Modeling of interface phenomena in liquid under vibration, using the chemical model

An analysis of interface phenomena in a liquid under a vibration field is presented, based on the chemical model of vibration in a liquid. The objects studied are a bubble, a solid surface, and a linear macromolecule, in a vibrated liquid. It is concluded that many sonochemical phenomena can be realized in some different (two or more) mechanisms, and mutually stimulate. Inharmonic effects and the influence of distant neighbors are analyzed.     

Distribution of chain ends at the surface of a polymer melt: Compensation effects and surface tension

We consider the surface of a nearly incompressible polymer melt, extending the usual ground-state analysis of self-consistent field theory to describe finite length polymers in the ground-state potential. To maintain self-consistency, further corrections to the potential are calculated within linear response theory. From this, we find an excess of ends near the surface, followed by a compensating depletion on the R_g length scale, which relies crucially on the finite compressibility of the melt. The attraction of ends to the surface can be described as resulting from a surface potential for ends with a strength on the order of k_BT. Our results address the long-standing controversies of the distribution of chain ends, the chain-length dependence of the surface tension, and the interaction between objects immersed in a melt. © 1995 John Wiley & Sons, Inc.     

Chemometric classification of traditional Chinese medicines by their geographical origins using near-infrared reflectance spectra.

Some raw materials that have different places of production for the plant sources of the drugs Astragalus membranaceus and ginseng have been studied, based on their near-infrared reflectance spectra. The experimentally recorded spectra represent heavily ill-posed and highly correlative data sets. Three related methods, i.e. the Fisher linear discriminant analysis (FLDA), the ridge-type linear discriminant analysis (RLDA) and a newly proposed penalized ridge-type linear discriminant analysis (PRLDA), have been investigated. FLDA over-fits for the training objects of the two data sets to a high extent and is unstable for the predictive objects of the two data sets. RLDA shows obvious improvement in terms of over-fitting and unstability, but the stability for the predictive objects of the two data sets is too sensitive to their ridge-type penalized weights, tending to produce erroneous discrimination results. The proposed PRLDA can circumvent the two aforementioned problems with a large domain of penalized weights for correct discriminant analysis of the two data sets studied. The combination of the PRLDA method and near infrared reflectance spectroscopy can be adapted for the discrimination of the production places of plant sources of these drugs.     

Importance of sample preparation on reliable surface characterisation of nano‐objects: ISO standard 20579‐4

The international ISO Standard 20579‐4, dealing with the history and preparation of nano‐objects for surface analysis, has been developed to help address some of the replication and reproducibility issues caused by the fundamental nature of nano‐objects. Although all types of samples requiring surface analysis need thoughtful preparation, nano‐objects, for which many properties are controlled by their surfaces, present additional challenges in order to avoid variations and artefacts due to the handling and preparation of materials prior to analysis. This international standard is part of a series of standards related to preparation of samples for surface chemical analysis. Parts 1 and 2 of ISO Standard series 20579 address general issues that apply to many samples. Part 3, which is still in development, will focus on biomaterials. Part 4 specifically considers issues that arise due to the inherent nature of nano‐objects. Because of sensitivity to their environment, the standard indicates the minimum information that needs to be reported about the handling and preparation of nano‐objects prior to surface analysis. This information should become part of sample provenance information that helps assure the reliability and usefulness of data obtained from surface‐analysis in the context of the synthesis, processing, and analysis history of a batch of material. Application of this standard can help address reproducibility and traceability issues associated with synthesis, processing, and characterization of nano‐objects in research and commercial applications.     

Morphology of the surface of sorbents based on a copolymer of styrene and divinylbenzene according to atomic force spectroscopy data

Studies of the surface of polymer complexing sorbents (PCSes) with an o, o′-dioxy-(1-azo-1′) functional analytic group were conducted by means of atomic force spectroscopy (AFM). The characteristic linear dimensions of surface relief objects and their fractal dimensions were determined. The PCS roughness parameters (the mean-root-square profile roughness and average arithmetic roughness) were established and the quantitative dependence between them and the scanning scale was found. The effect of temperature on the sorbents’ structural organization was demonstrated. The obtained data enable us to solve the problem of sorption process intensification through the targeted impact of the class of compounds under examination on the supramolecular structure and polymer substrate morphology in creating the optimum conditions of sorption with PCS participation.     

