glass transition temperature. A GIWAXS-derived orientation order parameter is used to quantify the anisotropy observed in the scattering patterns of the glasses. The GIWAXS-order parameter exhibits both positive and negative values as a function of substrate temperature, indicating either face-on or edge-on packing, and correlates well with a spectroscopic ellipsometry-derived order parameter that is sensitive to molecular orientation. We propose molecular packing arrangements based on the combination of the two order parameters and explore the relationship between kinetic stability and glass structure.

Transformation kinetics of vapor-deposited thin film organic glasses: the role of stability and molecular packing anisotropy.

While ordinary glasses transform into supercooled liquid via a homogeneous bulk mechanism, thin film glasses of higher stability transform heterogeneously by a front propagating from the surface and/or the interfaces. In this work, we use quasi-adiabatic fast scanning nanocalorimetry to determine the heat capacity of thin glassy layers of indomethacin vapor-deposited in a broad temperature range of 110 K below the glass transition temperature. Their variation in fictive temperature amounts to 40 K. We show that a propagating front is the initial transformation mechanism in all cases. Using an ad hoc surface normalization procedure we determine the corresponding growth front velocity for the whole range of deposition temperatures. Although the transformation rate changes by a factor of 10 between the most and less stable samples, the relation between the mobility of the front and the thermodynamic stability of the glass is not uniquely defined. Glasses grown above 280 K, which are at equilibrium with the supercooled liquid, present a different dependence of the growth front velocity on fictive temperature compared to glasses grown out of equilibrium at Tdep < 250 K. These glasses transform faster with increasing Tf. Our data clarify previous reports and support the evidence that the fictive temperature alone is not an absolute indicator of the properties of the glass, at least when its structure is not completely isotropic. To interpret the data, we propose that the growth front velocity depends on three terms: the mobility of the liquid at a given temperature, the mobility of the glass and the arrangement of the molecules in the glass.

Fiber Visualization with LIC Maps Using Multidirectional Anisotropic Glyph Samples.

Line integral convolution (LIC) is used as a texture-based technique in computer graphics for flow field visualization. In diffusion tensor imaging (DTI), LIC bridges the gap between local approaches, for example directionally encoded fractional anisotropy mapping and techniques analyzing global relationships between brain regions, such as streamline tracking. In this paper an advancement of a previously published multikernel LIC approach for high angular resolution diffusion imaging visualization is proposed: a novel sampling scheme is developed to generate anisotropic glyph samples that can be used as an input pattern to the LIC algorithm. Multicylindrical glyph samples, derived from fiber orientation distribution (FOD) functions, are used, which provide a method for anisotropic packing along integrated fiber lines controlled by a uniform random algorithm. This allows two- and three-dimensional LIC maps to be generated, depicting fiber structures with excellent contrast, even in regions of crossing and branching fibers. Furthermore, a color-coding model for the fused visualization of slices from T1 datasets together with directionally encoded LIC maps is proposed. The methodology is evaluated by a simulation study with a synthetic dataset, representing crossing and bending fibers. In addition, results from in vivo studies with a healthy volunteer and a brain tumor patient are presented to demonstrate the method's practicality.

Structural and mechanical properties of polymersomes formed by rod–coil diblock copolymers

Polymersomes formed by rod–coil diblock copolymers (RxCy) are fundamentally different from those of coil–coil diblock copolymers. RxCy denotes the polymer comprising of x rod-like beads and y coil-like beads. The morphological phase diagram of RxCy in selective solvents and the essential physical properties of the RxCy-polymersomes are explored by using dissipative particle dynamics. Our simulation results show that small-sized polymersomes can only take shape for short coil-block lengths. Moreover, the rod-block length cannot be too long and π–π stacking must be weak because anisotropic rod packing actually resists membrane bending and thus vesicle formation. The detailed membrane structures of polymersomes are also investigated and it is found that the rods within the membrane are highly interdigitated which is intrinsically different from the ordered bilayer of the liposomes formed by triblock copolymers (Rx)2Cy. The structural and mechanical properties of RxCy-polymersomes are studied as well. As the coil-block length is increased, both the thickness and area density of the rod domain decline. Since the coil stretching in the inner corona is more distinct than that in the outer one, significant interdigitation results due to the outward movement of the inner leaflet for relaxing overcrowded coil-blocks. The membrane tension exhibits a maximum while the stretching and bending moduli display a minimum at the intermediate coil-block length as y varies from 1 to 3. Fusion between two polymersomes of R5Cy is investigated and the outcome relates to the membrane tension. R5C2-polymersomes fuse most easily. However, R5C1-polymersomes do not proceed beyond the hemifusion stage and R5C3-polymersomes can not even move past the initial kissing stage.

Stress and fabric in granular material

It has been well recognized that, due to anisotropic packing structure of granular material, the true stress in a specimen is different from the applied stress. However, very few research efforts have been focused on quantifying the relationship between the true stress and applied stress. In this paper, we derive an explicit relationship among applied stress tensor, material-fabric tensor, and force-fabric tensor; and we propose a relationship between the true stress tensor and the applied stress tensor. The validity of this derived relationship is examined by using the discrete element simulation results for granular material under biaxial and triaxial loading conditions.

Interactions between Ether Phospholipids and Cholesterol As Determined by Scattering and Molecular Dynamics Simulations

Cholesterol and ether lipids are ubiquitous in mammalian cell membranes, and their interactions are crucial in ether lipid mediated cholesterol trafficking. We report on cholesterol's molecular interactions with ether lipids as determined using a combination of small-angle neutron and X-ray scattering, and all-atom molecular dynamics (MD) simulations. A scattering density profile model for an ether lipid bilayer was developed using MD simulations, which was then used to simultaneously fit the different experimental scattering data. From analysis of the data the various bilayer structural parameters were obtained. Surface area constrained MD simulations were also performed to reproduce the experimental data. This iterative analysis approach resulted in good agreement between the experimental and simulated form factors. The molecular interactions taking place between cholesterol and ether lipids were then determined from the validated MD simulations. We found that in ether membranes cholesterol primarily hydrogen bonds with the lipid headgroup phosphate oxygen, while in their ester membrane counterparts cholesterol hydrogen bonds with the backbone ester carbonyls. This different mode of interaction between ether lipids and cholesterol induces cholesterol to reside closer to the bilayer surface, dehydrating the headgroup's phosphate moiety. Moreover, the three-dimensional lipid chain spatial density distribution around cholesterol indicates anisotropic chain packing, causing cholesterol to tilt. These insights lend a better understanding of ether lipid-mediated cholesterol trafficking and the roles that the different lipid species have in determining the structural and dynamical properties of membrane associated biomolecules.