Magnetic quenching of positronium in organic solutions

The magnetic quenching of ortho-positronium (o-Ps) in some pure nonpolar liquids (n-hexane, cyclohexane and benzene) and solutions (nitrobenzene in n-hexane, cyclohexane and benzene; and carbon tetrachloride and biphenyl in n-hexane) is examined for steady magnetic fields up to 14 kG by the positron annihilation lifetime technique. The long lifetime of o-Ps is very sensitive to the strength of the external magnetic field, decreasing as the field strength increases. This effect follows from a well-known principle of atomic physics, the quadratic Zeeman effect. With one exception, all the liquids studied here appear to be normal in this regard. The exception is nitrobenzene in n-hexane, which shows a very marked enhancement of quenching beyond the Zeeman effect at low fields.     

Solvent and temperature effects on positronium annihilation parameters and on its quenching reactions with the free radical HTEMPO

Positron annihilation lifetime spectroscopy (LS) and the Doppler broadening of the annihilation radiation lineshape (DBARL) technique have been used in conjunction to study solvent and temperature effects on both the positronium (Ps) quenching reactions with the free-radical HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) and the annihilation parameters. A change in the nature of the quenching reaction is observed from spin conversion in benzene (Bz),N,N-dimethylacetamide (NDMA), andN-methylformamide (NMFA) to Ps oxidation inmeta cresol (m-C); it is attributed to a modification of the electron density distribution in the quenching molecule due to hydrogen bonding with them-C molecules. The data also indicate that the full-width at half-maximum of the momentum distribution associated to para-positronium (p-Ps) resulting from the spin conversion reaction is smaller by a factor of 2 than that forp-Ps directly formed in the positron spur. The ortho-positronium (o-Ps) pickoff lifetime and momentum distribution are shown to give access to physicochemical and structural properties of the solvents.     

On the peculiarities of positron annihilation features in silicalite-1 and Y-zeolites

Conditions that facilitate high Ps formation and interactions that modify the o-Ps lifetime were investigated by positron annihilation techniques in silicalite-1 and various Y-zeolites. Long lifetimes, up to 135 ns, and o-Ps fractions as high as 40% were found. The influence of heat treatment (in the range of 90–520 K), capillary condensation of N₂ (0.085 MPa) and correlation with water removal was examined in Y-zeolites and in silicalite-1, respectively. The latter matrix was also studied in the presence of liquids. In various samples unexpected features were found (peculiar changes in the 2γ/3γ ratio, inversion in the trend of lifetime variations, disappearance of specific components, etc.), denoting the complexity of the processes governing the fate of e⁺ and Ps.     

Analysis of swelling process of protein by positron annihilation lifetime spectroscopy and differential scanning calorimetry

The change in the nanoscopic structure and bound state of water in the protein gel were investigated using positron annihilation lifetime spectroscopy (PALS) and differential scanning calorimetry (DSC). Gelatin was used as a protein. To examine the bound state of water in gelatin gel, the amount of freezing and nonfreezing water in gelatin gels were evaluated by fusion enthalpy of DSC curves. Below water content of 40% (w/w), the whole amount of water was nonfreezing water, whereas above water content of 40% (w/w), the amount of freezing water increased according to increase in water content. To investigate the nanoscopic spatial structure under coexistence of polymer and water, positron annihilation lifetime measurement was performed. The lifetime of o‐Ps or the pore size increased according to increase in water content, particularly below the water content of 40% (w/w). When the water penetrates into the gelatin network, the water molecules form hydrogen bonds with hydrophilic groups inside the helical structure in gelatin gel. The water molecules inside the helical structure expand the structure outward, leading to increase in pore size. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2031–2037, 2007.     

Competitive positron and positronium trapping in porous media

Positron annihilation acquired acceptance for structural investigation of solids but results in porous media—where positron lifetime spectroscopy (LT) reveals substantial Ps formation—were ambiguous. Data on zeolites lead to the conclusion that Ps trapping in competing “extended free volume” sites, inhomogeneous regions and grain boundaries occurs. Furthermore, positron trapping must also be considered. Systematic errors due to incomplete time range selection are discussed, significance and importance of corrections for 3γ/2γ counting efficiency differences are shown in practice.     

Positron annihilation in some organic scintillators: magnetic quenching and three gamma spectroscopy results

We present positron annihilation data in some organic polycrystalline scintillators, obtained through lifetime and three gamma spectroscopies, as well as magnetic quenching measurements. Strong magnetic quenching effects at low fields were discovered, which cannot be explained in terms of simply “swollen” Positronium (qPs): a possible explanation in terms of interactions between the qPs and the magnetic moments of the spur products is proposed.     

