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Surfaces of ice act as sites of various chemical reactions of atmospheric acidic gases, which cause serious environmental issues, such as the catalytic ozone depletion by hydrogen chloride (HCl) ga...

A wet cotton rag becomes stiff after natural drying. We propose a model for this hardening phenomenon, which explains that the stiffness of cotton is caused by a cross-linked network between single fibers, mediated by capillary adhesion of bound water on the surface of cellulose. Here, with the aid of atomic force microscopy and atomic force microscopy-infrared spectroscopy, we reveal the existence of the bound water on the surface of a cotton single fiber under naturally dried conditions. We also find that the hydrogen bonding state of the bound water is distinct from that of the bulk water. Two stretching modes of OH groups are clearly decoupled from each other, which arise from the effects of the air-water (hydrophobic) and water-cellulose (hydrophilic) interfaces. This suggests a possible link between the microscopic nature of the bound water and the macroscopic mechanical behavior of cotton fabrics.

金沢大学学術メディア創成センター, Ice-crystal growth in supercooled water is one of the most familiar examples of phase-transition dynamics, playing essential roles in various natural phenomena on Earth. Despite its fundamental importance, the microscopic view at the elementary step level remains elusive. Here, using an advanced optical microscope, we find self-organization of elementary steps during ice-crystal growth, called step-bunching instability (SBI), driven by the competition between step dynamics, interfacial stiffness, and latent heat diffusions. We also find that the SBI transiently induces screw dislocations and resulting spiral growth in the late stage of the growth process. Furthermore, quantitative observations with a two-beam interferometer allow us to obtain insights into the relative importance of the various mechanisms of the step–step interactions. Our finding offers a significant clue to understanding the general mechanism of melt growth beyond ice-crystal growth, inseparably involving several broad research fields, including cryobiological, geophysical, and material branches.

Surface melting of ice crystals proceeds below the melting point (0 °C) and forms thin liquid water layers, called quasi-liquid layers (QLLs), which govern a wide variety of phenomena in nature. Hence, many studies have been performed so far; however, the lowest temperature above which QLLs exist on ice crystal surfaces varied from −90 to −1 °C. To reveal the cause of such significant variations, here we show, by laser confocal microscopy combined with Michelson interferometry, the behavior of QLLs on polycrystalline ice thin films that include a large amount of grain boundaries and defects. We found that the QLLs can exist stably on the polycrystalline ice thin films even at −16.2 °C (the lowest temperature adopted in this study), although the QLLs on ice single crystals disappear at temperature lower than −2.4 ± 0.5 °C. These results emphasize the importance of grain boundaries and defects for the presence of QLLs. In addition, we also found that critical water vapor pressure above which the QLLs can gr...

Surfaces of ice have attracted considerable attention as “reaction sites” where atmospheric gases cause various chemical reactions in nature. Hence, revealing the uptake mechanism of atmospheric gases on/in ice remains an experimental challenge. Here we show the direct observation of ice crystal surfaces by advanced optical microscopy in the presence of hydrogen chloride (HCl) gas, which triggers a series of chemical reactions that cause ozone depletion. We found that the HCl gas induced the appearance of droplets of HCl solution on ice crystal surfaces. Under supersaturated water vapor pressure, the HCl droplets were quickly embedded in the ice crystals during the growth of the ice. In contrast, under undersaturated conditions, the embedded HCl droplets reappeared on the ice crystal surfaces during the evaporation of the ice. We estimated that the mole fraction of HCl incorporated into the ice as the HCl droplets (0.19% at −15 °C) was ten times larger than the solubility of HCl gas in an ice crystal (0.0...

