Electrochemical characterization of Cu dissolution and chemical mechanical polishing in ammonium hydroxide–hydrogen peroxide based slurries

Chemical mechanical polishing (CMP) of copper in ammonium hydroxide based slurry in the presence of hydrogen peroxide was investigated. The polishing trend was found to be similar to that exhibited by other slurries containing hydrogen peroxide and various complexing agents used for Cu CMP. When the hydrogen peroxide concentration is increased, the polish rate increases, reaches a maximum and then decreases. The location and the magnitude of the maximum depend on the ammonium hydroxide concentration. The dissolution of copper in the NH₄OH–hydrogen peroxide solution was probed by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) experiments. Electrical equivalent circuit (EEC) and reaction mechanism analysis (RMA) were employed to determine the mechanistic reaction pathway of Cu dissolution in NH₄OH–hydrogen peroxide system. Based on the RMA analysis, a four step catalytic mechanism with two adsorbed intermediate species is proposed.     

A flexible nanobrush pad for the chemical mechanical planarization of Cu/ultra-low-к materials

A new idea of polishing pad called flexible nanobrush pad (FNP) has been proposed for the low down pressure chemical mechanical planarization (CMP) process of Cu/ultra-low-к materials. The FNP was designed with a surface layer of flexible brush-like nanofibers which can ‘actively’ carry nanoscale abrasives in slurry independent of the down pressure. Better planarization performances including high material removal rate, good planarization, good polishing uniformity, and low defectivity are expected in the CMP process under the low down pressure with such kind of pad. The FNP can be made by template-assisted replication or template-based synthesis methods, which will be driven by the development of the preparation technologies for ordered nanostructure arrays. The present work would potentially provide a new solution for the Cu/ultra-low-к CMP process.     

Microstructure and mechanical strength of diffusion-bonded silicon nitride–molybdenum joints

Solid-state bonding of reactive systems, such as Si₃N₄–Mo often results in the formation of excessively thick intermetallic layers that can be detrimental to the final strength of the joint. The objective of this work was to study the microstructural evolution of Si₃N₄–Mo interfaces, aiming at maximum joint strength via a balance between the fraction of bonded material and the amount of interfacial reaction. Joining was carried out under vacuum or nitrogen atmosphere for temperatures between 1100 and 1800°C. Microstructural analyses of the interfaces revealed the presence of Mo₃Si and Mo₅Si₃ along with residual pores. The results from shear strength tests revealed a strong relationship between the microstructure of the interface and the mechanical strength of the joint. ©     

Microstructure and mechanical properties of superplastically deformed silicon nitride–silicon oxynitride in situ composites

Silicon nitride–silicon oxynitride in situ composites were fabricated by plane-strain-compressing dense silicon nitrides, starting from 93 wt.% ultrafine β-Si₃N₄ and 7 wt.% cordierite, at 1600 °C under a constant load of 40 MPa and subsequent annealing at 1750 °C for 30 min. The resulting composites featured a microstructure of elongated Si₂N₂O grains (∼0.64 μm in diameter and ∼5.5 in aspect ratio) dispersed in a fine-grained β-Si₃N₄ matrix (∼ 0.30μm in diameter and ∼3.5 in aspect ratio), with the amount of Si₂N₂O, which had relatively strong textures, being strain-dependent. The mechanical properties were found to be improved due to the development of elongated Si₂N₂O grains, the texture formation, and the coarsening of β-Si₃N₄. Fracture toughness, however, was still low (∼5.2 MPa m^1/2) for these composites in comparison to self-reinforced silicon nitrides, resulted from the strong Si₂N₂O-matrix interfacial bond and nearly equiaxed β-Si₃N₄ with a small grain size. Anticipated property anisotropies were clearly observed as a result of the textured microstructure.     

XANES investigation of the enhanced chemical stability of Pd in supported Pd–Mo catalysts

The XANES (X-ray absorption near edge structure) technique was used to study Pd and Mo catalysts deposited on supported Al₂O₃/SiO₂ and Al₂O₃/Si-MCM-41 in the form of monometallic and bimetallic systems. The results indicate that Pd has stronger chemical stability when in the presence of Mo and is always in the metallic form, which is surprising, because the samples were not subjected to reducing conditions prior to the measurements. The increased stability was attributed to the formation of a core-shell structure with a Pd rich core and a Mo rich surface.     

