Linear corrosion rate

The data for the average decrease in metal thickness in 4 years and the linear corrosion rate are given in Table 4-2. In addition, extrapolations of the rate for 50 and 100 years are given, which are of interest for the corrosion likelihood of objects buried in earth. It can be seen from the results that film formation occurs in class I soil. In class II soils, the corrosion rate decreases with time only slightly. In class III soils, the decrease with time is still fairly insignificant. 

A second possibility is that a linear corrosion rate could also be maintained by the finite dissolution rate of the film in the environment. For this situation, the rate of film thickening would eventually be counterbalanced by the rate of film dissolution, leading to both a constant film thickness and a constant corrosion... 

E25.32(b) Two electrons are lost in the corrosion of each zinc atom, so the number of zinc atoms lost is half the number of electrons which flow per unit time, i.e. half the current divided by the electron charge. The volume taken up by those zinc atoms is their number divided by number density their number density is their mass density divided by molar mass times Avogadro s number. Dividing the volume of the corroded zinc over the surface from which they are corroded gives the linear corrosion rate this affects the calculation by changing the current to the current density. So the rate of corrosion is... 

Fig. 2.1 User guidelines for zinc corrosion rates linear corrosion rates in different types of atmosphere (BS 5493, 1977). Note The atmospheric corrosion rates shown here are typically 50% higher than those now prevailing.

In the hot-dip galvanising process (hot-galvanising), layer thicknesses of 0.040-0.150 mm are produced on the steel surface. This coating consists of an iron-zinc alloy layer at the phase limit to the steel and a layer of pure zinc over that. The protective effect of the coating is determined by the layer thickness of both layers. In the initial stress load phase, covering layers are formed by the reaction of the zinc coating with the seawater. After this, a stationary phase of corrosion is reached with mainly linear corrosion rates at an order of magnitude of 0.010-0.012 mm/a (0.39-0.47 mpy). 

In order to select the alloy best suited to this application, an extensive program of corrosion tests was carried out by ORNL (USA) on the available commercial nickel-base alloys and austenitic stainless steels [22,30—34]. These tests were performed in a temperature gradient system with various fluoride media and different temperatures (maximum temperature and temperature gradient). Chromium, which is added to most alloys for high-temperature oxidation resistance, is quite soluble in molten fluoride salts. Metallurgical examination of the surveillance specimens showed the corrosion to be associated with outward diffusion of Cr through the alloy. It was concluded that the chromium content shall be maintained as low as reasonably possible to keep appropriate air oxidation properties. The corrosion rate is marked by initial rapid attack associated with dissolution of Cr and is largely driven by the impurities in the salt [22,30—34]. This is followed by a period of slower linear corrosion rate... 

The relative susceptibHity of several commercial aHoys is presented in Table 8. The index used is a relative rating based on integrating performance in various environments. These environments include the harsh condition of exposure to moist ammonia, Hght-to-moderate industrial atmospheres, marine atmosphere, and an accelerated test in Mattsson s solution. The latter testing is described in ASTM G30 and G37 (35,36) and is intended to simulate industrial atmospheres. The index is linear. A rating of 1000 relates to the most susceptible and zero designates immunity to stress corrosion. 

Other Effects Stream concentration can have important effects on corrosion rates. Unfortunately, corrosion rates are seldom linear with concentration over wide ranges. In equipment such as distillation columns, reactors, and evaporators, concentration can change continuously, makiug prediction of corrosion rates rather difficult. Concentration is important during plant shutdown presence of moisture that collects during cooling can turn innocuous chemicals into dangerous corrosives. 

Corrosion Rate by CBD Somewhat similarly to the Tafel extrapolation method, the corrosion rate is found by intersecting the extrapolation of the linear poi tion of the second cathodic curve with the equihbrium stable corrosion potential. The intersection corrosion current is converted to a corrosion rate (mils penetration per year [mpy], 0.001 in/y) by use of a conversion factor (based upon Faraday s law, the electrochemical equivalent of the metal, its valence and gram atomic weight). For 13 alloys, this conversion factor ranges from 0.42 for nickel to 0.67 for Hastelloy B or C. For a qmck determination, 0.5 is used for most Fe, Cr, Ni, Mo, and Co alloy studies. Generally, the accuracy of the corrosion rate calculation is dependent upon the degree of linearity of the second cathodic curve when it is less than... 

Linear polarization re.slstance probe.s. LPR probes are more recent in origin, and are steadily gaining in use. These probes work on a principle outlined in an ASTM guide on making polarization resistance measurements, providing instantaneous corrosion rate measurements (G59, Standard Practice for Conducting Potentiodynamic Polarization Resistance Measurements ). 

Oxygen solubility decreases almost linearly with increasing temperature but the diffusion rate increases exponentially. This leads to a slight increase in corrosion rate with increasing temperature although in Eq. (4-6) the factor is assumed to be greater. For this reason an increase in corrosion rate of about 1.5 times is considered in tropical waters compared with the North Atlantic. 

