NMR studies of alkali C60 superconductors

The authors report¹³C,⁸⁷Rb,³⁹K, and¹³³Cs nuclear magnetic resonance (NMR) measurements of lineshapes, Knight shifts, and spin-lattice relaxation rates in the normal and superconducting states of M₃C₆₀, where M₃ = Rb₃, K₃, Rb₂K, RbK₂, Rb₂Cs, and RbCs₂. Measurements are used as a guide to a new ammonia solvent synthesis technique. Temperature dependence of the superconducting state electron spin susceptibility is found to follow BCS weak coupling predictions. The issue of the Hebel-Slichter coherence peak is addressed.     

Effects of Mechanical Grinding on C60 And Ca5C60 Superconductor

Abstract

The effects of mechanical grinding on polycrystalline C₆₀ and Ca₅C₆₀ superconductor are examined. It has been found that mechanical grinding may severely degrade phases of C₆₀ (fcc) and Ca₅C₆₀ (sc). The grinding destroys the long-range ordering of crystals and produces a partial amorphous state. The damage of crystal leads to the disappearance of superconductivity for Ca₅C₆₀. The samples with an amorphous phase can be recrystallized by annealing at 600°C for pure C₆₀ and Ca₅C₆₀. Magnetic susceptibility measurements indicated that the superconductivity of the degraded sample did not recover easily to the initial state.     

三元混合工质R407C热力参数模型分析

R407C是替代R22的一种极具前景的新工质,本文采用Peng-Robinson型方程对新工质R407C的热力学性质进行了全面的计算,并根据实验数据拟合出新工质的迁移特性计算公式。根据计算结果给出了新工质R407C的压焓图和温-熵图。计算关联式具有较高的精度,热力学参数计算误差小于1％,迁移特性参数误差小于4％。本文的研究结果为新工质R407C的系统分析和计算提供了准确、可靠的热力学性质和热物理性质分析计算结果。     

三元混合工质R407C热力参数模型分析

R407C是替代R22的一种极具前景的新工质，采用Peng—Robinson型方程对新工质R407C的热力学性质进行了全面的计算，并根据实验数据拟合出新工质的迁移特性计算公式。根据计算结果给出了新工质R407C的压焓图和温-熵图。计算关联式具有较高的精度，热力学参数计算误差小于l％，迁移特性参数误差小于4％。本文的研究结果为新工质R407C的系统分析和计算提供了准确、可靠的热力学性质和热物理性质分析计算结果。     

The effect of fullerene C60 on the thermooxidative degradation of a free-radical PMMA studied by thermogravimetry and calorimetry

Thermogravimetric and calorimetric study of the effect of fullerene C₆₀ on the thermooxidative degradation of free-radical poly(methyl methacrylate) revealed three stages in the process.     

Accurate quantitative 13C NMR spectroscopy: repeatability over time of site-specific 13C isotope ratio determination

The stability over time (repeatability) for the determination of site-specific 13C/12C ratios at natural abundance by quantitative 13C NMR spectroscopy has been tested on three probes: enriched bilabeled [1,2-13C2]ethanol; ethanol at natural abundance; and vanillin at natural abundance. It is shown in all three cases that the standard deviation for a series of measurements taken every 2-3 months over periods between 9 and 13 months is equal to or smaller than the standard deviation calculated from 5-10 replicate measurements made on a single sample. The precision which can be achieved using the present analytical 13C NMR protocol is higher than the prerequisite value of 1-2 per thousand for the determination of site-specific 13C/12C ratios at natural abundance (13C-SNIF-NMR). Hence, this technique permits the discrimination of very small variations in 13C/12C ratios between carbon positions, as found in biogenic natural products. This observed stability over time in 13C NMR spectroscopy indicates that further improvements in precision will depend primarily on improved signal-to-noise ratio.     

Effects of Annealing on the Conductivity of C60 Thin Films

Films of C₆₀, at different stages of annealing of T_t=200°and 300°C have been electrically characterized over the temperature domain from -130°C to T_t. X-ray diffraction revealed a random polycrystalline fee structure with stacking defects of an intrinsic nature, due to deposition conditions. The value of room-temperature conductivity was found to be in the range (6.3-1.0) *10^-10 (0cm)^-1. In the stable annealed state the conductivity showed an activated temperature dependence above 423 K and a non-activated dependence below 330-280 K. The activation energies E_a = 0.8 eV (film thickness 0.70 μm) and E_a = 1.0 eV (film thickness 2.40 μm) were in good agreement with the energy gap values (1.63 eV and 2.08 eV) which were deduced from the absorption spectral dependence. Annealing decreased the non-activated contribution to conduction, extending the intrinsic conduction temperature range.     

