Calculation of impurity diffusivities in α-Fe using first-principles methods

Self- and impurity diffusivities in body-centered-cubic (bcc) iron have been calculated within the formalisms of harmonic transition-state theory and the Le Claire nine-frequency model for vacancy-mediated diffusion. The approach combines first-principles calculations of vacancy formation, migration, and solute-binding enthalpies and entropies in the ferromagnetic phase, with an empirical relationship for the effect of magnetic disorder on diffusion activation energies. Calculated Fe self-diffusion and Mo and W impurity-diffusion coefficients are shown to agree within a factor of five with the most recent experimental measurements in both the ferromagnetic and paramagnetic phases. Calculated diffusion coefficients for Mo and W impurities are comparable to or larger than that for Fe self-diffusion at all temperatures below the α–γ phase transition. Calculated activation energies for Ta and Hf impurities suggest that these solutes should also display impurity-diffusion coefficients larger than that for self-diffusion in body-centered cubic Fe.     

Roles of In-Situ Forming Hard Particles in a Zr-Based Bulk-Metallic Glass during Monotonic and Cyclic Loading

Zr₆₇Ni₂₀Cu₅Al₈ (in at. pct) is a bulk-metallic glass (BMG) with in-situ forming hard particles. Some crystalline particles can be observed in the polished beam samples under optical microscopy (OM). The hardness measurements show that these crystalline particles are harder than the matrix of Zr₆₇Ni₂₀Cu₅Al₈. The energy-dispersive spectroscopy (EDS) analyses demonstrate that there is little difference in the compositions between the crystalline particles and the matrix. The Zr₆₇Ni₂₀Cu₅Al₈ BMG under compressive loading exhibits yield strength of 1580 MPa with an up to 7.7 pct fracture strain. The fatigue behavior of Zr₆₇Ni₂₀Cu₅Al₈ is investigated under four-point-bending loading. The fatigue results show that the fatigue limit of Zr₆₇Ni₂₀Cu₅Al₈ is approximately 361 MPa, based on the stress range. It is generally found that the fatigue cracks initiate from the hard particles. The influence of the hard inclusions on the fracture and fatigue behavior of Zr-based BMGs is discussed.     

Glass-Forming Ability and Competitive Crystalline Phases for Lightweight Ti-Be–Based Alloys

The glass-forming ability (GFA) for the Ti-Be–based alloys in the Ti-Be-Zr ternary system is systematically studied. It was found that the best GFA obtained at a composition of Ti₄₁Be₃₄Zr₂₅ (at. pct) in the Ti-Be-Zr ternary system, and the bulk-metallic-glass (BMG) rod samples with a diameter of 5 mm were fabricated by Cu-mold casting. The competitive crystalline phases around the composition of the best GFA materials were determined by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The GFA of the ternary alloys was further improved by an addition of 4 at. pct vanadium (V). The largest supercooled liquid region, ΔT _x (ΔT _x  = T _x − T _g , T _g is the glass-transition temperature, and T _x the crystallization temperature), in the ternary alloy system reaches about 110 K (110 °C) for the Ti₃₅Be₃₂Zr₃₃ alloy.     

Synthesis of 4‐link function generating mechanisms for optimum transmission angle

Abstract

A combined equation of the expression of optimum transmission angle μ and the loop displacement equation is presented for the synthesis of plane 4‐link function generating mechanisms with the highest minimum (or optimum) μ. The expression of optimum μ is derived via the sensitivity of a function generator, and covers various types of equal deviations of μ between |90 deg‐μ_min | and |90 deg‐|μ_max |. A numerical example is given.     

Preparation and catalysis of amorphous CoNiB and polymer-stabilized CoNiB catalysts for hydrogenation of unsaturated aldehydes

CoNiB and polymer polyvinylpyrrolidone (PVP)-stabilized CoNiB (PVP-CoNiB) catalysts were prepared by chemical reduction with NaBH₄. They were characterized and examined for their catalysis in the hydrogenation of unsaturated aldehydes. CoNiB and PVP-CoNiB catalysts were characterized by X-ray diffraction as amorphous structures and by transmission electron microscopy as having particle sizes in the range 3.5–7 nm – smaller than those of NiB (7–15 nm) and CoB (5–10 nm). CoNiB catalysts were significantly more active than NiB and CoB in the hydrogenations of furfural, crotonaldehyde and citral, and the PVP-CoNiB catalysts were significantly more active than CoNiB. The catalytic properties of CoNiB and PVP-CoNiB catalysts during the selective hydrogenations of crotonaldehyde and citral were similar to those of NiB, but different from those of CoB. The conjugated CC bonds in crotonaldehyde and citral were preferentially reduced to form butyraldehyde and citronellal. PVP-CoNiB could hydrogenate citral to citronellal at a low reaction temperature of 30 °C.     

