Cathodic corrosion of Cu substrates as a route to nanostructured Cu/M (M = Ag, Au, Pd) surfaces

The electrochemical formation of nanostructured materials is generally achieved by reduction of a metal salt onto a substrate that does not influence the composition of the deposit. In this work we report that Ag, Au and Pd electrodeposited onto Cu under conditions where galvanic replacement is not viable and hydrogen gas is evolved results in the formation of nanostructured surfaces that unexpectedly incorporate a high concentration of Cu in the final material. Under cathodic polarization conditions the electrodissolution/corrosion of Cu occurs which provides a source of ionic copper that is reduced at the surface-electrolyte interface. The nanostructured Cu/M (M = Ag, Au and Pd) surfaces are investigated for their catalytic activity for the reduction of 4 nitrophenol by NaBH4 where Cu/Ag was found to be extremely active. This work indicates that a substrate electrode can be utilized in an interesting manner t make bimetallic nanostructures with enhanced catalytic activity.

Some Considerations on the Occurrence of Intergranular Fracture during Fatigue Crack growth in Steels

The occurrence of a maximum in the percentage of intergranular fracture on the fracture surface during the transition from intermediate to low fatigue crack growth rates has been observed for a high strength steel. It is suggested that transgranular planar slip leading to slip localization is essential in promoting intergranular fracture when the cyclic plastic zone size becomes equal to the prior austenite grain size.

Mössbauer studies of the corrosion products of iron formed in aqueous ammonium nitrate solution

The products of corrosion reaction of electrolytic iron in 45% ammonium nitrate solution formed under various conditions of time, temperature and pH have been analysed mainly by Mössbauer spectroscopy, in combination with X-ray diffraction, infrared absorption and electron microscopy techniques. γ-Fe00H is found to be the major product of hydrolytic precipitation at pH > 5.6 while only α-FeOOH is formed at pH < 3.0. In the pH range 3.0 < pH < 5.0, α-Fe00H and ferrihydrite are both formed. However, once the nuclei of α-Fe00H are formed under low pH conditions, their growth is favoured even in the otherwise unfavourable slightly acidic medium, resulting in a hydrous α-Fe00H which has two distinct hyperfine fields at the 57Fe nucleus. Magnetite is always formed in the vicinity of the metal and its rate of formation on the surface increases with temperature. α-Fe203 is the major product of hydrolytic precipitation at temperatures >80C. The possible mechanisms for the formation of each of the corrosion products are discussed.

Absolute values of instantaneous corrosion rates by faradaic rectification

Doss and Agarwal 1 discovered the "redoxokinetic effect" which is now familiarly known as faradaic rectification. Subsequently, the theory and applications of faradaic rectification due to a single electrode reaction have been developed by several workers 2-5. The theory and application of faradaic rectification in the case of a corrosion cell sustaining mixed electrode reactions on a corroding metal was reported recently 6"7. This led to the development of a new electrochemical method of corrosion rate determination. It was shown that changes in the instantaneous corrosion rates of a metal are readily evaluated by faradaic rectification measurements at the corrosion potential of the metal in a given medium. The aim of the present work is to show that absolute values of instantaneous corrosion rates may also be obtained by the new method under certain conditions. The practical advantages that arise from this development are pointed out.

Kinetics and mechanism of hot corrosion of γ-Y 2Si 2O 7 in thin-film Na 2SO 4 molten salt

γ-Y 2Si 2O 7 is a promising candidate material both for hightemperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9×10 -6/K, 200°-1300°C), and low thermal conductivity (<3.0 W/ṁK above 300°C). The hot corrosion behavior of γ-Y 2Si 2O 7 in thin-film molten Na 2SO 4 at 850°-1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y 2Si 2O 7 exhibited good resistance against Na 2SO 4 molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na2SO4 and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y 2Si 2O 7 in Na 2SO 4 molten salt with flowing air was evaluated to be 255 kJ/mol.

Hot corrosion of γ-Y2Si2O7 in strongly basic Na2CO3 molten salt environment

γ-Y2Si2O7 is a promising candidate both for high temperature structural applications and as thermal barrier coatings due to its unique combination of properties, such as high melting point, good machinability, high thermal stability, low linear thermal expansion coefficient (3.9 × 10-6 K-1, 25-1400 °C) and low thermal conductivity (<3 W/m K above 300 °C). In this work, the hot corrosion behavior of γ-Y2Si2O7 in strongly basic Na2CO3 molten salt at 850-1000 °C for 20 h in flowing air was investigated. In the employed conditions, multi-layer corrosion scales with total thickness less than 90 μm were formed. At 850-900 °C, the outmost layer of the scale was composed of the reprecipitation of Y2O3, the bottom of a Si-rich Na2O·xSiO2 (x > 3.65) melt layer, and the middle of a NaYSiO4 layer. At 1000 °C, the corrosion products turned out to be a mixture of NaY9Si6O26 and Si-rich Na2O·xSiO2 (x > 3.65). In all cases, a thin layer of protective SiO2 formed under the Na2O·xSiO2 melt and protected the bulk material from further corrosion.

Measurement of the corrosion rate of aluminium in sodium hydroxide using holographic interferometry

The application of holographic interferometry to the measurement of the corrosion rate of aluminium in sodium hydroxide is investigated. Details of the fabrication of the corrosion cell and the experimental procedure are given. Thickness loss of aluminium was found for different dissolution times and compared with the conventional weight-loss method using a microbalance.

The influence of pH on the corrosion of medium strength aerospace alloys 8090, 2091 and 2014

The influence of pH on the corrosion behaviour of two aluminium-lithium-copper-magnesium-zirconium (8090 and 2091) alloys was studied and compared with a standard aircraft alloy, 2014 (Al-4.4% Cu) and 99.9% pure Al. In constant exposure and potentiodynamic polarization studies conducted in 3.5% NaCl solution having different pH values, all the alloys exhibited high corrosion rates in acidic and alkaline environments, with a minimum in less hostile environments close to neutral pH. The pitting potentials for aluminium-lithium alloys were slightly lower than those for 2014 and pure Al. The effect of pH on the passive current density was also less for aluminium-lithium alloys.

Role of Li+ ions in corrosion behaviour of 8090 Al-Li alloy and aluminium in pH 12 aqueous solutions

The influence of Li+ ions on the corrosion behaviour of the Al-Li alloy 8090-T851 and of commercially pure aluminium in aqueous solutions at pH 12 was studied by weight loss and electrochemical polarisation methods. The inhibiting role of Li+ was concentration dependent, corrosion rate decreasing lineally with log[Li+] in the concentration range 10(-4)-10(-1) mol L(-1). A change from general to pitting corrosion was evident from scanning election microscopy studies. Polarisation studies revealed that Li+ primarily acts as an anodic inhibitor (passivator). Passive film formation and stability also become more feasible with increasing Li+ concentration. Fitting potential was dependent on the Cl- ion concentration in the solution. Both materials were affected similarly by the presence of Li+ ions, the corrosion rate of the alloy being slightly lower. This is attributed to the lithium in the alloy acting as a source of lithium for passive film formation. (C) 1995 The Institute of Materials.