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CORROSION Study Note

Corrosion is the deterioration of metals due to environmental reactions, primarily occurring in aqueous solutions. It results in significant economic losses and can lead to catastrophic failures, posing risks to human life. Understanding the electrochemical processes involved in corrosion, including the roles of anodes, cathodes, and electrolytes, is crucial for effective corrosion control and prevention.

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7 views19 pages

CORROSION Study Note

Corrosion is the deterioration of metals due to environmental reactions, primarily occurring in aqueous solutions. It results in significant economic losses and can lead to catastrophic failures, posing risks to human life. Understanding the electrochemical processes involved in corrosion, including the roles of anodes, cathodes, and electrolytes, is crucial for effective corrosion control and prevention.

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(from Swain (1996) and Schultz (1997) What is corrosion? * Webster's Dictionary - corrode (v.) To eat away or be eaten away gradually, especially by chemical action, NACE Corrosion Basis - corrosion may be defined as the deterioration of a material (usually a metal) because of a reaction with the environment. Why do metals corrode? Most metals are found in nature as ores. The manufacturing process of converting these ores into metals involves the input of energy. During the corrosion reaction the energy added in manufacturing is released, and the metal is returned to its oxide state. Metal Ore St sites, Mota] Seton penne Corrosion Products In the marine environment, the corrosion process generally takes place in aqueous solutions and is therefore electrochemical in nature. Corrosion consequences Economic - corrosion results in the loss of $8 - $126 billion annually in the U.S. alone. This impact is primarily the result of: Downtime Product Loss Efficiency Loss Contamination Overdesign Safety / Loss of Life Corrosion can lead to catastrophic system failures which endanger human life and health. Examples include a 1967 bridge collapse in West Virginia which killed 46. The collapse was attributed to stress corrosion cracking (SCC). In another example, the fuselage of an airliner in Hawaii ripped open due to the combined action of stress and atmospheric corrosion. Corrsien cot cuts dv othe formation of ica als. Ia to occur five things are nacesury. Hany ofthese fcr ar eliminated, galvanic comosion wll no occur, THIS IS THE KEY TO CORROSION CONTROL! Thenesessry fist jon to proceed ANODE. the metal orsite onthe metal where oxidation occurs (los of electrons). The anode asa more negative ptcail with respect to (wrt the cathode ands termed les noble wit the cathode. CATHODE -the metal orsiteom the metal where redaction oscurs (gin of eestrons). The ‘cathode has a more positive potntial wat the anode and is termed tore noble wat the anode ELECTROLYTE - the electrically conducive medium in which the anode and shade resid ELECTRICAL CONNECTION - th anode ath enthode mst he electrical connected POTENTIAL DIFFERENCE - 4 votge difference must exist hetwsen the anode and the Schematic oF the worosion ell The electrochemical cell is driven by the potential difference between the anode and the cathode This causes a current to flow, the magnitude of which will be determined by the resistance of the electrochemical cireuit (i.e. Ohm’s Law, [=V/R). The three main types of electrochemical cel's are: Concentrati concentratio! These can be Bimetallic Cells - where the anode and cathode are different materi Thermo-galvanic Cells - where the anode and the cathode are of the same material and the composition of the electrolyte is the same but the temperature at the electrodes are different. Surface potential The surface potential of a metal is a measure of its activity. When a metal is immersed in an aqueous environment, both oxidation and reduction reactions occur until some equilibrium is reached. These