Corrosion of Aluminum and Aluminum Alloys IR. Davis, editor, p 1-24 DOL: 10,1361/eaa1999001 Copyright © 1999 ASM Intemational® All rights reserved, www.asmintemational.org, Chapter 1 Introduction ALUMINUM became an economic competitor in engineering applications toward the end of the 19th century. The reason aluminum was not used earlier ‘was the difficulty of extracting it from its ore. When the electrolytic reduction of aluminum oxide (Al,03) dissolved in molten cryolite was independently devel- coped by Charles Martin Hall in the United States and Paul T. Héroult in France, the aluminum industry was bom. ‘The emergence of three important industrial devel- ‘opments in the late 1800s and early 1900s would, by demanding material characteristics consistent with the ‘unique qualities of aluminum and its alloys, greatly benefit growth in the production and use of the new metal. The first of these was the introduction of the first interal-combustion-engine-powered vehicles Aluminum would play a role as an automotive mate rial of increasing engineering value. Secondly, elec- trification would require immense quantities of lightweight conductive metal for long-distance trans- mission and for construction of the towers needed to support the overhead network of cables that deliver electrical energy from sites of power generation. Within a few decades, a third important application area was made possible by the invention of the air- plane by the Wright brothers. This gave birth to an entirely new industry which grew in partnership with the aluminum industry development of structurally re- liable, song, and fracture-resistant parts for airframes, engines, and ultimately, for missile bodies, fuel cells, and satellite components. However, the aluminum industry growth was not limited to these developments. The first commercial applications of aluminum were novelty items such as mirror frames, house (address) numbers, and serving trays. Cooking utensils were also a major early market. In time, aluminum applications grew in diversity to the extent that virtually every aspect of modem life would bbe directly or indirectly affected by use. Today, alumi- ‘num is surpassed only by stee! in its use as a structural material Key Characteristics of Aluminum Aluminum offers a wide range of properties that can be engineered precisely to the demands of specific applications through the choice of alloy, temper, and fabrication process. The properties of aluminum and its alloys which give rise to their widespread usage include the following: ‘* Aluminum is light; its density is only one-third that of steel. Aluminum and aluminum alloys are available in a wide range of strength values—from highly ductile Jow-strength commercially pure aluminum to very tough high-strength alloys. with ultimate tensile strengths approaching 690 MPa (100 ksi). * Aluminum alloys have high strength-to-weight ratio. * Aluminum retains its strength at low temperatures and is often used for cryogenic applications. ‘Aluminum has high resistance to corrosion under the majority of service conditions, and no colored salts are formed to stain adjacent surfaces or dis- color products with which it comes into contact. ‘* Aluminum is an excellent conductor of heat and electricity. ‘Aluminum is highly reflective, Aluminum is nonferromagnetic, a property of im- portance in the electrical and electronics industries. ‘* Aluminum is nonpyrophoric, which is important in applications involving inflammable or explosive ‘materials handling or exposure. ‘* Aluminum is nontoxic and is routinely used in con- tainers for food and beverages.2./ Corrosion of Aluminum and Aluminum Alloys Aluminum has an attractive appearance in its natu- ral finish, which can be soft and lustrous or bright and shiny. Itcan be virtually any color or texture. ‘© Aluminumis recyclable. Aluminum has substantial scrap value and a well-established market for recy- cling, providing both economic and environmental benefits. © Aluminum is easily fabricated. Aluminum can be formed and fabricated by all common metalwork- ing and joining methods. ‘Table 1 lists the important physical properties of pure aluminum. Table 2 shows the characteristics of aluminum and their importance for different end uses. Low Density. Aluminum has a density of only 2.7 g/m}, approximately 35% that of steel (7.83 g/cm’) and 30% of copper (8.93 g/cm’) or brass (8.53 g/cm’). One cubic foot of steel weighs about 222 kg (490 Ib); a cubic foot of aluminum weighs only about 77 kg (170 1b). Table 1. Summary of the important physical properties of high-purity (29.95% Al) aluminum Proper Vane ‘Thema reutoncrsssection 0.242: 0003bamns Lanice constant (length of 4.0496 10" m 31298 K it cabe) Deni ok) 2699 xg? (hore density base on tie sacig) 2697-2699 kg/m? (Qoijeryaline materia) Dens sid 257k STK 2308 kg/m? a 1173 K 23x 10-1Ka1293K 237 Wim: Kat 298K 2655x1080: m Coefficient of expansion Themnal condectivity ‘Volume resistivity Magnetic suscepiibty 16x 10-3 stoma 298K Surface tension 868 dyneem al themelting point Viscosity 0.012 poise at themetting point Melting point 95k Boilingpoint 267K Heat of fusion 3970g Heat of vaporation 1.08 10-40/g- K Heat capacity 090g: K Strength. Commercially pure aluminum has a ten- sile strength of about 90 MPa (13 ksi). Thus its useful- ness as a structural material in this form is somewhat limited. By working the metal, as by cold rolling, its strength can be approximately doubled. Much larger increases in strength can be obtained by alloying alu- minum with small percentages of one ot more other ‘elements such as manganese, silicon, copper, magne- sium, or zinc. Like pure aluminum, the alloys are also made stronger by cold working. Some of the alloys are further strengthened and hardened by heat treatments. Figure 1 shows the range of strength levels of repre- sentative aluminum and aluminum alloys. High Strength-to-Weight Ratio. The strength- to-weight ratio of aluminum is much higher than that of many common grades of constructional steels— often double or more (Fig. 1). This property permits design and construction of strong, lightweight struc- ‘ures that are particularly advantageous for anything that ‘moves—space Vehicles and aircraft as well as all types of land- and water-borne vehicles. Corrosion Resistance. When aluminum surfaces are exposed to the atmosphere, a thin invisible oxide skin forms immediately, which protects the metal from further oxidation. This self-protecting characteristic gives aluminum its high resistance to corrosion. Un- less exposed to some substance or condition that de- stroys this protective oxide coating, the metal remains fully protected against corrosion. Aluminum is highly resistant to weathering, even in industrial atmospheres that often comode other metals. It is also corrosion resistant to many acids. Alkalis are among the few substances that attack the oxide skin and therefore are corrosive to aluminum. Although the metal can safely ‘be used in the presence of certain mild alkalis with the aid of inhibitors, in general, direct contact with alka- line substances should be avoided. The high thermal conductivity of aluminum (about 50 to 60% that of copper) came prominently into play in the very first large-scale commercial appli- cation of the metal in cooking utensils. This charac- teristic is important whenever the transfer of thermal ‘energy from one medium to another is involved, either heating or cooling. Thus aluminum heat exchangers are Table 2 Property combinations important for the use of aluminum in various application areas ‘Charsteries Gand et Decoratieaspecs— Catags snddedrial — Resstane —(wihorvithoat or ‘Typeatenitbricned products Wie Formed Impact Extruded and Bild otue Lighines,__conduehity cordon _surfcetretmen) forgings sheet extrusions sections cable Foil ‘Transpon 1 2 2 2 2 o 2 Building 2 2 1 2 . 2 Packaging 3 3 1 1 2 2 Brectical 3 1 2 or 2 2 2 Household 2 1 1 2 2 . 2 Machines, ' 2 2 2 2 2 ‘appliances Gemicalsandfood 2 2 1 2 3 2 a 2 2commonly used in the food, chemical, petroleum, air- craft, and other industries. High Electrical Conductivity. Aluminum is one of the two common metals having an electrical con- ductivity high enough for use as an electric conductor. ‘The conductivity of electric conductor grade (1350) is about 62% that of the International Annealed Copper Standard (IACS). Because aluminum has less than ‘one-third the specific gravity of copper, however, a pound of aluminum will go about twice as far as a ‘pound of copper when used for this purpose. Reflectivity. Smooth aluminum is highly reflective of the electromagnetic spectrum, from radio waves through visible light and on into the infrared and ther- ‘mal range. It bounces away about 80% of the visible light and 90% of the radiant heat striking its surface. Introduction / 3 The high reflectivity gives aluminum a decorative ap- pearance; it also makes aluminum a very effective bar- rier against thermal radiation, suitable for such appli cations as automotive heat shields. Nontoxic Characteristics, The fact that alumi- sum is nontoxic was discovered in the early days of the industry. It is this characteristic that permits the ‘metal to be used in cooking utensils without any harm- ful effect on the body. Today a great deal of aluminum equipment is used in the food processing industry. Nontoxicity permits aluminum foil wrapping to be used safely in direct contact with food products. Finishability. For the majority of applications, alurni- ‘num needs no protective coating. Mechanical finishes such as polishing, sand blasting, or wire brushing meet the majority of needs. In many instances, the surface 2800 wou 2000 F | wisi aa40 svete § col snereceamer z é rowan : i 5 : 2 4 AISI @ & too} [toss saa ! anos _ zo7818 soo} | asm [Saute p28 aoe | ™ soars 7 NKOTAHDE fats Las — [ socawie Ease gece: F2neo. — AZ8180 isos 7 Bs ted, Ttanin Admini Magnesium -7agem® “ays, aloys, ato, © “ABgem® -2 78 gen? Laden? so é anevecraost, a 300M 10V.2FeaAt 2 sia L earay rors-7ep HKDIASON 5B “AIS! 8649 i oe 5 sours L zor & asimans| gades [SITS . a8 asia Soe Lites game 8 Sts Ttanum ——Auninum — Magnesum » aloe ‘ays hye Fig. 1 Comparison faluminum alloys wih compaingsrueiral alloys on silo strongth in ks the basis off) io laren ond pec na sirengh en ied a by densty, in g/em4 / Corrosion of Aluminum and Aluminum Alloys finish supplied is entirely adequate without further fin- ishing. Where the plain aluminum surface does not suffice or where additional protection is required, any of a wide variety of surface finishes may be applied. Chemical, electrochemical, and paint finishes are all used. Many colors are available in both chemical and ‘electrochemical finishes. If paint, lacquer, or enamel is used, any color possible with these finishes can be applied. Vitreous enamels have been developed for aluminum, and the metal can also be electroplated. Ease of Fabrication. The ease with which alumi- ‘num can be fabricated into any form is one of its most important assets. Often it can compete successfully with cheaper materials having a lower degree of work- ability. The metal can be cast by any method known to foundrymen. It can be rolled to any desired thickness ‘down to foil thinner than paper; aluminum sheet can be stamped, drawn, spun or roll-formed. The metal also can be hammered or forged. Aluminum wire, drawn from rolled rod, may be stranded into cable or any desired size and type. There is almost no limit to the different profiles (shapes) in which the metal can be extruded. ‘The ease and speed with which aluminum can be machined is one of the important factors contributing to the low cost of finished aluminum parts. The metal can be tured, milled, bored, or machined in other manners at the maximum speeds of which most ma- chines are capable. Another advantage of its flexible ‘machining characteristics is that aluminum rod and bar ‘can readily be employed in the high-speed manufac- ture of parts by automatic screw machines. Almost any method of joining is applicable to alu- minum: riveting, welding, brazing, or soldering. A ‘wide variety of mechanical aluminum fasteners simpli- fies the assembly of many products. Adhesive bonding of aluminum parts is widely employed, particularly in joining aircraft components. Table 3 lists fabrication characteristics of commonly used wrought aluminum and aluminum alloys. Property Combinations Needed for Specific End Uses. In most applications, two or more key characteristics of aluminum come prominently into play—for example, light weight combined with strength in airplanes, railroad cars, trucks, and other transportation equipment, High resistance to corro- sion and high thermal conductivity are important in equipment for the chemical and petroleum industries; these properties combine with nontoxicity for food processing equipment. ‘Attractive appearance together with high resistance to weathering and low maintenance requirements have led to extensive use in buildings of all types. High reflectivity, excellent weathering characteristics, and light weight are all important in roofing materials. Light weight contributes to low handling and shipping costs, whatever the application. Table 2 reviews the material characteristics required for different markets and applications. Additional information can also be found in the section “Applications” in this chapter. Competing Metals for Lightweight Construction. ‘The light (ow density) metals and alloys of commer- cial importance are based on aluminum, magnesium, and titanium. Each of these metals has distinet quali- ties that make them suitable or preferred for certain applications. ‘With a density of 1.8 g/cm?, magnesium alloys are ‘among the lightest known structural alloys. This is their chief advantage when compared with aluminum and titanium. However, a low yield strength and modulus of elasticity combined with poor thermal and electrical conductivity limit their range of application. Figure 1 compares the properties of magnesium and aluminum alloys. The ‘combination of low density (~4.5 g/cm), out- standing corrosion resistance, and high strength make titanium and titanium alloys popular in the aerospace, chemical processing, and medical (prostheses) indus- tries. However, its high price (due to processing diffi culties) has limited the use of titanium to niche mar- kets. Figure 1 compares the properties of titanium and aluminum alloys. The Aluminum Industry Primary Aluminum Production Occurrence. Aluminum comprises about 8% of the earth's crust, making it second only to silicon (-28%). Iron is third at about 5%. The principal ore of aluminum, bauxite, usually consists of mixtures