用正电子湮没技术研究USY沸石的“二次孔”结构

测量了NaY及USY沸石的正电子寿命谱．得到NaY沸石有四个寿命分量：两个短寿命分量和两个长寿命分量．两个长寿命分量中，τ₃，τ₄分别是o-Ps在β笼和超笼中的湮没．USY沸石有五个寿命分量：两个短寿命分量和三个长寿命分量，三个长寿命分量中，τ₃为o-Ps在笼中的湮没，τ₄，τ₅分别为o-Ps在“二次微孔”和“二次中孔”中的湮没．与NaY沸石相比，在真空中，USY的τ₄增加到 关键词：     

Structural relaxation in polyethylene in the presence of silver oxide investigated by positron-lifetime spectroscopy

Structural relaxation in high-density virgin polyethylene and silver oxide doped polyethylene has been investigated using positron annihilation lifetime technique at 30 °C and 100 °C ageing temperatures. The ortho-positronium (o-Ps) pick-off lifetime and its intensity show no changes with isothermal ageing time for the virgin sample at 30 °C. In the case of the doped sample at 30 °C, the o-Ps intensity shows exponential relaxation in the short-time range. At 100 °C, the o-Ps lifetime remains almost constant, whereas the o-Ps intensity exhibits an exponential character in the virgin and doped samples, which can be fitted with exponential decay curves. The relaxation times have been evaluated from the structural relaxation function constructed using o-Ps intensity values, and the stretching exponent has been estimated using the Kohlrausch–Williams–Watts (KWW) function. Positron results indicate that the stretching exponent seems to be temperature dependent. PACS 78.70.Bj     

Resolution of the orthopositronium-lifetime puzzle

The long-standing discrepancy [G. S. Adkins, R. N. Fell, and J. Sapirstein, Ann. Phys. (N.Y.) 295, 136 (2002)]] between the theoretical calculations of the orthopositronium (o-Ps) annihilation decay rate (lambda(T)=1/lifetime) and some of the experimental measurements has been resolved. A focused beam of positrons incident on a special nanoporous silica film produces near-thermal energy o-Ps in vacuum that is slow enough to be virtually free of perturbing interactions. The fitted decay rate requires only a 500 ppm correction for nonthermal o-Ps effects. The new value of lambda(T)=7.0404(10)(8) micros(-1) is in excellent agreement with theory.     

Complex molecular dynamics of (CH3NH3)5Bi2Br11 (MAPBB) protons from NMR relaxation and second moment of NMR spectrum

Molecular dynamics of a polycrystalline sample of (CH(3)NH(3))(5)Bi(2)Br(11) (MAPBB) is studied on the basis of the proton T(1) (55.2 MHz) relaxation time and the proton second moment of NMR line. The T(1) (55.2 MHz) was measured for temperatures from 20K to 330 K, while the second moment M(2) for those from 40K to 330 K. The proton spin pairs of the methyl and ammonium groups perform a complex stochastic motion being a resultant of four components characterised by the correlation times τ(3)(T), τ(3)(H), τ(2), and τ(iso), referring to the tunnelling and over the barrier jumps in a triple potential, jumps between two equilibrium sites and isotropic rotation. The theoretical expressions for the spectral densities in the cases of the complex motion considered were derived. For τ(3)(H), τ(2), and τ(iso) the Arrhenius temperature dependence was assumed, while for τ(3)(T)-the Schr?dinger one. The correlation times τ(3)(H) for CH(3) and NH(3) groups differ, which indicates the uncorrelated motion of these groups. The stochastic tunnelling jumps are not present above the temperature T(tun) at which the thermal energy is higher than the activation energy of jumps over the barrier attributed to the hindered rotation of the CH(3) and NH(3) groups. The T(tun) temperature is 54.6 K for NH(3) group and 46.5 K for CH(3) group in MAPBB crystal. The tunnelling jumps of the methyl and ammonium protons are responsible for the flattening of T(1) temperature dependence at low temperatures. The isotropic tumbling is detectable only from the M(2) temperature dependence. The isotropic tumbling reduces the second moment to 4 G(2) which is the value of the intermolecular part of the second moment. The motion characterised by the correlation time τ(2) is well detectable from both T(1) and M(2) temperature dependences. This motion causes the appearance of T(1) minimum at 130 K and reduction of the second moment to the 7.7 G(2) value. The small tunnelling splitting ω(T) of the same value for the methyl and ammonium groups was estimated as 226 MHz from the Haupt equation or 80 MHz from the corrected by us Haupt equation. These frequencies correspond to 0.93 μeV and 0.34 μeV tunnel splitting energy.     

