In situ AFM study of the electrochemical deposition of polybithiophene from propylene carbonate solution

Early stages of galvanostatic deposition of polybithiophene onto highly oriented pyrolytic graphite (HOPG) from propylene carbonate solution were investigated using electrochemical atomic force microscopy (ECAFM). The polymer film thickness was evaluated in situ using surface modification with the AFM tip and was found to be proportional to the grafting charge Q and independent of the deposition current density i in the current density range from 0.1 mA/cm² to 2 mA/cm². The first stage of the deposition was the formation of polymer nuclei with an average height of ca. 1 nm; continuous film was formed at Q≥0.5 mC/cm². Even at the earliest stages, the polymer featured grain structure with the average grain size of ca. 50 nm. The presence of the crystalline phase in the films was demonstrated by the X-ray diffraction data.     

ZrV1.5Ni1.5 as electrode material in nickel-metal hydride batteries An in situ scanning tunnelling microscopy investigation

We have investigated the alloy ZrV_1.5Ni_1.5 by means of scanning electron microscopy (SEM) with electron probe X-ray microanalysis (EPMA), X-ray diffraction (XRD), in situ STM (scanning tunnelling microscopy in an electrolyte under controlled electrochemical potential) and electrochemical charge discharge measurements. By means of EPMA we found that the alloy is composed of three different crystallographic phases. The main phase (≈75 vol.%) is ZrV_0.81Ni_1.47, the second phase (≈20 vol.%) is V₉₂Ni₈ and the third (≈5 vol.%) is a ZrNi based phase. Using in situ STM we investigated the different corrosion behaviour of the phases. At a potential of −600 mV versus the Hg/HgO reference electrode we observed the corrosion of the vanadium rich phase while the other two phases passivated.     

SEM and TEM characterization of magnesium hydride catalyzed with Ni nano-particle or Nb2O5

The microstructures of MgH₂ catalyzed with Ni nano-particle or Nb₂O₅ mesoporous powders are examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. For MgH₂ catalyzed with Ni, the Ni particles with the diameter smaller than 1 μm were detected on the MgH₂ particles with the diameter smaller than 5 μm by the back scattering electron (BSE) microscopy. In details, the TEM micrograph indicates that the Ni particles distribute 20 nm in diameter on MgH₂ uniformly, which was the same size as the additive doped in MgH₂ before milling. On the other hand, for MgH₂ catalyzed with Nb₂O₅, the additive particles could not be found anywhere in the BSE image. Even in the TEM micrograph by much larger magnification than the SEM micrograph, the particles corresponding to the additive cannot be observed at all. Furthermore, an energy dispersive X-ray (EDX) analysis in spots with a diameter of 20 nm indicated that the existing ratio of Mg to Nb was evaluated to 98:2, being the same as the starting ratio before milling. Therefore, the metal oxide Nb₂O₅ becomes extremely small particle that could not be observed by the present work after milling compared to metal Ni^nano.     

Observations on the growth of Al–Ni–Co decagonal thin films by atomic force microscopy and transmission electron microscopy

Thin films of Al–Ni–Co alloy were produced by vacuum deposition technique using a substrate material of amorphous carbon thin-foil. Attempts were made to obtain a homogeneous decagonal quasicrystalline film, where the preparation technique was based on the direct evaporation of pre-alloyed ingot of Al₇₂Ni₁₅Co₁₃ onto the heated substrates. In order to explore early stages of the decagonal film growth, the Al–Ni–Co films with different thicknesses ranging from 2 nm to 30 nm were deposited on either substrates heated at 500 °C or non-heated substrates. The film samples so obtained were examined mainly by atomic force microscopy in combination with transmission electron diffraction and imaging techniques. On the basis of these observations, deposition conditions necessary for the growth of decagonal phase in the resulting films as well as the growth mechanism of the decagonal film will be discussed.     

Microstructure of martensitic phase in the Co39Ni33Al28 shape memory alloys revealed by transmission electron microscopy

In the Co₃₉Ni₃₃Al₂₈ alloy, the ferromagnetic shape memory effect was investigated. A martensitic transformation (MT) occurred in the Co₃₉Ni₃₃Al₂₈ alloy when the temperature was lower than the martensitic start transformation temperature, M_S = 233 K. The morphologies and microstructures of the martensitic phase characterized by transmission electron microscope (TEM) showed a new 28-layered (28M) modulated martensite consisting of pinstripes and co-existing with the non-modulated martensite. Anomalies in magnetic properties and strain emerging around the MT have been briefly discussed.     

