Effects of aging and oxidation on positronium formation in polyethylenes

Positron annihilation lifetimes (PAL) have been measured for polythylenes (PEs) under differenr conditions of heat treatment. It is shown that the intensity, I₃, of the long-lived component of positronium (Ps) shows hystereses between the heating and cooling processes due to aging effect. It is also shown that about half of Ps observed at low temperatures below the glass transition is inhibited after the sample is heat-treated above the melting point in the atmosphere containing oxygen. It is suggested that carbonyl groups (C=0) formed by thermal oxidation can inhibit Ps formation through trapping the precursors of Ps, e⁺ and/or e^-.     

Pressure effect on positronium reactions in organic solutions

The reaction rate constants of positronium (Ps) atoms with a series of nitrobenzene derivatives and nitromethane in toluene solutions have been determined as a function of external pressure up to 1000 kg cm⁻² (about 1000 atm). The rate constants for relatively weak Ps acceptors such as p-nitroanisole, 1,3-dimethyl-2-nitrobenzene and nitromethane increased considerably with external pressure, while those for relatively strong Ps acceptors like p-dinitrobenzene or nitrobenzene either decreased or changed little with external pressure. Comparison of the experimental results on pressure effects with those on temperature effects revealed that the application of external pressure suppresses the thermal decomposition of Ps complexes which are unstable at room temperature. The effect on a solvent of the Ps reaction was also studied by determining the reactivities of Ps atoms with nitrobenzene in various solvents as a function of external pressure.     

Positronium trapping in free volume of polymers

Positronium trapping process caused by slow thermalization of Ps inside intermolecular spaces of polymer is considered. The pickoff annihilation rate of Ps decreases from an initial value, characteristic for the delocalized Ps, to a final value, relating to its localized state. The elastic thermalization lifetime analysis of polymers spectra with a new ETLT program is proposed to determine the total Ps intensity (I_Ps), Ps trapping rate (γ), its initial (τ₀) and final (τ_∞) pickoff lifetimes as well as the relative e⁺–e⁻ contact density (η). The model is tested through the analysis of polyurethane spectra measured in a wide range of temperature, containing the glass transition point (T_g). In contrast to the conventional analysis, I_Ps does not display any change at T_g. The results indicated slow trapping rate (about 1 ns⁻¹) of Ps in the cavities.     

Electric field effect on positronium formation in gamma-irradiated polypropylene and polyethylene

The effect of an external electric field (up to 48 kV cm⁻¹) on positronium (Ps) formation in γ-irradiated polypropylene and polyethylene has been studied by means of positron lifetime spectroscopy. The application of an electric field to unirradiated polypropylene and polyethylene considerably decreased the Ps formation. For example, the intensity of the longest-lived component (I₃) for one of the polypropylene samples was reduced from 26% to 18% by a field of 48 kV cm⁻¹. It was found that the electric field effect for the irradiated samples becomes weaker when increasing the irradiation dose. This result is discussed on the basis of the spur reaction model of Ps formation.     

TRIPLET, RADICAL ANION AND RADICAL CATION SPECTRA OF FUROCOUMARINS

Abstract— Absorption spectra of triplets, radical anions and radical cations of four furocoumarins, psoralen (Ps), 8-methoxypsoralen (8MOP), 5-methoxypsoralen (5MOP) and 3-carbethoxypsoralen (3CPs), have been determined by laser flash photolysis and pulse radiolysis. The triplet spectra of 8MOP, 5MOP and 3CPs are strongly modified when going from an H-bonding solvent such as water to a non H-bonding solvent as benzene or acetonitrile while the triplet spectrum of Ps is solvent independent. Theoretical considerations using a CNDO/S method are able to explain the existence of these two different triplets. For 8MOP, 5MOP and 3CPs in water the triplets might be considered as triplet exciplexes ³(FC^δ-. H₂O^δ+) consistent with these triplet spectra being similar to the spectra of the corresponding radical anions.     

Cone angle radial profiles

Various methodologies have been reported in the literature for the evaluation of the size of a ligand or organic functional group, with the Tolman cone angle methodology proving to be most popular in inorganic chemistry. A procedure to extend the Tolman concept to the measurement of a ligand size, as a profile over a radial distance from the metal (apex), has been developed. The representation of the Tolman cone angle as a function of distance from the metal is termed a cone angle radial profile (CARP). CARPs for PH₃, PMe₃, PEt₃ and PPh₃ have been determined and are described. CARPs for molecules containing the constrained phosphite ligands P(OCH₂)₃CMe, as determined in actual structures (Cambridge Structural Database), have also been evaluated and indicate the invariant shape of the ligand in the different metal environments. The influence of the choice of the H atom van der Waals radius in steric measurements is also discussed.     

