In situ measurements of aggregation and disaggregation of Cu(II) complex at liquid/liquid interface

Aggregation of Cu(II)-5-(octadecyloxy)-2-(2-thiazolylazo)phenol (TARC18) complex at the heptane/water interface was measured directly by a centrifugal liquid membrane spectrometry and a two-phase microflow API-MS method. When the pH of an aqueous phase was increased from 4 to 6, the 1:1 complex of Cu(II)-TARC18, which was formed as a positively charged complex at the interface, formed further an aggregate, accompanied by the change of spectra suggesting its aggregation. The MS spectra of the interfacial species indicated the formation of 2:3 complex for Cu(II) and TARC18 under the conditions that the aggregate was formed. This observation allowed us to analyze the interfacial aggregation stoichiometrically: the aggregate of the 2:3 complex was formed from a 1:1 complex at the interface. The addition of purine base of adenine or guanine into the system resulted in the disruption of the aggregate by the formation of a new three-element complex of 1:1:1 for Cu(II), TARC18, and the base, showing a bathochromic shift in the spectra. Thus, the disaggregation experiment showed an interfacial molecular recognition ability of the Cu(II)-TARC18 aggregate for hydrophobic bases.     

Study of interface phenomena between bone and titanium and alumina surfaces in the case of monolithic and composite dental implants

The interface between mandibular bone and dental implants was examined with the in vivo dog model. Implant/bone interfaces were investigated for three types of materials: Ti–30 wt% Ta/Al2O3, titanium and Al2O3 using microscopy techniques covering a large magnification range: scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray analysis and Auger spectroscopy. During the interaction of the Al2O3 ceramic with bone, an interfacial layer about 15 m thick is formed. The same phenomenon was observed at the titanium bone interface, where the thickness of the layer was about 10 m. In all cases, interface layers were sharp with well-defined borders between bone tissue and implant materials. No calcification took place inside the interface layer. A chemical analysis performed on this layer shows the presence of titanium, calcium and phosphorus in the case of titanium implants, and aluminium, calcium and phosphorus in the case of alumina implants. A rapid decrease in metal composition with increasing distances from the implant surface is correlated to a slow increase in calcium and phosphorus in the direction of the bone. Direct contact between implant and bone was observed. No biocorrosive effects were detected at the Ti–30 wt% Ta/Al2O3 metal–ceramic interface.     

In situ measurement of Cl- concentrations and pH at the reinforcing steel/concrete interface by combination sensors

This paper presents an in situ, nondestructive method of monitoring Cl- concentrations and pH values at the steel/concrete interface. The Ag/AgCl electrodes prepared by the electrochemical anodization and the Ir/IrO2 electrodes prepared by thermal oxidation in carbonate served as Cl- concentration and pH sensors, respectively. The potentiometric response of the Ag/AgCl electrode to the logarithm of Cl- concentrations ranging from 1 x 10(-4) to 2 M in saturated Ca(OH)2 solution simulating the inner electrolytic medium of concrete shows good linearity. The Ir/IrO2 electrode also exhibits an ideal Nernstian response in the range of pH 1-14. The Ag/AgCl and Ir/IrO2 electrodes were combined into a multiplex Cl-/pH sensor, and the sensor was embedded in concrete close to the steel/concrete interface to realize an in situ and long-term measurement of Cl- concentrations and pH values. The results indicate that the combined sensor is robust and sensitive enough to in situ measure Cl- concentrations and pH quantitatively at the steel/concrete interface, which is of indispensable importance to the study of corrosion and protection of the steel in concrete.     

Growth of diffusion layers at liquid Al–solid Cu interface under uniform and gradient high magnetic field conditions

The effect of high magnetic fields on interfacial reactive diffusion in liquid/solid (Al/Cu) couples was experimentally investigated at a temperature of 973 K. Regardless of any magnetic field, compound layers consisting of the δ, ξ₂, η₂ and θ phases were produced at the interface. The magnetic flux density, B, exerted a non-monotonic influence on the growth of the diffusion layers. Moreover, the mean thickness of the diffusion layers (parallel to B) was found to be always greater than that of the diffusion layers (perpendicular to B) under the applied magnetic fields. These phenomena should be attributed to the effects of two types of the Lorentz force under a uniform high magnetic field on diffusion behavior. In addition, the growth of intermetallic phases could be retarded by a magnetic field gradient due to the magnetic force in the axial direction.     

