Experimental evidence for the vortex glass phase in untwinned, proton irradiated YBa2Cu3O7-delta

We report on magnetoresistance measurements of the effects of 9 MeV proton irradiation on a clean, untwinned single crystal of YBa2Cu3O7-delta. For the first time, evidence for a vortex glass transition is detected in an untwinned single crystal of YBa2Cu3O7-delta with induced pointlike disorder, in which the first order vortex melting transition is completely suppressed after proton irradiation. Our results suggest that a sufficiently high pinning disorder is required in order for the vortex glass phase to be observed.     

Phosphate Assisted Proton Transfer in Water and Sugar Glasses: A Study Using Fluorescence of Pyrene-1-carboxylate and IR Spectroscopy

The role of water’s H-bond percolation network in acid-assisted proton transfer was studied in water and glycerol solutions and in sugar glasses. Proton transfer rates were determined by the fluorescence of pyrene-1-carboxylate, a compound with a higher pK in its excited state relative to the ground state. Excitation of pyrene-1-COO⁻ produces fluorescence from pyrene-1-COOH when a proton is accepted during the excited singlet state lifetime of pyrene-1-COO⁻. The presence of glycerol as an aqueous cosolvent decreases proton transfer rates from phosphoric and acetic acid in a manner that does not follow the Stokes relationship on viscosity. In sugar glass composed of trehalose and sucrose, proton transfer occurs when phosphate is incorporated in the glass. Sugar glass containing phosphate retains water and it is suggested that proton transfer requires this water. The infrared (IR) frequency of water bending mode in sugar glass and in aqueous solution is affected by the presence of phosphate and the IR spectral bands of all phosphate species in water are temperature dependent; both results are consistent with H-bonding between water and phosphate. The fluorescence results, which studied the effect of cosolvent, highlight the role of water in assisting proton transfer in reactions involving biological acids, and the IR results, which give spectroscopic evidence for H-bonding between water and phosphate, are consistent with a mechanism of proton transfer involving H-bonding. The possibility that the phosphate-rich surface of membranes assists in proton equilibration in cells is discussed.     

Application of129Xe NMR to polymer blends

¹²⁹Xe NMR experiments on two different polymer blends are described. The first system, a blend of polypropylene (PP) and the copolymer of polypropylene and polyethylene (EP), shows separate domains of polypropylene and of the copolymer. The latter phase forms rubbery domains in the polypropylene matrix. The second system is the compatible blend of polyvinylidenefluoride and polymethylmethacrylate. For the incompatible blend two Xe resonances are found, one for Xe absorbed in the matrix and one for Xe in the rubbery EP phase. The chemical shift of the Xe absorbed in the rubbery phase can be related to the polyethylene content of the copolymer. The line widths and chemical shifts are affected by the polymer motions as a function of the temperature. Although the system has two very different glass transition temperatures, it is striking to see that upon approaching the polypropylene glass transition temperature the Xe resonance of Xe in the rubbery phase is also affected. Due to the dipolar interaction between Xe spins and polymer proton spins, cross-polarization experiments can be performed. This allows the measurement of correlated NMR spectra. The compatible blend shows only one line with a chemical shift proportional to the composition.     

质子辐照硼硅酸盐玻璃盖片的物理效应分析

作为航天器电源系统的重要组成部分,太阳电池需要更高的转换效率和可靠性以及更长的使用寿命。通过在太阳电池表面覆盖抗辐照玻璃盖片,可以增强太阳电池对粒子辐射的防护,延长太阳电池的服役寿命,使航天器获得可靠的能源供应。硼硅酸盐玻璃就是一种理想的太阳电池玻璃盖片材料。采用蒙特卡罗方法,结合SRIM软件模拟研究质子辐照硼硅酸盐玻璃的损伤物理机理。基于粒子与物质相互作用的理论以及基本公式,通过分析不同入射能量的质子在硼硅酸盐玻璃中的阻止本领、电离能损、位移能损、空位的产生情况,对辐照损伤的物理机制进行研究。结果表明:能量为30~120 keV的质子辐照损伤主要发生在硼硅酸盐玻璃表面;质子沉积、空位分布等均为Bragg峰型分布;电离能损是能量损失的主要部分,随入射能量的增加而增大,导致电子的电离和激发;位移能损在玻璃内部随能量降低而增大,导致硼、氧和硅等空位缺陷的产生;电离效应和缺陷的产生是硼硅酸盐玻璃色心形成的重要原因。     

Fast magic-angle spinning proton NMR studies of polymers at surfaces and interfaces

Solid-state proton NMR with fast magic-angle sample spinning has been used to study the structure and dynamics of polymers and the water interface in porous glass composites. The composites were prepared by photopolymerization of poly(ethyl acrylate) and other acrylate formulations in a high surface-area rigid glass matrix with 40-A interconnected pores. High resolution solid-state proton spectra were obtained for polymer films and composites with 15 kHz magic-angle sample spinning at temperatures above the polymer glass transition temperature. The solid-state proton spectra can be detected with high sensitivity and used to determine the composition of polymer and water filling the pores. These results and spin diffusion studies using 1H-29Si 2D heteronuclear correlation and wideline separation NMR show that the polymer fills the central 30 A of the pore, and that the remaining volume is filled with surface hydroxyl groups and water.     

