The Effect of Nanosizing on the Oxidation of Partially Oxidized Copper Nanoparticles.

Copper nanoparticles are of great interest in various applications, such as catalysis, cooling fluids, conductive inks or for their antibacterial activity. In this paper, the thermal behavior of copper nanoparticles was studied using thermogravimetry, differential thermal analysis and differential scanning calorimetry. Original Cu samples as well as the products of oxidation were analysed by X-ray diffraction, scanning/transmission electron microscopy and energy dispersive spectroscopy. A step-by-step oxidation mechanism during the oxidation of Cu nano-powders was observed. The Cu-nano oxidation starts slightly above 150 °C when bulk copper does not yet react. The dominant oxidation product in the first step is Cu2O while CuO was identified as the final state of oxidation. Our results confirm an easier oxidation process of Cu-nano than Cu-micro particles, which must be attributed to kinetic not thermodynamic aspects of oxidation reactions.

Formation of Phases in Reactively Sintered TiAl3 Alloy.

This work highlights new results on the synthesis of the TiAl3 intermetallic phase using self-propagating high-temperature synthesis. This method is considered a promising sintering route for intermetallic compounds. It was found that the reactions proceed in two stages. Below the melting point of aluminum, the Ti2Al5 phase forms at 450 °C after long annealing times by a direct solid-state reaction between the aluminum and titanium, and is converted consequently to TiAl3. This is a completely new finding; until now, many authors have believed in the preferential formation of the TiAl3 phase. The second stage, the self-propagating strongly exothermic reaction, proceeds above the melting point of aluminum. It leads to the formation of the TiAl3 phase accompanied by Ti2Al5 and Ti3Al phases. The reaction mechanism was shown in the form of chemical equations, which were supported by calculating Gibbs energy. Reaction temperatures (Tonset, Tmaximum, and Toffset) were determined after induction heating thanks to recording by an optical pyrometer. This finding provides completely new opportunities for the determination of activation energy at heating rates, in which common calorimeters are not able to detect a response or even measure. Now, the whole procedure will become accessible.

Size and Shape-Dependent Solubility of CuO Nanostructures.

In our theoretical study, the enhanced solubility of CuO nanoparticles in water saturated by air is predicted based on a simple thermodynamic model. CuO is considered in the form of nanoparticles with various shapes. The interfacial energy of a solid CuO/dilute aqueous solution interface was assessed by applying the average CuO surface energy and contact angle of a sessile drop of water. The equilibrium CuO solubility was calculated using Gibbs energy minimization technique. For the smallest spherical nanoparticles considered in this work (r = 2 nm), the solubility is significantly higher than the solubility of bulk material. In the case of cylindrical nanoparticles, the solubility increase is even more considerable. The CuO spherical nanoparticles solubility was also calculated using the Ostwald-Freundlich equation which is known to overestimate the solubility as discussed in this contribution.

Mechanism of the Intermediary Phase Formation in Ti-20 wt. % Al Mixture during Pressureless Reactive Sintering.

This work aims to describe the mechanism of intermediary phases formation in TiAl20 (wt. %) alloy composition during reactive sintering. The reaction between titanium and aluminum powders was studied by in situ diffraction and the results were confirmed by annealing at various temperatures. It was found that the Ti2Al5 phase formed preferentially and its formation was detected at 400 °C. So far, this phase has never been found in this alloy composition during reactive sintering processes. Subsequently, the Ti2Al5 phase reacted with the titanium, and the formation of the major phase, Ti3Al, was accompanied by the minor phase, TiAl. Equations of the proposed reactions are presented in this paper and their thermodynamic and kinetic feasibility are supported by Gibbs energies of reaction and reaction enthalpies.

Cytocompatibility of amine functionalized carbon nanoparticles grafted on polyethylene.

Five types of amide-amine Carbon Nano-Particles (CNPs) were prepared by functionalization of CNPs and characterized by several analytical methods. The successful grafting of amines on CNPs was verified by X-ray photoelectron spectroscopy (XPS), organic elemental analysis and electrokinetic analysis. The size and morphology of CNPs were determined from transmission electron microscopy. The surface area and porosity of CNPs were examined by adsorption and desorption isotherms. Differential scanning calorimetry was used to investigate thermal stability of CNPs. The amount of bonded amine depends on its dimensionality arrangement. Surface area and pore volumes of CNPs decrease several times after individual amino-compound grafting. Selected types of functionalized CNPs were grafted onto a plasma activated surface of HDPE. The successful grafting of CNPs on the polymer surface was verified by XPS. Wettability was determined by contact angle measurements. Surface morphology and roughness were studied by atomic force microscopy. A dramatic decrease of contact angle and surface morphology was observed on CNP grafted polymer surface. Cytocompatibility of modified surfaces was studied in vitro, by determination of adhesion, proliferation and viability of vascular smooth muscle cells (VSMCs). Grafting of CNPs onto the polymer surface has a positive effect on the adhesion, proliferation and viability of VSMCs.

Colloidal solutions of luminescent porous silicon clusters with different cluster sizes.

Silicon nanocrystals (Si-ncs) are promising for biological studies due to their supposed low cytotoxicity, good biocompatibility and biodegradability in living organisms. However, the bioresearchers' focus on Si-ncs has lasted only for a few recent years, and detailed studies of the interaction of various types of Si-ncs with biological environment are still rare. Suitable size and solubility of the Si-ncs in water-based isotonic solutions are important towards bringing the nanocrystals inside the living cells. We have prepared colloidal solutions of luminescent porous silicon of different cluster sizes in methanol, water and phosphate-buffered saline (PBS). By combination of ultrasonic treatment with filtration, we have obtained two different silicon cluster sizes in methanol (120 and 525 nm) and three different cluster sizes (85, 210 and 1,500 nm) in PBS. Nanoclusters of heavily oxidized porous silicon are hydrophilic and well soluble in water and/or PBS. They can be further used for studies on the biocompatibility of these materials and may be potentially employed as luminescent markers in living cells in biological research. PACS: 78.67.Rb; 78.67.-n; 87.85.Qr; 87.85.Rs; 81.07.-b.

Corrosion behavior of palladium-silver-copper alloys in model saliva.

OBJECTIVES: Palladium-silver system alloyed with other metals represents one of possible material choices in prosthetics. Its corrosion properties are influenced by minority components added in order to obtain the properties required for stomatological purposes. The objective of this work was to ascertain the influence of copper on the corrosion mechanism of palladium-silver alloys. METHODS: Corrosion properties of four palladium-silver-copper alloys were compared with the behavior of the palladium-silver binary system. Standard electrochemical measurements in a model saliva solution were complemented with an XPS analysis of the specimens surface. Experimental data were compared with the results of thermodynamic analysis. RESULTS: The foregoing study revealed formation of a saline layer of insoluble silver compounds as the dominant feature of the corrosion mechanism in a binary system. This process is suppressed in ternary alloys where electrochemical reactions of copper take place on the alloy-electrolyte phase boundary leading to the formation of a layer based on copper oxides. SIGNIFICANCE: The alloying of the palladium-silver binary system with copper results in an important change in the corrosion behavior of ternary alloys. A change in the mechanism of interaction with the environment leads to susceptibility to non-uniform corrosion.