氧气在 PVDF 片材中扩散的分子动力学模拟

目的研究气体在PVDF片材中的扩散。方法采用分子动力学模拟方法研究了氧气在其片材中的扩散行为,得到氧气在PVDF片材中的扩散系数,并讨论了时间、聚合度、温度及残余压力对扩散系数的影响。结果模拟时间太短对模拟结果不利,应以大于1000 fs为宜。当聚合度由400增加到800时,扩散系数由4.77×10-6cm2/s下降到1.78×10-6cm2/s;当温度从298 K提高到303 K时,扩散系数由1.06×10-6cm2/s增加到1.42×10-6cm2/s;当残余压力由60 kPa增大到100 kPa时,扩散系数由7.07×10-6cm2/s下降到3.06×10-6cm2/s。结论氧气在PVDF片层中的扩散系数随聚合度和残余压力的增大而变小,随温度的提高而变大。     

Natural and artificial radioactivity measurements in Eastern Black Sea region of Turkey

In the present work, naturally occurring radionuclides of ²²⁶Ra, ²³²Th and ⁴⁰K were measured in soil samples collected from the Eastern Black Sea region of Turkey. It was found that the activity concentrations ranged from 12 to 120 Bq kg⁻¹ for ²²⁶Ra, from 13 to 121 Bq kg⁻¹ for ²³²Th and from 204 to 1295 Bq kg⁻¹ for ⁴⁰K. Besides naturally occurring radionuclides, ¹³⁷Cs activity concentration was measured in soil, lichen and moss samples and it was found that ¹³⁷Cs activity concentration ranged from 27 to 775 Bq kg⁻¹ with for soil, from 29 to 879 Bq kg⁻¹ for lichen and from 67 to 1396 Bq kg⁻¹ for moss samples. Annual effective doses due to the naturally occurring radionuclides and ¹³⁷Cs were estimated. Ecological half-lives of ¹³⁷Cs in lichen and moss species were estimated. The decrease of the activity concentrations in the present measurements (2007) relative to those in 1993 indicated ecological half-lives between 1.36 and 2.96 years for lichen and between 1.35 and 2.85 years for moss species.     

The influence of pH and bath composition on the properties of Ni–Co coatings synthesized by electrodeposition

Ni–Co coatings were produced on Cu substrates by electrodeposition from electrolytes with different pH values and different Co²⁺ concentration. The current efficiency increases from 52.1% to 81.2% with the pH increasing from 2.0 to 5.4. It is clearly observed that the content of cobalt in the deposited coatings gradually increases from 9.4% to 19.6% as the pH value varies from 2.0 to 5.4. The Co content in the deposited coatings increases from 16.5% to 72.7% as the molar ratio of CoSO₄/NiSO₄ varying from 1:5 to 1:2 in electrolyte. XRD patterns reveal that the structure of the coatings strongly depends on the Co content in the binary coatings. Both granular and dendritic crystals were investigated by SEM and the different crystallization behaviors were illustrated. The saturation magnetization of the coatings goes up from 96.36 kAm⁻¹ to 136.08 kAm⁻¹ with the pH value increasing from 2.0 to 5.4. The saturation magnetization (M_s) and coercivity (H_c) move up from 144.84 kAm⁻¹ and 15.27 kAm⁻¹ to 175.13 kAm⁻¹ and 125.20 kAm⁻¹ with the increase of Co in the electrolyte, respectively.     

The influence of pH and bath composition on the properties of Ni-Co coatings synthesized by electrodeposition

Ni-Co coatings were produced on Cu substrates by electrodeposition from electrolytes with different pH values and different Co²⁺ concentration. The current efficiency increases from 52.1% to 81.2% with the pH increasing from 2.0 to 5.4. It is clearly observed that the content of cobalt in the deposited coatings gradually increases from 9.4% to 19.6% as the pH value varies from 2.0 to 5.4. The Co content in the deposited coatings increases from 16.5% to 72.7% as the molar ratio of CoSO₄/NiSO₄ varying from 1:5 to 1:2 in electrolyte. XRD patterns reveal that the structure of the coatings strongly depends on the Co content in the binary coatings. Both granular and dendritic crystals were investigated by SEM and the different crystallization behaviors were illustrated. The saturation magnetization of the coatings goes up from 96.36 kAm⁻¹ to 136.08 kAm⁻¹ with the pH value increasing from 2.0 to 5.4. The saturation magnetization (M_s) and coercivity (H_c) move up from 144.84 kAm⁻¹ and 15.27 kAm⁻¹ to 175.13 kAm⁻¹ and 125.20 kAm⁻¹ with the increase of Co in the electrolyte, respectively.     

