Evaluation of dew-water density by the Monte Carlo method

To construct a physical model of water vapor condensation with the formation of dew water, a geometrically based Monte Carlo method was developed. The hit and geometrical density functions of random space filling with identical spheres were determined. The parameters of these functions is the minimum allowable approach OO _min of spheres and their excess in comparison with the space capacity. The specificity of dew-water molecules and hydrogen bonds (HBs) between them appears at 2/3L _b < OO _min < 2L _b, where L _b is the HB length. As the approach OO _min = L _b, the random filling density does not exceed the packing density in the sphere models of I _h and I _c ices. The densities characteristic of the sphere model of water molecule packing in these ices are achievable at OO _min ≈ 0.8L _b and/or a significant HB kink, as well as at vapor supersaturation (excess of molecules over the space capacity).     

Melt crystalfization and crystal morphology of two low molecular weight linear polyethylene fractions

Melt-crystallization behavior and single-crystal morphology of two low molecular weight (LMW) linear polyethylene (PE) fractions of 3900 and 5800 have been investigated. Linear growth rates along the b axis (G _b) of these fractions were measured via polarized light microscopy (PLM). The two fractions show a growth rate change at an undercooling of 17°C (at 117°C and 120°C, respectively, for these two fractions), which may be identified as the regime I/II transition. This transition does not correspond to a single-crystal morphological change from a truncated lozenge with curved (200) and (110) planes to a lenticular crystal as proposed previously. However, this morphological change can be observed at a temperature higher than the regime transition (at 122°C and 124°C), at which the cusps of the G _b data can be observed for these two fractions. Based on our morphological study via PLM, transmission electron microscopy, electron diffraction, small-angle x-ray scattering (SAXS), and differential scanning calorimetry (DSC) experiments, it is found that within a 2°C temperature region, the G _b change is accompanied by a sharp long period increase and a drastic change in single-crystal morphology from a truncated lozenge with curved (200) and (110) planes to a lenticular-shape crystal. The morphological change may result from a sudden increase in the G _b coupled with a smaller change in the growth rate along the a axis with undercooling. This implies that, within this temperature region (2°C), the crystals may undergo substantial changes in the geometry of the (110) and (200) crystal growth fronts and chain folding behavior.     

3d Monte Carlo simulation of site-bond continuum percolation of spheres

We present off-lattice Monte Carlo simulations of site-bond percolation of semi-penetrable spheres or, equivalently, of hard spheres with a finite bond range. We will show that the crucial parameter is the effective volume fraction ( φ_e), i.e. the volume that is occupied or within the bond range of at least one particle. For the equivalent system of semi-penetrable spheres 1 - φ_e is the porosity. The bond percolation threshold (p _b) can be described in terms of φ_e by a simple analytical expression: log(φ_e)/log(φ_ec) + log(p _b)/log(p _bc) = 1, with p _bc = 0.12 independent of the bond range and φ_ec a constant that decreases with increasing bond range. Received: 10 March 2003 / Accepted: 23 April 2003 / Published online: 21 May 2003 RID="a" ID="a"e-mail: jean-christophe.gimel@univ-lemans.fr     

Proton NMR relaxation in albumin solutions doped with Mn(II)

The aim of this study is to obtain further information about the source of proton relaxation in the Mn(II)-human serum albumin complex. For this purpose, proton relaxation rates in albumin solutions 1/T ₁ and 1/T ₂ were measured versus increasing amounts of manganese [Mn_t]. The fractions of manganese bound to albumin [Mn_b] and free manganese [Mn_f] were then determined from proton relaxation rate enhancement data. Paramagnetic contributions of bound manganese to the observed relaxation rates (1/T _1p^*)_b and (1/T _2p^*)_b were also determined. Finally, the (1/T _2p^*)_b/(1/T _1p^*)_b ratio was used in a derived equation to estimate an effective correlation time τ. Mean τ value of the complex was found to be in the order of 3 ns, while the hydration number of bound manganese q was estimated to be about 4. The 1/τ was found to be the sum of the inverse values of rotational correlation time 1/τ _r, mean residence time of water in hydration spheres of the complex 1/τ _m, and longitudinal electronic relaxation time of manganese 1/τ _s in the complex. In conclusion, the relaxation mechanism in albumin solutions containing Mn(II) can be interpreted through dipolar and scalar interactions modulated by τ _r, τ _m and τ _s. This analysis enables one to get reasonable figures for the τ _r and q of Mn(II) in albumin solution.     

