Temperature dependence of the surface diffusion distance of bismuth atoms adsorbed on mica,carbon and silicon monoxide surfaces

The mean distance of surface diffusion of bismuth adatoms on mica, carbon and silicon monoxide surfaces has been determined at different temperatures by measurement of the instantaneous sticking coefficient and the nucleus density.The surface diffusion distance has been found to increase with decreasing temperature in accordance with the formula

$\text{X=}\text{1}\text{2}\text{a}{}_0\text{v}{}_{\mathrm{0d}}\text{v}{}_{\mathrm{0a}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{exp}\text{E}{}_{\mathrm{a}}\text{? E}{}_{\mathrm{d}}\text{2RT}$

at temperatures above 413, 373 and 383 K for mica, carbon and silicon monoxide respectively. Here X is one-half of the diffusion distance, E_a is the adsorption energy, E_d the activation energy for surface diffusion, a₀ the diffusion jump distance and v_0a and v_0d the vibrational frequencies associated with re-evaporation and with surface diffusion respectively. Below these temperatures it has been found that the temperature dependence of the diffusion distance deviates from the above formula; this can be explained by the presence of residual gas molecules adsorbed on the surfaces.From the temperature dependence of the diffusion distance, the respective values of the pre-exponential term $\text{a}{}_0\text{(}\text{v}{}_{\mathrm{0d}}\text{v}{}_{\mathrm{0a}}\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and the difference of energies E_a?E_d have been estimated as 7.6 Å and 5.8 kcal mol^?1 for mica, 17 Å and 3.2 kcal mol^?1 for carbon and 58 Å and 1.3 kcal mol^?1 for silicon monoxide.     

Rate law versus oxygen pressure in spinel oxidation to γ lacunar spinels

In the controlled oxidation of spinels (Fe²⁺Fe³⁺_2?xM³⁺_x)O^2?₄ (M³⁺=Al³⁺, Cr³⁺ ; 0 < x < 2) and (Fe²⁺Al³⁺_2?xCr³⁺_x)O^2?₄ to the metastable phases γ(Fe³⁺_1?yM³⁺_y)₂O^2?₃ and $\text{γ(}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Al}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext><mtext>?</mtext><mtext>y</mtext>}}\text{Cr}{}^{\mathrm{3+}}{}_{\mathrm{<mtext>y</mtext>}}\text{O}{}^{\mathrm{2?}}{}_{\mathrm{3?}}\text{(0 <}\text{y}\text{<}\text{2}\text{3}\text{)}$, over the temperature range 200–450°C, the rate law is usually v = k Pⁿ_(O2) with $\text{n}\text{=}\text{1}\text{2}$. This law is well interpreted if we consider a total association vacancy-positive charge. However, for low oxidation extents a (a < 0.3) the law written as is in better agreement with a partial association of defects. For a total dissociation of defects exponent n of the pressure law is always smaller.     

Chromium-doped CdF2 crystals by ESR spectroscopy

Single crystals of Cr-doped CdF₂ in which only Cr²⁺ ions were present were obtained by heating CdF₂:CrF₃ samples in Cd vapors. The crystals produced were studied by ESR spectroscopy at X band at 4.2 ^oK. The spectrum obtained is described by the effective spin Hamiltonian:

g⁽²⁾_eff = 4g_zcosΘ, g⁽¹⁾_eff = 2g_zcosΘ, where i = 1 for the doublet of the spin S = 1, and i = 2 for the doublet of the spin S = 2; net effective spin $\text{S}\text{=}\text{1}\text{2}$; g_z=1.85±0.03; |Δ₍₂₎|=3.08±0.07 GHz; |Δ₍₁₎|=5.85±0.07 GHz; $\text{1}\text{6}\text{(Δ}{}^{\mathrm{o}}{}_{\mathrm{(2)}}\text{? Δ}{}^{\mathrm{o}}{}_{\mathrm{(1)}}\text{)=?11.01±0.02}\text{GHz}$.     

