Corrosion Activity in 1965 - ACS Publications

Oct 6, 2016 - data from boiling “ 0 3 ... for a sulfuric a d c~nunbotor (&700/0 acid). .... 1. (66F) i (67F) tion reactor. Inorganic solutions. Galv...
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Corrosion Activity in 1965 Part I1

J. H. S. Haggin

in the August issue. For compactness, a number of minor subjects have been incorporated into single sections-e.g., the refractory metals are considered as a group. T h e patent citations of Section K include titles in lieu of any formal mention in a text.

STAINLESS STEEL

An rxmnpkof lllodmtnnnicaros’mp~tto~k baymt h44&robooc bring inrpscrnl =jW sndngcod.Mb joroMyrm to pro^ ht for a sulfuric a d c~nunbotor(&700/0 acid). Tk ka&r coppn &I1 which was electroclad with iantalutn

Reviews have been devoted to intergranular corrosion of nonsensitized stainless steels with emphasis on experience with nitric-dichromate solutions (3F), prevention of intercrystalline corrosion (37F),heat resistant alloys (47F),and plant construction applications (6F). Heat treatments have been developed for precipitation hardening stainless steels which result in uniform carbide dispersions (IF). This has led to new applications in severe marine service. The sensitization of stainless steels and related corrosion problems have yielded a new wealth of test data. Time-temperaturesensitization charts for Types 347, 304L, and 316L have been determined (ZIF) with corresponding corrosion tests. data from boiling “ 0 3 Welds in 18-8 stainless steel have been observed to exhibit “knifelike” corrosion along the fusion lines (73F). Such corrosion seems to be minimized by welding with minimum input energy and by employing the curious expedient of a filler metal more corrosive than the base metal. A general consideration of the effects of heat treating on intercrystalline corrosion of castings has POL 5 8

NO. 1 1

NOVEMBER 1 9 6 6

33

also been published (23F). Along the same lines, the added effect of superimposing a regulated electric current has been investigated (2QF) indicating that activation occurs only at grain boundaries. Heating prior to cold working results in unusually high sensitization, at least for Type 430 steel ( 5 1 F ) . I n the category of unusual applications, a wire cloth was used to replace part of a rib cage but became severely pitted in 3 weeks ( 1 3 F ) . For such prosthetic applications the galvanic effects caused by normal body fluids require stabilized metals and elimination of the possibility of galvanic e.m.f.'s. A lengthy study of Cr-Mn-N systems ( 2 6 F ) leads the investigators to believe that there is now a finite possibility that such steels will provide the long-sought stainless steel with immunity to transgranular stress cracking. I n addition to the routine evaluation of test procedures ( S g F ) , there has also appeared a critical evaluation of accelerated Strauss testing (62F). For most practical purposes the test is inadequate and inaccurate. The extent of intergranular attack does seem determinable by modifying the test. Mechanisms of stainless steel corrosion have been proposed for a number of systems. For high tensile steels (52F) a proposed mechanism suggests an accelerated test for stress corrosion cracking. The reconstruction of surfaces exposed to hot exhausts seems due to surface crystal growth at about the same rate as surface oxide films ( 5 3 F ) . A similar mechanism seems to prevent oxidation of surface impurities, causing further surface irregularity (41F). Intergranular corrosion has been attributed to an electrochemical mechanism ( 3 5 F ) associated with the depletion of Cr at grain boundaries. Though possibly contributory, the depletion is not thought to be necessary. Anodic protection by galvanic coupling with platinum (gF),and in strong acid media (22F), has been reported. The latter paper (22F) by Foroulis is one of a series distinguished by its thoroughness and basic insight, and is recommended highly. A mathematical model of corrosion by flowing sodium has been proposed (46F) with agreement between theory and experimental data. The remainder of the work published on stainless steel consists of the acquisition of test and performance data for specific circumstances. The work is summarized in Table I.

COATINGS AND PLATE Vitreous Coatings

TABLE I . TEST AND PERFORMANCE DATA FOR STAIN LESS STEELS TYP e

The difficulties associated with the addition of molten bitumens with clay emulsions for application to metals were reviewed (38G). 34

INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY

Environment

I

Reference

18-8 9 Assorted types Various alloys 304

Acids Aerated H$O( solutions

(8F) ( 7 IF)

6 Assorted types

Salt coated in ambient conditions Isobutylene extract

(12F)

IKh18K9T Assorted types Kot specified 3 Assorted types 316 1Kh18N9T 25 Assorted types Not specified Assorted special types

Liquid sodium Acidic surfactants Acids Saline solutions iYeak acids

Not specified 316 3 Assorted types

Exhaust gases and ash Boiling potassium Special test environment Dilute acids, water Nitric acid

2Kh18N9 1Kh18N9 E!?-229 304-L, HAPO-20 18-8, 316, 304 Assorted types H18N9T

( 74F)

Valve stems Boiling II"3

5 Assorted types XI7 .4ssorted types 6 '4ssorted types

( 43F, 48Fu ) (44F)

High temp. " 0 3 Iligh temp. HSOa CuSO4 and mineral acids Nitric acid

Cr18-Ni14-Si4 .I-

Austenitic Assorted types Kh18N9T

Assorted 2 Types Austenitic Not specified 18-10 Assorted types Not specified

General reviews of vitreous (43G) and zinc dustsodium silicate coatings (23G) have been published. Bitumens

I

16 Assorted types

Assorted types 3 Assorted Austenitic 304, 410 and

H&, Na& alkalies, water Valve-stem packings HNO3-HC1, H N O r H F , "03-HC1-HF mixtures Maleic acid solutions Ductility tests

,

(56F)

Soybean oil epoxidation reactor Pitting tests Boiling " 0 3 Inorganic solutions and slurries Galvanic coupling with titanium

I

(63F)

Industrial service Fluoride ions CuSO4, mineral acids Cold worked surfaces

1

(64F)

i

(66F)

1

(70F) (77F) (72F)

'

(67F)

Natural Polymers and Oils

A universal paste for sealing welded seams (76G) and gossypol resin (a waste product from cottonseed oil refining) for general below-grade service (47G) have been suggested. Synthetic Polymers

A review of polymeric coatings (8G) and of inhibiting coatings (35G) has appeared. Except for polystyrene, ethyl cellulose, and natural rubber, multicoat protection systems for protecting uranium gave more severe corrosion than did single coats (30G). The effect is explained by the selective permeability of the usual materials for water vapor over oxygen. An evaluation test for water absorption of synthetic coatings, particularly for new coatings, was described by Oono (29G). Dificulties with adhesion of coatings where cathodic protection is necessary may be due to chemical changes in vinyl coatings over specimens in seawater (2G). Erosion of a number of materials in severe environments (hydrocyclones) has been studied with appropriate recommendations for particular designs (15G). The mechanisms of protection due to pigmented materials (26G) and in cases of 0 - H type corrosion (QG)have been reviewed. I n most instances, zinc dust fillers and primers are responsible for protection where they are used in marine environments (28G). Other reviews were devoted to general atmospheric protection (7G), to the effects of a compressible film (79G), and to the use of radiotracers in the study of mechanisms (46G). Electroplate

I n studies on the effects of impurities on the protection afforded by electrodeposited nickel, corrosion rates with impure plate were high owing to the increased anodic current necessary to passivate the Ni (72G). Porosity of qickel plate was determined by electrolytic means

(24G). The conditions for the deposition of crack free Crplate have been determined (33G), and a detailed analysis of the behavior of various anodes in Crz(SO4)3 electrolysis has been made (25G). Bimetallic plate of Ni-Cr has been reviewed by Bache (3G), and the effects of active substrates on the protection offered by Ni-Cr plate have been evaluated (73G). I n evaluating defects in Ni-Cr plate, cracks seem to result from stresses in the plating of Cr and may be prevented by removing the stresses in the substrate surface through electropolishing (4G). The mechanism of Cu-Ni plating and corrosion therein has been reviewed by Ades (7G). A more general review of Ni, Cu, and Cr plating has also been provided by R a u b and Disam (32G). The codeposition of Zn and Ni from ammonia solutions has been discussed by Domnikov ( 7 7G). Tin-plate study has been the most actively pursued, on the basis of the amount of publication. Subjects include the passivation of tin-plate containers (3QG),the

effect of substrate on plating quality (40G), the application of cadmium-tin alloy plating to threaded fasteners (47G), corrosion of tinplate surface (42G), and deposition of films by vacuum metallizing (45G). Miscellaneous studies have been reported on the vacuum deposition of Cu, Cr, and Cd plate (31G), the corrosion stability of plate in tropical climates (5G), and performance testing of Zn, Cd, Sn, Ni, Zn-Cr, and Cu-Ni-Cr plating systems (6G).

