Tantalum passivity

Nitric acid reacts with all metals except gold, iridium, platinum, rhodium, tantalum, titanium, and certain alloys. It reacts violentiy with sodium and potassium to produce nitrogen. Most metals are converted iato nitrates arsenic, antimony, and tin form oxides. Chrome, iron, and aluminum readily dissolve ia dilute nitric acid but with concentrated acid form a metal oxide layer that passivates the metal, ie, prevents further reaction. 

Tantalum is not resistant to substances that can react with the protective oxide layer. The most aggressive chemicals are hydrofluoric acid and acidic solutions containing fluoride. Fuming sulfuric acid, concentrated sulfuric acid above 175°C, and hot concentrated aLkaU solutions destroy the oxide layer and, therefore, cause the metal to corrode. In these cases, the corrosion process occurs because the passivating oxide layer is destroyed and the underlying tantalum reacts with even mild oxidising agents present in the system. 

The corrosion resistance imparted to tantalum by the passivating surface thermal oxide layer makes the metal inert to most ha2ards associated with metals. Tantalum is noncorrosive in biological systems and consequently has a no chronic health ha2ard MSDS rating. 

Good housekeeping practices to prevent the accumulation of tantalum dust and a proper passivation procedure will prevent most tantalum fires. AH equipment used to handle the powder should be properly grounded and contact with hot surfaces or flames should be avoided. 

This example of aluminium illustrates the importance of the protective him, and hlms that are hard, dense and adherent will provide better protection than those that are loosely adherent or that are brittle and therefore crack and spall when the metal is subjected to stress. The ability of the metal to reform a protective him is highly important and metals like titanium and tantalum that are readily passivated are more resistant to erosion-corrosion than copper, brass, lead and some of the stainless steels. There is some evidence that the hardness of a metal is a signihcant factor in resistance to erosion-corrosion, but since alloying to increase hardness will also affect the chemical properties of the alloy it is difficult to separate these two factors. Thus althou copper is highly susceptible to impingement attack its resistance increases with increase in zinc content, with a corresponding increase in hardness. However, the increase in resistance to attack is due to the formation of a more protective him rather than to an increase in hardness. 

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.)... 

The passive films formed by the addition of sufficient amounts of valve metals to amorphous nickel-valve-metal alloys are exclusively composed of valve-metal oxyhydroxides or oxides such as TaOjCOH) , Nb02(OH) or TajO,. Consequently, amorphous alloys containing strongly passivating elements, such as chromium, niobium and tantalum, have a very high ability... 

Niobium like tantalum relies for its corrosion resistance on a highly adherent passive oxide film it is however not as resistant as tantalum in the more aggressive media. In no case reported in the literature is niobium inert to corrosives that attack tantalum. Niobium has not therefore been used extensively for corrosion resistant applications and little information is available on its performance in service conditions. It is more susceptible than tantalum to embrittlement by hydrogen and to corrosion by many aqueous corrodants. Although it is possible to prevent hydrogen embrittlement of niobium under some conditions by contacting it with platinum the method does not seem to be broadly effective. Niobium is attacked at room temperature by hydrofluoric acid and at 100°C by concentrated hydrochloric, sulphuric and phosphoric acids. It is embrittled by sodium hydroxide presumably as the result of hydrogen absorption and it is not suited for use with sodium sulphide. 

In hydrochloric acid at temperatures up to 100°C, the corrosion rate decreases with time and ferric iron concentration . The presence of air does not affect the general corrosion rate but in IOn acid it promotes pitting attack, which also arises in chloride-containing methanolic solutions in the absence of sufficient water to effect passivation . Alloying niobium with 2.5% or more of tantalum significantly decreases corrosion rates in hydrochloric acid . 

Tantalum is one of the most versatile corrosion-resistant metals. Its corrosion behaviour can be compared with that of glass in most environments. This behaviour is attributed to the stable passive film of TajO, produced on the surface during exposure. 

Available reports indicate that tantalum is an effective passive metal in most of the chemical environments, at ambient temperature and up to about 100°C. There are only a few environments in which tantalum corrodes in a rate higher than Imm/y, at temperatures up to about 100°C. 