We measured the velocity Vstep of isolated elementary spiral steps and the distance Leq between adjacent equivalent spiral steps on ice basal faces by advanced optical microscopy. We determined the step kinetic coefficient β from Vstep measured under various supersaturations. We performed similar experiments under various temperatures T, and determined the temperature dependence of β of ice basal faces, for the first time, in the temperature range of −26.0 to −2.7 °C. When −6.2 ≤ T ≤ −2.7 °C, the value of β decreased significantly with decreasing T. In contrast, when −15.0 ≤ T ≤ −6.2 °C, the value of β increased with decreasing T, and had the maximum at T ≈ −15 °C. When −26.0 ≤ T ≤ −15.0 °C, the value of β decreased monotonically with decreasing T. Such complicated temperature dependence of β strongly implies the existence of unknown phenomena in the temperature range examined. To obtain a clue to the complicated behavior of β, we also measured dependence of Leq on surface supersaturation Δμsurf. When −13...

Ice is one of the most abundant materials on the earth's surface, and its growth governs various natural phenomena. Hence, the molecular-level understanding of ice crystal surfaces is crucially important. However, it is generally acknowledged that the molecular-level observation of ice crystal surfaces by ordinary microscopy techniques, such as atomic force microscopy and scanning electron microscopy, is very difficult at temperatures near the melting point (0 °C). To overcome such difficulties, we have developed laser confocal microscopy combined with differential interference contrast microscopy (LCM-DIM). We proved that LCM-DIM can visualize individual elementary steps (0.37 nm in thickness) on a basal face by observing two-dimensional nucleation growth. Then we found by LCM-DIM that spiral steps on a basal face exhibit a double-spiral pattern, which can be expected from ice's crystallographic structure. In addition, we revealed that temperature dependence of growth kinetics of elementary spiral steps on a basal face exhibits complicated behaviors, which show the presence of unknown phenomena in the growth kinetics. Furthermore, we proved that surface diffusion of water admolecules on a basal face plays a crucially important role in the lateral growth of elementary steps when the distance between adjacent spiral steps is smaller than 15 µm. These findings will provide a clue for unlocking growth kinetics of ice crystals. In addition, through the use of LCM-DIM much progress has been made in studies on the surface melting of ice and the interaction between ice and atmospheric gasses.

It has been implicitly assumed that ices on grains in molecular clouds and proto planetary disks are formed by homogeneous layers regardless of their composition or crystallinity. To verify this assumption, we observed the H2O deposition onto refractory substrates and the crystallization of amorphous ices (H2O, CO2, and CO) using an ultra-high-vacuum transmission electron microscope. In the H2O-deposition experiments, we found that three-dimensional islands of crystalline ice (Ic) were formed at temperatures above 130 K. The crystallization experiments showed that uniform thin films of amorphous CO and H2O became three-dimensional islands of polyhedral crystals; amorphous CO2, on the other hand, became a thin film of nano crystalline CO2 covering the amorphous H2O. Our observations show that crystal morphologies strongly depend not only on the ice composition, but also on the substrate. Using experimental data concerning the crystallinity of deposited ices and the crystallization timescale of amorphous ices, we illustrated the criteria for ice crystallinity in space and outlined the macroscopic morphology of icy grains in molecular clouds as follows: amorphous H2O covered the refractory grain uniformly, CO2 nano-crystals were embedded in the amorphous H2O, and a polyhedral CO crystal was attached to the amorphous H2O. Furthermore, a change in the grain morphology in a proto-planetary disk is shown. These results have important implications for the chemical evolution of molecules, non-thermal desorption, collision of icy grains, and sintering., 60 pages, 18 figures, 3 tables, published in ApJ

Liquid–liquid transition (LLT) is the transformation of one liquid to another via first-order phase transition. For example, LLT in a molecular liquid, triphenyl phosphite, is macroscopically the transformation from liquid I in a supercooled state to liquid II in a glassy state. Reflecting the transformation from the liquid to glassy state, the LLT is accompanied by considerable slowing down of overall molecular dynamics, but little is known about how this proceeds at a molecular level coupled with the evolution of the order parameter. We report such information by performing time-resolved simultaneous measurements of dielectric spectroscopy and phase contrast microscopy/Raman spectroscopy by using a dielectric cell with transparent electrodes. We find that the temporal change in molecular mobility crucially depends on whether LLT is nucleation growth type occurring in the metastable state or SD type occurring in the unstable state. Furthermore, our results suggest that the molecular mobility is controlled by the local order parameter: more specifically, the local activation energy of molecular rotation is controlled by the local fraction of locally favored structures formed in the liquid. Our study sheds light on the temporal change in the molecular dynamics during LLT and its link to the order parameter evolution.

