Deposition pattern of drying droplets

The drying of liquid droplets is a common daily life phenomenon that has long held a special interest in scientific research. When the droplet includes nonvolatile solutes, the evaporation of the solvent induces rich deposition patterns of solutes on the substrate. Understanding the formation mechanism of these patterns has important ramifications for technical applications,ranging from coating to inkjet printing to disease detection. This topical review addresses the development of physical understanding of tailoring the specific ring-like deposition patterns of drying droplets. We start with a brief introduction of the experimental techniques that are developed to control these patterns of sessile droplets. We then summarize the development of the corresponding theory. Particular attention herein is focused on advances and issues related to applying the Onsager variational principle (OVP) theory to the study of the deposition patterns of drying droplets. The main obstacle to conventional theory is the requirement of complex numerical solutions, but fortunately there has been recent groundbreaking progress due to the OVP theory. The advantage of the OVP theory is that it can be used as an approximation tool to reduce the high-order conventional hydrodynamic equations to first-order evolution equations,facilitating the analysis of soft matter dynamic problems. As such, OVP theory is now well poised to become a theory of choice for predicting deposition patterns of drying droplets.     

Strain-induced matrix and droplets anisotropic deformation in liquid crystalline cellulose dispersed liquid crystal films

The present work deals with the preparation of new liquid crystalline cellulose dispersed liquid crystal films (100 μm) using a shearing casting technique. The matrix of the films presents the so-called band texture perpendicular to the shear direction. The nematic low molecular weight liquid crystal is encapsulated in micron and submicron size ellipsoids. The ratio between the lengths of the main axis and the short axis is around 1.23. The main axis is oriented, on average, 28° away from the shear direction. The evolution of the band texture and of the ellipsoidal liquid crystal droplets is investigated by polarizing optical microscopy and light scattering techniques as a function of the strain imposed along and perpendicular to the shear direction. Stretch along shear with strain equal to 0.8 seems to have no effect on the banded structure of the matrix, while the nematic liquid crystal ellipsoids slightly orient the main axis to the stress direction and their shape anisotropy increases by a factor of 2. Deformation in the direction transverse to the shear direction induces a deep change of the polymeric matrix and, at the end, a fibrillar structure is found. The nematic ellipsoids rotate their main axis and align along the stretch direction. Their shape anisotropy evolves from a value of 1.23 to 1 for intermediate deformations with strain equal to 0.5, to a final value of 5 with strain equal to 0.8, in the perpendicular direction.     

Structure and mobility in ferroelectric liquid crystalline elastomers

Time-resolved Fourier transform infrared (FTIR) spectroscopy with polarized light was employed to study the structure and mobility of a homologous series of ferroelectric liquid crystalline polymers (FLCPs) and ferroelectric liquid crystalline elastomers (FLCEs) in response to an external electric field. The chemical composition of the samples, besides the cross-linking units, is similar. For the elastomers, two different cross-linking architectures are realized: “intralayer” cross-linking leads to the formation of two-dimensional networks, whereas “interlayer” cross-linking forms three-dimensional networks. Due to its specificity, FTIR spectroscopy enables analysis of the reorientational dynamics for the different molecular moieties in detail, thus revealing information about reorientation times, angular excursion, and the phase relationship in the rearrangement of the various molecular groups. In comparison to the un-cross-linked FLCP, both elastomeric samples exhibited smaller reorientation angles and an increase of the reorientation times. In the case of the interlayer cross-linked FLCE, an elastic memory effect was observed: For the reversal from negative to positive field polarity, the reorientation times were longer than for those in the opposite direction. For the intralayer cross-linked sample, it was shown that the backbone molecules reorient slower than the other molecular units (“locomotive effect”). For the un-cross-linked FLCP and the two FLCE samples, different coupling mechanisms between the network and the mesogenic parts are derived from the measurements.     

Laser-induced pattern formation in liquid sulfur

Liquid sulfur is a well-known liquid which exhibits a polymerization transition at T_p=159 °C. Recently, it was found from our experiments that such a transition can be induced below T_p through laser illumination and that an iridescent pattern appears under strong illumination with a pulsed laser of more than 60 mJ/cm² pulse. It is proposed that the visible change in iridescence is due to a macroscopic reconstruction of laser-generated polymers and that a laser-induced phase transition takes place from a freely expanded polymer phase to an ordered polymer phase when increasing the laser illumination. To further examine this possibility, the time variation of the iridescent pattern has been fully investigated using a macro lens, a polarized microscope and an optical microscope. In an analysis of the iridescent pattern, a rapid decrease in the area was observed after an initial slow decrease, suggesting a type of phase transition. Results from the observation of a quenched sulfur sample with a polarized microscope gave evidence that the iridescent region consists of polymers. Through observation of the liquid with a microscope, a striped pattern with micrometer sized spacing was noted in the iridescent pattern. A drastic color change was observed in the pattern from its generation to its disappearance. Sample thickness dependence of the pattern was also observed. These results were well explained by assuming the self-arrangement of laser-generated colloidal polymers.     