reacti dons tend to create an electrical double layer at the surface which establish an electrical potential. The more positive metals are said to be more noble and less reactive, while the more negative metals are called base metals and are highly reactive, The standard potential of metals are given in the following table termed the standard electromotive force series. It should be made clear however that a metal’s actual potential can be greatly altered by its environment. Cathode half-cell reaction The reduction half-cell reaction at the cathode depends mainly on environmental conditions. The following six reactions represent common cathodic reactions along with the conditions in which they generally occ O, +2H,0+ 4e" > 40H~ aerated neutral to alkaline water O, +4H* +4e” > 2H,0 aerated acidic solutions 2H" +2e > H,T hydrogen evolution (in acids) M™ +ne—>M metal deposition MY se Mem metal reduction Example: Magnesium is submerged into a bath of HCI. What would the predominate anodic and cathodic reactions be? Anodic Mg > Mg” +2e° Cathodic 2H’ +2e > H,t Overall reaction Mg +2HCI—> MgCl, +H, 7 Corrosion thermodynamics Acwe have observed comosion estos invitbly involve electron transfer. Fo this eso the reactions may be consid olcrochonied inane, Themed namics an provide a ass for ‘he understanding ofthe energy changes astocintd with the omosion ton. ean i gnea pedit when comesion is possible, Thennodjumicscanot pee comesion tates, The ate a hick therein procods is poverned by knto The Gites ay given bythe following uation, provides ws tool with which 1 nF n= elseonstransfrdin oxiation reetion ale Faraday constant (6.500400 2 =Stundandomt poesia," +8, as) saw Fete te bat =0441y Ove maston 27440, +2140 924 02, fad] Bata Hal eee Fea seats on ha be wien fe AG=-244531) tion, a write, is possible Zn (s) + Cu* (ag) > Zn** (aq) + Cu (s) a aaa eg ogo!) =03715 Mota willbelot rom th ouside ofthe dis timo Electrochemical We now have a tool to predict if the corrosion reaction is possible, but it would also be handy to predict how fast the reaction will proceed. In theory, Faraday’s law can be used do this. Faraday’s Taw may be stated as where: m = mass of metal lost to corrosion (grams) 1 = corrosion current (amps) electrochemical equivalent a (ya-s) a a =atomic weight of corrodin; electrons transfered in F = Faraday’ idation reaction (mol e) onstant (96,500 A-s/mol e*) 1 = time of reaction (seconds) ou |) RS eva 7 Se ee + Gogen toplam elktrik ko (Coulomb) = Q = I+ Sa eet) ee ee eet i) Beet es See ears ra Cee oA) cs) Reference electrodes The reaction potential isn hydrogen half-ell provides the basic standard, but in practice is awkward to use. Foe this reason, several other reference half-cells have heen developed. Some ofthese reference cells are listed in the following table along with cheir potential with respect othe hydrogen halfeul and location of ‘Comanonly used half-ells [from Swain Classnotes (1996)] Falrcal Poiontal Ret] Environment SHE Copper Copper Suline 0.3160 Sal Tenth Normal Calomel (03337 | Laborato Normal Calomel ‘0.2800 | Laboratory ‘Saturated Calomel 02415 | Laboratory Silver : Silver Chiorde (DIM RCD ‘0.2880 Seawater Silver: Silver Choride (Seawater) 0. Seawater Silver: Silver Chloride G.8M KCI) 0.1990 Seawater Hydrogen 0 Taboratory Zine 600 Seawater Galvanie series The electrochemical series presented earlier can only be applied to oxide free surfaces at ion concentrations for which the standard potentials are valid. When metals are exposed in a more complex electrolyte such as seawater, the galvanic series may be used to help predict if corrosion of a metal is possible. ‘The galvanic series for many commonly used metals is given in the table on the next page. It should be noted that for some metals, such as the stainless steels, there are significant differences in the potential they are likely to exhibit. These differences are generally ‘owed to the condition of the metal surface, For example, 316 stainless steel has a potential of about -0.1v ref saturated calomel when itis passive (protected by a thin oxide film). Ifthe oxide layer is compromised, the potential may shift to -0.4v and corrode. In service, severe localized attack may oceur at active sites. The rate of corrosion (or current density) is determined by the potential difference beween the anode and the cathode and the resistance of the corrosion cell. The corrosion current is therefore: The resistance of the cell may be as a result of electrical resistance or electrode polarization. The greater the resistance the lower the corrosion current and from Faraday’ law the lower the mass loss. A high resistance within the corrosion cell is beneficial for control. This resistance may result from one or more of the following factors Resistance of the electrical connection between anode and cathode. Resistance of the electrolyte. High concentration of anode metal ions in solution, Reactant build-up at the cathode. Lack of reactants at the cathode. The action of these resistances may be expressed in a polarization diagram. These diagrams plot potential difference versus eurrent (or log current). ‘The slope of the curve represents the resistance. Polarization Polarization may be defined the shift in eleetrode potential which results from the effects of current flow wart the zero cuttent flow potential. All corrosion reactions involve euttent flow and will ater the potential of the metal surfaces involved. The degree of polarization will be determined by the resistance of the corrosion cell. The higher the cell resistance, the larger the shift in potential, VeR The two types of polarization that may be encountered at the electrode surfae Activation polarization - this isthe energy required to overcome the exchange current density to allow the electrode reaction to procec Concentration polarization - this is the shift in potential due to concentration ch environment adjacent to the electrode surface. (CURRENT DENSITY (Aven?) Polarization diagram [from Jones (1996)] Passivating films Passivity can be defined as the loss of chemical reactivity exhibited by certain metals under specific environmental conditions. In some cases, oxide films which form on the surface of a ‘metal expesed in an electrolyte can have a marked effect on its corrosion behavior. This is notable ‘with metals near the tp of the electromotive series. Aluminum, for example, would corrode rapidly in seawater if it were not protected by a thin oxid film. Alloys containing chromium, iron, nickel, and titanium can become “passive” in strong oxidizing solutions when they form protective surface films. In this state, they may have a resistance to corrosion which is orders of magnitude greater than the unfilmed or “active” metal surface. The stainless steels can often exhibit this behavior. The passivating film is usually of the order of only 3 nm in hickness, however. This means that the film can be quite delicate. The ability of the surface film to adhere or self heal if compromised by turbulence or mechanical effects can be the determining factor in tt c. cases Which the surface film does not remain intact that stainless steels can undergo severe localized attack reLarive “faessve “POWER (corrosion ivating (left)/ passivating metal (right) [from Corrosion Basics (1984)] Te eee eee eee tet) Sol Grafik: Nonpassivating Metal (Pasflegmeyen Metal) wa Seas iets reyes Be yi ht cy ieee eo ee een Cd Cr ite oO eee wi u cD Fe eee ake ae) re a _ eee ee er en (past fm re ee eee a ee ee ee eee CRS ent te teeta 0 taster Sesiseice Oe fe eee ee ee eee ee 0 Cry aS Pay cece This passage explains concentration cells, which are electrochemical cells formed due to differences in eee ee ee cee a ce See ee ee ete eed creates turbulent flow, increasing ion diffusion. This leads to corrosion on the outer edge, where ion concentration is lower. Copper and its alloys are expecially prone to forming such cells ‘+ Incontrast, a rotating iron disk in aerated seawater forms an oxygen concentration cell. Turbulent flow ‘enhances oxygen diffusion at the periphery, while oxygen is less available at the