In situ surface-enhanced infrared study of hydrogen bond pairing of complementary nucleic acid bases at the electrochemical interface

Surface-enhanced infrared absorption spectroscopy with a Kretschmann-type attenuated total reflection configuration has been used to study hydrogen-bonded pairing between 6-amino-8-purinethiol, a thiol-derivatized adenine, immobilized on a gold electrode surface, and thymidine, a complimentary base derivative of adenine, in 0.1 M NaClO4 aqueous solution as a function of applied potential. 6-Amino-8-purinethiol is adsorbed on a gold surface via a sulfur atom to form a S-Au bond. Nearly half of the adsorbed molecules are protonated, and the long axis of the adenine moiety is tilted from the surface normal at open circuit potential. As the potential increases, the acid-base equilibrium is shifted toward the unprotonated form and the adenine moiety is reoriented toward a nearly perpendicular configuration. The hydrogen bond interaction between the adsorbed 6-amino-8-purinethiol with thymidine in solution is greatly affected by the protonation and orientation of the adenine moiety and is controllable by the applied potential. Due to steric hindrance, an adenine-thymine-type hydrogen bond pair is formed only at potentials more positive than 0.1 V (vs SCE) where the unprotonated adenine moiety is perpendicularly oriented.     

Thermodynamic studies of the interaction at the solid/liquid interface between metal ions and cellulose modified with ethylenediamine

The chelate molecule, ethylenediamine, has been incorporated onto the surface of cellulose by sequential reaction of cellulose fibres with phosphorous oxychloride followed by the chelating agent. The modified material (CelNN) retained its fibrous nature and was shown to be efficient at adsorbing divalent metal cations from water by complexation. Adsorption isotherms were determined for suspensions of CelNN in metal ion solutions of different concentrations, and the data were adjusted to fit the modified Langmuir equation. The maximum numbers of moles of Cu2+, Ni2+ and Zn2+ adsorbed per gram of modified cellulose were 1.64 x 10(-3), 5.25 x 10(-4) and 1.06 x 10(-3), respectively. The thermodynamic effects related to the adsorption of metal ion onto the cellulose surface were determined by calorimetric titration. Gibbs free energy was spontaneous for all interactions. The adsorption processes all exhibited endothermic enthalpy values and were accompanied by increases in entropy.     

Simulation studies of the hydrodynamics in high-temperature solutions for crystal growth. VI. Temperature fluctuations at the crystal/liquid interface

The temperature fluctuations at the crystal/liquid interface have been studied using model liquids. The character of the fluctuations varied depending on whether in the liquid there was only free convection or both free and forced convections were simultaneously present. It has been established that in the second case the amplitude of fluctuations is determined mainly by the rate of the resultant convection flow and the liquid viscosity. A maximum amplitude of fluctuations is observed at a resultant flow rate w_fl = O when the free and forced convections proceed in opposite directions, and at w_fl = min when both convection flows have the same direction. Larger amplitudes of temperature fluctuations are registered in low-viscosity liquids. The conditions under which a flat crystal/liquid interface showing no temperature fluctuations should be formed have been determined for crystal diameters of 10, 15 and 20 mm, respectively.     

Molecular modelling studies of clay–exopolysaccharide complexes: Soil aggregation and water retention phenomena

In soils, the bacterial exopolysaccharides (EPS) aggregate mineral particles, enhancing their cohesion and their ability to retain water. These phenomena have been studied at the atomic scale by molecular modelling; we have considered seven rhizospheric polysaccharides interacting with the basal surfaces of montmorillonite. Models accounted for the aggregation phenomena induced by EPS: some segments of the polysaccharide were adsorbed on the mineral surfaces while others formed loops and bridges linking two surfaces. Adsorption energies were favourable and depended mostly on the interacting area. Cohesion of aggregates was estimated by the adhesion work, predicted values differed from one EPS to the other, suggesting that the chemical structure influences interaction strength with the mineral surface. Mechanisms of water uptake and release have also been investigated: hydration energies revealed that EPS strongly retain water at low water concentrations.     

Initiation and short crack growth in austenitic–ferritic duplex steel‐effect of positive mean stress

The effect of the mean stress on the crack initiation and short crack growth of austenitic–ferritic duplex steel has been studied. High mean stresses and stress amplitudes result in appreciable mean strain relaxation and long‐term hardening. Mean stress produces unidirectional slip bands and slip steps that serve as nuclei for persistent slip bands and persistent slip markings. It leads to the acceleration of the crack initiation and production of a high density of cracks. Crack linkage contributes to the growth of short cracks. The concept of equivalent crack was used to describe the crack growth. The kinetics of short crack growth with positive mean stress is similar to that in symmetric loading, that is, exponential growth is observed. Positive mean stress results in earlier crack initiation and in the acceleration of the crack growth rate. Both factors contribute to the decrease of the fatigue life.     

