Bipolar Electrochemical Synthesis of WS2 Nanoparticles and Their Application in Magneto‐Immunosandwich Assay

WS₂ nanoparticles are prepared using bipolar electrochemistry. Obtained material exhibits high activity for hydrogen evolution reaction (HER) and it is used as a label in standard magneto‐immunosandwich assay for protein detection through HER. This new system shows high analytical performance in terms of a wide range, selectivity, sensitivity, and reproducibility.     

Identification of viscoelastic C-S-H behavior in mature cement paste by FFT-based homogenization method

A powerful and robust numerical homogenization method based on fast Fourier transform (FFT) is formulated to identify the viscoelastic behavior of calcium silicate hydrates (C-S-H) in hardened cement paste from its heterogeneous composition. The identification is contingent upon the linearity of the creep law. To characterize cement paste microstructure, the model developed by Bentz at the National Institute of Standards and Technology, which has the resolution of 1 μm, is adopted. Model B3 for concrete creep is adapted to characterize the creep of C-S-H in cement paste. It is found that the adaptation requires increasing the exponent of power law asymptote of creep compliance. This modification means that the rate of attenuation of creep with time is lower in C-S-H than in cement paste, and is explained by differences in stress redistribution. In cement paste, the stress is gradually transferred from the creeping C-S-H to the non-creeping components. The viscoelastic properties of C-S-H at the resolution of 1 μm were identified from creep experiments on cement pastes 2 and 30 years old, having the water-cement ratio of 0.5. The irreversible part of C-S-H creep, obtained from these old specimens at almost saturated state, is found to be negligible unless the specimens undergo drying and resaturation prior to the creep test.     

Macroscopic fracture characteristics of random particle systems

This paper deals with determination of macroscopic fracture characteristics of random particle systems, which represents a fundamental but little explored problem of micromechanics of quasibrittle materials. The particle locations are randomly generated and the mechanical properties are characterized by a triangular softening force-displacement diagram for the interparticle links. An efficient algorithm, which is used to repetitively solve large systems, is developed. This algorithm is based on the replacement of stiffness changes by inelastic forces applied as external loads. It makes it possible to calculate the exact displacement increments in each step without iterations and using only the elastic stiffness matrix. The size effect method is used to determine the dependence of the mean macroscopic fracture energy and the mean effective process zone size of two-dimensional particle systems on the basic microscopic characteristics such as the microscopic fracture energy, the dominant inhomogeneity spacing (particle size) and the coefficients of variation of the microstrength and the microductility. Some general trends are revealed and discussed.Walter P. Murphy Professor of Civil Engineering and Materials Science.     

Choice of standard fracture test for concrete and its statistical evaluation

The main characteristics of the cohesive (or fictitious) crack model, which is now generally accepted as the best simple fracture model for concrete, are (aside from tensile strength) the fracture energies G _F and G _f corresponding to the areas under the complete softening stress-separation curve and under the initial tangent of this curve. Although these are two independent fracture characteristics which both should be measured, the basic (level I) standard test is supposed to measure only one. First, it is argued that the level I test should measure G _f, for statistical reasons and because of relevance to prediction of maximum loads of structures. Second, various methods for measuring G _f (or the corresponding fracture toughness), including the size effect method, the Jenq-Shah method (TPFM), and the Guinea et al. method, are discussed. The last is clearly the most robust and optimal because: (1) it is based on the exact solution of the bilinear cohesive crack model and (2) necessitates nothing more than measurement of the maximum loads of notched specimens of one size, supplemented by tensile strength measurements. Since the identification of material fracture parameters from test data involves two random variables, f_t (tensile strength) and G _f, statistical regression should be applied. But regression is not feasible in the original Guinea et al.'s method. The present study proposes an improved version of Guinea et al.'s method which reduces the statistical problem to linear regression thanks to exploiting the systematic trend of size effect. This is made possible by noting that, according to the cohesive (or fictitious) crack model, the zero-size limit _N0 of nominal strength _N of a notched specimen is independent of F _f and thus can be easily calculated from the measured f_t. Then, the values of _N0 obtained from the measured f_t values, together with the measured _N-values of notched specimens, are used in statistical regression based on the exact size effect curve calculated in advance from the cohesive crack model for the chosen specimen geometry. This has several advantages: (1) the linear regression is the most robust statistical approach; (2) the difficult question of statistical correlation between measured f_t and the nominal strength of notched specimens is bypassed, by virtue of knowing the size effect trend; (3) the resulting coefficient of variation of mean G _f is very different and much more realistic than in the original version; (4) the coefficient of variation of the deviations of individual data from the regression line is very different from the coefficient of variation of individual notched test data and represents a much more realistic measure of scatter; and (5) possible accuracy improvements through the testing of notched specimens with different notch lengths and the same size, or notched specimens of different sizes, are in the regression setting straightforward. For engineering purposes where high accuracy is not needed, the simplest approach is the previously proposed zero-brittleness method, which can be regarded as a simplification of Guinea et al.' method. Finally, the errors of TPFM due to random variability of unloading-reloading properties from one concrete to another are quantitatively estimated.     

