Nonlinear rheological behavior of a concentrated spherical silica suspension

Linear and nonlinear viscoelastic properties were examined for a 50 wt% suspension of spherical silica particles (with radius of 40 nm) in a viscous medium, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture. The effective volume fraction of the particles evaluated from zero-shear viscosities of the suspension and medium was 0.53. At a quiescent state the particles had a liquid-like, isotropic spatial distribution in the medium. Dynamic moduli G^* obtained for small oscillatory strain (in the linear viscoelastic regime) exhibited a relaxation process that reflected the equilibrium Brownian motion of those particles. In the stress relaxation experiments, the linear relaxation modulus G(t) was obtained for small step strain (0.2) while the nonlinear relaxation modulus G(t, ) characterizing strong stress damping behavior was obtained for large (>0.2). G(t, ) obeyed the time-strain separability at long time scales, and the damping function h() (–G(t, )/G(t)) was determined. Steady flow measurements revealed shear-thinning of the steady state viscosity () for small shear rates (< ^–1; = linear viscoelastic relaxation time) and shear-thickening for larger (>^–1). Corresponding changes were observed also for the viscosity growth and decay functions on start up and cessation of flow, + (t, ) and _– (t, ). In the shear-thinning regime, the and dependence of ₊(t,) and _–(t,) as well as the dependence of () were well described by a BKZ-type constitutive equation using the G(t) and h() data. On the other hand, this equation completely failed in describing the behavior in the shear-thickening regime. These applicabilities of the BKZ equation were utilized to discuss the shearthinning and shear-thickening mechanisms in relation to shear effects on the structure (spatial distribution) and motion of the suspended particles.Dedicated to the memory of Prof. Dale S. Parson     

Phase structure change and ER effect in liquid crystalline polymer/dimethylsiloxane blends

The mechanism of the electrorheological (ER) effect in two types of liquid crystalline polymer (LCP)/dimethylsiloxane (DMS) blends was investigated by rheological measurements and by structure observation under electric field and shear flow. The results show that the phase structures of these immiscible blends can be categorized into slipping (low viscosity) and non-slipping (high viscosity) states. In the non-slipping state, higher viscosity LCP domains connect the electrodes. In the slipping state, on the other hand, LCP domains do not connect the electrodes and the shear is mainly confined in the lower viscosity DMS domains. The ER effect (electrically induced viscosity increase) originates from the electrically induced slipping to non-slipping transition. In one of the blends, the ER effect occurs only at high shear rate, since this blend is in non-slipping state even under no field if the shear rate is low. Received: 29 April 1997 Accepted: 3 November 1997     

Experimental investigation of a buckled beam under high-frequency excitation

In this paper, we investigate theoretically and experimentally dynamics of a buckled beam under high-frequency excitation. It is theoretically predicted from linear analysis that the high-frequency excitation shifts the pitchfork bifurcation point and increases the buckling force. The shifting amount increases as the excitation amplitude or frequency increases. Namely, under the compressive force exceeding the buckling one, high-frequency excitation can stabilize the beam to the straight position. Some experiments are performed to investigate effects of the high-frequency excitation on the buckled beam. The dependency of the buckling force on the amounts of excitation amplitude and frequency is compared with theoretical results. The transient state is observed in which the beam is recovered from the buckled position to the straight position due to the excitation. Furthermore, the bifurcation diagrams are measured in the cases with and without high-frequency excitation. It is experimentally clarified that the high-frequency excitation changes the nonlinear property of the bifurcation from supercritical pitchfork bifurcation to subcritical pitchfork bifurcation and then the stable steady state of the beam exhibits hysteresis as the compressive force is reversed. This work was partially supported by the Japanese Ministry of Education, Culture, Sports, Science, and Technology, under Grants-in-Aid for Scientific Research 16560377.     

Rheology of poly(methyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-styrene) particles suspended in water: effects of electrostatic surface layer

 Linear and nonlinear viscoelastic properties were examined for aqueous suspensions of monodisperse poly(methyl methacrylate-co-styrene) (MS) particles having the radius a ₀ =45 nm and the volume fractions φ=0.428−0.448. These particles had surface charges and the resulting electrostatic surface layer (electric double layer) had a thickness of t_s=5.7 nm. At low frequencies in the linear viscoelastic regime, the MS particles behaved approximately as the Brownian hard particles having an effective radius a _eff=a ₀ + t_s, and the dependence of their zero-shear viscosity η₀ on an effective volume fraction φ_eff (={a _eff/a ₀}³φ) agreed with the φ dependence of η₀ of ideal hard-core silica suspensions. In a range of φ_eff < 0.63, this φ_eff dependence was well described by the Brady theory. However, the φ_eff dependence of the high-frequency plateau modulus was weaker and the terminal relaxation mode distribution was narrower for the MS suspensions than for the hard-core suspensions. This result suggested that the electrostatic surface layer of the MS particles was soft and penetrable (at high frequencies). In fact, this “softness” was more clearly observed in the nonlinear regime: the nonlinear damping against step strain was weaker and the thinning under steady shear was less significant for the MS suspension than for the hard-core silica suspensions having the same φ_eff. These weaker nonlinearities of the concentrated MS particles with φ_eff∼ 0.63 (maximum volume fraction for random packing) suggested that the surface layers of those particles were mutually penetrating to provide the particles with a rather large mobility. Received: 10 July 2001 Accepted: 2 November 2001     

Inertial instability of the Stewartson -layer

Inertial stability of a vertical shear layer (Stewartson E^1/4-layer) on the sidewall of a cylindrical tank with respect to stationary axisymmetric perturbations is inverstigated by means of a linear theory. The stability is determined by two non-dimensional parameters, the Rossby number Ro = U/2ΩL and Ekman number E = v/ΩH², where U and L = (E/4)1/4H are the characteristic velocity and width of the shear layer, respectively, Ω the angular velocity of the basic rotation, v the kinematic viscosity and H the depth of the tank.