Prediction of chaotic dynamics in sheared liquid crystalline polymers

A rheological model for rodlike polymers in the nematic liquid-crystalline phase is analyzed to characterize irregular dynamical response under pure shear flows. The model is studied with a continuation approach, and a period doubling scenario is detected. Time series generated via simulation are studied with nonlinear analysis tools to prove the existence of chaotic regimes.     

Imaging the translational dynamics of CF3 in liquid helium droplets

The translational dynamics of CF3 in liquid helium have been investigated by photodissociating CF3I dissolved in helium droplets consisting of several thousands of atoms. The velocity distribution of CF3 fragments that have escaped from the droplets has been determined using ion imaging techniques and is found to be considerably shifted to lower speeds with respect to the photodissociation of gas phase CF3I. The fragments furthermore show a speed dependent angular distribution that is isotropic for the slowest and approaches the gas phase distribution for the faster fragments. These distributions point to a nonthermal escape process in which, at least for the speeds relevant for the present experiment, the kinetic energy and momentum transfer from the fragments to the solvent appears to be governed by binary collisions with the individual helium atoms.     

Early dynamics of guest-host interaction in dye-doped liquid crystalline materials

We have studied in detail the early dynamics of laser-induced molecular reorientation in a dye-doped liquid crystalline (LC) medium that exhibits a significant enhancement of the optical Kerr nonlinearity due to guest-host interaction. Experimental results agree quantitatively with theory based on a model in which the anisotropic dye excitation helps reorient the LC molecules through a mean-field intermolecular interaction.     

溶液液滴蒸发变干的环状沉积

液体蒸发驱动的颗粒自组装现象在许多的工业技术中有重要应用. 本文利用显微镜观测含有颗粒物质的液滴变干后留在固体表面的颗粒形成的环状沉积图案. 采用微米粒径的SiO₂小球水溶液液滴蒸发变干模拟咖啡环的形成过程, 结果发现液滴蒸发过程中接触线的钉扎是环状沉积的必要条件. 在液滴蒸发过程中颗粒随着补偿流不断的向液滴边缘移动, 聚集在接触线处形成环. 液滴蒸发变干后残留在液滴内部的颗粒数随颗粒质量分数的增加而增加, 可以达到单层的颗粒排列. 而玻璃衬底上的颗粒环在颗粒质量分数很小时, 形成单层排列, 且一排一排地生长. 蒸发过程中颗粒环由于液滴边缘的尺寸限制向液滴中心缓慢移动. 这会导致液滴中不同大小颗粒的分离. 关键词： 液滴 接触线 蒸发 颗粒     

Preparation and electron microscopy of liquid crystalline condensates of DNA

Summary A brief survey of thein vitro methods of preparing DNA mesomorphic phases is presented. The significance of thesein vitro preparations for thein vivo condensed states of DNA is also discussed. The procedure of preparing a dispersion of mesomorphic condensates of unsonicated calf thymus DNA by using polyethylene glycol was investigated by the circular dichroism (CD) technique. The operational conditions able to provide at the same time good packing of the DNA chains and reproducible CD signals were searched. The morphology of the condensates thus obtained was studied by transmission electron microscopy. Work presented at the second USSR-Italy Bilateral Meeting on Liquid Crystals held in Moscow, September 15–21, 1988.     

On the crack pattern formation in a freely drying protein film

As shown for the first time by Rapis [7, 8], cracks appearing on the surface of an aqueous protein solution upon its dehydration under normal conditions usually form the same pattern. In this work, a model of processes responsible for the formation of this pattern is proposed.     

GPU-accelerated molecular dynamics simulation for study of liquid crystalline flows

We have developed a GPU-based molecular dynamics simulation for the study of flows of fluids with anisotropic molecules such as liquid crystals. An application of the simulation to the study of macroscopic flow (backflow) generation by molecular reorientation in a nematic liquid crystal under the application of an electric field is presented. The computations of intermolecular force and torque are parallelized on the GPU using the cell-list method, and an efficient algorithm to update the cell lists was proposed. Some important issues in the implementation of computations that involve a large number of arithmetic operations and data on the GPU that has limited high-speed memory resources are addressed extensively. Despite the relatively low GPU occupancy in the calculation of intermolecular force and torque, the computation on a recent GPU is about 50 times faster than that on a single core of a recent CPU, thus simulations involving a large number of molecules using a personal computer are possible. The GPU-based simulation should allow an extensive investigation of the molecular-level mechanisms underlying various macroscopic flow phenomena in fluids with anisotropic molecules.     