Thermodynamic Properties of He@C60

Abstract

Contributions to thermodynamic properties of the endohedral He@C₆₀, resulting from motion of He inside the cage, are calculated. The contribution to C _v shows a maximum at low temperatures. The maxima for ³He@C₆₀ and ⁴He@C₆₀ are at about 41 K and 30 K, respectively.     

Computations on Metallofullerenes Derivatized during Extraction: La@C80-C6H3Cl2 and La@C82-C6H3Cl2

Recently, an extraction of la metallofullerenes from soot using 1,2,4-trichlorobenzene has been reported for La@C₈₀ and La@C₈₂. In both cases, the cages were derivatized by the solvent (forming La@C₈₀-C₆H₃Cl₂ and La@C₈₂-C₆H₃Cl₂) and the following X-ray analysis disclosed rather unexpected cages: C₈₀(C _2v ;3) and C₈₂(C _3v ;7). In order to explain the challenging observations, a two-step computational treatment is presented. The first step deals with the high-temperature gas-phase formation of the underivatized endohedrals while the second step models the reaction with the solvent. The Gibbs free energies were evaluated for representative temperatures and the computational scheme was able to confirm high relative populations for the observed derivatized cages.     

Changes in the NPL orifice conductance on a transition from molecular gas flow to transitional flow

The conductance of an NPL orifice in the molecular regime is constant and can be exactly calculated from the geometric dimensions. For smaller Knudsen numbers the conductance increases and correction functions are employed to reduce the uncertainty in this range of pressures. The conductance is also constant in the viscous regime during flow into a vacuum and can also be calculated. A suitable function has been chosen with one free parameter, which is constant for both very low and sufficiently high pressures and the parameter was determined on the basis of the experimentally measured course of the conductance at the borderline between molecular and transitional flow. The function fits the experimental data very well and can be used to calculate the conductance of the orifice up to Knudsen number ≈1.     

Quantum-chemical model evaluations of thermodynamics and kinetics of oxygen atom additions to narrow nanotubes

This paper reports a computational study of oxygen additions to narrow nanotubes, a problem frequently studied with fullerenes. In fact, fullerene oxides were the first observed fullerene derivatives, and they have naturally attracted the attention of both experiment and theory. C60O had represented a long-standing case of experiment-theory disagreement, and there has been a similar problem with C60O2. The disagreement has been explained by kinetic rather than thermodynamic control. In this paper a similar computational approach is applied to narrow nanotubes. Recently, very narrow nanotubes have been observed with a diameter of 5 A and even with a diameter of 4 A. It has been supposed that the narrow nanotubes are closed by fragments of small fullerenes like C36 or C20. In this report we perform calculations for oxygen additions to such model nanotubes capped by fragments of D2d C36, D4d C32, and Ih C20 fullerenic cages (though the computational models have to be rather short). The three models have the following carbon contents: C84, C80, and C80. Both thermodynamic enthalpy changes and kinetic activation barriers for oxygen addition to six selected bonds are computed and analyzed. The lowest isomer (thermodynamically the most stable) is never of the 6/6 type, that is, the enthalpically favored structures are produced by oxygen additions to the nanotube tips. Interestingly enough, the lowest energy isomer has, for the D2d C36 and D4d C32 cases, the lowest kinetic activation barrier as well.     

Time lag in measuring pore humidity in concrete by a gage in finite cavity

Measurements of the relative humidity of water vapor in concrete are important for understanding, predicting and controlling the shrinkage and creep of concrete, as well as other processes such as the ASR. A sufficient time is required for the pore water to diffuse into (or out of) the gage cavity. To determine this time, the nonlinear partial differential equation of diffusion of moisture through concrete is solved numerically. The cavity is simplified as spherical and its volume is considered to be far smaller than the volume of surrounding concrete, which permits assuming spherical symmetry of the pore humidity field. The body of the surrounding concrete is assumed to be so large that the water escape into (or intake from) the cavity does not change the pore humidity in concrete appreciably. For the current measurement practice, the humidity difference between the concrete pores and the cavity is found to drop below the inevitable error of the gage after the lapse of about 24 h, and an acceptable error of about 1% is achieved in about 10 h. It is shown that extrapolation by a decaying power function of time can shorten this time to 2 h. A further shortening could be achieved by reducing the volume of the cavity, although any contact of the gage with the concrete must be avoided.