Radon exhalation rate measurement in the environment of Hassan district of southern India

The radon exhalation rate from soil and building materials collected from the Hassan district of southern India was studied by the sealed can technique. The surface exhalation rates of the building materials were found to vary from 13.07 ± 0.19 to 430 ± 9 mBq m^–2 h^–1 with a mean value of 141 ± 4 mBq m^–2 h^–1. The surface exhalation rates of the soil samples were found to vary from 36.5 ± 0.8 mBq m^–2 h^–1 to 376 ± 7 mBq m^–2 h^–1 with a mean value of 140 ± 4 mBq m^–2 h^–1. Good positive correlation was observed between the effective radium content and radon exhalation rate for both soil and building materials. Annual effective dose and α-index have also been estimated for the population of the region.     

Radon Exhalation Rate Study of Sand Samples Collected from Sea Coast of Tirur,Kerala, India Using Track Etch Technique

The sand samples have been collecting from the sea coast (Unniyal beach) of Tirur of Malappuram district of Kerala state (India) by the grab sampling method. Radon exhalation rates have measured by “Sealed Can Technique” using LR-115 type II plastic track detector to estimate the health risk level in the environment. The value of radon activity varies from 444.44 to 2204.44 becquerel meter^?3 (Bq m^?3) with a geometric mean (G.M.)/standard deviation (S.D.) value of 1017.21 Bq m^?3/433.27. The value of mass exhalation rate for radon varies from 0.01 to 0.05 Bq kg^?1 h^?1 with a G.M./S.D. value of 0.024 Bq kg^?1 h^?1/0.010. The value of area exhalation rate for radon varies from 0.27 to 1.33 Bq m^?2 h^?1 with a G.M./S.D. value of 0.62 Bq m^?2 h^?1/0.26. The values of radon emanation ranged from 2.90?×?10^?3 to 2.98?×?10^?3 (%) with a G.M./S.D. value of 2.98?×?10^?3(%)/0.05. The alpha dose equivalent of the studied area is found and it varies from 0.68 to 1.66 milli sievert year^?1 (mSv yr^?1) with a G.M./S.D. value of 1.03 mSv yr^?1/0.24. Good positive correlation is observed between the effective radium content and area exhalation rate for sand samples. Therefore, the obtained result shows that this region is safe as for as the health risk effects of radium and radon exhalation rate are concerned.     

Investigation of the transport properties of microcrystalline silicon by time-of-flight (TOF)

The transport properties of microcrystalline silicon have been studied by the time-of-flight technique on a 6.3-μm thick n-i-p solar cell illuminated from the p-side (n-side) to obtain electron (hole) current transients. The transients exhibit dispersive behavior. At room temperature, drift-mobility values of about 2–4 cm² V^?1 s^?1 and 2 cm² V^?1 s^?1 were deduced for electrons and holes, respectively. The dispersion parameters α₁ and α₂, as determined from the pre- and post-transit slopes of the current transients were similar to those for a-Si : H.     

Sorption of Pu and Np on chitin-containing materials from strongly alkaline solutions

Sorption of Pu and Np on chitin, chitosan, and chitin-containing materials from strongly alkaline (1–4 M NaOH) solutions was studied under the static and dynamic conditions in the presence of large amounts of NaNO₃. The Pu(IV) distribution coefficient (K _d) between the solutions with the NaOH concentration ranging from 1 to 4 M and different chitin-containing sorbents varies from 3000 to 6000 cm³ g^?1. The K _d of Np(V) with different sorbents decreases from 2000–4000 to 600–1200 cm³ g^?1 with increasing NaOH concentration.     

