Water transbilayer diffusion in macroscopically oriented lipid bilayers as studied by pulsed field gradient NMR

Water self-diffusion in lipid bilayers macroscopically oriented on glass plates was studied by pulsed field gradient¹H nuclear magnetic resonance technique. Diffusion decays were multicomponent with a distribution of diffusion coefficients ranging from about 10⁻¹⁰ to about 10⁻¹³ m²/s. A number of measurements with variations of the sample orientation, diffusion time and the distance between the glass plates showed that the “fast” component of diffusion corresponds to water in the bilayer “cracks”. The “slow” component of diffusion corresponds to transbilayer water diffusion in the long-diffusion-time regime. For a more reliable separation of parts corresponding to fast and slow diffusion of water, a “component-resolved spectroscopy” method for the global analysis of correlated spectral data (P. Stilbs, K. Paulsen, P.C. Griffiths: J. Phys. Chem. 100, 8180, 1996) was applied.     

Low temperature diffusion in thin-film couples of polycristalline silver and gold

Limited diffusion spaces which may be easily traversed by atoms diffusing along grain boundaries generally cause thin-film diffusion to differ from common bulk diffusion. These peculiarities were studied in Ag−Au thin-film couples by means of electrical resistance measurements. Diffusion coefficients were found to decrease with annealing time mainly as a consequence of recrystallisation and recovery in the films during the diffusion anneal. It is shown that the rate of homogenisation is fairly independent of the film thickness thus giving evidence that diffusion into the crystallites occurs out of the grain boundary network rather than directly through the couple interface. Effective diffusion coefficients determined between 150 and 250° C ranged from 10⁻¹⁴ to 10⁻¹⁶ cm² s⁻¹ revealing an activation energy of 25 kcal mol⁻¹.     

Quantum diffusion of muonium in GaAs

The diffusion rate of muonium in the III–V compound semiconductor GaAs has been determined from measurements of muon spinT ₁ relaxation induced by motion in the presence of nuclear hyperfine interactions. It is shown for the first time in a semiconductor that (a) there is a crossover of the transport mechanism at about 90 K from stochastic to zero-phonon hopping, as evidenced by a steep rise in the hop rate at lower temperatures, and that (b) the muonium diffuses at the hop rate of 10¹⁰ s⁻¹ (corresponding diffusion constantD≈10⁻⁶ cm²s⁻¹) at lower temperatures as well as at room temperature.     

Dislocation diffusion mechanism in Pd/Ag crystals

In epitaxial Pd/Ag crystals, dislocations in the palladium film have a large influence on the effective diffusion coefficient. In silver the diffusion coefficient hardly depends on the dislocation density. With a dislocation density of 10¹⁰m⁻² the diffusion coefficient in silver is larger than in the palladium, and at 773 K it is 10⁻¹⁸ m²/s. At a dislocation density of 3·10¹² m⁻², the diffusion coefficient in the palladium becomes larger than in silver, and at 773 K it is 3·10⁻¹⁸ m²/s. It is most likely that diffusion in silver takes place via the lattice, while in palladium it occurs at mobile dislocation sites. State Technical University, Samarsk. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 8, pp. 116–118, August, 1996.     

Photothermal deflection measurement of effective gas diffusion coefficient of a porous medium

In this work, an effective gas diffusion coefficient of a porous medium was measured using photothermal deflection (PD) technique. An in-house made Loschmidt diffusion cell with a photothermal-deflection probe were employed to measure the effective gas diffusion coefficient of a gas diffusion layer (GDL) with a porosity ε ≈ 0.7. The concentration evolutions of CO₂ in O₂ with and without the GDL were measured, respectively, using a transverse normal PD technique. The concentration variations were used to deduce the gas diffusion coefficients in the presence and absence of the GDL by solving mass diffusion equations. The effective gas diffusion coefficient of the GDL was calculated from the diffusion coefficients using a model of an equivalent resistance to diffusion and found to be 4.39 × 10^-6 m²s^-1, demonstrating that PD technique can be employed to determine the effective gas diffusion coefficient of a porous medium.     

