Chemical diffusion in CoO

Equilibration kinetics of CoO have been studied over the range 1–10^?5 atm oxygen pressure and 900–1300°C by both thermogravimetric and electrical conductivity techniques. The former technique gives excellent agreement with theory based on bulk diffusion and results in a chemical diffusion coefficient given by, $\text{D}\text{?}\text{= 4.8×10}{}^{\mathrm{?3}}\text{exp (?22,500/RT)}$ cm${}^2\text{sec}$. The defect diffusion coefficient (Dinvinco) is equal to $\text{i}\text{?}\text{tD}\text{2}$. No dependence of ?tD on defect concentration was observed. The electrical conductivity technique qualitatively supports these results.     

Stroboscopic observation of quadrupole hyperfine interactions

A stroboscopic technique for the observation of quadrupole hyperfine interactions of isomeric nuclear states has been successfully developed. The inherent precision and resolution of this technique have been demonstrated by measuring the quadrupole hyperfine frequency for ${}^{69}\text{Ge(}\text{9}\text{2}{}^{\mathrm{+}}{}_1\text{, τ = 4.0μ)}$ in Zn metal at several temperatures; ω₀ = [19.67 ± 0.06] × 10⁶s^?1 (at 623 ± 3 K).     

Static structure factor of gaseous helium

The static structure factor of helium gas has been measured at densities of 3.45 × 10^?3, 2.66 × 10^?3 and $\text{1.95 × 10}{}^{\mathrm{?3}}\text{moles}\text{cm}{}^3$ at a temperature of 4.995 K. The results are in qualitative agreement with the limited theoretical work available.     

Diffusion and ionic conductivity in sodium beta alumina

Measurements of sodium tracer diffusion (D_t) and ionic conductivity (σ) have been made on the same single crystals of sodium beta-alumina of composition 1.23 Na₂0.11 Al₂O₃. The σ- measurements were made over the temperature 390–660 K using reversible (liquid sodium) electrodes. A fit to the conductivity data gives $\text{σT = 2470}\text{exp}\text{(?0.142}\text{eV}\text{kT}\text{)Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}\text{K}$. The D_t, measurements employed two techniques, i.e. nondestructive profiling over the temperature range 210–750 K and cation exchange over the temperature range 505–970 K. The results of the two techniques were in close agreement and can be expressed as $\text{D = 2.12 ×10}{}^{\mathrm{?4}}\text{exp}\text{(?0.169}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}{}^{\mathrm{?1}}$ for T>520K and $\text{D = 2.45 × 10}{}^{\mathrm{?4}}\text{exp}\text{(?0.164}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}\text{470}\text{K}$. The “transition” region between 470 and 520 K is not observed in the conductivity measurements. Silver cation exchange was used to determine the number of mobile sodium ions. A comparison of D_t and σ data yielded a Haven ratio that is temperature dependent, ranging in value from 0.45 at 870 K to 0.35 at 370 K.     

Ellipsometric investigation of the skeletonization process of langmuir-blodgett films

When Langmuir-Blodgett films, consisting of a mixture of a long chain carboxylic acid and its salt are immersed in benzene, the acid dissolves, while the salt remains as a skeleton. The density of the film is lowered in this way and so is the refractive index. The process can thus be followed by performing ellipsometric measurements as a function of time of skeletonization. It is established that skeletonization is, in first instance, a diffusion-controlled process with a diffusion coefficient of about $\text{5 × 10}{}^{\mathrm{?14}}\text{cm}{}^2\text{sec}$ at room temperature. The salt also slowly dissolves at a rate of about $\text{1.6 × 10}{}^{10}\text{molecules}\text{/}\text{sec}\text{cm}{}^2$.     

Oscillator strengths in the Cameron system of carbon monoxide

Relative oscillator strengths in the Cameron system of CO(a³Π ← X¹Σ) have been observed in absorption for six bands (υ′ = 0–5, υ″ = 0) with the result, normalized to the absolute (0, 0) band measurement of Hasson and Nicholls, $\text{?}{}_{00}\text{= (1.62±0.07) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{10}\text{= (1.96±0.09) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{20}\text{= (1.41±0.04) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{\mathrm{3\; 0}}\text{= (0.72±0.03) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{40}\text{= (0.31±0.02) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{50}\text{= (0.14±0.01) × 10}{}^{\mathrm{?7}}$. The density of CO was modulated with a motor-driven vacuum valve and synchronous fluctuations (?1 per cent) in the transmitted intensity detected with a lock-in amplifier. Peak pressure in the 21 cm absorption cell was approximately 10 torr. A curve of growth analysis was used to correct saturation effects by less than 3 per cent.     

