电磁搅拌下低合金钢柱状晶向等轴晶转变准则(二)

在枝晶破碎理论基础上,讨论了电磁搅拌强度及合金元素碳、锰含量对钢凝固组织的影响。分析并获得了线性电磁搅拌下柱状晶向等轴晶转变(CET)的准则。观察到凝固过程中电磁搅拌产生的枝晶碎片,得到了临界固相分率、碳含量和液体平均流速之间的关系。发现低碳情况下,锰含量提高使CET更难;高碳情况下,锰含量提高对CET几乎没影响。     

A stochastic approach for continuous and discontinuous crack growth in polycarbonate under cyclic loading

This article presents a stochastic approach to predict fatigue crack propagation (FCP) diagrams of continuous crack growth (CCG) and discontinuous crack growth (DCG) in polycarbonate (PC) under cyclic loading. First, it is assumed that the macroscopic fatigue crack propagates stochastically. The transition probability is then expressed in conjunction with the craze fibril breakdown model for CCG. Second, the stochastic process is applied to DCG assuming that DCG occurs because of an unstable crack growth in the craze zone. A fracture criterion using a stress intensity factor is introduced for the unstable crack growth. As a result, we obtain an FCP diagram where the rate in CCG is lower than that in DCG. The stress intensity factor range for the DCG–CCG transition can be theoretically determined. Finally, to verify the present approach, the experimental data of DCG and CCG of PC are fitted to the Paris equation. In addition, the relationship between the DCG band size and the number of cycles required for DCG is predicted in order to compare it with the experiment data. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Absolute Mass and Size Measurement of Monodisperse Particles Using a Modified Millikan's Method: Part I—Theoretical Framework of the Electro-Gravitational Aerosol Balance

A new method for accurate mass and size measurement of monodisperse particles is proposed. In this method, charged aerosol particles are introduced into parallel plate electrodes similar to the Millikan cell, and the number of particles left suspended after a certainty holding time has elapsed is measured. The particle survival rate as a function of the voltage applied to the electrodes is used to determine the particle mass. The particle size is deduced by using the particle density which is determined in a separate experiment. The expression of the particle survival function, which is defined as the survival rate as a function of the mass, for particles with and without Brownian diffusion is derived. The sensitivity of this method to the number average diameter, as well as other size distribution parameters, is analyzed on the basis of the survival function.     

Development of a food frequency questionnaire to estimate habitual dietary intake in Japanese children

Background  

Food frequency questionnaires (FFQ) are used for epidemiological studies. Because of the wide variations in dietary habits within different populations, a FFQ must be developed to suit the specific group. To date, no FFQ has been developed for Japanese children. In this study, we developed a FFQ to assess the regular dietary intake of Japanese children. The FFQ included questions regarding both individual food items and mixed dishes.     

Controlling factors of the particle size of spherical silica synthesized by a dry process

Silica is an important inorganic compound used in many materials, including quartz products and resin fillers. To synthesize silica by a dry process, combustion methods using organosilicon compounds as raw monomers have been extensively studied. However, few studies have considered mass production or compared preparation methods using different types of organosilicon compounds and the same equipment. In this study, we used six starting materials in a dry process and examined the effect of monomer species on particle shape and size. The amount of raw monomer supplied was adjusted so that the calorific value of combustion was the same for all the raw monomers. We focused on the calorific value because it affects the construction cost of industrial-scale production plants. For example, when the calorific value is high, the manufacturing plant is large and costly because the heat generated after the reaction must be removed. We obtained spherical silica particles by a dry process using six monomers. The particle size depended on both the basic unit of the monomer and the required oxygen (RO) ratio of the primary burner gas. This combination was essential in determining the speed of the initial reaction, number of nuclei, and residence time. Consequently, we established a factor that determines the size of spherical silica particles and successfully adjusted the particle size.     

Synthesis of 3‐Aryl‐1‐trifluoromethyltetrahydroisoquinolines by Brønsted Acid‐Catalyzed C(sp3)?H Bond Functionalization

A concise route to 3‐aryl‐1‐trifluoromethyltetrahydroisoquinolines by a benzylic [1,5]‐hydride shift‐mediated C H bond functionalization was developed. The [1,5]‐hydride shift of the benzylic C(sp³) H bond to the trifluoromethylketimine derived from para‐anisidine occurred smoothly to produce cis‐1‐trifluoromethyl‐3‐aryltetrahydroisoquinolines in good to excellent chemical yields with good diastereoselectivities. In contrast, use of the N H ketimine furnished N‐unprotected tetrahydroisoquinolines in good yields in favor of the trans‐isomer.