Two Hard Spheres in a Spherical Pore: Exact Analytic Results in Two and Three Dimensions

The partition function and the one- and two-body distribution functions are evaluated for two hard spheres with different sizes constrained into a spherical pore. The equivalent problem for hard disks is addressed too. We establish a relation valid for any dimension between these partition functions, second virial coefficient for inhomogeneous systems in a spherical pore, and third virial coefficients for polydisperse hard spheres mixtures. Using the established relation we were able to evaluate the cluster integral b ₂(V) related with the second virial coefficient for the Hard Disc system into a circular pore. Finally, we analyse the behaviour of the obtained expressions near the maximum density.     

Permeability of mixed soft and hard granular material: Hydrogels as drainage modifiers

We measure the flow of water through mixed packings of glass spheres and soft swellable hydrogel grains, at constant sample volume. Permeability values are obtained at constant sample volume and at porosities smaller than random close packing, for different glass bead diameters D and for variable gel grain diameter d, as controlled by the salinity of the water. The gel content is also varied. We find that the permeability decays exponentially in n(D/d ) ^b , where n = N _gel/N _glass is the gel to glass bead number ratio and b is approximately 3. Therefore, flow properties are determined by the volume fraction of gel beads. A simple model based on the porosity of overlapping spheres is used to account for these observations.     

Preparation and photocatalytic activity of nitrogen-doped TiO2 hollow nanospheres

TiO₂ hollow nanospheres were prepared using silicon oxide as a template. N-doped titanium oxide hollow spheres, TiO_2−xN_x were synthesized by reacting TiO₂ hollow spheres with thiourea at 500 °C. XRD and XPS data showed that oxygen was successfully substituted by nitrogen through the nitrogen-doping reaction, and finally N-doped TiO₂ hollow spheres were formed. The N-doped TiO₂ hollow spheres showed new absorption shoulder in visible light region so that they were expected to exhibit photocatalytic activity in the visible light. The photocatalytic activity of N-doped TiO₂ hollow spheres under visible light was similar to that of normal spherical TiO_2−xN_x in spite of the structural difference.     

Third virial coefficient for quantum hard spheres: Two-point Padé approximants for direct and exchange parts

The method of two-point Padé approximants is used to interpolate between the low-temperature and high-temperature expansions of the second and third cluster integrals (b ₂ andb ₃) of a quantum hard-sphere gas.b ₂ is used as a test case, since accurate numerical values are available. Using only a limited number of terms from the series (about as many as are available forb ₃), we are able to represent both the direct and exchange parts to better than 1% over the entire temperature range. Forb ₃ there are no accurate values available, but the qualitative similarity of the results to those forb ₂ leads us to believe that we have a reasonably good representation of both the direct and exchange parts ofb ₃.     

Viscosity at small scales in polymer melts

Flows around small colloidal particles of diameter b, or in thin films, capillaries, etc., cannot always be described in terms of the macroscopic polymer viscosity. We discuss these features for entangled polymer melts, where two distinct regimes can be found: (a) the thin regime where b is smaller than the coil radius R₀, but larger than the diameter of the Edwards tube; (b) the ultrathin regime, where . We consider (i) non adsorbing particles, where slippage may occur between the melt and the solid surface; (ii) “hairy” particles, which carry some bound polymer chains. We obtain scaling predictions for mobilities of spheres, of needles, and of clusters of particles. We also discuss translational and rotational diffusion of needles. Received 19 April 1999     