In situ technique for synthesizing multiple ceramic particulates reinforced titanium matrix composites (TiB + TiC + Y2O3)/Ti

In situ synthesized titanium matrix composites reinforced with multiple ceramic particulates including TiB, TiC and Y₂O₃ were fabricated by non-consumable arc-melting technique utilizing the chemical reaction among Ti, B₂O₃, B₄C and Y. The thermodynamic feasibility of the in situ reactions has been considered. X-ray diffraction (XRD) was used to identify the phases in the composites. Microstructures of the composites were observed by means of optical microscope (OM), scanning electron microscope (SEM) and electron probe. It is concluded that multiple reinforcements are synthesized and they show different shapes: TiB grows in needle shape; TiC grows in near-equiaxed and rod-like shapes; Y₂O₃ grows in near-equiaxed shapes when the content of Y is 0.6 wt.% and grows in dendritic shapes when the content of Y increases to 1.8 wt.%. Reinforcements TiB, TiC and Y₂O₃ are distributed uniformly in the titanium matrix.     

Synthesis, characterization and electrical properties of CdI2 doped Al2O3 and TiO2 superionic conductors

Superionic conductors were prepared by admixing metallic oxides (alumina and titania) with cadmium iodide in different proportions using direct mixing method. The synthesized materials were characterized by various qualitative techniques such as XRD (X-ray diffraction), DSC (differential scanning calorimetry) and SEM (scanning electron microscopy). Pure CdI₂ shows the standard pattern which corresponds to β-phase stable at room temperature, however, the diffractograms of the mixtures shows two phase nature of the materials with no effect of the second phase on the peak positions of the first, i.e. CdI₂. DSC curves also confirmed the formation of composite. SEM micrographs show the presence of great number of space charge regions which are very important in creating a great number of surfaces which in turn act as additional sources of point defects. It was also found that the conductivity of CdI₂ increases with mole fractions of dopants till x = 0.5 for alumina and x = 0.3 for titania. Arrhenius equation was used to study the temperature dependence of electrical conductivity and the activation energy of pure cadmium iodide was found to be 0.792 eV.     

CTAB-assisted hydrothermal synthesis of NiFe2O4 and its magnetic characterization

A simple hydrothermal route is demonstrated for the synthesis of nickel ferrite nanocrystals, NiFe₂O₄, using cetyltrimethylammonium bromide (CTAB) as the surfactant and NH₃ and NaOH as hydrolyzing agents. Synthesized materials have been characterized by XRD, FTIR, ESR, and TEM techniques. It was found that crystallization in both hydrolyzing agent led to nanometric in size. Average particle size of prepared samples was calculated from TEM micrographs and varied significantly between samples prepared using different hydrolyzing agents; it was 12 nm when conc. NH₃ was used and 50 nm when 2 M NaOH was used. Crystallite size obtained using Scherrer equation agreed well with the TEM observations with the respective values of 15 and 55 nm. ESR analysis showed single broad bands which might indicate the phase homogeneity of the materials. Furthermore, linewidths were observed to differ due to the difference in magnetization that depends on the particle size; NiFe₂O₄ sample hydrolysed with NH₃ has a larger linewidth revealing its smaller particle size as confirmed by XRD and TEM techniques.     

Effect of Al 2 O3 film on weld appearance of stationary electron beam welded aluminum

Aluminum specimens with and without chemically cleaning were welded by electron beam to investigate the effect of、Al ₂ O₃ film on weld appearance. The removal mechanism of Al ₂ O₃ film during vacuum electron beam welding of aluminum was analyzed and the effect of Al ₂ O₃ film on molten pool flow behavior and weld appearance was investigated. The results showed that the weld width of the specimen was enlarged by chemically cleaning. The solid Al ₂ O₃ film transformed into gaseous Al ₂ O via the reaction with liquid aluminum at the temperature higher than 1 350 K was the main reason for the removal of the film. The weld width was narrowed down by the oxide film due to the inhibition of outward flow driven by the surface tension gradient and the drag force between the Al ₂ O₃ film and liquid Al. The weld penetration was reduced in the initial stage and then enhanced in the metastable stage.     

Morphology of M23C6 precipitation in L12-ordered Ni3(Al, Cr)

A transmission electron microscope investigation has been performed on the morphology of M₂₃C₆ precipitation in L1₂-ordered Ni₃(Al, Cr) containing 0.1–0.5 mol% of carbon. By aging at temperatures around 1073 K after solution annealing at 1423 K, fine octahedral-shaped precipitates of M₂₃C₆ bounded by {111} facets appear first on the dislocations and then in the matrix. The shapes of the precipitates are not always equilateral but tetragonal or elongated octahedral ones appear during aging. Planar growth faults were observed in some of the octahedral precipitates. After prolonged aging or by aging at higher temperatures, these shapes of precipitates become unstable. The M₂₃C₆ precipitates then adopt a rod-like morphology elongated parallel to the 100 directions and characterized by steps bounded by {111} facets.     