The electrical properties of HgTe and HgSe under very high pressure

The electrical properties of HgTe and HgSe have been investigated at pressures up to 200 kbar in an octahedral apparatus. Measurements of the electrical resistivity at room temperature showed that, beyond the well-known transition from the semimetallic to semiconductive state, both become metallic, at 84 kbar and 155 kbar, respectively. The energy gap at various fixed pressures was obtained from the resistance-temperature relationships. The energy gap of semiconducting HgTe decreases monotonically with pressure, the coefficient being ?l.53 × 10^?5$\text{eV}\text{bar}$. The energy gap of HgSe is rather insensitive to pressures up to 75 kbar, above which it decreases continuously ($\text{dE}\text{dP}$ = ?1.59 × 10^?5$\text{eV}\text{bar}$) before vanishing around 150 kbar. At high pressures the temperature coefficient of the resistance in the metallic state is 3.25 ~ 4.70 × $\text{10}{}^{\mathrm{?3}}\text{deg}$ for HgTe, and 5.7 ~ 5.9 × $\text{10}{}^{\mathrm{?3}}\text{deg}$ for HgSe.     

New experimental data on the proton electromagnetic polarizabilities

The γp-elastic scattering cross section has been measured in the photon energy range 70–110 MeV. As a monitor process the electron Compton-scattering was simultaneously measured. The values of the electric ($\text{α}$) and magnetic ($\text{β}$) polarizabilities of the proton were obtained from the experimental data: $\text{α}\text{= (10.7 ± 1.1) × 10}{}^{\mathrm{?43}}\text{cm}{}^3$; $\text{β}\text{= (?0.7 ± 1.6) × 10}{}^{\mathrm{?43}}\text{cm}{}^3$.     

Vacancy diffusion in magnetite

The chemical diffusion coefficient in a single crystal of magnetite was measured by observing the relaxation of deviations from stoichiometry responding to a stepwise change in oxygen partial pressure between 1300 and 1450°C. The chemical diffusion coefficient was proportional to $\text{(?}\text{In}\text{δ}\text{?}\text{In}\text{p}{}_{\mathrm{o2}}\text{)}{}^{\mathrm{?1}}$. The vacancy diffusion coefficient was calculated with the help of nonstoichiometric data and was found to be independent of the vacancy composition. The value of D_v was

$\text{D}{}_{\mathrm{v}}\text{= (0.14 ± 0.08)}\text{exp}\text{(?}\text{(32,500 ± 1800)}\text{RT)}\text{cm}{}^2\text{s}{}^{\mathrm{?1}}$

.     

Diffusion of water in additively colored potassium iodide crystals

The diffusion of water into additively colored potassium iodide has been studied in the range 15–45°C. Penetration depths, measured by decrease in the F-band absorption, increase with $\text{t}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. The diffusion coefficient, D = 0·58 exp (?6496/T) cm² sec^?1 agrees very well with that determined by other workers. The Henry's law constant, $\text{K =}\text{C}{}_0\text{p}{}_{\mathrm{w}}\text{= 1·3 × 10}{}^9\text{exp}\text{(+4882/T)}\text{cm}{}^{\mathrm{?3}}\text{torr}{}^{\mathrm{?1}}$ implies a water concentration of C₀ ? 10¹⁷ molecules per cm³ in the surface of KI crystals in equilibrium with an environment at 25°C and 35 per cent relative humidity. The large C₀ makes penetration very rapid. Diffusion occurs by interstitial migration of water molecules with an entropy of activation of 9.4 cal/mol deg and an enthalpy of activation of 12·9 kcal/mol.     

Simultaneous diffusion of calcium and strontium in KCl single crystals

Concentration dependent diffusion coefficients for ⁴⁵Ca²⁺ and ⁸⁵Sr²⁺ in purified KCl were measured using a sectioning method. KCl was purified by an ion exchange — Cl₂?HCl process and the crystals grown under $\text{1}\text{6}$ atmosphere of HCl. The tracers were purified on small disposable ion exchange columns to remove precessor and daughter impurities prior to use in a diffusion anneal. Isothermal diffusion anneals were made in the temperature range from 451% to 669%C. At temperatures above 580%C (the lowest melting eutectic in this system) diffusion was from a vapor source: below 580%C surface depositied sources were used. The saturation diffusion coefficients. enthalpies and entropies of impurity-vacancy associations were calculated using the common ion model for simultaneous diffusion of divalent ions in alkali halides. In KCl the saturation diffusion coefficients D_S(ca) and D_s(Sr) are given by

$\text{D}{}_{\mathrm{s}}\text{(Ca) = 9.93 × 10}{}^{\mathrm{?5}}\text{exp(?0.592}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}$