Diffusion coefficients of positronium in polycarbonate at low temperatures

Diffusion coefficients of positronium (Ps) in polycarbonate (PC) have been determined at temperatures between 20 and 300 K by means of positron lifetime spectroscopy. 2,2-dinitrobiphenyl (DNB) was added to the polymer as a Ps quencher and the diffusion coefficients were determined from measured Ps quenching rate constants, assuming that the reaction between Ps and DNB is completely diffusion-controlled.     

Temperature effects on positronium formation and inhibition: A contribution to the elucidation of early spur processes. II. Ethyleneglycol solutions

Further experiments on the temperature effects on positronium (Ps) formation and inhibition in liquids have been performed using ethyleneglycol as solvent. Positron lifetime spectroscopy and the Doppler broadening of annihilation lineshape (DBARL) technique have been used in conjunction for a better insight. The existence of two classes of inhibitors is confirmed: whereas NO₃^? is able to completely inhibit Ps formation at high enough concentration. Cl^? and ClO₄^? can only suppress a fraction of Ps. This fraction is temperature dependent and is found to be the same for these two latter solutes, although the inhibition mechanisms appear to be different, involving positron and electron scavenging, respectively. The temperature sensitivity of the inhibition constants is diverse: the inhibiting ability of NO₃^? decreases with temperature while that of Cl^? is markedly enhanced and K_ClO4^? remains unchanged. These findings point to the implication of different salvation states of the positron and of the electron in the Ps formation mechanism. Although Cl^? very probably reacts with positrons to form (e⁺ Cl^?), analysis of the DBARL data suggests more than one positron bound state may be involved. This possiblity is discussed.     

Study of solid-state polymerization by positron lifetime measurements

The positron lifetime measurement technique was applied to analyze the structural changes occurring in solid-state polymerization of acrylamide and trioxane. Positronium (Ps) parameters, τ₂ and I₂, which show a marked change as a function of the γ-ray irradiation dose, signaled the presence of three clearly defined stages in the polymerization process: initiation, propagation, and saturation. The initial increase in τ₂, may very well be the result of efficient trapping of Ps in vacancies created around the polymer nuclei. The complicated behavior of I₂ may be explained as a chemical reaction between Ps precursors and the radiolysis products of this polymerization process.     

The design of a spin-polarized slow positron beam

Spin-polarized low-energy positrons were considered as useful probes for studying electron spin states of both surface and bulk materials. Due to the spin-dependent interactions between electrons and positrons, the formation of positronium (Ps), an electron-positron bound system, can be distinguished from different electron spin states. Recently, a positron source of ¹⁸F has been developed for a spin polarized slow positron beam at the institute of physical and chemical research (RIKEN). The design of an electrostatic positron beam will be discussed in conjunction with a spin rotator.     

Further studies of the spur process of positronium formation in mixtures of organic liquids

To test some predictions of the spur model of positronium (Ps) formation, positron lifetime studies were made of the following binary organic mixtures: (a) carbondisulphide mixtures with n-tetradecane, n-hexane, isooctane, neopentane, and tetramethylsilane (TMS); (b) neopentane mixtures with methanol, ethanol, cyclohexanol, and methylcyclohexane; (c) cis-2-butene/trans-2-butene, and benzene/ethanol. The results were in agreement with the model. A minimum in the Ps yield versus CS₂ concentration, explained as being caused by electron localization on CS₂ at low and delocalization on several CS₂ molecules at higher CS₂ concentration, depended on the electron work function V_o of the solvent. This minimum was pronounced (shallow or absent) at high (low) V_o. Solvation of electrons and positrons in alcohol clusters strongly influenced the Ps yield for the neopentane mixtures. The Ps yield was higher in cis- than in trans-2-butene. The Ps formation process in polar liquids is discussed. Experiment facts do not preclude that Ps is also formed by the encounter pair process of fully solvated particles in the positron spur.     

The temperature dependence of the two positronium bubble states in liquid SF6

Positron lifetime measurements have been performed on liquid SF₆ in the temperature range from −45°C to 71°C (T_c = 45.65°C). The positron lifetime spectra were resolved into four lifetime components. In the order of increasing lifetimes the four lifetime components are associated with the decay of para-positronium (p-Ps), free positrons, ortho-positronium (o-Ps) from a small bubble state, and o-Ps from a large bubble state. The lifetime of o-Ps annihilating from the large bubble state τ₄ increases from 5.7 ns at −45°C to 19.5 ns at 53°C. The lifetime of o-Ps annihilating from the small bubble state τ₃ was found to be 2–2.5 ns in the main part of the temperature range studied. Apparently, this is the first observation of two different o-Ps states in a liquid. The intensity I₄ (I₃) increases (decreases) from 16.9% (16%) at −45°C to 47.2% (6.4%) at the critical point while above I₃ and I₄ are essentially temperature independent. The large Ps bubble state seems to be similar to the Ps bubble state found in most liquids.     