Thermal properties of MoSi2 and SiC whisker-reinforced MoSi2

The heat capacity, thermal conductivity and coefficient of thermal expansion of MoSi₂ and 18 vol % SiC whisker-reinforced MoSi₂ were investigated as a function of temperature. The materials were prepared by hot isostatic pressing between 1650 and 1700 °C, the hold time at temperature being 4 h. The heat capacity of MoSi₂ showed an increase from about 0.44 Wsg^–11K^–1 at room temperature to 0.53 at 700 °C. Whisker reinforcement increased heat capacity by about 10%. Thermal conductivity exhibited a decreasing trend from 0.63 Wcm^–1 K^–1 at room temperature to 0.28 Wem^–1 K^–1 at 1400°C. Whiskers reduced conductivity by about 10%. The thermal expansion coefficient increased from 7.42 °C^–1 between room temperature and 200 °C to 9.13 °C^–1 between room temperature and 1200 °C. There was a 10% decrease resulting from the whiskers. The measured data are compared with literature values. The trends in the data and their potential implications for high-temperature aerospace applications of MoSi₂ are discussed.     

Absolute Isotopic Abundance Ratios and Atomic Weight of a Reference Sample of Nickel

Absolute values have been obtained for the isotopic abundance ratios of a reference sample of nickel (Standard Reference Material 986), using thermal ionization mass spectrometry. Samples of known isotopic composition, prepared from nearly isotopically pure separated nickel isotopes, were used to calibrate the mass spectrometers. The resulting absolute isotopic ratios are: ⁵⁸Ni/⁶⁰Ni=2.596061±0.000728, ⁶¹Ni/⁶⁰Ni=0.043469±0.000015,⁶²Ni/⁶⁰Ni=0.138600±0.000045, and ⁶⁴Ni/⁶⁰Ni=0.035295±0.000024, which yield atom percents of ⁵⁸Ni=68.076886 ±0.005919, ⁶⁰Ni = 26.223146±0.005144,⁶¹Ni=1.139894±0.000433, ⁶²Ni =3.634528±0.001142, and ⁶⁴Ni =0.925546±0.000599. The atomic weight calculated from this isotopic composition is 58.693353 ±0.000147. The indicated uncertainties are overall limits of error based on two standard deviations of the mean and allowances for the effects of known sources of possible systematic error.     

Bidirectional Regulation of Singlet Oxygen Generation from Luminescent Gold Nanoparticles through Surface Manipulation

Singlet oxygen (¹O₂) generation has been observed from ultrasmall luminescent gold nanoparticles (AuNPs), but regulation of ¹O₂ generation ability from the nanosized noble metals has remained challenging. Herein, the ¹O₂ generation ability of ultrasmall AuNPs (d ≈ 1.8 nm) is reported to be highly correlated to the surface factors including the amount of Au(I) species and surface charge. By taking the advantages of facile in situ PEGylation, it is discovered that a high amount of Au(I) species and surface charge results in strong ability in generation of ¹O₂, whereas a relative low amount of Au(I) species and surface charge leads to weak ability in ¹O₂ production. A feasible general strategy is then developed to controllably regulate the ¹O₂ generation efficiency of the AuNPs through facile ligand exchange with positively‐charged or negatively‐charged thiolated ligands. The AuNPs as nanophotosensitizer for ¹O₂ generation in the cellular level is also demonstrated to be highly controllable through surface ligand exchange with synergistical effects of ¹O₂ generation ability and subcellular distribution to lysosome or mitochondria. The strategy in the bidirectional regulation of ¹O₂ generation from ultrasmall AuNPs provides guidance for future design of nanosized metal nanomedicine toward specific disease diagnosis and treatment.     

Sorption of strontium ions from solutions onto calcium and magnesium phosphates

A comparative study of the uptake of Sr ions from aqueous solutions with calcium and magnesium phosphates of various chemical compositions was made. Calcium and magnesium phosphates in the concentration range 10–5000 mg L^?1 absorb up to 280 mg g^?1 Sr, with the ability of magnesium phosphates to take up Sr ions exceeding that of calcium phosphates by an order of magnitude. The degree of decontamination of solutions from ⁹⁰Sr with the magnesium-containing samples exceeds 80%, and the distribution coefficient is (4.7–5.4) × 10³ cm³ g^?1.     