Gamma and positron irradiation effects on polypropylene studied by coincidence Doppler broadening spectroscopy

The coincidence Doppler broadening (CDB) technique was applied to study the positron source irradiation effect on γ-irradiated and unirradiated polypropylene. CDB results showed presence of carbonyl groups (CG) whose concentration increase with the γ-irradiation dose. Positron annihilation lifetime (PAL) spectroscopy was used to monitor the positronium (Ps) formation. The γ-irradiation effect on Ps inhibition was significantly weaker than the positron irradiation effect. The joined examination of CDB and PAL data showed that the annihilation on CGs oxygen was not the main reason for the detected Ps inhibition during the positron-irradiation.     

Use of central-field potentials for describing H2(D2) elastic scattering by other molecules

Differential elastic scattering cross sections have been measured for the systems H₂ + O₂, SF₆, NH₃, CO and CH₄ and for D₂ + O₂, SF₆, and NH₃ using crossed molecular beams. These experiments represent a wide variation in the size, anisotropy and initial relative collision energy E of the scattering partners, and of the corresponding de Broglie wavelengths. In all cases, rapid quantum oscillations have been resolved. From these differential cross sections, central-field potentials have been obtained which were independent of the energy and the isotopic composition of the hydrogen molecule used, as required for such potentials to be physically meaningful. Therefore, anisotropy effects do not seem important in describing the differential elastic scattering of these H₂(D₂) systems.     

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.     

丙烯酰胺-丙烯酸钠共聚物的键结构和光散射研究

用溶液聚合方法制备了一组单体含量相同、分子量不同的丙烯酰胺-丙烯酸钠(AM-AA)共聚物样品,用¹³CNMR和常规光散射方法进行了表征。该组样品的化学组成是均一的(AA摩尔含量16.9±1.1%),AA单体在大分子链中的序列分布为孤立、无规的,聚电解质在盐水体系中的光散射理论适用于共聚物在0.12mol/LNaCl水溶液体系。用恒化学位下的折光指数增量代替恒盐组成的折光指数增量,可从一次常规光散射实验分别求得共聚物样品的真实、第二维利系数A₂和均方旋转半径〈R²〉_z,其关系为:A₂=0.0619M_w^-0.21,〈R²〉_z^1/2=0.0210M_w^0.54.     

Effect of ionization on the temperature- and pressure-induced phase transitions of poly(N-isopropylacrylamide) gels

The ionization effects on the pressure-induced phase transition of weakly charged poly(N-isopropylacrylamide-co-acrylic acid) (PNIPA-AAc) gels have been investigated by small-angle neutron scattering. At low temperature, T, and pressure, P, the structure factor of PNIPA-AAc gels was well represented by a Lorentzian (L) function, which was similar to noncharged PNIPA gels. However, at high Ps, the contribution of inhomogeneities became large and a squared-Lorentzian term had to be added in addition to the L term. At high Ts, on the other hand, a scattering maximum appeared, indicating microphase separation. This scattering maximum was suppressed by increasing P up to P approximately 100 MPa and then reincreased at higher Ps. The following facts were disclosed: (1) The peak position and height were very sensitive to P, which is mainly ascribed to strong pressure dependence of hydrophobic interaction, (2) ionization leads to microphase separation at elevated temperatures, (3) the re-entrant phase behavior is commonly observed in the P-T plane due to the parabolic variation of the polymer-solvent interaction with P, and (4) the pressure and temperature dependence of the structure factor was reproduced with the Rabin-Panyukov theory and was interpreted with a convexity of hydrophobic interaction with respect to pressure.     

Viscoelastic behaviour of ferro- and antiferroelectric phases

We have investigated the viscoelastic behaviour exhibited by chiral smectic C* phases in homeotropic orientation. For an appropriate scattering geometry and using the light scattering technique, the orientational diffusivities associated with the Goldsone mode in ferro- and antiferroelectric phases of C₁₁thiobenzoate and C₈tolane compounds have been measured. (SmC_A*) is about 100 times weaker than (SmC*). This divergence may be largely attributed to the mode of the molecular arrangement in ferro- and antiferroelectric phases, in spite of the same helical structure observed in the two phases.     