Mortality attributable to cigarette smoking in Taiwan: a 12-year follow-up study

BACKGROUND—Assessment of the impact of cigarette smoking on mortality helps to indicate the importance of tobacco control in a given country.
OBJECTIVES—To examine the relative risk of dying from various diseases for cigarette smoking and to estimate annual mortality attributable to cigarette smoking in Taiwan.
DESIGN—Prospective cohort study.
SUBJECTS AND SETTING—A cohort of 14 397 male and female residents aged 40 years or older recruited from 12 townships and precincts in Taiwan from 1982 to 1986. Information on cigarette smoking was collected from each subject at local health centres through a standardised personal interview based on a structured questionnaire. They were followed up regularly to determine their vital status until 1994.
MAIN OUTCOME MEASURES—Cox's proportional hazards regression models were used to derive relative risks of cause-specific mortality for current cigarette smokers compared with never-smokers, and to examine dose-response relationships between mortality from various causes and several measures of cigarette smoking (daily consumption, duration, age of initiation, and cumulative smoking in pack-years).
RESULTS—A total of 2552 persons died during the study period. Among men, cigarette smoking was significantly associated with an increased risk of dying from all causes combined (relative risk (RR) = 1.3); cancer of all sites combined (RR = 1.5); cancers of the stomach (RR = 1.9), liver (RR = 2.2), and lung (RR = 3.7); ischaemic heart disease (RR = 1.8); other heart diseases (RR = 1.4); and chronic obstructive pulmonary disease (RR = 1.9). Among women, cigarette smoking was significantly associated with an increased risk of dying from all causes combined (RR = 1.8), cancer of the lung (RR = 3.6), and peptic ulcer (RR = 17.8). The estimated number of deaths attributable to cigarette smoking in Taiwan in 1994 was 8161 (13.9% of total deaths) for men and 1216 (3.3% of total deaths) for women. In the same year cigarette smoking caused 21.3% and 2.9% of cancer deaths in men and women, respectively, in Taiwan.
CONCLUSIONS—Cigarette smoking has a striking impact on overall mortality and deaths from various causes in the Taiwanese population. Tobacco control should be established as the top priority in public health programmes in Taiwan.


Keywords: mortality; smoking-attributable diseases; Taiwan     

Collective motion of inelastic particles between two oscillating walls

This study theoretically considers the motion of N identical inelastic particles between two oscillating walls. The particles’ average energy increases abruptly at certain critical filling fractions, wherein the system changes into a solid-like phase with particles clustered in their compact form. Molecular dynamics simulations of the system show that the critical filling fraction is a decreasing function of vibration amplitude independent of vibration frequency, which is consistent with previous experimental results. This study considers the entire group of particles as a giant pseudo-particle with an effective size and an effective coefficient of restitution. The N-particles system is then analytically treated as a one-particle problem. The critical filling fraction’s dependence on vibration amplitude can be explained as a necessary condition for a stable resonant solution. The fluctuation to the system’s mean flow energy is also studied to show the relation between the granular temperature and the system phase.     

Average plasmonic enhancement of molecules-doped Au-NS@SiO2 on fluorescence

The average plasmonic enhancement of Au nanoshell (Au-NS) coated by a molecules-doped silica layer (Au-NS@SiO2) on molecular fluorescence is studied theoretically to estimate the overall performance of a large number of Au-NS@SiO2. Using Mie theory and dyadic Green's functions, analytical solutions of the excitation rate and the apparent quantum yield are obtained to calculate the enhancement factor of Au-NS@SiO2 on the fluorescence of a molecule with a specific orientation and location at a specific excitation wavelength lambda ex and an emission wavelength lambda em. Subsequently, the average enhancement factor (AEF) is calculated by averaging all possible orientations and locations of the molecule. For example, AEF of Au-NS@SiO2 (a3 = 50 nm t2 = 15 nm, t1 = 25 nm) is 4.544 for a NIR fluorescence at lambda ex = 780 nm and lambda em = 820 nm. Our results show that Au-NS is a broadband enhancer for NIR fluorescence; the bandwidth and the peak depend on the core size and the thickness of Au shell.     

Selective removal of CO from hydrogen-rich stream over CuO/CexSn1−xO2–Al2O3 catalysts

The solid solutions of Ce_xSn_1−xO₂ incorporated with alumina to form Ce_xSn_1−xO₂–Al₂O₃ mixed oxides, by the suspension/co-precipitation method, were used to prepare CuO/Ce_xSn_1−xO₂–Al₂O₃ catalysts for the selective oxidation of CO in excess hydrogen. Incorporating Al₂O₃ increased the dispersion of Ce_xSn_1−xO₂, but did not change their main structures and did not weaken their redox properties. Doping Sn⁴⁺ into CeO₂ increased the mobility of lattice oxygen and enhanced the activity of the 7%CuO/Ce_xSn_1−xO₂–Al₂O₃ catalyst in the selective oxidation of CO. The selective oxidation of CO was weakened as the doped fraction of Sn⁴⁺ exceeded 0.5. Incorporating appropriate amounts of Sn⁴⁺ and Al₂O₃ could obtain good candidates 7%CuO/Ce_xSn_1−xO₂–Al₂O₃(20%), 1–x=0.1–0.5, for a preferential oxidation (PROX) unit in a polymer electrolyte membrane fuel cell system for removing CO. Its activity was comparable with, and its selectivity was much larger than, that of the noble catalyst 5%Pt/Al₂O₃.     

Cyclic deformation of nanocrystalline and ultrafine-grained nickel

The cyclic deformation behavior of ultrafine-grained (UFG) Ni samples synthesized by the electrodeposition method was studied. Different from those made by severely plastic deformation, the UFG samples used in this study are characterized by large-angle grain boundaries. Behaviors from nanocrystalline Ni and coarse-grained Ni samples were compared with that of ultrafine-grained Ni. With in situ neutron diffraction, unusual evolutions of residual lattice strains as well as cyclic hardening and softening behavior were demonstrated during the cyclic deformation. The microstructural changes investigated by TEM are discussed with respect to the unusual lattice strain and cyclic hardening/softening.