Viscoelastic behaviour of fluids with steeply repulsive potentials

We analyse the shear stress, C _s(t) and pressure or ‘bulk’, C _b(t) time-correlation functions for steeply repulsive inverse power fluids (SRP) in which the particles interact via a pair potential with the analytic form, φ(r) = ε(σ/r) ⁿ , in a new approach to the understanding of their viscoelastic properties. We show analytically, and confirm by molecular dynamics simulations, that close to the hard-sphere limit both these time-correlation functions have the analytic form, C _s(t)/C _s(0) and C _b(t)/C _b(0) = 1 – T*(nt*)²+ O((nt*)⁴), where T* = k _B T/ε, is the reduced temperature, k _B is Boltzmann's constant and t* = (ε/mσ²)^½ t is the reduced time. This leads to an alternative and much simpler derivation of formulae for the shear and bulk viscosities which for the limiting case of hard spheres are numerically very close to the traditional Enskog relations. These simple relations for the finite and continuous SRP interaction are in satisfactory agreement with the essentially exact molecular dynamics simulation results for ca. n ≥ 18.     

High-temperature exchange third virial coefficient for hard spheres via an asymptotic method for path integrals

The exchange part of the third cluster integral can be divided into two parts:b ₃(exch-1), which arises from the exchange of two particles, andb ₃(exch-2), which arises from the cyclic exchange of all three particles. The first few terms ofb ₃(exch-1) are calculated by arguing thatb ₃(exch-1) =-[9a³/(4³)]b₂(exch)[1 + O(/a)], whereb ₂(exch) is the exchange second cluster integral, is the thermal de Broglie wavelength, anda is the hardsphere diameter. The first three terms ofb ₃(exch-2) are calculated by writing it in path integral form and expanding about the shortest path.     

亚微米聚苯乙烯微球在气-液界面组装的机理研究

系统地研究了亚微米聚苯乙烯微球在气-液界面的组装机理.聚苯乙烯微球在介质对流的带动下会到达悬浮液的表面并在气-液界面组装，气-液界面处聚苯乙烯微球间由弯液面产生的毛细管力是组装的推动力.界面处聚苯乙烯微球在干燥过程中其润湿性发生了转变，由完全润湿到部分润湿并最终变成不润湿，相应的聚苯乙烯微球与分散介质间接触角也逐渐增大.研究表明，只有接触角达到或超过某数值θ′_critical时，才能够出现气-液界面组装现象.考虑到PS胶粒晶体的表面是“规则”粗糙的表面，由Wenzel公式知θ′_critical大于测量值θ＝22°.聚苯乙烯微球润湿性的转变是界面组装发生和持续进行的关键性因素. 关键词： 自组装 胶粒晶体 聚苯乙烯微球 润湿性     

Effect of strain-induced order-parameter coupling on the ferroelastic behaviour of lead phosohate-arsenate

The phase diagram of ferroelastic Pb₃(PO₄)₂-Pb₃(AsO₄)₂ has been reinvestigated and four new phase transitions have been found from birefringence measurements at low temperatures. The first-order phase transition between the phases b (C2/c) and c (P2₁/c) in Pb₃(AsO₄)₂ becomes continuous with increasing P-content.

In Pb₃(P_0.2As_0.8O₄)₂, a monoclinic intermediate phase b_c was identified from the measurements of the spontaneous strain, the morphic birefringence and the orientation of the optical indicatrix.

The experimental results are interpreted using the Landau theory of biquadratically coupled order parameters. Phase b is related to an order parameter of L-point symmetry in the paraelastic phase a (3). The phase c is due to a critical F-point in 3. The intermediate phase b_c is the consequence of the biquadratic coupling of order parameters with L-and F-point symmetry.

Model calculations for Pb₃(P_0.2As_0.8O₄)₂ relate the free energies of the phases b, b_c and c and the temperature dependence of the order parameters with the measured optical birefringence. They explain well the occurrence of an intermediate phase with monoclinic symmetry from the movement of the thermodynamic stability point in the vector space diagram of order parameters.     

