Technical Note N-915 CORROSION OF MATERIALS IN HYDROSPACE PART IL -- NICKEL AND NICKEL ALLOYS BY Fred M. Reinhart August 1967 INTERNAL WORKING PAPER "This document has been approved for public release and sale; its distribution is unlimited." , / U. S. NAVAL CIVIL ENGINEERING LABORATORY Port Hueneme, California TN QS CORROSION OF MATERIALS IN HYDROSPACE. PART II - NICKEL AND NICKEL ALLOYS Technical Note N-915 Y-F015-01-05-002A by Fred M. Reinhart ABSTRACT A total of 635 specimens of 75 different nickel alloys were exposed at two different depths in the Pacific Ocean for periods of time varying from 123 to 1064 days to determine the effects of deep ocean environments on their corrosion resistance. Corrosion rates, types of corrosion, pit depths, effects of welding, stress corrosion cracking resistance, changes in mechanical properties and analyses of corrosion products of the alloys are presented, Of thase alloys tested, the following were practically immune to corrosion; nickel-chromium-iron alloy 718; nickel-iron-chromium alloys, except 902; nickel-chromium-molybdenum alloys; nickel-cobalt- chromium alloy; nickel-chromium-iron-molybdenum alloys; nickel- chromium-cobalt alloy; and nickel-molybdenum-chromium alloy. Alloys attacked by uniform or general corrosion were the cast nickel-copper alloys; nickel-molybdenum-iron alloy; and nickel-molybdenum alloy. Alloys attacked by crevice or pitting corrosion were the nickels; wrought nickel-copper alloys; nickel-chromium-iron alloys except 718; nickel-iron-chromium alloy 902; nickel-tin-zine alloy; nickel-beryllium alloy; nickel-chromium alloys; and nickel-silicon alioy. Corrosion resistance of welds in the nickel alloys depends upon the selection of the proper welding electrodes. The nickel alloys were not susceptible to stress corrosion cracking. Corrosion pro- ducts consisted of oxides, hydroxides, chlorides and oxychlorides. Mechanical properties of the alloys were not adversely affected in a significant way. The bottom sediments were less aggressive than sea water environ- ments and the lower oxygen content sea water was less aggressive than the higher oxygen content sea water. Each transmittal of this document outside the agencies of the U. S. Government must have prior approval of the U. S. Naval Civil Engineering Laboratory. won Ii 0301 0040 PREFACE The U. S. Naval Civil Engineering Laboratory is conducting a research program to determine the effects of deep ocean environ- ments on materials. It is expected that this research will establish the best materials to be used in deep ocean structures. A Submersible Test Unit (STU) was designed, on which many test specimens can be mounted. The STU can be lowered to the ocean floor and left for long periods of exposure. Thus far, two deep ocean test sites in the Pacific Ocean have been selected. Six STUs have been exposed and recovered. Test Site I (nominal depth of 6,000 feet) is approximately 81 nautical miles west-southwest of Port Hueneme, California, latitude 33°44'N and longitude 120°45'W. Test Site II (nominal depth of 2,500 feet) is 75 nautical miles west of Port Hueneme, California, latitude 34°06'N and longitude 120942'wW. This report presents the results of the evaluation of nickel and nickel alloys. INTRODUCTION The development of deep diving submarines which can stay sub- merged for long periods of time has focused attention on the deep ocean as an operating environment. This has created a need for information about the behavior of common materials of construction as well as newly developed materials with promising potentials, at depths in the ocean. To study the problems of construction in the deep ocean, project "Deep Ocean Studies'' was established. Fundamental to the design, construction and operation of structures, and their related facilities is information about the deterioration of materials in these deep ocean environments. This report is devoted to the portion of the project concerned with determining the effects of these environments on the corrosion of metals and alloys. The test sites for the deep ocean exposures are shown in Figure 1 and their specific geographical locations are given in Table l. The complete oceanographic data at these sites obtained during NCEL eruises from 1961 to 1967 are summarized in Figure 2. Because of the minimum-oxygen concentration zone found between the 2,000-3,000 foot depths during the early oceanographic cruises, it was decided to establish the second exposure site (STU TI-1 and II-2) at a nominal depth of 2,500 feet. A summary of the characteristics of the bottom waters 10 feet above the bottom sediments at the different exposure sites is given in Table 1. Sources of information pertaining to the biological character- istics of the bottom sediments, biological deterioration of materials, detailed oceanographic data, and construction, emplacement and re- trieval of STU structures are given in Reference l. The procedures for the preparation of the specimens for exposure and for evaluating them after exposure are described in Reference 2. Previous reports pertaining to the performance of materials in the deep ocean environments are given in References 1 through 6. This report is a discussion of the corrosion of nickel and some nickel alloys for the six exposure periods shown in Table 1. RESULTS AND DISCUSSIONS The results presented and discussed herein also include the corrosion data for the nickels and nickel alloys exposed on the STU structures for the International Nickel Company, Incorporated. Per- mission for their incorporation in this report has been granted by the International Nickel Company, Incorporated, Reference 7. Results from other participants in the NCEL study are also included, U. S. Navy Marine Engineering Laboratory (Reference 8) and Chemistry Division, NCEL (Reference 9). Deep ocean