Passivity cobalt

A critical issue is the stabiUty of the hydride electrode in the cell environment. A number of hydride formulations have been developed. Table 5 shows hydride materials that are now the focus of attention. Most of these are Misch metal hydrides containing additions of cobalt, aluminum, or manganese. The hydrides are prepared by making melts of the formulations and then grinding to fine powers. The electrodes are prepared by pasting and or pressing the powders into metal screens or felt. The additives are reported to retard the formation of passive oxide films on the hydrides. 

MetaUic cobalt dissolves readily in dilute H2SO4, HCl, or HNO to form cobaltous salts (see also Cobalt compounds). Like iron, cobalt is passivated by strong oxidizing agents, such as dichromates and HNO, and cobalt is slowly attacked by NH OH and NaOH. 

Similar initial reactions occur on many metals such as iron and cobalt. This intermediate can now react further in one of two ways. Oxidation and protonation of the intermediate to Ni(II) leads to dissolved nickel ions (active corrosion) which are unable to passivate the metal ... 

The incorporation of anions from the electrolyte, such as borate and carbonate, into the oxide has also been shown to occur on iron and cobalt, such anions being restricted to the outer layers of the film. Attempts to find incorporation of chloride into passive iron surfaces from... 

The corrosion behaviour of amorphous alloys has received particular attention since the extraordinarily high corrosion resistance of amorphous iron-chromium-metalloid alloys was reported. The majority of amorphous ferrous alloys contain large amounts of metalloids. The corrosion rate of amorphous iron-metalloid alloys decreases with the addition of most second metallic elements such as titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium and platinum . The addition of chromium is particularly effective. For instance amorphous Fe-8Cr-13P-7C alloy passivates spontaneously even in 2 N HCl at ambient temperature ". (The number denoting the concentration of an alloy element in the amorphous alloy formulae is the atomic percent unless otherwise stated.)... 

Amorphous Fe-3Cr-13P-7C alloys containing 2 at% molybdenum, tungsten or other metallic elements are passivated by anodic polarisation in 1 N HCl at ambient temperature". Chromium addition is also effective in improving the corrosion resistance of amorphous cobalt-metalloid and nickel-metalloid alloys (Fig. 3.67). The combined addition of chromium and molybdenum is further effective. Some amorphous Fe-Cr-Mo-metalloid alloys passivate spontaneously even in 12 N HCl at 60° C. Critical concentrations of chromium and molybdenum necessary for spontaneous passivation of amorphous Fe-Cr-Mo-13P-7C and Fe-Cr-Mo-18C alloys in hydrochloric acids of various concentrations and different temperatures are shown in Fig. 3.68 ... 

Environmental tests have been combined with conventional electrochemical measurements by Smallen et al. [131] and by Novotny and Staud [132], The first electrochemical tests on CoCr thin-film alloys were published by Wang et al. [133]. Kobayashi et al. [134] reported electrochemical data coupled with surface analysis of anodically oxidized amorphous CoX alloys, with X = Ta, Nb, Ti or Zr. Brusic et al. [125] presented potentiodynamic polarization curves obtained on electroless CoP and sputtered Co, CoNi, CoTi, and CoCr in distilled water. The results indicate that the thin-film alloys behave similarly to the bulk materials [133], The protective film is less than 5 nm thick [127] and rich in a passivating metal oxide, such as chromium oxide [133, 134], Such an oxide forms preferentially if the Cr content in the alloy is, depending on the author, above 10% [130], 14% [131], 16% [127], or 17% [133], It is thought to stabilize the non-passivating cobalt oxides [123], Once covered by stable oxide, the alloy surface shows much higher corrosion potential and lower corrosion rate than Co, i.e. it shows more noble behavior [125]. 

