The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.

Development of an on-demand beam pulsing system for Pixe-analysis of thick targets

This work concerns the developnent of a proton irduced X-ray emission (PIXE) analysis system and a multi-sample scattering chamber facility. The characteristics of the beam pulsing system and its counting rate capabilities were evaluated by observing the ion-induced X-ray emission from pure thick copper targets, with and without beam pulsing operation. The characteristic X-rays were detected with a high resolution Si(Li) detector coupled to a rrulti-channel analyser. The removal of the pile-up continuum by the use of the on-demand beam pulsing is clearly demonstrated in this work. This new on-demand pu1sirg system with its counting rate capability of 25, 18 and 10 kPPS corresponding to 2, 4 am 8 usec main amplifier time constant respectively enables thick targets to be analysed more readily. Reproducibility tests of the on-demard beam pulsing system operation were checked by repeated measurements of the system throughput curves, with and without beam pulsing. The reproducibility of the analysis performed using this system was also checked by repeated measurements of the intensity ratios from a number of standard binary alloys during the experimental work. A computer programme has been developed to evaluate the calculations of the X-ray yields from thick targets bornbarded by protons, taking into account the secondary X-ray yield production due to characteristic X-ray fluorescence from an element energetically higher than the absorption edge energy of the other element present in the target. This effect was studied on metallic binary alloys such as Fe/Ni and Cr/Fe. The quantitative analysis of Fe/Ni and Cr/Fe alloy samples to determine their elemental composition taking into account the enhancement has been demonstrated in this work. Furthermore, the usefulness of the Rutherford backscattering (R.B.S.) technique to obtain the depth profiles of the elements in the upper micron of the sample is discussed.

Electrodeposition of corrosion resistant zinc alloy coatings

With the increase use of de-icing salts on roads for safety, the need for improved corrosion resistance of the traditional galvanized automobile bodies has never been greater. In the present work, Zn alloy coatings (Zn-Ni and Zn-Co) were studied as an alternative to pure Zn coatings. The production of these deposits involved formulation of various acidic (pH of about 5.5) chloride based solutions. These showed anomalous deposition, that is, alloys were deposited much more easily than expected from the noble behaviour of Ni and Co metals. Coating compositions ranging from 0 to about 37% Ni and 20% Co were obtained. The chemical composition of the coatings depended very much on the electrolytes nature and operating conditions. The Ni content of deposits increased with increase in Ni bath concentration, temperature, pH and solution agitation but decreased considerably with increase in current density. The throwing power of the Zn-Ni solution deteriorated as Ni metal bath concentration increased. The Co content of deposits also increased with increase in Co bath concentration and temperature, and decreased with increase in current density. However, the addition of commercial organic additives to Zn-Co plating solutions suppressed considerably the amount of Co in the coatings. The Co content of deposits plated from Zincrolyte solution was found to be more sensitive to variation in current density than in the case of deposits plated from the alkaline Canning solution. The chromating procedures were carried out using laboratory formulated solution and commercially available ones. The deposit surface state was of great significance in influencing the formulation of conversion coatings. Bright and smooth deposits acquired an iridescent colour when treated with the laboratory formulated solution. However, the dull deposits acquired a brownish appearance. The correlation between the electrochemical test results and the neutral salt spray in marine environment was good. Non-chromated Zn-Ni coatings containing about 11-14% Ni increased in corrosion resistance compared to pure Zn. Non-chromated Zn-Co deposits of composition 4-8% were required to show a significant improvement in corrosion resistance Corrosion resistance was improved considerably by conversion coating. However, the type of conversion coating was very important. Samples treated in a laboratory solution performed badly compared to those treated in commercial solutions. Zn alloy coatings were superior to pure Zn, the Schloetter sample (13.8% Ni) had the lowest corrosion rate, followed by the Canning sample (1.0% Co) and then Zincrolyte (0.3% Co).Neither the chromium content of the conversion films nor the chromium state was found to have an effect on corrosion performance of the coatings.