Investigation of the free volume and ionic conducting mechanism of poly（ethylene oxide）-LiClO_4 polymeric electrolyte by positron annihilating lifetime spectroscopy

The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite（OREC） content and temperature in a range from 160 K to 300 K.According to the variation of ortho-positronium（o-Ps） lifetime with temperature,the glassy transition temperature is determined.The continuous maximum entropy lifetime（MELT） analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution.The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher（VTF） and Williams-Landel-Ferry（WLF） equations,implying a free-volume transport mechanism.A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation.It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte,which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.     

Investigation of the free volume and ionic conducting mechanism of poly（ethylene oxide）-LiClO₄ polymeric electrolyte by positron annihilating lifetime spectroscopy

The positron annihilation lifetime and ionic conductivity are each measured as a function of organophilic rectorite(OREC) content and temperature in a range from 160 K to 300 K.According to the variation of ortho-positronium(o-Ps) lifetime with temperature,the glassy transition temperature is determined.The continuous maximum entropy lifetime(MELT) analysis clearly shows that the OREC and temperature have important effects on o-Ps lifetime and free volume distribution.The experimental results show that the temperature dependence of ionic conductivity obeys the Vogel-Tammann-Fulcher(VTF) and Williams-Landel-Ferry(WLF) equations,implying a free-volume transport mechanism.A linear least-squares procedure is used to evaluate the apparent activation energy related to the ionic transport in the VTF equation and several important parameters in the WLF equation.It is worthwhile to notice that a direct linear relationship between the ionic conductivity and free volume fraction is established using the WLF equation based on the free volume theory for nanocomposite electrolyte,which indicates that the segmental chain migration and ionic migration and diffusion could be explained by the free volume theory.     

Positron annihilation response and broadband dielectric spectroscopy: Salol

A phenomenological analysis of the ortho-positronium (o-Ps) annihilation from positron annihilation lifetime spectroscopy (PALS) and the dynamics from broadband dielectric spectroscopy (BDS) are reported on a small molecular glass former of intermediate H-bonding and fragility: salol. The dielectric spectra extend over a very broad frequency range of about 2 × 10⁻²−3.5 × 10¹¹ Hz, providing information on the α-relaxation, the secondary relaxation giving rise to the excess wing, and the shallow high-frequency minimum in the micro- to milli-meter wave range. A number of empirical correlations between the o-Ps lifetime, τ ₃(T), and the various spectral and relaxation features have been observed. Thus, the phenomenological evaluation of the τ ₃(T) dependence of the PALS response of the amorphous sample reveals three characteristic PALS temperatures: T _g ^PALS, T _b1 ^L = 1.15T _g ^PALS and T _b2 ^L = 1.25T _g ^PALS, which are discussed in relation to similar findings for some typical small molecular vdW- and H-bonded glass formers. A slighter change of the slope at T _b1 ^L appears to be related to the transition from excess wing to the primary α-process-dominated behavior, with the secondary process dominating in the deeply supercooled liquid state below T _b1 ^L . The high-temperature plateau effect in the τ ₃(T) plot occurs at T _b2 ^L and agrees with the characteristic Stickel temperature, T _B ^ST, marking a qualitative change of the primary α process, but it does not follow the relation T _b2 ^L < T _α [τ ₃(T _b2) < τ _α ]. Both effects at T _b1 ^L and T _b2 ^L correlate with two crossovers in the spectral shape and related non-exponentiality parameter of the structural relaxation, β _KWW. Finally, the application of the two-order parameter (TOP) model to the structural relaxation as represented by the primary α relaxation times from BDS leads to the characteristic TOP temperature, T _m ^c , close to T _b1 from PALS. Within this model the phenomenological interpretation is offered based on changes in the probability of occurrence of solid-like and liquid-like domains to explain the dynamic as well as PALS responses. In summary, all the empirical correlations support further very close connections between the PALS response and the dielectric relaxation behavior in small molecule glass formers.     