Fabrication and dry sliding wear behavior of in situ Al–K2ZrF6–KBF4 composites reinforced by Al3Zr and ZrB2 particles

Aluminum matrix composites reinforced by Al₃Zr and ZrB₂ particles were fabricated from Al–x wt.%(K₂ZrF₆–KBF₄) (x = 5, 10, 15, 20, 25) systems via magnetochemistry in situ reaction and the dry sliding wear properties and behavior of the composites were investigated. XRD and SEM analysis show that ZrB₂ and Al₃Zr reinforcement phases have been obtained and been distributed uniformly in the aluminum matrix. Wear test results show that the values of wear weight loss of the composites decrease with the increase of x under all identical wear conditions, and that of the relative wear resistance R_relat. increases under the applied load of 100 N. Especially, when x = 25, the wear weight loss (under a sliding time of 120 min and an applied load of 100 N), which is 0.245 to that of the A356 alloy, and the R_relat. (under the intermediate wear-sliding stage and an applied load of 100 N) is 4.772, which is 1.513 to that of the primary stage, respectively. Two modes of the wear mechanisms of the as-prepared composites were identified.     

Improvement of the electrochemical performance of LiMn2O4 cathode active material by lithium borosilicate (LBS) surface coating for lithium-ion batteries

The LBS coating on the surface of spinel LiMn₂O₄ powder was carried out using the solid-state method, followed by heating at 425 °C for 5 h in air. The powder X-ray diffraction pattern of the LBS-coated spinel LiMn₂O₄ showed that the LBS coating medium was not incorporated in the spinel bulk structure. The SEM result showed that the LBS coating particles were homogeneously distributed on the surface of the LiMn₂O₄ powder particles. The effect of the lithium borosilicate (LBS) coating on the charge-discharge cycling performance of spinel powder (LiMn₂O₄) was studied in the range of 3.5-4.5 V at 1C. The electrochemical results showed that LBS-coated spinel exhibited a more stable cycle performance than bare spinel. The capacity retention of LBS-coated spinel was more than 93.3% after 70 cycles at room temperature, which was maintained at 71.6% after 70 cycles at 55 °C. The improvement of electrochemical performance may be attributed to suppression of Mn²⁺ dissolution into the electrolyte via the LBS glass layer.     

Effects of CeO2 additive on the microstructure and mechanical properties of in situ TiB2/Al composite

In this paper, CeO₂ was investigated as an additive for in situ preparation of TiB₂/Al composite using an exothermic reaction process via K₂TiF₆ and KBF₄ salts. Experimental results indicated that when 0.5 wt.% CeO₂ additive was added, the dispersion of TiB₂ particles was improved significantly. Meanwhile, α-Al matrix grain was further refined. Compared with the composite without CeO₂, the ultimate tensile strength, yield strength, elastic modulus and tensile elongation increased by 8%, 7%, 26% and 14%, respectively in as-cast condition, and the tensile fracture behavior of the composite with CeO₂ belonged to a typical ductile fracture with microvoid coalescence.     

In situ deposition behavior of SiO2 on YSZ-TBC-coated IN738LC during a burner rig test

This work was planned as a preliminary test to obtain an optimal condition for in situ deposition of SiO₂ on zirconia-based thermal barrier coating (TBC)-coated IN738LC specimens using a burner rig. The effect of the in situ deposited SiO₂ on the long-term reliability of TBCs upon cyclic burner rig operations will be tested in the next study. Tetraethylorthosilicate (TEOS), the precursor for the deposition, was fed admixed with methanol into the combustion chamber of the burner rig at an exhaust flame temperature of 1530 °C. All five coating processes were selected by varying the concentration of TEOS in the mixture and applied to hollow type pin specimens infixed to the rotating carousel to face the downstream exhaust gas vertically. A total of 1500 cc of the mixture at a given vol.% TEOS was fed evenly to the burner rig for 54 min during the coating process.     

Synthesis, characterization, magnetic and electrical properties of the novel conductive and magnetic Polyaniline/MgFe2O4 nanocomposite having the core-shell structure