Nitrogen implantation of tool steels and engineering coatings

Ion implantation modifies the surface composition and properties of materials by bombardment with high energy ions. The low temperature of the process ensures the avoidance of distortion and degradation of the surface or bulk mechanical properties of components. In the present work nitrogen ion implantation at 90 keV and doses above 1017 ions/cm2 has been carried out on AISI M2, D2 and 420 steels and engineering coatings such as hard chromium, electroless Ni-P and a brush plated Co-W alloy. Evaluation of wear and frictional properties of these materials was performed with a lubricated Falex wear test at high loads up to 900 N and a dry pin-on-disc apparatus at loads up to 40 N. It was found that nitrogen implantation reduced the wear of AISI 420 stainless steel by a factor of 2.5 under high load lubricated conditions and by a factor of 5.5 in low load dry testing. Lower but significant reductions in wear were achieved for AISI M2 and D2 steels. Wear resistance of coating materials was improved by up to 4 times in lubricated wear of hard Cr coatings implanted at the optimum dose but lower improvements were obtained for the Co-W alloy coating. However, hardened electroless Ni-P coatings showed no enhancement in wear properties. The benefits obtained in wear behaviour for the above materials were generally accompanied by a significant decrease in the running-in friction. Nitrogen implantation hardened the surface of steels and Cr and Co-W coatings. An ultra-microhardness technique showed that the true hardness of implanted layers was greater than the values obtained by conventional micro-hardness methods, which often result in penetration below the implanted depth. Scanning electron microscopy revealed that implantation reduced the ploughing effect during wear and a change in wear mechanism from an abrasive-adhesive type to a mild oxidative mode was evident. Retention of nitrogen after implantation was studied by Nuclear Reaction Analysis and Auger Electron Spectroscopy. It was shown that maximum nitrogen retention occurs in hard Cr coatings and AISI 420 stainless steel, which explains the improvements obtained in wear resistance and hardness. X-ray photoelectron spectroscopy on these materials revealed that nitrogen is almost entirely bound to Cr, forming chromium nitrides. It was concluded that nitrogen implantation at 90 keV and doses above 3x1017 ions/cm2 produced the most significant improvements in mechanical properties in materials containing nitride formers by precipitation strengthening, improving the load bearing capacity of the surface and changing the wear mechanism from adhesive-abrasive to oxidative.

In-Vivo Corrosion and Fretting of Modular TI-6AL-4V/CO-CR-MO Hip Prostheses: The Influence of Microstructure and Design Parameters

The purpose of this study was to evaluate the incidence of corrosion and fretting in 48 retrieved titanium-6aluminum-4vanadium and/or cobalt-chromium-molybdenum modular total hip prosthesis with respect to alloy material microstructure and design parameters. The results revealed vastly different performance results for the wide array of microstructures examined. Severe corrosion/fretting was seen in 100% of as-cast, 24% of low carbon wrought, 9% of high carbon wrought and 5% of solution heat treated cobalt-chrome. Severe corrosion/fretting was observed in 60% of Ti-6Al-4V components. Design features which allow for fluid entry and stagnation, amplification of contact pressure and/or increased micromotion were also shown to play a role. 75% of prosthesis with high femoral head-trunnion offset exhibited poor performance compared to 15% with a low offset. Large femoral heads (>32mm) did not exhibit poor corrosion or fretting. Implantation time was not sufficient to cause poor performance; 54% of prosthesis with greater than 10 years in-vivo demonstrated none or mild corrosion/fretting.

