Positron annihilation spectroscopy for surface and interface studies in nanoscale polymeric films

Positron annihilation spectroscopy (PAS), coupled with a variable mono-energetic positron beam, has been used to investigate surface and interfacial properties in thin polymeric films. Free-volume properties have been measured from ortho-Positronium (o-Ps) lifetime and the S parameter of Doppler broadening of energy spectra from annihilation radiation as a function of the depth and of the temperature in thin polymeric films. Depth profiles of glass transition temperature and nanoscale layered structures in polystyrene (PS) thin films on the Si substrate are presented.     

Application of positron annihilation induced Auger Electron Spectroscopy to the study of surface chemistry

Positron annihilation induced Auger Electron Spectroscopy (PAES), makes use a beam of low energy positrons to excite Auger transitions by annihilating core electrons. This novel mechanism provides PAES with a number of unique features which distinguishes it from other methods of surface analysis. In PAES the very large collisionally induced secondary electron background which is present under the low energy Auger peaks using conventional tecniques can be eliminated by using a positron beam whose energy is below the range of Auger electron energies. In addition, PAES is more surface selective than conventional Auger Spectroscopy because the PAES signal originates almost exclusively from the topmost atomic layer due to the fact that the positrons annihilating with the core electrons are trapped in an image correlation well just outside the surface. In this paper, recent applications of Positron Annihilation Induced Auger Electron Spectroscopy (PAES) to the study of surface structure and surface chemistry will be discussed including studies of the growth, alloying and inter-diffusion of ultrathin layers of metals, metals on semiconductors, and semiconductors on semiconductors. In addition, the possibilities for future application of PAES to the study of catalysis and surface chemistry will be outlined.     

Positron annihilation in hypercrosslinked polystyrenes

Positron annihilation in hypercrosslinked polystyrene, called CPS(0.3)150E, has been studied as a function of temperature in the range from 35 to 370 K. The positron lifetime spectra were resolved into five components using the PATFIT and MELT programs. The annihilation rate constant of the longest-lived component was found to increase linearly with increasing temperature. Remarkably, the distribution of o-Ps lifetimes resolved by MELT was shown to broaden with decreasing temperature. Moreover, an effect of the oxygen pressure on the positronium characteristics was also investigated in another hypercrosslinked polystyrene, CPS(0.3)100E. The oxygen pressure varied from vacuum to 6 atm. The annihilation rate constants of the long-lived components were observed to increase linearly as a function of the oxygen pressure, which demonstrates a dependence of the kinetic of o-Ps quenching on the pore size.     

Studies of the Auger spectrum from the (100) surface of GaAs using positron annihilation induced Auger electron spectroscopy

Measurements of the first high-resolution positron annihilation induced Auger spectrum from GaAs(100) are presented. The spectrum displays six As and three Ga Auger peaks below 110 eV, including a strong As M_4,5VV peak at 28 eV and a less intense Ga M_2,3M_4,5M_4,5 peak at 53 eV. The Auger peak intensities are used to obtain experimental annihilation probabilities for relevant core-level electrons. Experimental results are compared with first-principles calculations of positron surface states and annihilation characteristics of surface trapped positrons.     

Positron age-momentum correlation studies of free volumes in toughened cyanate resin networks

Positron age-momentum correlation (AMOC) spectroscopy is applied to study the associations between the momentum distributions and positron annihilation in the toughened CE networks. The Doppler profile of the positron annihilation process is much broader for the toughened CE than pure CE network. This is due to positron trapping on high polar groups of the added elastomers or nano-CaCO₃ and annihilation with the electrons of high momenta. The broadening momentum distribution of ortho-positronium annihilation process indicates that the pick-off annihilation process is strongly influenced by the added high polar elastomers or nano-CaCO₃. The potential of AMOC spectroscopy for free volume analysis in polymer blends was demonstrated.     

Long-living positron and positronium states in zeolites and microcrystalline oxides

Positron annihilation (PA) investigations were performed on zeolites (X, Y and ZSM-5) and on microcrystalline MgO, Al₂O₃ and SiO₂, providing long lifetime components attributed to o-Ps atoms. In addition to the positron lifetime (LT) measurement, the energy distribution (ED) of the annihilation gamma radiation spectrum was recorded in the 30 keV–1.5 MeV range for different samples and was compared to reference distributions for Si and GaAs samples, where no long-living Ps states are formed. Apart from the strong correlation with the water content in the samples, the positron data collected testify much more pronounced positronium hosting features for powders of the mentioned oxides than for zeolites. Positron LT spectroscopy combined with recording of the ED of the annihilation radiation provides reliable information on the formation of long living 3 states.     

