Papers by Author: Yoshinori Kobayashi

Abstract: Sealed radioactive sources of ²²Na for positron annihilation lifetime spectroscopy (PALS), free from the legal regulations, are commercially available from an American company. However, thick foils are used to seal ²²Na in these sources and large fractions of the positrons annihilate in the sealing materials. Further, it is pointed out that a long lifetime component over 1 ns appears in the positron lifetime spectrum acquired with the Kapton sealed source (POSK-22, IPL Inc.). In this research, attempts were made to develop high quality sealed positron sources, potentially free from regulations, for ubiquitous application of PALS. The sources prepared in the present work are of high quality and applicable to our new PALS, which does not require sample cutting and is potentially applicable to truly nondestructive, onsite inspection of various materials

Abstract: Positron annihilation lifetime spectroscopy (PALS) has widely been used for probing open volume defects in various materials. PALS is in principle non-destructive, yet conventional PALS is not strictly non-destructive because cutting out of two specimens from the material is required. Recently we developed a novel method of PALS, which is potentially applicable to non-destructive, onsite material inspection. In order to explore the possibility of onsite monitoring of polymer degradation by this novel method of PALS, we studied variations of positron lifetime and mechanical properties of ultra high molecular weight polyethylene (UHMWPE) subjected to γ-irradiation. Correlations were found between the mechanical properties and ortho-positronium lifetimes, suggesting the feasibility of non-destructive, onsite monitoring of polymer degradation by PALS. The effect of γ-irradiation on positronium formation is discussed.

Abstract: Mesoporous silica films on Si wafers were prepared via a sol-gel process using a triblock copolymer as the structural template. Spin-coated films were dried and subsequently subjected to Ar plasma treatments for decomposing the polymeric porogen. Mesopore formation in the silica film upon Ar plasma treatments was investigated by positron annihilation lifetime spectroscopy. In comparison with calcined silica film, much larger pores, more heterogeneous in size were found in silica film prepared with Ar plasma decomposition of the porogen.

Abstract: Commercial composite membranes for water purification were studied by means of the variable-energy positron annihilation γ-ray technique. The positron incident energy E dependence of R parameter (3γ/2γ ratio) analyzed from positron annihilation γ-ray spectra revealed the layer structure consisting of a dense top layer and a porous substrate for the membranes. Thickness of the dense layer for each membrane was evaluated from the R(E) based on a positron implantation stopping profile.

Abstract: Positron chemistry refers to chemical processes of high-energy positrons injected into molecular substances, the most interesting of which is the formation of positronium (Ps), the hydrogen-like bound state between a positron and an electron. Ps is formed predominantly by fast intra-track radiation chemical processes. In polymers it tends to be localized in intra/inter-molecular open space in the sparsely packed amorphous structure. Whilst short-lived singlet para-positronium (p-Ps) undergoes self-annihilation, the positron in long-lived triplet ortho-positronium (o-Ps) annihilates with one of the spin opposite electrons bound in the surrounding polymer molecules. This process is called pick-off annihilation. The pick-off annihilation lifetime reflects the polymer chain packing through the size of the volume, where Ps is localized. Positrons are used to probe the amorphous structure of various polymeric systems. In this article, basic concepts and experimental techniques of positron chemistry in polymers as well as applications to the characterization of functional polymeric materials are overviewed.

Abstract: A good correlation is found between ortho-positronium (o-Ps) pick-off annihilation lifetimes and surface tensions of molecular liquids and polymers. Systematic shortening of the o-Ps lifetime with increasing surface tension suggests that the hole for Ps localization in polymers may be that subjected to considerable expansion as in liquids. The driving force of this hole expansion is the large quantum mechanical zero-point energy of a light particle confined in an angstrom size space. The hole expansion is insignificant in a larger nm scale pore, where the zero-point energy is much lowered.

Abstract: An interlaboratory comparison for positron annihilation lifetime (PAL) measurements for pure nickel and fused silica was performed. Based on the reported positron (for nickel) and positronium (for fused silica) lifetimes, the uncertainties in the PAL measurements were estimated.

Abstract: The mechanism of gas permeation in sulfonated polymers such as Nafion and sulfonated polyethersulfone (SPES) for polymer electrolyte fuel cells has been investigated from the viewpoint of free volume. Free volume was quantified using the positron annihilation lifetime (PAL) technique and O2 permeability was measured as a function of temperature or ion exchange capacity (IEC). Good linear correlations between the logarithm of the permeabilities and reciprocal free volume indicate that gas permeation in the sulfonated polymers depends strongly on the free volume. Comparison of Nafion with SPES and other relatively flexible chain polymers showed that the stiff chains of the perfluoroethylene backbone in Nafion make the O2 permeability much smaller than the corresponding flexible chain polymer with a similar free volume size. The O2 permeability in the K+-form of Nafion is systematically smaller than the H+-form, showing that the chain stiffness is enhanced by the ion exchange.

Abstract: Age-momentum correlation (AMOC) spectroscopy, which can sensitively probe momentum distributions of positrons and positronium (Ps), was conducted for studying the pick-off process of the triplet bound state ortho-Ps (o-Ps) with electrons at the walls of the free volume holes. Influences of different chemical elements forming free volume and the size of the free volume are investigated. It is found that the momentum distribution of o-Ps pick off annihilation sensitively depends on the electronic state. The feasibility of the chemical analysis relevant to the free volume in insulating materials is discussed.