Redução in situ de NIO durante a sinterização de misturas NI/NIO produzidas por metalurgia do pó

The nickel alloys are widely used in the production of various materials, especially those that require mechanical strength characteristics associated with resistance to corrosion, for example, the stainless steel. Another use is the production of nickel alloy sintered from powder of metallic nickel. A promising alternative for the production of sintered components of nickel with an important reduction in costs of starting material is the use of mixtures of powders of Ni-NiO. This work aimed to study in situ reduction of NiO during sintering mixtures of Ni / NiO produced by powder metallurgy. The nickel mixtures have been processed by the technique of powder metallurgy and were pre-sintered in an oven under plasma reducing atmosphere of hydrogen. Mixtures Ni +15%NiO, Ni +25%NiO and Ni +35%NiO were studied and compared with samples consisting only of metallic Ni. Dilatometric tests were performed to study the sintering conditions of the mixtures. The consolidated material was analyzed for their microstructure and microhardness. Dilatometry graphs showed that the addition of nickel oxide in all compositions the active sintering the mixtures studied. In tests of microhardness indentations were made at different points of the sample surface. All compositions showed microhardness values close to the consolidated material from metallic nickel. However, sample containing Ni+35% NiO, showed a large dispersion of the values of microhardness tests performed at different points of the sample surface. Microstructural analysis of the material showed a higher concentration of voids and the presence of oxides in the waste composition of the mixtures Ni 35% NiO. The samples containing Ni+15%NiO showed microstructural characteristics and mechanical properties similar to metallic nickel consolidated under the same conditions of the compositions studied in this work and therefore had great potential for production of sintered nickel alloys

Caracterização elementar de ligas metálicas em implantes dentários

An ideal biomaterial for dental implants must have very high biocompatibility, which means that such materials should not provoke any serious adverse tissue response. Also, used metal alloys must have high fatigue resistance due the masticatory force and good corrosion resistance. These properties are rendered by using alpha and beta stabilizers, such as Al, V, Ni, Fe, Cr, Cu, Zn. Commercially pure titanium (TiCP) is used often for dental and orthopedic implants manufacturing. However, sometimes other alloys are employed and consequently it is essential to research the chemical elements present in those alloys that could bring prejudice for the health. Present work investigated TiCP metal alloys used for dental implant manufacturing and evaluated the presence of stabilizing elements within existing limits and standards for such materials. For alloy characterization and identification of stabilizing elements it was used EDXRF technique. This method allows to perform qualitative and quantitative analysis of the materials using the spectra of the characteristic X-rays emitted by the elements present in the metal samples. The experimental setup was based on two X- rays tubes (AMPTEK Mini X model with Ag and Au targets), a X-123SDD detector (AMPTEK) and a 0.5mm Cu collimator, developed due to the sample characteristics. The other experimental setup used as a complementary technique is composed of an X-ray tube with a Mo target, collimator 0.65mm and XFlash (SDD) detector - ARTAX 200 (BRUKER). Other method for elemental characterization by energy dispersive spectroscopy (EDS) applied in present work was based on Scanning Electron Microscopy (SEM) EVO® (Zeeis). This method also was used to evaluate the surface microstructure of the sample. The percentual of Ti obtained in the elementary characterization was among 93.35 ± 0.17% and 95.34 ± 0.19 %. These values are considered below the reference limit of 98.635% to 99.5% for TiCP, established by Association of metals centric materials engineers and scientists Society (ASM). The presence of elements Al and V in all samples also contributed to underpin the fact that are not TiCP implants. The values for Al vary between 6.3 ± 1.3% and 3.7 ± 2.0% and for V, between 0.26 ± 0.09% and 0.112 ± 0.048%. According to the American Society for Testing and Materials (ASTM), these elements should not be present in TiCP and in accordance with the National Institute of Standards and Technology (NIST), the presence of Al should be <0.01% and V should be of 0.009 ± 0.001%. Obtained results showed that implant materials are not exactly TiCP but, were manufactured using Ti-Al-V alloy, which contained Fe, Ni, Cu and Zn. The quantitative analysis and elementary characterization of experimental results shows that the best accuracy and precision were reached with X-Ray tube with Au target and collimator of 0.5 mm. Use of technique of EDS confirmed the results of EDXRF for Ti-Al-V alloy. Evaluating the surface microstructure by SEM of the implants, it was possible to infer that ten of the thirteen studied samples are contemporaneous, rough surface and three with machined surface.