Method for measuring chemical diffusion coefficients in solids

Experiments were performed with temperature programmed desorption of hydrogen and deuterium adsorbates on small platinum spheres. Beyond the expected desorption peak of these adsorbates at around 300 K sample temperature an additional desorption peak at higher temperatures was observed. This additional peak is explained by the diffusion of hydrogen or deuterium atoms from the inside of the spheres to their surfaces with final desorption from these surfaces. The visibility of this second high temperature desorption peak is supported by a small diameter of the platinum spheres. Platinum spheres with diameters around 64 μm were used. The sample temperature at which the second peak was observed depends on the parameters: diameter of the platinum spheres, heating rate of the sample and chemical diffusion coefficient of hydrogen or deuterium in platinum. A theory, which assumes that the chemical diffusion coefficient can be described with an Arrhenius ansatz, was developed to simulate the occurrence of the second peak. The combination of these kinds of experiments with the theory gives a method to measure chemical diffusion coefficients. This method can be called temperature programmed diffusion. At 510 K sample temperature the diffusion coefficient 1.61×10⁻¹² m²/s of hydrogen in platinum and the diffusion coefficient 1.40×10⁻¹² m²/s of deuterium in platinum was measured.     

Study of water diffusion in human dentin by optical coherent tomography

The diffusion of chemical agents in dental tissues is of interest for many problems of dental tissue physiology (diffusion of liquor and water), dental healing (diffusion of preparations), and cosmetic dental treatment (diffusion of whitening agents). The water diffusion in samples of human dentin was monitored using optical coherent tomography (OCT). This diffusion manifests itself as a change in the slope and amplitude of the OCT signal from the sample. It is shown that the average dentin permeability with respect to water is (15.11 ± 21.73) × 10⁻⁶ cm/s. These experimental results demonstrate the OCT efficiency for studying the diffusion in hard biological tissues.     

Fast magnetic relaxation, studied by microwave absorption in neutron-irradiated YBa2Cu3O7−x ceramic

A contactless microwave method is used to measure the fast magnetic relaxation of granular ceramic samples of YBa₂Cu₃O_7−x irradiated by neutrons with fluences of 10¹⁶–10¹⁹ cm⁻². An experimental study of the time dependence of the relaxation of high-frequency (rf) absorption (f=100 MHz) after the action of an external magnetic field pulse has shown the magnetic relaxation times τ ₀ to be in the time interval of 0.5–150 ms. The rf-absorption mechanism is discussed in terms of an intergranular system with a thermally activated flux of vortices and their diffusion in the granular medium. Fiz. Tverd. Tela (St. Petersburg) 39, 977–981 (June 1997)     

Erbium incorporation in LiNbO3 by diffusion-doping

 The erbium incorporation into LiNbO₃ by diffusion doping is investigated in detail by means of Secondary Ion Mass Spectrometry, Secondary Neutral Mass Spectrometry, Rutherford Backscattering, Atomic Force Microscopy, X-ray Standing Wave technique and optical site-selective spectroscopy. The diffusion of erbium in LiNbO₃ can be described by Fick’s laws of diffusion with a concentration-independent diffusion coefficient. The diffusion constants and activation energies for Z-cut (X-cut) LiNbO₃ are 4.8×10^-5 cm²/s (12.0×10^-5 cm²/s) and 2.28 eV (2.44 eV), respectively. A limited solubility of erbium in LiNbO₃ has to be taken into account increasing exponentially with rising temperature. During the first step of diffusion an Er _x Nb _y -oxide layer is formed at the surface of the sample acting as diffusion reservoir. Erbium is incorporated into LiNbO₃ on vacant Li-sites slightly shifted from the original Li-position along the (-c)-direction. Site-selective spectroscopy found four distinguishable energetically different erbium centres at this lattice site resulting from locally different symmetries of the crystal field. Received: 21 March 1996 / Accepted: 12 August 1996     

Determination of proton diffusion in solid electrolytes

Two electrochemical methods have been used to determine the proton diffusion in solid electrolytes. One is based on transient ionic current measurements and a reasonable physical model; the other one is a quick determination using steady-state transport. The results of proton diffusion coefficients of 10⁻⁶ and 10⁻⁵ cm²/s obtained for the α- and β-phases of Li₂SO₄, respectively, using these two methods are in a good agreement with published results. The methods turned out to be very useful for determining proton diffusion in solid electrolytes, especially when the electrolytes contain more than one type of the mobile ionic species and a low concentration of the protons. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Investigation of thin film all-solid-state lithium ion battery materials

All-solid-state thin film batteries are feasible by employing Al as anode and LiPON as electrolyte which are subsequently deposited by sputtering. The lithium ion conductivity of ∼ 10⁻⁶ S/cm for the thin film LiPON is in agreement with data reported for bulk material. The high voltage cathode Li₂CoMn₃O₈ could be prepared by forming the compound by the combustion method andsubsequent e-beam evaporation of this material with the addition of 20 wt.-% LiNO₃ at an oxygen partial pressure of 10⁻⁵ mbar. The thin film cells could be operated between 3 and 5 V vs. Al, LiAl. The chemical diffusion coefficient was found to be in the range from 10⁻¹³ to 10⁻¹² cm²/s at room temperature by employing the GIT-technique for the composition x of Li_2-xCoMn₃O₈ in the range from 0.1 to 1.6. Impedance studies of the complete battery system revealed a charge transfer resistance of 290 Θ, a double layer capacity of ∼ 45–70 μF for an electrode area of 6.7 cm² and a rate determining chemical diffusion coefficient in the range from 10⁻¹² to 10⁻¹¹ cm²/s. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15–21, 2002.     

