Determination of the oxidizing ability of HTSC materials containing two elements with a variable degree of oxidation

The presence of mixed valence states of elements is supposed to be a common characteristic feature of the high-T _c superconductors, based on copper oxides. Methods have been suggested for the determination of Cu(III) in the Y-Ba-Cu-O ceramics and separate determination of two oxidants: Bi(V) and Cu(III), Tl(III) and Cu(III) in the corresponding materials. Compounds of Bi(V) oxidize in the ions of Mn(II) to MnO ₄ ⁻ in the acidic medium. Active oxygen, bound to Cu(III) is isolated, not oxidizing Mn(II). MnO ₄ ⁻ is titrated then with a solution of Fe(II) sulphate. For the determination of Tl(III) the sample is dissolved in the acid, Cu(III) is reduced to Cu(II) and Tl(III) is titrated with the hydroquinone solution. The compounds of Bi(V), Tl(III) and Cu(III), having high oxidation-reduction potentials can oxidize the complex Co(II)-EDTA to Co(III)-EDTA. The colour intensity of the latter is proportional to the content of Cu(III) or to the sum of Bi(V) and Cu(III) or Tl(III) and Cu(III). The content of Cu(III) in Bi- and Tl-containing materials is determined by the difference.     

On the energy-release rate associated with diffusional crack growth

A general expression for the energy release rate (G) that arises during steady state crack propagation by diffusion is derived from the standpoint of irreversible thermodynamics. Three contributing components of G are identified: (i) the Griffith energy (G _Gr); (ii) heat generated in the process of surface diffution; and (iii) grain-boundary diffusion. Further, the total G is shown to be directly related to the well-known J-integral if formulated in the framework of finite deformation elasticity. This expression for G is valid in general even if the response of the material is not linear and the mass transport kinetics does not follow Fick's law. Quantitative evaluations of each component are made for the linear case where field solutions are available. The results show that component (ii) is approximately equal to G _Gr and is independent of the crack velocity (v) whereas component (iii) is a monotonically increasing function with G starting from 0.85 G _Gr when v is at threshold value; and that the local strain energy influence on matter diffusion is negligible leading to 229-1. This means that G is not primarily associated with the release of the strain energy at the crack tip but rather, it stems mostly from the (negative) work done (converted to heat) by the normal stresses on the thickening of the grain boundary due to non-uniform deposition of matter along it.     

Orientation and growth behavior of CaHfO3 thin films on non-oxide substrates

The growth behavior of CaHfO₃ on (001) Ni and Ge substrates was examined. CaHfO₃ is a perovskite insulator that is suitable for applications as a buffer layer or gate dielectric. The tendency for CaHfO₃ growth on both (001) Ni and (001) Ge substrates is to orient with the CaHfO₃ (200) + (121) planes parallel to the surface, which corresponds to the (110) orientation in the pseudo-cubic geometry. This differs from that of CaHfO₃ on perovskites, such as (001) LaAlO₃, where a pseudo-cube-on-cube orientation is observed.     

Origin of diameter-dependent growth direction of silicon nanowires

A nucleation thermodynamic model was developed to clarify the diameter-dependent crystallographic orientation of silicon nanowires (SiNWs) grown via the vapor-liquid-solid (VLS) mechanism with an Au catalyst. The calculated critical energies (E(r*)) and corresponding critical radii (r*) of the SiNWs with <111> and <110> orientations as a function of Au-catalyst size (D(Au)) revealed that the 110-oriented SiNW with r is preferred below D(Au) = approximately 25 nm, but the preferred direction changes to <111> above D(Au) = approximately 25 nm. The model indicated that the nucleated SiNW with a radius (r) above r is stable and continues to grow until the diameter becomes equal to D(Au) but that the crystallographic orientation is maintained. Thus, the predicted growth direction of the final SiNW with a size of D(Au) is <110> for D(Au) < approximately 25 nm and <111> for D(Au) > approximately 25 nm, which is in excellent agreement with reported experimental results.     

POP-IN AND CRACK ARREST IN AN HY80 WELD

It is generally thought that, when a material is in its brittle to ductile transition, it is more difficult to design for crack arrest than to prevent crack initiation (cleavage). This report shows that this is not always true for weldments. Comparison is made between compact crack arrest (CCA), K_a, and crack tip opening displacement (CTOD), K_Jc, toughness for the same HY80 weld. The value of K_a is shown to be much higher than the minimum K_Jc for pop-in fracture initiation. It is considered that the results support the conclusion of Japanese research workers (Arimochi and Isaka) that small pop-ins (in the CTOD test) propagate and arrest without load drop. It follows that prediction of structural failure for weldments need not be based on minimum pop-in toughness from CTOD tests.     

