CORROSION

Cross Country Petroleum Pipelines

Corrosion

CORROSION
CORROSION FUNDAMENTALS Corrosion is deterioration of a substance or its properties due to a reaction of the substance with its environment. All materials can thus corrode regardless of structure or constituent parts.

Any element or group of elements found in nature that are not in their most environmentally stable form in the environment that they are currently exposed, will corrode to a more stable form.

Forms of corrosion: There are two forms of corrosion namely Dry corrosion Wet corrosion or Electrochemical Corrosion Dry corrosion is characterized as a reaction occurring in the absence of an electrically conductive medium. Wet corrosion or Electrochemical corrosion, occurs in the presence of an electrically conductive medium, an Electrolyte. Corrosion can be further classified in following types: Types of Corrosion

Non Aqueous High Temperature, (usually > 315C by contact with gases liquid metals fused salts non-metals Uniform (rare in the oil field) Localized

Aqueous

Macroscopic Galvanic Erosion Pitting Concentration Cell Selective Leaching

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Microscopic Stress Corrosion Cracking Sulfide Stress Cracking Fatigue

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ELECTROCHEMICAL CORROSION When there is a flow of electrons from one area of a surface to another area through an electrolyte; corrosion of the surface from which the electrons flow will occur. In the case of metals; this area is called the Anode, has a positive charge (+) and will corrode into the electrolyte. The metal dissolved at the anode becomes an Ion, and must have a positive charge as it loses electrons to the metal and to the electrolyte. As a positively charged ion, the metal will naturally move away from the positively charged anode. Reactions at the anode:
Feo Iron in metal Fe++ + Iron Ion + + 2eElectrons 3e2e-

ALo AL+++ Aluminium in metal Cuo Copper in metal Cu++

In order for an electrical flow or the process of corrosion to proceed, there must be a place for the electrons liberated at the anode to be discharged to complete the circuit. This negatively charged substance is called a Cathode. Reactions at the cathode: Acid solutions:
H2O 2H+ + O= + 2H + 2e H2 h Hydrogen gas evolution at the cathode = + 2H2O 2O + 4H

2O= +2H2O + 4e4OH++ o M + 2e M Metal plating at cathode

Neutral or Basic solutions:

Basic requirements of an electrochemical corrosion cell 1. 2. 3. 4. An anode A cathode An electrolyte A connecting circuit

The common battery is a corrosion cell. The Zinc case serves as the anode. Ammonium chloride is the electrolyte. A Carbon (Graphite) rod is the cathode. The Zinc case and the Carbon rod are separated by an insulator (non-conductive material). When a piece of copper wire(highly conductive) or strip of copper connects the Zinc case to the Carbon rod; corrosion of the Zinc case occurs generating a flow of electrons from the anode
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through the electrolyte(Ammonium chloride) into the connecting circuit (copper wire or strip) to the Carbon rod(cathode). PIPELINE INTERNAL CORROSION IN OIL AND GAS SYSTEMS 1. Carbon Dioxide (Sweet Corrosion) Carbon dioxide (CO2) is a corrosive compound found in natural gas, crude oil, condensate, and produced water. CO2 corrosion, or sweet corrosion, is common in the natural gas and crude oil industry. CO2 is composed of one atom of carbon with two atoms of oxygen. When combined with water (H2O), carbon dioxide produces carbonic acid (H2CO2). Carbonic acid causes a reduction in the pH of water and results in corrosion when it comes in contact with steel. When iron (Fe) combines with carbonic acid, it produces iron carbonate (FeCO2). Corrosion Reaction
H 2O Fe++ + 2e1) Fe 2 2) CO + H2O H2CO3 H2O 3) H2 CO3 H+ + HCO32H+ + CO3= = 4) Combined 1) + 3) Fe++ + CO3 FeCO3

Iron carbonate is not as strong as the refined iron or steel used to make the well components. The damage caused by sweet corrosion in oil wells usually results in pitted sucker rods and the formation of hairline cracks. The important factors governing the solubility of carbon dioxide are pressure, temperature, and composition of the water. Pressure increases the solubility. Temperature decreases the solubility, and many dissolved minerals may buffer the water (prevent pH reduction). Corrosion test coupons can be inserted into the lines to indicate the level of iron removal and other corrosive conditions. Caliper surveys can also be used to determine the extent of tubing damage. Chemical injection, alloys, and protective coatings are used to combat the problem. 2. Hydrogen Sulfide (Sour Corrosion) Corrosion due to H2S is often referred to as sour corrosion. In most cases a layer of protective sulphide is formed; weak spots in this layer can lead to enhanced corrosion. With ferritic steels (stainless steels with a chromium content in the range of 12- 18%),