Some experimental observations on the Poisson's ratio of sea-ice

Measurements were made on the longitudinal and transverse strain of sea-ice beams loaded in flexure. The specimens were tested with stress rates varying from 10 to 600 kPa s^?1 and temperatures ranging from ?5°C to ?40°C. Under these conditions, the effective strain ratio μ increases with increasing temperature and decreasing stress rate. The strong influence of the stress rate, σ, suggests an empirical law of the form: μ = 0.24$\text{(}\text{σ}\text{?}\text{σ}\text{?}{}_1\text{)}{}^{\mathrm{?0.29}}\text{+ μ}{}_{\mathrm{D}}$ where σ is the stress rate (kPa s^?1), $\text{σ}\text{?}{}_1$ is a unit stress ratio (1 kPa s^?1) and μ_D is a dynamic value of Poisson's rate which depends on the temperature.     

Relations for hydration enthalpies of metalion-hydrates and stability constants of metal-dibenzoylmethane chelate complexes

Absolute hydration enthalpy (H) for cations relates well to lgK_Σ, the sum of the logarithms of the individual step chelation constants for metal-dibenzoylmethane complexes. The products $\text{d}{}^2$H and $\text{d}{}^2$lgK_Σ, where $\text{d}$ is the bond length, are essentially constant for a given cation valence (v) and increases as v². These relations fit a simple electrostatic model wherein the polarization of coordinating chelate or hydrate oxygen atoms is proportional to cation charge.     

Study of the oxidation kinetics of finely-divided magnetites IV. Influence of zinc substitution

The oxidation kinetics of zinc substituted magnetites (Fe²⁺_1?xZn²⁺_xFe³⁺₂)O^2?₄ (O < x < 1) into the γ defect phase of type x(Zn²⁺Fe³⁺₂O^2?₄), $\text{3}\text{2}\text{(1?}\text{x}\text{)}\text{Fe}{}^{\mathrm{3+}}{}_2\text{O}{}^{\mathrm{2?}}{}_3$ is found to be governed by the diffusion with a chemical diffusion coefficient depending on vacancy concentration. For compounds rich in zinc the diffusion coefficient is constant and the rate law written as v = k Pⁿ_(O2) with $\text{n}\text{=}\text{1}\text{4}$ is in agreement with a partial association of defects. For low substitution extents the diffusion coefficient varies with the transformation extent α and exponent n from the pressure law is equal to $\text{1}\text{2}$, which agrees with a total association of defects.     

Copper doped zinc oxide Y2BaZnO5: ERS and optical investigation

In copper doped Y₂BaZnO₅ oxides, copper exhibits a distorted square pyramidal coordination which is consistant with the values of g and A tensors obtained from O band ERS spectrum for a sample containing about 1 % Cu. Three values for g and A are observed, g₁ = 2.049₅, g₂ = 2.051₅, g₃ = 2.275, $\text{¦}\text{A}{}_1\text{¦ = 13 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$, $\text{¦}\text{A}{}_2\text{¦ = 10 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$ and $\text{¦}\text{A}{}_3\text{¦ = 147.5 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$. Since $\text{g}{}_1\text{?}\text{g}{}_2$ an approximate C_4v point symmetry can be assumed for copper. The electronic spectrum shows three bands at 11700, 14500 and 20500 cm^?1 which can be assigned to the transitions A₁ → B₁, B₂ → B₁ and E → B₁ respectively. The orbital reduction parameters are calculated and the bonding covalency is discussed.     

Nature de la fluorescence de l'europium divalent dans les fluorures

The levels of the ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ (4f⁷) and 4f⁶5d¹ states of europium (+II) have been determined from fluorescence spectra in a series of fluorides M_xB_yF_z (M = alkaline-earth element, B = Li, Be, Mg, Y, Si). As in BaY₂F₈, SrSiF₆ and BaSiF₆, the ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ level lies even at room temperature far below the 4f⁶5d¹ band, only the f → f emission is observed. The influence of the choice of the alkaline-earth and the B cations and of the coordination of europium on the relative positions of the energy levels is discussed.     