Tantalum is severely attacked at ambient temperatures and up to about 100°C in aqueous atmospheric environments in the presence of fluorine and hydrofluoric acids. Flourine, hydrofluoric acid and fluoride salt solutions represent typical aggressive environments in which tantalum corrodes at ambient temperatures. Under exposure to these environments the protective TajOj oxide film is attacked and the metal is transformed from a passive to an active state. The corrosion mechanism of tantalum in these environments is mainly based on dissolution reactions to give fluoro complexes. The composition depends markedly on the conditions. The existence of oxidizing agents such as sulphur trioxide or peroxides in aqueous fluoride environments enhance the corrosion rate of tantalum owing to rapid formation of oxofluoro complexes. 

Body fluids and tissues Tantalum is a very stable passive metal and completely inert to body fluids and tissues. Bone and tissue do not recede from tantalum, which makes it attractive as an implant material for the human body" . 

Tantalum-Niobium Alloying tantalum usually decreases the corrosion resistance of the metal due to metallic contamination of the TajOj passive film. The corrosion rates in HCl and H2SO4 environments increase roughly... 

The anodic behaviour of platinum and certain of its alloys is of considerable technical importance, since they can be employed under a wide range of conditions without appreciable corrosion, and often in circumstances where no other metal can be used. Their use industrially has recently been extended by applying them as thin coatings to a substrate of a passive metal such as tantalum or, more commonly nowadays, titanium, to reduce the cost. Platinised titanium anodes are discussed in detail in Section 11.3. 

Resistors, which are passive devices limiting the flow of electrical current in proportion to the applied voltage and usually made of tantalum, nichrome, titanium, or tungsten. 

For a number of metals the oxidizing action of air oxygen is sufficient to produce the passive state. In their air-oxidized state, metals such as tantalum, titanium, and chromium are very stable in aqueous solutions. 

Continuous (barrier, passivation) films have a high resistivity (106Q cm or more), with a maximum thickness of 10 4cm. During their formation, the metal cation does not enter the solution, but rather oxidation occurs at the metal-film interface. Oxide films at tantalum, zirconium, aluminium and niobium are examples of these films. 

The silvery, shiny, ductile metal is passivated with an oxide layer. Chemically very similar to and always found with zirconium (like chemical twins, with almost identical ionic radii) the two are difficult to separate. Used in control rods in nuclear reactors (e.g. in nuclear submarines), as it absorbs electrons more effectively than any other element. Also used in special lamps and flash devices. Alloys with niobium and tantalum are used in the construction of chemical plants. Hafnium dioxide is a better insulator than Si02. Hafnium carbide (HfC) has the highest melting point of all solid substances (3890 °C record ). 

Titanium as a carrier metal Titanium (or a similar metal such as tantalum, etc.) cannot work directly as anode because a semiconducting oxide layer inhibits any electron transport in anodic direction ( valve metal ). But coated with an electrocatalytic layer, for example, of platinum or of metal oxides (see below), it is an interesting carrier metal due to the excellent corrosion stability in aqueous media, caused by the self-healing passivation layer (e.g. stability against chlorine in the large scale industrial application of Dimension Stable Anodes DSA , see below). 

It should be mentioned that by changing the conditions of electrochemical synthesis — such as nature of the alcohol, the purity of the metal used as anode, the nature and concentration of the conductive additive, the voltage (usually 30 — 110 V DC is applied), the temperature, and even the construction of the cell — one can significantly effect the process of the anodic dissolution or even change its mechanism. As it has already been mentioned, the electrochemical dissolution of iron in alifatic alcohols gives insoluble iron (II) alkoxides [1005], while in 2-methoxyethanol a soluble iron (HI) complex is obtained [1514], Another example is provided by tantalum dissolution in isopropanol while high-purity metal is rapidly dissolved anodically [1639], the one containing impurities is passivated. Therefore, it is quite clear that each synthesis requires careful study, optimization of parameters of electrochemical synthesis, and isolation and purification of final products. 

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