Free volumes in solids under high pressure

A review of experimental work on ortho-positronium (o-Ps) lifetime in solids under the pressures up to 1 GPa is presented. Among the effects observed at high pressure one can mention: the disappearance of the energy level for Ps at the reduction of free volume size; pressure induced phase transitions; variation of Ps formation intensity with time; increase of o-Ps lifetime after intercalation of high pressure gas to the paraffin samples.     

Mechanism of enhanced positronium formation in low-temperature polymers

An enhanced positronium (Ps) formation in low-temperature polymers has been widely observed. The additional positronium formation is due to shallow trapped electrons in them. Positron annihilation lifetime spectroscopy was applied to investigate the Ps formation in a series of polymers, such as low-density polyethylene, ethylene-methyl methacrylate copolymers with various methyl methacrylate contents, and pure poly(methyl methacrylate) at low temperature. An analysis of the experimental data based on simple kinetic equations enables one to understand the Ps formation mechanism in polymers during low-temperature positron annihilation experiments as functions of the temperature and elapsed time. Good fittings of the experimental data were obtained. The fitting parameters seemed to show clear physical meanings.     

Detection of free volumes in polyaniline complexes with various acids by using positron lifetime spectroscopy

The positron lifetime spectroscopy (PLS), a non-destructive characterization method, utilizes positronium (Ps; an electron–positron bound state) as a probe and measures its lifetime in polymer free volumes. For the first time the free volumes have been estimated by PLS in polyaniline (PANI) complexes with various inorganic and organic acids. It was found that the o-Ps lifetime increases and the intensity decreases with increasing ionic radius of the counter-ions in PANI complexes. Obviously, larger counter anions result in enhanced mean size of the voids corresponding to the free volume in the bulk polymer.Electrical conductivity has been measured by conventional four-probe technique. The glass transition temperature and temperature of removal of the absorbed water have been determined by using differential scanning calorimetry. It was established fairly well correlation of the mentioned polymer parameters with the o-Ps lifetime and the free volume of PANI complexes, respectively. The greater free-volume results in a decrease of conductivity, glass transition temperature and temperature of removal of the absorbed water.     

Positron annihilation lifetime measurements of mechanically fatigued polystyrene samples

Early stages of cyclic fatigue‐loaded polystyrene (PS) specimens were investigated by positron annihilation lifetime spectroscopy (PALS) at a maximum stress amplitude of 15 MPa. PALS yields information about the average unoccupied hole volume. A linear increase in the ortho‐positronium (o‐Ps) lifetime was observed in a range from 0 to 50,000 cycles. This increase occurs homogeneously distributed at different positions along a sample of 170 mm. The average unoccupied void volume increases by 1.2%. On the other hand, the o‐Ps intensity shows no systematic change upon cycling. The results suggest a homogeneous and linear increase in free volume prior to craze formation. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1991–1995, 2008     

Wire‐Active Microrheology to Differentiate Viscoelastic Liquids from Soft Solids

Viscoelastic liquids are characterized by a finite static viscosity and a yield stress of zero, whereas soft solids have an infinite viscosity and a non‐zero yield stress. The rheological nature of viscoelastic materials has long been a challenge and is still a matter of debate. Here, we provide for the first time the constitutive equations of linear viscoelasticity for magnetic wires in yield‐stress materials, together with experimental measurements by using magnetic rotational spectroscopy (MRS). In MRS, the wires were subjected to a rotational magnetic field as a function of frequency and the motion of the wire was monitored by using time‐lapse microscopy. The studied soft solids were aqueous dispersions of gel‐forming polysaccharide (gellan gum) at concentrations above the gelification point. It was found that soft solids exhibited a clear and distinctive signature compared with viscous and viscoelastic liquids. In particular, the average wire rotation velocity equaled zero over a broad frequency range. We also showed that the MRS technique is quantitative. The equilibrium elastic modulus was retrieved from the wire oscillation amplitudes, and agrees with polymer‐dynamics theory.     

A study on free‐volume properties of styrene‐acrylic ester type copolymers

The positron annihilation lifetime measurements have been performed on a number of amorphous styrene–methyl acrylate copolymers and styrene–butyl methacrylate copolymers. The densities of copolymers were obtained with immersion method by using a capillary pycnometer and the average molecular weights were determined by gel chromatography. The lifetime τ₃ of ortho‐positronium (o‐Ps) pick‐off annihilation have been found to correlate with side group volume and polarity of macromolecular chains in the copolymers, and relative intensity I₃ is attributed mainly to the electron‐attracting groups trapping the spur electrons and positrons. The experimental results have been discussed on the basis of the structural variation of macromolecular chains. In addition, the PALS measurement as a function of time for polystyrene and several styrene–methyl acrylate copolymers has also been performed. The result shows that an electric field is built in polymers during extended positron annihilation spectroscopy measurement, and the field effect is a main factor which causes the decrease in I₃ with time. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2476–2485, 1999