The influence of different forms of surface oxide on the fast states of germanium

The alternating field effect was used to study the kinetics of the influence of water molecules on the fastN _t centres on the surface of germanium. It was observed that the time dependence in the adsorption of water and in the change in concentration of the fast centres caused by this adsorbed water differs, indicating that the water diffuses through the oxide to the fast centres with a diffusion constantD approximately equal to 10^–15-10^–14 cm²/sec. The magnitude of the diffusion constantD constantly increased after annealing the sample in a wet atmosphere, and temporarily decreased after annealing in a dry atmosphere. The influence of annealing on the concentration of the fast states and the penetrability of the water through the oxide layer of germanium was also studied.The author thanks S. Koc, C.Sc., for advice and the interest he showed in the work.     

Growth velocity and the topography of Ni-Zn binary alloy electrodeposits

We show that the electrodeposition of Ni-Zn alloys at the lowest growth velocities, v < 0.5μm/s, exclusively proceeds from an abnormal co-deposition phenomenon. The growth process in this v region greatly depends on the initial [Co²⁺] concentration of the film deposition bath. A theoretical approach of this process including the role of the saturation surface roughness of the alloy, , leads to an estimation of the transport properties of the ad-atoms involved during the deposit formation. Their surface diffusion coefficient varying between 1.76×10^-10 and 2.40×10^-8 cm^-2/s exhibits a minimal value, D _s = 2.10×10^-10 cm^-2/s located between v = 0.17 and 0.35μm/s. The spatial scaling analysis of the local roughness, σ, examined according to the power-law σ≈L ^α reveals that the resulting roughness exponents concurs with the Kardar-Parisi-Zhang dynamics including the restricted surface diffusion. Two main v regions leads to different fractal textural features of the alloy film surface. Below 0.10 μm/s, the roughness exponent obtained is α≈ 0.6, depicting a limited ad-atom mobility. Over v = 0.30μm/s, this exponent stabilises at α≈ 0.82, indicating an increase of the surface diffusion. Received 16 August 2000 and Received in final form 20 June 2001     

Diffusion of sodium,potassium, calcium,manganese, and radon in tuff and clinoptilolite under leaching

Nuclear physics methods are used to determine the diffusion coefficients of Na, Ca, Mn, K, and ²²²Rn in clinoptilolite (Sokirnitsa occurrence, Ukraine) and in natural tuff (Yucca Mountain, Nevada, United States) and in tuff irradiated by γ-quanta (E _max = 23 MeV) to a dose of 10⁷ Gy at a leaching temperature of 37°C. The diffusion coefficients of sodium and potassium in clinoptilolite are found to differ considerably: 4 × 10⁻¹⁷ and 2 × 10⁻²⁰ m²/s, respectively. This indicates the influence of aquacomplexes on the cation transfer. The diffusion coefficient of radon in these materials is determined: in clinoptilolite it equals 2.5 × 10⁻¹² m²/s.     

Sorption and diffusion behaviours of strontium in sodium-type bentonite bed

Sorption and diffusion of Sr were examined using a typical Japanese bentonite. The experimental results showed that Sr sorption on the bentonite had linear relationship between the equilibrium Sr concentration and Sr sorption amount, i.e., Henry’s type of sorption, in wide initial Sr concentration from 1.1×10⁻⁹ to 1.1×10⁻⁴ mol L⁻¹ at pH 10. The Sr sorption also indicated pH dependence in pH range between 2 and 12. Sorption modelling calculation indicated that cation-exchange reactions contributed to Sr sorption in the pH range studied and a surface complexation reaction was predominant above pH 8. Diffusion of Sr in loosely compacted bentonite bed was described by pore and surface diffusion and surface complexation of Sr. Chemical-transport calculations reproduce the diffusion data at pH 5 using the cation-exchange parameters obtained in the analysis of the batch sorption experiment.     