     

Mechanisms of single-walled carbon nanotube nucleation, growth, and healing determined using QM/MD methods

Since their discovery in the early 1990s, single-walled carbon nanotubes (SWNTs) have spawned previously unimaginable commercial and industrial technologies. Their versatility stems from their unique electronic, physical/chemical, and mechanical properties, which set them apart from traditional materials. Many researchers have investigated SWNT growth mechanisms in the years since their discovery. The most prevalent of these is the vapor-liquid-solid (VLS) mechanism, which is based on experimental observations. Within the VLS mechanism, researchers assume that the formation of a SWNT starts with co-condensation of carbon and metal atoms from vapor to form liquid metal carbide. Once the liquid reaches supersaturation, the solid phase nanotubes begin to grow. The growth process is partitioned into three distinct stages: nucleation of a carbon "cap-precursor," "cap-to-tube" transformation, and continued SWNT growth. In recent years, molecular dynamics (MD) simulations have come to the fore with respect to SWNT growth. MD simulations lead to spatial and temporal resolutions of these processes that are superior to those possible using current experimental techniques, and so provide valuable information regarding the growth process that researchers cannot obtain experimentally. In this Account, we review our own recent efforts to simulate SWNT nucleation, growth, and healing phenomena on transition-metal catalysts using quantum mechanical molecular dynamics (QM/MD) methods. In particular, we have validated each stage of the SWNT condensation mechanism using a self-consistent-charge density-functional tight-binding (SCC-DFTB) methodology. With respect to the nucleation of a SWNT cap-precursor (stage 1), we have shown that the presence of a transition-metal carbide particle is not a necessary prerequisite for SWNT nucleation, contrary to conventional experimental presumptions. The formation and coalescence of polyyne chains on the metal surface occur first, followed by the formation of the SWNT cap-precursor, "ring condensation", and the creation of an sp(2)-hybridized carbon structure. In our simulations, the nucleation process takes approximately 400 ps. This first step occurs over a much longer time scale than the second stage of SWNT condensation (approximately 50 ps). We therefore observe SWNT nucleation to be akin to the rate-limiting step of the SWNT formation process. In addition to the QM/MD simulation of various stages of SWNT nucleation, growth, and healing processes, we have determined the effects of temperature, catalyst composition, and catalyst size on the kinetics and mechanism of SWNT growth. With respect to temperature dependence, we observe a "sweet-spot" with respect to the efficiency of SWNT growth. In addition, Ni-catalyzed SWNT growth is observed to be 70-100% faster compared to Fe-catalyzed SWNT growth, depending on the catalyst particle size. We also observe a noticeable increase in SWNT growth rates using smaller catalyst particles. Finally, we review our recent QM/MD investigation of SWNT healing. In particular, we recount mechanisms by which adatom defects, monovacancy defects, and a "5-7 defect" are removed from a nascent SWNT. The effectiveness of these healing mechanisms depends on the rate at which carbon moieties are incorporated into the growing SWNT. Explicitly, we observe that healing is promoted using a slower carbon supply rate. From this rudimentary control of SWNT healing, we propose a route towards chirality-controlled SWNT growth.     

Structure-selective recognition by voltammetry: enantiomeric determination of amines using azophenolic crowns in aprotic solvent

The enantiomeric recognition of amines by voltammetry using electroactive macrocyclic molecules, nitroazophenolic crown ethers, is reported. The oxidation potential of the nitroazophenol moiety in nitroazophenols with 18-crown-6 sensitively depends on the structure of alkyl amines. Based on this phenomenon, enantiomeric amines and even the quantitative assay of the R/S ratio in enantiomeric mixtures can be selectively recognized by using 18-crown-6 azophenol (3-H) with chiral centers. In the case of phenylglycinol, the association constants (K) of 3-H for the R and S forms have an R/S value of 3.5. The peak potential of the R form in square-wave voltammograms reproducibly differs from that of the S form by 32 mV, within which the peak potential linearly varies with the enantiomeric ratio. Free energy perturbation and molecular dynamics simulation provide deeper understanding of the enantiomeric recognition in this system. The theoretical analysis indicates that the free energy difference between diastereomeric complexes agrees well with the experimental results, and the pi-pi or charge-charge interaction plays a key role in enantiomeric recognition.     

Vibro-acoustography beam formation with reconfigurable arrays

In this work, we present a numerical study of the use of reconfigurable arrays (RCA) for vibro-acoustography (VA) beam formation. A parametric study of the aperture selection, number of channels, number of elements, focal distance, and steering parameters is presented to show the feasibility and evaluate the performance of VA imaging based on RCA. The transducer aperture was based on two concentric arrays driven by two continuous-wave or toneburst signals at slightly different frequencies. The mathematical model considers a homogeneous, isotropic, inviscid medium. The pointspread function of the system is calculated based on angular spectrum methods using the Fresnel approximation for rectangular sources. Simulations considering arrays with 50 x 50 to 200 x 200 elements with number of channels varying in the range of 32 to 128 are evaluated to identify the best configuration for VA. Advantages of two-dimensional and RCA arrays and aspects related to clinical importance of the RCA implementation in VA, such as spatial resolution, image frame rate, and commercial machine implementation, are discussed. It is concluded that RCA transducers can produce spatial resolution similar to confocal transducers and steering is possible in the elevational and azimuthal planes. Optimal settings for number of elements, number of channels, maximum steering, and focal distance are suggested for VA clinical applications. Furthermore, an optimization for beam steering based on the channel assignment is proposed for balancing the contribution of the two waves in the steered focus.