1

TECHNICAL DATA GENERAL

Corrosion Definitions:

Anode - An electrode at which oxidation of the surface or some component of the solution is occurring. Practically, this is the electrode at which corrosion occurs. Ampere - The practical unit of electrical current equal to that produced by one volt applied across a resistance of one ohm. Ampere-hour - The unit quantity of electricity equal to that produced by one ampere of current in a one hour period. Cathode - An electrode at which reduction is occuring. Practically, this is the electrode at which protection occurs in a cathodic protection system. Corrosion - The deterioration of material, usually metal, from a reaction with its environment. Current Density - The applied electrical current per unit area. Electrolyte - The common environment with which both a cathode and anode are in contact. Practically, this is the soil or water to which a metal structure is exposed. Galvanic Anode - A metal that provides cathodic protection when connected to other metals, as a result of its relative position in the Galvanic eries. Galvanic Series - A listing of metals in order of reactivity when exposed to an electrolyte. Impressed Current Cathodic Protection - A cathodic protection system derived from the application of external electrical energy from sources such as common electrical power, thermoelectric generators, and solar panels. Ohm - The practical unit of electrical resistance equal to the resistance of a circuit in which a potential difference of one volt produces a current of one ampere. Sacrificial Cathodic Protection - A cathodic protection system derived from the internal electrical energy developed by coupling to more reactive metals such as aluminum, magnesium, and !inc. Volt - The practical unit of electrical potential difference required to produce a current flow of one ampere across a resistance of one ohm.

Introduction to Corrosion

Introduction
"orrosion is usually defined as the deterioration of a metal or its properties caused by a reaction with its environment. #ost metals occur naturally in the form of oxides and are usually chemically stable. $hen exposed to oxygen and other oxidi!ing agents, the refined metal will try to revert to its natural oxide state. %n the case of iron, the oxides will be in the form of ferrous or ferric oxide, commonly &nown as rust. #etallic corrosion generally involves the loss of metal at a particular location on an exposed surface. "orrosion occurs in various forms ranging from a generali!ed attac& over the entire surface to a severe concentrated attac&. %n most cases, it is impossible or economically impractical to completely arrest the corrosion process' however, it is usually possible to control the process to acceptable levels. The (. . government funded a detailed study of the annual cost of corrosion in )*+,. The total cost of metallic corrosion to the (. . economy was estimated at -. of the G/P 01+2 billion dollars3. 4f that, approximately 52. was defined as avoidable. Ad6ustment based on today7s current economy puts total current costs in the 1522 billion range with over 1)22 billion of that avoidable.

Corrosion Process 3

#etallic corrosion is caused by the flow of direct current from one part of the metal surface to another. This flow of direct current causes the loss of metal at the point where current discharges into the environment 0oxidation or anodic reaction3. Protection occurs at the point where current returns to the metal surface 0reduction or cathodic reaction. The rate of corrosion is proportional to the magnitude of the corrosion current. 4ne ampere of direct current removes approximately twenty pounds of steel in one year. $here corrosion occurs and to what extent depends upon the environment to which the metal is exposed.

8our conditions must be met for corrosion to occur. 9limination of any of the four conditions will halt the corrosion reaction. Anode - the oxidation reaction occurs here. "urrent discharge into the environment and metal loss are associated with this reaction. Cathode - the reduction reaction occurs here. "urrent acceptance and metal protection are associated with this reaction. Electrolyte - the environment to which both the cathode and the anode are exposed. The electrolyte must have the capacity to conduct electrical current through the flow of ions. Metallic path - the anode and the cathode must be connected via a metallic connection that conducts electrical current flow through the flow of electrons.

Causes of Corrosion "orrosion is a natural process. The primary driving force of corrosion is based upon the transformation of iron from its natural state to steel. The refining of iron ore into steel requires the 4

addition of energy. teel is essentially an unstable state of iron and corrosion is the process of iron returning to its natural state. The energy used in the refining process is the driving force of corrosion. "orrosion cells are established on underground pipelines for a variety of causes. A primary cause of corrosion is due to an effect &nown as galvanic corrosion. All metals have different natural electrical potentials. $here two metals with different potentials are connected to each other in a common environment, current will flow causing corrosion to occur. The coupling of steel to a different metal, such as copper, will cause a corrosion circuit to be established. :irect coupling of copper to steel will cause the steel to corrode much faster than normal. Another form of this is the coupling of rusty pipe to new, clean steel. The natural difference in potential causes the new steel to corrode more rapidly than the old steel. 4ther causes of pipeline corrosion cells include the effect of different soil types, oxygen availability, stray current interference and microbiological growth.

Two other unique causes 0and sometimes related3 are stress and hydrogen. Stress Corrosion occurs when even a very small pit forms in a metal under stress. The concentrated stress either deepens and extends the pit, or crac&s the protective film which tends to form. (nder continued exposure to the corrosive medium and stress, the crac& extends by alternate corrosion and stress failure. ydro!en Em"rittlement and hydrogen attac& results when atomic hydrogen penetrates into the grain boundaries of steel producing microcrac&s, blistering and loss of ductility. The atomic hydrogen combines into molecules and results in blistering and laminations.

#orms of Corrosion "orrosion exhibits itself in a number of ways. A brief description of some of these is provided below. 5

General Corrosion is the most common form of corrosion. %t exhibits itself in an overall attac& of the metal surface with no apparent concentrations. An example is the effect of atmospheric corrosion. Pittin! Corrosion results in a locali!ed, concentrated attac& and has the appearance of holes or craters. Crevice Corrosion occurs in shielded areas where stagnant corrosive electrolyte accumulates. This type of corrosion occurs under bolt heads, gas&et surfaces, and overlapping metal connections. Erosion-Corrosion is a combination of electrochemical and mechanical damage that occurs in environments of high fluid velocities or mechanical movement between two metals. Selective $eachin! results in one constituent of an alloy being selectively removed, leaving a porous replica of the original alloy. An example is the de!incification of brass or bron!e and the graphiti!ation of cast iron where iron is removed selectively, leaving a replica composed of carbon or graphite.

Control of Corrosion The five general methods used in the control of corrosion are coating, cathodic protection, material selection, environmental modification, and design practices. "ontrol of underground corrosion is 6

primarily achieved by two methods; coating and cathodic protection. An effective external coating can provide corrosion protection to over **. of the exposed pipe surface. The protective coating is usually applied to the pipe or tan& before burial. The coating serves to electrically insulate the metal from the soil. %f the metal could be completely isolated, then the establishment of corrosion cells would be prevented and no corrosion current would flow. <owever, no coating can be considered a perfect coating. :amage to the coating as a result of handling, transportation, installation, thermal stresses, and soil stresses will eventually create defects or =holidays= that expose the underlying steel to the environment. "athodic protection is an electrochemical technique for preventing corrosion of a metal exposed to an electrolyte. The process involves application of :" electrical current to the metal surface from an external source. >y forcing the metal surface to accept current from the environment, the underground metal becomes a cathode and protection occurs. The external source can use outside A" power through a rectifier and groundbed or by attaching sacrificial metals such as magnesium or aluminum to the structure to be protected. %t is used extensively in preventing corrosion to underground and submerged steel structures' such as pipelines, production well casings, and tan&s. 9ffective application of cathodic protection can provide complete protection to any exposed areas for the life of the structure. The combination of an external coating and cathodic protection provides the most economical and effective choice for protection of underground and submerged pipelines. 8or bare or ineffectively coated existing pipeline systems, cathodic protection often becomes the only practical alternative for corrosion protection. "athodic protection is a mandated requirement of federal and state regulations governing underground transmission pipelines, gas distribution systems, and underground fuel tan&s. These requirements include installation, monitoring, and maintenance of cathodic protection systems.