A microscopic understanding of crystal-melt interfaces, inseparably involved in the dynamics of crystallization, is a long-standing challenge in condensed matter physics. Here, using an advanced optical microscopy, we directly visualize growing interfaces between ice basal faces and quasiliquid layers (QLLs) during ice crystal growth. This system serves as a model for studying the molecular incorporation process of the crystal growth from a supercooled melt (the so-called melt growth), often hidden by inevitable latent heat diffusion and/or the extremely high crystal growth rate. We reveal that the growth of basal faces inside QLLs proceeds layer by layer via two-dimensional nucleation of monomolecular islands. We also find that the lateral growth rate of the islands is well described by the Wilson-Frenkel law, taking into account the slowing down of the dynamics of water molecules interfaced with ice. These results clearly indicate that, after averaging surface molecular fluctuations, the layer by layer stacking still survives even at the topmost layer on basal faces, which supports the kink-step-terrace picture even for the melt growth.

In this experimental course, attendees will learn how to obtain useful information about growth processes of crystals using ordinary optical microscopes, which are usually available in laboratories. We will demonstrate how thicknesses of crystals can be estimated from interference colors. We will also show in-situ observations of spiral steps and strain distributions by differential interference contrast microscopy and polarizing microscopy, respectively.

Surface melting of ice crystals forms quasi-liquid layers (QLLs) on ice surfaces, and affects a wide variety of natural phenomena. Since QLLs enhance various chemical reactions in ice clouds, the formation of QLLs by atmospheric gases has been studied intensively. However, such studies were performed using spectroscopy techniques, which have low spatial resolution. Here we show the first direct visualization of QLLs on ice basal faces in the presence of hydrogen chloride (HCl) gas (model atmospheric gas) by advanced optical microscopy, which can visualize individual 0.37 nm-thick elementary steps on ice crystal surfaces. We found that the HCl gas induced the appearances of QLLs with a droplet shape in the temperature range from −15.0 to −1.5 °C, where no QLL appears in the absence of HCl gas. This result indicates that HCl gas adsorbed on ice crystal surfaces probably changed the surface structure of ice crystals and then induced the subsequent melting of ice surfaces. We also observed the movement, shape...

The surfaces of ice crystals near the melting point are covered with thin liquid water layers, called quasi-liquid layers (QLLs), which play crucial roles in various chemical reactions in nature. So far, there have been many spectroscopic studies of such chemical reactions on ice surfaces, however, revealing the effects of atmospheric gases on ice surfaces remains an experimental challenge. In this study, we chose HNO3 as a model atmospheric gas, and directly observed the ice basal faces by advanced optical microscopy under partial pressure of HNO3 (~10&minus, 4 Pa), relevant to those found in the atmosphere. We found that droplets (HNO3-QLLs) appeared on ice surfaces at temperatures ranging from &minus, 0.9 to &minus, 0.2 &deg, C with an increase in temperature, and that they disappeared at temperatures ranging from &minus, 0.6 to &minus, 1.3 &deg, C with decreasing temperature. We also found that the size of the HNO3-QLLs decreased immediately after we started reducing the temperature. From the changes in size and the liquid&ndash, solid phase diagram of the HNO3-H2O binary system, we concluded that the HNO3-QLLs did not consist of pure water, but rather aqueous HNO3 solutions, and that the temperature and HNO3 concentration of the HNO3-QLLs also coincided with those along a liquidus line.