Donor/acceptor effects on the nonlinear optical properties of 1,3 diphenyl propenones

Employing the single beam Z-scan technique with nanosecond laser pulses at 532 nm, the refractive and absorptive nonlinearities of donor and acceptor substituted (2E)-1-(3,4-dimethoxyphenyl)-3-phenylprop-2-en-1-one have been studied. The sign of the nonlinear index of refraction (n ₂) is found to be negative and the magnitude of n ₂ is in the order of 10^?11 esu. The second-order molecular hyperpolarizability (γ_h) is calculated to be in the order of 10^?32 esu. The variation of nonlinear absorption coefficient (β_eff) with input intensity (I ₀) is studied and the nonlinear absorption mechanism is found to be reverse saturable absorption (RSA). The enhancement of nonlinearity due to the donor and acceptor substitution is in accordance with the variation in π electron delocalization in the molecules. The compounds exhibit good optical limiting as well.     

Modeling of an isolated liquid hydrogen droplet evaporation and combustion

In this model, diffusive governing equations of Liquid Hydrogen (LH) evaporation and combustion were solved. The simulation reveals that, there exists a critical radius (a_cri) where radiation heat is equal to conduction heat (Q_rad = Q_cond) and a_cri is a function of ambient temperature during LH droplet evaporation process. Under pure evaporation condition, for large liquid hydrogen droplets (a > a_cri) radiation heat is dominant at a given environment temperature, but as liquid droplet size decreases, radiation heat becomes insignificant and thermal conduction will be dominant for liquid evaporation. When LH droplet is burned in a cold environment (T_∞ = 300 K), there are two films above the LH surface, Film I is from LH surface to flame front within which a dense hydrogen gas cloud is formed; Film II is from flame front to the free stream where oxygen is diffused inward to react with hydrogen. The flame front is located about 95 times of the droplet radius (r_f = 95a) and the flame temperature could rise up to 2077 K. When an LH droplet is immersed in a hot environment (T_∞ = 2050 K), the flame front is located at a similar distance to the LH droplet (r_f/a = 114) and flame temperature could go up to 3769 K.     

Optimization of photochemical machining process parameters for manufacturing microfluidic channel

In the present study, the investigation on photochemical machining (PCM) of stainless steel (SS-304) by ferric chloride as etchant is reported. SS-304 is machined by PCM process to obtain accurate dimensions and better geometrical features. Weighted grey relational analysis (WGRA) technique is used in optimization of PCM process parameters. DoE (L₂₇) orthogonal array is applied to evaluate machining parameters, such as concentration of etchant, etching time, and temperature of etchant. The multiobjective optimization technique is used to optimize material removal rate (MRR), surface roughness (R_a), undercut (U_c) and etch factor (EF). Weighted grey relational grade is calculated to minimize U_c and surface roughness and to maximize MRR and EF. The quality characteristics MRR, EF, U_c, and R_a are reporting the improvement after the confirmatory test. The optimum machining parameters are processed to manufacture the microfluidic channel used in biomedical applications. The microfluidic channels and its assembly with Y-type for mixing of fluid with a size of 100 µm, 200 µm, and 300 µm are developed and investigated.     

Poly(ethylene glycol) interactions with alumina and silica powders determined via DRIFT

Diffuse reflection infrared spectroscopy (DRIFT) is used to determine interfacial interactions between poly(ethylene glycol) (PEG), alumina and silica powders. The interactions are created by grafting in high temperature and low moisture environments due to preferential adsorption between PEG and water. Under these grafting conditions, a shoulder appears on the C–O–C stretching band of the DRIFT spectrum. This is found to occur when PEG is in the presence of a hydrogen donor such as surface hydroxyls on alumina and silica. The shoulder is reported as an interaction band due to hydrogen bonding between the PEG etheric oxygen and the surface hydroxyls of alumina and silica. Specific band positions are measured when the PEG chain is interacting with alumina (1090 cm^–1), silica (1080 cm^–1), or water (1085 cm^–1).     

Enhancing FMEA assessment by integrating grey relational analysis and the decision making trial and evaluation laboratory approach

Failure modes and effects analysis (FMEA) is used widely to improve product quality and system reliability, employing a risk priority number (RPN) to assess the influence of failures. The RPN is a product of three indicators—severity (S), occurrence (O), and detection (D)—on a numerical scale from 1 to 10. However, the traditional RPN method has been criticized for its four chief shortcomings: its (1) high duplication rate; (2) assumption of equal importance of S, O, and D; (3) not following the ordered weighted rule; and (4) failure to consider the direct and indirect relationships between failure modes (FMs) and causes of failure (CFs). To resolve these drawbacks, we propose a novel approach, integrating grey relational analysis (GRA) and the decision-making trial and evaluation laboratory (DEMATEL) method, to rank the risk of failure, wherein the GRA is used to modify RPN values to lower duplications and the ordered weighted rule is followed; then, the DEMATEL method is applied to examine the direct and indirect relationships between FMs and CFs, giving higher priority when a single CF causes FMs to occur multiple times. Finally, an actual case of the TFT-LCD cell process is presented to verify the effectiveness of our method compared with other methods in providing decision-makers more reasonable reference information.     

