Monday, 25 July 2016

Corrosion behavior of Nickel and its alloys in Alkalies

Corrosion rates in chemical media usually reduce with increase in pH values. In alkaline media, the hydrogen ion is available in small contents. However various metal receive nominal corrosion at some pH, usually basic and then become quickly corrosive as pH increases. Often corrosion because of alkaline media causes localized and pitting attack by the development of cathodic layers and corrosion is extreme at the sensitive anodic areas. Austenitic grades and various nickel based alloys receive stress corrosion cracking or general corrosion in hot concentrated caustic.
Addition of nickel in an alloy increases corrosion resistance in alkaline media. Nickel 200 and various high nickel alloys provide suitable service in dealing with this media. The commonly used nickel alloys in alkali media are nickel 200, Monel 400, Inconel 600 and alloy 625.

Nickel 200
The great corrosion resistance characteristic of alloy 200 is its potential against caustic soda and other alkalies. The alloy is not affected by anhydrous ammonia or ammonium hydroxide in contents of 1%. Larger contents are resulted by fast corrosion in the presence of dissolved oxygen.

Nickel 200 offers good resistance to whole concentration percentage of caustic soda or sodium hydroxide at the different temperature limits including the melting point. Below 50% concentration, corrosion rates are low, usually below 0.1 mpy or 0.003 mm/a actually in boiling points. The increased content and temperature limits result in slightly accelerated corrosion rates.

The major influencing factor of nickel alloy in highly concentrated caustic soda is the same nature of layer developed while exposing the caustic soda. In the diverse media, a security layer of black nickel oxide is developed that results in a considerable reduction in the corrosion rates during prolong experience. For example, specimens of alloy 201 were exposed to caustic solutions consisting of 500 cc of water to 2kg of technical caustic flakes followed by heating in nickel 201 at temperature limit of 790oF – 830oF. The corrosion rate in the first 24 hours was average 21 mpy. The specimens were exposed to test without the elimination of oxide layer. During the weekends the overall corrosion rates decrease to 2.8 mpy or 0.07 mm/a.

The presence of chlorates in caustic soda solutions accelerates the corrosion of alloy 200 considerably. Taking the damaging effects into account, it is preferred to avoid chlorates fully prior evaporation at the high temperatures in the presence of nickel. It is also known that the presence of oxidizable sulphur compounds increases the corrosivity of caustic for nickel. This effect is noticed normally with sulphides such as hydrogen sulphide, mercaptans, sodium sulphide and to a small limit with slightly oxidizing media containing thiosulfates and sulphates.

The effect of oxidizable sulfur compounds can be eliminated by the addition of caustic solution of suitable sodium peroxide to oxidize them to sulfates. Wide peroxide does not appear to alter the corrosiveness of caustic soda to nickel.

In the other media, when nickel is used at temperatures above 600oF, the preferred metal is a low carbon alternative for example Nickel 201.

Monel 400
The high nickel content, alloy 400 provides good resistance identical to the Pure Nickel alloy 200 to caustic soda for the several concentration limits, although causing stress corrosion cracking in the strong alkalis at the elevated temperatures. The corrosion rates of alloy 400 are higher in concentrated caustic soda and caustic potash at the high temperatures. Alloy 400 also offers good resistance to anhydrous ammonia and ammonium hydroxide solutions comprising of 3% alkali concentration in the absence of dissolved oxygen.

Incoloy Grades
The alloys provide excellent resistance to alkaline solutions, getting a corrosion rate of 0.5 mpy or 0.01 mm/a in the boiling 50% sodium hydroxide, their resistance is below that provided by Nickel 200, are used in alkaline conditions except other corrosive media is included. They can also get stress corrosion cracking in warm concentrated alkalis. They also prevent corrosion in ammonia and ammonium hydroxide solutions in the various service media.
Inconel 600
In the high temperature caustic conditions containing sulfur, alloy 600 offers superior performance than alloy 201. However alloy 600 can receive stress corrosion cracking in specific alkali media. So it should be stress relieved prior service and service stresses must be used to the minimum. Alloy 600 provides good resistance to sodium hydroxide at the boiling temperatures in concentrations about 80%.
For nickel 200, the presence of chlorates in caustic soda accelerates the corrosion rates. For its con
For Nickel alloy 200, the availability of chlorates in caustic soda increases the corrosion rates. Due to its concentration of chromium, Inconel alloy 600 is fully resistant to corrosion by ammonia for a complete range of concentrations and temperatures.
While offering good corrosion resistance, Inconel grades are not often required for service in absolute caustic media. They can be advantageous for use in halide media.

Salt
Salt and water combination offers good conductivity of salts and therefore they become able to take higher corrosion currents. Therefore the galvanic effects are more noticeable in the salt solutions instead in pure water.

The commonly used nickel alloys in the process media involving sulfate salts are Incoloy 825, Inconel 625, Hastelloy C276 etc. For media containing chloride salts, the commonly used alloys are alloy 400, alloy 825, alloy 625, etc.

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