Spin Polarization of Fluorine Nuclei in the Si/CaF<Subscript>2</Subscript> Nanostructure Under Optical Excitation

The laws of fluorine nuclear spin polarization in the Si/CaF₂ nanostructure under optical excitation of the charge carriers in it has been considered theoretically. It has been shown that maximum values (up to 3% of the concentration of nuclei in the lattice) are attained under a high rate of optical excitation (>10⁻⁹ sec⁻¹) when the nuclear spin diffusion process and the Auger recombination prevail. In this case, the nuclear relaxation time in an individual layer reaches 100–300 sec and the spin diffusion radius decreases to 0.3 nm. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 397–403, May–June, 2005.     

Dynamics of different molecules adsorbed in porous media

We present in this paper a comparative study on the dynamics of benzene, cyclohexane, and methanol molecules, confined in the pores of MCM-41 molecular sieve and HZSM-5 zeolite. The quasi-elastic neutron scattering (QENS) measurements revealed that the physical state of these adsorbed molecules depended not only on the structural characteristics of the host matrix but also on the chemical properties, such as dipole moment, of the guest molecules. Thus, while no motion was observed in the time-scale of 10⁻¹⁰−10⁻¹² s in the case of methanol, the larger size benzene and cyclohexane molecules are found to perform six-fold and three-fold jump rotation, respectively, when adsorbed inside the cages of HZSM-5 at room temperature. At the same time, all the three molecules are found to undergo a translational motion inside the pores of MCM-41 molecular sieves, the value of diffusion constant being the lowest in case of methanol because of its higher polarity. Translationl motion of the guest molecules inside the pores of MCM-41 can be satisfactorily described by Chudley-Eliott fixed jump length diffusion and accordingly the residence time, jump length and diffusion constant are estimated.     

Diffusion study of <Superscript>15</Superscript>N implanted into α-Ti using the nuclear resonance technique

The diffusion of ¹⁵N in α-Ti was studied in the 673–1023 K temperature range by using the ion implantation and nuclear resonance techniques. The measurements show that the diffusion coefficients follow an Arrhenius behavior D(T)=D₀ ^-Q/RT, where D₀=(1.1±0.8)×10^-7 m² s^-1 and Q=(183±2) kJ/mol. A comparison with previous results is also given. PACS 66.30.Jt; 85.40.Ry     

Phosphorus distribution profiles in 100-silicon using a spin-on source at low temperatures

 Incorporation of phosphorus into silicon from a spin-on dopant layer (SOD) at 400 ^°C is described. Annealing experiments were carried out with SOD films deposited on (100) silicon substrates by using the spin-on technique. Conventional heating on a hotplate in normal atmosphere and a temperature range up to 400 ^°C was used to study the dopant incorporation. After removing the SOD-films one part of the silicon substrates was annealed at higher temperatures. Investigations were carried out by SIMS, SAM, XPS, HTEM, stripping Hall and Van der Pauw measurements before and after the high temperature annealing. Chemical phosphorus concentration profiles obtained from low temperature annealed samples showed diffusion depths of 60–80 nm (extrapolated to a substrate doping level of 10¹⁶ cm^-3) and surface concentrations of 10¹⁹–10²⁰ cm^-3. Electron concentration profiles exhibiting maximum values around 2⋅10¹⁹ cm^-3 could be measured on high temperature annealed samples only. Received: 28 March 1996/Accepted: 19 August 1996     

Stepwise synthesis of fine crystalline Ce-doped yttrium aluminum garnet in water medium in subcritical and supercritical conditions

In this paper the continuous stepwise method of a production of fine crystalline yttrium aluminum garnet doped with cerium (YAG: Ce³⁺) in supercritical water fluid (SCWF) are represented. The synthesis was carried out in water medium in two stages: first in subcritical conditions and then in an atmosphere of supercritical water fluid. The stoichiometric mixture of yttrium oxide and aluminum hydroxide in a water solution of cerium nitrate was maintained the certain time at 280°C and under vapor water pressure 6.3 MPa. Then temperature and pressure were risen up to a supercritical condition (T = 392–400°C, P_{H2 O}P_{H_2 O} = 22 MPa). The concentration of cerium ions in reaction medium was changed in the interval 0.012–0.706 wt %. The products, obtained on various stages of synthesis, were investigated by physical-chemical methods. During the first stage, the crystals of boehmite and yttrium hydroxide under hydrothermal conditions were arising, and eventually poorly formed YAG: Ce³⁺ were appearing. At this stage, the diffusion of cerium ions into intermediate products takes place. Because of this, at the second step of synthesis, in supercritical conditions, YAG: Ce³⁺, phosphor with high luminescence intensity at 530 nm, was obtained. In supercritical conditions well-faceted crystals of 0.5–3.0 μm with rhombododecahedral habitus were produced.