NONFERROUS METALS Alkali Metals, Amalgams, and Rare Metals

Corrosion involving alkali metals is invariably associated with molten metal heat transfer. I n some cases the salts of the transfer media (12H) rather than the metals themselves are corrodants. Calcium has also been investigated as an alloying agent for protection in marine service (73H) and found to be as good as magnesium. The second of the series of physical property reviews dealing with the corrosive behavior of materials toward Na, K , and NaK has appeared (16H).A very extensive bibliography of liquid metals corrosion information has been compiled by the AEC (77H). Several versions of a study of the kinetics of mercury corrosion (9H-77H) in a two-phase system have appeared. Corrosion by mercury was determined for Fe-, Ni-, and Co-based alloys. Kinetic studies were also made on oxygen reduction at the amalgam-acid solution interface ( 5 H ) . A polarographic study of the anodic behavior of mercury in KC1 solutions has been reported ( 78H). Nearly all the corrosion in rare metals is associated with electronic applications. Magnetic properties of Co-P deposits offer a means of assessing corrosion in some cases ( 3 H ) . The onset of corrosion on Ge, Si, and other n-fi junctions in strong etching agents was studied (6H), and corrosion resistant alloys based on precious metals have been reviewed both in the Gnited States ( 4 H ) and in the Soviet Union ( 7 H ) . Anodic dissolution was studied for gallium in alkaline solutions ( 2 H ) and for Ge by simultaneous chemical and electrochemical oxidation (74H). Liquid and vapor cesium has some peculiar corrosive effects on a number of container metals including stainless steel ( 7 H ) . The most susceptible material appears to be Mo which is somewhat soluble in Cs. Additional data have been reported for gold alloys in thiocyanate solutions ( 8 H ) and experimental thorium base alloys ( 7 9 H ) . A further review of corrosion during phase transitions in the Ag-S system has been published (75H). A basic study of liquid metal corrosion as a solution phenomenon includes dissolution in static systems and solubility data for Ni, Cr, and Fe in several liquid metals (2OH). Aluminum

I n the area of basic studies, an automatic apparatus far accelerated electrochemical studies has been introduced (67H). The apparatus is essentially a polaroVOL. 5 8

NO. 1 1 N O V E M B E R 1 9 6 6

35

graph and is said to give reproducible results in pitting and contact corrosion studies. Metallurgical investigations include those on corrosion in specific boundary the influence of structure modification regions (ZIH), due to copper (29H), the effect of purity in 1.2y0manganese alloys (47H), and intergranular penetration in age-hardenable alloys ( M H , 64H). The mechanisms of pitting and crevice corrosion (65H)and corrosion fatigue (69H)have also been studied. Basic studies, including environmental effects, have been reported for aluminum in contact with other metals in chloride solutions (66H),for the protective action of anode-oxide coatings on Magnalium (6ZH), on the effects of cathodic currents on alloys (60H),for the anticorrosion effect of phosphoric acid in the aluminum

TABLE II. CORROSION TESTS ON ALUMINUM Material Alloy condenser tubes Aluminum welds Alloy sheet Alloy cooling tubes Structural alloys Pure metal Anodized alloys Structnral alloys Alloys Alloy conduits Structural alloys Structural alloys Structural alloys Structural alloys ,Alloy sheets Alloy tubing .illoy piping Alloy piping Alloy vessels Alloy process equipment Structural alloys Coated pure metal Sealed, anodized alloys Anodized and sealed alloys Pure metal Riveted plates Structural alloys Alloys -4110~tubing Alloy panels Vacuum deposited metal Anodized alloys Structural alloys Structural alloys

36

Environment

1

Referencr

Petroleum refinery

1

(22H)

Severe industrial exposure Underground service Refrigeration units Aircraft structures Alkaline solutions Not specified .\ircraft structures H 2 S a t high pressures Alkaline soils General purpose Building materials in humid climates Chlor-alkali plants Roofing Tropical marine environment Coolers and condensers Pipelines Pipelines Ammonia plants Food industry

Copper

The literature on the corrosion of copper and copper alloys contains a higher percentage of basic and developmental studies than for any other class of metals except the rare metals. Typical of the developmental studies is that on the dealuminization of Al-bronzes utilizing an electron-probe scanner (77H).A quantitative anodic replica for application in measuring solute distributions and concentrations has been introduced and used (72H). Das has made kinetic studies of the reaction between copper sheet and iodine in MeOH solutions (74". The rate controlling step is diffusion of iodine to the surface. I n other work the effect of additives on the thermal effect produced by the dissolution of copper in C u S 0 4has been determined (77H), and the effect of oscillating potentials on the dissolution of copper in phosphoric acid has also been determined. Electrochemical behavior of the Cu-Zn system under the influences of temperature changes produced what is believed to be a more representative procedure for determining corrosion than the weight loss method (9OH). From the metallurgical viewpoint, the severe dealumination of Al-bronzes in marine environments has been studied in terms of heat treatment and microstructural changes (SOH). For the Cu-Mn system, the physical

TABLE 1 1 1 .

SERVICE TESTS FOR CUPROUS MATERIALS

Material

I

Ag-plated wire

Marine atmospheres Saline solutions Not specified Presumably atmospheric

cladding of fuel plates (57H),and for aluminum over nitric acid solutions (4511). Two special studies dealt with bacterial contamination in alloy fuel tanks (4OH) and the stepwise corrosion at silver-aluminum boundaries (27H). The remainder of the work was predominantly service and field testing and is summarized in Table 11.

1

(50H)

.'iqueous solutions Industrial and municipal atmospheres Aircraft Moltm salt tests Conduits in concrete hlarine atmospheres Atmospheric Petroleum and petrochemical plants .9ircraft Seawater

INDUSTRIAL AND ENGINEERING CHEMISTRY

Alloys Heat-exc hanger tubing Pure metal Various alloy? Cu-Ni alloys Constantan Alpha brass Condenser tubes Cu-Zn alloys Naval alloys Z n and A1 alloys Pure metal Evaporator tubing Various alloys Brasses Cu-A1 alloys M'ater pipe Brass fittings Gold plated braces Heat tranTfer tubes

1

Environment

I

Reference

Teflon insulated electrical wire Marine service General service

1

(70H)

KOH-aminophenols Sub surface construction Marine apparatu? Thermocouples Stressed structures in N H 3 Power stations HZS-air Marine service Aqueous solutions Mineral acids Dilute HC1 Air and H2S Food solutions Aqueous solutions General service Aqueous Saline solutions Acidic solutions of Fe+

1

-

(73W

(75H)

and mechanical properties have been reviewed (86H) with rolling mill operations in mind. Potentiostats have been employed in the study of brass dezincification (97H) and cathodic polarization in Fe+ solutions. Further electrolytic study has been given to anodic passivation of copper in electrolytic polishing ( 705H),the thermogalvanic corrosion of copper in acidic CuSO4 solutions (84H),and the general anodic behavior of brasses (97H).Additional electrochemical equilibrium diagrams for a number of Cu-aqueous solution systems (87H) and for copper in concentrated alkalies (88H) are reported. The remainder of the literature on copper and copper alloys consisted of service testing and is summarized in Table 111.

TABLE IV. Material Pure metal Alloy-sheet Mg-Zn alloys Mg-Cu alloys Mg-Sn alloys Various alloys Mg-Li alloys Mg-Zn alloys Various alloys Mg-Zn alloys

CORROSION TESTING OF MAGN ESI UM Environment

Reference

Cladding for nuclear fuel Saline solutions Chloride solutions Saline solutions Chloride solutions Mg-salt solutions Concentrated H2S04 Atmospheric NaCl and H2S04 solutions KC1 solutions

( 119H) (720H) (121H) (122H) ( 723H) ( 724H) ( 725H) (126H) ( 127H) ( 128H)

Nickel

The literature on nickel was primarily devoted to its electrochemical behavior with a few references on service testing. The conditions necessary for the formation of “black coatings” on Ni-P alloys in mixed sulfatephosphate electrolytes have been determined (729H). Other studies have been on pure nickel in sulfuric and perchloric acid solutions (730H), and on Cr-, Mo-, W-, and Fe- alloys in boiling, dilute HC1 (732H). Continuing previous work, Klyachko and Mal’tseva determined the effect of anions with varying charge on the value of anodic polarization of Ni-base alloys (735H). China clay suspensions, when added to the electrolyte, improved the resistance of composite Ni Cr plate by decreasing porosity of the plate (737H). Deposition of homogeneous Ni surfaces from ethanolic media (734H) has been studied. Now under way is a study of Ni-200 as a potential construction material for nuclear spent-fuel recovery plants (737H). No data were reported. The anodic dissolution of Ni in HzS04has been studied by Kuzub (736H), and a questionable accelerated corrosion test for electrodeposited nickel has been reported by Fellows (733H).

+

lead

The corrosion of lead in soft water may be controlled by a number of wood extracts used in taming, as well as by a number of synthetic materials (772H). Other

suggested controllers are irradiated potato starch ( 7 74H) and agar gel ( 7 75H). I n sulfuric acids, corrosion control may be exercised by alloying with heavy metals (773H), and by galvanic means (708H). I n electrolytic service a superimposed a.c. voltage accelerates the corrosion of lead the most a t 50 cycles/sec. but to a lesser extent at higher and lower frequencies ( 7 78H). Further studies on lead alloys with tin (709H) for bearing surfaces and with antimony (707H) and silver ( I 77H) for electrode service indicate that such alloys are beneficial in diminishing corrosion. The corrosion kinetics of lead in fatty acids have also been deduced ( 7 7 7H). The corrosion in high temperature electric motors appears in the form of efflorescence on piston surfaces as the result of reaction between lead compounds in fuels and the piston metal (770H). Magnesium

The literature on magnesium corrosion was confined to service testing as summarized in Table IV. Refractory Metals

As would be expected, the literature on refractory metals is almost totally concerned with high temperatures. Cr-Ni plating of molybdenum is suggested as a general preventive (748H). Design data have been produced for Mo in molten chlorides (144H) and in molten Mg (738H). Though the refractory metals have been suggested as construction materials for alkali-metal cooled reactors, serious compatibility problems due to impurities

TABLE V.

