Defect and Diffusion Forum Vols. 312-315

Abstract: This paper reviews typical results of tracer diffusion and ionic conduction in soda-lime silicate glass and in single-alkali and mixed-alkali borate glass obtained in our laboratory and published in detail elsewhere. We have studied tracer diffusion of modifier cations and ionic conduction as functions of composition, temperature and, in the case of borate glass, also as function of pressure. We compare tracer diffusion with charge diffusion and in the case of soda-lime glass also with viscosity diffusion. The Haven ratios for soda-lime glass are temperature independent. For sodium borate glass the Haven ratio is almost temperature- and pressure-independent, whereas it decreases significantly with decreasing temperature and increasing pressure for rubidium borate glass. It also decreases with increasing alkali content. We attribute these facts to collective atomic jump events, in which several ions move simultaneously in a string-like or chain-like fashion. We also illustrate the mixed-alkali effect, which was studied by conductivity measurements and by tracer diffusion for mixed sodium-rubidium borate glasses.

Abstract: The iron ore raw materials and coke quality is the basic reserve of improvement of blast furnace technology. Some of the quality indicators of iron ore raw materials and coke and their influence on the main parameters of the blast furnace smelting are considered in this paper.

Abstract: One of the problems of powder metallurgy still remaining is the problem of billets shrinkage at sintering. Introduction of a small impurity coating consisting of a very thin layer of the particles on the basic powder is a known method of compacting at sintering of powder materials. The mathematical modeling of such a process encounters ambiguity some issues of the sintering theory of metal powders, therefore forcedly leans on experiments. A mathematical model of powder metal sintering with nano- and microadditives is presented.

Abstract: It was shown more recently in our Laboratory [1,2,3] that having a substrate/diffusant/thin-film/cap-layer structure (the thin film was typically several 10 nm thick, with the same order of magnitude of grain size; the refractory metal cap layer was used just to avoid the oxidation), first the diffusant atoms migrated very fast across the thin film and segregated at the film/cap-layer interface. The accumulated atoms at the film/cap layer interface form a secondary diffusion reservoir and atoms diffuse back to the layer. Later on, the thin film was gradually filled up with the diffusing atoms and composition depth profiles, determined by Secondary Neutral Mass Spectroscopy (SNMS), showed a maximum at the cap layer-thin film interface. The accumulated atoms at this interface formed a secondary diffusion reservoir and atoms diffused back to the layer. These observations can be interpreted supposing a bimodal grain boundary structure with different (fast and low) diffusivities. The observed grain boundary diffusion phenomena can be classified as C-type diffusion. The appearance of the peak observed at the cap layer interface can be used as a tool to determine the grain boundary diffusivity along the fast boundaries. Because the fast boundaries were saturated in the first stage of the process, this back-diffusion took place along the low-diffusivity boundaries only. Thus the SNMS depth-profiling is a good method to determine grain boundary diffusivities in a bimodal structure. In addition, from the overall impurity content inside the film the segregation can also be estimated, if the bulk solubility is low and the GB density is known. Numerical simulations of C-type GB diffusion in thin films with a bimodal structure confirmed that the interpretation of the result depicted above is reasonable [4]. In order to estimate roughly the GB diffusion data we determined the fast diffusivity using the first appearance method. The lower diffusivity was determined from the time evolution of the broadening of the diffusant/thin film interface. In addition both (slow and fast) diffusivities were also estimated from fitting numerical solutions obtained in [4] too.

Abstract: The diffusion of charged species in solids is a very important part of the study of the electrical properties of materials. Electrical measurements using alternating current (ac) impedance is a powerful technique to study diffusing species in metal oxides as well as polymers. Three case studies are being presented here whereby the electrical properties of LiTaO3, Poly[2-methoxy-5-(2’-ethylhexyloxy)-(p-phenylenevinylene)] (MEH-PPV) and its composite are being studied using the same ac impedance technique. LiTaO3 is a metal oxide while MEH-PPV is a polymer. They are very different and therefore present very good examples for the versatility and power of ac impedance method. Electrical parameters such as conductivity and conduction behaviours of the conducting species can be extracted from the studies. The kinetics of the diffusing species can be elucidated by using proper analytical techniques.

Abstract: LiTaO3 is an important optical material. It may also be possible to use this material as a solid electrolyte for lithium-ion batteries which may be applicable in thin film solid-state batteries. Generally, ceramics have a wide range of impedances. Many ceramics have mixed charged species consisting of electronic as well as ionic charge carriers. This work investigates the conductivity of LiTaO3 materials using ac impedance spectroscopy technique measured as a function of temperature.

Abstract: When metals that present bcc crystalline structure receive the addition of interstitial atoms as oxygen, nitrogen, hydrogen and carbon, they undergo significant changes in their physical properties because they are able to dissolve great amounts of those interstitial elements, and thus form solid solutions. Niobium and most of its alloys possess a bcc crystalline structure and, because Brazil is the largest world exporter of this metal, it is fundamental to understand the interaction mechanisms between interstitial elements and niobium or its alloys. In this study, mechanical spectroscopy (internal friction) measurements were performed on Nb-8.9wt%Ta alloys containing oxygen in solid solution. The experimental results presented complex internal friction spectra. With the addition of substitutional solute, interactions between the two types of solutes (substitutional and interstitial) were observed, considering that the random distribution of the interstitial atoms was affected by the presence of substitutional atoms. Interstitial diffusion coefficients, pre-exponential factors and activation energies were calculated for oxygen in this alloy.

Abstract: This study consists of the characterization of the anelastic properties of a Bulk Metallic Glasses (BMG) by mechanical spectroscopy, which can be defined as an energy absorption technique. The equipment used was the acoustic elastometer system, the anelastic relaxation spectra were carried out with a heating rate of 1 K/min and vacuum better than 10-5 torr, in the temperature range of 300 K to 640 K. The amorphous sample studied, with nominal composition of Cu53.5Zr42Al4.5, was processed by skull push-pull casting technique in a rectangular cavity cooper mould. Differential scanning calorimeter (DSC) curves have evidenced the amorphous structure although the X-ray diffraction (XDR) pattern has indicated a heterogeneous microstructure with amorphous matrix and some metaestable nanocrystalline phases which have not been identified yet. The dynamical elastic modulus of this alloy (between 54 GPa and 58 GPa at room temperature) and internal friction patterns as temperature function implied an increase of the crystalline phase during the measurements. This effect was confirmed with new X-ray diffraction measurements after the internal friction experiments.

Abstract: In this work, nanocomposites of ultrahigh molecular weight polyethylene (UHMWPE) reinforced with multiwalled carbon nanotubes (MWCNTs) were evaluated for their ability to produce nanocomposites with superior mechanical properties. As homogeneity of the nanocomposite plays an important role into final mechanical properties, mechanical ball-milling is used to prepare homogeneous UHMWPE/MWCNTs powders, where special emphasis is given to milling-time optimization. Mechanical ball-milling seems to be a suitable and rather simple technique for preparing nanocomposites even outside laboratory conditions and it is presented here as an interesting technique for nanoscience industrial applications. A fact that is worth noting since the great majority of research breakthroughs fail due to lack of industrial accomplishment. The powder mixture was further processed through compression moulding in a hot plate press. The impact of milling time on mechanical properties of the nanocomposites was evaluated. Nanocomposites with different volume fractions of MWCNTs were prepared using the optimized milling time, processed via compression moulding and their mechanical properties were evaluated. It was observed an enhancement of the Young’s modulus of about 80%, for higher volume fractions of MWCNTs (1.0%), as compared with the pure UHMWPE.