Predictive approach to thermodynamic properties of the metastable Cr3C carbide

In thermodynamic modeling of phase diagrams it is often necessary to deal with the properties of metastable compounds, which are not known from experiments. As an illustrative example, we choose the Cr₃C(oP16) carbide, which is involved in the modeling of the Me₃C(oP16) (cementite) structure of the Fe-Cr-C system but is metastable in the Cr-C system. We discuss in detail the estimation of its thermodynamic properties, relying on regularities in bonding properties of 3d-transition metal carbides, and an account of the vibrational entropy through the so-called entropy Debye temperature. Our predictions are compared with values derived in thermodynamic modeling of the Fe-Cr-C phase diagram. Relying on the present results, we perform calculations of metastable phase equilibria in the Cr-C system and use them in analyzing information about Cr₃C from splat-quenching experiments.     

Cryogenic probe 13C NMR spectroscopy of urine for metabonomic studies

Cryogenic probe technology can significantly compensate for the inherently low sensitivity of natural abundance 13C NMR spectroscopy. This now permits its routine use in NMR spectroscopy of biofluids, such as urine or plasma, with acquisition times that enable a high throughput of samples. Metabonomic studies often generate numerous samples in order to characterize fully the time-dependent biochemical response to stimuli, but until now, they have been largely conducted using 1H NMR spectroscopy because of its high sensitivity and hence efficient data acquisition. Here, we demonstrate that information-rich 13C NMR spectra of rat urine can be obtained using appropriately short acquisition times suitable for biochemical samples when using a cryogenic probe. Furthermore, these data were amenable to automated pattern recognition analysis, which produced a profile of the metabolic response to the model hepatotoxin hydrazine that was consistent with earlier studies. Thus, a new source of detailed and complementary information is available to metabonomics using cryogenic probe 13C NMR spectroscopy.     

Molecular motions of banana-shaped liquid crystals studied by NMR spectroscopy

Recent studies based on NMR spectroscopy put in evidence the occurrence of a slow motion regime in bent-shaped liquid crystals having the aromatic core formed by five phenyl rings linked by ester groups both in the isotropic and in the nematic phases. In this paper a brief overview of these NMR studies is presented and additional new relaxation data recorded on a banana-shaped mesogen are reported and discussed. In particular, proton spin-lattice relaxation times, T₁, were acquired at different Larmor frequencies from 8 MHz to 5 kHz by means of NMR relaxometry in a wide range of temperatures from the isotropic to the crystalline phases. These data confirm that NMR relaxation in bent-core liquid crystals is affected by much slower dynamics than that observed in common rod-like liquid crystals and that overall molecular reorientations are responsible of this slow motion regime. This finding is discussed in the frame of the results obtained by means of several NMR methods, such as ²H NMR T₂ analysis and ¹H self-diffusion NMR measurements, on the same bent-core molecule.     

Quantitative 13C NMR spectroscopic studies on the equilibrium of formaldehyde with its releasing cosmetic preservatives

The aim of our study was to show that NMR spectroscopy is an excellent method to obtain reliable information about the equilibrium between free formaldehyde and its formaldehyde releasers. For this purpose, we compared several O- and N-formal-based formaldehyde releasers used in industrial and consumer products. The underlying chemical structures as well as the release of formaldehyde were followed quantitatively as a function of the pH and dilution. It was shown that only the amide-based N-formals are a reservoir for formaldehyde in the concentrations normally used in cosmetic products, whereas O-formals and the amine-based N-formals decompose completely. Since NMR spectroscopy does not affect the equilibrium between free and bound formaldehyde, we think that it is the only method for unequivocal determination of free formaldehyde. Measurements on finished products showed that free formaldehyde can be quantified down to concentrations as low as approximately 0.002 wt % in an acceptable measuring time.     

Optimized quantitative DEPT and quantitative POMMIE experiments for 13C NMR

In quantitative analysis, inverse gated (1)H decoupled (13)C NMR provides higher resolution than (1)H NMR. However, due to the lower sensitivity and longer relaxation time, (13)C NMR experiment takes much longer time to obtain a spectrum with adequate signal-to-noise ratio. The sensitivity can be enhanced with DEPT and INEPT approaches by transferring polarization from (1)H (I) to (13)C (S), but since the enhancements depend on coupling constants ( (1) J SI) and spin systems (SI, SI 2, SI 3), the enhancements for different spin systems are not uniform and quantitative analyses are seriously affected. To overcome these problems, Henderson proposed a quantitative DEPT (Q-DEPT) method by cycling selected read pulse angles and polarization-transfer delays (Henderson, T. J. J. Am. Chem. Soc. 2004, 126, 3682-3683), and satisfactory results for SI system are achieved. However, the optimization is incomplete for the SI 2 and SI 3 systems. Here, we present an improved version of Q-DEPT (Q-DEPT (+)) and a quantitative POMMIE (Q-POMMIE) where the cyclic delays and read pulse phases are applied. The improved methods prove to be suitable for all spin systems over a large J-coupling range (90-230 Hz), and the (13)C signals are nearly equally enhanced with standard deviation less than 5%.     