CORROSION TESTS ON TITANIUM

Material

Environment

Pure T i Pure T i VT3-1 alloys Pure T i Ti-Pt alloys High strength alloys T i welds Pure T i T i welds Ti-Zr alloys Pure T i Heat exchanger tubes T i welds T i alloys Ti-Nb alloys 0 2% Pd-alloy Various alloys Process equipment Pure T i Pure T i Alloy equipment 2%-Pd alloy Pure T i Pure T i

Reference

Mineral acids Organic acids Heat treating Inhibited H2S04 Not specified Low temperatures Boiling mineral acids High temperature HC1 Mineral acids KOH Various Viscose factory

( 749H) ( 750H) ( 752H) ( 753H) ( 754H) ( 755H) (159H) ( 760H) ( 762H) ( 763H) ( 164H) ( 765H)

Autoclave H l S 0 4 solutions Electrolytic service Oxidative conditions Aqueous and organic solutions Chlor-alkali plants Chlorine solutions Mineral acids Food processing HzS04 solutions Halogen acids HzS04

(166H) ( 767H) ( 768H) ( 169H) ( 770H)

VOL. 5 8

NO. 1 1

(771H) (772H) (774H) ( 175H) (776H) ( 777H) (778H)

NOVEMBER 1 9 6 6

37

remain (7398). Additional data on corrosion of refractory metals by Zn-Mg-U and halide salt systems have been obtained (7438). Processes at tungsten-gas interfaces have been studied (74OH,742H), and the anodic behavior of a number of refractory materials has been determined (747H). Corrosion of niobium and tantalum has been studied by a number of investigators (745H-747H). Titanium

Among the basic studies on titanium corrosion are an election-diffraction investigation of titanium corrosion products from acid solutions (7738),a study of alloy composition on sulfuric acid resistance (767H), and an electronic determination of the surface oxide composition after exposure in a molten salt bath (158H). The first of an expected series of works on pitting corrosion was devoted to titanium (757H), and anodic dissolution studies

TABLE VI. TEST DATA FOR Z I N C

Zn Zn strip Electrodeposited Zn Not specified Casting alloys Coated Zn Zn alloys Zn-plated items Zn-plated pipe



1

TABLE V I I .

( 183”) ( 784H) ( 188H)

Dry-cell cases Gal\ anizing scrvice Coatings in marine atmospheres Phosphate cleaning baths Aqueous salt solutions Normal atmosphere Atmospheric Hot, humid atmospheres Saline atmosphercs

1

~

1

(189H) ( 790H) (191H) (792H) ( 794H) (782H)

have been made (7578,7568). The remaining literature was devoted to service testing and is summarized in Table V. Zinc

I n associated reports, the influence of anions (7868) and cations (785H)on the anodic behavior of zinc is shown to be what would be expected. Further studies of anodic behavior made use of voltamperometric techniques in anodic polarization of zinc (797H) and in dissolution and passivation in alkaline solutions (798H). Still another related study measured concentrations in the convection current during dissolution via refractometry (787H). Two papers were also devoted to the effect of a.c. leakage on zinc corrosion (7798,780H). The remainder of the literature dealt with service tests as summarized in Table VI. Zirconium

Except for a single basic paper on carbon diffusion in @-zirconium (ZOZH), the literature was restricted to development and service tests. A design program to exploit Zr alloys has been proposed (ZOlH),and the corrosion resistances of Zr alloys in molten KCl and NaCl (203H), superheated steam (ZUOH), and high pressure water (7998) have been determined. iron and Steels Other Than Stainless

The literature on this subject was extremely varied in content and organization. However, most of it was concerned with corrosion in specific circumstances. -4 tabular summary is given in Table V I I .

S U M M A R Y OF CORROSION INVESTIGATIONS FOR I R O N AND STEELS OTHER T H A N STAINLESS En’ncironment

Substrate

Corrodant

Galvanized mild steel C steel pipes General types C steels

Air-SOz, H ~ S O Iseawater, , “01, NH 4 0 1 I Concrete and mortar Saline soils CS, mfg. plants Oxidizing solutions

61-, so4-2 Sulfur compds. Acidic chromates, dichromates

Misc. plated steels C steel Mild steel C, Cr, W, Nb, V, T i alloys Armco Fe

Humid air Deep soil Ammoniacal liquor High press. process equipment High temp. silicate melts

Saline droplets Carbonates Traces of HnS and H C N Hydrogen Molten oxides

Mild steel C steel Co-Cr-W alloys Mild steel coated with films C-Mn-Si-S-P alloys Mild steel

High press.-high temp. caustic solutions Acetic acid solutions Acid media ‘Xtmosphere h’C1-benzene solutions Chromate-chloride solutions

Caustic

:\rsenic-containing steels

Acid attack HCl, ClC1-

_____._

Aerosal cans Exhaust gases Citrates Superheated steam

Various Various Ammoniacal citrates Oxidants and neutrons

Mild steel C steels for ships

Tidal waters

Saline waters microbe attack

38

INDUSTRIAL A N D ENGINEERING CHEMISTRY

-

(7J)

Su plate Cr alloys Mild steels Nb alloys

-_

R#erence

1

(2J) (3J)

,

(4J) (5J)

( 7OJ)

Mild Galvanized mild steel Fe and mild steels

Petroleum storage tanks Tropical marine atm. Solid-liquid metal interface

Fe, Inconel-stainless Mild steel Engine alloys Low alloy steels Cr alloys

High temp. water Chlorinated hydrocarbons Hydrocarbon combustion exhausts Demineralized water Turbine engines

Sulfur and sea salt

Reinforcing steels Reinforcing steels Unspecified alloy Armco Fe Mild steels

Concrete Concrete Marine (Kort Nozzle) H z S 0 4 (aqueous solutions) Marine

Galvanic macropile Galvanic action Acid galvanic attack NS

Mild steels Gears Diodes for cattiodic of marine equip. Alloys (misc ) Fe-C-Si alloys

Acid media Marine atm. Marine Coal tar waters HCl

Acetylenic compounds ClSaline components Mineral acids Galvanic action

Carbon steel Cold drawn wire Fe and mild steels Cold drawn wire C steel

HzS04 Neutral Neutral Neutral Greases

Galvanic Galvanic Galvanic Galvanic

Oil well tubing Sintered Fe-Cr Process vessels

Oil field Processing of sintered compounds Amine gases

Cast iron Carbon steels

Concd. HzS04 Mineral acids and brines

diamine HzS04 Mineral acids and brines

Fe-Cr alloys Cast irons Aluminized mild steel Hastelloy, Zircalloy Incoloy

Dilute mineral acids Mine waters Corrosive atmospheres Processing plants Steam reformer

Acids Acids and salts Sulfur compounds Mineral acids S-containing gas-oil

Low alloy steel

HCl Steam Tests H C N and H z S solutions Welded joints

Effect of adding U Liquid bismuth S-complexes Boiling “ 0 3

Cr-steel

Ammonium-base pulping liquor Sulfide brines Formic acid acetic acid Solutions containing C U + ~KOH, , K3[Fe(CN)al Processing vessels

Sulfur and NH4 compounds S compounds, dissolved 0 2 Acids Solutions containing Cuf2, KOH, K B[Fe(CN)sl Liquid aluminum

Cr-steel Steels Misc. steels C and stainless steels Cu-coated steel wire

Processing vessels Oxosynthesis processing vessels Production of diphenylolpropane Cd-Mg-Zn heat transfer media Industrial atmospheres

Liquid zinc Carbonyls Acids Molten metals Sulfur oxides and moisture

Ductile iron Steels

Dilute acids Processing equipment for manufacture of naphthalenes Reinforcement for prestressed concrete I Reinforcement for prestressed concrete I1 Acidic solutions

Oxygen Acids

Surgical steels Carbon steel Steels Cr-Ni steels Pulp digester Pipelines Highly alloyed Ferritic-austenitic steels

Steel wire Steel wire Steels 18-8

perchlorate solutions sulfate and perchlorate solutions perchlorate solutions and viscous oils

High strength Steels Steel

Cold work in surface Welded steel assemblies at high cyclic temperature “Sour” condensate lines Liquid Na Chemical plants

Iron Cr-Ni steels

P-organic solutions Test environment

Steels

Mineral acids Dissolved oxygen Dissolved Moisture Halogen acids

c1-

action action action action

Brines

N-( 2-hydroxyethyl)2-ethylene-

- __

Oxygen

0

2

exhaust gases

HzS Na Chemicals Environment

VOL. 5 8

+0

NO. 1 1

NOVEMBER 1 9 6 6

39

12yoNi-maraging steel

Marine environments Aqueous condensates Chromic acid

Sea water

Turbine alloys Carbon steel Steels Iron Specialty steels

Exhaust gases Benzene plant DistiIlation plant N H ~ N O S - H ~solutions O W/a.c. current neutral and acidic solutions