The features of electron dose distributions in circular objects: Comparison of Monte Carlo calculation predictions with dosimetry

The features of electron dose field formation in the multi-layer circular objects are related with its surface irregularity such as convexity, concavity and roundness of inner and outer layers. The simulation of dose distributions in multi-layer tubes irradiated with a scanned electron beam (EB) was carried out by Monte Carlo (MC) method with utilization of the software ModeCEB. The effects of mutual influence on dose field formation in contacting multi-layers tubes irradiated with EB were MC simulated and measured with a film dosimetry. An experimental validation of the obtained simulation predictions for dose distributions in multi-layer tubes irradiated with 10 MeV electrons was performed on radiation facility with linear electron accelerator LAE 13/9, INCT, Warsaw. Comparison of MC simulation results with a film dosimetry is discussed in the report.     

A linear learning machine program for a microcomputer

The linear learning machine (LLM) has become an established procedure in chemical pattern recognition. It examines whether two classes of objects, represented as points in a multidimensional space with the variables as coordinates, can be separated by means of a linear hyperplane. The position of the hyperplane is determine by an iterative procedure, using feedback corrections. In most applications, the computations are done on minicomputers. In this communication, a “micro-LLM” is described, i.e., a linear learning machine implemented on a microcomputer.     

Rubber-based substrates modified with carbon nanotubes inks to build flexible electrochemical sensors

The development of a solid-contact potentiometric sensor based on conducting rubbers using a carbon nanotubes ink is described here. Commercial rubbers are turned into conductive ones by a simple and versatile method, i.e. painting an aqueous dispersion of single-walled carbon nanotubes on the polymer surface. On this substrate, both the working ion-selective electrode and the reference electrode are built in order to form an integrated potentiometric cell. As a proof-of-principle, selective potassium electrodes are fully characterized giving comparable performances to conventional electrodes (sensitivity, selectivity, stability, linear range, limit of detection and reproducibility). As an application of the rubber-based electrodes, a bracelet was constructed to measure potassium levels in artificial sweat. Since rubbers are ubiquitous in our quotidian life, this approach offers great promise for the generation of chemical information through daily objects.     

Micellar aggregation in blends of linear and cyclic poly(styrene-b-isoprene) diblock copolymers

The morphology of micelles formed from blends of linear and cyclic poly(styrene-b-isoprene) (PS-b-PI) block copolymers has been investigated in solution using dynamic light scattering (DLS) and in thin solid deposits by atomic force microscopy (AFM) and transmission electron microscopy under cryogenic conditions (cryo-TEM). Micelles of the pure cyclic PS(290)-b-PI(110) copolymers are wormlike cylindrical objects built by unidirectional aggregation of 33 nm wide sunflower micelles, while the linear block copolymer having the same volume fraction and molar mass forms spherical micelles 40 nm in diameter. The DLS, AFM, and cryo-TEM results consistently show that the addition of the linear copolymer (even for amounts as low as 5% w/w) to the cyclic copolymer rather favors the formation of spherical micelles at the expense of the cylindrical aggregates. Those results clearly show that the linear block copolymer chains can be used to stabilize the thermodynamically unstable elementary sunflower micelle. The thermal stability of the micelles (from the pure copolymers and from the blends) has been examined in solid deposits with in situ AFM measurements. Coalescence starts at about 70 degrees C, and the surface roughness shows a two-step decrease toward a fully homogeneous and flat structure.     

Influence of the bulk and surface morphology on adhesion of polystyrene-inter-poly-cross-2-ethylhexyl-methacrylate films and particles

The adhesion behavior of semi-interpenetrating polymer networks (semi-IPNs) of linear polystyrene (PS) in crosslinked poly-2-ethylhexylmethacrylate (EHMA) was studied by variation of the bulk and surface morphology, i.e., domain size, continuity, and concentration in the domains. Semi-IPNs were prepared by liquid-liquid demixing upon cooling of a homogeneous solution of PS in methacrylate monomer, followed by gelation of the PS-rich phase and UV polymerization of the methacrylate resin. Welding of films allowed the preparation of larger objects provided that (1) the samples were phase separated to a high degree and contained domains with a high PS concentration (>90%) and (2) polystyrene was present at the interface. For semi-IPN films, a linear dependence of the adhesion strength on the (crack healing time)^1/4 was obtained. Based on these considerations, a process was developed to obtain melt-processable semi-IPN particles, by quenching droplets of the polymer solution into a cold liquid. These particles obtained a PS-rich skin layer and showed good adhesion after blending with a thermoplast. © 1996 John Wiley & Sons, Inc.     