Evaluation of scintillators and semiconductor detectors to image three-photon positron annihilation for positron emission tomography

Positron emission tomography (PET) is rapidly becoming the main nuclear imaging modality of the present century. The future of PET instrumentation relies on semiconductor detectors because of their excellent characteristics. Three-photon positron annihilation has been recently investigated as a novel imaging modality, which demands the crucial high energy resolution of semiconductor detector. In this work the evaluation of the NaI(Tl) scintillator and HPGe and CdZTe semiconductor detectors, to construct a simple three-photon positron annihilation scanner has been explored. The effect of detector and scanner size on spatial resolution (FWHM) is discussed. The characteristics: energy resolution versus count rate and point-spread function of the three-photon positron annihilation image profile from triple coincidence measurements were investigated.     

Slow positron studies of anodized aluminium

Porous anodic layers were grown on aluminium alloys under different anodizing conditions. Positron annihilation energy spectra were measured as a function of the positron energy. Ortho-positronium formation in the porous layer was detected. The positron characteristics could be correlated to known parameters of the layers. This demonstrates that the positron annihilation method is a particularly useful technique to characterise the anodic layers.     

Positron band structures for beryllium

We report on the band structure and wave functions of positrons, annihilating with electrons, from the thermalized state k⁺ = 0. We find that the bottom of the band to which the positron thermalizes in this metal is definitely nonambiguous. It is also found that even though the first few Bloch terms in the wave function can give the gross shape of the positron annihilation curve for this metal, the higher momentum components of high orders are definitely important if one is to assay the fine details of the curve.     

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.     

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.     

正电子湮没与沸石内静电场

本文测定了不同类型沸石的正电子寿命谱。发现o-Ps的湮没寿命, 与沸石静电场之间有良好的对应关系, 静电场愈强, 湮没寿命愈短。根据正电子寿命谱结果。含不同阳离子的Y沸石的静电场强弱次序为KY相似文献   

Life science research using positron annihilation spectroscopy: UV-irradiated mouse skin

Positron annihilation spectroscopy (PAS) is applied to study mouse skin under different UV irradiations as a function of positron incident energy (0–30 keV). Significant variations in the depth profile of S parameter are observed in a period of hours and of days for UVA and UVB exposures, respectively. The high sensitivity of positron annihilation signals responding to UV irradiation shows that PAS may be developed as a new noninvasive technique for the detection of molecular damage in life science research.     

Effect of Surface Decoration of CNTs on the Interfacial Interaction and Microstructure of Epoxy/MWNT Nanocomposites

Epoxy resin nanocomposites with different contents of multiwalled carbon nanotubes (MWNTs) are prepared. The interaction between MWNTs and the epoxy resin matrix and the microstructure and mechanical properties of the composites are systematically investigated by Fourier‐transform infrared (FTIR) spectroscopy, transmission electron microscopy, scanning electron microscopy, and positron annihilation technology. FTIR spectra reveal that two kinds of hydrogen bonds exist at the interface for the nanocomposites modified by amine, one between the epoxy group on the side chain and the NH group, and the other between the epoxy group on the alicycle and the NH group. Compared to unmodified MWNT composites, the modified MWNT composites possess better mechanical properties, which are attributed to stronger interfacial interaction resulting from an efficient load transfer from matrix to MWNTs. Positron annihilation lifetime spectroscopy is used to characterize the microstructure of the epoxy/MWNT composites. The subtransition and glass transition temperatures are determined by finite‐term positron lifetime analysis and the variation of the free‐volume size as a function of temperature. Shifts of structure transition temperatures of the composites are observed with increasing MWNT weight content. Interestingly, the continuous lifetime analysis reveals the existence of two long‐lived lifetime components above the glass transition temperature, which may be attributed to the formation of local ordered regions related to the packing density of chains.     