Fuel-oil ash C1 compounds CS2 1320 vapor

Iron and steels Ni-base alloys Ni-base alloys Ni-base alloys Coated fasteners

Mine atmospheres Hydrofluorinator Hydrofluorinator Hydrofluorinator Damp wood

Steel Iron

I

Atm. oxygen

+

Electrically augmented H +

I

-

1

Air, H a 0 Fused salts Fused salts Fused salts HC1, humid air

i

H ~ SN , H ~ ,coZ, CN-

i

Concrete components Oxygen Dissolved salts Dissolved salts

~

.____

Alloys Mild steel Pure Fe Steels Piping steels

Damp, fuel gas Concrete reinforcement Steam, water, alk, solutions 2 Immiscible liquids Saline soils

Piping steels Piping stecls Austenite steel Coated piping steels Carbon steels

Crude oil wells Saline soils Liquid metals Soils Boiling water reactor

Dissolved salts

Low Fe alloys U-Pu-Fe alloys Low C steel Fe Cr-steel

Hot air Chill casting Formalin solutions Concentrated aqueous media Aqueous solutions

Moist O2 Atm. .\cids

I

(82J) (8,?.J) (84.1)

I

H*S

~--

1

(QOJ)

I j

(974 (Q2.J) (QJJ) (Sd.1)

I

(95.1)

1

__ ..___

( 70OJ) (7OlJ) ( 702J) ( 70.3J) ( 704.J)

c1-, so&-2

2 dissolved in Na Galvanic system 0

0 2

Vegetable and animal juices __ C1 and S NHs-synthesis gas HzS, HzSO4, Coz, 0 Seawater Galvanic

Piping steels Mild and alloy steels Structural C steels New alloy Alloy steels

Petroleum distillation plant Gas-scrubbing equipment Industrial structures Marine Inclusions in steels

Iron Mild steel Mild steel Mild steel Iron

Aqueous solutions SO2 in industrial atm. Gas strippers Industrial atmospheres Gas strippers

HzS-CO2-Hz0

Various alloys Alloys and nitrides Steels Iron and steels Piping steels

High tcmp.-high press. gases Lab samples Saline waters Industrial atmospheres Hot water

Carbonyl groups Galvanic action NaC1, NaN03, CaCl,, Fe-oxides, Fe-sulfates Oxygrn

0

(105J) ( 106J) (107J) ( 70XJ) ( 709,J) ~..

( 170J) (i11J) ( 172J) ( 7 13J) ( 7 14J) ( 7 75J) ( 776J) (7775) ( 7 7RJ) ( 71QJ)

2

S and S-containing salts

C02

so2 + I120

(12OJ) 0 2

(727J) (122J)

1

(723-T)

(12?J) I

(725J) (726J) ( 127),1 (728J) (72YJ)

l

~

1 I

I

__

(73OJ) (737J) (732.J) (133.J) ( 734J)

Cr-Ni alloys

40

Industrial

INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY

Fatty acids

(740'05) (741J) ( 742.1) (743J) ( 7445)

Cu in C steel Cr steels HzO storage tanks Fe and Ni Fe alloys

_ 17 Metals and alloys

I3zSO4 0 0 Urea

High temp. industrial Petroleum refinery

Methacrylic acid Acids

0, coz

_ ~ _ _ __

Cr-Ni steels

(745J) ( 746J) (7475) (7485) (749J)

Acids Hot air Hot water Atmospheric Aqueous solutions

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I

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( 750J)

(757J)

Piehl, R. L., Proc. Am. Petrol. Inst. Sect. III 44, 189, discussion 197 (1964). Plante, G., Compt. Rend. 261 (4) (Gronpe 7), 994 (1965) (Fr.), Pouillard, M., Corrosion Anti-Corrosion 11, 264 (1963) (Fr.). Pouillard., E... Finckbonner.. A... Re”. Met. (Parts) (Fr.). , . 62., 721 (1965) . Reynolds, H. J., Jr., Proc. A m . Petrol. Inst., Sect. ZII 44, 138, discussion 152. (59F) Rozenfel’d, I. L., Novitskaya, M. A., Selezneva, T. V., Zashchita Metal. 1 (3). . . , 265 (19651 . , 1Russ.). . ~ , (60F) Sakiyama, K., Hayashi, D., Boshoku Gijutsu 13 (6), 252 (1964) (Japan.). (61F) Savitskii, E. M., Popov, V. F., Keis, N. V., Lyubimov, V. M., Yap7 Teorii i Primeneniyn Redkorem. Metal., Akad. Nauk S S S R 1964, p. 214 (Russ.). (62F) Scaarfstein, L. R., Eisenhrown, C. M., Am. Sac. Testing Mater. Spec. Tech. Publ. 369,235 (1963). (63F) Schmutzler, G., Suckert, R.,fPIaste Kautschok 12 (51, 283 (1965) (Ger.). (64F) Schwenk, W., Corrosin Sci. 5 (4), 245 (1965) (Ger.). (65F) Schwenk, W., Ternes, H., Arch. Eisenhueftenw. 36 ( Z ) , 109 (1965) (Ger.). (66F) Shibad, P. R., Balachandra, J., Trans. Indinn I n s t . Metals. 18, 59 (March 1965). (67F) Takao, A., Nakano, K., Takamura, A., Nirpon Kinroku Gakkaishi, 24 (6). 380 (1960). (68F) Tilman, M. M., U. S. Bur. Mines Rept. Invest. No. 6591(2), 17 pp. (1965). (69F) Truman, J. E., Kirby, H. W., Metnllurgia 72 (430), 67 (1965). (70F) Tsinman, A. I., Kuzub, V. S., Sokolova, L. A., Znshchita Metal. 1 ( Z ) , 173 (1965) (Russ.). (71F) Tupholme, C. D., Bouchier, H. G. C., Iron Steel Inst. (London) Spec. Rept. 86, 238 11964). (72F) Warzee, M., Hennaut, J., Maurice, M., Sonnen, C., Waty, J., Berge, Ph., J. Electrochem. Soc. 112 (7), 670 (1965). (73F) Yurchenko, Yu. F., Avtomat.Svarka 18 (6), 41 (1965) (Russ.).

(54F) (55F) (56F) (57F) (58F)

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COATINGS AND PLATE (1G) Ades, L., Gulvanotech. Oberfaechenschuts 5 (101, 195 (1964) (Ger., Fr.). (2G) Anderton, W. A., O@. Di,!., J . Puint. Technol. Eng. 36 (477), 1210 (1964). (3G) Bache, H. J., Prod.Finishing (London) 18 (2), 62 (1965). (4G) Beacom S. E. Hardest D W., Doty, W, R . , Galuanotech. Ober~archenschults5 (7), 139, 16i (196;) ( G e r . , k . ) : (5‘2) Biestek, T., Pmce. Insf. Mech. Precyzyjnej 11, (1963) (Pol.). (6G) Ibid., p. 11. (7G) Blom, A. V., Korrosion 17, 58 (1963) (Ger.). (8G) Bruins, P. F., Chem. Engr. (London) 183, CE268 (1964). (9G) Rukowiecki, A . , Schriffenreihe Forsck. Gemeinrch. Schweiz. Lackfabrikanfen 1963, p. 177 (Ger.). (10G) Cerveny, L., Vychytil, P., Beranek, E., Korose Ochrana Mater. 1965 (2). p. 38 (Czech.). (11G) Domnikov, L., Metal Finishing 63 (31, 63 (1965). (12G) Elze, J., Korrosion 16, 227 (1963). (13G) Flint G. N., Melbourne, S. H., Proc. Australian Conf. Electrochem., Ist., Sydney, Hdbart, Airstralia 1963, 399 (1965). (14G) Garlock, J. P., et a/., Mater. Protect. 4 (9), 82 (1965). (15G) Ionescu, I., Enculescu, M., Ghinescu, P., Materiale P l a ~ t .2, ( Z ) , 91 (1965) (Rom.). (16G) Iskanderov, Z. M Kosmachevskii B. P. Vestn. Tekhn. i Ekon. Inform. Nauchn.-Zssled. Inst. Tekh‘;.-Ekon. Issled. Gds. Kom.’Khim. i Neft. Prom. pri Gosplone S S S R 1963 (lo), p. 46 (Rusa.). (17G) Jones, H. L., Cianciarulo, A. N., Chem. Eng. Progr. 61 (4), 65 (1965). (18G) Karabiberov, S., Bartonicek, R., Korose Ochrona Mater. 1965 ( l ) , p. 13 (Czech.). (19G) Karagounis, C., Thuemen, G., Werkstojfe Korrosion 16 (6), 490 (1965) (Ger. ). (20G) Kerle, E. J., Chem. Eng. Progr. 61 (4), 74 (1965). (21G) Leitheiser R . H Dalluge, M . D., ACS Div. Org. Coatings, Plastics Chem., Preprints 23 (2;, 301 (i963). (22G) Leitheiser, R. H., Dalluge,. M. D., Proc. Am. Petrol. Inst. Sect. III 44, 154. discussion 163 (1 964). (23G) McKenzie, M. G., Mater. Protect. 4 (4), 40, 43, 45 (1965). (24G) Maestri, Daniel, Talbot, Jean, Compt. Rend. 260 (25) (Groupe 7), 6606 (1965) (Fr.). (25G) Matantsev, A. I., Falicheva, A. I., Korzon, N. A., Zh. Prikl. Khim. 37 (ll), 2426 (1964) (Russ.). (26G) Mayne, J. E. O., Trans. Inst. Metal Finishing 41 (4), 121 (1964). (27G) Munger, C. G., Paint Varnish Prod. 54 (10) 59 (1964). (28G) Newton, D. S., Sampson, F. C., J . Oil Colour Chemists’ Assoc. 48, 383 (1765). (29G) Oono, M., Matsunaga, T., Kagaku Kogaku 27 (lo), 709 (1763) (Japan.). (30G) Orman, S.,Walker, P., J . Oil Colour Chemists’ Assoc. 48, 233 (1965). (31G) Popova, I. N., Slepova, E. Z Tr. Proektn. Tekhnol. i Nauchn.-Isslcd. Inst. Volgo-Vyotsk. Sou. Nor. Khor. 1963 (;j, 14 (Russ.). (32G) Raub, E., Disam, A., MetalIoberJaeche 19 (61, 173 (1965) (Ger.). (33G) Reidt, M. J., Metolen 19 (8), 216; (9), 258 (1964) (Dutch). (34G) Remizov, A., Z h . Obshch. Khim. 34 (lo), 3187 (1964).