Introduction to Cathodic Protection

Introduction 7

"athodic protection is an electrochemical technique for preventing corrosion of a metal exposed to an electrolyte. The process involves application of :" electrical current to the metal surface from an external source. The external source can be either a commercial power source or through connection to sacrificial metals such as magnesium or aluminum. %t is used extensively in preventing corrosion to underground and submerged steel structures' such as pipelines, production well casings, and tan&s. 9ffective application of cathodic protection can provide complete protection to any exposed areas for the life of the structure. The combination of an external coating and cathodic protection provides the most economical and effective choice for protection of underground and submerged pipelines. 8or bare or ineffectively coated existing pipeline systems, cathodic protection often becomes the only practical alternative for corrosion protection. "athodic protection is a mandated requirement of federal and state regulations governing underground transmission pipeline, gas distribution systems, and underground petroleum tan&s. These requirements include installation, monitoring, and maintenance of cathodic protection systems.

Process of Cathodic Protection "athodic protection essentially means the reduction or elimination of corrosion on a metal surface by forcing the metal to become a cathode. The two general types of cathodic protection systems are impressed current and sacrificial. >oth types of systems can effectively transfer the corrosion reaction 0oxidation3 from the metal surface to an external anode. %f all exposed parts of a structure become cathodic with respect to the electrolyte, corrosion of the structure is eliminated.

Sacrificial Anode Cathodic Protection acrificial cathodic protection occurs when a metal is coupled to a more reactive 0anodic3 metal. This connection is referred to as a galvanic couple. %n order to effectively transfer corrosion from the metal structure, the anode material must have a large enough natural voltage difference to produce an electrical current flow. 8

9ffective application of cathodic protection can provide complete protection to any exposed areas for the life of the structure. The combination of an external coating and cathodic protection provides the most economical and effective choice for protection of underground and submerged pipelines. 8or bare or ineffectively coated existing pipeline systems, cathodic protection often becomes the only practical alternative for corrosion protection.

Three metals are commonly utili!ed for cathodic protection of steel. The selection of the anodic metal is dependent upon resistivity and electrolyte. A general application guide for these metals are; #agnesium - soil and freshwater applications ?inc - low resistivity soils and saltwater Aluminum - saltwater and limited freshwater applications An advantage of sacrificial anode systems is the flexibility in application. Anodes can be installed in a variety of applications and configurations. /o outside power is required for cathodic protection to be effective. Another advantage is the minimal maintenance required for these systems to function. :isadvantages of sacrificial anode systems include the limited protection current available and limited life. acrificial anodes are sub6ect to rapid corrosion 0consumption3 and require replacement on a regular basis. Typical design life of a pipeline system anode is five to ten years. Impressed Current Cathodic Protection %mpressed current cathodic protection involves the application of an external :" current through longlasting anodes. A typical source of power for an impressed current system is A" power converted to :" by a rectifier. %n order to be effective, impressed current anodes must be designed for long life at high current output. This requires selection of materials with very low corrosion 0consumption3 rates. The typical expectation of impressed current anode life is over twenty years. Anode materials that have proven to 9

be suitable for impressed current systems include treated graphite, high silicon cast iron, mixed metal oxide, and to a lesser extent platinum and magnetite. Anodes are normally installed in grouped configurations in the electrolyte. These groupings 0both hori!ontal and vertical3 in an underground application are called groundbeds. The groundbeds are connected to the power by a positive cable to the power source. A negative cable connects the power source to the structure.

Advantages of impressed current systems include the unlimited current opportunities and longer life. %mpressed current systems are typically installed where the structure to be protected is large, requiring higher levels of current. :isadvantages include the requirement for an outside power source and higher maintenance requirements. 4utside power might come from sources such as commercial A" converted to :" through a rectifier, thermoelectric generator, or solar panels. A significantly higher monitoring and maintenance effort is required by comparison to sacrificial anode systems.

Cathodic Protection Applications "athodic protection can be effectively applied to most steel structures in consistent contact with a corrosive electrolyte. "ommonly protected structures include buried pipelines, underground tan&s 0( T7s3, aboveground tan& bottoms 0A T7s3, well casings, internal surfaces of tan&s and treating vessels, and off-shore structures.

10

%nder!round Pipelines are the primary mar&et for cathodic protection. >oth sacrificial and impressed current systems are used. 8ederal and state regulations require cathodic protection for most petroleum or gas pipeline systems. %nder!round Stora!e &an's 0( T7s3 used for fuel are now required by 9PA to either have functional cathodic protection systems or to be of a non-corrosive material. >oth types of systems are widely used. A"ove!round Stora!e &an' 0A T7s3 bottoms can be protected from soil-side corrosion with cathodic protection. #ost ma6or tan& operators include cathodic protection in their corrosion control program. (nique problems involved with tan& applications include the difficulty of distributing current uniformly over the tan& bottom and monitoring the effectiveness of the systems. Production (ell Casin!s usually require impressed current systems due to higher current requirements. The economics of cathodic protection are excellent until production volumes decline and fields near the end of their effective life. This application of cathodic protection is common' but tends to be concentrated in established fields with &nown corrosion history. Internal surfaces of tan&s and vessels are commonly protected by cathodic protection systems. $ith some exceptions, most of these utili!e sacrificial anodes. Possible applications range from heater-treaters, heat exchangers, water storage tan&s, and hot water heaters. Offshore structures such as production platforms, doc&s, and pipelines are almost always protected with cathodic protection systems. acrificial anode systems with aluminum anodes are the most common application. Cathodic Protection Criteria

"athodic protection is considered to be effective when active corrosion is transferred from the metal surface to the installed anode. The effectiveness of the transference can be determined by electrical measurements. %ndustry accepted criteria for effective protection using these measurements are fully described in various /A"9 %nternational publications including the tandard @ecommended Practice =@P2)A*-*A "ontrol of 9xternal "orrosion on (nderground or ubmerged #etallic Piping ystems=. 4f the available techniques, the primary measurement used by industry to determine effectiveness of protection is &nown as the -2.B,2 volt, pipe-to-soil potential criteria. This technique measures the voltage difference between the protected structure and a copper-copper sulfate electrode placed in or on the electrolyte near the structure. %f the voltage difference is more negative than -2.B,2 volts, then the structure is considered protected. %f the value is more positive than -2.B,2 volts, the structure is either unprotected or only partially protected. /ormal values of unprotected steel in soil typically range from -2.,22 to -2.+22 volts with respect to copper sulfate. The interpretation of pipe-to-soil potentials requires consideration of the effects of measurement errors such as %@ drop in the soil between the pipe and the electrode. The most common consideration of this effect is through an =instant off= measurement obtained by interrupting current sources. 4ther techniques include potential measurement at permanent =coupon type test stations=. Desi!n Considerations There are four primary questions to be answered when designing a cathodic protection system.