On the Physical Meaning of Disperse Parameters of Frequency Dependence of Dielectric Permittivity in the Havriliak–Negami Model

This paper is devoted to an analysis of the frequency dispersion of dielectric permittivity in order to establish the physical meaning of the dispersion parameters α and β in the Havriliak–Negami model. It is found that parameter α is associated with the spectrum broadening of relaxation time τ. Examples with the appearance of a dispersion with parameter α of about 0.4 and 0.7 are presented. A conclusion is drawn that disorder creates a broadening of the relaxation times. Dispersion parameters α and β are introduced to preserve the unified relaxation time. The possibility of the analysis of experimental results on the basis of the Debye model in order to obtain the relaxation time distribution and determine parameters α and β according to the log(τ_HN/τ) chart is shown.     

SMMA/SMA共聚物共混物的自由体积的热动态特性与相分离行为的PALS研究

基于自由体积理论，利用正电子湮灭寿命谱仪(PALS)分别研究在不同升温速率条件下，聚苯乙烯-甲基丙烯酸甲酯共聚物(SMMA)和聚苯乙烯-马来酸酐共聚物(SMA)混合物(30/70)的自由体积参数的温度依赖性，探索相容共混物相行为的热动态特性.在PALS实验中，在玻璃化转变温度T_g以上，当结构松弛的弛豫时间与等温停留时间相当，发现在某一段温度范围内，共混物的自由体积参数随着温度的变化明显地偏离线性关系.从自由体积孔的浓度I₃值在该段的变化趋势，初步推断共混物在该温 关键词： 正电子湮没 正电子素 聚合物共混物 相分离     

Polydimethylsiloxane rubber gamma radiation effect studies by positron annihilation lifetime spectroscopy

Polydimethylsiloxane rubber was irradiated at various radiation doses up to 800 kGy in air. The lifetime and intensity of the long component τ₃ were obtained by positron annihilation lifetime spectroscopy (PALS). The crystallization property and the molecular flexibility were estimated using the differential scanning calorimetry and dynamic thermomechanic analysis. Thermal volatile property was determined by thermogravimetry analysis. It was proved that the cross-linking reaction made the chain flexibility of the rubber to reduce gradually during gamma radiation, which resulted in the reduction of the o-Ps intensity observed by PALS. Although the degradation effect existed during gamma radiation, it was still less significant than the cross-linking effect when the radiation dose was up to 800 kGy.     

ON THE NATURE OF THE MEDIUM LIFETIME COMPONENT OF POSITRON ANNIHILATION IN TEFLON POLYMER

The nature of the medium lifetime component of positron annihilation in Teflon (PTFE) polymer has been investigated by using a recently developed time-selecting γ ray energy spectro-meter with and without magnetic field.It has been assigned to o-Ps quenching annihilation too,just like the case of the longest lifetime component.     

PdAgHx金属氢化物正电子湮没研究

在77—295 K温区和氢浓度0—0.35范围采用正电子湮没寿命测量方法研究了Pd0.75Ag0.25H_x氢化物合金. 充氢后正电子湮没寿命谱可以用两个寿命成分表征. 短寿命成分τ1不随温度和氢浓度变化, 是自由正电子湮没寿命; 长寿命成分τ2及其相对强度I2不随温度变化, 但随氢浓度的增加分别增大和减小, τ2是氢气泡捕获的正电子湮没寿命, τ2增大和I2减小说明随氢浓度增大氢聚集成的气泡的尺度增大, 而浓度减小. 实验结果表明, 氢脆的微观机理是氢气泡致脆. The metal hydride PdAgHx with a hydrogen concentration x ranging from 0 to 0.35 has been investigated by positron annihilation lifetime method in the temperature region between 77 K and 295 K. The measured lifetime spectra in metal hydride PdAgHx are characterized by two lifetimes τ1 and τ2. The short lifetime τ1 is independent of both hydrogen concentration and temperature, which is ascribed to the annihilation lifetime of free positrons. The long lifetime τ2 and its intensity I2 do not change with temperature, while τ2 increases and I2 decreases with increasing of hydrogen concentration. τ2 is attributed to the lifetime of positrons trapped at the hydrogen bubble. The increase of τ2 indicates the growth of the hydrogen bubble, and the decrease of I2 shows the reduction of the hydrogen bubble concentration. The experimental result shows a microscopic mechanism that the hydrogen bubble produced causes hydrogen embrittlement.     