Characterization of the phosphatic mineral of the barnacle Ibla cumingi at atomic level by solid-state nuclear magnetic resonance: comparison with other phosphatic biominerals

Ibliform barnacles are among the few invertebrate animals harnessing calcium phosphate to construct hard tissue. The ³¹P solid-state NMR (SSNMR) signal from the shell plates of Ibla cumingi (Iblidae) is broader than that of bone, and shifted by ca 1 ppm to low frequency. ¹H–³¹P heteronuclear correlation (HETCOR) experiments show a continuum of different phosphorus/phosphate atomic environments, close to hydrogen populations with resonance frequencies between ca 10 and 20 ppm. Associated ¹H and ³¹P chemical shifts argue the coexistence of weakly (high ³¹P frequency, low ¹H frequency) to more strongly (lower ³¹P frequency, higher ¹H frequency) hydrogen-bonded hydrogen phosphate-like molecular/ionic species. There is no resolved signal from discrete OH⁻ ions. ¹³C SSNMR shows chitin, protein and other organic biomolecules but, unlike bone, there are no significant atomic scale organic matrix–mineral contacts. The poorly ordered hydrogen phosphate-like iblid mineral is strikingly different, structurally and compositionally, from both vertebrate bone mineral and the more crystalline fluoroapatite of the linguliform brachiopods. It probably represents a previously poorly characterized calcium phosphate biomineral, the evolution of which may have reflected either the chemical conditions of ancestral seas or the mechanical advantages of phosphatic biomineralization over a calcium carbonate equivalent.     

Deformation mechanism transition in Fe–17Mn–0.4C–0.06V TWIP steel with different strain rates

The dynamic tensile behaviour and deformation mechanism of the Fe–17Mn–0.4C–0.06V twinning-induced plasticity (TWIP) steel were investigated over a wide range of strain rates from 10^?4 to 10³ s^?1. With increasing strain rate, the stacking fault energy increased due to the increase of adiabatic heating temperature, ΔT. At 10^?4 to 10¹ s^?1, the transformation-induced plasticity (TRIP) effect coexisted with the TWIP effect and weakened with increasing strain rate. With the increase of strain rate in the range of 10^?1 to 10¹ s^?1, the TWIP effect strengthened gradually and intersected deformation twins were formed. When the strain rate was higher than 10¹ s^?1, the TRIP effect disappeared and the twinning was inhibited since the adiabatic heating effect elevated.     

Atomic carbon in magnesium oxide Part VII: Infrared analysis of OH-containing defects

The multitude of OH stretching bands in the near IR in arc-fused MgO can be divided into two main groups, a triangular shaped band at 3548 cm^?1 (300K) which strongly shifts and splits to a triplet at 3571, 3566 and 3550 cm^?1 upon cooling to 82 K, a quadruplet at 3297, 3312, 3327 and 3342 cm^?1 (82 K), plus a broad background absorption extending from 3600 – 3300 cm^?1. The H-H band at 4150 cm^?1 points at molecular H formed by charge transfer from [OH^· V″_Ma HO^·]^x = [O^· (H₂)″_Mg O^·]^x. The broad background absorption is assigned to interstitial protons, H^·₁. The 3300 and 3550 cm^?1 groups are assigned to the diamagnetic defects [OH^· V″_Ma]¹ and [OH^· V″_Mg HO^·]^x respectively. Their multiplet structure is explained by interaction of the OH oscillator with near-by C^x₁ atoms on interstitial sites surrounded by an elastic strain halo which causes local lattice expansion.     

Polyacrylonitrile-based electrospun nanofibers carrying gold nanoparticles in situ formed by photochemical assembly

Polyacrylonitrile (PAN) nanofibrous fabrics carrying gold nanoparticles (AuNPs) were prepared via the combination of electrospinning of PAN solution containing HAuCl₄ and in situ gold formation induced by ultraviolet (UV) irradiation. The factors to control the diameter of AuNPs were first investigated, and then their applicability to catalytic reaction using the obtained fibers was presented. The initial contents of Au ranging from 3 to 21 wt% did not exert a significant effect on the size of AuNPs formed in/on the PAN fibers, giving 4.7–5.4 nm in diameter, for 5 days of UV irradiation. On the other hand, the sizes of formed AuNPs were found to change from 5.2 to 2.7 nm with varying UV irradiation time from 5 to 1 day. The first-order rate constants obtained for the reduction of 4-nitrophenol increased from 1.1 × 10^?3, 3.5 × 10^?3 to 4.0 × 10^?3 s^?1, under a fixed volume of the fibers with AuNPs as catalysts, with increasing content of Au from 3, 13 to 21 wt%. The PAN catalysts with decreased size of AuNPs obtained through 1 day of UV irradiation gave a higher rate constant of 2.7 × 10^?2 s^?1. The highest rate constant per Au content and turnover frequency obtained in this study were 8.3 × 10^?2 s^?1 μmol-Au^?1 and 71 h^?1, respectively.     

