Takuro Matsunaga

Highly Elastic and Deformable Hydrogel Formed from Tetra-arm Polymers

After decades of efforts by many researchers, we have succeeded in realizing a near-ideal polymer network. This network, the Tetra network, is made by cross-end-coupling of tetra-arm polymer modules. The mechanical energy dissipation was extremely low (tan δ ≈ 10(-4) ). The macroscopic stress-strain relationship of the Tetra network was in good agreement with that of microscopic elastic blobs. The maximum breaking strength was extremely high (≥27 MPa). These results indicate that the Tetra network is closer to an ideal polymer network than any other conventional model networks. Because the Tetra network can be treated as uniformly packed elastic blobs, it should help apply the knowledge of single polymer chains seamlessly to the design of polymer materials and help further develop the theory of rubber elasticity.

Rheo-SANS Studies on Shear-Thickening/Thinning in Aqueous Rodlike Micellar Solutions

Shear-induced thickening/thinning phenomena of aqueous rodlike micellar solutions of cetyltrimethylammonium bromide (CTAB) and sodium p-toluene sulfonate (NapTS) were investigated by means of simultaneous measurements of rheology and small-angle neutron scattering (SANS), the so-called Rheo-SANS. The aqueous CTAB/NapTS solutions were classified into five different categories dependent on their flow behavior and micellar structure. By increasing salt concentration and/or shear rates, the micelles underwent morphological transition from (i) spherical or short rodlike micelles to (ii) long rodlike micelles without entanglements, followed by (iii) those with entanglements. These transitions were recognized as changes in flow behavior from Newtonian to shear-thickening and shear-thinning flow, respectively. In the latter two cases, anisotropic SANS patterns appeared around these critical shear rates. The physical meaning of the anisotropic SANS patterns accompanied by shear-thickening flow behavior is discussed in conjunction with other shear-thickening systems.

Rheological Study on Rapid Recovery of Hydrogel Based on Oligomeric Electrolyte

The hydrogel consisting of an oligomeric electrolyte, poly[pyridinium-1,4-diyl-iminocarbonyl-1,4-phenylenemethylene chloride] (1-Cl) underwent self-healing at temperatures lower than its gelation temperature after destruction of the gel network in a shear flow. The self-healing mechanism was investigated by rheological measurements on three different kinds of gels including a low-molecular weight organogelator and a polymeric hydrogelator. Although all of the three gels exhibited thermo-reversible hysteresis loops in the shear moduli, only 1-Cl hydrogel recovered its mechanical properties after vigorous agitation. It is conjectured that the self-healing is due to formation of network structure via a chlorine ion mediated hydrogen bond for which the activation energy is on the order of 10 kJ/mol.

Evaluation of incoherent scattering intensity by transmission and sample thickness

The H atom has a large incoherent scattering cross section and is a major source of incoherent scattering intensity, (dΣ/dΩ)inc, in small-angle neutron scattering. By taking account of multiple scattering from H atoms, a useful method (the transmission method or T method) is proposed for the estimation of (dΣ/dΩ)inc for various types of hydrogen-containing systems. The incoherent scattering intensity is calculated simply from the transmission, T, and the thickness of the sample, t, i.e. (dΣ/dΩ)inc ≅ [exp(Σtott) − 1]/(4πt) = (1 − T)/(4πtT), where Σtot ≡ −(lnT)/t is the macroscopic total cross section per unit volume. This method provides a reasonably accurate value of incoherent scattering intensity for various systems. The validity and the extent of applicability of the T method are examined for several samples, including light/heavy water mixtures, polymer gels and surfactant aqueous dispersions.

Structure and Rheology of a Self-Standing Nanoemulsion

A stable nanoemulsion consisting of nanometer-sized oil droplets in water having a self-standing capability was prepared by high-pressure emulsification. The nanoemulsion does not flow and has a yield stress. This nonfluidity is ascribed to the crystal-like lattice structure of nanodroplets. The lattice structure was observed by transmission electron microscopy of a freeze-fractured surface of the specimen. Small-angle neutron scattering (SANS) revealed the presence of an ordered structure in addition to spherical domains with a radius of 17 nm. This long-range order is, in principle, due to electrostatic repulsive interaction between charged nanodroplets. Dynamic light scattering (DLS) showed two relaxation modes, one for the collective motion of the lattice and the other for the translational diffusion of the nanodroplets. Dilution of the nanoemulsion resulted in a transition from a crystal-like structure to a typical colloidal solution.

Dispersion of Rod-like Particles of Nafion in Salt-Free Water/1-Propanol and Water/Ethanol Solutions.