The Shear‐Dependent Phase Separation Behavior of the Ternary Blend Polystyrene/Polyvinyl Methyl Ether/Styrene–Acrylonitrile Copolymer

The phase behavior and phase separation dynamics of a PS/PVME/SAN ternary blend using light scattering under a shear rate range of 0.1～40 s^?1 were investigated. The cloud point temperature first increases and then decreases with the increase of shear rates. At higher shear rates, the cloud point temperature again increases. The phase separation behavior in the early and later stages under shear field can be explained by the Cahn–Hilliard theory and the exponential growth law, respectively. The delay time τ _d ?, the apparent diffusion coefficient D _app, the growth rate R(q), and the exponent term show strong dependence on the difference between the experimental temperature and the cloud point temperature (ΔT), and on the shear rates. Compared with PS/PVME binary blends at lower shear rates, τ _d for a PS/PVME/SAN ternary blend is smaller, while at higher shear rates τ _d is larger. At higher shear rates, the introduction of the third component SAN to a PS/PVME binary blends slows the phase separation process.     

Positron annihilation in synthetic zeolites

Both lifetime and angular correlation of positron annihilation have been measured for a series of synthetic zeolites for which the void structures are known fairly well. All of the zeolites had long lifetime components and a narrow momentum component which are ascribable to o-Ps and p-Ps annihilations in the voids, respectively. The correlation between the width of the p-Ps narrow component and the size of the largest voids showed a remarkable agreement with a theoretical estimate based on the spherical potential well model. The measurement of p-Ps momentum thus appears to be prospective as a tool to determine the size of voids of materials. The lifetime of the long lifetime component, on the other hand, showed a poor correlation with the void size even from a qualitative viewpoint, suggesting that factors other than the simple void size effect are dominant in determining the o-Ps lifetimes. Discussion is made on the cause of the different dependences of o-Ps and p-Ps annihilation parameters on the void size. It has also been found that p-Ps fraction is always larger than one third of the o-Ps fraction in all the zeolites studied. A discussion is presented on this point, too.Formerly, RIISOM     

不同气氛下多孔硅中电子偶素湮没行为研究

使用正电子湮没谱学方法,在不同气氛下对电化学腐蚀法制备的多孔硅中电子偶素的湮没行为进行了系统的研究.正电子湮没寿命谱测试结果表明,样品中存在长达40 ns的电子偶素湮没成分,并且进入多孔硅膜层的正电子约有80%形成电子偶素,具有非常高的电子偶素产额;在氧气气氛下,由于气体导致o-Ps发生自旋转化猝灭是使多孔硅样品中电子偶素寿命缩短的主要原因.结合正电子寿命-动量关联谱测量结果,分析了不同气氛下多孔硅样品中电子偶素湮没寿命及动量变化关系,讨论了多孔硅中电子偶素的湮没机理以及气氛对孔径计算理论模型的影响. 关键词： 电子偶素 正电子湮没谱学方法 多孔硅     

Quasi-elastic neutron scattering studies of the slow dynamics of supercooled and glassy aspirin