Conductive and magnetic Polyaniline/MgFe₂O₄ nanocomposite was successfully synthesized in the form of core-shell via in situ chemical polymerization of aniline in the presence of MgFe₂O₄ nano-particles. X-ray powder diffraction of ferrites indicated that the structure of the core material is having the spinel structure, and demonstrated the formation of PAni/MgFe₂O₄ nanocomposite. XRD and TEM photographs showed that the particle's size of the MgFe₂O₄ core-material were around 30-35 nm before coating with Polyaniline, and grown up to 45 nm in the core-shell nanocomposite after coating. Although PAni has a relatively smaller electrical field coefficient than the core-shell nanocomposite, the resistivity of the core-shell material decreased, and hence its conductivity increased after a certain threshold voltage of 0.98 V equivalent to threshold electric field value equals 5.5 V cm⁻¹. The magnetic hysteresis loops investigated with VSM indicated that coating MgFe₂O₄ with Polyaniline has an healing effect which covers the ferrite surface defects, thus decreasing the magnetic surface anisotropy of ferrite particles leading to a decrease of the saturated magnetization (Ms) from 21.33 emu/g to 5.905 emu/g and a decrease of the coercivity (Hc) from 88.66 Oe to 81.6 Oe for MgFe₂O₄ and the core-shell nanocomposite respectively due to the amount of Polyaniline added. TGA and DTA revealed improved thermal stability of the core-shell nanocomposite with respect to that of Polyaniline due to the incorporation of ferrites. Raman spectroscopy confirmed TGA, DTA and XRD studies, and revealed that pure PAni is less stable than the corresponding core-shell nanocomposite with respect to molecular changes which might occur during heating at elevated temperatures. Moreover, Raman study confirmed the interfacial interaction between the core and the shell materials, and lead to an assumption about the presence of different conjugation chain lengths and types, such as the presence of the semi-quinones aside the quinone rings in the polymer chain, which showed different response upon heating the sample.     

Correlation between the synthesis conditions and the compositional and magnetic properties of Co2(Cr1−xFex)Al Heusler alloys

In this study we give evidence for the strong dependence of the compositional and magnetic properties on the synthesis conditions of polycrystalline Co₂(Cr_1−xFe_x)Al Heusler alloys (0 ≤ x ≤ 1) by comparing the properties of as-grown and annealed compounds. Strong chemical inhomogeneities are found at the micrometric level depending on the compound and the synthesis method. Moreover, we find that the Co content is homogeneous at the micrometric level in all the studied samples in sharp contrast with significant inhomogeneous distribution of (Fe/Cr) and Al at the micrometric level, especially for Cr-rich compounds (x ≤ 0.4). We have found that the magnetic properties (the Curie temperature and the saturation magnetization) are strongly depressed in the annealed compounds with respect to the corresponding as-grown compounds. For the as-grown compounds the saturation magnetization is close to the theoretically predicted one for x ≥ 0.7 whereas it is lower than the theoretically predicted one for x ≤ 0.4, which correlates with the observed chemical inhomogeneity.     

Synthesis of Er2Ti2O7 nanocrystals and its electrochemical hydrogen storage behavior

Ultrafine Er₂Ti₂O₇ was synthesized at 700 °C within 2 h by a soft-chemistry route named citric acid sol–gel method (CAM). The obtained Er₂Ti₂O₇ with high dispersibility was square-like and the average size was about 70 nm. The prepared Er₂Ti₂O₇ nanocrystals in 6 M KOH aqueous solutions were investigated as a hydrogen storage material. It was found that the Er₂Ti₂O₇ powders would function as electrochemical hydrogen storage, showed fair electrochemical reversibility, and considerably high charge–discharge capacity. The reversible discharge capacity of the Er₂Ti₂O₇ electrode was found to exceed 320 mAh/g and adsorption capability of hydrogen is up to 1.27% at a current rate of 100 mA/g. In addition, the cycling ability and high rate capability of the Er₂Ti₂O₇ electrode are fairly good with only 4% capacity decay after 25 cycles. Cyclic voltammograms (CVs) were carried out to further examine the electrochemical hydrogen storage mechanism of Er₂Ti₂O₇.     

Formation, properties and microstructure of amorphous/crystalline composite Ag20Cu30Ti50 alloy using miscibility gap

The aim of the work was to produce the amorphous/crystalline composite with uniform distribution of fine crystalline soft phase. Silver–copper–titanium Ag₂₀Cu₃₀Ti₅₀ alloy was prepared using 99.95 wt% Ag, 99.95 wt% Cu, 99.95 wt% Ti that were arc-melted in argon atmosphere. Then the alloy was melt spun on a copper wheel with linear velocity of 33 m/s. Investigation of the microstructure for both arc-melt massive sample and melt-spun ribbons was performed with use of scanning electron microscope (SEM) with EDS, light microscope (LM) and X-ray diffraction. The thermal stability was evaluated by differential scanning calorimetry (DSC). The properties such as Young modulus and Vickers hardness number before and after crystallization of the amorphous matrix were measured with use of nanoindenter. The microstructure was investigated by transmission electron microscope (TEM). It was found, that the alloy has a tendency for separation within the liquid state due to the miscibility gap which resulted in segregation into Ti–Cu–Ag matrix and Ag-base spherical particles after arc-melting. During rapid cooling through the melt spinning the Ag₂₀Cu₃₀Ti₅₀ alloy formed an amorphous/crystalline composite of fcc silver-rich spherical particles within the amorphous Ti–Cu–Ag matrix.