center. This leads to Ce ena ee eee ees Oe eee ou eee ee ec Ror Pees In all these cases, the Nernst equation can be used to predict the corrosion potential ifthe concentrations ey Bu metin, kensantrasyon hilcreleri (concentration cells) olarak adlandinlan bir korozyon mekanizmasin! aciklamaktadir. Konsantrasyon hiicreleri, metal ydzeyindeki reaktant konsantrasyonlarinin farklilik Pere ei ee Lee ee ee ca uo i Daur Peto rate Le eke Omegin, dénen bir balar diskte, disk cevresindeh ea eee Ty COR OD tun ac ee aR eee ao ea Tey Cr RCO ee Wee Cae ea ca a ST aun Se eo ae ae Sea ae Bir diger Grnekte ise, dénen bir demir disk havalandinimis deniz suyuna konuldugunda, korozyonun bu sefer diskin merkezinde meydana geldigi gézlemlenir. Bunun nederi, oksijen konsantrasyonu hiicresi Oe Ae Reece Oe eno Rake cum ie PRE ee eS a ee Pee teas eee ‘Aynica bu hiicreler yanklar (crevice) gibi dar bélgelerde de olugabilir. Metal iyonu hiicresinde korozyon yangin disinda gerceklesirken, oksijen hiicresinde yarigin icinde olur. Tam bu durumlarda, Nernst denklemi, konsantrasyon farklannin olusturdugu potansiyel farklarint hacanlamak icin fullanulahilir best of Alloying the unout of oxidizing ager in soon an havea ret eet the a meal (Choosing pope lloying metas fora given meal an have a similar eet. Not only cn aly reduce the cit federal oak the ntl go “psive” bit alao ede the omosion tof the metal while itis in he passive sae, A go example would he ang 18% homium oon. This produces wha ere ere sails tee, The cosion sare 1 33 ge 7 se | . 5S . 3s 221 ae 1Cr- Fe 28 * 7 J 1 tao CORROSION RATE OPY) 0 coos eo Corson Bases (194) ‘teu be son tha the stainless ta aces pasty ta mc ower eosion pote and its coronas peste mihIOwe SE rae {plot fara given meal which expreses its pense vrs pH, is tees. Pours gra, These include + Proistingifcorosion wil Finding wat the comosion pods nay be. ng wate exviomsental change ty hve on oreo. ving isa Pouraix diagram fron mm Some interesting informauon can be gleaned irom ins diagram. tne most trang ing stat 1 ieon is kept at a potential of less than 1.2 v with respect to a hydrogen half cell it should not commode in solution oF any pH, To keep the iron protected, however, and extemal voltage would be quired. This is the besis of cathodic protection, which we wil discuss later in more detail, It can also be observed that in a potential range of about 0.7 v and -0.6 v and pl below 9, the comosion product will be the ferrous ion. At more postive potentials, the ferric ion would be produced. In othe cases, ferric or ferrous hydroxide and complex iron ions may be formed BASICS OF CORROSION - BIMETALLIC CORROSION What is bimetallic corrosion? Bimetallic corrosion is the accelerated corrosion of one metal placed in contact with a ent more noble (less corroding) metal a problem’ it is usually localized and if the area of the corrodi metal itis in contact with can occur very rapidly Where does it occur typically? Around fixings such as nuts and bolts, rivets or welds but g different metals are in contact and can become wet. environment that they are exposed to. This can be looked up in a table. Ranking in sea water (top of table is most noble) a water is salty, contains about 2% NaCl Noble Platinum Gold Ca tne ed Titanium Dee eee ee ese Ee Eee eae Stainless Steel 316 (passive state) ; Brasse Se ee ee Tin ter ee orn Lead eee ee ee Stainless steel 316 (active state) es ane Carbon steel Aluminium alloys eer ee etc) Zine Ce en eas Magnesium a Pee ee ee Dee ee a Doe ee oe cu eet} SES Aqueows sotution felearolyte) MOH Cathodic reaction 20H" 320, + H:0 + 26°-+ 20H me Er Ce ee eee een ee eee ee + Atthe anode, metal atoms release electrons and become metal ions. * These metal ions combine with OH” ions produced at the cathode to form metal hydroxides, such as oy + Electrons travel through the metal; ions mave through the solution to close the circuit. De etna Se ne ee eet ad CO ee eens Pee Sera eet Cee er en ee ee Te ene ae ae cca Sen Coe oot ind Cees ee ee eee eae etd Po a ee oa ee ee res Oe eee ee eee ee) ecieed ee ee eee ee es Pee ge ad See er eee ee eee ee easly reach the surfce. eee ere eee a nog + coroson rots form dees ad continuous od yer hey Back ion ant mati, See eee es Nea Lod eer one Se ere ee ee eet er ert ee Dee oe en eC econ oy eed See ee as Peed ee eens 0 ae Terr eee eo Pe ed Ce ees en een eee ee ere ere eee cad Co Ce res Seer ere eee ee ert eet) Prevention Measures sion prevention aims at removing or reducing cleeting ¢ material that hanging the Gahibitors). 