The spiral growth of crystals, mediated by their screw dislocations, is a general crystal-growth mechanism observed over a large variety of crystalline solids. Despite its general nature, direct observations of the spiral growth of ice have been rarely reported so far. Here, with the aid of advanced optical microscopy, we succeed in making in situ observations of the perfect spiral growth during the vapor growth of ice. We find that the spiral steps observed are well described by the classical Burton--Cabrera--Frank theory, taking into account surface diffusion of water admolecules between adjacent steps. This is distinct from the dominant growth mode that we have assigned as spiral in our recent studies, which accompanies fluctuations of the adjacent step interval. We also successfully capture the birth of a screw dislocation and the ensuing spiral growth, originating in the lattice mismatch arising from the coalescence of single ice crystals. Furthermore, we demonstrate that the nucleation of quasi-liquid layers (QLLs) takes place at the spiral center immediately after the birth of the dislocation, which suggests a link between screw dislocations and the generation of QLLs near the ice melting point.

A liquid-liquid transition (LLT) in a single-component substance is an unconventional phase transition from one liquid to another. LLT has recently attracted considerable attention because of its fundamental importance in our understanding of the liquid state. To access the order parameter governing LLT from a microscopic viewpoint, here we follow the structural evolution during the LLT of an organic molecular liquid, triphenyl phosphite (TPP), by time-resolved small- and wide-angle X-ray scattering measurements. We find that locally favored clusters, whose characteristic size is a few nanometers, are spontaneously formed and their number density monotonically increases during LLT. This strongly suggests that the order parameter of LLT is the number density of locally favored structures and of nonconserved nature. We also show that the locally favored structures are distinct from the crystal structure and these two types of orderings compete with each other. Thus, our study not only experimentally identifies the structural order parameter governing LLT, but also may settle a long-standing debate on the nature of the transition in TPP, i.e., whether the transition is LLT or merely microcrystal formation.

UV-irradiated interstellar ice analog behaves like a liquid at 50 to 150 kelvin, below its crystallization temperature., Interstellar ice is believed to be a cradle of complex organic compounds, commonly found within icy comets and interstellar clouds, in association with ultraviolet (UV) irradiation and subsequent warming. We found that UV-irradiated amorphous ices composed of H2O, CH3OH, and NH3 and of pure H2O behave like liquids over the temperature ranges of 65 to 150 kelvin and 50 to 140 kelvin, respectively. This low-viscosity liquid-like ice may enhance the formation of organic compounds including prebiotic molecules and the accretion of icy dust to form icy planetesimals under certain interstellar conditions.

The free growth of ice crystals in supercooled bulk water containing an impurity of glycoprotein, a bio-macromolecule that functions as ‘antifreeze’ in living organisms in a subzero environment, was observed under microgravity conditions on the International Space Station. We observed the acceleration and oscillation of the normal growth rates as a result of the interfacial adsorption of these protein molecules, which is a newly discovered impurity effect for crystal growth. As the convection caused by gravity may mitigate or modify this effect, secure observations of this effect were first made possible by continuous measurements of normal growth rates under long-term microgravity condition realized only in the spacecraft. Our findings will lead to a better understanding of a novel kinetic process for growth oscillation in relation to growth promotion due to the adsorption of protein molecules and will shed light on the role that crystal growth kinetics has in the onset of the mysterious antifreeze effect in living organisms, namely, how this protein may prevent fish freezing.

Liquid-liquid transition (LLT) in single-component liquids is one of the most mysterious phenomena in condensed matter. So far this problem has attracted attention mainly from the purely scientific viewpoint. Here we report the first experimental study on an impact of surface nano-structuring on LLT by using a surface treatment called rubbing, which is the key technology for the production of liquid crystal displays. We find that such a rubbing treatment has a significant impact on the kinetics of liquid-liquid transition (LLT) of an isotropic molecular liquid, triphenyl phosphite. For a liquid confined between rubbed surfaces, surface-induced barrier-less formation of the liquid II phase is observed even in a metastable state, where there should be a barrier for nucleation of the liquid II phase in bulk. Thus, surface rubbing of substrates not only changes the ordering behavior, but also accelerates the kinetics significantly. This spatio-temporal pattern modulation of LLT can be explained by a wedge filling transition and the resulting drastic reduction of the nucleation barrier. However, this effect completely disappears in the unstable (spinodal) regime, indicating the absence of the activation barrier even for bulk LLT. This confirms the presence of nucleation-growth-type and spinodal-decomposition-type LLT, supporting that LLT is truly a first-order transition with criticality. Our finding also opens up a new way to control the kinetics of LLT of a liquid confined in a solid cell by structuring its surface on a mesoscopic lengthscale, which may contribute to making LLT useful for micro-fluidics and other industrial applications., Comment: 14 pages, 5 figures in the main text; 2 pages, 2 figures in Supplementary Materials