(1) and

$\text{D}{}_{\mathrm{s}}\text{(Sr) = 1.20 × 10}{}^{\mathrm{?3}}\text{exp(?0.871}\text{eV}\text{kT}\text{)}\text{cm}{}^2\text{sec}$

(2) for calcium and strontium, respectively. The Gibbs free energy of association of the impurity vacancy complex in KCl for calcium can be represented by

$\text{Δg(Ca) = ?-0.507 eV + (2.25 × 10}{}^{\mathrm{?4}}\text{eV}\text{\%K}\text{)T}$

(3) and that for strontium by

$\text{Δg(Sr) = ?0.575 eV + (2.90 × 10}{}^{\mathrm{?4}}\text{eV}\text{\%K}\text{)T}$

. (4)     

Lithium mobility in the layered oxide Li1−xCoO2

The Li⁺-ion chemical diffusion coefficient in the layered oxide Li_0.65CoO₂ has been measured to be $\text{D}\text{?}\text{= 5 × 10}{}^{\mathrm{?12}}$ m² s^?1 by three independent techniques: (1) from the Warburg prefactor, (2) from the transition frequency for semi-infinite to finite diffusion lengths in steady-state ac-impedence measurements and (3) from a modified Tubandt method that uses ac-impedance data to distinguish interfacial and surface-layer resistances from the bulk resistance of the sample. This value and a small increase in D? with (1 ? x) in Li_1?xCoO₂, 0.45 < (1 ? x) < 0.80, compare favorably with the $\text{D}\text{?}\text{= 5}\text{to}\text{7 × 10}{}^{-12}\text{m}{}^2\text{s}{}^{-1}$ obtained by Honders for this system with pulse techniques. A qualitative discussion is presented as to why this composition dependence and why D? for this system is a factor of five larger than that for Li⁺-ion diffusion in Li_xTiS₂.     

Chemical diffusion measurements in single crystalline cuprous oxide

Using electrical conductivity measurements in the temperature range 650–1100°C and for oxygen pressure greater than 10^?6atm., the variation of the chemical diffusion coefficient in cuprous oxide with temperature has been determined as:

$\text{D}\text{?}\text{= 1.2 10}{}^{\mathrm{?3}}\text{exp}\text{(}\text{? 7800}\text{RT}\text{)}\text{cm}{}^2\text{sec}{}^{\mathrm{?1}}$

.Taking into account the nature of the prevailing defects in cuprous oxide one can show that $\text{D}\text{?}\text{?D}{}_{\mathrm{<mtext>Cu</mtext>}}\text{[V}{}^{\mathrm{x}}{}_{\mathrm{<mtext>Cu</mtext>}}\text{]}$. This relation permits the results to be compared with those determined by tracer diffusivities. Using a value for the enthalpy of formation of non ionized copper vacancies in the range 12–16 kcal mol^?1, the results are shown to be in agreement with the value of the activation enthalpy for self-diffusion of copper of 24 kcal mol^?.     

Cyclotron resonance of positive holes in AgBr

The first observation of cyclotron resonance of holes in AgBr is reported. Measurements have been made at 34 GHz and 1.7 K. It is shown that the energy surfaces for the hole polaron consist of a set of spheroids oriented along the [111] directions with the mass parameters $\text{m}{}^1{}_{\mathrm{l}}\text{= (1.71±0.06)m}{}_0$ and $\text{m}{}^1{}_{\mathrm{t}}\text{=(0.79±0.01)m}{}_0$. The mobility of the hole polaron is determined to be about $\text{1.5 × 10}{}^5\text{cm}{}^2\text{Vsec}$ at 1.7 K.     

Chemical diffusion in nonstoichiometric chromium sulfide,Cr2+yS3

Using the re-equilibration kinetic method the chemical diffusion coefficient in nonstoichiometric chromium sesquisulfide, Cr_2+yS₃, has been determined as a function of temperature (1073–1373 K) and sulphur vapour pressure (10?10⁴ Pa). It has been found that this coefficient is independent of sulphur pressure and can be described by the following empirical equation: $\text{D}\text{?}\text{Cr}{}_{\mathrm{2+y}}\text{S}{}_3\text{=50.86}\text{exp(-39070 cal/mole/}\text{RT)}\text{(cm}{}^2\text{s}{}^{\mathrm{?1)}}$. It has been shown that the mobility of the point defects inCr_2+yS₃ is independent of their concentration and that the self-diffusion coefficient of chromium in this sulfide has the following function of temperature and sulphur pressure: . (cm²s^?1).     