VOL. 5 8

NO. 1 1

NOVEMBER 1 9 6 6

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(35G) Rozenfel’d, I. L., Rubinshtein, F. I., Lakokrasochnye Materiaiy i ikh Primenenid 1965 ( l ) , p . 4 0 (Russ.1. (36G) Rudram, A. T. S., Warner, L. M., Met. Res. 9 (34), 179 (1964). (37G) Schlitt, F. W., Linde Be,. Tech. Wiss. 1964 (l?), p. 49 (Ger.). (38G) ShkatuJov, D. R., Podval’nyi, A. hf., Prom. Stroit. 42 (5), 25 (1965) (Russ.). (39G) Teindl, J., Vondrasek, V., Sb. Ved. Praci Vysoke Skoly Banske Ostraoe 10 (3), 271 (1964) (Czech.). (40G) Teindl, J., Sb. Ved. Praci Vysoke Sko!? Bonske Ostraoe 10 (3), 265-70 (1964) (Czech.). (41G) Turner, I . T . , Plating52 (7), 677 (1965). (42G) Ueda, Y., Bosiioku Gijutru 13 (12), 532 (1964) (Japan.). (43G) Verma, S. S., Cenlra! Glass Ceramic Res. Inst., Bull. (India) 12 ( l ) , 38 (1965). (44G) West, P., Mater. Design Eng. 61 (l), 9 2 (1965). (45G) Williams, B. J., 2‘roductFinishin.e (London) 18 ( 7 ) , 52 (1965). (46G) Winnicki, R., Przemys! Chem. 44 (7), 391 (1965) (Pol.). (47G) Zamyshlyaeva, .4.M., Slozina, G. Z . , A s j d ’ t Gidroizoiyatsii Sb. 1963, p . 372 (Russ.).

NONFERROUS METALS

Alkali Metals, Amalgams, Rare Metals (1H) Chandler, W. T . , Hoffman, N. J., AD 405432, avail. CFSTI, 183 pp. (1963). (2H) Hurlen, T., Electrochim. Acta 9 ( 1 1 ) 1449 (1964). (3H) Judge J. S Morrison, J. R., Speliotis, D. E., Bate, G., J . Electrochem. Soc. 112 (7), 661 (16i5). (4H) Klima, S. J., Smith, T.V. F., Sokolowski, T., Elertrochem. Technol. 9 (7-E), 198 (196.5). (5H) Madi, I., Nature 205 (4968), 278 (1965). (6H) Matveev, 0. A., Tarkhin, D. V., Pribory i Tekhn. Eksperim. 9 (3), 217 (1964) (Russ.).

(7H) Mes’kin, V. S., Metallooed i Term. Obrabolka Metal. 1965 (7), p. 46 (Russ.). (8H) Monien, H., Werkstoj/e Korroszon 16 ( Z ) , 127 (1965) (Ger.). (9H) Kejedlik, J. F., Vargo, E. J., Corrosion 20 (12), 384t (1964). (10H) Ne,jedlik, J. F., Vargo, E. J., Electrochem. ?echnol. 3 (9-lo), 250 (1965). (11H) Nrjedlik, J. F., Vargo, E. J., U.S. Atomic Energy Comm. CONF-492-3, 3 0 p p . (1964). (12H) Niles, W. D., Siegmund, C. W., Mrrh. Corrosion Fuel Impurities, Proc. Intern. Conf,, Mnrchwood near Soulhamptotr, Hampshire, p. 332 (1 963). (13H) Pechmtkovskii, E. L . , Zoshchtln M e l d . 1 (4), 401 (1965) (Russ.). (14H) Reid, W. E., Jr., J . Phys. Chem. 69 (7) 2269 (1965). (ISH) Rickert, H., Korrosion 16, 85 (1963) (Ger.). (16H) Spiller, K . H., Alomkernenergie 10 (5/6), 215 (1965) (Ger.). (17H) Studt P. I.., Rehn, I . M., Jouthas, J. T., AEC Accession No. 929, Rept. N o . NP-14434,’avail. AEC, 513 pp. (1963). (18H) Toshima, S., Okinaka, Y., Ichimura, M., Adaniya, T., Denki Kagnkil 32 (6), 441 (1964) (Japan.). (19H) \Vang, J. Y., N., U. S. Atomic Energy Comm. ANL-7006, 12 pp. (1965). (20H) Weeks, J. R., Zbid., NASA-SP-41, 6 pp. (1965).

A1um inum (21H) Arora, 0. P. University Microfilms (Ann Arbor, Mich.), Order No. 657066,49 pp. (22H) Bird, D. B., Flournoy, R . W., Mater. Pro!etl. 3 ( l l ) , 58 (1964). (23H) Blervett, R. V., Skerrey, E. JV., Miinlluroin 71 (424), 73 (1965). (24H) Camphell, H. S., J . Ins!. M e t a l s 93 (4), 97 (1964). (25H) Cherepakhova, G . L., Klinov, I. Ya., Shrider, A . V., T r . M o s k . Inst. Khim. Moshinoslr. 28, 117 (1964) ( R ~ s s . ) . (26H) Chi5holm, S. L., M o t e r . Protecl. 4 (4), 48 (1965). (27H) Csanady, A , , Strausz, T., Wollitzer, G . , Hirndmiech. Ipori Kulato Znt. Kozemen. 5 (11, 5 (1965) (Hung.). (28H) Dionis’ev, S. D., Antropov, L. I., Diagrammy Plaukosti .Vekotorykh Solebykh Szrtrrn Sb. 1964, p . 60 (Russ.). (29H) Di Russo, E., Lenzi, P. L.,Prati, A,: Ailuminio 33 ( l l ) , 557 (1964) (Ital.). (30H) D i Russo, E., Prati, A., Ibzd., 31 (5), 229 (1962) (Ital.). (31H) Erben, A. R , , Maler. Protect. 4 ( 8 ) , 18 (1965). (32H) Erstling, R., Cherniker 2.8 6 , 889 (1962) (Ger.). (33H) Fishgang, F. Z . , Izu. Vpsshikh L’chebn. Zooedenii, Nej! i . Gaz 8 (3), 50 (1965) (Russ.). (34H) Flournoy, R . W.; Mater. Protect. 3 ( l l ) , 45 (1964). (35H) Gauvry, R . , RZLEM Bull. No. 24, 61 (1964) (Fr,). (36H) Gleekman, L. W‘.,Modod.Mefals 21 (21, 62 (1965). (37H) Grundig, W.,M e ! . Assoc. Bmrii. ,Wetnils 21 (87), 135, discussion 145 (1965) (Port.). (38H) Guilhaudis, A., RILEM Bu!!. No. 24, 71 (1964) (Fr.). (39H) Gutzeit, J., Mater. Protect. 4 (7), 28 (1965). (40H) Hendey, N. I., Bri!. Myrol. Soc., Trans. 47, 467 (1964). (41) Hewes, F. W., Oilzvek 16 (24), 37 (1965). (42H) Zbid., (25), pp. 38, 40. (43H) Hines, J. C., Allurninio 34 (S), 231 (1965) (Ital.). (44H) Izmailov, A. V., Danilova, N. N., Izo. Qsshikh Uchebn. Zauedenii, Pirhcheuap Tekhnol. 1963 (5), pp. 98 (Russ.). (45H) Jago R. Univ. Microfilms, Order No. 65-530, 170 p p , ; Disserfniion Abstr. 25 (lo), s’SlO’(1965). (46H) Karlashov, A. V., Tomnikov, Yu. V., Fzz.-K/tim. Mekhon. Mnterinlou, Akod. Nauk U k r . SSR 1 ( Z ) , 188 (1965) (Russ.). (47H) Leoni, M . , L u f t , G., Alluminio 30 (4), 185 (1961) (Ital.). (48H) Lepina, L., Vaivade, A., Lotuijas PSR Tinatnu Akad. Vestis, Kim.Ser. 1964 (5), pp. 527 (Russ.). (49H) Lichtenherger, E., iMunnyug 2 (5), 15001 (1965) (Hung.). (50H) Llowarch, D., Corrosion Sri. 5 (P), 663 (1965). (51H) I.orking, K . F., Commonwealth, Dept. Supply Aeron. Res. Lab., Repl. MET 55, 13 pp. (1964). (52H) Luft, G., Alliuminio 30 (9), 401 (1961) (Ital.). (53H) Martin, G., M a t e r . Protect. 4 ( E ) , 23, 26 (1965).