3. Using a design that will avoid corzesion metal surface can be kept dy 4. Changing counteracting the natural tend smtal to the envizonment Applying coatings onthe metal surf ee ees Ce eee merece I 1. Thickness Reduction per Unit Time (e.g.. mmvyear or mpy): a ee eee eee ears Pee eet eet! eee eens &b 2. Weight Loss per Unit Area and Time: eee ee Oe ee ee ee eer ete Reed cecesiorg pieeeete eras cere ee eee ce eS td Ree ee ee md th rn eee ee Seer) Ee eee ee ec eee ea A ire eee ee a -nviconment, ¢ removing the oxygs he potential, most often by making the metal more negative ey of the po usually in order to mak the effect of one or more ofthe eancitions ‘or adding anticorrasin chemicals collection of water o thatthe thus ive metal ions to be transferred from the a barriee between the erence ern ee ene Soren eee eee 2 eyes Seer ee eee cata) Reed + 11 Corrosion: Teen en eo ee Ge ee ae ed leading to material loss or transformation. Physical damages like melting or abrasion are excluded. OMe Pareto Re Renee ear d Corrosion involving electrode reactions — typically dissolution of met PRED ecco Always includes at least one anodic and one cathodic reaction, occurring either together on a uniform ne asec + 14 Corrosion Potential (E_corr): The potential a corroding metal naturally assumes in an electrolyte without external current. * 15 Corrosion Rate (V_corr) & Corrosion Current (I_corr): Pan aed ed et eee ES * Leorr: Corrosion current based on Faraday’s law: Dt mn acs Difference between actual electrode potential and corrosion potential. SAU eke csr Carrosion occurs evenly over the surface; rate is position-independent. Takes ttre 1.8 Non-U Corrosion varies across the surface due to structural or environmental inhomogeneity. includes: Oa ccna Senn eee BERS eRe ad Occurs in alloys when one component corrodes preferentially, altering the composition in the Rear Seo Re aR ed This section defines cortosion behavior in both active and passive states, and explains related tovms for Cus eae ry Oe ee soe Se Een + Corrosion current increases with more positive electrode potential Brkt ry Se ee eee ee Ree eet aS ee ‘+ Passive state involves limited fon transfer through the film or growth of the film. eee ee COLL ORS ca mee as OR re eS eee cee Ber) + Transition from active to passive state due to passive film formation. Saeco Oe eee een ae re + Reduced agents or oxidized species in the environment Srey curly Set enh ee ae ORC ek en aire riad + Cathodic current Dern cr Oe enn Ee Beate go Ce SRE eR Reece oe oe CaCO CS aap) Dee Cuma SC ue uu BRR es eo ‘Occurs when film thickness and corrosion current are constant over time. Oe Cee eo Cs Cea Serene ea eo Ss Oe ‘+ In passive state, corrosion current may increase or decrease with potential, depending on film Es Ge ee clectrode potential and environmental factors influence corrosion behavior ecco See a eae Ce eee eee eee eee ee a Ken eke) Beene ee ee a See ee ec eee * 3.2 Contact Corrosion (Galvanic Corrosion) Seu Ran et cee ad See Cee ca eee ae ere eee eee ee eee eens ee ee eee co eee ee roy eee eee cs De ey eee eee eto DE ry CC ee ee Ea cee eee es Cee eo Ly eed ere cas cas ce Bee ee See ees cae eee ee ete See ee + Seite eee ey eee eee ate eee eee See ee eon et ony ce ee eee Cy Cee eee Cee eee ec Te PSC Laie oe ee reac ee ee ce eae eee en eee Design Considerations (for prevention): Oca Dey Se Installation challenges Drees nod Ee Modifications or repairs Dee eed eee) ee ee es ee eee ee Dee ee ca Se es Seen te ee SS ees ee eee Ree ee eee renee Cerra Ce ee ee ee Nee ee ees

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