Linear polarization instruments provide an instantaneous corrosion-rate data, by utilizing polarization phenomena. These instruments are commercially available as two-electrode Corrater and three electrode Pairmeter (Figure 4-472). The instruments are portable, with probes that can be utilized at several locations in the drilling fluid circulatory systems. In both Corrater and Pairmeter, the technique involves monitoring electrical potential of one of the electrodes with respect to one of the other electrodes as a small electrical current is applied. The amount of applied current necessary to change potential (no more than 10 to 20 mV) is proportional to corrosion intensity. The electronic meter converts the amount of current to read out a number that represents the corrosion rate in mpy. Before recording the data, sufficient time should be allowed for the electrodes to reach equilibrium with the environment. The corrosion-rate reading obtained by these instruments is due to corrosion of the probe element at that instant [184]. 

Lead, aluminium and copper corrode initially but eventually form completely protective films". Nickel in urban atmospheres does not form a completely protective film, the corrosion/time curve being nearly parabolic". The corrosion rate of zinc appears to become linear after an initial period of decreasing corrosion rate". 

Aluminium is a very reactive metal with a high affinity for oxygen. The metal is nevertheless highly resistant to most atmospheres and to a great variety of chemical agents. This resistance is due to the inert and protective character of the aluminium oxide film which forms on the metal surface (Section 1.5). In most environments, therefore, the rate of corrosion of aluminium decreases rapidly with time. In only a few cases, e.g. in caustic soda, does the corrosion rate approximate to the linear. A corrosion rate increasing with time is rarely encountered with aluminium, except in aqueous solutions at high temperatures and pressures. 

Mechanistically, in approximately neutral solutions, solid state diffusion is dominant. At higher or lower pH values, iron becomes increasingly soluble and the corrosion rate increases with the kinetics approaching linearity, ultimately being limited by the rate of diffusion of iron species through the pores in the oxide layer. In more concentrated solutions, e.g. pH values of less than 3 or greater than 12 (relative to 25°C) the oxide becomes detached from the metal and therefore unprotective . It may be noted that similar Arrhenius factors have been found at 75 C to those given by extrapolation of Potter and Mann s data from 300°C. 

Although important contributions in the use of electrical measurements in testing have been made by numerous workers it is appropriate here to refer to the work of Stern and his co-workerswho have developed the important concept of linear polarisation, which led to a rapid electrochemical method for determining corrosion rates, both in the laboratory and in plant. Pourbaix and his co-workers on the basis of a purely thermodynamic approach to corrosion constructed potential-pH diagrams for the majority of metal-HjO systems, and by means of a combined thermodynamic and kinetic approach developed a method of predicting the conditions under which a metal will (a) corrode uniformly, (b) pit, (c) passivate or (d) remain immune. Laboratory tests for crevice corrosion and pitting, in which electrochemical measurements are used, are discussed later. 

Derivation of Linear Polarisation Method for Determining Corrosion Rates... 

Tafe plots The linear part of the anodic or cathodic polarisation log-current and potential plot is extrapolated to intersect the corrosion potential line ". Low corrosion rates can be measured relatively quickly. Note that resultant oxide films may be of different composition from those occurring in practice owing to the several decades of current applied which may not relate to actual plant practice. Portable apparatus including computing facilities is commercially available for plant testing. 

Polarisation resistance This technique, sometimes referred to as linear polarisation resistance (LPR), has been applied widely in industrial monitoring because of its ability to react instantaneously to a corrosion situation or change in corrosion rate " " . The limitation of the technique arises from the necessity to have a defined electrolyte as the corrosive (the author has seen an LPR probe installed in a dry gas-line in an oil refinery). 

Stern, M., A Method for Determinining Corrosion Rates from Linear Polarisation Data , Corrosion, 14 No. 9, 440t-444t, September (1958)... 

The corrosion rate of a metal in terms of weight loss per unit area (g m" d ) or rate of penetration (mm y" ) can be calculated from Faraday s law if the current density is known. Conversely, the corrosion current density can be evaluated from the weight loss per unit area or from the rate of penetration. The following symbols and units have been adopted in deriving these relationships in which it is assumed that corrosion is uniform and the rate is linear ... 

A simplification of the polarization resistance technique is the linear polarization technique in which it is assumed that the relationship between E and i is linear in a narrow range around E . Usually only two points ( , 0 are measured and B is assumed to have a constant value of about 20 mV. This approach is used in field tests and forms the basis of commercial corrosion rate monitors. Rp can also be determined as the dc limit of the electrochemical impedance. Mansfeld et al. used the linear polarization technique to determine Rp for mild steel sensors embedded in concrete exposed to a sewer environment for about 9 months. One sensor was periodically flushed with sewage in an attempt to remove the sulfuric acid produced by sulfur-oxidizing bacteria within a biofilm another sensor was used as a control. A data logging system collected Rp at 10-min intervals simultaneously for the two corrosion sensors and two pH electrodes placed at the concrete surface. Figure 2 shows the cumulative corrosion loss (Z INT) obtained by integration of the MRp time curves as ... 

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