A model for fatigue crack growth in a threshold region

The prediction of fatigue crack growth at very low ΔK values, and in particular for the threshold region, is important in design and in many engineering applications. A simple model for cyclic crack propagation in ductile materials is discussed and the expression

$\text{da}\text{dN}\text{=}\text{2}{}^{\mathrm{1+n}}\text{(1?2v)(ΔK}{}^2{}_{\mathrm{eff}}\text{?ΔK}{}^2{}_{\mathrm{c,eff}}\text{)}\text{4(1+n)π σ}{}^{\mathrm{1?n}}{}_{\mathrm{yc}}\text{E}{}^{\mathrm{1+n}}\text{?}{}^{\mathrm{1+n}}{}_{\mathrm{f}}$

developed. Here, n is the cyclic strain hardening exponent, σ_yc is cyclic yield, and ε_f is the true fracture strain. The model is successfully used in the analysis of fatigue data BS 4360-50D steel.     

Etude par spectrometrie d'absorption infra-rouge des facteurs influencant la transformation ordre-desordre de ferrites γ lacunaires derivant de l'oxydation de spinelles ferreux

The order-disorder phenomenon in defect γ-spinels of type $\text{(Fe}{}_{\mathrm{<mtext>(8?8y)</mtext><mtext>3</mtext>}}{}^{\mathrm{3+}}\text{M}{}_{\mathrm{<mtext>8y</mtext><mtext>3</mtext>}}{}^{\mathrm{3+}}\text{□}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{)O}{}_4{}^{\mathrm{2?}}$ and $\text{Fe}{}_{\mathrm{<mtext>(8?2x)</mtext><mtext>3</mtext>}}{}^{\mathrm{3+}}\text{M}{}_{\mathrm{x}}{}^{\mathrm{2+}}\text{□}{}_{\mathrm{<mtext>(1?x)</mtext><mtext>3</mtext>}}\text{)O}{}_4{}^{\mathrm{2?}}$ with M³⁺ = A1³⁺, Cr³⁺ and M²⁺ = Zn²⁺, Co²⁺, Mn²⁺ obtained from ferrous spinels was investigated using IR spectrometry. These compounds possess a vacancy ordering on octahedral sites for substitution extents of less than 0.30 and no ordering has been observed for substitution extent > 0.40. The ordering process is also influenced by the nature and position of the trivalent or divalent cation, particle size, heating temperature and oxidation time.     

Structure determination of (3D) P2NbS8

Tridimensional P₂NbS₈ crystallizes in P4?n2 tetragonal space group, with $\text{a}\text{= 12.0483(4)}\text{A}\text{?}$, $\text{c}\text{= 7.2070(5)}\text{A}\text{?}$, $\text{V}\text{= 1046.2(1)}\text{A}\text{?}{}^3$ and Z = 4. The structure was anisotropically refined down to R = 2.3% from 468 reflexions and 53 variables. It is built from [Nb₂S₁₂] biprismatic bicapped units (average $\text{d}{}_{\mathrm{Nb?S}}\text{= 2.571}\text{A}\text{?}$) made of S^?II and S^?II₂ anions (dianionic distance of 2.014(3) Å). The niobium atoms are found as isolated Nb^IV ? Nb^IV pairs ($\text{d}{}_{\mathrm{Nb?Nb}}\text{= 2.859(1)}\text{A}\text{?}$) in these niobium group otherwise linked to each other through (PS₄) tetrahedral units (average $\text{d}{}_{\mathrm{P?S}}\text{= 2.051}\text{A}\text{?}$) themselves constituting interbonded [P₄S₁₂] rings. The P₂NbS₈ three-dimensional network thus obtained is compared to the (2D) P₂NbS₈, layered phase already described.     