Aspirin, also known as acetylsalicylic acid (ASA), is not only a wonderful drug, but also a good glass former. Therefore, it serves as an important molecular system to study the near-arrest and arrested phenomena. In this paper, a high-resolution quasi-elastic neutron scattering (QENS) technique is used to investigate the slow dynamics of supercooled liquid and glassy aspirin from 410 down to 350 K. The measured QENS spectra can be analyzed with a stretched exponential model. We find that (i) the stretched exponent β(Q) is independent of the wavevector transfer Q in the measured Q range and (ii) the structural relaxation time τ(Q) follows a power-law dependence on Q. Consequently, the Q-independent structural relaxation time τ(0) can be extracted for each temperature to characterize the slow dynamics of aspirin. The temperature dependence of τ(0) can be fitted with the mode-coupling power law, the Vogel-Fulcher-Tammann equation and a universal equation for fragile glass forming liquids recently proposed by Tokuyama in the measured temperature range. The calculated dynamic response function χ(T)(Q, t) using the experimentally determined self-intermediate scattering function of the hydrogen atoms of aspirin shows direct evidence of the enhanced dynamic fluctuations as the aspirin is increasingly supercooled, in agreement with the fixed-time mean squared displacement ?x(2)? and the non-Gaussian parameter α(2) extracted from the elastic scattering.     

The role of positronium decoherence in positron annihilation in matter

A small difference between the energies of the para-positronium (p-Ps) and ortho-positronium (o-Ps) states suggests the possibility of the superposition of p-Ps and o-Ps during the formation of positronium (Ps) from pre-Ps, terminating its migration in the matter in a void. It is shown that such a superposition decoheres in the basis of p-Ps and o-Ps. The decoherence time scale estimated here motivates a correction in the precise analysis of the positron annihilation lifetime spectra. More generally, the superposited Ps state should contribute to the theory of the evolution of positronium in matter.     

Al-4%Ag合金中Ag原子偏析的低温正电子湮没参数研究

分别研究了823 K淬火处理和20%形变量的Al-4%Ag低温下Ag析出物对正电子的捕获行为的变化。采用正电子湮没寿命谱(PALS)技术和符合多普勒展宽能谱(CDBS)在温度范围10~293 K内对其进行表征。多普勒展宽能谱结果表明2种样品中均存在Ag析出物。正电子寿命谱的解谱结果中的各组分给出了Ag析出物随测量温度的变化规律。在170 ~273 K之间,正电子湮没行为具有较强的温度依赖性。但对于两个具有不同类型缺陷的样品,在低于170 K时观察到样品中Ag析出物捕获正电子能力出现了差异。随着测量温度的降低,淬火样品中的Ag析出物的正电子寿命和强度基本不变。在低于170 K的测量中,形变样品中的Ag析出物对正电子的捕获能力仍旧存在着较强的温度依赖性,但是变化幅度在逐渐减弱。当测量温度提升到室温(273~293 K),越来越多的正电子从Ag析出物中逃逸,逐渐回到自由状态或被其他深陷阱所捕获,失去了对温度的依赖性。     

Positron annihilation study of spin-crossover in [Fe x Zn1−x (ptz)6](BF4)2 single crystals

Positron lifetime measurements were carried out on [Fe _x Zn_1–x (ptz)₆](BF₄)₂ single crystals in the temperature range of 72–300 K. Complementary Doppler broadening spectra were also recorded at room temperature. The probability of the formation of o-Ps (lifetime 500–1400 ps) was between 10–30%. Both the spin density and the lattice parameters of the sample affected the lifetime of o-Ps through the ortho-para conversion and the pick-off annihilation, respectively. The positron annihilation technique proved to be a sensitive detector of the spin-crossover⁵T₂ ¹A₁ and of the concomitant phase transformation.     

Quantum critical transport near the Mott transition

We perform a systematic study of incoherent transport in the high temperature crossover region of the half filled one-band Hubbard model. We demonstrate that the family of resistivity curves displays characteristic quantum critical scaling of the form ρ(T, δU) = ρ(c)(T)f(T/T?(δU)), with T?(δU) ~ |δU|(zν), and ρ(c)(T) ~ T. The corresponding β function displays a "strong coupling" form β ~ ln(ρ(c)/ρ), reflecting the peculiar mirror symmetry of the scaling curves. This behavior, which is surprisingly similar to some experimental findings, indicates that Mott quantum criticality may be acting as the fundamental mechanism behind the unusual transport phenomena in many systems near the metal-insulator transition.