42

INDUSTRIAL A N D ENGINEERING CHEMISTRY

(54H) Miller, P. D., Stephan, E. F., Sriegelmeyer, W Atomic Energy Comm. BMI-X-316, 13 pp. (1964). (55H) Monfore, G . E., Ost. B., Res. Deuelop. Lob. 7 (11, 10 (1965). (56H) Mor, E . , Luft, G., Alluminio 30 (6), 299 (1961) (Ital.). (57H) Nakamura, K., Genrhlrpku I 972,072 (7 Oct. 1964).

Netherlands (178K) Aktien=esellschaft Brown Boveri 8; Cie. “Coating resistant t o corrosion and heat for met&” Neth. Patent i89,OZO (25 M&h 1965). (179K) Beer, E . , Beer, H. J., “Electrode system for the prevention of corrosion of metals In electrolytes,” Neth. .4ppl. 288,527 (10 hlarch 1965). (180K) Beer. E., Beer, H . J . , “Prevention of corrosion of metals in electrolytes,” Ibid.. 287,931 (10 Ivlarch 1965). (181K) Deutsche Gold- und Silber-Scheideanstalt vorm. Roesslcr, “Preventing acid dew point corrosion of and deposits in rhe colder parts of combustion apparatus,” Zeth. Patent 6,401,084 (14 Aug. 1964). (182K) Firma August Klueber, “Corrosion protection of metallic water-carrying systems,” Neth. Appl. 6,412,541 (3 May 1965). (183K) Geigy Co., Ltd., “Purification of benzotriazole,” Neth. Pateni 6,408,573 (28 Jan. 1965). (184K) F g y , J. R., .%.-G.>“Corrosion inhibitor for heat-transfer and hydraulic fluids, Ibid., 6,400,949 (7 Aug. 1964). (1 8SK) Grigy, .I. R., A.-G., “Preparation of 5-subsiituted benzotriazoles.” Neth. Appl. 6,414,144 (6 Dec. 1964). (186K) Hoechsr, F., A . G . , “Corrosion inhibitors for brake fluids,” Neth. Patent 302,392 (25 June 1964). (187K) Hooker Chemical Corp., “Heat storage and transport media,” Ibid., 6,414,337 (10 June 1965). (188K) Imperial Chemical Industries, Ltd. “Corrosion inhibiting additive for cooling water of engins,” Neth. Patent 6,460,470 (23 July 1964). (189K) Imperial Metal Industries (Kynoch) Ltd., “Active anode and electrolytic cell,” Ibid., 6,402,526 (14 Sept. 1964). (190K) Magneto-Chemie, N. V., “Corrosion resistant electrode,” Ibid., 108,009 (15 April 1964). (191K) Mallorv Batteries Lrd. “.4lkaline secondary cell with an amalgam anode,” Ibid., 6,400,259 (17 July’l964$. (192K) Monsanto Co., “Srahilization of poly(pheny1 ethers),” Zbid., 6,402,494 (14Sept.1964). (193K) N . V. Research Holland, “Corrosion-resistant composite nickel plating,“ Neth. Appl. Patent 287,611 (25 Feb. 1965).

(194K) N. V. Research Holland, “Corrosion resistant nickel chromium plating,’’ Ibid.,287,612 (25 Feh. 1965). (195K) Raytheon Co., “Sea water resistant coatings,” Zbid., 6,408,317 (25 Jan. 1965). (196K) Rohm and Haas, Co., ,“Corrosion inhihitors,” Ibid., 6,401,002 (10 Aug 1964). (197K) Shell Internationale Research Maatschappij N. V., “Applying a corrosionresistant layer on a wet surface or on a surface under water,” Neth. Appl. 6,412,887 (6 May 1965). (198K) shell Internationale Research Maatschappij N. V., “Protecting chemical reactorsfrom corrosiv- vapors,” Neth. Appl. Patent 6,402,134 (7 Sept. 1964). (199K) Societe General d u Vide, “Protective coating,” Neth. Appl. Patent 6,400,547 (27 July 1965). (200K) Socony Mobil Oil Co., Inc., “Corrosion inhibition in lubricating greases,” Neth. Appl. 6,412,692 (3 May 1965). (201K) Union Carbide Corp., “Organosilicon compounds,” Ibid., 6,409,873 (1 March 1965).

Norway (202K) Brun J., “Prevention of iron sulfide formation on iron contact bolts in carbon anohes for aluminum electrolysis,” Norw. Patent 104,752 (25 July 1964).

Poland (203K) Kiewlicz, W., Kiewlicz, J., “Anticorrosion agent for steel,’: Pol. Patent 48,202 (30 April 1964). (204K) Kra‘ewski S. “Galvanizer for anodizing,” (to Instytut Mechanaki Precyzynej), fbid., 48,6!h (24 Nov. 1964). (205K) Ligezowa, S., Patzau, S., “Protective coatings for roller bearings,” (to Instytut Mechanaki Precyzynej), Ibzd., 48,772.

United States (206K) Andress, H . J., Gee, P. Y. C “Multipurpose distillate fuel additives,” (to Socony Mobil Oil Co.), U . S. Patezt 3,199,965 (Aug. 10, 1965). (207K) Bertea, O., Gross, J . R., Seagle S. R. “Strong corrosion-resisting zirconium alloys containing niobium,” (to ’Natio;al Distillers and Chemical Corp.), Ibid.,3,205,070 (Sept.?, 1965). (208K) Bishop, C. R., B y c h W. J., “Corrosion-resistant nickel-base alloys for elevated temperatures, (to’ Union Carbide Corp.), Zbrd., 3,188,204 (Oct. 7, 1965). (209K) Bloom, M . C., Krufeld, M., Newport G . N., “Protective film formation in high pressure steam generators,” (to U. S. dovernment), Z62d., 3,173,404 (March 16. 1965). (210K) Boiselle A. “Allenic phosphinyl compounds,” (to Lubrizol Corp.), Zbid., 3,189,636 (J&e 115, 1965). (211K) Braunwarth, J. B., Kimble, R . C . , Joo, L. A “Detergentsnoncorrosive t o metal surfaces,” (to Pure Oil Co.), Ibtd., 3,200,078 %up. 10, 1965). (212K) Budde W. M “Sulfurization of Schiff base,” (to Archer-Daniels-Midland Co.) Ibid., 3,i13,076’(Oct. 19, 1965). (213K) Canevari G . P. “Sacrificial anode bonded with epoxy resin,” (to Esso Research and 6nginee;ing Co.), Zbid., 3,202,596 (Aug. 24, 1965). (214K) Carlton R . H., “Retarding corrosion in heat exchangers,” (to Universal Oil Products bo.),Ibid., 3,189,537 (June 15, 1965). (215K) Chittum, J. F., Schremp, F. W., “Inhibiting Oil Well corrosion by mixtures offerrocyanides borates and molybdenum salts,” (to California Research Corp.), Ibid., 3,182,018’(May 4,’1965). (216K) Cizek, A , , ‘‘Fuel Oil compositions containing an N-alk 1 aminopropionitrile salt of an alkyl phosphoric acid ester,” (to Armour and eo.), Zbid., 3,207,586 (Sept. 21,1965). (217K) Clayton J. O., “Multipurpose ashless detergent lubricating oil additives,” ( t o California’Research Corp.), Ibid., 3,185,645 (May 26, 1965). (21RK) Copson, H . R Lans, F. S ‘(Stainless steel resistant t o stress corrosion cracking,” ( t o InterAAtional Nickei’Co.), Ibid., 3,159,479 (Dec. 1, 1964). (219K) Coyne, D. hl., Riggs, 0. L “Corrosion inhibition (unsaturated diol-polyalkylene polyamine condensation) products),” (to Continental Oil Co.), Zbid., 3,211,667 (Oct. 12,1965). (220K) Creech, B. C . , Collings, L. V., Shapiro, P., “Complex arsenic compound acts as corrosion inhibitor in a ueous ammoniacal solutions,” (to Sinclair Research, Inc.), Ibid., 3,168,392 (Fet. 2, 1965). (221K) Cupper, R . A Wofl C A., “Urea corrosion inhibitor for ester lubricants,” (to Union Carbide 8orp.),’Ib;d., 3,164,553 (Jan. 5 , 1965). (222K) Dooley, K . J., Thomson, H. C “Corrosion resistant coatings,” (to Du-Lite Chemical Corp.), Ibid.. 3,189,673 (A:g. 3,1965). (223K) Du Rosr, A. B., Stern, R . L., “Duplex deposits of sulfur containing nickel,” (to Harshaw Chemical Co.), Ibid., 3,183,067 (May 11, 1965). (224K) Dudd J. C “Preparation offuel cell electitjdes,” (to the Electric Storage Battery Co.f Zbid.:’3,171,757 (March 2, 1965). (225K) Dvoracek L. M., Neff L L., “Corrosion prevention,” (to Union Oil Co. of California), Zbih., 3,162,550 ’(Dkc. 2 2 , 1964). (226K) Emrick, D. D., “Multifunctional gasoline additives,” (to Standard Oil Co. of Ohio), Ibid., 3,157,477 (Nov. 17, 1964). (227K) Ender, H., “Corrosion inhibiting amino-organosilicone-epoxy finishing compositions,” (to Union Carbide Corp.), Ibid., 3,166,527 (Jan. 19, 1965). (228K) English J. B “Aluminum alloys for best reflectance when anodized,” (to Reynolds Meials Cb’.), Zbid., 3,187,428 (June 8, 1965). (229K) Ernst R . B. “Pi erazinoalkylamides of polybasic carboxylic acids,” (to Textila;a, Gorp.), Zbil, 3,167,554 (Jan. 26, 1965). (230K) E u p n k , L. D., “Aluminum-silicon alloy coatings for uranium nuclear fuel rods, (to U. S. Atomic Energy Commission), Zbid., 3,211,628 (Oct. 12, 1965). (231K) Field J. H Bienstock D . “Corrosion inhibition in purifying gases,” (to U. S. DLpt. of ;he Interior): Ibi;., 3,181,929 (May 4, 1965). (232K) Fowler, R . M . Bishop C R “Corrosion resistance of stainless steel,” (to Union Carbide Cdrp.), Ibih., 3,19$,715 (Aug. 3,1965). (233K) Frank, ,S. M “Reducing corrosion in hydrogen production,” (to the Pullman Co.),Zbid., 3,150,931 (Sept. 29, 1964). (234K) Freedman A. J. “Water treatment compositions,” (to Nalco Chemical Co.),Ibid.,3,17i,864 (March16, 1965). (235K) Gault, F. M., “Brazing or soldering fluxes containing phosphate for preventionofcorrosion,”Zbid., 3,156,041 (Nov. 10, 1964). (236K) Gee, P. Y. C., Andress, H . J., “Multifunctional fuel oil additives,” (to Socony Mobil Oil Co.), Ibid., 3,192,160 (June 29, 1965).