<ow much current is necessaryC $hat source of direct current should be usedC <ow should installation be designedC 11

<ow can effectiveness be measuredC

Dimitations of cathodic protection must be recogni!ed during the design process. "athodic protection will be effective only on metal surfaces in continual contact to the electrolyte. Above-ground structures will not be protected. The distribution of current to desired areas becomes difficult in congested or remote areas. 9xamples include multiple pipeline right-of-ways and storage tan& bottoms. #ultiple variables should be considered during the design process. Two primary factors include the effectiveness of an external coating and resistivity of the electrolyte. The existence of a high quality coating minimi!es current requirements of a structure and greatly influences the design. 9lectrolyte resistivity affects the choice between sacrificial and impressed current as well as the type of groundbed. 4ther design factors include foreign system interference, power availability, maintenance requirements, and economics.

Practical Galvanic Series Metal "ommercially pure magnesium ?inc Aluminum alloy 0,. !inc3 "ommercially pure aluminum #ild steel 0clean E shiny3 #ild steel 0rusted3 "ast %ron 0not graphiti!ed3 Dead #ild steel in concrete "opper, brass, bron!e <igh silcon cast iron #ill scale on steel "arbon, graphite, co&e Volts -).+, -).) -).2, -2.B -2., to -2.B -2.F to -2., -2., -2., -2.F -2.F -2.F -2.F G2.5

#agnesium alloy 0A. AD, 5. An, 2.),. #n3 -).A

Typical potential normally observed in neutral soils and water, measured with respect to copperHcopper sulfate reference electrode. "opyright I )**) by /A"9 %nternational. @eprinted from Corrosion Engineers Reference Book with permission by /A"9. All rights reserved.

Galvanic Anode &echnical Data Environment ulfuric acid pic&le 0hot3 ea water - "oo& %nlet 12 mA)ft* 5,,222 5, - -2 mA)m* 5B2,222 5B2 - -52

mmm /orth ea mmm Persian Gulf mmm (. . - $est "oast mmm Gulf of #exico mmm %ndonesia oil Poorly coated steel in soil or water $ell coated steel in soil or water

B - ), + - )2 +-B ,-A ,-A )-5 2.) 2.225

*2 - )A2 B2 - ))2 B2 - *2 ,2 - A2 ,2 - A2 )2 - 52 ) 2.25

Jery well coated steel in soil or water 2.2225 or less 2.225 or less
"opyright I )**) by /A"9 %nternational. @eprinted from Corrosion Engineers Reference Book with permission by /A"9. All rights reserved.

Comparison of +eference Electrodes &o convert reference potential Structure)electrolyte potential Volta!e measurements to the e,uivalent e,uivalent to -./01. volts 2ith Difference potential 2ith respect to respect to copper)copper sulfate copper)copper sulfate 2 -,2 mv -+2 mv -))22 mv -2.B,2 volt -2.B22 volt -2.+B2 volt G2.F,2 volts ubtract 2.2,2 volts ubtract 2.2+2 volts ubtract ).)2 volts

+eference Electrode "opperH"opper ulfate ilverH ilver "hloride tandard "alomel ?inc

"omparison of different electrodes K F,L "

+esistance and +esistivity Appro3imate +esistivity of (ater

13

$here; T is ppm dissolved solids @ is resistance in ohm-cm. +esistance of a Sin!le +od Anode to Earth456

+esistance of Multiple Vertical Anodes to Earth 456

(1)

Derived from H ! D"i#$t %&u'tions +ou!h Indications of Electrolyte Corrosivity vs/ +esistivity Ohm - Cm >elow )22 )22 - ),222 ),222 - F,,22 F,,22 - +,,22 +,,22 - ),,222 4ver ),,222 Corrosivity 9xtremely corrosive Jery corrosive "orrosive #oderately corrosive #ildly corrosive Progressively less corrosive

SACRIFICIAL CATHODIC PROTECTION

Galvanic Anode Properties Anode

Efficiency Ener!y Capa"ility Consumption +ate Potential vs CuCuSO8 476 4Ah)l"6 4l")Ay6 4volts6

14

?inc Aluminum 0Al, ?n, %n3 #agnesium 0<-) Alloy3 #agnesium 0<igh Potential Alloy3

*, B, ,2 ,2

55, )),2 ,22 ,22

F5., A., B.+ B.+

-).)2 -).)2 -).-, -).+2

Ma!nesium Anode +evie2

Introduction #agnesium anodes are the primary sacrificial anode used for underground cathodic protection. There is a great deal of technical information and many publications detailing the application of magnesium anodes. This review is intended to provide summary information and brief guidelines in the selection of anodes. Ma!nesium Alloy Two alloys are commonly used for cathodic protection applications. These alloys are generically &nown as <igh-Potential #agnesium and <-) alloy. <igh potential alloys are produced from primary magnesium refined from saltwater. This alloy provides the maximum output with open circuit voltage exceeding -).+2 volts relative to copper sulfate. <-) alloy also &nown as A?-A5 is produced from secondary magnesium sources through recycling facilities. This alloy provides a much lower driving voltage in the range of -).-2 volts relative to copper sulfate. The selection of alloy requires consideration of current requirements, soil resistivity, and costs. %n most cases where current demand requires the use of multiple anodes, high potential alloy is the most economical choice. tandard chemistry requirements for the two alloys are; i!h Potential Anode Chemistry Per AS&M 908: Industry Standard for hi!h potential ma!nesium anodes Aluminum Man!anese Copper Silicon Iron ;ic'el Others< each Ma!nesium ./.57 ma3 ./1. - 5/:7 ./.*7 ma3 ./.17 ma3 ./.:7 ma3 ./..57 ma3 ./.17 ma3 +emainder

Element

-5 Ma!nesium Alloy Chemistry Content 7 Grade A Grade 9= Grade C 15

Aluminum ?inc #anganese ilicon "opper /ic&el %ron 4ther %mpurities

,.5-A.+ F.,-5., .), #in. .)2 #ax. .2F #ax. .22F #ax .225 #ax. .F2 #ax.

,.5-A.+ F.,-5., .), #in. .F2 #ax. .2, #ax. .225 #ax .225 #ax. .F2 #ax.

,.5-A.+ F.,-5., .), #in. .52 #ax. .)2 #ax .225 #ax .225 #ax. .52 #ax.

#agnesium @emainder @emainder @emainder M The <-) alloy supplied is Grade >

#a"rication #agnesium anodes are generally provided with a low resistivity bac&fill surrounding the anode. The bac&fill material provides a uniform environment for the anode and enhances performance by extending life and lowering the local resistivity. The prepared bac&fill consists of a mixture of +,. gypsum, F2. bentonite, and ,. sodium sulfate. Gypsum is primarily a filler material, bentonite absorbs and retains moisture, and sodium sulfate lowers bac&fill resistivity. The bac&fill is contained around the anode using cloth bags. The pac&aged anode is installed directly into the soil and then connected to the structure by a wire. Anodes are normally provided with ten 0)23 foot of N)F A$G wire.

Current Output "urrent output is controlled by three factors; Soil resistivity - "urrent output increases as soil resistivity decreases. Generally magnesium anodes are installed in relatively low resistivity soils. 9conomic application decreases significantly in soil resistivities exceeding ,,222 ohm-cm. Practically, magnesium anodes are not effective above )2,222 ohm-cm. 16

Anode surface area - "urrent output is proportional to surface area. As the surface area increases, current output increases. %ncreased surface area is usually achieved by increasing the length of the anode. Alloy potential - <igh potential anodes have open circuit potentials approximately F2-F,. higher than <-) alloy. 0-).+, volts versus -).-2 volts3. This creates a higher anode current and results in a lower total anode requirement.