氟乙烷热力性质研究

介绍了氟乙烷HFC-161热力性质的研究进展,包括p-v-T性质、饱和蒸气压和饱和气液密度实验数据发表情况.结合饱和热力性质研究成果,给出了HFC-161的饱和蒸发焓关联式.     

C60H18, C60H36 and C70H36 Fullerene Hydrides: Study by Methods of IR,NMR, XPS,EELS and Magnetochemistry

Abstract

Fullerene hydrides of C₆₀H₁₈, C₆₀H₃₆ and C₇₀H₃₆ are studied by using IR, ¹H and ¹³C NMR, X-ray photoelectron and electron energy loss spectroscopies, and magnetochemistry. The comparison of IR and solid state ¹H and ¹³C NMR data for C₆₀H₃₆ with the theoretical ones allows the suggestion that fullerene hydride has a T symmetric structure and contains 4 isolated benzenoid rings located at tetrahedral positions on the surface of a closed skeleton of the molecule. The EELS revealed that the transition from fullerene to the hydride is accompanied by the decrease of the density of valence electrons. Magnetization measurements showed C₆₀H₃₆ to be a ferromagnet. The hydrogenated fullerenes were prepared by transfer hydrogenation procedures involving 9,10-dihydroanthracene. The compositions of the hydrides are determined by field desorption mass-spectral analysis.     

C60H18, C60H36 and C70H36 Fullerene Hydrides: Study by Methods of IR, NMR, XPS, EELS and Magnetochemistry

Fullerene hydrides of C₆₀H₁₈, C₆₀H₃₆ and C₇₀H₃₆ are studied by using IR, ¹H and ¹³C NMR, X-ray photoelectron and electron energy loss spectroscopies, and magnetochemistry. The comparison of IR and solid state ¹H and ¹³C NMR data for C₆₀H₃₆ with the theoretical ones allows the suggestion that fullerene hydride has a T symmetric structure and contains 4 isolated benzenoid rings located at tetrahedral positions on the surface of a closed skeleton of the molecule. The EELS revealed that the transition from fullerene to the hydride is accompanied by the decrease of the density of valence electrons. Magnetization measurements showed C₆₀H₃₆ to be a ferromagnet. The hydrogenated fullerenes were prepared by transfer hydrogenation procedures involving 9,10-dihydroanthracene. The compositions of the hydrides are determined by field desorption mass-spectral analysis.     

Effects of high magnetic field on thermodynamic properties of pure Fe and Cu

By the use of PPMS (Physics Property Measurement System), specific heat values of pure Cu at 2–300 K were determined under the magnetic field of 0, 3, 6 and 9 T, respectively. Magnetization curves of pure Fe under the magnetic field of 0–9 Twere obtained at different temperature ranging from 5 to 300 K. Analyses of the experimental results indicate that below 300 K, magnetic fields have no effects on the specific heat values of diamagnetic Cu and very little effects on those of ferromagnetic Fe.     

Effects of prestrain on the fracture properties of pressure vessel steel

In this paper, various methods have been used to measure the effects of prestrain on the fracture toughness of 20 g steel experimentally. Based on elastic-plastic FEM analysis, the relationships between crack tip opening displacement _T and the maximum strain _maxc have been obtained and the effects of prestrain _p on the critical fracture strain _maxc have been examined. At the same time, based on the Rice-Tracey's void growth model [4], the cause of the void formation ahead of the crack tip, the condition of the principal crack propagation and the effects of prestrain _p on the fracture properties of 20 g steel were investigated. For ductile material there was a maximum value of V _G ahead of the crack tip that was the cause of the void formation in that place. It is believed that when the maximum value of V _G ahead of the crack tip reaches a critical value, it may be the principal crack propagating condition for high ductile material.     

Quantitation in the solid-state 13C NMR analysis of soil and organic soil fractions

13C CP-MAS and DP-MAS spin-counting experiments have been carried out on an absolute basis for a specific whole soil and its humin, humic acid, and fulvic acid fractions, as well as a sample of the soil that was treated with 2% HF(aq). The results confirm previous conclusions that a substantial fraction of the carbon content indicated by classic elemental analysis is missed in some samples, especially whole soil and humin, by both CP-MAS and DP-MAS 13C NMR methods, and that the problem is more serious for CP-MAS than for DP-MAS. This study also confirms the fact that treatment of soil organic matter with 2% HF(aq) dramatically reduces this problem but may generate some structural uncertainties associated with significant structural alterations that accompany the HF(aq) treatment, as indicated by the 13C NMR data. The relationship between the "missing carbon" problem and the concentration of paramagnetic centers, especially Fe(III) centers, is explored in substantial detail.