An impurity effect on ice crystal growth in supercooled water is an important subject in relation to ice crystal formation in various conditions in the Earth's cryosphere regions. In this review, we consider antifreeze glycoprotein molecules as an impurity. These molecules are well known as functional molecules for controlling ice crystal growth by their adsorption on growing ice/water interfaces. Experiments on free growth of ice crystals in supercooled water containing an antifreeze protein were conducted on the ground and in the International Space Station, and the normal growth rates for the main crystallographic faces of ice, namely, basal and prismatic faces, were precisely measured as functions of growth conditions and time. The crystal-plane-dependent functions of AFGP molecules for ice crystal growth were clearly shown. Based on the magnitude relationship for normal growth rates among basal, prismatic and pyramidal faces, we explain the formation of a dodecahedral external shape of an ice crystal in relation to the key principle governing the growth of polyhedral crystals. Finally, we emphasize that the crystal-plane dependence of the function of antifreeze proteins on ice crystal growth relates to the freezing prevention of living organisms in sub-zero temperature conditions. This article is part of the theme issue ‘The physics and chemistry of ice: scaffolding across scales, from the viability of life to the formation of planets’.

Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice–vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs.

The existence of more than two liquid states in a single-component substance and the ensuing liquid-liquid transitions (LLTs) has attracted considerable attention because of its counterintuitive nature and its importance in the fundamental understanding of the liquid state. Here we report direct experimental evidence for a genuine (isocompositional) LLT without macroscopic phase separation in an aqueous solution of glycerol. We show that liquid I transforms into liquid II by way of two types of kinetics: nucleation and growth, and spinodal decomposition. Although liquid II is metastable against crystallization, we could access both its static and dynamical properties experimentally. We find that liquids I and II differ in density, refractive index, structure, hydrogen bonding state, glass transition temperature and fragility, and that the transition between the two liquids is mainly driven by the local structuring of water rather than of glycerol, suggesting a link to a plausible LLT in pure water.

We have experimentally determined the surface tension-to-shear viscosity ratio (the so-called characteristic velocity) of quasiliquid layers (QLLs) on ice crystal surfaces from their wetting dynamics. Using an advanced optical microscope, whose resolution reaches the molecular level in the height direction, we directly observed the coalescent process of QLLs and followed the relaxation modes of their contact lines. The relaxation dynamics is known to be governed by the characteristic velocity, which allows us to access the physical properties of QLLs in a noninvasive way. Here we quantitatively demonstrate that QLLs, when completely wetting ices, have a thickness of 9 +/- 3 nm and an approximately 200 times lower characteristic velocity than bulk water, whereas QLLs, when partially wetting ices, have a velocity that is 20 times lower than the bulk. This indicates that ice crystal surfaces significantly affect the physical properties of QLLs localized near the surfaces at a nanometer scale.