of hy- drated aluminum oxide, either AIO(OH) or AI(OH)s. Besides these compounds, bauxite contains iron oxide (which gives it a reddish-brown color), as well as sili- cates (clay and quartz), and titanium oxide, The baux- ites used for the production of aluminum typically contain 35 to 60% total aluminum oxide. Extraction or Refining Methods. The most ‘widely used technology for producing aluminum involves two steps: extraction and purification of aluminum ox- ide (alumina) from ores (primarily bauxite although alternate raw matesials can be used), and electrolysis of, the oxide after it has been dissolved in fused cryolit. ‘The Bayer process is almost universally employed for the purification of bauxite. In this process, which ‘was developed by Austrian Karl Joseph Bayer in 1892, the crushed and ground bauxite is digested with caus- tic soda solution, at elevated temperature and under Pressure, and the alumina is dissolved out as a solution of sodium aluminate. ‘The residue, known as “red mud,” contains the oxides of iron, silicon, and titanium and is separated by settling and filtration. Aluminum hydrate is separated from the solution of sodium alu- minate by seeding and precipitation and is converted to the oxide, AlzOs, by calcination. Present practice for aluminum electrolysis involves the use of the Hall-Héroult cell as pictured in Fig. 2 ‘The cell is fined with carbon, which acts as the cath- code; steel bars are embedded in the cathode lining to provide a path for current flow. The anodes are also ofIntroduction / 5 Table 3 Comparative fabrication characteristics of wrought aluminum olloys Weldahiiy) ald Redaance ley Temper workaiiya) _Machiabiley(a) Gay __Are_spot and eam _Braseabiliy(b) _Solderabii(c) 109 0 A E en B A A HR A EB ee A a a Ha a D AL a A a HIG B D AA A a N Hie B D AOR A A A 100 =O A E AA B A A Hi A E AOA A A nN Ha A D AA A A N HG B D AA A nN A Hig B D ers A A a 0 0 A EB as B a A roy a E AOA A a a Ha A D AA A nN nN Hi6 B D A 8 A a A HI © D Aw A a A 4s 0 A E Aw B A a HR A E AOA A A a Ha A D ia a A a Hi6 B D A a A i Hie B D mA a nN i 190 A E sa B A a Hi A E AOA A A nN Hid a D AOA A ‘a a Hi6 B D AOA a A Aa nie B D AOA a ‘ A nO A E AOA B ‘ A #2, H A E AOA A A A Hid, Ht A D AOA nN nN A HIG, #25 B D AOA A A A Hi8 B D a A A A mon c A DED D D ¢ 14,1451 B A DD D D ¢ 8 D A DEED D D ¢ m4 0 D DD B D © 73,74, 7451 c B Do oB B D € 16, 1651, 16510, 76511 D B DoB B D € a) D DD D D c 14,73, 7355,T3510,T3511 C B c oB B D c 1361 D B Dec B D c 16 c B DEC B D c 861, T8i,7851, 78510, D B DE ic B D c T8541 ™ B m6 OT B © B B D 2iM TES D B Dc B D € mis To c c ™m a B D c mo 0 : Deer B D ‘T3i,7351,73510, T3511 € B BK A D NA co D B AA a D Tei, T851, T8510, T8511 D B AA nN D 187 D B AA a D 2618 Tot a doc B D NA 308 in E a B ia a Ha A gE AA A A A Ha B D AA A‘ A N His c D ms a A A His © D nA a a a #25 B D AOA a A A (contimes) (a) Ratings A tbxough D for cold workability and A through Efor macinability are reativeratngsin dereasing order of merit (b) Ratings A trough D for weldabilcy and brazeabilty ae relative ratings definedas follows: A, generally weldabe by aicommercial procedures and mesbods; B, weld- sie with special techniques or for specific applications and requiring preliminary tral o testing to deveiop welding procedawe and weld peror- ‘mance; C limited weldabilitybocause of crack sensitivity or os in resistance tocorosionand mechanical popenies;D, nocommonly used welding methods have beendeveioped.(e) Ratings A trough DandNA forsolderability are eitiveratings defined as follows: A, excelent; B, good: ar poor, NA, no applicable6/ Corrosion of Aluminum and Aluminum Alloys Table 3 (continued) Solderabiity sasaanamsemS Sane saeogeas Siz adeqcanccecugece ‘Are _spotendseam _ Brazeabiiy() Weis <4eeeeeececagec< aaeagc<< erkaiiya) Mackinabiley() Gas aavvummananaumee 2r -133 among structural metals, only beryllium and magne- 714,*27 9 Bee sium are more reactive. As mentioned, aluminumowes firs + 4-5 ta its excellent corrosion resistance and its usage as one Us te U ar of the primary metals of commerce to the barrier oxide Be™*+ 2e-—> Be mas film that is bonded strongly to its surface. The normal M8 + 2 > Mg oy surface film formed in air at ambient temperature is G..5 NGy Baa only about 5 nm (50 A) thick (much thicker films can K+4,--9K 93 be produced at higher temperatures, in water near its Lit se Li ~305 boiling point, or in steam). If damaged (for example, a freshly abraded surface), this thin film re-forms SHE, standardhydrogen clectrode26 / Corrosion of Aluminum and Aluminum Alloys removed or damaged under conditions such that self repair cannot occur, corrosion takes place. ‘As shown in Fig. 1, the oxide film that develops in normal atmospheres is composed of two layers (Ref 1). The inner oxide layer next to the metal is a compact amorphous barrier layer of a thickness determined solely by the temperature of the environment. At