Corrosion rate temperature

Normal distribution in corrosion rates (temperature dependent)... 

Under dissolution-controlled conditions, corrosion by liquid metals should increase with increasing temp)erature. For example, assuming all other factors affecting corrosion are fixed, the corrosion rate-temperature relationship can be expected to follow the classical Arrhenius expression, log k exp(-0/RT), where k is corrosion rate, Q is the activation energy, R is the gas constant, and T is the absolute temperature. This is shown graphically in Fig. 4 for type 316 stainless steel in sodium. In this case, the corrosion rate can be related directly to mass loss, which can be expressed m terms of wall thinning. 

High temperature naphthenic acid corrosion can normally be observed at temperatures ranging from 230°C to 400°C. Some of the literature has reported two peaks on the corrosion rate-temperature curves, the first peak at 270-280°C and the second at 350-400°C. 

The corrosion rate of steel in carbonic acid is faster than in hydrochloric acid Correlations are available to predict the rate of steel corrosion for different partial pressures of CO2 and different temperatures. At high temperatures the iron carbonate forms a film of protective scale on the steel s surface, but this is easily washed away at lower temperatures (again a corrosion nomogram is available to predict the impact of the scale on the corrosion rate at various CO2 partial pressures and temperatures). 

Atmospheric corrosion results from a metal s ambient-temperature reaction, with the earth s atmosphere as the corrosive environment. Atmospheric corrosion is electrochemical in nature, but differs from corrosion in aqueous solutions in that the electrochemical reactions occur under very thin layers of electrolyte on the metal surface. This influences the amount of oxygen present on the metal surface, since diffusion of oxygen from the atmosphere/electrolyte solution interface to the solution/metal interface is rapid. Atmospheric corrosion rates of metals are strongly influenced by moisture, temperature and presence of contaminants (e.g., NaCl, SO2,. ..). Hence, significantly different resistances to atmospheric corrosion are observed depending on the geographical location, whether mral, urban or marine. 

Fluorine can be handled using a variety of materials (100—103). Table 4 shows the corrosion rates of some of these as a function of temperature. System cleanliness and passivation ate critical to success. Materials such as nickel, Monel, aluminum, magnesium, copper, brass, stainless steel, and carbon steel ate commonly used. Mote information is available in the Hterature (20,104). 

For most alloys, the corrosion rate displays a maximum at 850—900°C, and decreases very rapidly at temperatures up to 1000°C (28), again strongly suggesting that a molten salt is necessary in order to initiate hot corrosion. 

Gaseous Hydrogen Chloride. Cast Hon (qv), mild steel, and steel alloys are resistant to attack by dry, pure HCl at ambient conditions and can be used at temperatures up to the dissociation temperature of HCl. The corrosion rate at 300°C is reported to be 0.25 cm/yr and no ignition point has been found for mild steel at 760°C, at which temperature HCl is dissociated to the extent of 0.2%. 

When moisture films are formed, water vapor can accelerate the corrosion rate. Hence, it is necessary to maintain the temperature above the dew point of the gas mixture by at least 20°C, to prevent the formation of moisture films. A temperature of 130°C or above, at atmospheric pressure, can be used for all mixtures of HCl gas and water vapor because the a2eotropic boiling point is 108.6°C. The boiling point of a2eotropic mixtures can be used as a guide at other pressures (see Table 6). 

HCl gas reacts with metal oxides to form chlorides, oxychlorides, and water. Therefore, all the steel equipment should be pickled to remove the oxide scales before it is put in service. Because oxidi2ing agents in the HCl gas such as oxygen or chlorine significantly affect the corrosion rate, it is essential that the operating temperature of the steel equipment be kept below the temperature (316°C) at which ferric chloride is vapori2ed from the metal surface. 

Stainless steel alloys show exceUent corrosion resistance to HCl gas up to a temperature of 400°C. However, these are normally not recommended for process equipment owing to stress corrosion cracking during periods of cooling and shut down. The corrosion rate of Monel is similar to that of mild steel. Pure (99.6%) nickel and high nickel alloys such as Inconel 600 can be used for operation at temperatures up to 525°C where the corrosion rate is reported to be about 0.08 cm/yr (see Nickel and nickel alloys). 

Naphthenic acid corrosion has been a problem ia petroleum-refining operations siace the early 1900s. Naphthenic acid corrosion data have been reported for various materials of constmction (16), and correlations have been found relating corrosion rates to temperature and total acid number (17). Refineries processing highly naphthenic cmdes must use steel alloys 316 stainless steel [11107-04-3] is the material of choice. Conversely, naphthenic acid derivatives find use as corrosion inhibitors ia oil-weU and petroleum refinery appHcations. 

The reactor coolant pH is controlled using lithium-7 hydroxide [72255-97-17, LiOH. Reactor coolant pH at 300°C, as a function of boric acid and lithium hydroxide concentrations, is shown in Figure 3 (4). A pure boric acid solution is only slightly more acidic than pure water, 5.6 at 300°C, because of the relatively low ionisation of boric acid at operating primary temperatures (see Boron COMPOUNDS). Thus the presence of lithium hydroxide, which has a much higher ionisation, increases the pH ca 1—2 units above that of pure water at operating temperatures. This leads to a reduction in corrosion rates of system materials (see Hydrogen-ION activity). 