亚微米聚苯乙烯微球在气-液界面组装的机理研究

系统地研究了亚微米聚苯乙烯微球在气-液界面的组装机理.聚苯乙烯微球在介质对流的带动下会到达悬浮液的表面并在气-液界面组装，气-液界面处聚苯乙烯微球间由弯液面产生的毛细管力是组装的推动力.界面处聚苯乙烯微球在干燥过程中其润湿性发生了转变，由完全润湿到部分润湿并最终变成不润湿，相应的聚苯乙烯微球与分散介质间接触角也逐渐增大.研究表明，只有接触角达到或超过某数值θ′_critical时，才能够出现气-液界面组装现象.考虑到PS胶粒晶体的表面是“规则”粗糙的表面，由Wenzel公式知θ′_critical大于测量值θ＝22°.聚苯乙烯微球润湿性的转变是界面组装发生和持续进行的关键性因素. 关键词： 自组装 胶粒晶体 聚苯乙烯微球 润湿性     

Application of Inverse Laplace Transformation Method for Analysis of Plasma Emission Formed by Laser Ablation of Pb‐Bi‐Sr‐Ca‐Cu‐O

The inverse Laplace transformation method was used to interpret the time‐resolved emission spectra of Sr* and describe the dynamics of the laser plume formed in the laser ablation of Pb‐Bi‐Sr‐Ca‐Cu‐O. Three kinds of processes characterized by rate constants b₁, b₂ and b₃ were found in the laser plume. The rate constant of the slowest process b₃ increases with the pressure and can be assigned to deexcitation of Sr*. The next two rate constants b₁ and b₂ describe processes occurring during the laser pulse and immediately after it.     

Stimulated Raman spectra of a strong bichromatic field interacting with a three-level atom

We have studied the stimulated Raman spectra arising from the interaction of a three-level atom with two strong electromagnetic fields whose initially populated modes ω _a and ω _b are in resonance with the two atomic transition frequencies. The Green's function formalism has been used in the limit of high photon densities to calculate the excitation spectra near the frequencies ω = ± ω _ab = ± (ω _a - ω _b ). Expressions are derived for the relative intensities, which describe, apart from the usual Raman peak at the frequency ω = ω _ab , four pairs of lorentzian lines peaked at the frequencies ω - ω _ab = ± Ω _a /√2, ± Ω _b /√2, ± Ω and ± 2Ω, respectively, and having spectra widths of the order of 3γ₀/4. The parameter Ω is defined as Ω² = (Ω _a ² + Ω _b ²)/2, where Ω _a and Ω _b are the Rabi frequencies of the two laser fields and γ₀ is the spontaneous emission probability. Numerical calculations for selected values of the Rabi frequencies are graphically presented and discussed. Conditions have been established for which Raman gain processes are anticipated to take place.     

Electrocatalytically Active Hollow Carbon Nanospheres Derived from PS‐b‐P4VP Micelles

A facile method using polystyrene‐b‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) micelles is demonstrated to synthesize N/FeN₄‐doped hollow carbon nanospheres (N/FeN₄‐CHNS) with high electrocatalytic activity for oxygen reduction reactions (ORRs). Uniform spherical micelles with PS core and P4VP shell are prepared by exposing PS‐b‐P4VP in a mixture of ethanol/tetrahydrofuran. Pyridinic N in shell cooperates with Fe³⁺ to induce an in situ polymerization of pyrrole. Tuning molecular composition of PS‐b‐P4VP can form hollow carbon spheres with controlled size down to sub‐100 nm that remains challenge using traditional hard template strategies. N/FeN₄‐CHNS possesses a series of desirable properties as electrode materials, including easy fabrication, high reproducibility, large surface area, and highly accessible porous surface. This electrocatalyst exhibits excellent ORR activity (onset potential of 0.976 V vs reversible hydrogen electrode (RHE) and half‐wave potential of 0.852 V vs RHE), higher than that of commercial Pt/C (20 wt%) in an alkaline media, and shows a good activity in an acidic media as well. In addition to its higher stability and methanol tolerance than Pt/C in both alkaline and acidic electrolytes, highly competitive single cell performance is achieved in a proton exchange membrane fuel cell. This work provides a general approach to preparing functionalized small hollow nanospheres based on self‐assembly of block copolymers.     