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dissolved H2S causes H-atoms to diffuse into the metal. This causes the metal to become brittle. H2S in water solution yields 2H -- Hydronium ions + a single HS ion. This HS ion further disassociates in water solution to 2H + S + OH. The combined metallic Iron and hydrogen sulfide reaction equation combines the Fe with the S to form FeS Iron sulfide precipitate. Corrosion Reaction
H2O 1) Fe Fe++ + 2eH+ + HS2) H2S + H2O 2H+ + S= + OH3) HS + H2O 4) Combined 1) + 3) Fe++ + S= FeS

The combination of H2S and CO2 is more aggressive than H2S alone and is found in oil field environments. Due to the rapid reaction of CO2 and H2S with the Fe(OH)2 and any Fe++, no equilibrium is ever reached between Fe and Fe++.
1) Fe(OH)2 + CO2 2) Fe(OH)2 + H2S 3) FeCO3 + H2S 4) Fe++ + H2S FeCO3 + H2O FeS + 2H20 FeS + CO2 + H2O FeS + H2

As can be seen from these reactions, there is a continuing demand for iron ion, since as soon as it is formed, it is taken out of solution by one of the above mechanisms. Though iron is used in this example, other metals react in essentially the same manner to produce metallic sulfides. The iron sulfide produced by this reaction generally adheres to the steel surface, as a black powder or scale. The scale tends to cause a local acceleration of corrosion because the iron sulfide is cathodic to the steel. This reaction results in deep pitting. Hydrogen sulfide generally appears in oil, gas, and water produced from the oil well. It can also be generated by sulphate-reducing bacteria, either underground or in surface equipment, and by thermal degradation of organic additives found in some mud cakes. With the use of chemicals, alloys and coatings the damage can be reduced. 3. Oxygen Corrosion Oxygen corrosion is the most common form of corrosion. On steel and iron, oxidation typically takes the form of rust. Oxygen corrosion begins when equipment makes contact with the atmosphere and moisture. Under these conditions, the iron and
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oxygen react with each other to form ferric oxide (Fe2O3), which is commonly referred to as rust. Corrosion Reaction
(H+ OH- ) with 02 H 2O 1) Fe Fe++ + 2e2) 4 Fe++ + 6H2O + 3O2 4Fe (OH)3 3) Combined 1) + 2) 2Fe++ (OH=)3 Fe2O3 + 3H2O

Of the three dissolved gases mentioned, oxygen is the worst of the group. It can cause severe corrosion at very low concentrations (less than 1 ppm); if either or both of the other two gases are dissolved in the water, it drastically increases their corrosivity. Oxygen combines slowly with many metals even at temperatures below 100 F; on moist surfaces it rapidly oxidizes iron and steel. Effect of Pressure & Fluid Velocity on Corrosion Pressure decreases can cause corrosive conditions to occur. The formation of scales, paraffins and other solids are directly related to pressure and temperature decreases creating environments for both acid gas corrosion and Microbiologically Induced Corrosion (MIC) to occur. Water that is in a vapor phase or emulsified can be dropped out of these states creating water wet conditions resulting in acid gas corrosion due to pressure and temperature drops. Velocity of produced fluids is also a very important factor to consider where the nature of the corrosiveness of a fluid is concerned. The general rule is that corrosive conditions increase with increased fluid velocity. In actual field and laboratory practice it is found that increased velocity can many times reduce corrosion rates by spreading out the points of attack of the corrosion reactions and also by inhibiting the abilities of bacteria to establish sessile colonies under which severe pitting attack can occur. Low velocity and stagnant fluids conditions in metal systems are known to be among the most corrosive conditions occurring in oil and gas handling. MICROBIOLOGICAL CORROSION Microbes (bacteria) can also cause corrosion. The bacteria do not directly eat the steel or metal, but their waste products are corrosive. They also can cause the development of differential concentration cells, leading to pitting. The most common type is the sulphate reducing bacteria or SRB's, which convert sulphates to sulphides and H2S. The environmental conditions under which these microorganisms normally operate are: Temperatures: from 20 to 30 C pH: from 6 to 8 Soil resistivities: from 500 to 20,000 ohm.cm