A Perfect Plastic Material for Studies on Self-Propelled Motion on the Water Surface

We describe a novel plastic material composed of camphene, camphor, and polypropylene that seems perfectly suited for studies on self-propelled objects on the water surface. Self-motion is one of the attributes of life, and chemically propelled objects show numerous similarities with animated motion. One of important questions is the relationship between the object shape and its motility. In our paper published in 2019, we presented a novel hybrid material, obtained from the solution of camphor in camphene, that allowed making objects of various shapes. This hybrid material has wax-like mechanical properties, but it has a very high tackiness. Here, we report that a small amount of polypropylene removed this undesirable feature. We investigated the properties of camphor–camphene–polypropylene plastic by performing the statistical analysis of a pill trajectory inside a Petri dish and compared them with those of camphor-camphene wax. The plastic showed the stable character of motion for over an hour-long experiment. The surface activity of objects made of plastic did not significantly depend on the weight ratios of the compounds. Such a significant increase in usefulness came from the polypropylene, which controlled the dissipation of camphor and camphene molecules.     

Critical chromatography and mass spectrometry of macromolecules: Determination of the position of a functional group in a chain

The potentials inherent in the method of critical chromatography of macromolecules combined with mass spectrometry for the study of the most complicated characteristic of the macromolecular structure—the determination of the position (the number) of a defect unit or functional group in a sequence of chain units—are considered. Polyurethanes based on poly(propylene oxide) oligomers were used as research objects. Such macromolecules contain a small amount of urethane groups in a chain that differ from mainchain units in the energy of interaction with the surface. Variation in the molecular-mass distribution of the initial poly(propylene oxide) oligomers makes it possible to prepare linear polyurethane macromolecules with different positions of urethane groups. Critical chromatography offers a way to separate macromolecules with different amounts of urethane groups and positions of these groups in chains.     

Complementarity of pixe and pige for the characterization of gold items of ancient jewelry

By using strictly non destructive and non radioactive methods of elemental analysis (PIXE and PIGE), using a 3 MeV proton beam to induce prompt emission of characteristic X-rays or gamma-rays of the elements and simultaneous photon-spectroscopy with energy dispersive solid state detectors [Si(Li) and Ge(Li)] followed by a computer assisted data handling system, we have determined the relative amounts of copper, silver, cadmium and gold at the surface of more than 30 ancient gold objects. Results on only two items are discussed here. Traces or significant concentrations of cadmium have been detected at nearly all points on or in the neighbourhood of solders on many objects dating from Roman to early Byzantine times. Cadmium concentrations range between 2 to 75 parts per thousand. This range of variation and the relative concentrations of Au, Ag, Cu and Cd at the surface of the objects studied are very different from the figures obtained during analyses of modern soldering alloys. New approaches to solve the problem of Cadmium in ancient jewelry are indicated.     

Finite-thickness-enhanced attractions for oppositely charged membranes and colloidal platelets

Within linearized Poisson-Boltzmann theory, we study the disjoining pressure of two oppositely charged parallel objects (membranes and colloidal platelets) in a 1:1 electrolyte, with a focus on the effects of their finite thickness. This extension of the standard Gouy-Chapman model from an interacting pair of double layers to a quartet (one on each side of the two interacting objects) is shown to enhance the regime of attractive interactions significantly, in particular, when the separation and the thickness are on the order of the Debye length of the solvent, provided the dielectric mismatch between objects and solvent is not too extreme. The enhancement of attractions occurs for objects with fixed charge as well as for those that exhibit charge regulation but not for those with a constant surface potential. The underlying mechanism for this enhancement for thin objects is the transfer of net ionic charge from the electrolyte in between to the other sides. For biological membranes in water, this effect is small; however, it is due to strong image charge effects.     