Fracture toughness of the interface between Ni–Cr/ceramic,alumina/ceramic and zirconia/ceramic systems

Few studies have focused on the interface fracture performance of bi‐layered structures, which have an important role in dental restorations, using ceramic materials. The purpose of this study is to evaluate the fracture mechanics performance of the Ni–Cr/ceramic, alumina/ceramic and zirconia/ceramic interfaces by investigating the propagation of an interfacial crack under a wide range of mode mixities. The effect of the mechanical properties of the base materials and the interface, on the crack initiation and crack path, will also be studied. The finite element method (FEM) was used to calibrate the production of the experimental specimens, allowing to obtain the minimum dimensions and amounts of material needed to correctly characterize the fracture event. The specimens were tested until failure using a three‐point bending test machine. The interface fracture parameters were obtained using the FEM. For all specimens, the cracks propagated into the ceramic. The results suggest that, in Ni–Cr/ceramic, alumina/ceramic and zirconia/ceramic bi‐layered structures, the ceramic is weaker than the interface, which can be used to explain the clinical phenomenon that the ceramic chipping rate is larger than interface delamination rate. Consequently, a ceramic material with a larger fracture toughness is needed to decrease the failure rate of ceramic restorations.     

Photographic studies of light induced nucleation of boiling at the interface of a solid and superheated liquid helium I

We report the results of photographic studies which show that light induces the nucleation of vapour bubbles in superheated liquid helium I. We believe that these bubbles are associated with the cooling that we have previously observed to result from a flash of visible light applied to the surface of a bismuth crystal heater-thermometer immersed in the superheated liquid. We have used this photographic technique to study vapour bubble growth dynamics and compare our results with the theory.     

Controllable synthesis of uncapped metal nanoparticle assembly at the air–water interface

A two-dimensional self-assembly of uncapped Ag nanoparticles was prepared at the air–water interface. In the experiment, ethanol was added into the Ag-based colloid to reduce the surface charge density on the nanoparticles and the air–water interfacial energy, leading to the nanoparticles adsorption and assembling at the air–water interface. It was found that the array structure was controllable. The ordered nanoparticle array could be changed to a fractal structure by varying gradually the amount of the added ethanol. Moreover, it was demonstrated that the assembly was sensitive to the surface charge density on the particles, the Debye length in the colloid and the interfacial tension between nanoparticle/water (air).     

In situ synthesis mechanism and characterization of ZrB2–ZrC–SiC ultra high-temperature ceramics

The synthesis route, microstructure and properties of ZrB₂–ZrC–SiC composites prepared from a mixture of Zr–B₄C–Si powders by in situ reactive synthesis were investigated. The reactive path and synthesized mechanism of ZrB₂–ZrC–SiC composite were studied through series of pressureless heat treatments ranging from 800 °C to 1700 °C in argon. The in situ ZrB₂–ZrC–SiC composites were fabricated under different synthesis processing. The one with 88.4% relative density performed poorly in mechanical properties due to the occurring of self-propagating high-temperature synthesis (SHS). The fully dense ZrB₂–ZrC–SiC composite was obtained under the optimized synthesis processing without SHS reactions. Its Vickers hardness, flexural strength and fracture toughness were 20.22 ± 0.56 GPa, 526 ± 9 MPa and 6.70 ± 0.20 MPa m^1/2, respectively.     

In situ localization of apoptotic changes in the interface membrane of aseptically loosened orthopaedic implants