Influence of nano–micrometre powder blends on microstructure and mechanical properties of silicon nitride

Abstract

A well known route to making tough silicon nitride compositions is to control the grain size and aspect ratio distributions. This is usually done by choosing the appropriate powder characteristics, sintering conditions, as well as sintering additives. The effect of hot pressing a blend of nano and micrometre scale silicon nitride powder is explored here. Microstructures and mechanical properties are determined for these hot pressed ceramics and are compared with a reference silicon nitride. Hardness and fracture toughness are determined at room temperature using hardness indents produced by a macro Vickers hardness indenter. Grain size and aspect ratio distributions and their impact on mechanical properties are presented. Blending of nano and micrometre scale powder is shown to result in a refined microstructure with an increase in the area/volume fraction of finer grains. Rising R curves are established for these ceramics demonstrating toughening behaviour. Crack bridging and crack path deviation are identified as possible toughening mechanisms.     

Effect of ZnO content on the physical,mechanical and chemical properties of glass-ceramics in the CaO–SiO2–Al2O3 system

The objective of this study was to evaluate the effect of ZnO content on the physical, mechanical and chemical properties of CaO–Al₂O₃–SiO₂ (CAS) glass-ceramics produced from Colombian wastes, such as fly ash, granulated blast furnace slag and glass cullet. The CaO/SiO₂ molar ratio of the mixtures was held constant (0.36). ZnO was added to the mixtures in proportions of 4, 7 and 10 wt%. The glass-ceramics were produced by the controlled crystallization of a parent glass. The values of crystallization temperature (T_p) show a fall up to 7 wt% and then shoots up with 10 wt% concentration of ZnO, but in general, ZnO addition lowers the temperature required for the formation of crystalline phases. In general, anorthite (CaAl₂Si₂O₈) is the main phase observed in all heat treated samples, in addition to albite (Na(AlSi₃O₈)) and labradorite (Na_0.45 Ca_0.55 Al_1.55 Si_2.45 O₈). The crystalline phases hardystonite (Ca₂ZnSi₂O₇) and willemite (Zn₂SiO₄) were also identified in the samples with 7 and 10 wt% ZnO. The densities of the glass-ceramics were between 2658 and 2848 kg/m³, and it was found that ZnO helps to increase the density of glass-ceramics. The elastic modulus was in the 100–105 GPa range, the fracture toughness was between 0.45 and 0.64 MPa m^1/2, and the Vickers microhardness was between 632 and 653 MPa. With regards to the durability, the weight loss of the glass-ceramics immersed in alkaline solution (NaOH) did not exceed 1.5 wt% after immersion for 6 h at 80 °C. The results of this study confirm that the vitrification process is a favorable option to utilize these industrial wastes.     

Spark plasma sintering of titanium nitride in nitrogen: Does it affect the sinterability and the mechanical properties?

Titanium nitride ceramics have an intrinsic interest due to its optical and structural applications. However, the conditions for sintering of dense pieces are not still clarified. This research work is focused on the spark plasma sintering (SPS) of near-fully dense fine-grained TiN. The main goal is giving a response to a longstanding debate: can the external atmosphere favor sintering? Different sintering atmospheres, either vacuum or a nitrogen flow, have been used during SPS heating to this purpose. X ray diffraction analysis has showed the presence of TiN as the main phase with traces of Ti₄O₇ in optimal SPS conditions (1600?°C, one minute dwell time). Our results show that the use of a nitrogen flow while heating can improve sinterability very slightly, but mechanical properties are essentially unaltered within the experimental uncertainty. The hardness reaches values as high as 20GPa whereas fracture toughness can be evaluated around 4?MPam^1/2.     

Electrochemical investigation of the diffusion of lithium in β-LiAl alloy at room temperature

The chemical diffusion coefficients of lithium in -LiAl alloy were measured by the use of transient techniques such as chronopotentiometry, chronoamperometry and a.c. impedance spectroscopy in 1 M LiClO₄-propylene carbonate at 25° C. A -LiAl layer, formed by electrodepositing lithium on a thin aluminium substrate having a microstructure of preferred (100) orientation, was mainly used. The values of the diffusion coefficients were found to be of the order of 10^–10 cm²s^–1, which are close to those reported in the literature. A scatter in the coefficient was discussed in terms of the formation and disruption of the passivating layer on the alloy.     

Electrochemical deposition of zinc–polystyrene composites in the presence of surfactants

The electrochemical codeposition of polystyrene particles and zinc on a rotating cylinder electrode was investigated. Rheological measurements indicate strong aggregation of the PS particles in the zinc deposition electrolyte. Addition of cetylpyridinium chloride, a cationic surfactant, prevents aggregation and enhances polystyrene codeposition. Other surfactants also increase suspension stability, but diminish polystyrene codeposition, irrespective of their charge. Hence, the surfactant charge does not affect polystyrene codeposition. The variation of polystyrene incorporation with the amount of suspended polystyrene, current density and electrode rotation speed signifies that polystyrene codeposition with zinc is determined by the competition between particle removal forces and particle adhesion forces at the cathode surface. The effect of the surfactants can be related to changes in surface roughness of zinc due to surfactant adsorbed on the electrode. Cetylpyridinium chloride behaves differently from the other surfactants, because it is reduced at the cathode.     