any given temperature, the limiting barier thickness is the same in oxygen, dry air, or moist air. Covering the barrier layer is thicker, more permeable outer layer of hydrated oxide, Most of the interpretation of aluminum corrosion processes has been developed in terms of the chemical properties of these oxide layers. ‘At lower temperatures, the predominant form pro- duced by corrosion is bayerite, aluminum trihydroxide Poresin the oxide ayer ‘Auuminum 98.99% Schematic of the passive oxide film thot forms on aluminum AIH), whereas at higher temperatures, it is bochmite, AIO(OH). During the complex course of the aging of aluminum hydroxide, which is first formed during corrosion in an amorphous form, still another aluminum tihydroxide, gibbsite or hydrargilite, can also be formed, especially if ions of the alkali metals are resent. Beginning at a temperature of about 230 °C (445 °F), a protective film no longer develops in water fr steam, and the reaction progresses rapidly until eventually all the aluminum exposed in these media is converted into oxide. ‘The natural film can be visualized as the result of a dynamic equilibrium between opposing forces—those, tending to form the compact barrier layer and those tending to break it down. If the destructive forces are absent, as in dry air, the natural film will consist only of the barrier layer and will form rapidly to the limiting thickness. If the destructive forces are too strong, the oxide will be hydrated faster than it is formed, and little barrier will remain, Between these extremes, ‘where the opposing forces reach a reasonable balance, relatively thick (20 to 200 nm, or 200 to 2000 A) natural films are formed (Ref 2). ‘The conditions for thermodynamic stability of the oxide film are expressed by the Pourbaix (potential versus pH) diagram shown in Fig. 2. As shown by this diagram, aluminum is passive (is protected by its oxide film) in the pH range of about 4 to 8.5. The limits of this range, however, vary somewhat with temperature, with the specific form of oxide film present, and with 12 08 Corrosion Passivation Corrosion Potential (E), V (SHE) I Fig. 2 ee ee Pourbaix diagram for aluminum showing the conditions ofeorrosion, im- ‘munity, ond passivation of cluminum ot 25 °C (77°F), ossuming protec tion by fn of bayerite, AljOy3H,O. Source: Ref3Understanding the Corrosion Behavior of Aluminum / 27 the presence of substances that can form soluble com- plexes or insoluble salts with aluminum. The relative inertness in the passive range is further illustrated in Fig. 3, which gives results of weight loss measure- ments for alloy 3004-14 specimens exposed in water and in salt solutions at various pH values. Beyond the limits of its passive range, aluminum orrodes in aqueous solutions because its oxides are soluble in many acids and bases, yielding AI* ions in acids and A1O> (aluminate) ions in bases. There are, however, instances when corrosion does not occur out- side the passive range, for example, when the oxide film is insoluble or when the film is maintained by the oxidizing nature of the solution (Ref 4). Additional information on the effect of pH on corrosion behavior of aluminum can be found in the section “Environ- ‘mental Variables” in this chapter. Causes and Forms of Corrosion In most environments, the corrosion of aluminum (ike that of other common structural metals) is associ ated with the flow of electric current between anodic and cathodic regions. Electrochemical corrosion pro- duced depends on the potentials of these regions. Solution Potentials Because of the electrochemical nature of most cor- rosion processes, relationships among solution poten- tials of different alurninum alloys, as well as between potentials of aluminum alloys and those of other met- als, are of considerable importance. Furthermore, the solution-potential (or corrosion-potential) relation- ships among the microstructural constituents of a par- ticular alloy significantly affect its corrosion behavior. ‘Compositions of solid solutions and additional phases, as well as amounts and spatial distributions of the additional phases, can affect both the type and extent of corrosion. ‘The solution potential (Ego) of an aluminum alloy is primarily determined by the composition of the aluminum-rich solid solution, which constitutes the predominant volume fraction and area fraction of the alloy microstructure (Ref 5). Solution potential is not affected significantly be second-phase particles of mi- ‘croscopic size. Because these particles frequently have solution potentials differing from that of the solid- solution matrix in which they occur, localized galvanic cells can be formed between second-phase particles and the matrix. ‘The effects of principal alloying elements on solu- tion potential of high-purity aluminum are shown in Fig. 4. For each element, the significant changes that