Catalysts - A commercial Raney nickel (RNi-C) and a laboratory Raney nickel (RNi-L) were used in this study. RNi-C was supplied in an aqueous suspension (pH < 10.5, A1 < 7 wt %, particle size 0.012-0.128 mm). Prior to the activity test, RNi-C catalyst (2 g wet, 1.4 g dry, aqueous suspension) was washed three times with ethanol (20 ml) and twice with cyclohexane (CH) (20 mL) in order to remove water from the catalyst. RCN was then exchanged for the cyclohexane and the catalyst sample was introduced into the reactor as a suspension in the substrate. RNi-L catalyst was prepared from a 50 % Ni-50 % A1 alloy (0.045-0.1 mm in size) by treatment with NaOH which dissolved most of the Al. This catalyst was stored in passivated and dried form. Prior to the activity test, the catalyst (0.3 g) was treated in H2 at 250 °C for 2 h and then introduced to the reactor under CH. Raney cobalt (RCo), a commercial product, was treated likewise. Alumina supported Ru, Rh, Pd and Pt catalysts (powder) containing 5 wt. % of metal were purchased from Engelhard in reduced form. Prior to the activity test, catalyst (1.5 g) was treated in H2 at 250 °C for 2 h and then introduced to the reactor under solvent. 10 % Ni and 10 % Co/y-Al203 (200 m2/g) catalysts were prepared by incipient wetness impregnation using nitrate precursors. After drying the samples were calcined and reduced at 500 °C for 2 h and were then introduced to the reactor under CH. 

Mechanism 3 involves NiOH in at least three reactions, and Ni(OH)2 as the active Ni reactant in solution. Since increasing the concentration of the complex-ant(s) in solution will reduce the concentration of both unhydrolyzed and hydrolyzed metal ions, arguments of complexation cannot be readily employed to either support or discount this mechanism. However, it has been this author s experience in formulating electroless Co-P solutions with various complexants for Co2+ that improper complexation which results in even a faint precipitate of hydrolyzed cobalt ions yields an inactive electroless Co-P solution. Furthermore, anodic oxidation of hypo-phosphite at Ni anodes does not proceed at a significant rate under conditions where the surface is most probably covered with a passive film of nickel oxide [48], e.g. NiO.H20, which would be expected to oxidize the reducing agent via a cyclic redox mechanism. 

In addition, a number of other deep level impurities have been hydrogen passivated. They include nickel, cadmium, tellurium, zirconium, titanium, chromium, and cobalt (Pearton et al., 1987). Most of these studies have been qualitative, and important work remains to be done if the hydrogenation of these and most probably additional impurities, such as gold, palladium, platinum and iron, is to be fully understood. 

Cobalt is an essential element for animals but not for plants, found in vitamin B12 and is utilized by micro-organisms. Vitamin B12, in common with a range of other organic substances can be taken up passively by plants. Plants products can therefore, contain considerable quantities of vitamin B12 although it is not essential for normal plant development (Mozafar 1994 Lundegardh and Martensson 2003). 

Concentrated nitric acid passivates many metals, such as, iron, cobalt, nickel, aluminum and chromium, forming a protective film of oxides on their surfaces, thus preventing any further reaction. Very dilute nitric acid is reduced by a strong reducing agents, such as metallic zinc, to form ammonia and hydroxylamine, NH2OH. 

Another process of physical protection is the formation of an oxide layer that makes the metal passive. This procedure is used for aluminium. Aluminium is normally anodized in 10 per cent sulphuric acid with steel or copper cathodes until an oxide thickness of 10-100 pm is obtained. As the more superficial part of the oxide layer has a fairly open structure it is possible to deposit metals (cobalt, nickel, etc.) or organic pigments in the pores and seal with boiling water or with an alkaline solution. The colours after metallic deposition are due to interference effects. Chromic and oxalic acids are also used significantly as electrolyte. 

The behavior of nickel on anodic polarization is matched by the behavior of iron and cobalt on the surface of which oxygen is also liberated at higher current densities. Chromium anode dissolves at low current densities to form bivalent cations. When it becomes passive its potential increases by about 1 Volt. With further inorease of potential chromium enters a state called transpassive state in which instead of bivalent ions hexavalent ions are formed which reaot with the hydroxyl ions present in the electrolyte to form chromate ions according to equation ... 

Cobalt thus resembles iron in exhibiting passivity, although to a less extent. Concentrated nitric acid attacks it, but acid in the proportion of one part water with two parts concentrated acid dissolves cobalt with extreme slowness.6... 

Like iron and cobalt, nickel exhibits passivity,9 being rendered passive in a variety of ways, such as by immersion in concentrated nitric acid, or by making it the anode in various solutions.10... 

Passivity.—It is now a matter of common knowledge that platinum, like iron, cobalt, and nickel, exhibits passivity under certain conditions.5 Possibly this is due to the formation of a superficial layer of oxide which protects the underlying metal from attack. This explanation is supported by the fact that during the electrolysis of platinum chloride solution with platinum electrodes, the anode becomes slightly coated with oxide,6 and the same is true when dilute sulphuric acid containing from 2-5 to 10 per cent, of acid is similarly electrolysed.7... 

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