Anomalous surface diffusion of water compared to aprotic liquids in nanopores

1H nuclear magnetic relaxation dispersion experiments show remarkable differences between water and acetone in contact with microporous glass surfaces containing trace paramagnetic impurities. Analyzed with surface relaxation theory on a model porous system, the data obtained for water show that proton surface diffusion limited by chemical exchange with the bulk phase permits long-range effectively one-dimensional exploration along the pores. This magnetic-field dependence coupled with the anomalous temperature dependence of the relaxation rates permits a direct interpretation in terms of the proton translational diffusion coefficient at the surface of the pores. A universal rescaling applied to these data collected for different pore sizes and on a large variety of frequencies and temperatures, supports this interpretation. The analysis demonstrates that acetone diffuses more slowly, which increases the apparent confinement and results in a two-dimensional model for the molecular dynamics close to surface relaxation sinks. Surface-enhanced water proton diffusion, however, permits the proton to explore a greater spatial extent of the pore, which results in an apparent one-dimensional model for the diffusive motions of the water that dominate nuclear spin relaxation.     

Dosimetric verification of treatment planning system superficial dose calculations for proton beam

To investigate the accuracy of Eclipse treatment planning system (TPS) dose calculations at the surface. It is desirable to know the accuracy of the proton treatment planning system in predicting dose at superficial region. All measurements were performed in a clinical proton beam at the National Cancer Center in Korea. Proton treatment plans were developed for a superficial planning target volume (PTV) contoured on a cylindrical polymethylmethacrylate phantom specially designed for this study. Dose was then measured at the surface and also in the PTV for these treatment plans and compared against the TPS calculations. For our study, a model GD-301 glass dosimeters were used. The proton treatment planning system overestimated the superficial dose without use of bolus as much as by 7–14% when compared to glass dosimeter. On the other hand, with use of bolus to cover the superficial region, surface dose between the calculation from Eclipse and measurement using the glass dosimeter are approximately within 3%.     

石英玻璃低能质子辐照损伤动力学研究

地面模拟研究了JGS3光学石英玻璃在真空、热沉和能量低于200keV的低能质子辐照下表面光学性能变化的基本规律．并建立了辐照损伤色心演化的动力学唯象模型。试验结果表明．大通量低能质子辐照对石英玻璃表层具有明显的表面损伤效应。随着辐照吸收剂量的增加,光密度变化先以线性规律迅速增加．加进一步增加时逐渐呈现饱和趋势;采用较高能量辐照作用后光密度变化出现饱和趋势的拐点提前,且饱和数值降低。根据对试验结果的分析,建立了低能质子辐照下石英玻璃色心演化的动力学模型．并给出了光密度变化的表达式。采用模型结果进行数学模拟,模拟曲线与试验结果曲线相似。因此所建立的动力学模型可以用来定量描述低能质子辐照下石英玻璃光学性能随辐照吸收剂量的变化规律。     

Changes in K-208 glass transmittance spectra under ionizing radiation and molecular fluxes

The effect of 40-keV electron and proton radiation with a flux density of 5 × 10 cm^?2 s^?1 on the deposition of products of thermostimulated gas release from a polymer composite on a substrate made from protective K-208 glass used for the protection of spacecraft solar panels is experimentally investigated. Analysis of the obtained results shows that, unlike proton radiation, electron radiation results in an increase in the optical density of the glass and stimulates the deposition of gas-release products. It is established that the majority of effects generated as a result of exposure of the substrate to electron radiation are neutralized by protons upon combined irradiation with electrons and protons.     

High-speed 1H MAS NMR investigations of the weathered surface of a phosphate glass

Solid-state high-speed 1H MAS NMR spectroscopy was used to investigate the weathered surface of a potassium aluminum phosphate (KAP) glass exposed to a humid environment (30K2O10Al2O360P2O5, mol%). Through the combination of spin-spin relaxation and double quantum (DQ) filtering it was possible to resolve seven or eight different proton environments within the weathered surface of the KAP glass. Two-dimensional (2D) DQ and 2D NOESY NMR correlation experiments were performed to probe the spatial proximity of these different proton species. These 1H-1H correlation experiments helped confirm the spectral assignments. The analysis of these different 1H environments provides additional information about the chemical processes that occur at the weathered glass surface.     

Molecular dynamics in concentrated sugar solutions and glasses: an NMR field cycling study

The frequency dependence of the proton longitudinal relaxation time in concentrated sugar in water solutions and glasses is compared with various theoretical models and used to derive correlation times characterizing the dynamic state of the water and sugar. It is shown that the water retains a high degree of molecular mobility even in the ‘sugar glass’, while the spectral density of the 3-dimensional glass lattice shows no evidence for a distribution of correlation times.     