Twenty specimens of bone-implant interface membrane from THR/TKR were used for in situ localization of apoptotic changes. A panel of antibodies was used to label leukocyte antigens (CD68 and CD3) cytokines (IL-1 and IL-1) and apoptosis inhibiting and promoting proteins (bcl-2 and bax) by means of immunohistochemical techniques. A DNA fragment test on the tissue sections was also carried out to confirm actual cell death using the enzyme terminal deoxy nucleotidyl transferase (TdT) to incorporate biotinylated nucleotide with the 3-OH DNA ends. Leukocyte antigen staining showed that there were large numbers of CD68 positive macrophages as well as multinucleate giant cells (MNGC) but that CD3 positive lymphocytes were also present in the interface membrane. The leukocyte surface antigen staining pattern corresponded to previous findings [1]. Immunostaining with bcl-2 and bax antibodies revealed that both of these proteins were expressed in the cytoplasm of the cells in the interface membrane but they showed different cellular patterns. Bcl-2 was localized in a small number of lymphocyte-like cells while bax was expressed by large numbers of cells, mainly macrophages. The number of cells which expressed bcl-2 was significantly lower than that of bax (P < 0.01). DNA fragment localization occurred mostly in a layer of cells (13 cells deep) next to the implant surface. Again the level of DNA fragment-containing cells was significantly lower than that of bax positive cells (P < 0.01). The results, for the first time, indicate that there is an apoptotic activity occurring in cells in the interface membrane, but not all the cells which express apoptosis-promoting protein (i.e. bax) will enter into the phase of cell death.     

Evaluation of some self-sustained capillary effects taking place in slag at the interface during desulphurization process

In the paper are presented and analyzed some specific problems of instability and of Marangoni convection in desulphurizing slags at 1873.15 K, due to the presence of sulphur, during liquid steel treatments. Starting from the quantity sulphide capacity, a limit of sulphur solubility in a homogeneous liquid slag is established. The thermodynamic effect of sulphur in the slag is evaluated using an enthalpy of interaction of sulphur containing the balance of the partial molar enthalpy of mixing for CaS and CaO. The sulphur effect in slag, on the enhancement of the mass transfer coefficient through the interface is evaluated based on the expression of the concentration coefficient of the surface tension related to the mole fraction, the solutal Marangoni number and of the sulphur mass transfer enhancement parameters. It is concluded that during desulphurization, self-sustained capillary effects are present in slags.     

In situ studies of nonlinear d-spacing changes in titanium and steel alloys

We traced element-partitioning behavior by measuring d-spacing changes in situ during phase transformations of titanium and steel alloys using a hybrid in situ observation system. For titanium alloy, nonlinear changes are clearly evident during heating and cooling and are related to element partitioning and microstructural evolution. For low-carbon-low-alloy steel, nonlinear changes are evident during cooling and are related to bainite and carbon-enriched austenite formation.     

In situ Raman cell for high pressure and temperature studies of metal and complex hydrides

A novel cell for in situ Raman studies at hydrogen pressures up to 200 bar and at temperatures as high as 400 °C is presented. This device permits in situ monitoring of the formation and decomposition of chemical structures under high pressure via Raman scattering. The performance of the cell under extreme conditions is stable as the design of this device compensates much of the thermal expansion during heating which avoids defocusing of the laser beam. Several complex and metal hydrides were analyzed to demonstrate the advantageous use of this in situ cell. Temperature calibration was performed by monitoring the structural phase transformation and melting point of LiBH(4). The feasibility of the cell in hydrogen atmosphere was confirmed by in situ studies of the decomposition of NaAlH(4) with added TiCl(3) at different hydrogen pressures and the decomposition and rehydrogenation of MgH(2) and LiNH(2).     

In situ adsorption studies at silica/solution interfaces by attenuated total internal reflection fourier transform infrared spectroscopy: examination of adsorption models in normal-phase liquid chromatography

ATR-FT-IR spectroscopy was employed to the study the adsorption of ethyl acetate and 2-propanol to the surface of thin silica sol-gel films in contact with n-heptane solutions. In situ vibrational spectra of silica-adsorbed species provided information regarding the mechanisms of solute retention and elution in normal-phase chromatography. Previous normal-phase chromatographic studies of ethyl acetate adsorption revealed nonlinear isotherms which were explained by both bilayer and adsorbate delocalization models. Infrared spectra of ethyl acetate at the silica surface versus concentration showed that nonlinear adsorption can be attributed to site heterogeneity, where adsorption to free silanols and surface-adsorbed water can be distinguished. Least-squares modeling of the data produced resolved spectra for the two sites and adsorption equilibrium constants that differed by about an order of magnitude. Adsorption of 2-propanol was best modeled by a single Langmuir isotherm showing no significant difference in adsorption energy for the two sites; 2-propanol was shown to easily displace ethyl acetate from the silica surface. Ethyl acetate could also displace 2-propanol from the silica, and least-squares modeling again revealed two-adsorbed-component spectra for ethyl acetate that were indistinguishable from spectra obtained when ethyl acetate adsorbed directly onto the surface.