occur do so within the range in which the element is completely in solid solution. Further addition of the same element, which forms a second phase, causes little additional change in solution potential. Most commercial aluminum alloys contain addi- tions of more than one of the principal alloying ele- ‘ments, Effects of multiple elements in solid solution on solution potential are approximately additive. The amounts retained in solid solution, particularly for more highly alloyed compositions, depend highly on fabrication and thermal processing so that heat treat- ‘ment and other processing variables influence the final electrode potential of the product. Tables 210-4 present representative solution potentials of commercial alu- minum alloys. The corrosion potential values in these tables were measured against a 0.1 N calomel elec- trode in a solution containing 53 g/L of sodium chio- ride (NaCl) and 3 g/L of hydrogen peroxide (H,0,). 0.08 0.05 | 0.04 Weight loss, 9 0.02 0.01 7 8 98 0 Mt pH Fig, 3 Woighlos ofalay 2004414 oxpoed 1 wook ndiallod wales ond in solsion of var: ous pH values. 5 10s of solutions ware odju imons wore 1.6 x 13 75 mm (0.06 > 0.5 x 3.0 in]. The pH val- wilh HCl ond NaOH. Tes lemperolure was 60 °C (140 F)28 / Corrosion of Aluminum and Aluminum Alloys Measurements of the solution potentials of aluminum alloys have been standardized in ASTM G 69 (Ref 6). ‘The experimental procedure described in this standard uses an oxygenated saltwater test solution that has 58.5 g of NaCl and 9 mL of 30% HzO, added per liter of Aistlled oF deionized water. Table 5 provides a listing of solution potentials of aluminum alloys and of sev- eral other metals and alloys determined using ASTM G 69 test procedures. ‘The amounts of second phases present in aluminum and aluminum alloys products vary from nearly zero in products of aluminum 1199 and some others that also are nearly pure solid solutions. Second-phase amounts in other such products total more than 20% in hypereu- tectic aluminumrsilicon casting alloys, such as 392.0 and 393.0. These phases are generally intermetallic ‘compounds of binary, ternary, or higher-order compo- sitions, although some elements in excess oftheir solid solubility are present as elemental phases. Electrode po- tentials of some of the simpler second-phase consttu- ents have been measured and are shown in Table 6. ‘Solution-potential measurements are useful for the investigation of heat-treating, quenching, and aging Practices, and they are applied principally to alloys containing copper, magnesium, or zinc. In aluminum- copper and alumninum-copper-magnesium (2x«) alloys, Table 2 Solution potentials of non-heat- treatable commercial wrought aluminum alloys Bey 1060 084 100 0.83 3008 “0.83 3008 “084 3030 “084 50s “085 sist 0.86 554 -0.%6 5036 “08 5856 087 sia 0.87 soa om 5086 “08s on 096 "Nove: Values are the same fo all empers of cach alloy.) Potential versus stndand calome' eiecttode measured in an aqueaus sojation of 53 gL NaCiplus3 g/L HO 125 °C 077 4 Ey Eu) Mote cathodic —e- 5 0.78 082 Si 086 Potential, (0.1 Nealome! scale) Zn 102 Sold solution In excess of sola gouton 1.08 1.10 = More anodic o 1 2 @ ‘Added element, wt% mainlained ol 25°C (77 *F) 4 5 6 7 8B oni of lution ‘ect g/t HO;Understanding the Corrosion Behavior of Aluminum / 29 Table 3 Solution potentials of heat-treatable Table 5 Solution potentials of aluminum alloys commercial wrought aluminum alloys and motals based on ASTM G 69 ay Tee Poca V of Tame Ghee Matratos Far Vt ois 1 200) 6 0.78 Cr(9.9%) 2B +032 nw 3 Do0) 11270 sample wn % Dei) Staines tet 316 O70 won 16 ~080 (C0 (99,999%) 0.11 40.00 -+0.08 w “a2 Brows Ca94-506) 008 om mom B “D650 Tals ous +2 ™ “a690) Brass CuS3-2037 030 “a0 ws ost 5109998) 040 8 Te 082 Zr 9.9%) 0.20 0M 0% 14 0.72 ‘Mn 0.80 040 2180 Tees 083 MoeisooniescusR2 “08 “0% ‘oop 7 80 Staines te 321 43 0% “0 10 % “178 Fe ow 08 si 1 “083 arte 05 035 “054 si ts “083 INTL wTEIDAT,.TE 0 0D 09 oss ts “oa 2-7 08 16 “a8 D367. T4 oH 08 ss 1s “08 2036.16 2090-7, 16 “065 1 “083 097%) 06% «ois 7005 1s “O54 mor Ts 076 “61 “06s x7016 %% “86 201476 208-74 0@ xr02i % “099 5090-73 10-74 0:70 xn 1s “oss » on as x76 1% “102 2008-16 oi on “070 708 7 “aKe) nt6T an on on Te “aK amare on “on 1050 m3 ase) st-t4, ca05-t4 on 6 086) 3.76.78 a4 on 7015 Ts 1830) rs T6.717676 0% 0M 0 7 03K) 3003, 110, 616,033,603 on Te “aste) 3074, 250778 on 775 Ts “aa 139598) 4% om 07 7 ase) Tos-7, 509077, 07-075 OB Ts “aK 00.47, 7475-77 18 Ts “one ps7 075 on 30, 1061, 5080 “05 ()Pocaial vemussuniadcsloneicewotemesielinanamens 52, 5086 Alea 224, 0% souonf53 JU NaC pus 3g a0991 25°C 07) vars AKad 2014 3001 ¥wihqtencingrae (0 Varies 20.02 Vwidpenchingrte SISK, SES, 5254 5082 on -—-OTTrv—oo——veeit 556,707.16, st, 5182 on 7039-76, 7e, 7008 08 70, alla 300%, Alclad 61, on Table 4 Solution potentials of cast aluminum Alclad 7075 alloys 03 094 a eae -io “a9 Tear