Rheological and mechanical properties of polycarbonate–liquid-crystalline polymer blends with controlled chemical reactions

Chemical reactions can occur during the melt blending of polymers containing an ester group because ester groups are usually unstable at high temperatures; this instability generally deteriorates the mechanical properties of blends. Here, effects of chemical reactions on the rheological and mechanical properties of polycarbonate (PC)/liquid-crystalline polymer (LCP) blends are carefully investigated to determine a method for minimizing such undesirable impacts. For comparison, a physical blend, in which chemical reactions were minimized, was prepared at 300 °C in a twin-screw extruder. Both shear viscosity and complex viscosities of reactive blends were lower than those of physical blends, being almost proportional to [M_w ]^3.4 as a result of depolymerization and transesterification. Because of the enhanced miscibility, the tensile modulus of reactive blends increased compared with that of physical blend, according to the increase in the degree of incorporation (DI). It was also possible to increase tensile modulus if triester was added to the reactive blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2799–2807, 2001     

Microstructural and mechanical investigation of hydroxyapatite–zirconia nanocomposites prepared by spark plasma sintering

Nano hydroxyapatite (nHA)–zirconia (ZrO₂) composites have been produced by spark plasma sintering (SPS). During the SPS process low temperatures (600–950 °C) and short dwelling time (5 min) have been applied to avoid the decomposition of nHA as well as the reaction between nHA and ZrO₂. The grain size of the sintered composites was between 200 and 1000 nm. Carbon diffusion was induced from the graphite die and layered composite structure was formed. These observations might be related to the spark plasma sintering side effects. The microstructure and mechanical properties of high hydroxyapatite content zirconia composites have been found to be influenced and strongly correlated with the specialties of SPS method.     

Effects of NCO:OH ratio on the mechanical properties and chemical structure of Kraft lignin–based polyurethane adhesive

ABSTRACT

This work aimed to evaluate the influence of the aliphatic and aromatic hydroxyl level on the polyurethane adhesive property and chemical structure. This adhesive was obtained through the reaction of technical Kraft lignin (TKL) as polyol with diphenylmethane diisocyanate (MDI). Thus, lignopolyurethane adhesives were obtained with NCO:OH ratios of 0.8:1.0, 0.9:1.0, 1.0:1.0, 1.1:1.0, and 1.2:1.0. Initially only the TKL aliphatic hydroxyl level was taken into consideration in the stoichiometry in order to define the mass ratio between MDI and polyol. Subsequently, lignopolyurethane adhesive was obtained using the same NCO:OH ratios considering TKL total hydroxyls’ level, and aromatic and aliphatic hydroxyls. The chemical structures of the synthesized adhesives were analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹³C NMR). The mechanical property of the adhesively bonded joints, comprising wood substrates and synthesized adhesives, was measured using single lap shear tests. Results illustrated that by increasing the NCO:OH ratio, there is an increase in the free isocyanate content leading to higher shear strength values. Higher free isocyanate content leads to MDI dimer formation in the lignopolyurethane structure.     

Thermal,mechanical and structural investigation of copolyimide–silica hybrids containing phosphine oxide

In this study, a novel hybrid copolyimide was synthesized from copolyamic acid solutions (PAAs) obtained by the reaction between bis(3-aminophenoxy-4-phenyl)phenylphosphine oxide (m-BAPPO), 3,3′-diaminodiphenyl sulfone (DDS) and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), followed by thermal imidization. Hybrid materials containing 5% SiO₂ were synthesized by sol–gel technique. The polyimide–silica hybrids were characterized by Fourier Transform Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Thermogravimetric analysis showed that the weight loss of hybrids is shifted to the higher temperature compared to the neat copolyimide. The contact angle measurements confirmed the hydrophobic surface of hybrids. Moreover, the gas permeability measurements were also done to take a step for forthcoming gas separation studies. The tensile modulus and strength of the copolyimides are good.     

CFD and experimental investigation of the gas–liquid flow in the distributor of a compact heat exchanger

High performance of compact heat exchangers is conditioned by correct fluid distribution. This is especially true for gas–liquid heat exchangers where a uniform distribution is particularly delicate to obtain and where maldistribution entails significant performance deterioration. Several phenomena can lead to phase distribution problems: the fins may be subject to manufacturing defects or fouling, leading to shortcuts or dead zones. But the first source of maldistribution may be a poor distribution at the outlet of the entrance distributor. This distributor aims at mixing the phases and distributing them across the channels.     