Elemental Anisotropic Growth and Atomic-Scale Structure of Shape-Controlled Octahedral Pt–Ni–Co Alloy Nanocatalysts

Multimetallic shape-controlled nanoparticles offer great opportunities to tune the activity, selectivity, and stability of electrocatalytic surface reactions. However, in many cases, our synthetic control over particle size, composition, and shape is limited requiring trial and error. Deeper atomic-scale insight in the particle formation process would enable more rational syntheses. Here we exemplify this using a family of trimetallic PtNiCo nanooctahedra obtained via a low-temperature, surfactant-free solvothermal synthesis. We analyze the competition between Ni and Co precursors under coreduction “one-step” conditions when the Ni reduction rates prevailed. To tune the Co reduction rate and final content, we develop a “two-step” route and track the evolution of the composition and morphology of the particles at the atomic scale. To achieve this, scanning transmission electron microscopy and energy dispersive X-ray elemental mapping techniques are used. We provide evidence of a heterogeneous element distribution caused by element-specific anisotropic growth and create octahedral nanoparticles with tailored atomic composition like Pt1.5M, PtM, and PtM1.5 (M = Ni + Co). These trimetallic electrocatalysts have been tested toward the oxygen reduction reaction (ORR), showing a greatly enhanced mass activity related to commercial Pt/C and less activity loss than binary PtNi and PtCo after 4000 potential cycles.

Procesos hopping a través del modelo difusional en materiales nanocristalinos usados para aplicaciones fotovoltaicas

Se presentan los modelos de hopping de rango variable (variable range hopping; VRH), vecinos cercanos (nearest neighbor hopping; NNH) y barreras de potencial presentes en las fronteras de grano; como mecanismos de transporte eléctrico predominantes en los materiales semiconductores para aplicaciones fotovoltaicas. Las medidas de conductividad a oscuras en función de temperatura fueron realizadas para región de bajas temperaturas entre 120 y 400 K con Si y compuestos Cu3BiS2 y Cu2ZnSnSe4. Siguiendo la teoría de percolación, se obtuvieron parámetros hopping y la densidad de estados cerca del nivel de Fermi, N(EF), para todas las muestras. A partir de los planteamientos dados por Mott para VRH, se presentó el modelo difusional, que permitió establecer la relación entre la conductividad y la densidad de estados de defecto o estados localizados en el gap del material. El análisis comparativo entre modelos, evidenció, que es posible obtener mejora hasta de un orden de magnitud en valores para cada uno de los parámetros hopping que caracterizan el material.

Characterisation of Ni carbonate-bearing minerals by UV-Vis-NIR spectroscopy

Four nickel carbonate-bearing minerals from Australia have been investigated to study the effect of Ni for Mg substitution. The spectra of nullaginite, zaratite, widgiemoolthalite and takovite show three main features in the range of 26,720–25,855 cm−1 (ν1-band), 15,230–14,740 cm−1 (ν2-band) and 9,200–9,145 cm−1 (ν3-band) which are characteristic of divalent nickel in six-fold coordination. The Crystal Field Stabilization Energy (CFSE) of Ni2+ in the four carbonates is calculated from the observed 3A2g(3F) → 3T2g(3F) transition. CFSE is dependent on mineralogy, crystallinity and chemical composition (Al/Mg-content). The splitting of the ν1- and ν3-bands and non-Gaussian shape of ν3-band in the minerals are the effects of Ni-site distortion from regular octahedral. The effect of structural cation substitutions (Mg2+, Ni2+, Fe2+ and trivalent cations, Al3+, Fe3+) in the carbonate minerals is noticed on band shifts. Thus, electronic bands in the UV–Vis–NIR spectra and the overtones and combination bands of OH and carbonate ion in NIR show shifts to higher wavenumbers, particularly for widgiemoolthalite and takovite.