Tete Pac. ae man : 7 jos fr aanum iy inode wee calcite oo e aa tein Ret oy ang #92 mV. Source Ree Ts “on Ta “on 260 Ts on an 7 th Table 6 Solution potentials of some second- F 46 phase constituents in aluminum alloys 3550 1% “078 Fine Paslo, 1% on 3560 % sn s 028 30 F 08 AGN 0% F “an gee 036 siso E “os sca 07 s200 t “089 Aiea 08s 700 F 099 AiaMg “100 AlyMas 124 (2) S, sand; P, permuneat. (o) Potential versus standard calomel electrode measured in an aqueous soiution of 53 g/L NaCl plus 3 g/L. (4) Pten 1020125 °C (71°F) sition 3 verzus standard calomel electrode measured inanaqueous 53 yLNaCl plus 3 g/LH,0, a1 25°C 17°F)30 / Corrosion of Aluminum and Aluminum Alloys potential measurements can determine the effective- ness of solution heat treatment by measuring the amount of copper in solid solution. Also, by measuring the potentials of grain boundaries and grain bodies sepa- rately, the difference in potential responsible for inter- ‘granular corrosion, exfoliation, and stress-corrosion cracking (SCC) can be quantified. Solution-potential ‘measurements of alloys containing copper also show the progress of artificial aging as increased amounts of precipitates are formed and the matrix is depleted of copper. Potential measurements are valuable with zinc- containing (7xxx) alloys for evaluating the effective- a : = & = 7 3 i — Anodic raaction More \Scaoinae ere 0+ Cathodic reaction 4 we 0? FOO Current density, Amm2 ‘Anodic poerization curve for aluminum olloy Fig. 5 tico" Secinon wore ioe fh aul doaeraied NaCl soliton ee of eathodlc reactant. Piling dovolops only al potentials mere cathodic than ihe piling polonilE,. The inersocion of he anedie curve fr alum: ‘num (soli ine) wih @ curve forthe applicable cathodic re- ‘ction foe ofthe represeniative dashed lines) dermis the potential o which he aluminum is polarized, ether by calhodie rection onthe aluminum isalfor on ancthor metal ‘lactcaly connected [The poteial fe which he olumi- rum is polarized by a specific cathode reaction delrmines corrosion eurrnt densly and corresion roe. -03 i | 2 — "© Kaesche © Béhni and Uhlig Potential, V (SHE) Cr eT) (Cr activity Fig. 6 Ellecotchlordoon cctivtyon pling poten {igl of oluminum 1199 in NeCl solutions. Source: Ref }Oand 11 ness of the solution heat treatment, for following the aging process, and for differentiating the various artfi- cially aged tempers. These factors can affect the corro- sion behavior. In the magnesium-containing (Siccx) al- Joys, potential measurements can detect low-temperature precipitation and are useful in qualitatively evaluating siress-corrosion behavior. Potential measurements can also be used to follow the diffusion of zinc or copper in alclad products, thus determining whether the sacrifi- cial cladding can continue to protect the core alloy. Ref 9). Pitting Corrosion Corrosion of aluminum in the passive range is local- ized and is usually manifested by random formation of pits. The pitting-potential principle establishes the Conditions under which metals in the passive state are subject to corrosion by pitting (Ref 10-12). Simply stated, pitting potential (E>) is that potential in a par- ticular solution above which pits will initiate and be- Jow which they will not. Four laboratory procedures have been developed to measure E,. One is based on fixed current, and the other three are based on controlled potential (Ref 13). ‘The most widely used is controlled potential, in which the potential of a specimen, usually immersed in a deacrated electrolyte of interes, is made more positive. ‘The resulting current density from the specimen is measured. The potential at which the current density increases sharply and remains high is called the oxide breakdown potential (E,,). With polished specimens in many electrolytes, Ey is a close approximation of Ep, and the two are used interchangeably. ‘An example is shown in Fig. 5. A specimen of aluminum alloy 1100 was immersed in neutral deaer- ated sodium chloride (NaCI) solution, and the relation- ship between anode potential and current density was plotted (Golid line, Fig. 5) At potentials more active than E,, where the oxide layer can maintain its integ- rity, anodic polarization is easy, and corrosion is slow and uniform. Above £,, anodic polarization is diffi cult, and the current density sharply increases. The oxide ruptures at random weak points in the barrier layer and cannot repair itself, and localized corrosion develops at these points. Potential-current relationships for various cathodic reactions are indicated by the dashed lines in Fig. 5. Only when the cathodic reaction is sufficient to polar- ize the metal to its piting potential will significant current flow and pitting corrosion start. For aluminum, pitting corrosion is most commonly produced by halide ions, of which chloride (CI*) is the ‘most frequently encountered in service. The effect of chloride