Structure and frustration in liquid crystalline polyacrylates I. Bulk behaviour

The phase behaviour and structure are reported of a new type of frustrated side-chain liquid crystalline (LC) polymer, a polyacrylate with phenylbenzoate mesogenic side groups and a narrow polydispersity. At a high degree of polymerisation the LC polymers show a nematic, a smectic-A_d, a re-entrant nematic and a C phase, for shorter chains only a nematic and a C phase. This constitutes a new example of nematic re-entrance for which the driving field is the length of the polymer chain. The smectic-A_d layers consist of partially overlapped side groups while in the C phase the side chains are rearranged into chevron-like blocks of bilayers. We propose an explanation of the frustrated phase behaviour in terms of these two different competing length scales and their coupling to the backbone conformations. Received 28 February 2001 and Received in final form 6 August 2001     

Structure and frustration in liquid crystalline polyacrylates II. Thin-film properties

We report on the thin-film behaviour of a polyacrylate with phenyl benzoate mesogenic side groups and a narrow polydispersity. Depending on the degree of polymerisation, these polymers show a nematic, a smectic-A _d, a re-entrant nematic and a C phase with a two-dimensional monoclinic lattice. X-ray reflectivity and atomic-force microscopy have been used to characterize the structure and surface morphology. The system exhibits two stable side-chain packing configurations with incommensurate spacings that can be both stabilized at a free surface. Thin films in the nematic phase show a structural dewetting induced by the growth of surface domains of the C phase. Additionally, surface-induced ripples with a nanoscale lateral period form at the air-film interface. We attribute these patterns to a coupling between the local liquid crystalline ordering of the mesogenic side groups and the surface curvature energy. Received 28 February 2001 and Received in final form 6 August 2001     

Nonlocal interaction effects on pattern formation in population dynamics

We consider a model for population dynamics such as for the evolution of bacterial colonies which is of the Fisher type but where the competitive interaction among individuals is nonlocal, and show that spatial structures with interesting features emerge. These features depend on the nature of the competitive interaction as well as on its range, specifically on the presence or absence of tails in, and the central curvature of, the influence function of the interaction.     

From lag synchronization to pattern formation in networked dynamics

The relationship between lag synchronization and pattern formation is investigated in this article by taking networked dynamics as spatio–temporal models. Firstly some results in two-dimensional open flow models with unidirectional coupling term are presented, and sufficient conditions for globally asymptotically stable lag synchronization in discrete and continuous cases are revealed by analytic method to elucidate the wave pattern evoked by the lag synchronization in such models. Then, an ad hoc network topology, a so-called “tier-network”, is introduced, which is an acyclic digraph with one center node and all the directed pathways from any other node to the center node are equal in length. And the dynamics in tier-networks is investigated. Some similarly sufficient conditions for globally asymptotically stable lag synchronization is obtained by analytic method, and the wave pattern in tier-networks evoked by lag synchronization is illustrated. The above results are supported by the numerical simulation in discrete case.     

Onset of buckling in drying droplets of colloidal suspensions

Minute concentrations of suspended particles can dramatically alter the behavior of a drying droplet. After a period of isotropic shrinkage, similar to droplets of a pure liquid, these droplets suddenly buckle like an elastic shell. While linear elasticity is able to describe the morphology of the buckled droplets, it fails to predict the onset of buckling. Instead, we find that buckling is coincident with a stress-induced fluid to solid transition in a shell of particles at a droplet's surface, occurring when attractive capillary forces overcome stabilizing electrostatic forces between particles.     

Investigations on the liquid crystalline phases of cation-induced condensed DNA

Viral and nonviral condensing agents are used in gene therapy to compact oligonucleotides and plasmid DNA into nanostructures for their efficient transport through the cell membranes. Whereas viral vectors are best by the toxic effects on the immune system, most of the nonviral delivery vehicles are not effective for use in clinical system. Recent investigations indicate that the supramolecular organization of DNA in the condensed state is liquid crystalline. The present level of understanding of the liquid crystalline phase of DNA is inadequate and a thorough investigation is required to understand the nature, stability, texture and the influence of various environmental conditions on the structure of the phase. The present study is mainly concerned with the physicochemical investigations on the liquid crystalline transitions during compaction of DNA by cationic species such as polyamines and metallic cations. As a preliminary to the above investigation, studies were conducted on the evolution of mesophase transitions of DNA with various cationic counterion species using polarized light microscopy. These studies indicated significant variations in the phase behaviour of DNA in the presence of Li and other ions. Apart from the neutralization of the charges on the DNA molecule, these ions are found to influence selectively the hydration sphere of DNA that in turn influences the induction and stabilization of the LC phases. The higher stability observed with the liquid crystalline phases of Li-DNA system could be useful in the production of nanostructured DNA. In the case of the polyamine, a structural specificity effect depending on the nature, charge and structure of the polyamine used has been found to be favoured in the crystallization of DNA.