Rainbow scattering for Ar + Ar and Xe + Xe

Elastic differential scattering measurements have been performed on Ar⁺ + Ar and Xe⁺ + Xe. The rainbow scattering angle is found at τ = Eθ ≈ 115 eV deg for Ar⁺₂ and τ ≈ 93 eV deg for Xe⁺₂. These data are consistent with a potential well depth of 1.25 eV for Ar⁺₂ and 0.97 eV for Xe⁺₂.     

A diffusing wave spectroscopy study of the kinetics of Ostwald ripening in protein-stabilised oil/water emulsions

Diffusing wave spectroscopy (DWS) has been used to study the kinetics of ageing processes in n-decane/water emulsions, stabilised by the milk protein _S1-casein. A particular advantage of this particle size measuring technique is its direct applicability to the concentrated emulsion, avoiding the necessity for dilution to single scattering levels demanded by traditional dynamic light scattering methods. The observed droplet growth rates were found to conform to the kinetic law of Ostwald ripening. Monotonic increases in coarsening rates have been observed with increasing oil volume fraction and these results are compared with theoretical predictions. The effect of excess protein has also been measured but no evidence for depletion flocculation due to free _S1-casein was detectable.     

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.     

粘度法和超离心沉降法测定环型聚苯乙烯分子量

本文介绍了测定环型聚苯乙烯分子量的两个计算关系式。     

Dynamics of water studied by coherent and incoherent inelastic neutron scattering

This paper reviews the more recent results obtained on the dynamics of water by neutron scattering and shows that some information can be obtained by this technique at the microscopic level of the hydrogen bond. It also accounts for some very recent results obtained with the hydrated protein C-phycocyanin.

Incoherent quasi-elastic and inelastic neutron scattering by water has been performed in a temperature range extending to the supercooled state. The analysis of the quasi-elastic spectrum separates two main components and gives two characteristic times, one of them being related to the hydrogen-bond lifetime. The inelastic spectra extend until 600 meV, i.e. covering the intramolecular vibration region, showing for the first time the stretching band.

Collective excitations propagating at 3310 m s⁻¹ have been observed by coherent inelastic neutron scattering. This result was predicted by previous computer molecular dynamics simulations of water. The data are interpreted as a manifestation of short wavelength collective modes propagating within patches of highly bonded water molecules, and distinct from the ordinary sound wave.     

Studies of adsorbed molecules by X-ray photoelectron diffraction (XPD)

The angular intensity distribution of photoelectrons (or Augerelectrons) with high kinetic energy (> 400 eV), emitted from atoms of adsorbed molecules on single crystal surfaces, may exhibit pronounced peaks that are due to the high cross section for forward scattering by nearest neighbor atoms. This well-known effect can be utilized to study the orientation of bond axes of such molecules relative to the surface normal if they have the same orientation. The molecules should preferably be located in identical bonding sites but long range order not required. Atom-specific photoelectrons are excited by photons from a laboratory X-ray source or a synchrotron and analyzed for their spatial distribution by rotating the sample. For an ordered adsorbed layer of high coverage it is possible to observe also inter-molecular forward scattering peaks that are related to the registry of the layer. Molecules such as CO, N₂, C₂H₄, CH₃O and C₂H₄O have been studied in this fashion. Several of these results will be reviewed and discussed.     

Research on radiation stability of polypropylene

The effect of isotacticity of polypropylene(PP) on its radiation stability has been investigated in the present work. It was found that (1) The G value of H₂ and CH₄ is smaller if isotacticity of PP is higher; (2) It is easier to be crosslinked by radiation for the PP with higher isotacticity; (3) The shape of DSC peak changes smaller after irradiation for PP with higher isotacticity. These results have been explained by the measurement of ¹³C-NMR and small angle X-ray scattering.     

Determination of Proteins at Nanogram Levels by Enhanced Rayleigh Light Scattering Technique with Tetra-Substituted Sulphonated Aluminum Phthalocyanine

In recent years, Rayleigh light scattering has become a new tool for determining the content of biological molecules and studying the interaction mechanism of organic dyes with biological molecules^[1]. According to the macroscopic fluctuation theory, in a transparent isotropic medium, when the light scattering is caused by molecular particles 20-fold smaller than the wavelength of the incident beam, the Rayleigh scattering law is obeyed, namely I∝1/λ^4[2]. However, if the wavelength of the incident beam is close to that of the absorption band of the molecular particles which exist as aggregates, Rayleigh scattering will deviate from the law and enhanced RLS can be expected^[3]. Using this technique, a method for the determination of proteins in aqueous solution has been developed based on the enhancement effect of proteins on die Rayleigh light scattering (RLS) of organic dyes^[4].