Colloidal clusters are an unusual state of matter where tunable interactions enable a sufficient reduction in their degrees of freedom that their energy landscapes can become tractable — they form a playground for statistical mechanics and promise unprecedented control of structure on the submicron lengthscale. We study colloidal clusters in a system where a short-ranged polymer-induced attraction drives clustering, while a weak, long-ranged electrostatic repulsion prevents extensive aggregation. We compare experimental yields of cluster structures with theory which assumes simple addition of competing isotropic interactions between the colloids. Here we show that for clusters of size 4 ≤ m ≤ 7, the yield of minimum energy clusters is much less than expected. We attribute this to an anisotropic self-organized surface charge distribution which leads to unexpected kinetic trapping. We introduce a model for the coupling between counterions and binding sites on the colloid surface with which we interpret our findings. published

Contrary to the conventional wisdom that there exists only one unique liquid state for any material, there are growing experimental and numerical evidence for the existence of more than two liquid states in a single component substance. The transition between them is called liquid-liquid transition (LLT). LLT has attracted considerable attention because of its counterintuitive nature and its importance in the fundamental understanding of the liquid state. However, the physical nature of the transition has remained elusive. Particularly for water, the possible existence of LLT has special implications not only on its fundamental understanding, but also on a link of various thermodynamic and transport anomalies with critical anomaly associated with LLT. In this paper, we show experimental indications for a LLT in aqueous solutions of glycerol. We demonstrated that LLT proceeds through two types of kinetics characteristic of the first order transition: nucleation-growth (NG) and spinodal-decomposition (SD) type transformation. We also reveal that local tetrahedral ordering of water molecules play a key role, which is suggestive of the presence of LLT in pure water.

Even a single-component liquid may have more than two liquid states. The transition between them is called a 'liquid–liquid transition' (LLT). Such LLTs have recently attracted considerable attention mainly because of the fundamental interest in the physical origin of this counter-intuitive phenomenon. In this study, we report the first observation of wetting effects on LLT for a molecular liquid, triphenyl phosphite. We find a transition from partial to complete wetting for nucleation-growth-type LLT when approaching the spinodal temperature of LLT. Some features unique to LLT are also revealed, reflecting for example the non-conserved nature of its order parameter. We also find that the wetting behaviour is not induced by dispersion forces, but by weak hydrogen bonding to a solid substrate, implying its important role in the LLT itself. Using wetting effects may open a new possibility to control kinetics and spatial patterns of nucleation-growth-type LLT., A phase transition between two liquid states is a counterintuitive phenomenon, but one that is known to happen in certain materials. Murata and Tanaka now show in tryphenyl phosphite that this can also produce a change in the wetting of a surface, from partial to complete, at the transition temperature.

AIDS患者末梢血NK活性が抑制されている事が知られているが，このNK活性の抑制機構を解析した。無症候性キャリアのNK活性は抑制を受けておらず，その時のキャリアの末梢血のCD4+細胞は0%であった。つぎに， HIVの外殻糖蛋白質gp41の一部で，レトロウイルスに保存されている17個のアミノ酸から成るペプチドと，その類似構造をしたペプチドを3種合成した。これらの合成ペプチドは，正常コントロールのNK活性も，無症候性キャリアのNK活性も共に抑制したが，キャリアに対する抑制が著しかった。正常コントロールNK活性に対する合成ペプチドの作用段階は， NK細胞と標的癌細胞の結合にも，標的細胞によるNK細胞のTriggeringにも合成ペプチドが影響を与えないことから， Triggering以後の段階であると考えられた。一般には， AIDSの発症には，HIVがCD4+細胞に感染し，その機能が損われる事が重要だと考えられており，多くの研究が為されているが，以上の結果より，無症候性キャリアが発症するに至るプロセスには，それ以外のNK等の免疫機能の抑制が何らかの役割を果たしていると考えられた。, Three kinds of peptides termed ABJ917, ABJ918 and ABJ919 were synthesized and tested their capability of inhibition of Natural Killer (NK) cell mediated cytotoxicity. ABJ917, which is conserved among various retroviral transmembrane envelope proteins inhibited NK activities of the peripheral blood Iymphocytes (PBLs) of both asymptomatic carriers and normal controls. ABJ918 or ABJ919 which correspond to this conserved region also inhibited NK activities. To know the mechanism of inhibition of NK cells by these synthetic peptides, conjugate formation assay and triggering assays were then performed. ABJ917 which inhibited overall NK cytotoxicity did inhibit neither NK and target tumor cell binding nor NK cell triggering by target K562 tumor cells. These results show that the inhibition of NK cytotoxic activity by synthetic HIV peptide is caused in the stage of post-triggering. Peripheral blood CD4+ cell rate of the asymptomatic carriers of HIV was almost 0% when we obtained enough NK activities and these carriers were still quite healthy. Taken together, the immunosuppression of AIDS patients is thought to be caused at least partly from some defects of post-triggering lytic activity of NK cells by HIV transmembrane peptides., 日本熱帯医学会雑誌, vol.19(1), pp.33-38; 1991