(237K) Gerjovich, H. J . , “N,N-Dialkyl-N’-arylamidines,” (to E. I. du Pont d e Nemours & Co.), Zbtd., 3,189,648 (Junc 15, 1965). (238K) Green, U. S., “Water conditioner for scale prevention,” (to Aquatron Engineering Corp.), Zbid., 3,202,601 (Aug. 24, 1965). (239K)’Guarnaccio, A. J., Latos, E. J., “Amine salts of oxyalkylenated hydroxy hydrocarbon phosphates for improving lubricants,” (to Universal Oil Products Co.),Zhid., 3,169,923 (Feb.16, 1965). (240K) Handwerk, J. H., White, G . n., Shalek, P. D., “Uranium monosulfidemonocarbide nuclear fuel element,” (to U. S. Atomic Energy Commission), Zbid.,3,194,745 (July 13, 1965.). (241K) Harkins, T.R., Zaremski, D. R . , “Preparation of stainless steel automobile body trim for good corrosion resistance of body and trim,” (to Allegheny Ludlum SteelCorp.),Zbid.,3,201,210(Aug. 17, 1965). (242K) Harpster N.H . “Nonroping chromium ferritic stainless steels and their products,’ (to bniversal-Cyclops Steel Corp.), Ibid., 3,183,080 (May 11, 1965). (243K) Harpster N . R “Stainless steels for outdoor exposure,” (to UniversalCyclops Steel do.), Ibih., 3,201,231 (Aug. 17, 1965). (244K). Hedlund, R . C “Corrosion rcsistant organosilicon coatings,” (to Dow Corning Corp.), Zbid., $,175,921 (March 30, 1965). (245K) Henricks J A., “Zinc phosphate coating compositions,” (to G. D. Henricks), Ibid., 3,178,319’(Aprill3, 1965). (246K) Hollin sworth E. H. “Strong aluminum alloys colored yellow by anodizing,” (to %umin;m Co. i f America), Zbid., 3,180,806 (April 27, 1965). (247K) Huber F. Blomgren M . S., “Fabricating a capacitor,” (to Philco Corp.), Zbid., 3,179,5$6 (April 20, 1665). (248K) Hutchinson, M . , Riggg, 0. L., J r . , Sudbury J. D. “Electrolytic bridge assembly for the anodic passivation of metals,” (t: ContiAental Oil Co.), Zbid., 3;152,058 (Oct. 6, 1964). (249K) Joo, L. $. Kramer W. E Kimhle R . I?., “Detergents noncorrosive t o metal surfaces, (to Pure Oil Co.,yIbid., 3,;00,079 (Aug. 10, 1965). (250K)’ Jorda, R. M. “Treating water-wetted surfaces with corrosion resistant coating material,” (;o Shell Oil Co.) Zbid., 3,159,499 (Dec. 1, 1964). (251K) Kesaler, S., “Craze rcsistant anodized aluminum,” (to Kaiser Aluminum and Chemical Co.), Zbid., 3,175,963 (March 30, 1965). (252K) Keyes H E “Rrcovering copper f r o m sulfate solutions by replacement with iron,” ibid: 3;i94,635 (July 13, 1965). (253K3) KiFmel, A. L “Phosphate trcatment composition for iron and steel Droducts., (.t o Marsh’kteel and Aluminum Co.). (.June 29. 1965). ., Ibid.., 3.192.075 , , . (254K) Kirby B. H Jr., James T., “Lightfast dycs for anodized aluminum,” Ibid., 3,172,?86 (M&h 9, 1965). (255K) Kirkpatrick, W. H., Seal?, V. L., Noe, H . C., “Salts of partial amides of alk 1Pnepolyamines with polyethylenc glycol chlori.de for inhibiting corronion of &rous metals by crude oil,” (to Nalco Chcmiral Co.), Zbtd., 3,201,430 (Aug. 17, 1965). (256K) Klingenmaier, 0. J., “Sealing anodized coatings on aluminum,” (to General Motors Corp.), Ibid., 3,171,797 (March 2, 1965). (257K) Little, R. Q., Deluga, S. S. “Sulfur corrosion ihhihitor,” (to Standard Oil Co., Indiana), Zbid., 3,139,545 (June 15, 1965). (258K) Lloyd G. R “Corrosion clectro- otentiometrr probe,” (to Esso Research and Enginehriog &.), Ibid., 3,166,485 (pan. 19, 1965). (259K) Lowe W “Lubricants containing metal-free detergents for reducing corrosion,” (to’caiifornia Research Corp.), Zbid., 3,184,411 (May 18, 1965). (260K) Lutz, C. .WJ, “Liquid fertilizers inhibited against corrosion,” (to F M C Corp.), Zbtd., 3,199,301 (July 28, 1965). (261K) Maissrl, L. I. “Capacitors and capacitive circuit elements,” (to International Business M a c k n e s Go.),Zbid., 3,190,819 (June 22, 1965). (262K) Marsh,,, G . A., Littler, R . I , ~“Method , and apparatus for estimating corrosion rates, Zbid., 3,197,388 (July 27, 1965). (263K) Marsh, G . A,, Scharchl, E., “Anodic protection,” (to Pure Oil Co.), Zbid., 3,186,931 (June 1,1965). (264K) McCord, A. T . , “Additives t o reduce corrosion and deposits in boilers due to vanadium compounds in fuel,” (to Carborundum Co.), Zbid., 3,205,053 (Sept.7,1965). (26510 Michael, H.J “High-temperature ceramic protective coating,” (to North American Aviation,’inc.), Zbid., 3,175,920 (hlarch 30, 1965). (266K) Neish R . A. “Corrosion rcsistant phosphate-chromate coatings for steel,” (to United h a t e s i t e e l Cdrp.) Zbid., 3,160,532 (nec. 8, 1964). (267K) Nelson J. W “Rust inhibitor for light dietillate fuels,” (to Sinclair Research Inc.),’Zbid., 3,’190,734 (June 22, 1965). (268K) Nielsen, M . L., “Amine salts of trimctxphosphimic acid,” (to Monsanto Co.),Zbid.,3,185,733 (May 25, 1965). (269K) Pirotte, E., “Alkylated and arylatrd thioureas used as acid pickling corrosion inhibitors ” (to VCB-Union Chimique-Chemische Bedrijven-Societe Anon.),Zbid.,3,18’8,292 (June8, 1965). (270K) Prapas, A. G . ,“Monohydrazinium salts of hydroxypolyalkoxyalkylalkylenediamines,” (to W. R. Grace & Co.), Zbid., 3,189,653 (Jun? 15, 1965). (271K) Prieser, H . S., Cook F. E . , “Corrosion-erosion-cavitation protection for marine propellers,” (to E&o Research and Engineering Co.), Zbid., 3,169,105 (Feb. 9,1965). (272K) Pryor M. J. Keir, n. S S erry P. R., “Aluminum-tin alloy anodes for preventing dorrosidn of steel,” (io 81in Mathieson Chemical Co.), Zbid., 3,180,728 (April 27, 1965). (273K) Pryor, M . J., Sperry, P. R., Krir, D. S., “Aluminum-tin sacrificial alloys for preventing galvanic corrosion of steel,” (to O h - M a t h e i s o n Chemical Co.), Zbid.,3,186,836 ( J u n c l , 1965). (274K) Rai C Braunwarth, J. R “Mineral lubricating oil compositions,” (to P u r e O i l &.j,’Ibid., 3,175,974 (M&h 30, 1965). (275K) R i gs, 0. L., “Acidizing corrosion inhibitor,” (to Continental Oil Co.), Zbid., 3,1$7,403 (July 27, 1965). (276K) Rogier, E. R . , “Cyanoeth lated amino hydroxy nitriles,” (to General Mills, Inc.),fbid., 3,157,689 (Nov. 17, r964). (277K) Rogier, E. R., “a-Aminopropylaminohydroxalkyl amines,” (to General Mills, Inc.),Z>id., 3,169,991 (Feb. 16, 1965). (27RK) Rudel, H . W., Seits, W., “Polyhydric alcohol esters of alkyl mercapto fatty acids as ruht preventivc additives for lubricating oils,” (to Esso Research and Engineering Co.), Ibid., 3,158,576 (Nov. 24, 1964). (279K) Rust, F. G “Stainless steel corrosion reduction,” (to U.S. Atomic Energy Comm.),Zbid., 3,?74,818 (March 23, 1965). ( 2 8 0 K ) Scanle,y, C. S., Siegle, F. H “CorroRion inhibitors,” (to American CyanamidCo.),Ibid.,3,172,854 (March;, 1965). (281K) Scharfstein, L. R . “Alloy steels resistant t o stress corrosion cracking,” (to Carpenter Steel Co.),ibid., 3,168,397 (Flh. 2,1965). (282K) Schaschl, E . , Marsh, 0. A., “Anticorrosive back-fill,” (to Pure Oil Co.), Ibid.,3,192,720 (July6, 1965).