Reorientational motion of the OH− ion in cubic sodium hydroxide

The rotational motion of the OH^? ion was studied in cubic NaOH at 575 K with quasielastic incoherent neutron scattering. The data are compared to two simple models yielding values for the radius of rotation R, the translational mean square displacement 〈u²〉_H, the rotational jump rate τ^?1 and the rotational diffusion coefficient D_R. The following parameter values are obtained: (a) rotational jump model: $\text{R = 0.95}\text{A}\text{?}$, $\text{〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.052}\text{A}\text{?}{}^2\text{, τ}{}^{\mathrm{?1}}\text{= 2}\text{meV}$, (b) rotational diffusion model: $\text{R = 0.99}\text{A}\text{?}\text{, 〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.046}\text{A}\text{?}{}^2\text{, D}{}_{\mathrm{R}}\text{= 0.72}\text{meV}$.     

Electronic conductivity of AgI using D.C. polarization and charge transfer techniques

A Study of electronic conductivity using the d.c. polarization technique has been carried out in α and β-AgI which shows the former is a hole and the latter an electron conductor. Activation energies of undoped and Cu-doped single crystals and polycrystalline β-AgI were found to be 0.46 eV, 0.34 eV and 0.44 eV respectively and can be related to electron trap depths. The electron transference number ($\text{σ}{}_{\mathrm{\theta }}\text{σ}{}_{\mathrm{t}}$) for polycrystalline β-AgI was found to be 0.008 at 306 K. The activation energy for hole conduction in α-AgI was determined to be 0.97 eV in agreement with previous XPS studies.Transient measurements have also been conducted using the charge transfer technique in double cells of polycrystalline β-AgI. The carrier concentration C_θ and electron mobility μ_θ, have thus been estimated to be 1.8 × $\text{10}{}^{15}\text{cm}{}^3$ and 5.14 × 10^?5$\text{cm}{}^2\text{V}$?sec. respectively at 306 K, while the double layer capacitance was 0.496 $\text{μF}\text{cm}{}^2$.     

Ω− produced in K−p reactions at 4.2 GeV/c

Forty $\text{Ω}{}^{\mathrm{?}}$ events have been observed in a large (133 events/βb) experiment at 4.2 GeV/c incident K^? momentum. Thirty nine of the events come from the three-body reaction $\text{K}{}^{\mathrm{?}}\text{p}\text{→Ω}{}^{\mathrm{?}}\text{K}{}^{\mathrm{+}}\text{K}{}^0$. The $\text{Ω}{}^{\mathrm{?}}$ is mainly produced in the forward hemisphere (direction of the incident K^?). The lifetime is measured to be τ = (0.75 _+0.14?0.11 × 10^?10 sec substantially less than the Particle Data Group value of (1.3 _?0.3^+0.2) × 10^?10 sec. The mass is determined to be 1671.7 ± 0.6 MeV, in good agreement with other determinations. The decay asymmetry parameter α (for the decay mode $\text{Ω}{}^{\mathrm{?}}\text{→ Λ}\text{K}{}^{\mathrm{?}}$) is found to be ?0.2 ± 0.4.     

A new upper limit for the branching ratio (Ξ− → nπ−)(Ξ− → Λπ−)

From a sample of 735 000 Ξ^? decays, we have obtained a new upper limit for the branching ratio $\text{(Ξ}{}^{\mathrm{?}}\text{→}\text{n}\text{π}{}^{\mathrm{?}}\text{)}\text{(Ξ}{}^{\mathrm{?}}\text{→ Λπ}{}^{\mathrm{?}}\text{)}$. The result is 1.9 × 10^?5 at the 90% confidence level.     

Electrical conductivity and chemical diffusion coefficient measurements in single crystalline nickel oxide at high temperatures

Electrical conductivity measurements on nickel oxide have been performed at high temperatures (1273 K<T< 1673 K) and in partial pressures of oxygen ranging from Po₂ = 1.89 × 10^?4 atm to Po₂ = 1 atm. The $\text{po}{}_2{}^{\mathrm{<mtext>1</mtext><mtext>n</mtext>}}$ dependence of the conductivity decreases from about $\text{1}\text{4}$ for Po₂ = 1 atm to smaller values for lower partial pressures of oxygen. The activation enthalpy for conduction increases for decreasing oxygen partial pressures (from 22.5 kcal mol^?1 at Po₂ = 1 atm to 26.0 kcal mol^?1 for Po₂ = 1.89 × 10^?4 atm). This behaviour can be explained by the simultaneous presence of singly and doubly ionized nickel vacancies, with different energies of formation.Furthermore, chemical diffusion coefficient measurements have been performed in the same temperature range, using the conductivity technique, and leading to the result:

$\text{D}\text{?}\text{= 0.244 exp (?}\text{36,600}\text{RT}\text{) cm}{}^2\text{s}{}^{\mathrm{?1}}$

.