Matter in its liquid state is convenient for processing and controlling chemical reactions, owing to its fluidity. Recently much evidence has been accumulated for the existence of a liquid–liquid transition (LLT) in single-component liquids. Here, we report that we can control, by the LLT of a molecular liquid, triphenyl phosphite (TPP), the fluidity and miscibility of its mixture with another molecular liquid. For a mixture of TPP with toluene or aniline, we find that both liquid I and II mix well and liquid II remains in a ‘liquid’ state, in contrast to pure TPP, where liquid II is a non-ergodic amorphous state. This is the first example of a ‘true’ LLT in a molecular liquid. Furthermore, we find demixing induced by the LLT for a mixture of TPP with diethyl ether or ethanol. These findings will open a new phase of research towards various applications of the LLT. Recent work has provided evidence for the existence of a liquid–liquid transition (LLT) in some single-component fluids. It is now shown that the LLT can be used to control the fluidity and miscibility of triphenyl phosphite with another molecular liquid, demonstrating the possibility of the first definite application for exploiting this phenomenon.

Recently it was revealed that even a single‐component liquid can have more than two liquid states. The transition between these liquid states is called “liquid‐liquid transition”. This phenomenon has attracted a considerable attention because of its counter‐intuitive character and the fundamental importance for our understanding of the liquid state of matter. The connection between the liquid‐liquid transition and polyamorphism is also an interesting issue. In many cases, liquid‐liquid transitions exist in a region which is difficult to access experimentally. Because of this experimental difficulty, the physical nature and kinetics of the transition remains elusive. However, a recent finding of liquid‐liquid transition in molecular liquids opens up a possibility to study the kinetics in detail. Here we report the first detailed comparison between experiments and a phenomenological theory for the liquid‐liquid transition of a molecular liquid, triphenyl phosphite. Both nucleation‐growth‐type and spinodal‐decomposition‐type liquid‐liquid transformation are remarkably well reproduced by a two‐order‐parameter model of liquid that regards the liquid‐liquid transition as the cooperative formation of locally favored structures. This may shed new light on the nature and the dynamics of the liquid‐liquid transition. We also show evidence that this second order parameter controls the fragility of the liquid. We also discuss a possibility of controlling liquid‐liquid transition by spatial confinement. Remaining open questions on the nature of the transition are also discussed.

We performed broadband dielectric measurements for the process of liquid‐liquid transformation in triphenyl phosphite (TPP). According to our dielectric measurements, the static dielectric constant monotonically decreases and the distribution of the relaxation time becomes broader during the liquid‐liquid transformation from liquid I to II. The direct comparison with morphological evolution provides key information on the dynamical and structural evolution during LLT.

A test method to evaluate the complex permittivity of materials with thin configuration (thickness of 50–300μm) is presented. We evaluate the complex permittivity of materials with various mechanical and electrical characteristics (films, powders, and liquids) at frequencies from 100 MHz to 20 GHz and at temperatures from 293 to 353 K using an experimental method presented in this paper. We have developed a fixture having a circular parallel-plate capacitor which is suitable for the measurement of materials with thin configuration. Our method is based on theoretical consideration of wave propagation in the capacitor, which is associated with multiple reflections along the diameter of the sample. The consideration of time delay in the sample section makes it possible to evaluate the permittivity of high dielectric constant materials in the frequency range up to 20 GHz. In addition, some examples for the measurements show that the resolution with tanδ is as low as 0.001. Our method is powerful to understand...