Hitoshi Washizu

Organophosphates are well-known as the canonical additives for lubricants. Thus, understanding of the additive behaviour is a key aspect in the design of films on metal surfaces. Different types of phosphates are added to improve their antiwear properties, but the contributions of individual esters to these properties has not been studied using a combination of practical and theoretical approaches. In this study, organophosphates were isolated with high purity and their tribological characteristics were evaluated by using a Bowden-type reciprocating friction tester and a four-ball wear tester. Mono-oleylphosphate had a lower friction than di-oleylphosphate and exhibited excellent antiwear characteristics. Analysis of the sliding surfaces using desorption electrospray ionization-mass spectrometry (DESI-MS) and X-ray photoelectron spectroscopy (XPS) indicated that the film structure could predict the occurrence factor of the tribological characteristics of the oleylphosphates. Then the adsorption energies of the monoester on iron and iron oxide surfaces were higher than those of the diester, as assessed using density functional theory (DFT) calculations, owing to the difference in their chemisorption processes, as confirmed by further DFT analysis. Studies on the reactivity of additives and their interactions with surfaces are important for understanding the tribochemistry of additives.

In recent years, substantial advancements have been achieved in augmenting the energy efficiency of hydraulic fluids through the integration of polymers. This study employs a multiscale approach, encompassing an analysis of polymer coil size evolution and flow field characteristics, with the aim of investigating the behavior of both dipole and non-dipole polymers within the host solvent. The ultimate goal is to establish a comprehensive understanding of the correlation between atomic properties of additives and the macroscopic properties of the polymer solution. To achieve this, the study employs an atomistic-continuum hybrid model that combines Brownian Dynamics and Lattice Boltzmann techniques within the bead-spring concept framework. Four chains, each comprising 64 particles, are subjected to varying shear rates. The primary focus centers on the examination of alterations in the radius of gyration and the velocity field within the polymer solution. Notably, the inclusion of dipole-dipole interactions exerts a profound influence on the configuration of the polymers. The results illuminate that non-dipole polymers display a more pronounced coupling with bulk flow hydrodynamics, leading to the confinement of particle motion in directions perpendicular to the primary stream. In contrast, dipole polymers experience a slower increase in coil size when compared to their non-dipole counterparts. These findings furnish valuable insights for the enhancement of energy-efficient hydraulic fluids and contribute to a fundamental comprehension of polymer behavior in lubricants, charting the course for the development of advanced hydraulic fluids in the future.

Reentrant phenomena in soft matter and biosystems have attracted considerable attention because their properties are closely related to high functionality. Here, we report a combined experimental and computational study on the self-assembly and reentrant behavior of a single-component thermotropic smectic liquid crystal toward the realization of dynamically functional materials. We have designed and synthesized a mesogenic molecule consisting of an alicyclic trans,trans -bicyclohexyl mesogen and a polar cyclic carbonate group connected by a flexible tetra(oxyethylene) spacer. The molecule exhibits an unprecedented sequence of layered smectic phases, in the order: smectic A-smectic B-reentrant smectic A. Electron density profiles and large-scale molecular dynamics simulations indicate that competition between the stacking of bicyclohexyl mesogens and the conformational flexibility of tetra(oxyethylene) chains induces this unusual reentrant behavior. Ion-conductive reentrant liquid-crystalline materials have been developed, which undergo the multistep conductivity changes in response to temperature. The reentrant liquid crystals have potential as new mesogenic materials exhibiting switching functions.

In this paper, we classified the types of water in the vicinity of the chitosan polymer and gold plate by applying an electric field of magnitude 1 V Å-1 in various directions at varying temperatures by using molecular dynamics simulation. The three types of water were categorized by analyzing the data through the tetrahedral order method with four water regions separated in the distance from 1 to 6 Å around polymers. The interaction between water molecules and functional groups, such as hydroxyl, ether, and ester, leads to the formation of intermediate and nonfreezing water. Under an electric field, this formation appeared more clearly due to the transformation of liquid water to crystal cubic ice with two structural formations depending on gold plates at a temperature of 300 K. The enhancement of the tetrahedral order of water in cubic ice is related to the existence of a four-fold H-bonded structure and lower ones in the XES experiment.

Polyethylene (PE) and branched PE are common materials inserted inside contacts for medical and industrial applications. Consequently, their tribological properties have been extensively investigated in the past. This paper aims to determine the lubrication behavior of polyethylethylene (PEE) for iron contact and the two main factors of temperature and carbon chain length influencing the lubrication in the high-pressure lubrication regime by molecular dynamics simulations. Additionally, the influences of pressure and sliding velocity on the friction are also considered. These factors are found to be significantly influencing the lubricity. The obtained results mainly originated from shear and stretching of the PEE molecules, condensed situation of the lubricants, and adhesion between the lubricants and the iron surfaces. These observations are explained in detail.

Bulk copolymerization of alkyl acrylates and cyclodextrin (CD) host monomers produced a single movable cross-network (SC). The CD units acted as movable crosslinking points in the obtained SC elastomer. Introducing movable crosslinks into a poly(ethyl acrylate/butyl acrylate) copolymer resulted in good toughness (G(f)) and stress dispersion. Here, to improve the Young's modulus (E) and G(f) of movable cross-network elastomers, the bulk copolymerization of liquid alkyl acrylate monomer swelling in SC gave another type of movable cross-network elastomer with penetrating polymers (SCPs). Moreover, the bulk copolymerization of alkyl acrylate and the CD monomer in the presence of SC resulted in dual cross-network (DC) elastomers. The G(f) of the DC elastomer with a suitable weight % (wt%) of the secondary movable cross-network polymer was higher than those of the SCP or SC elastomers. The combination of suitable hydrophobicity and glass transition of the secondary network was important for improving G(f). Small-angle X-ray scattering (SAXS) indicated that the DC elastomers exhibited heterogeneity at the nanoscale. The DC elastomers showed a significantly broader relaxation time distribution than the SC and SCP elastomers. Thus, the nanoscale heterogeneity and broader relaxation time distribution were important to increase G(f). This method to fabricate SCP and DC elastomers with penetrating polymers would be applicable to improve the G(f) of conventional polymeric materials.