Flow boiling of non-azeotropic mixture R32/R1234ze(E) in horizontal microfin tubes

Flow boiling of a potential refrigerant R32/R1234ze(E) in a horizontal microfin tube of 5.21 mm inner diameter is experimentally investigated. The heat transfer coefficient (HTC) and pressure drop are measured at a saturation temperature of 10 °C, heat fluxes of 10 and 15 kW m^?2, and mass velocities from 150 to 400 kg m^?2 s^?1. The HTC of R1234ze(E) is lower than that of R32. Degradation in the HTC of the R32/R1234ze(E) mixture is significant; the HTC is even lower than that of R1234ze(E). The HTC is minimized at the composition 0.2/0.8 by mass, where the temperature glide and the mass fraction distribution are maximized. A predicting correlation based on Momoki et al. (1995) associated with the correction methods of Thome (1981) to consider the mass transfer resistance and Stephan (1992) to consider the additionally required sensible heat is proposed and validated with the experimental results.     

Generalised critical free-surface flows

Nonlinear waves in a forced channel flow are considered. The forcing is due to a bottom obstruction. The study is restricted to steady flows. A weakly nonlinear analysis shows that for a given obstruction, there are two important values of the Froude number, which is the ratio of the upstream uniform velocity to the critical speed of shallow water waves, F _C>1 and F _L<1 such that: (i) when F<F _L, there is a unique downstream cnoidal wave matched with the upstream (subcritical) uniform flow; (ii) when F=F _L, the period of the cnoidal wave extends to infinity and the solution becomes a hydraulic fall (conjugate flow solution) – the flow is subcritical upstream and supercritical downstream; (iii) when F>F _C, there are two symmetric solitary waves sustained over the site of forcing, and at F=F _C the two solitary waves merge into one; (iv) when F>F _C, there is also a one-parameter family of solutions matching the upstream (supercritical) uniform flow with a cnoidal wave downstream; (v) for a particular value of F>F _C, the downstream wave can be eliminated and the solution becomes a reversed hydraulic fall (it is the same as solution (ii), except that the flow is reversed!). Flows of type (iv), including the hydraulic fall (v) as a special case, are computed here using the full Euler equations. The problem is solved numerically by a boundary-integral-equation method due to Forbes and Schwartz. It is confirmed that there is a three-parameter family of solutions with a train of waves downstream. The three parameters can be chosen as the Froude number, the obstruction size and the wavelength of the downstream waves. This three-parameter family differs from the classical two-parameter family of subcritical flows (i) but includes as a particular case the hydraulic falls (ii) or equivalently (v) computed by Forbes.     

Congestion, ramp metering and tolls

The cell transmission model of a freeway is used to compare four congestion-reducing schemes: (R) ramp control only; (T) one lane is tolled and ramps are uncontrolled; (B) bottlenecks are tolled and ramps are uncontrolled; and (RB) ramps are controlled and bottlenecks are tolled. In the base case, ramps are uncontrolled and there are no tolls. It is found that (T) is inefficient and may leave all travellers worse off; (R), (B) and (RB) can achieve efficient freeway use; (B) can eliminate queues, but has adverse spatial and equity side effects; (RB) minimizes these side effects. (RB) is likely to be least costly to implement and maintain.     

The influence of unusual counterions on the electrochemistry and physical properties of polypyrrole

A series of different counterions have been incorporated into polypyrrole electrochemically. These include toluenesulphonate (TS), pyrenesulphonate (PSA), Pyrene-1,3,6,8-tetrasulphonate (PTSA), dodecylbenzenesulphonate (DBS), 1,2-bis (decyloxycarbonyl)ethane-1-sulphonate (DOCES), octachloro-dirhenate (Re₂Cl₈) and tetraphenylborate (TPB). Electrochemical redox behaviour of the pyrrole monomer and the polypyrrole incorporating these different anions was investigated and is discussed. From scanning electron microscopy (SEM), it is shown that the different counterions incorporated strongly affect the morphology of the polymer films, they vary from fully dense to open structures. Chemical and physical characterization of the materials is presented and suggests that the sizes of the different counterions incorporated also influence the polymer chain structures, packings and their thermal stabilities. The pyrrole to counterion stoichiometries are very different, ranging from 1 to 13. In most cases, the redox potential of the polymer can be related to the size of the counterion but the electrical conductivity, which ranges from 2×10^–3 to 50 Scm^–1, is not simply related to the counterion but is dependent on both chain structure and bulk morphology.     