Evidence for a quasi-two-dimensional proton glass state in Cs5H3(SO4)(4); xH(2)O Crystals

We describe damping of hypersonic and ultrasonic longitudinal acoustic (LA) phonons in crystals of Cs 5H (3)(SO (4))(4);xH 2O (PCHS) between 100 and 360 K. The damping of LA phonons exhibits strong dispersion caused by relaxation processes in the region of transformation into the glasslike phase (T(g) approximately 260 K). Near T(g) the damping of ultrasonic phonons propagating in the basal plane reflects the cooperative freezing of acid protons. The damping of LA phonons propagating perpendicular to the basal plane can be fit by the Debye model and is due to the interaction between protons and LA phonons. This suggests that the proton glass state that is realized at T相似文献   

The heat of hydration of the proton in the gas and liquid phases

The literature data on the experimental heats of hydration in the sequential addition of water molecules to the proton in the gas phase and the integral heat of solution of the proton in water are analyzed. The integral heat of hydration of the proton in the gas phase was found to exceed the heat of solution of the proton in water by no less than 40.1 kcal/mol. The suggestion was made that this energy was spent for the rearrangement of the system of H-bonds in water caused by the solution of the proton.     

Spherical 2 + p spin-glass model: an exactly solvable model for glass to spin-glass transition

We present the full phase diagram of the spherical 2 + p spin-glass model with p > or = 4. The main outcome is the presence of a phase with both properties of full replica symmetry breaking phases of discrete models, e.g., the Sherrington-Kirkpatrick model, and those of one replica symmetry breaking. This phase has a finite complexity which leads to different dynamic and static properties. The phase diagram is rich enough to allow the study of different kinds of glass to spin glass and spin glass to spin glass phase transitions.     

Physical properties of [Formula: see text] polymer electrolytes: nuclear magnetic resonance investigation and comparison with [Formula: see text

The physical properties of the ionic conductor [Formula: see text], obtained by dissolution of lithium trifluoromethanesulphonylimide in poly(propylene oxide), have been investigated for several values of n. The glass transition temperature [Formula: see text] has been established from both DSC and NMR techniques. The diffusion coefficients of [Formula: see text]-containing species have been determined by the pulsed magnetic field gradient technique. The behaviour of the proton relaxation time [Formula: see text] versus temperature and concentration has been correlated to the glass temperature. The behaviour of the proton transverse relaxation function, obtained by the spin-echo technique, has been interpreted using a simple model in which two regimes and consequently two transverse relaxation times coexist and are assigned to the `entangled' and `non-entangled' parts of the high-molecular-weight polymer chains investigated.     

玻璃基质与纳米颗粒相互影响的光谱学研究

通过低温选择激发玻璃陶瓷中的LaF3:Tm3+的1D2能级,成功地分开了两种局域环境中Tm3+离子的发射谱,使一些频率的发射谱仅来自于晶相,而另一些则仪来自于玻璃相.讨论了玻璃陶瓷中形成玻璃的氧化物和以晶相析出的氟化物之间的相互作用对两种局域环境中Tm3+离子的光学性能的影响.结果表明:晶粒较大时,氧化物玻璃对处于纳米晶体局域环境的稀土离子的影响减弱,纳米晶体对处于氧化物玻璃局域环境的稀土离子的影响增强;晶粒较小时,氧化物玻璃和晶粒接触面的增加会降低处于纳米晶体局域环境的稀土离子的发光效率,但纳米晶体对处于氧化物玻璃局域环境的稀土离子的影响减弱.晶粒越大,氧化物玻璃对处于纳米品体局域环境的稀土离子的发光影响越小,发光性能越好.玻璃基质中SiO2的含量能影响两种局域环境的Tm3+离子发光效率.     

Superconductivity of spin glasses

The coexistence of superconducting and spin glass phases is investigated. The dependence of the phase transition temperature in the spin glass state both on the impurity concentration and the superconductivity state is given. The influence of the spin glass phase on the renormalized frequency and the order parameter of the conduction electrons is determined.     

固体高分辨NMR研究PPU/PMAs,AB-交联聚合物中的分子运动和相容性

本文使用固体高分辨NMR测量了PPU/PMAs,AB-交联聚合物中PPU的侧甲基的¹³C自旋-晶格弛豫时间(T₁)。使用内旋转运动的平均谱密度函数分析了PPU侧甲基的内旋转和PMA的侧基的多重内旋转运动。结果表明PMA中的侧基距主链越远,其旋转速度越快并且PPU侧甲基的内旋转速度随ABCP中PMA侧链长度增加而变快。还使用质子的T_1ρ和T₂及自旋扩散研究了体系的相容性和相行为。得到了有关相应尺度下的每相的组成和软相微区尺度的信息。     

Impurity proton NMR signals from common "proton-free" laboratory materials

For the study of small samples (tens of microns cubed) by NMR, impurities from the environment and construction materials (Teflon, Kel-F, glass NMR tubes, etc.) can dominate the signal, in particular for proton NMR. Using pulsed NMR with a resolution of several microseconds, we have studied a number of common construction materials considered to be proton-free and find considerable proton impurity. We present results in terms of impurity proton spins per milligram and discuss procedures to minimize the effects of impurity signal.