Anode current output is calculated using 4hm7s Daw; % O current in amperes J O potential differential in volts @ O anode resistance in ohms The voltage difference is the protected potential of -2.B, volts subtracted from the open circuit potential of the anode. 8or high potential anodes, the difference is -2.* volts. 8or <-) alloy, the difference is -2.,, volts. @esistance to earth can be calculated by :wight7s 9quation;

@ O resistance in ohms O soil resistivity in ohm-cm D O anode length in feet d O anode diameter in feet Tefan&6ian, in his article =Application and #aintenance of "ontrol 8acilities= offers a simple process for determining anode current output with consideration of coating, potential, and multiple anode installation. The process involves calculation of anode current for a single high-potential anode installed )27 away from a bare pipeline using the formula;

im O current output in mA P O soil resistivity in ohn-cm f O si!e correction factor - Table ) P O potential correction factor - Table F Step 5> 8or a well-coated pipeline, the constant of ),2,222 should be reduced F2. to )F2,222. Step *> elect anode si!e correction factor from Table ).

Anode (ei!ht 4pounds6 5:5 ,:5 *:5 )+:5 F2:F

Standard Anodes 0pac&aged3 0pac&aged3 0pac&aged3 0pac&aged3 0pac&aged3 17

#actor 4f6 2.,5 2.A2 2.+) ).22 ).A2

5F:5 -B:,

0pac&aged3 0pac&aged3

).2A ).2*

Step :> elect potential correction factor from Table F. P)S -2.+2 -2.B2 -2.B, -2.*2 -).22 -).)2 -).F2 Ma!nesium ).)).2+ ).22 2.*5 2.+* 2.A2.,2

Step 8> "alculate anode current output with formula. Step 1> Ad6ust for multiple anode installation by application of ad6ustment factors in Table 5. ;o/ of Anodes in Parallel F 5 , A + B * )2 AD?%S&I;G #AC&O+S Anode Spacin! in #eet 1@ ).B5* F.-,, 5.25A 5.,B* -.)F, -.A,F ,.),F ,.A+2 A.)A) 5.@ ).*F2 F.+2, 5.-,, -.)BB -.*2F ,.,*B A.F++ A.*A+.A-5 51@ ).*-A F.+*, 5.AF, -.-F* ,.FF5 A.222 A.+AB +.,5A B.52*.@ ).*AF.B-B 5.+)-.,A5 ,.-)) A.F5F +.25A +.B+, B.A+*

As Tefan&6ian states in his article, the above process should be used only as a guide to estimate current output. Anode $ife and Efficiency Dife of a magnesium anode is directly proportional to its current efficiency. #agnesium anode alloys have a nominal efficiency of ,2.. <owever, significant variation from this efficiency will directly impact anode life. %t is not uncommon for anodes meeting all chemistry requirements to still exhibit efficiencies much lower than the nominal ,2.. Anode efficiency should be a critical part of the anode specification. #inimum efficiency should not fall below -,.. %n his boo& ="ontrol of Pipeline "orrosion=, Peabody provides a formula for calculation of anode life. 18

D O life in years $t O weight in pounds % O current in amperes :. A. Tefan&6ian in his article, =Application and #aintenance of "ontrol 8acilities= offers the following formula for calculating anode life.

D O life in years $t O weight in pounds % O current in milliamperes &a"le of Current Output and $ife Estimates
The following table provides estimates of current output and life for a single high potential anode, assuming a well-coated pipeline with an B,. effective use of the metal.

AD: 5BD: *.D* :*D1 80D1 Soil +esistivity Output $ife Output $ife Output $ife Output $ife Output $ife
ohm-cm )222 F222 5222 -222 ,222 A222 +222 B222 *222 )2222 ),222 F2222 mA )FF A) -) 5) FF2 )+ ), ))F B A years 5.A + )) ))B FF F, F* 5F 5A ,+F mA )A5 B) ,-2 55 F+ F5 F2 )B )A )) B years , )2 ), F2 F, 5) 5A -) -A ,) ++ )2F mA FA2 )52 B+ A, ,F -5 5+ 55 F* FA )+ )5 years B )) ), )* FF FA 52 55 5+ ,A +mA )AA B5 ,, -) 55 FB FF) )B )A )) B years * )* FB 5B -+ ,, A, +, BA *)-) )BB mA F2B )2A* ,F -) 5, 52 FA F5 F) ))2 years )) FF 5-, ,A A+ +B *2 )2) ))F )AB FF-

Desi!n Process :esign of magnesium anode systems requires a thorough evaluation of the application with consideration of the important variables. 4nce these variables are measured or assumed, the process typically is divided into the following steps.

19

Calculate e3posed surface area - This requires an assumption of coating quality. A high quality coating can provide protection to over **. of the total surface area. A conservative assumption of coating efficiency is *,.. Calculate total current re,uirements - This requires an assumption of current density. The typical range of current density for steel in common soils is ) to 5 milliamperes per square foot of exposed surface. A conservative assumption is F milliamperes per square foot. Calculate anode current output - (sing previous discussed formulas, calculate anode output considering the effect of coating, soil resistivity, alloy selection, and anode spacing. everal anode si!es should be evaluated. Select anode siCe "ased on life - 4nce anode current outputs have been calculated, the appropriate anode si!e can be selected by evaluating the pro6ected life. Typical design lives range from )2 to F2 years. Calculate total anode ,uantity - :ivide the total current requirement in amperes by the calculated anode output in amperes. The result is the estimated total number of anodes required. Determine anode location and confi!uration - This is primarily based on local site conditions and an even distribution of current from the anodes.

Desi!n Process :esign of magnesium anode systems requires a thorough evaluation of the application with consideration of the important variables. 4nce these variables are measured or assumed, the process typically is divided into the following steps.

Calculate e3posed surface area - This requires an assumption of coating quality. A high quality coating can provide protection to over **. of the total surface area. A conservative assumption of coating efficiency is *,.. Calculate total current re,uirements - This requires an assumption of current density. The typical range of current density for steel in common soils is ) to 5 milliamperes per square foot of exposed surface. A conservative assumption is F milliamperes per square foot. Calculate anode current output - (sing previous discussed formulas, calculate anode output considering the effect of coating, soil resistivity, alloy selection, and anode spacing. everal anode si!es should be evaluated. Select anode siCe "ased on life - 4nce anode current outputs have been calculated, the appropriate anode si!e can be selected by evaluating the pro6ected life. Typical design lives range from )2 to F2 years. Calculate total anode ,uantity - :ivide the total current requirement in amperes by the calculated anode output in amperes. The result is the estimated total number of anodes required. Determine anode location and confi!uration - This is primarily based on local site conditions and an even distribution of current from the anodes 9are Pipe Chart Soil +esistivity in ohm-cm Anode +ecommendation 5D *D :D 8D 1D ED BD 0D AD 5.D 80F 80F :*F 5BF 5BF AF AF AF AF AF 20

;ominal Output in milliamperes ;ominal $ife in years Pipe inch * 8 E 0 5. 5* 58 5E 50 *. ** *8 *E *0 :. :* :8 :E O/D/ inch */*B1 8/1. E/E*1 0/E*1 5./B1 5*/B1 58/.. 5E/.. 50/.. *./.. **/.. *8/.. *E/.. *0/.. :./.. :*/.. :8/.. :E/.. Surface Area #t*)$/#/ ./E. 5/50 5/B: */*E */05 :/:8 :/EE 8/5A 8/B5 1/*: 1/BE E/*0 E/0. B/:: B/01 0/:B 0/A. A/8* Current +e,mt/ mA)$/#/ 5/5A */:E :/8B 8/15 1/E: E/EB B/:: 0/:B A/8* 5./8B 55/15 5*/1E 5:/E5 58/E1 51/B. 5E/B1 5B/BA 50/08

