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Index

Activation potential of grain boundaries, 118 Active state, definition, 55 Adsorbed oxygen film and potential shift,

13 Adsorbed electrochemical theory, 12 Adsorption-oxide film, combined theory of

passivity, 13 Alloying component, ordered structures and

passivity, 68 Alloying to increase passivation, mechanism,

67 Anode-cathode area, ratio for optimum pas-

sivation, 158 Anodic activation, 60 Anodic coatings, definition, 163 Anodic corrosion inhibitors, definition, 181 Anodic current, and corrosion protection (see

anodic protection), 7 Anodic passivation of alloys, factors de­

termining, 68 Anodic polarization and potentiostatic curves,

43 Anodic polarization curve, including self

dissolution current, 55 Anodic polarization in corrosion, 10 Anodic polarization curve, true, 61 Anodic potentiostatic curves, conditions for

establishing, 53 effect of ,alloy and medium composition,

76,77

Anodic process, inhibition to increase pas­sivity, 67

kinetics of, 38 on the passive electrode, 38

Anodic protection, definition (see specific topics), 107

effectiveness, 107 effect of various factors on parameters,

110 in isobutylene extraction process, 114 parameters, III conditions for, 149 practical applications of, 144 difficulties encountered, 149

Anodic overprotection, phenomenon for tita­nium, 141

Anodizing, definition, 43

205

Barrier layer, definition, 43 Breakdown potential, definition, 42

Carbon steels, anodic protection of, 129 in alkaline aluminate, 134 in vessels containing fuming H2S04, 145

Cathodic alloying elements, mechanism for passivity, 83

significance of anodic passivation, 86 Cathodic coatings, 163-164

definition, 164 Cathodic couples, and corrosion protection, 7 CathodiC loop, definition, 57 Cathodic polarization in corrosion, 10 Cathodic protector, definition, 151

for various metals, 156 Cathodic reduction curves, 18 Cation additives, 169

at elevated temperatures, 170 Cationic vacancies, film containing, 20 Cations of electropositive metals in corrosive

medium, 167 Charge curves, anodic galvanostatic, 17

anodic potentiostatic, 14 Chloride, effect of in passivity of 18-8 steels,

78 Chrome-nickel steels, effect of Mo or Si, 78 Chromium alloyed with Pt or Pd, 95 Chromium and cathodic additives (see also

cathodic couples), 91-95 Chromium and chromium-nickel alloys in

H2S04, effect of cathodic additives, 90 Chromium steels, alloying with molybdenum,

72 alloying with nickel, 71 passivation of, 23

Corrosion cracking, anodic polarization and, 125

Corrosion, electrochemical, rate equation, 5 Corrosion process, kinetics of and corrosion

resistance. 5 Corrosion protection, classification of,

methods for (see also protection), 7 Corrosion rate of mild steel in H2S04 with and

without anodic protection, 131 Corrosion rate - potential curves, construc­

tlOn of, 61

206

Corrosion, reduction by increasing effec­tiveness of cathodic process, 81

Corrosion, resistance and thermodynamic stability, 5

Corrosion resistance of stainless steels coated with platinum and copper (see also cathodic coatings), 164

Corrosion system, spontaneously passiv­ating, 60

Concentration, critical of oxidizer Fe3+ (see also oxidizers), 197

Critical temperature zone for intergranular cracking (see also intergranular corro­sion), 118

Deposits, in electrodeposition of metals, optimum conditions for, 169

Diagram, potential - pH (see Pourbaix diagram),3

Double layer capacity, measurement of, 25

Electrochemical behavior, stainless steels­platinum in H2S04, 152

stainless steel- cathodic protector (graphite, Mn0z), 158

Electrodeposition of metals, optimum condi­tions for, 169

Electrode polarization, with alternating cur­rent, 28

with square wave current, 28 EMF of corrosion cells, 5

Electropositive metal ions in corrosive media, 167

Etching character of 18-8 stainless steels with potential and heat treatment, 124

Ferric hydroxide, equilibrium with ferrous ions, 4

Ferric oxide, equilibrium with iron, 4 Film breakdown potential, 60 Film composition, effect of alloy composition,

37 effect of prior surface preparation, 36 electron diffraction determinations of,

34 microchemical method for determining,

36 Film, containing cationic vacancies, 20 Film formation, by chemical reaction between

anode and anions, 41 Film rupture, definition, 42 Film structure, changes with water desorp­

tion, 38 Film thickness, optical method for deter­

mining, 32 Flade potential, definition, 39

Galvanostatic polarization curve, 44 Gold, and thermudynamic stability, 3 Grain boundaries, activation potential of, 118

Halide ions, effect of on anodic protection, 126

Halide ions in solution and pitting, 60 Hydrogen embrittlement, 163

INDEX

Index of intergranular corrosion, 120 Inhibiting effect on stages of electrochemical

corrosion process, 7 Inhibitors, higher valence metallic cations,

186 Inhibitors, anodic process retarding, 183 Inhibitors, parameters for effectiveness, 191 Intergranular corrosion, and anodic protec-

tion, 117 dependence between potential and suscep­

tibility, 123 of austenitic stainless steel, effect of

anodic polarization on, 118 at elevated temperatures, 121 index of, 120

Iron, alloying with nickel, 71 aUoying with various elements, 74 composition of passive film, 21 effect of chromates, 188 in aqueous media, potential-pH diagrams

for, 3 in sodium borate and boric acid, 19 cathodic curves of, effect of prior polar i-

zation on, 20 protection with deposited copper, 171 single crystals in 0.1 N NaNOz, 32 with phosphates as passivators, 188