Thermodynamic functions of ideal two- and three-dimensional Fermi gases

Several common thermodynamic functions of ideal two- and three-dimensional Fermi gases of spin1/2 have been tabulated as functions oft=T/T _F, whereT is the temperature andT _F is the Fermi temperature. The tables, presented elsewhere, are discussed. The entries in the tables are given at intervals of δt=0.001 for 0≤t≤5. The functions which are tabulated are: (i) the reduced chemical potential ζ(t) ≡ μ(t)/μ(0), (ii) the reduced internal energyu(t)=U(t)/U(0), (iii) the reduced entropys(t)=S(t)/Nk, and (iv) the reduced magnetic susceptibility ?(t)=χ(t)/χ(0). In these expressions,N is the number of particles in the gas andk is Boltzmann's constant. The first of these functions, ζ(t), is given to eight places beyond the decimal point, while the others are given to six places.     

Oxidation of Np(IV) with hydrogen peroxide in carbonate solutions

Oxidation of Np(IV) with hydrogen peroxide in NaHCO₃-Na₂CO₃ solutions was studied by spectrophotometry. In NaHCO₃ solution, Np(IV) is oxidized to Np(V) and partially to Np(VI). It follows from the electronic absorption spectra that Np(IV) in 1 M Na₂CO₃ forms with H₂O₂ a mixed peroxide-carbonate complex. Its stability constant β is estimated at 25–30. The Np(IV) bound in the mixed complex disappears in a first-order reaction with respect to [Np(IV)]. The first-order rate constant k’ is proportional to [H₂O₂] in the H₂O₂ concentration range 2.5–11 mM, but further increase in [H₂O₂] leads to a decrease in k′. The bimolecular rate constant k = k′/[H₂O₂] in solutions containing up to 11 mM H₂O₂ increases in going from 1 M NaHCO₃ to 1 M Na₂CO₃ and significantly decreases with a further increase in the carbonate content. The activated complex is formed from Np(IV) peroxide-carbonate and carbonate complexes. Synchronous or successive electron transfer leads to the oxidation of Np(IV) to Np(V). Large excess of H₂O₂ oxidizes Np(V) to Np(VI), which is then slowly reduced. As a result, Np(V) is formed in carbonate solutions at any Np(IV) and H₂O₂ concentrations.     

Epitaxial and polycrystalline CuInS2 thin films: A comparison of opto-electronic properties

Epitaxial and polycrystalline thin CuInS₂ (CIS) layers were grown by means of molecular beam epitaxy (MBE) on single crystalline silicon substrates of 4 inch diameter. Photoluminescence (PL) studies were performed to investigate the opto-electronic properties of these layers. For the epitaxial CIS, low-energy-hydrogen implantation leads to the passivation of deep defects and several donor-acceptor (DA) pair recombinations (from 1.034 eV to 1.439 eV) and two free-to-bound (FB) transitions (at 1.436 eV and 1.485 eV) become observable at low temperatures (5 to 100 K). Excitonic luminescence is completely absent for all investigated epitaxial CIS layers. This contrasts sharply with the PL of the polycrystalline films which is dominated by excitonic luminescence (1.527 eV). Also a donor-to-valence band transition at 1.465 eV (BF-1) and one donor-acceptor recombination at 1.435 eV (DA-1) were observed, while luminescence from deep levels is not present at all. Based on these data, a refined defect model for CuInS₂ with two donor and two acceptor states is presented. Under comparable growth conditions, the electronic quality of polycrystalline CIS is superior to epitaxially grown material.     

Strong Ferromagnetic Manipulation of SrTiO3 from CO2-Straining Effect on Electronic Structure Modulation

2D magnetic materials are ideal to fabricate magneto-optical, magneto-electric, and data storage devices, which are proposed to be critical to the next generation of information technologies. Benefited from their labile structures, 2D perovskites are amenable for magnetic manipulation through structural optimization. In this work, 2D room-temperature ferromagnetic SrTiO₃ is achieved through straining effect induced by supercritical carbon dioxide (SC CO₂). According to experimental results, the cubic phase of SrTiO₃ is converted to tetragonal with exposure of (110), (200), (111), and (211) planes over the SC CO₂ treatment, leading to significant ferromagnetic enhancement. Theoretical calculations illustrate that over the conversion from cubic to tetragonal, the electronic structure of SrTiO₃ is significantly modulated. Specifically, the spin density of planes of (200), (111), and (211) is enhanced, presumably due to the stabilization of the highest occupied molecular orbital over straining by SC CO₂, leading to magnetic optimizations. This work suggests that magnetic optimization can be achieved from SC CO₂-induced electronic structure modulation.