*.0 5.8 11 8. :: *. 5B 51 58 5* 55 ** *0 *. *1 ** *1 *A :* :E ;ominal Anode Spacin! in feet 5B1 0B 8E :8 *0 5B 58 5: 5* 5. 00 88 *: 5B 58 E. :. 5E 5* 5. 8E *: 5* :B 50 5. :5 5E *0 58 *1 5* ** 55 *. 5. 50 5B 51 58 5: 5* 5* 55 A 0 0 B B E E E 0 0 B E 1 1 8 8 8 8 : : : A B E 1 1 8 8 : : : : : * * * B E 1 1 8 8 : : : * * * * * * 0 E 8 8 : : * * * * * 5 5 5 5 5 5 B 1 8 : : * * * * 5 5 5 5 5 5 5 5 E 8 : : * * * * 5 5 5 5 5 5 5 5 5 E 8 : * * * * 5 5 5 5 5 5 5 5 5 5 1 : : * * * 5 5 5 5 5 5 5 5 5 5 5

Calculated values "ased on current density of * milliamperes per s,uare foot/

Coated Pipe Chart

21

Soil +esistivity in ohm-cm Anode +ecommendation ;ominal Output in milliamperes ;ominal $ife in years Pipe inch * 8 E 0 5. 5* 58 5E 50 *. ** *8 *E *0 :. :* :8 :E O/D/ inch */*B1 8/1. E/E*1 0/E*1 5./B1 5*/B1 58/.. 5E/.. 50/.. *./.. **/.. *8/.. *E/.. *0/.. :./.. :*/.. :8/.. :E/.. Surface Area #t*)$/#/ ./E. 5/50 5/B: */*E */05 :/:8 :/EE 8/5A 8/B5 1/*: 1/BE E/*0 E/0. B/:: B/01 0/:B 0/A. A/8* Current +e,mt/ mA)$/#/ ./.E ./5* ./5B ./*: ./*0 ./:: ./:B ./8* ./8B ./1* ./10 ./E: ./E0 ./B: ./BA ./08 ./0A ./A8

5D

*D

:D 8D 1D ED BD 0D AD 5.D AF 5* :E

80F 80F :*F 5BF 5BF AF AF AF AF *.0 5.8 11 8. :: *. 5B 51 58 55 ** *0 *. *1 ** *1 *A :*

;ominal Anode Spacin! in feet :8A8 5B8B A*8 EB* 118 ::E *0E *1* *:1 *.* 5BEE 00: 8EB :8. *0. 5B. 588 5*B 55A 5.* 5*.. E.. :5B *:5 5A. 551 A0 0B 05 A** 8E5 *88 5BB 58E 0A B1 EE E* B:A :B. 5AE 58* 55B B5 E. 1: 1. E*: :5* 5E1 5*. AA E. 15 81 8* 1E0 *08 51. 5.A A. 11 8E 85 :0 8AB *80 5:5 AE BA 80 85 :E :: 88* **5 55B 01 B. 8* :E :* :. :AB 5AA 5.1 BE E: :0 :* *A *B :E5 505 AE EA 1B :1 :. *E *8 ::5 5EE 00 E8 1: :* *B *8 ** :.E 51: 05 1A 8A *A *1 ** *5 *08 58* B1 11 81 *B *: *. 5A *E1 5:* B. 15 8* *1 ** 5A 50 *80 5*8 EE 80 :A *8 *. 50 5B *:8 55B E* 81 :B ** 5A 5B 5E **5 55. 10 8* :1 *5 50 5E 51 EA 1: 8: :E :: *A *1 *: *5 5A 50 5E 51 58 5: 5:

Calculated values are "ased on current density of * milliamperes per s,uare foot/ Calculated values "ased on a coatin! efficiency of A17

22

%nder!round Anode Installation Instructions Galvanic anodes are installed on underground pipelines to provide locali!ed cathodic protection for that segment of line. The amount of protection derived from an anode is dependent upon several variables including coating quality, line si!e, and soil resistivity. (nderground anodes are generally installed in a pac&aged form, with the anode surrounded by a prepared bac&fill. The installation process is generally the same for all anode si!es. A preferred method of installation is with the anode connected to the pipe through a test station. This configuration permits monitoring of anode performance. The other method of installation is to directly connect the anode wire to the pipe. Anodes may be installed either hori!ontally or vertically. A minimum separation distance of ,7 is desirable to maximi!e the performance of the anode. This separation can be achieved either hori!ontally or vertically depending on local conditions. %n most cases, anodes should be installed no shallower than pipe depth. %n dry soils, additional depth may enhance anode performance by reaching lower resistivity soil. $etting the anode with approximately five gallons of water after installation will activate the anode faster and provide initial current output data.

IMPRESSED CURRENT CATHODIC PROTECTION Impressed Current Anode istory The origins of cathodic protection date to the days of ir <umphry :avy with the use of sacrificial 23

anodes on ship hulls. Jirtually all of the early efforts in cathodic protection were related to sacrificial anode systems. %n one of the first documented attempts to use impressed current, Thomas 9dison tried to apply current onto ship hulls in the )B*27s. <e had trouble with selection of suitable anode materials and power supplies. %t wasn7t until the )*F27s that the commercial use of impressed current systems appears to have begun. The development and use of impressed anode materials has gone through three general phases. Prior to $orld $ar %%, the principal anode materials were iron, steel, and carbon. After $orld $ar %%, graphite and cast iron anodes were developed. The )*A27s brought on the development of dimensionally stable anodes. These anodes include the precious metals and ceramic anode materials. The development of new anode materials continues. 9ven today however' many of the early anode materials are still in widespread use. +eactions Anodic reactions occur at the surface of anodes in a corrosion cell. Although there are several possible reactions, gas evolution is the primary oxidation effect of impressed current systems. The two primary anodic reactions in impressed current systems are chlorine evolution and oxygen evolution. "hlorine evolution occurs when an anode is in the presence of chloride ions. This reaction will predominate in seawater and high chloride environments. The chlorine evolution reaction is; *C$ Cl* G *e-

"hlorine gas then reacts with water to form hypochlorous and hydrochloric acid. 4xygen evolution occurs in low chloride ion concentrations or when sulfate ions are present. This occurs in underground applications where chloride ion depletion and restriction of ion migration allows the oxygen evolution reaction to dominate. The oxygen evolution reactions are; *
*

O
*

*SO8 G *

O* G 8 G G 8eH * *SO8 G O* G 8e-

These anodic reactions decrease the p< of the solution in the vicinity of the anode. Anodic consumption of co&e carbon particles also contribute to lowering p< of the anode environment. Anodic environments with a p< as low as ).2 have been observed. %n order to be effective, anode materials must be resistant to acid attac&. Anode Material 9ffective impressed current anodes should possess the following qualities;

Good electrical properties #echanically tough 9conomical 9asily formed into useable shapes 24