For a given Ekman number, the flow is more unstable for larger values of the Rossby number. For E = 10⁻⁴, which is a typical value of the Ekman number realized in rotating tank experiments, the critical Rossby number Ro_c for instability and the critical axial wavenumber m_c non-dimensionalized by L⁻¹ are found to be 1.3670 and 8.97, respectively. The value of Ro_c increases and that of m_c decreases with increasing E.     

The mucosal immune system: From dentistry to vaccine development

The oral cavity is the beginning of the aero-digestive tract, which is covered by mucosal epithelium continuously under the threat of invasion of pathogens, it is thus protected by the mucosal immune system. In the early phase of our scientific efforts for the demonstration of mucosal immune system, dental science was one of major driving forces due to their foreseeability to use oral immunity for the control of oral diseases. The mucosal immune system is divided functionally into, but interconnected inductive and effector sites. Intestinal Peyer’s patches (PPs) are an inductive site containing antigen-sampling M cells and immunocompetent cells required to initiate antigen-specific immune responses. At effector sites, PP-originated antigen-specific IgA B cells become plasma cells to produce polymeric IgA and form secretory IgA by binding to poly-Ig receptor expressed on epithelial cells for protective immunity. The development of new-generation mucosal vaccines, including the rice-based oral vaccine MucoRice, on the basis of the coordinated mucosal immune system is a promising strategy for the control of mucosal infectious diseases.     

Direct analysis of anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption-dielectric barrier discharge ionization mass spectrometry

Rapid detection of trace level anabolic steroids in urine is highly desirable to monitor the consumption of performance enhancing anabolic steroids by athletes. The present article describes a novel strategy for identifying the trace anabolic steroids in urine using Leidenfrost phenomenon assisted thermal desorption (LPTD) coupled to dielectric barrier discharge (DBD) ionization mass spectrometry. Using this method the steroid molecules are enriched within a liquid droplet during the thermal desorption process and desorbed all-together at the last moment of droplet evaporation in a short time domain. The desorbed molecules were ionized using a dielectric barrier discharge ion-source in front of the mass spectrometer inlet at open atmosphere. This process facilitates the sensitivity enhancement with several orders of magnitude compared to the thermal desorption at a lower temperature. The limits of detection (LODs) of various steroid molecules were found to be in the range of 0.05–0.1 ng mL⁻¹ for standard solutions and around two orders of magnitude higher for synthetic urine samples. The detection limits of urinary anabolic steroids could be lowered by using a simple and rapid dichloromethane extraction technique. The analytical figures of merit of this technique were evaluated at open atmosphere using suitable internal standards. The technique is simple and rapid for high sensitivity and high throughput screening of anabolic steroids in urine.     

Possible Involvement of a Tetrahydrobiopterin in Photoreception for UV‐B‐induced Anthocyanin Synthesis in Carrot

Our previous studies of action spectra for UV‐B‐induced anthocyanin accumulation in cultured carrot cells indicated that a reduced form of pterin, possibly tetrahydrobiopterin, contributes to UV‐B photoreception. In this report, we provide additional evidence for the involvement of pterin in UV‐B light sensing. UV‐B‐induced phenylalanine ammonia‐lyase (PAL) activity was considerably suppressed by N‐acetylserotonin (an inhibitor of tetrahydrobiopterin biosynthesis), and this suppression was partially recovered by adding biopterin or tetrahydrobiobiopterin. In addition, protein(s) specifically bound to biopterin were detected by radiolabeling experiments in N‐acetylserotonin‐treated cells. Furthermore, diphenyleneiodonium, a potent inhibitor of electron transfer, completely suppressed UV‐B‐induced PAL activity. These results suggest the occurrence of an unidentified UV‐B photoreceptor (other than UVR8, the tryptophan‐based UV‐B sensor originally identified in Arabidopsis) with reduced pterin in carrot cells. After reexamining published action spectra, we suggest that anthocyanin synthesis is coordinately regulated by these two UV‐B sensors.     

Novel synthesis of alkoxy substituted oxa[9]helicenes by the reaction of helical quinone with alcohols

The reaction of helical quinone with alcohols in the presence of Brønsted acid such as para-toluenesulfonic acid (pTSA) or HCl proceeded smoothly to produce the corresponding alkoxy substituted oxa[9]helicenes in good yields.     

A theoretical investigation on optimal structures of ethane clusters (C2H6)n with n ≤ 25 and their building-up principle

Geometry optimization of ethane clusters (C(2)H(6))(n) in the range of n ≤ 25 is carried out with a Morse potential. A heuristic method based on perturbations of geometries is used to locate global minima of the clusters. The following perturbations are carried out: (1) the molecule or group with the highest energy is moved to the interior of a cluster, (2) it is moved to stable positions on the surface of a cluster, and (3) orientations of one and two molecules are randomly modified. The geometry obtained after each perturbation is optimized by a quasi-Newton method. The global minimum of the dimer is consistent with that previously reported. The putative global minima of the clusters with 3 ≤ n ≤ 25 are first proposed and their building-up principle is discussed.