Vitreous silica is susceptible to attack by alkaline solutions, especially at higher concentrations and temperatures. For 5% NaOH at 95°C, although craving may be evident, surface corrosion is only 10 p.m after 24 h (87). For 45 wt % NaOH at 200°C, dissolution proceeds at 0.54 mm /h (88). The corrosion rates in other alkaline solutions are Hsted in Table 3. Alkaline-earth ions inhibit alkaline solution attack on vitreous siUca. Their presence leads to the formation of hydrated metal siUcate films which protect the glass surface (90). 

Carbon steel is not normally a suitable piping material for concentrated sulfuric acid because of high corrosion rates in flowing acid. However, where temperatures and flow rates are low, heavy waU steel pipe is sometimes used for transferring product acid. 

The exposed surface area of a tank is relatively large, thus heated tanks are almost always insulated. Another reason for insulating is that the external corrosion rate of the steel owing to atmospheric conditions increases with increasing temperature. Insulation, if propedy installed, reduces external... 

Zirconium is completely resistant to sulfuric acid up to Foiling temperatures, at concentrations up to 70 wt %, except that the heat-affected zones at welds have lower resistance in >55 wt % concentration acid (Fig. 1). Fluoride ions must be excluded from the sulfuric acid. Cupric, ferric, or nitrate ions significantly increase the corrosion rate of zirconium in 65—75 wt % sulfuric acid. 

Materials of Construction. Glass has excellent corrosion-resistance to wet or dry bromine. Lead is very usefiil for bromine service if water is less than 70 ppm. The bromine corrosion rate increases with concentrations of water and organics. Tantalum and niobium have excellent corrosion-resistance to wet or dry bromine. Nickel has usefiil resistance for dry bromine but is rapidly attacked by wet bromine. The fluoropolymers Kynar, Halar, and Teflon are highly resistant to bromine but are somewhat permeable. The rate depends on temperature, pressure, and stmcture (density) of fluoropolymer (63). 

Titanium, HasteUoy (grades C22 and C276), and 316 stainless steel all exhibit corrosion rates of less than 0.08 mm/yr at room temperature in 35 wt % chloric acid solutions (2). 

The concentration dependence of iron corrosion in potassium chloride [7447-40-7] sodium chloride [7647-14-5] and lithium chloride [7447-44-8] solutions is shown in Figure 5 (21). In all three cases there is a maximum in corrosion rate. For NaCl this maximum is at approximately 0.5 Ai (about 3 wt %). Oxygen solubiUty decreases with increasing salt concentration, thus the lower corrosion rate at higher salt concentrations. The initial iacrease in the iron corrosion rate is related to the action of the chloride ion in concert with oxygen. The corrosion rate of iron reaches a maximum at ca 70°C. As for salt concentration, the increased rate of chemical reaction achieved with increased temperature is balanced by a decrease in oxygen solubiUty. 

The second class of anodic inhibitors contains ions which need oxygen to passivate a metal. Tungstate and molybdate, for example, requke the presence of oxygen to passivate a steel. The concentration of the anodic inhibitor is critical for corrosion protection. Insufficient concentrations can lead to pitting corrosion or an increase in the corrosion rate. The use of anodic inhibitors is more difficult at higher salt concentrations, higher temperatures, lower pH values, and in some cases, at lower oxygen concentrations (37). 

Corrosivity. Corrosivity is an important factor in the economics of distillation. Corrosion rates increase rapidly with temperature, and in distillation the separation is made at boiling temperatures. The boiling temperatures may require distillation equipment of expensive materials of constmction however, some of these corrosion-resistant materials are difficult to fabricate. For some materials, eg, ceramics (qv), random packings may be specified, and this has been a classical appHcation of packings for highly corrosive services. On the other hand, the extensive surface areas of metal packings may make these more susceptible to corrosion than plates. Again, cost may be the final arbiter (see Corrosion and corrosion control). 

Acid-soluble metals such as iron have a relationship as shown in Fig. 28-2 7, In the middle pH range ( 4 to 10), the corrosion rate is controlled by the rate of transport of oxidizer (usually dissolved O9) to the metal surface. Iron is weakly amphoteric. At very high temperatures such as those encountered in boilers, the corrosion rate increases with increasing basicity, as shown by the dashed line. 

Cold walls, as in coolers or condensers, usually have somewhat decreased corrosion rates for the reason just described. However, in some cases, the decrease in temperature may allow the formation of a more corrosive second phase, thereby increasing corrosion. 

Carbon steel is easily the most commonly used material in process plants despite its somewhat limited corrosion resistance. It is routinely used for most organic chemicals and neutral or basic aqueous solutions at moderate temperatures. It is also used routinely for the storage of concentrated sulfuric acid and caustic soda [up to 50 percent and 55°C (I30°F)]. Because of its availability, low cost, and ease of fabrication steel is frequently used in services with corrosion rates of 0.13 to 0.5 mm/y (5 to 20 mils/y), with added thickness (corrosion allowance) to assure the achievement of desired service life. Product quahty requirements must be considered in such cases. 

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