Dow consumption rates through wide range of environments

Any material possessing these properties could be used as an impressed current anode. #aterials that have been utili!ed in commercial applications are; teel Graphite "ast %ron Platinum #ixed #etal 4xide "onductive Polymer Dead #agnetite

Steel
The first &nown appearance of iron or steel as an anode were installations of iron =wastage plates= in the early )*227s in condensers and boilers. Although unintentional, steel acted as an anode on some early :" traction systems. #any of the corrosion failures experienced on these systems were due to :" current discharge from the rails. Probably the first planned use of steel as an anode was in the )*527s. crap steel was commonly used, either in the form of old railroad rails or used pipe. teel anodes can ta&e many forms. crap materials include buried structures which have been abandoned in place' such as pipelines or well casings. crap pipe, tubing, or railroad rails are commonly used. Any shape is capable of use' however, massive shapes are more conducive to practical use. A ma6or problem in the use of steel as an anode is maintaining electrical connections. #ultiple connections are typically used. #ethods of protecting the connections and maintaining electrical continuity includes coating the structure in the vicinity of connection and continuous coating strips 25

along the length of the anode. The consumption rate of steel is approximately F2 pounds per ampere year. "omplete consumption of anode material is not typically achieved because of non-uniform corrosion and the difficulty of maintaining electrical connection. There is no established maximum recommended current density. teel can be used in hori!ontal, vertical, or deep groundbeds, with or without carbonaceous bac&fill. $ith proper application, steel will perform well as an anode material. The ma6or disadvantages of steel as an anode material are;

(nodic corrosion )roduct fi*ms m'+ ,ui*d u) on 'node surf'ce- incre'sin# t$e resist'nce to e'rt$ .$is effect m'+ ,e )'rti'**+ overcome ,+ inst'**'tion in c'r,on'ceous ,'c/fi**s 0referenti'* corrosion m'+ occur in t$e 're' of t$e connection 1'int'inin# e*ectric'* connections 2'r#e m'ss re&uirements

Although most people would consider the use of steel as an anode as outmoded' there are operators who currently use steel in groundbeds with successful results.

Graphite Graphite anodes have been used for impressed current systems since the )*527s. Although the development is not attributed to a specific application, it probably resulted from the early recognition of carbon as a possible anode material. Graphite anodes are made from ground petroleum co&e mixed with a coal tar pitch binder. The mixture is heated and extruded into cylinders. After extrusion, the cylinders are cooled in special vats, placed in an oven, pac&ed in a mixture of sand and petroleum co&e, and heated to approximately *22 degrees "elsius to fully carboni!e the pitch binder. The sand-petroleum co&e pac&ing material aids heat transfer and supports the anode during its plastic stage. After cooling in a reducing atmosphere, the anodes are stac&ed in an Atchison or graphite furnace between two electrodes, covered with petroleum co&e and an insulating sand layer, and single phase A2 <! A" is passed through the pile. This process raises the temperature of the anodes to approximately FA22 degrees "elsius and completes the graphiti!ation process. The produced graphite material used for anodes typically has the following properties; Electrical +esistivity #aximum resistivity )2 micro ohm-meters Mechanical Stren!th "ompression - 5222 pounds per square inch 8lexural - FA22 pounds per square inch. Density **.FA poundsHft.5 &hermal Conductivity BB >(THhr. ft. 8. Porosity Dess than ,. Coefficient of thermal 2.+F x )2-AH8 e3pansion 26

#ost anode shapes are cylindrical rods. The common si!es used are a 5= diameter x A2= length and a -= diameter x B2= length. quare cross section graphite anodes have also been used. 9xtremely large shapes up to F-= x +F= have been used for offshore application. &reatment The produced graphite anode has a porosity of less than ,.. The anode life is improved significantly by filling the pores with an insulating material. This impregnation reduces the tendency for electrochemical activity to occur in the pores of the anode itself. %t also acts as a barrier against moisture intrusion which can cause deterioration of the anode and the anode connection. The most common materials used for graphite treatment are wax, linseed oil, or resin. (se of untreated graphite anodes for any application is not recommended. Paraffin wax has been successfully used for graphite anode treating for many years. The wax material is in a solid form at ambient temperature. Treating is accomplished by heating the wax to over F228 and submerging anodes in the melted wax. Although treatment time can vary with temperature, moisture content, etc., complete impregnation of -= diameter rods can normally be accomplished in a F- hour exposure. After cooling, the wax within the anode solidifies and remains stable under most environmental conditions. >ecause the wax is a solid at normal temperatures, there is no tendency for the material to leach out of the anode. Dinseed oil has also been widely used as an anode impregnant. The normal treatment procedure involves submersion of anodes in heated linseed oil in an autoclave under pressure conditions. Typically, the anodes are placed in the treatment vessel and a vacuum is drawn to remove all air from the anode pores. Preheated double boiled linseed oil is introduced into the vessel until the anodes are completely covered. The vessel is then pressuri!ed and temperature maintained until complete impregnation is achieved. This process normally ta&es F to - hours. ince the oil is liquid at normal temperatures' this treatment material will have a tendency to leach or oo!e out of the anode over a period of time. This effect is visible through the oil film on the surface of the treated anode. 8or extremely severe service applications, graphite anodes can be treated with a phenolic resin material. Phenolic resin sets up very hard. Typical properties of the graphite anode are only slightly affected by the resin treating except for a -2. increase in flexural strength. Anodes are surfaced to remove any s&in layers and placed in an autoclave. A vacuum is drawn to remove air from the pores in the graphite. $hile vacuum is maintained, resin is pumped into the autoclave. After all anodes are completely submerged with the liquid resin, pressure is applied to ensure filling the pores with resin. 9xcess resin is drained from the autoclave and anodes are heat treated to polymeri!e or cure the resin within the graphite pores. 8inally the anode surface is again surfaced to remove surface resin that could electrically insulate the anode from its environment. Proper impregnation with resin requires speciali!ed handling equipment. %n addition, there are some toxicity problems with the resin components. As a result, resin impregnation is normally only performed by the graphite manufacturer.

#a"rication 9ach graphite anode is normally provided with an individual cable of varying length. There have been numerous methods and procedures for connecting cable to graphite anodes. These range from a simple tamped lead connection to threaded metallic connectors. 4ne of the methods most commonly 27

used is a lead ferrule which is si!ed to the hole drilled in the anode. The ferrule is soldered to the anode cable and inserted in the hole. The ferrule is then expanded by a pneumatic or hydraulic tool which imposes a longitudinal force of up to )B22 pounds on the ferrule. This method results in connections with pull-out strengths exceeding that of the cable. Graphite anodes can be end connected or center connected. 9nd connections are made by drilling a A= to B= deep hole from one end. <oles can be easily drilled with hand tools. "enter connections are accomplished by drilling a hole to the longitudinal center of the anode from one end. This procedure requires more sophisticated gun drill type tools to maintain the hole in the center of the anode. 8ollowing cable connection, the annular space around the cable must be filled with a high quality electrical sealant. "ommon sealants are asphaltic electrical potting compounds. "are must be exercised to insure the compound is at the proper pouring temperature and that there are no voids or air poc&ets within the cavity. Anode caps such as epoxy or heat shrin&able caps are commonly used for additional protection. Graphite anodes can be prepac&aged in steel canisters with carbonaceous bac&fill. "ommon canister si!es are B= x +F=, B= x B-=, B= x *A=, )2= x B-=, )2= x *A=, )F= x B-=, and )F= x *A=. Desi!n Parameters Published values of graphite consumption range from 2.F, pounds per ampere-year to , pounds per ampere-year. $here oxygen evolution is the primary anode reaction, anode treatment should decrease consumption rate by at least F2.. $here chlorine evolution is the primary reaction, treatment should decrease consumption rate by at least ,2.. %n free flowing seawater and in some other applications where chlorine is the primary gas evolved at the anode, the graphite consumption rate should be in the 2., pound per ampere year range. %n neutral soil or fresh water service, consumption rates may increase to F.2 pounds per ampere year. "onsumption rates are significantly lowered by surrounding the anode with a carbonaceous bac&fill. The decrease in consumption can be in the order of +,.. A design consumption rate of graphite in a co&e bree!e bac&fill is ) lbHAmp-Pear. The recommended maximum current density is 2.,2 amperes per square foot in a co&e bree!e bac&fill.