Micro-computed tomography for the investigation of stationary liquid–liquid and liquid–gas interfaces in capillaries

For better understanding and optimization of multiphase flow in miniaturized devices, micro-computed tomography (μCT) is a promising visualization tool, as it is nondestructive, three-dimensional, and offers a high spatial resolution. Today, computed tomography (CT) is a standard imaging technique. However, using CT in microfluidics is still challenging, since X-ray related artifacts, low phase contrast, and limited spatial resolution complicate the exact localization of interfaces. We apply μCT for the characterization of stationary interfaces in thin capillaries. The entire workflow for imaging stationary interfaces in capillaries, from image acquisition to the analysis of interfaces, is presented. Special emphasis is given to an in-house developed segmentation routine. For demonstration purposes, contact angles of water, liquid polydimethylsiloxane, and air in FEP, glass, and PMMA are determined and the influence of gravity on interface formation is discussed. This work comprises the first steps for a systematic 3D investigation of multiphase flows in capillaries using μCT.     

Characterization and AC conductivity of polyaniline–montmorillonite nanocomposites synthesized by mechanical/chemical reaction

Polyaniline–clay nanocomposites were prepared by solid state polymerization of aniline chloride in the interlayer of montmorillonite through the use of persulfate of ammonium as oxidant. The proportion of aniline to clay and the molar ratio of oxidant to aniline are being varied. The analyse of UV visible and FTIR spectroscopy demonstrated that aniline has been polymerized to polyaniline (PANI) in its conducting emeraldine form. The conformation adopted by PANI chains in the clay interlayer depended on the molar ratio of aniline to montmorillonite. Thermogravimetric analysis of the nanocomposites suggested that polyaniline chains are more thermally stable than those of free polyaniline prepared by solid–solid reaction. The AC conductivity data of different synthesized nanocomposites were analyzed as a function of frequency. Low frequency conductivities of polyaniline/montmorillonite nanocomposites materials ranges from 0.18 to 5.6 × 10^?3 S/cm. All characterization data were compared to those of free polyaniline that was synthesized using a solid–solid reaction.     

Kinetics and mechanism of cubic boron nitride formation in the AlN–BN system at 6 GPa

The kinetics of hBN-into-cBN transformation at 6 GPa and 1770, 1880 and 1990 K in the presence of AlN have been studied. The transformation proceeds without liquid phase. It has been established that a limiting stage of the transformation is diffusion of boron and nitrogen atoms in wurtzitic aluminum nitride. Activation energy of the transformation is 170±40 kJ/mol. On the basis of our results we conclude that hexagonal BN dissolves in aluminum nitride solid solution and supersaturates it with respect to cBN, and then cubic boron nitride precipitates from the supersaturated solution of BN in AlN. An AlN–BN system phase diagram is proposed.     

Electrochemical investigation of chromium nanocarbide coated Ti–6Al–4V and Co–Cr–Mo alloy substrates

This study investigated the electrochemical behavior of chromium nano-carbide cermet coating applied on Ti–6Al–4V and Co–Cr–Mo alloys for potential application as wear and corrosion resistant bearing surfaces. The cermet coating consisted of a highly heterogeneous combination of carbides embedded in a metal matrix. The main factors studied were the effect of substrate (Ti–6Al–4V vs. Co–Cr–Mo), solution conditions (physiological vs. 1 M H₂O₂ of pH 2), time of immersion (1 vs. 24 h) and post coating treatments (passivation and gamma sterilization). The coatings were produced with high velocity oxygen fuel (HVOF) thermal spray technique at atmospheric conditions to a thickness of 250 μm then ground and polished to a finished thickness of 100 μm and gamma sterilized. Native Ti–6Al–4V and Co–Cr–Mo alloys were used as controls. The corrosion behavior was evaluated using potentiodynamic polarization, mechanical abrasion and electrochemical impedance spectroscopy under physiologically representative test solution conditions (phosphate buffered saline, pH 7.4, 37 °C) as well as harsh corrosion environments (pH ～ 2, 1 M H₂O₂, T = 65 °C). Severe environmental conditions were used to assess how susceptible coatings are to conditions that derive from possible crevice-like environments, and the presence of inflammatory species like H₂O₂. SEM analysis was performed on the coating surface and cross-section. The results show that the corrosion current values of the coatings (0.4–4 μA/cm²) were in a range similar to Co–Cr–Mo alloy. The heterogeneous microstructure of the coating influenced the corrosion performance. It was observed that the coating impedances for all groups decreased significantly in aggressive environments compared with neutral and also dropped over exposure time. The low frequency impedances of coatings were lower than controls. Among the coated samples, passivated nanocarbide coating on Co–Cr–Mo alloy displayed the least corrosion resistance. However, all the coated materials demonstrated higher corrosion resistance to mechanical abrasion compared to the native alloys.