VOL. 5 8

NO. 1 1

NOVEMBER 1 9 6 6

47

(283K) Sexsmith, D. R., Frazza, E. G., “Haloalkvl styrene-phosphine copolymers for coatings, paper sizing, and textile treatment,” ( t o American Cyanamid Co.), Ibid., 3,168,502 (Feh. 2, 1965). (284K) Shaoiro P. Collings L. V Counts T. 0 “Corrosion protection,” (to Sinclair Rbse&ch,’Inc.), Ibth.,3,1Q6,455 (Feb. 2, 19i’S). (285K) Sheldahl, D. €I“Disulfonatc ., fatty diamine salts of dicarboxylic acids as corrosion inhibitors in mineral acids,” ( t o Sinclair Research Inc.), Ibid., 3,153,171 (Oct. 13, 1964). (286K) Shepard, J. W., Shely, B. L., “High-contrast films for radiation photography,” (to Minnesota Mining and Manufacturing Co.), Ibid., 3,172,828 (March 9 , 1965). (287K,) Smith E. J. Vucich M . G. Austin L. W. “Aluminum-manganese alloy .Diatrnp.,” - (tdNatidna1 Steei Corp.),’Ibid., 33167,408 (Jan. 26, 1965). (288K) Spivack J . P., “Primary amines containing tertiary amino groups,” (to Geigy Chemich Corp.), Ibid., 3,201,472 (Aug. 17, 1965). (289K) Sreinberg, H., Hunter, D. L.,, Pickard, M. H., Petterson L. L. “Glvcoi monoborate salts as corrosion inhibitors for brake fluids,” (to S . Bbrax and Chemical Co.), Ibid., 3,163,506 (Dec. 29, 1964). (290K) Storcheim S. “Corrosion resistant strip from powdered iron ” (to Alloy Research 8; Ma4ufa)cturing Go.), Continuation-in-part of U. S. P a t e i t 3,163,527. (291Kj StromberR, W. I,., “C,orrosion inhibitor for oil wells,” ( t o Petrolite Corp,), U. S . Patent 3,200,071 ( h u g . 10, 1965). (292K) Strombcrg, V. L I‘Ester amide acid compounds as corrosion inhibitors,” (to Petrolite Corp.), I&;., 3,172,853 (March 9 , 1965). (293K) Tomono R. “Chromate processes,” ( t o Okuno Chemical Industry Go.), I b i d . , 3,259,506 (D&. I , 1964). (294K) Tousi-nant W. F “Oxazoles and Thiazoks,” (to Dow Chemical Co.), Ibtd.,3,1.52,?41 (Oct. 6, i b 6 4 ) . (295K) Udelhofen J. H. “Corrosion inhibitor oils,” (to Stand3rd Oil Co., Ind.), Ibid., 3,123,634 ( M a d 3, 1964). (296K) Udelhofen J. H. “Corrosion inhibitors for gasolinrs,” (to Standard Oil Co. of Ind.), Ibih., 3,189,069 (May 11, 1965). (297K) Van Poolen, H . K . “Corrosion inhibition l o petroleum production,” (to Marathon Oil Co.), Ibid.,’3,194,314 (July 13, 1965).

e.

(298K) White, J. C., Schuldiner, S . , “Fuel cell anode,” (to U. S. Dept. oItheNavy), Ibid., 3,183,122 (May 11, 1965). (299K) Wick, W. C.. “ H a r d nickel-base alloys for valve seat liners,’’ (to Wells Manufacturing Co.), Ibid.,3,167,424 (Jan. 26, 1965). (300K) Williams D “Design of fuel elements or nuclear reactors ” (to United Kingdom AtoAic h r g y Auihority), Itrid., 3,157,580 (Nov. 17, 1924). (301K) Wright, C. S . , “Boron phosphate esters as gasoline adaitivcs,” (to Pure Oil Co.), Ibid., 3,158,452 (Kov. 24, 1964). A., “Phosphating process and composition,” (to Purex Corp. (302K) Yager, Ltd.), Ibid., 3,181,976 (May 4, 1965).

U.S.S.R. (303K) Efimova, A . K., Shatunova, A. M., Sapoznikova E. A . “Preparation of corrosion inhibitor for metals,” (to Scientific-Research’Institdte for Petroleum Kefining), L.S.S.R. Patent 166,428 (19 K o v . 1964). (304K) Golyanitshii, 0. I., “Protection of metals from atmospheric corrosion with the aid of quaternary ammonium bases,’’ Ibid., 168,577 (18 Feb. 1965). (305K) Lipin, A. I., Golovkina N. P “Increaqing the anticorrosion protection of steel parts.” Ibti.. 169.’969 (17 Iharch 1965). --,. .phosphatized . , (306K) A‘egreev, y. F., Kydzimov A . hl. “Protrction of aluminum and its alloys from corrosion in alkaline media,” Ibid.: 167,115 (12 Dec. 1964). (307K) Segreev, V . F., Mamedov, I. A., Kotel’nikov, B. P., Divenko, A. P., “Corrosion inhibitors,“ Ibid., 168,827 (26 Feb. 1965). (3??K) Shtern M . A . , Danyushevskaya X. E . , Alekseeva, 0.V. Bogatyrev P. M Preparationi of calcium chromate-& anticorrosion pigment‘” (io stat6 ScieAl tific-Research and Design Institute of the Paint and Varnish Industry), Ibid., 167,592 (18 Jan. 1965). (309K) Smirnova, T. N.:,Zuhakhin, B. T., D’yakova, L. P., “Preserving articles made of ferrous metals, Ibid.,165,958 (26 Oct. 1964). (310K) Tkachepko, S. D., Rovinskii, E. A , , ‘‘Stirrer for mixing a hot, predominantly corrosive liquid,” (to Scientific-Research and Project-Technological Institute for the Automization and Mechanization of Machine Building, South Ural Council of h-ational Economy), Ibid., 169,497 (17 March 1965). I

,

.

~~

COR R ECTl ON Due to a publisher’s error, the following corrected derivation was not included in the paper, “Reaction Mechanisms for Engineering Design,” appearing in Vol. 58 (9), 21 (1966). T h e following substitution should be made between Equations 11 and 21, inclusive: If no products are initially present, the first case gives the Laplace transforms for [ B ]and [ C] as follows :

Moreover, if

k3

>> kz’,

it is reasonable to suppose that

F is present in undetectably small amount, and that the quasisteady-state approximation can be applied. We thus find for the intermediate F:

d[Fl = kn’[B] - k3[F] = dt

0

or

where s is the Laplace transform variable and A. is the initial concentration of A .

Then

and the concentration of the final product [C] is given by

which leads to the Laplace transform

I n the second case C(s) = S(S

+

A okikz ’k3 kd(s 4-kz’)(s

+

(1 4) k3)

Equation 14 is of different form from Equation 12, and [C] includes three exponential terms: [C] = A0

We note that Equation 1 9 is identical with Equation 12 in form, and thus the introduction of a n extra intermediate step along with the use of the quasisteady-state approximation leaves the form of [C] unaffected. The expression for [ B ]will not be affected either. I n the first case, we find

+ I n the second case,

However, if k 3 is much greater than k i and kz’, the solution for [C] reduces to Equation 13, where we take kz = kz‘. 48

INDUSTRIAL AND ENGINEERING CHEMISTRY

When kz‘ = kz, this is identical with Equation 20. Thus, only if F is directly observable, will it be possible to be sure of its kinetic significance.