Self‐Sorting of 10‐µm‐Long Single‐Walled Carbon Nanotubes in Aqueous Solution

Single‐walled carbon nanotubes (SWCNTs) are a class of 1D nanomaterials that exhibit extraordinary electrical and optical properties. However, many of their fundamental studies and practical applications are stymied by sample polydispersity. SWCNTs are synthesized in bulk with broad structural (chirality) and geometrical (length and diameter) distributions; problematically, all known post‐synthetic sorting methods rely on ultrasonication, which cuts SWCNTs into short segments (typically <1 µm). It is demonstrated that ultralong (>10 µm) SWCNTs can be efficiently separated from shorter ones through a solution‐phase “self‐sorting”. It is shown that thin‐film transistors fabricated from long semiconducting SWCNTs exhibit a carrier mobility as high as ≈90 cm² V^?1 s^?1, which is ≈10 times higher than those which use shorter counterparts and well exceeds other known materials such as organic semiconducting polymers (<1 cm² V^?1 s^?1), amorphous silicon (≈1 cm² V^?1 s^?1), and nanocrystalline silicon (≈50 cm² V^?1 s^?1). Mechanistic studies suggest that this self‐sorting is driven by the length‐dependent solution phase behavior of rigid rods. This length sorting technique shows a path to attain long‐sought ultralong, electronically pure carbon nanotube materials through scalable solution processing.     

Comparison of the quench rates attained in gas-atomized powders and melt-spun ribbons of Co- and Ni-base superalloys: influence on resulting microstructures

The cooling rates of gas-atomized Stellite 6 powders range from 10³ to 10⁶ K sec^–1 for 400 to 10m diameter powder particles, respectively. The microstructures vary from the equiaxed type in the coarser particles to dendritic and finally microcrystalline in the finer particles. In the melt-spun ribbons, the microstructure along a cross-section of the ribbon changes from microcrystalline at cooling rates higher than 10⁷ K sec^–1 to columnar dendritic at cooling rates of the order of 10⁶ K sec^–1.     

Whisker reinforcement of glass-ceramics

Silicon carbide whisker reinforcement of anorthite and cordierite glass ceramics has been studied. At 25 vol% whisker loading the flexural strengths increased from 65–103 MPa to 380–410 MPa, the fracture toughnesses increased from 1.0–1.5 MPa m^1/2 to 5.2–5.5 MPa m^1/2. The strengths decline to 240–276 MPa at 1200 °C. The reasons for the decrease in strength with temperature are discussed. Whiskers from two different sources with differences in diameters and aspect ratios were evaluated and the effect of the whisker morphology on the composite properties was studied. It was found that larger diameter, higher aspect ratio whiskers result in improved composite performance. The composites were also characterized in terms of their thermal properties, i.e. thermal expansions and thermal conductivities. The thermal expansion coefficient from 25–1000 °C for anorthite-based composite was 4.6×10^–6 °C^–1 and that for the cordierite-based composite was 3.62×10^–6 °C^–1. The thermal conductivities at 1000 °C were 3.75 and 4.1 Wm^–1 K^–1 for cordierite and anorthite composites, respectively.     

High-strain-rate superplasticity of SiC p /8090 aluminum composite

Superplastic tensile tests of a 17 vol.% SiC _p /8090 Al-Li composite were carried out at strain rates ranging from 7.25 × 10^-4 s^-1 to 3.46 × 10^-1 s^-1 and at temperatures from 773 K to 873 K. A maximum elongation of 300% was obtained at a strain rate of 1.83 × 10^-1 s^-1 when tested at a temperature of 848 K which was slightly above the solidus temperature of the composite. The effect of a small fraction of liquid phase on high-strain-rate superplasticity was discussed. Finally, the activation energy of high-strain-rate superplastic deformation was calculated and high-strain-rate superplastic mechanism was discussed.