Iron ferrates and Pourbaix diagram. 4 Iron-chrome alloys with less than 13%chrome

in nitric acid, 81 action of alloying additives, 63

Limiting thickness, definition, 43

Manganese dioxide protectors, 159 Manganese in iron chrome steel, 74 Mechanical strength, dependence of, on cur-

rent density for polarization, 126 Metal ions, noble, critical concentration of,

172 Mild steel, corrosion rate of, in H2S04, 131

Oxidation-reduction process and character of passive state, 80

Oxide cathodes, protection With, 156 Oxide film-adsorption, combined theory of

passivity, 13 Oxide film and potential shift, 13 Oxides of the spinel type, formation of, 61 Oxidizers, and passivation, 181

effectiveness and redox potential, 191 effect of concentration on corrosion rate

and potential, 190 pa s siva ting effect, 183 reduction kinetics, 194 inhibiting action on corrosion process,

183 to increase effectiveness of cathodic

process, 185

INDEX

Oxidizing inhibitors, mechanism, 181 nature of, 188

Passivation current, limiting definition, 40 Passive-active state, definition, 56 Passive state, methods to increase stability,

67 and insoluble reaction products, 4 spontaneously stable, 58

Passive film, breakdown region, 60 composition on iron, 21

Passivity, definition, 9, 10 effect of anodic process in alloys, 79 electrochemical methods for investiga-

ting, 14 film mechanism of, 12, theory of, 12 of alloys, effect ofthe cathodic process, 82 phenomenon of, history, 9 electron configuration theory, 23

pH, decrease, effect on passivity, 78 Pit formation, 42, 60 Polarization curve, galvanostatic, 44 Polarization, cathodic and anodic as factors

in corrosion, 10 mean cathodic, 7 mean anodic, 7

Potential drop curves, 23 Potential, effect of inhibitor potential on

corrosion, 189 of film breakdown, 60 oxidation reduction and passivity, 11 standard electrode and thermodynamic

instability, 1 Potentiostat, classical, 45

electronic, 47 mechanical, 47

Potentiostatic curves, construction 14, 44 methods for determining, 43 potentiodynamic and potentiokinetic, 50 static, 50

Pourbaix diagram, example, 3

Protection by metal cations, condition for, 168

by metallic cathodes, 152 Protection, hydrogen embrittlement and cor­

rosion cracking, 163 Protective films, of metal compounds, non­

porous, 14 Protective potential, lower limit of, on tita-

nium in Hel, 141 Protector-anode couple definition, 151 Protector life, calculation for, 161 Protectors to assure high initial current

denSities, 162

Radioactivity and metal ion deposition, 176 Radius of effective anodic protection, 114 Range of protective potentials, neutral and

alkaline solutions, 113-114 Ratio of anodic to cathodic inhibition, 10

207

Region of passivity (see Pourbaix diagram), 4

Region of maximum passivity, effect of various parameters, 112

Region of stable passivity for stainless steels, effect of concentration and temperature, 120-121

Secondary passivity, 60 Solid solutions, changes in internal structure

and passivity, 68 Stainless steel, alloying with various ele­

ments, 74 alloyed with titanium and niobium, 74 alloyed with platinum or palladium in non­

oxidizing aCid, 83 and cathodic additives, 91-95 and cathodic protector, electrochemical

behavior of, 158 definition, 69 effect of chloride on passivity, 78 effect of prior surface preparation on

passive film composition, 36 in H2S04, film thickness on, 34 and platinum couple in H2S04, 152

Steels, experimental, effect of alloy composi­tion on film composition, 37

Structure analysis of metallic electrodes and potentiostatic curves, 44-45

Suifonation equipment, protection of, 144 Surface layer enrichment of metallic solu­

tions and passivity, 68

Tantalum, protection against hydrogen em­brittlement, 163

Temperature, critical zone for intergranular cracking, 118

Temperature, increase and passivity, 78 Thermodynamic stability, definition, 3 Throwing power, 114 Titanium, alloyed with Pt or Pd in Hz

atmosphere, potentials of, 88 anodic protection of, 135 in Hel, 138 in HzS04, 136 in presence of gaseous el2, 142 in contact with stainless steel and Hastel­loy, 153

in Hel, lower limit of protective potential, 141

platinum coating on, 166 molybdenum alloys in reducing media,

101

in H2S04 with alternating currents, 29 in 02 atmosphere, 88 in H2S04, corrosion rate potential curves,

62 formation of passive film on, 30 effect of noble metal ions in H2S04, Hel,

171 alloyed with Pd in Hel, H2S04, 81 and cathodic additives, 91-95

208

and adsorption theory, 13 coupled to Pt group metals, corrosion

behavior of, 154 effect of metallic cathodes on corrosion

rate in H2S04, 152-153 Transpassive state, 60

definition, 58 Transpassivity, definition, 42

INDEX

Tungsten, as alloying additive in Cr-Ni-Fe alloys, 74

Water desorption, changes in film structure, 38

Zinc, in alkalic solutions, 17 Zirconium and cathodic additions, 91-95