Thermal analysis of synthetic reevesite and cobalt substituted reevesite (Ni,Co)6Fe2(OH)16(CO3)•4H2O

The mineral reevesite and the cobalt substituted reevesite have been synthesised. The d(003) spacings of the minerals ranged from 7.54 to 7.95 Å. The maximum d(003) value occurred at around Ni:Co 0.4:0.6. This maximum in interlayer distance is proposed to be due to a greater number of carbonate anions and water molecules intercalated into the structure. The stability of the reevesite and cobalt doped reevesite was determined by thermogravimetric analysis. The maximum temperature of the reevesite occurs for the unsubstituted reevesite and is around 220°C. The effect of cobalt substitution results in a decrease in thermal stability of the reevesites. Four thermal decomposition steps are observed and are attributed to dehydration, dehydroxylation and decarbonation, decomposition of the formed carbonate and oxygen loss at ~807 °C. A mechanism for the thermal decomposition of the reevesite and the cobalt substituted reevesite is proposed.

Fusionless scoliosis correction using shape memory alloy staples

Severe spinal deformity in young children is a formidable challenge for optimal treatment. Standard interventions for adolescents, such as spinal deformity correction and fusion, may not be appropriate for young patients with considerable growth remaining. Alternative surgical options that provide deformity correction and protect the growth remaining in the spine are needed to treat this group of patients 1, 2. One such method is the use of shape memory alloy staples. We report our experience to date using video-assisted thoracoscopic insertion of shape memory alloy staples. A retrospective review was conducted of 13 patients with scoliosis, aged 7 to 13 years, who underwent video-assisted thoracoscopic insertion of shape memory staples. In our experience, video-assisted thoracoscopic insertion of shape memory alloy staples is a safe procedure with no complications noted. It is a reliable method of providing curve stability, however the follow up results to date indicate that the effectiveness of the procedure is greater in younger patients.

Scale-dependent fracture mode in Cu-Ni laminate composites

Fracture behavior of Cu-Ni laminate composites has been investigated by tensile testing. It was found that as the individual layer thickness decreases from 100 to 20nm, the resultant fracture angle of the Cu-Ni laminate changes from 72 degrees to 50 degrees. Cross-sectional observations reveal that the fracture of the Ni layers transforms from opening to shear mode as the layer thickness decreases while that of the Cu layers keeps shear mode. Competition mechanisms were proposed to understand the variation in fracture mode of the metallic laminate composites associated with length scale.

Raman spectroscopic study of the antimonate mineral bottinoite Ni[Sb2(OH)12].6H2O and in comparison with brandholzite Mg[Sb5+2(OH)12]•6H2O

Raman spectra of bottinoite Ni[Sb(OH)6].6H2O were studied, and related to the molecular structure of the mineral. An intense sharp Raman band at 618 cm-1 is attributed to the SbO symmetric stretching mode. The low intensity band at 735 cm-1 is ascribed to the SbO antisymmetric stretching vibration. Low intensity Raman bands were found at 501, 516 and 578 cm-1. Four Raman bands observed at 1045, 1080, 1111 and 1163 cm-1 are assigned to δ SbOH deformation modes. A complex pattern resulting from the overlapping band of the water and hydroxyl units is observed. Raman bands are observed at 3223, 3228, 3368, 3291, 3458 and 3510 cm-1. The first two Raman bands are assigned to water stretching vibrations. The two higher wavenumber Raman bands observed at 3466 and 3552 cm-1 and two infrared bands at 3434 and 3565 cm-1 are assigned to the stretching vibrations of the hydroxyl units. Observed Raman and infrared bands are connected with O-H…O hydrogen bonds and their lengths 2.72, 2.79, 2.86, 2.88 and 3.0 Å (Raman) and 2.73, 2.83 and 3.07 Å (infrared).