On the cofactors of zero-sum matrices of higher nullity

A generalization of the equicofactor property of zero-sum matrices is considered. Let Y be a square matrix of order m · n. Consider partitioning of Y to into m² square submatrices Y(i,j); ij = 1,2,3.,m resulting from partitioning of the sets of rows and columns of into m equal subsets, each of which contains n successive rows or columns. Subbpose that each of these submatrices has the zero-sum property and choose an arbitrary element y_{ji, ki} in each of the diagonal submatrices Y(i,i); i = 1,2,3.,m. It is shown in the paper that all the cofactors of the products

in the expansion of the determinant |Y| are equal     

Deformation and fracture processes during creep of 12Cr12Mo14V ferritic steel

The creep and fracture properties of $\text{1}\text{2}\text{Cr}\text{1}\text{2}\text{Mo}\text{1}\text{4}\text{V}$ ferritic steel have been determined over the stress range 125 to 362 MNm^?2 at 838 K using high precision, constant stress equipment. When the variation of the rupture life, t_f, and the secondary creep rate, $\text{?}\text{dot}{}_{\mathrm{<mtext>s</mtext>}}$, with stress, σ, was described as ${}_{\mathrm{<mtext>f</mtext>}}\text{α}\text{?}\text{dot}{}_{\mathrm{<mtext>s</mtext>}}\text{ασ}{}^{\mathrm{n}}$ a stress exponent of was recorded. Comparison with long term data then established that, at stresses below ～ 100 MNn^?2, n decreased gradually until values close to unity were obtained at stresses approaching those encountered in electricity generating plant. This decrease in stress exponent is shown to be attributable to a progressive loss of creep resistance associated with changes in carbide dispersion rather than to any change in the mechanisms by which deformation and failure occur.     

Mass spectrometry of a silane glow discharge during plasma deposition of a-Si: H films

We undertook a mass spectrometric investigation of the ionic and neutral species present during the deposition of a-Si: H using an r.f. glow discharge in silane (mixed with helium or hydrogen). A correlation between the neutral composition of the plasma and the nature of the IR vibrational modes in the deposited film is proposed. The ionic species extracted from the silane discharge are not characteristic of the direct ionization of SiH₄. The predominance of the SiH₃⁺ ion is attributed to the ion-molecule reaction $\text{SiH}{}_2{}^{\mathrm{+}}\text{+ SiH}{}_4\text{→ SiH}{}_3{}^{\mathrm{+}}\text{+ SiH}{}_3$ Secondary ions Si₂H_n⁺ (n = 1?7) are also observed. Mass spectrometry of the ionic species resulting from the interaction of a hydrogen plasma with the a-Si: film suggests that atomic hydrogen plays an active role during the growth of the film.     

Lithium organic electrolyte cells using the copper chevrel phase as cathode

The copper Chevrel phase, Cu_xMo₆S_8?z (x=0–4, z=0-0.2), was evaluated as the cathodes in lithium organic electrolyte cells. The cells $\text{Li}\text{Cu}{}_{\mathrm{x}}\text{Mo}{}_6\text{S}{}_{\mathrm{<mtext>8?</mtext><mtext>z</mtext>}}$ showed a good discharge performance for the charge transferred range of 0.5 to 3.5 $\text{electron(e)}\text{Cu}{}_{\mathrm{x}}\text{Mo}{}_6\text{S}{}_{\mathrm{<mtext>8?</mtext><mtext>z</mtext>}}$ under a high current density such as 3mA/cm². The charge and discharge cycle tests of the $\text{Li}\text{Cu}{}_2\text{Mo}{}_6\text{S}{}_{\mathrm{7·8}}$ cell indicated a good rechargeability for the range of 0.5 to $\text{2.5}\text{e}\text{Cu}{}_{\mathrm{x}}\text{Mo}{}_6\text{S}{}_{\mathrm{<mtext>8?</mtext><mtext>z</mtext>}}$. The electrode reaction mechanism was discussed with the help of x-ray diffraction analysis of the cathode reaction products.     