The dispersion of perfluorinated sulfonic acid ionomers in catalyst inks is an important factor controlling the performance of catalyst layers in membrane electrode assemblies of proton exchange membrane fuel cells (PEMFCs). The effect of water/alcohol composition on the dispersion of H-Nafion in water/1-propanol and water/ethanol solutions was studied by dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and (19)F nuclear magnetic resonance ((19)F NMR) spectroscopy. Hydrodynamic radii calculated from DLS decay profiles and the radii and interparticle distance of rod-like particles derived from SAXS profiles showed almost the same dependence on alcohol concentration. 1-Propanol was more effective than ethanol to induce changes in the characteristic lengths of the rod-like particles. The motional narrowing in the (19)F NMR spectra by addition of 1-propanol indicates selective solvation of the rod-like particles. We suppose this might have decreased their radii and induced their elongation, which eventually led to extension of the ordered regions as observed in the hydrodynamic radii. Our study helps to clarify the dispersion of Nafion in aqueous alcohol solutions, which has implications for the performance of PEMFCs.

Microscopic insights into ion gel dynamics using neutron spectroscopy

We have investigated the microscopic dynamics of ion gels consisting of a PMMA [poly(methyl methacrylate)] network and EMITFSI [1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide] as the ionic liquid by means of quasi-elastic neutron scattering (QENS). These ion gels interestingly exhibit two glass transitions (Tgs) which drastically decrease as the ionic liquid content increases. QENS allows us to probe the dynamics of PMMA and the EMI [1-ethyl-3-methylimidazolium] cation separately, by selectively deuterating the individual components, and gain insight into the glassy properties of this system. A comprehensive analysis of the QENS spectra was performed, revealing a number of characteristic relaxations, including intramolecular ones, each of which was assigned. We found that the activation energy for PMMA diffusion decreases with increasing ionic liquid content, corresponding to the plasticization of the polymer. The ionic liquid showed two characteristic relaxations: a motion strongly coupled to the motion of PMMA which we argue to be the motion of part of the ionic liquid which is bound to the PMMA giving rise to a higher effective Tg and an ionic diffusion associated with ionic liquid molecules far from the polymer chains which behave nearly as free liquid, exhibiting a lower Tg.

Visualization of Phospholipid Particle Fusion Induced by Duramycin

We visualized nanometer-scale phospholipid particle fusion by scanning tunneling microscopy (STM) on an alkanethiol-modified gold substrate, induced by duramycin, a tetracyclic antibiotic peptide with 19 amino residues. Ultrasonic homogenization generated a suspension mainly consisting of minimal lipid particles (MLP) from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) in a phosphate buffer solution, confirmed by dynamic light scattering (DLS). In situ STM discerned individual MLP as particles (diameter approximately 8 nm) spread on Au(111), modified with alkanethiol, within the suspension. The MLP became fragile by the presence of duramycin, and the MLP were easily scratched by the scanning tip into multilayers along the surface. This process of particle fusion on the gold surface coincides with the aggregation of MLP in the suspension, observed by DLS. It was demonstrated that STM is capable of discerning and monitoring the nanometer-scale features of phospholipid particles altered by antibiotics with biochemical impact. STM might allow in situ, real-space, nanometer-scale observations of minute particles composed of phospholipids within the real cells with the highest magnification ratio.

In situ small-angle neutron scattering and rheological measurements of shear-induced gelation.

The microscopic structure of shear-induced gels for a mixed solution of 2-hydroxyethyl cellulose and nanometer-size spherical droplets has been investigated by in situ small-angle neutron scattering (SANS) with a Couette geometry as a function of shear rate gamma. With increasing gamma, the viscosity increased rapidly at gamma approximately 4.0 s(-1), followed by a shear thinning. After cessation of shear, the system exhibited an extraordinarily large steady viscosity. This phenomenon was observed as a shear-induced sol-gel transition. Real-time SANS measurements showed an increase in the scattering intensity exclusively at low scattering angle region. However, neither orientation of polymer chains nor droplet deformation was detected and the SANS patterns remained isotropic irrespective of gamma. It took about a few days for the gel to recover its original sol state. A possible mechanism of gelation is proposed from the viewpoint of shear-induced percolation transition.

Structural Characterization of Ionic Gelator Studied by Dynamic Light Scattering and Small-Angle Neutron Scattering

Structural characterization of a hydrogel consisting of an oligomeric electrolyte, poly[pyridinium-1,4-diyliminocarbonyl-1,4-phenylenemethylene chloride] (1-Cl) as an ionic gelator was carried out by static and dynamic light scattering (SLS/DLS) and small-angle neutron scattering (SANS) techniques. All the measurements were performed by changing the concentration and temperature. We have successfully obtained the weight average molecular weight and the degree of polymerization of poly(1-Cl) by SLS. The sol-gel transition was clearly observed as large fluctuations in the scattering intensity of the time-intensity correlation function. Time correlation function of the scattering light intensity entailed a power law behavior at the sol-gel transition. 1-Cl hydrogel showed strong hysteresis and its hysteresis loop was observed both by DLS and theological methods. We have estimated the critical concentration of gelation and the gelation temperature by DLS. The enthalpy change for gelation was estimated to be ca. -10 kJ/mol. SANS experiments revealed that the unit structure of the gel network is responsible for the gelation of 1-Cl hydrogel.