Scattering structure factor of colloidal gels characterized by static light scattering, small-angle light scattering, and small-angle neutron scattering measurements

The scattering structure factor of a colloidal gel in a q range of 5 orders of magnitude has been determined by combining static light scattering, small-angle light scattering, and neutron scattering measurements. It exhibits simultaneously two types of structure information: a mass fractal scaling within the clusters that constitute the gel and a surface fractal scaling for length scales larger than that of the clusters. Such scattering behavior can be well interpreted by the pair-correlation function proposed in the literature to model an ideal structure constituted of mass fractal objects inside surface fractal objects.     

Synthesis of molecular objects: Two-dimensional polymers

Throughout this century polymer science has studied the linear chain and its architectural derivatives which include familiar forms such as the branched chain and the three dimensional network. Other derivatives with unique properties have been investigated more recently and include macromolecular rings, dendrimers, stars, combs and ladders. The objective of this work is to depart from the focus on linear chains and explore the “bulk” synthesis and properties of polymer molecules that can be considered molecular objects. Ideal molecular objects should be macromolecules with well defined shapes that persist as systems transform reversibly from solids to melts or solutions. The limited access to conformational space which is required in order to define and maintain shape in liquid and solid states of the system is an unusual molecular characteristic in common polymers. Our ability to create such objects through bulk reactions of reasonable scale will undoubtedly extend the current boundaries of polymer science and technology. Shapes that are particularly interesting are those not common in the conformational space of linear chains, for example, two-dimensional polymers shaped as plates and macromolecular bundles shaped as cylinders or parallelepipeds. The molecular object to be discussed in this lecture is a rigid and anisotropic two-dimensional polymer with planar dimensions greater than its thickness and a shape-granting skeleton built by covalent bonds. We have so far developed three different strategies for their synthesis, all involving systems in which reactive oligomers organize spontaneously into the necessary planar assemblies to form the object. In one strategy molecular recognition driven by homochiral interactions plays a key role in the formation of two-dimensional polymers.¹ A different methodology relies on entropy-driven nanophase separation in rodcoil block molecules in which a rigid segment is covalently bonded to a flexible one sharing the same backbone. The third strategy involves the folding of oligomers into hairpin structures which self assemble into two-dimensional liquids. The lecture will also describe examples of unique properties that could be achieved in materials containing these rigid two-dimensional objects. These examples will include bulk materials with self-organized surfaces and also remarkably stable nonlinear optical properties.     

Meniscus-climbing behavior and its minimum free-energy mechanism

Some insects can climb up the top of the meniscus surface generated by a hydrophilic wall by fixing their posture without moving their appendages [Baudoin, R. Bull. Biol. Fr. Belg. 1955, 89, 16. Hu, D. L.; Bush, J. W. M. Nature 2005, 437, 733]. To better understand this interesting phenomenon, we did meniscus-climbing experiments of bent copper sheets. It was found that the sheets do not always climb up the top of the meniscus surface but may stop and stably stay at various positions on the meniscus surface, depending upon their curvatures and masses, and that bent copper sheets can self-assemble into an oriented array (or an anisotropic form) through self-rotating on the water surface. The minimum energy mechanism of meniscus-climbing and self-rotating was then numerically studied. It was further shown that the meniscus-climbing and the rotating behavior is not only a general phenomenon for floating objects with hydrophilic surfaces, even those with fairly large sizes and weights (e.g., a metal bottle cap), but is also conditionally realizable for floating objects with hydrophobic surfaces.     

Binary liquid mixtures. The relation between surface tension and surface composition as studied by MIES (metastable induced electron spectroscopy)

For a binary liquid mixture, we define the surface fraction of a component as the fraction of the surface which is covered by this species. The perfectly surface-sensitive electron spectroscopy MIES (metastable induced electron spectroscopy) allows to derive this quantity in a very direct manner from experiment with no model assumption needed. We find for several binary mixtures that the surface tension depends linearly on the surface fraction with striking accuracy. Even more surprising is the fact that for a system which deviates from this simple linear behavior the surface tension turns out to be a piecewise linear function of the surface fraction. Tentatively, we introduce as possible explanation the concept of phase separation within the surface layer. Further, we show that the surface molar fraction, i.e., the molar fraction within the top surface layer, deviates significantly from a linear or a piecewise linear relation to the surface tension.