Applications Graphite is one of the most commonly used impressed current anode material for underground applications. (nderground applications include deep, shallow vertical, or hori!ontal ground beds with carbonaceous bac&fill. 4peration of anodes at higher than recommended outputs can cause an extremely low p< environment at the anode surface' resulting in a brea&down of the coal tar pitch binder. $hen this occurs, large sections of graphite can =slough= off the anode. Premature failures of untreated anodes have been reported as a result of water penetration through the body of the anode to the metallic lead wire connection. 9lectrolytic current flow between the connector and the anode will cause corrosion of the connector' resulting in connection failure. ome early failures of graphite anodes occurred prior to anode installation as a result of thermal expansion of the anode connector andHor the connection sealing compound. These failures occurred under conditions that resulted in temperatures in excess 28

of )-2 8. The ma6ority of anode fabricators now use methods and materials that eliminate this problem. The use of carbonaceous bac&fill materials is highly recommended with graphite anodes. Accelerated corrosion rates can occur when the oxygen evolution reaction predominates. "arbonaceous bac&fills can act as an extended anode' minimi!ing the effects of increased consumption rates.

Cast Iron %ron containing a high silicon percentage was developed in the early )*227s. The cast material was extremely hard and brittle. %t was first seriously considered for impressed current anode application in the early )*,27s. %t was introduced as an anode material in )*,-. A subsequent modification to the alloy in )*,* produced better anode performance characteristics. This alloy consisted of the addition of -.,. chromium. This anode material has been widely used and accepted in the industry. <igh silicon chromium cast iron is a solid, non-porous material. This alloy consists of a matrix of silico-ferrite in which the ma6ority of the carbon is in the form of graphite fla&es at grain boundaries. Adding chromium results in eliminating graphite. The produced cast iron material used for anodes typically has the following mechanical properties; Electrical +esistivity> #aximum resistivity +F micro ohm-cm Mechanical "ompression - )22222 Stren!th> pounds per square inch 8lexural - ),222 pounds per square inch. Coefficient of 2.+F x )2-AH8 thermal e3pansion>

The standard metallurgical composition of cast iron anodes conforms to A T# tandard A,)B-BA Grade 5 as follows; Silicon> )-.F2-)-.+,. Chromium> 5.F,-,.22. 29

Car"on> 2.+2-).)2. Man!anese> ).,2. maximum Copper> 2.,2. maximum Moly"denum> 2.F2. maximum

This alloy is cast by several methods including sand mold casting, chill-casting, and centrifugal casting. A variety of anode shapes and si!es are available. The most common anode shapes are cylindrical tubes and solid bars in lengths up to B-=, diameters from )= to A=, and weights up to FB2 pounds. The standard length for the solid bar anodes is A2=. The standard length for tubular shapes is B-=.

#a"rication 9ach cast iron anode is normally provided with an individual cable of varying length. "ast iron anodes are provided in both end-connected and center-connected configurations. The solid bar anodes are cast with a hole at one end to accommodate a connecting cable. "enter-connections are used for cylindrical tube shapes. There have been numerous methods and procedures for connecting cable to cast iron anodes. The most common connector for solid anodes is a poured and tamped lead connection in the cast hole. "enter-connected anodes utili!e a one or two piece lead assembly attached to the interior center of the anode. 8ollowing cable connection, the annular space around the cable is filled with a high quality electrical sealant. "ommon sealants are asphaltic electrical potting compounds. "are must be exercised to insure the compound is at the proper pouring temperature and that there are no voids or air poc&ets within the cavity. Anode caps such as epoxy or heat shrin&able caps are commonly used for additional protection. "ast iron anodes can be prepac&aged in steel canisters with carbonaceous bac&fill. "ommon canister si!es are B= x +F=, B= x B-=, B= x *A=, )2= x B-=, )2= x *A=, )F= x B-=, and )F= x *A=. Desi!n Parameters The reported consumption rate is between 2.F and ).F pounds per ampere-year. The controlling factor appears to be the environment. #anufacturer recommendations for anodes surrounded by carbonaceous bac&fill is 2.+ pounds per amp-year. "urrent densities should be limited to approximately ) ampere per square foot. Applications <igh silicon cast iron anodes are widely used in underground applications in both shallow and deep groundbeds. Although the performance is improved with co&e bree!e' its use is not critical. This material is also widely used in freshwater and saltwater environments. The performance of cast iron as an anode is dependent upon the formation of a thin layer of silicon dioxide on the surface of the anode. 4xidation of the alloy is necessary to form this protective film. 30

ilicon-chromium cast iron is highly resistant to acid solutions. %t does not perform particularly well in al&aline environments or in the presence of sulfate ions. There have been some reports of early failure when silicon iron anodes are exposed to environments in which both sulfate and chloride ions are present. 4ther cases are reported where these anodes increase significantly in resistance when exposed to drying conditions. %t is thought that this condition interferes with the formation of the conductive silicon dioxide film.

PlatiniCed &itanium ) ;io"ium The first published results on the use of platini!ed titanium as anode were in )*,B. 8urther development of the anode material has resulted in the use of superior substrates other than titanium. %ts use has gone through several phases' however, it is recogni!ed for its superior anodic properties. Platinum is an excellent anode material due to its high conductivity and low consumption rate. <owever, because of its high cost, it is not economical to use platinum by itself. Platinum is made practical for use by cladding or electroplating a thin layer of platinum over a lower cost substrate. This also extends the effective anode surface area. The substrate must also have the ability to form an insulating oxide film under anodic conditions. The two substrate materials most commonly used are titanium and niobium. Titanium and niobium both form insulating oxide films when exposed to anodic conditions. Titanium is less expensive' however, it has a much lower brea&down potential than niobium. The titanium oxide is reported to brea& down at anodic potentials in the )2J range. The niobium film is resistant to brea&down up to B2J. /iobium is also a much better electrical conductor than titanium. /iobium is normally used with a copper core. This reduces the cost and also provides a much better electrical conductivity. Platinum coated anodes are available as rod, wire, sheet, tube, strip, and mesh. @od and wire si!es normally range from 2.25) inches to )=. Platinum thic&nesses range from F, micro-inches to )222 micro-inches. "onnection to platinum coated anodes depends upon the anode shape. $ire type anodes normally use a soldered connection. @od anodes generally have a drilled, threaded connection to the substrate material. The mechanism of deterioration of a platinum based anode is consumption of the platinum coating. @ate of consumption is controlled by many factors, primarily environment and current density. The consumption rate of platinum in seawater is approximately B mgHA-yr. %n fresh and brac&ish waters, 31

consumption is F to 5 times greater at low current densities 0)2 AHsq. ft3. At high current densities, consumption is much higher. The use of platinum is now primarily limited to water environments. %ts predominant use is probably in fresh water tan& applications' with secondary applications such as condenser water boxes, reinforced concrete, process equipment, doc&s, etc. Anode manufacturers indicate that platinum can be successfully used underground, both in surface beds and deep anode beds. <owever, most operators experience has been negative. There have been numerous reports of anode failures when installed underground. The primary failure mechanism is felt to be excessive consumption in small areas and loss of substrate oxide. This could be a result of non-uniform electrolyte resistivities andHor non-linear current distribution in the anode conductor core. Platinum has performed well in water applications. %t is probably the most widely used impressed anode material in fresh water applications such as storage tan&s and condensers.