Modification of microstructure of the surface and the bulk in ion-irradiated membrane studied using positron annihilation spectroscopy

The effect of ion irradiation and etching on the microstructure of polyethyleneterephthalate (PET) membrane has been studied using positron annihilation spectroscopy. PET membrane of 25 μm thickness was irradiated by 100 MeV ³⁵Cl beam (7×10⁷ ions/cm²) and then etched with NaOH for 45 min. The modification in the microstructure at the surface of the membrane was probed by depth-dependent Doppler-broadened S-parameter and positronium 3γ–2γ annihilation ratio using a slow positron beam, while the free volume properties in the bulk of the membrane were studied using the conventional positron lifetime technique. Positron annihilation parameters were found to be very sensitive to the microstructural changes occurring in the polymer at such a low fluence. It was observed that on ion-irradiation, the surface of the membrane is modified in a different way than the bulk. While the ion-irradiation produces large fraction of excess free volumes at the surface of the membrane due to chain scission, the free volumes are reduced in the bulk of the membrane due to cross-linking. FTIR and XRD measurements were also carried out to investigate the changes occurring in the chemical structure and crystallinity of the polymer samples on ion-irradiation and etching.     

硅胶表面键合物的正电子湮没谱研究

本文在多孔无定形硅胶的表面上键合了不同极性的化学基团, 制成一系列相同基体, 但表面基团不同的样品, 测定了其正电子湮没寿命谱, 发现寿命谱的最长寿命组份随表面键合基不同, 寿命值有明显差别。寿命值与基团的极性及基团的体积有关, 正电子湮没谱的最长寿命组份能灵敏地表征表面的极性和化学性, 可作为表面化学定性分析的有用技术。     

What do Positrons Say about the Structure and Properties of Fluids?

Applications of positron annihilation spectroscopy to fluid state physics and chemistry are discussed. Special attention is paid to problems of surface (interface) layer structure, molecular orientations in the layer, and the effects of freesurface curvature and age on surface tension. Positron investigations of the structure of liquid mixtures, including microheterogeneity studies, are considered.     

Y沸石中的正电子湮没

本文测量了NaY、HY和NH_4Y在不同抽空温度下的正电子寿命谱, 得到了四个寿命组份, 并对它们的归属进行了讨论。其中两个长寿命组份τ_s和τ_4归结为沸石内表面和笼内o-Ps的湮没。o-Ps容易被沸石内的质子酸氧化, 而使其湮没寿命τ_3和τ_4缩短。利用正电子寿命谱可以监测NH_4Y沸石的脱氨过程。质子酸的存在对o-Ps的形成并无影响, 但随着质子酸浓度增加, o-Ps在沸石内表面湮没的几率大于笼内, 故I_3大于I_4。o-Ps的在沸石内表面和笼内的湮没速率与质子酸浓度成线性关系, 以一级反应动力学处理得到的o-Ps在沸石内表面和笼内的氧化反应表观速率常数分别为9.67×10~7(mmol/g)_~(-1)s~(-1)和2.36×10~7(mmol/g)~(-1)s~(-1)。     

Positron/positronium annihilation in nanocrystalline silicon thin films

Positron and positronium annihilation investigations were applied to nanocrystalline silicon (nc-Si) thin films, for the first time. The nc-Si thin films with average grain diameters of 3–5 nm show intense blue luminescence at room temperature. The nanometer-sized Si crystallites formed in amorphous Si (a-Si) matrix give rise to this luminescence. Very highS-parameters up to 0.62 were observed in the as-grown a-Si thin film suggesting positronium formation in the a-Si layer. The average lifetime of the positrons in the a-Si was determined to be about 520 ps. TheS-parameters dropped significantly to 0.53 by crystallization of the thin film at 800 °C for 10 seconds, which was almost the same to the value observed in bulk Si (100) substrate. Further crystallization from 60 seconds to 1 hour showed smaller change in theS-parameters than that from the a-Si to 10 seconds. The large change in theS-parameters due to the annealing might be caused by the formation of Si nanocrystallites in a-Si matrix suggesting that positron is a sensitive probe for structural investigations of the nc-Si materials.     

Positron annihilation lifetime measurements in collagen biopolymer

Lifetime measurement in Positron Annihilation Spectroscopy (PAS) is applied to the study of free-volume collagen characteristics as a function of concentration. The lifetimes of positrons were measured by a conventional fast-fast coincidence system. All lifetime data are fitted in three components by using the computer program POSITRON-FIT and resolved. For each concentration, lifetime distributions were analyzed in order to obtain the different components, thus we have observed three components of which one long component τ₃. This long lived component can be associated with a pick-off annihilation of ortho-positronium (o-Ps) trapped in free volumes of amorphous region. This investigation shows the potential of positron annihilation spectroscopy in the study of biopolymer microstructures.