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The solutions to this problem are not giving the bacteria anything to eat (sulphates, nitrates, sources for carbon which they also need) and killing them by injection of bactericides or chlorination. CRACKING Stress Corrosion Cracking: Stress Corrosion Cracking is a form of Environmental Assisted Cracking (EAC). The term EAC is used to describe all types of cracking in pipeline that is influenced by the environment and stress. In a pipeline environment when water comes in contact with steel there is potential for the minerals and gases to create an initial corrosion site that is acted on by stresses that result in crack growth. Contributing factors to crack growth are residual stresses, temperature, load stress, bending, and local stresses. If there is no stress then crack growth will not occur and the result will be general wall thinning or pitting through corrosion. The conditions that are present during crack growth dictate the type of SCC that may occur. High pH conditions cause intergranular cracks while low pH conditions create non-classical SCC that result in transgranular cracks with mixed modes at the crack tip. High pH SCC typically occurs within 15 miles downstream of pipeline compressor or pump stations where temperatures of the transported medium may exceed 100 F. Along with the elevated temperatures, a groundwater/carbonate/ bicarbonate solution (high pH) would have to be in contact with the pipe through a defect in the pipeline coating. Near-neutral pH SCC typically occurs in pipe where a combination of inadequate cathodic protection (corrosion protection) and coating defects exist which is then exposed to a groundwater solution containing dissolved carbon dioxide. The source of the carbon dioxide is typically the decay of organic matter in the soil. Crack Profiles: Crack characteristics can vary greatly depending on the cause of the crack, the materials being cracked, and the environment causing the cracking. Figures 1 to 3 show examples of crack profiles. Figure 1 shows a cross section of two SCC cracks that were located in pipeline steel within the body of the pipe. Cracks may have a single main branch or be composed of several smaller branch tips. In addition, the proximity of a crack to adjacent cracks may vary significantly as shown in Figure 1 and 2. Figure 3 shows two co-parallel cracks close together located within the weld cap.

Fig 1: Photomicrograph of a SCC crack in pipelineFig 2: Photograph of a SCC crack at the weld fusion steel. line (toe crack). Branching nature that may occur at the crack tip can clearly be seen in this profile.

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Figure 3 shows a crack occurring at the fusion line of the weld and the parent material. Fusion line cracks are commonly known as toe cracks.

Fig 3: Photomicrograph of a SCC in a weld. The two indications shown are located adjacent to one another and both occur within the weld material.

SCC tends to propagate as crack clusters or colonies as pipeline stress opens cracks that are subject to corrosion, which are then corroded further, weakening the pipeline metal by further cracking.

Pipeline Failure Rates from Stress Corrosion Cracking The majority of pipeline incidents due to SCC are found on natural gas pipelines due to higher pipeline temperatures. In comparison, the occurrence rate for hazardous liquid pipelines is low. The failure rate due to SCC is low, approximately 1%. Corrosion Fatigue Corrosion fatigue is defined as a combination of normal fatigue and corrosion that causes failure below the metals normal endurance limit. Thus, it is normally encountered not as a visible degradation of the metal but as a premature failure of a component under cyclic conditions. To minimize SCC and corrosion fatigue, following methods may be considered:
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Stress-relieve susceptible material after welding. This heat-treatment procedure will lower the level of residual tensile and cyclic stresses in the component. Create compressive stresses by shot peening, which puts the outer surface in compression. Because fatigue and SCC require tension stresses, greater resistance can be obtained by shot peening. Avoid stress raisers by blending welds to the level of the base metal. Use butt welds instead of fillet welds, because fillet welds are much more susceptible to corrosion fatigue and SCC. Blend grinding marks, rough edges, and rough machine marks. Avoid unnecessary cold work. Cold-working the material using various fabrication methods increases the residual stresses that may make a component more susceptible to corrosion fatigue and SCC.

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PIPELINE EXTERNAL CORROSION IN SOILS External Corrosion in pipelines is an electrochemical process. Anodic reactions involve oxidation of metal to its ions, e.g. for steel the following reaction occurs. Fe > Fe2+ + 2e (1) The cathodic process involves reduction and several reactions are possible. In acidic water, where hydrogen ions (H+) are plentiful, the following reaction occurs. 2H+ + 2e > H2 (2) Reactions (1) and (2) are shown schematically in Fig 1 where anodic and cathodic sites are nearby on the surface of a piece of metal. Electrolyte (Soil)