ion concentration on the pitting potential of aluminum 1199 (99.99+% Al) is shown in Fig. 6. Pit- ting of aluminum in halide solutions open to the air occurs because, in the presence of oxygen, the metal is readily polarized to its pitting potential. In the absence of dissolved oxygen or other cathodic reactant, alumi- ‘num will not corrode by pitting because itis not polar-Understanding the Corrosion Behavior of Aluminum / 31 ized to its pitting potential Generally, aluminum does not develop pitting in aerated solutions of most non- halide salts because its pitting potential in these solu- tions in considerably more noble (cathodic) than in halide solutions, and it is not polarized to these poten- tials in normal service (Ref 12) Pitting potentials for selected aluminum alloys in several electrolytes are reported in Ref. 13. Examples of application of pitting-potential analysis to particular corrosion problems are given in Ref 14 and 15, Galvanic Relations ‘Table 7 is a galvanic series of aluminum alloys and other metals representative of their electrochemical be- havior in seawater and in most natural waters and atmospheres. As is evident in Table 7, aluminum and its alloys become the anodes in galvanic cells with ‘most metals, and aluminum corrodes sacrificially to protect other metals. Only magnesium and zinc (in- ‘cluding galvanized steel) are more anodic and corrode to protect aluminum. Because they have nearly the same electrode potential, neither aluminum nor cad- mium corrodes sacrificially in a galvanic cell, The degree to which aluminum corrodes when cou- pled to a more cathodic metal depends on the degree to which it is polarized in the galvanic cell. It is espe- cially important to avoid contact with a more cathodic metal where aluminum is polarized to its pitting poten- tial because, as shown in Fig. 5, a small increase in potential produces a large increase in corrosion cur- Tent. In particular, contact with copper and its alloys should be avoided because of the low degree of polari- zation of these metals. In atmospheric and other mild environments, aluminum can be used in contact with chromium and stainless steel with only slight accelera- tion of corrosion. In these environments, the two met- als polarized highly so that the additional corrosion Current impressed onto aluminum with them in a gal- vanic cell is small To minimize corrosion of aluminum in contact with ‘other metals, the ratio of the exposed area of aluminum to that of the more cathodic metal should be kept as high as possible, Such a ratio reduces the current den- sity on the aluminum, Paints and other coatings for this purpose can be applied to both the aluminum and the cathodic metal, of to the cathodic metal alone. Paints and coatings should never be applied to only the alu- minum because of the difficulty in applying and main- taining them free of defects. Galvanic corrosion of aluminum by more cathodic metals in solutions of nonhalide salts is usually less than in solutions of halide ones because the aluminum is less likely to be polarized to its pitting potential. In any solution, galvanic corrosion is reduced by removal of the cathodic reactant. Thus, the corrosion rate of aluminum coupled to copper in seawater is reduced greatly when the seawater is deaerated. In closed mul- timetallic systems, the rate, even though it might be high initially, decreases to a low value whenever the cathodic reactant is depleted. Galvanic corrosion is also low where the electrical resistivity is low, as in high-purity water. ‘Some semiconductors, such as graphite and magnet- ite, are cathodic to aluminum, and in contact with them, aluminum corrodes sacrificially. The problems associated with galvanic corrosion of aluminum- graphite composites are described in Chapter 10. Forms of Corrosion ‘When corrosion of aluminum and aluminum alloys ‘occurs, itis usually of a localized nature and is most commonly caused by pitting or at points of contact with dissimilar metals in a conductive environment Table 7 Galvanic serios of metals exposed to seawater ‘Active end (anodic or least noble) Magnesium Magnesiumalloys Zine Galvanized steel ‘Ajuminum 1100 ‘Aluminum 6053. AAklad Cadmium Aluminum 2024 (4.5 Cu, [.SMg, 0.6 Mn) Mild steel ‘Weoughtiton Castiron 135 chromium stainless steel 1ype410 (active) 18-8 stuniessstoel type 304 (ative) 18-12-3 stainless steel type 316 (ative) Lead solders Lead Mantz meta Manganese brenze Navalbrass Nickel active) IGN-16Cr-TFe ally (active) @ONi-30Mo-6Fe-IMn Yellow brass Admiralty brass ‘Aluminum bass Red brass Copper Siliconbronze 70:30 Cupro Nickel G-broawe Mebronze Silver solder ickel (passive) 16Cr-7Feallay (passive) 33Cualloy (Mone) 136 chromium stainless steel type 410 (passive) ‘Titanium 18-8 stainless ste type 410 (passive) 18-12-3staines tel type 316 (passive) Silver Gnphite Gola Platinum Passiveend (cathodic or most noble)