Mi3ed Metal O3ide #ixed metal oxide anodes have been used in groundbeds since the early )*B27s. The anodes were originally developed in 9urope in the )*A27s for use in the chlor-al&ali industry. This material consists of a high purity titanium substrate with an applied coating consisting of a mixture of oxides. The titanium serves as a support for the oxide coating. Titanium functions as a =valve metal= which form thin, self-healing, adherent oxide films which are acid resistant and resist the passage of anodic current. The oxide is formed on the titanium substrate by thermal decomposition of precious metal salts that have been applied onto the substrate. 8our configurations of these anode materials have been used for underground applications. These are tubular, wire or rod, mesh or net, and strips. "ommon tubular anode si!es are ).A cm and F., cm diameter tubes, ,2 cm and )22 cm long. $ireHrod anodes range in diameter from )., to )F mm. 9xpanded mesh anodes made from thin gauge titanium strip have been used in confined spaces. This form of anode operates at much lower current density, typically less than 2., amps per square meter. Anode strips with widths less than ,2 mm have been used in confined spaces. everal different connection designs have been utili!ed. The tubular anodes are attached to a conductor cable using a mechanical or welded center connection. #ultiple anodes are often attached to a single cable creating anode strings. $ireHrod anodes and meshHstrip anodes have generally used crimped end connections that are sealed with tape, heat shrin&, and epoxy materials. >oth tubular anodes and wireHrod anodes are commonly pac&aged in steel canisters ranging in length from 57 to )27 and in diameter from F= to A=. The anodes are surrounded by fine carbonaceous co&e bree!e bac&fills in these containers. Anode properties include high electrical conductivity, low consumption rate, and a high surface area to cataly!e oxidation reactions. "onsumption rates of the anode oxide are on the order of ) mg per amp year for a chlorine evolution environment such as seawater. 8or an oxygen evolution environment, consumption rates are on the order of , mg per amp year. 32

#aximum recommended current densities for underground application with a co&e bree!e bac&fill material is )22 AHsq. m 0*.5 AHsq.ft3. This current density relates to a design life of F2 years. "urrent densities for muds and freshwater may be reduced by over half, depending upon temperature and life. #ixed metal oxide anodes are now commonly used in underground, and water environments. They are also the predominant anode material used for protection of tan& bottoms when installed with nonconductive secondary containment liners. There have been some instances of bed drying which have resulted in increased groundbed resistance. There have also been failures with anodes on strings where soil resistivity varied within the groundbed. This may be more of a concern in deep anode bed applications. Jariations in resistivity can result in widely varying currents among the anodes. This has lead to accelerated consumption of anodes that were operating at current densities exceeding manufacturer7s recommendation. Generation of chlorine has led to attac& of the standard cable insulation used for tubular anodes. %n these cases, a dual extrusion cable material is utili!ed. Conductive Polymer This anode material has been available since the early )*B27s. The anode material consists of a continuous semiconducting polymer material extruded on a copper wire. The active anode component is carbon contained in a polymer matrix. %t is a flexible wire-li&e anode and is provided on continuous rolls. The material has an outer diameter of )HF= with an inner core of NA A$G stranded copper wire. The anode is also provided prepac&aged in carbonaceous bac&fill. The pac&age is a nylon sheath containing the anode and bac&fill, provided on continuous rolls. "onnections of the inner copper core to a main cable are normally with mechanical crimped connectors. The ends of the anode and connections are normally sealed with manufacturer-provided heat shrin& enclosures. The manufacturers recommended maximum current density for the conductive polymer anode is )A milliamperes per lineal foot, when installed underground. $hen this material is used in long-line parallel applications, the attenuation of current in the conductor must be considered. Typically, a heavy gauge parallel copper cable is installed with the anode and multiple connections are made at regular spacings along the anode length. This material is used extensively for long line anode system installed parallel to pipelines in areas where coating has deteriorated or where sub-surface conditions do not permit efficient current distribution from conventional current sources. %t is normally installed with a surrounding carbonaceous bac&fill. "onductive polymer anodes have also been installed in confined areas such as between tan& bottoms and non-conductive secondary containment liners. "onductive polymer anodes can provide uniform low-current density output over their entire lengths. @eports have generally been very good. There are some reports of failures in areas where the wireli&e anode was not installed in carbonaceous bac&fill and accelerated consumption of the carbon occurred. These cases have almost all been related to excessive current discharge in low resistivity wet areas such as cree& or stream crossings.

33

Application &a"le The selection of an impressed current anode should be based upon a thorough evaluation of the application. %tems of consideration include environment, current requirements, life requirements, space, and economics. There is probably no anode material that is optimum or even capable of effectively meeting the requirements of every situation. The anode materials developed within the past 52 years certainly expand the arsenal of the corrosion engineer. <owever, for underground application' the use of materials such as graphite and high silicon cast iron still far exceed those of the newer materials. IMP+ESSED C%++E;& A;ODE APP$ICA&IO; C A+& Anode teel Graphite <% % "ast %ron Platinum #ixed #etal 4xide "onductive Polymer Q Q Soil with Coke Soil without Coke Freshwater Saltwater Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q

34

Anode Comparison &a"le

Anode Environment Consumption Rate
lb/amp-year

amps/SqFt

Design Current Density /one 2., /@ F.2

Si e

!eight Sur"a#e %a&' pounds Area Design Sq Ft$ (utput

)soil* Amps

teel Graphite oil 8reshwater altwater

F2.2 ).2 F.2 2.,

5= x A2= -= x B2= <% % "ast %ron oil 8reshwater altwater 2.+ ).2 2., ).2 F., F., ).,= x A2= F= x A2= F= x A2= 5= x A2= -.,= x A2= F.F= x B-= F.A= x B-= 5.B= x B-= -.B= x B-= Platinum oil 8reshwater /@ B mgHA-yr /@ ,2

52 +F

-.2 +.5

F.2 5.A

F+ -A2 ))2 FF2 ,2 A*, )FF

F.2 F.A F.+ -.2 ,., -.F -.* +.2 B.B

F.2 F.A F.+ -.2 ,., -.F -.* +.2 B.B

35

altwater #ixed #etal 4xide oil 8reshwater altwater

B mgHA-yr , mgHA-yr , mgHA-yr ) mgHA-yr

,2 )2 )2 ,2 ).A x ,2 cm ).A x )22 cm F., x ,2 cm F., x )22 cm /A /A /A /A 2.F+, 2.,A 2.-2.BB F., ,.2 -.2 B.2

"onductive Polymer

oil 8reshwater altwater

)A ma per D8 5 ma per D8 /@

= "ased on co'e "reeCe "ac'fill

36