This electro-chemical corrosion can result from two basically different mechanisms. These mechanisms can be referred to as electrolytic corrosion, i.e., stray current corrosion and as galvanic corrosion. Galvanic Corrosion: A pipe in the ground can be shown to be analogous to a group of electrically interconnected galvanic cells, such as the ordinary dry cell. In the dry cell the negative electrode or anode is the zinc and the positive electrode or cathode is the carbon. The zinc or anode is the electrode which is attacked by corrosion. Similarly on an underground pipe which is attacked by galvanic action, the more negative locations are those at which damage will occur. Galvanic corrosion can be classified into three main categories as follows: 1. Local action 2. Long line corrosion or concentrated attack 3. Bi-metallic corrosion
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Local action is often due to direct attack of the environment on the metal. The attack is uniformly distributed over the entire surface of the metal. The anodes and cathodes on the metal surface are very close to one another and the anodic areas are in continual migration. The migration is a direct affect of the corrosion products on the potential gradient that exists on the surface of the metal. Long line corrosion (concentrated corrosion) on underground pipelines is a selective type of corrosion which attacks only portions of a given length of pipe. This type of corrosion usually appears when the pipe traverses soils of different composition, and as a result, one section of the pipe becomes anodic with respect to another. For example, if a given length of pipe is laid in soil of which some is of high resistivity, and some is of low resistivity, the section of the pipe in the low resistivity soil becomes anodic with respect to the portion of the pipe in the high resistivity soil and corrosion will occur at the anodic portion. Long line corrosion differs from local action corrosion in the fact that the anodic areas and cathodic areas are more widely separated in the former than in the latter. Another important cause is the coupling of new pipe to pipe that has been installed for a number of years. In this case, the new pipe will corrode more rapidly. When new steel pipe is connected to old rusty pipe, generally, the new pipe is anodic to the old pipe. Bi-metallic corrosion results when two underground pipes of different metals are installed close to one another and are electrically connected to one another through some common structural connection. This type of corrosion appears frequently when copper water service pipe are laid adjacent to steel gas service pipes. In this case the steel is anodic with respect to the copper and the steel will corrode. The rate of corrosion is governed among other things by the resistivity of the soil and distance between two pipes. Thus if the soil is of low resistivity and the two pipes are very close to one another, failure resulting from this type of corrosion can be very rapid. Stray current corrosion is a result of current which is introduced into the ground from neighboring sources of DC current such as: 1) 2) 3) 4) 5) Electric railways or tram or trolley bus system DC machinery Cathodic protection of other nearby underground pipelines High voltage DC transmission systems etc. Occasionally disturbances in earths magnetic fields (Magnetic storm or Telluric) also cause stray currents.

Stray current represents current flow in the electrolyte that does not originate from the CP system designed to protect the pipeline. Such "external" current sources can disrupt the "ideal" current distribution of the CP system and consequently can lead to corrosion. This phenomenon is illustrated schematically below.

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Stray Current Mapper (SCM) can be used to identity the source of stray current, locate discharge points and locate pick-up points. The problem of stray current corrosion can be overcome by using coatings, electrical shields, use of galvanic anodes at the point of railway crossings etc. and by bonding pipelines at pipeline crossings. FACTORS AFFECTING CORROSION IN SOILS 1. Soil Characteristics The most frequent causes of underground corrosion are considered to be found in the soil itself, and are as follows: A. Differential aeration B. Soluble salts in the soil C. Differences in characteristics of the soil at different points of contact 2. Physical Characteristics of Soils Well aerated and well drained soils are usually less corrosive than poorly aerated and poorly drained soils. Therefore, the physical characteristics which are important in corrosion are those which are associated with the aeration of the soil and its retentiveness of water. Aeration and moisture content are governed to a large degree by the texture of the soil. Soils of coarse textures such as those with high percentage of sand and gravel will be well aerated and non-retentive of water. Since the physical characteristics of soils which are favorable to corrosion are poor aeration and high moisture content, the heavy clay, poorly drained soils are those more often associated with corrosion.

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3. Soil Resistivity One of the most common criterion of corrosiveness of a given soil is its electrical resistivity. Corrosiveness of soil is very often an inverse function of the resistivity, and soils with lower resistivities are likely to be more corrosive than soils of high resistivities. The following table is the generally accepted classification of soils according to resistivity in ohm-centimeter. Soil Resistivity Classification & Corrosiveness Resistivity Category Corrosiveness OHM Centimeters 0 1,000 Very Low Very corrosive 1,000 5,000 Low Aggressive 5,000 10, 000 Medium Mildly corrosive 10,000 20,000 High Slightly corrosive Progressively less 20,000 30,000 Very High corrosive 30,000 1,00,000 Extremely High Not corrosive In addition to the usefulness of soil resistivity measurements in the determination of the corrosion pattern, these measurements are necessary in the design of a cathodic protection system for the mitigation of corrosion. It is one of the factors used to determine whether a galvanic anode type system or an impressed current type system should be permanently installed. If a galvanic anode type system is indicated, soil resistivity is one of the factors necessary in determining the size and number of anodes required. If an impressed current type system is indicated, soil resistivity is one of the factors necessary in determining the location and number of anodes required and the output capacity of the power source (rectifier unit) to be used. Measurements of soil resistivity are made by using the Wenner four pin method. This method consists of finding the change in voltage across a given section of soil for particular current that is made to pass through the soil. Four pins are placed in the soil a given distance. The outer two pins are known as the voltage electrodes. By determining the change in voltage across the inner pins for a given current that is made to pass through the outer pins, the average resistivity of the soil between the surface and a depth C can be determined from the formula: R+191.5 AE I R = Soil resistivity, ohm-centimeters A = Distance between electrodes, feet E = Change in voltage across inner electrodes, volts I = Current through outer electrodes, amperes
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Where