Un nouveau conducteur protonique [H(H2O)n]12Sb12O36 (n ⩽ 1)

Single crystals of K₁₄Sb₁₂O₃₆F₂ undergo rapid ion exchange in 9N sulfuric acid to produce “hydronium” compound (H(H₂O)_n)₁₂Sb₁₂O₃₆ (n ? 1). Between 30 and 140°C this phase undergoes a partial and reversible dehydratation in which approximately 85 % of its “H₃O⁺” content is converted to H⁺.The structures of hydrated and dehydrated phases have been refined by full-matrix least squares, respectively to factor R = 0.030 and 0.047. The conductivity of $\text{(H(H}{}_2\text{O)}{}_{\mathrm{<mtext>n</mtext>}}\text{)}{}_{12}\text{Sb}{}_{12}\text{O}{}_{36}\text{(σ}{}_{20}\text{? 1O}{}^7\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$) increases in an Arrhenius relationship with an activation energy of 8.8 kcal.mole^?1, the dehydrated compound (H(H₂O)_0.33)₁₂Sb₁₂O₃₆ has a much lower conductivity but the same activation energy.     

Nucleation mechanism of stress corrosion cracking from notches

Crack nucleation mechanism of hydrogen assisted cracking at notched cracks in aqueous solutions is investigated, using the compact type specimens with various notch radius in low-tempered 4340 steel. A detached crack initiates at some distance ahead of the notch root. The crack nucleation at the notched root is determined by the electrical potential method. When the crack initiates, the voltage difference starts to increase. The crack nucleation site is examined by SEM. The time for crack nucleation increases with the notch root radius, ρ, and decreases with the apparent stress intensity factor K_ρ. A linear relationship between the crack nucleation time, t_n, and the parameter ${}^2\text{K}{}_{\mathrm{\rho }}\text{/(πρ)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-(2K}{}_{\mathrm{\rho }}\text{/(πρ)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}_{\mathrm{th}}\text{}}$ is seen in semi-log diagram, where $\text{(2K}{}_{\mathrm{\rho }}\text{/(πρ)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}_{\mathrm{th}}$ is almost equal to the yield shear strength.In order to explain these experimental results, a new model of micromechanics is proposed on the basis of stress induced diffusion of hydrogen in the high stress region ahead of the notch root. This model suggests that the detached crack initiates at the elasto-plastic boundary where the hydrogen concentration is from 2 to 5 times higher than that of the notch root surface. The theory agrees with experiments with respect to $\text{{2K}{}_{\mathrm{\rho }}\text{/(πρ)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-(2K}{}_{\mathrm{\rho }}\text{/(πρ)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)}{}_{\mathrm{th}}\text{}}$ vs t_n and t_n vs ρ.The empirical equation holds under constant t_n, K_ρ = K_o(ρ/ρ_eff)^m where K₀ is the stress intensity factor with ρ ≈ 0 under the present environment, ρeff is the effective notch radius and m is constant. The value of m is 0.25 for the crack nucleation time (t_n)_th corresponding to the threshold stress intensity factor (K_ρ)_th, 0.5 for t_n < (t_n)_th and 0 for ρ ≦ ρ_eff. The above equation agrees with the theoretical equation proposed by Tanaka and Mura for any t_n and ρ_eff.     

Electronic and spin configurations of Co3+ and Ni3+ ions in oxides of K2NiF4 structure: A magnetic susceptibility study

In La₄LiCoO₈, Li⁺ and Co³⁺ ions are ordered in two dimensions and Co³⁺ ions undergo transitions from the low-spin to the intermediate as well as the high-spin states. Both Sr₄TaCoO₈ and Sr₄NbCoO₈ exhibit low to intermediate-spin state transitions of Co³⁺ ions. In the system LaSr_1?xBa_xNiO₄, the e_g electrons are essentially in extended states forming a band. With increase in x, the band width decreases accompanying an increase in unit cell volume; high-spin Ni³⁺ ions are formed to a small extent with increasing x, but there is no spin-state transition. In LaSrAl_1?xNi_xO₄, at small x, there is a small proportion of high-spin Ni³⁺; when x ≈ 0.6, there is an abrupt decrease in the $\text{c}$/$\text{a}$ ratio, signalling the formation of the band. In LnSrNiO₄, the $\text{c}$/$\text{a}$ ratio decreases sharply between Ln = La and Nd; this is likely to be accompanied by a broadening of the band.