Computer simulation of cavity pair distribution functions of hard spheres in a hard slit pore

We describe efficient Monte Carlo computer simulation techniques to calculate conditional distribution functions for pairs of hard-sphere (HS) cavities in a hard slit pore of width L, n* (z ₁,z ₂,r), and use these as an efficient route to calculating the corresponding dimensionless excess chemical potentials μ ^e (z ₁,z ₂,r). z_i is the distance of an HS centre from a (specified) wall and r is the distance between the cavity centres. This is the first calculation of such functions, which are of interest in their own right and provide data for the testing of theories, in addition to providing data for a simple model for the infinite dilution behaviour of a polyatomic solute in a simple molecularly confined solvent. Results are presented for special cases for the cavity functions n* (z ₁,z ₂,r) which occur when the spheres are in the same plane, when the line of sphere centres is perpendicular to the walls, and when the spheres are in contact. We compare results obtained using the Kirkwood superposition approximation in conjunction with results obtained from the computer simulation data using the first member of the BGY integral equation hierarchy. The approximation is found to be exact in certain limiting geometrical situations, but in general is quantitatively poor.     

Acid Synthesis of Luminescent Amine-functionalized or Erbium-doped Silica Spheres for Biological Applications

In this work we discuss and investigate the morphological and optical properties of luminescent silica spheres which can have interesting applications in bioimaging and biosensing. The spheres are synthesized following an acid route by the hydrolysis and condensation of tetraethylortosilicate (TEOS) and can be functionalized by incorporation of aminopropyl-triethoxysilane (APTES) during the synthesis, inducing a significant luminescence that can be attributed to a recombination mechanism from localized organic defects related to –NH₂ groups. It is shown that the acid synthesis route produces very regular spherical particles, but their diameter vary in the range of 200–4,000 nm. The luminescence properties have been investigated and optimized by variation of the annealing temperature for the functionalized spheres, obtaining the most efficient PL emission after a thermal treatment of 1 h at 600 °C in air. Moreover, the possibility to introduce rare earths like erbium in the spheres was also studied and the corresponding Er³ luminescence emission at 1.53 μm is reported in terms of intensity and lifetime, pointing out that erbium can be easily and efficiently incorporated during the acid synthesis giving high PL intensity with a good lifetime of 3.9 ms.     

掺Gd3+钼酸盐AMoO4 (A=Ca,Sr, Ba,Pb)自旋哈密顿参量的理论计算

采用基于单电子晶体场机制的对角化能量矩阵方法, 计算了Gd³⁺在钼酸盐AMoO₄ (A=Ca, Sr, Ba, Pb)晶体中的自旋哈密顿参量(g因子g_//, g_⊥和零场分裂b₂⁰, b₄⁰, b₄⁴, b₆⁰, b₆⁴). 矩阵中的晶体场参量采用重叠模型计算. 计算结果显示, 应用三个合理的可调参量[即重叠模型中的内禀参量A₂ (R₀), A₄ (R₀)和A₆ (R₀)], 计算的七个自旋哈密顿参量与实验结果符合甚好, 表明该方法可用于计算或解释Gd³⁺在晶体中的自旋哈密顿参量. 关键词： AMoO₄ (A=Ca,Sr,Ba,Pb):Gd³⁺晶体')" href="#">AMoO₄ (A=Ca,Sr,Ba,Pb):Gd³⁺晶体 自旋哈密顿参量 晶体场理论 对角化能量矩阵