data from the Atlantic Ocean (References 10 and 11), surface data from the Atlantic Ocean (Reference 12) and surface data from the Pacific Ocean (References 13 and 14) are included for comparison purposes. NICKEL The chemical compositions of the nickels are given in Table 2, their corrosion rates and types of corrosion in Table 3, and changes in mechanical properties in Table 4. Nickel is passive (resistant). in moving sea water but is subject to local attack or pitting in stagnant sea water. Fouling organisms, deposits, and crevices cause pitting and crevice (oxygen concentration cell) corrosion. The corrosion rates and types of corrosion of seven nickels (94 percent minimum nickel) are given in Table 3. Crevice corrosion and edge corrosion (on the ends) were the two types which were respon- sible for practically all the corrosion damage. Corrosion rates calculated from weight losses are most meaningful and valuable when the type of corrosion is either uniform or general; therefore, cor- rosion rates for nickels would not be the best criteria for assessing corrosion. To obtain a complete evaluation of the corrosion of an alloy, corrosion rates, maximum and average pit depths, pitting fre- quency or pitting factor, type of corrosion, changes in mechanical properties, and resistance to stress corrosion cracking should be determined. In the case of the nickels, there was very little surface cor- rosion so little emphasis can be placed on corrosion rates. The two types of corrosion encountered (crevice and edge penetration) can be extremely damaging from the standpoint of reliability. The edge penetration was caused by the microcracks formed during the shearing operation which illustrates dramatically the corrosion damage which can be caused by this fabricating procedure. Penetration of as much as an inch during six months of exposure was found. For sea water applications, shearing or punching of holes should not be permitted; only sawing, machining or drilling. The Naval Applied Science Laboratory! reported that nickel 200 was practically unattacked after 199 days of exposure at a depth of 4,500 feet in the Tongue-of-the-Ocean (TOTO), Atlantic Ocean. This is in contrast to the results obtained in the Pacific Ocean where the corrosion rates in the water were low at both depths; from less than 0.1 to 0.7 MPY at 5,640 feet for 123 days and 0.5 MPY at 2,340 feet for 197 days, but there was crevice corrosion on nickel at both depths. Although the Naval Research Laboratory! reported concentration cell and pitting (average depth, 125 to 143 mils) corrosion of nickel 200 in surface sea water at Fort Amador, Panama Canal Zone, Pacific Ocean, the corrosion rate of nickel decreased with time of exposure as shown in Figure 3. However, as also shown in Figure 3, the cor- rosion rates of nickel 200 at a nominal depth of 6,000 feet in the Pacific Ocean increased sharply with time of exposure to 2 years and then decreased. After 2 years of exposure they are comparable with those for surface sea waters at Fort Amador. As previously emphasized, more weight must be given to concentration cell, crevice and pitting types of corrosion as a basis for recommending nickels for sea water applications than to corrosion rates calculated from weight loss determinations. There was no definite correlation between corrosion rates of most of the nickels at the nominal 6,000 foot depth and at the nominal 2,500 foot depth. Only cast nickel-210 and nickel-301 cor- roded at consistently slower rates at the 2,500 foot depth than at the 6,000 foot depth both in the sea water and in the bottom sedi- ments. At both depths these two nickels corroded at slower rates in the bottom sediment than in the sea water. The nickel containing 4.5 percent aluminum (nickel 301) was more susceptible to crevice corrosion than the other nickels. Cast nickel (nickel 210) was less susceptible to crevice corrosion than the other nickels but was attacked more by the pitting type of corrosion. The weld beads were preferentially corroded after 402 days of exposure at a depth of 2,370 feet in the sea water when nickel was welded by the inert gas welding technique using filler metal 61 and by the metal-arc welding technique using welding electrode 141. The preferential corrosion of filler metal 61 is shown in Figure 4. How- ever, in the bottom sediment the weld bead made with filler metal 61 was not preferentially corroded. Metallographic examinations of the weld materials and the ad- jacent-heatzaffected-zones showed no evidence of selective corrosion at grain boundaries. It is, therefore, concluded that the weld bead alloy was anodic to the parent nickel in the sea water but not in the bottom sediment. Nickel 200 was not susceptible to stress corrosion cracking when exposed at a depth of 2,370 feet for 402 days at tensile stresses equivalent to 50 and 75 percent of its yield strength (12,500 and 18,700 psi, respectively). Exposures for periods of time as long as 1064 days at a depth of 5,300 feet were not detrimental to the mechanical properties of nickel 200, Table 4, NICKEL-COPPER ALLOYS The chemical compositions of the nickel-cooper alloys are given in Table 5, their corrosion rates and types of corrosion in Table 6 and changes in mechanical properties in Table 7. The nickel-copper alloys have excellent corrosion resistance in sea water except that in slowly moving or stagnant sea water they are subject to pitting. This is particularly true if fouling orga- nisms are present and attach themselves to the metal. They are inherently passive, hence in environments deficient in oxygen this passivity is destroyed locally and they pit at these local anodes or corrode by oxygen concentration cell type of corrosion in crevices. The corrosion rates of nickel-copper 400 alloy at depth and at the surface in both the Atlantic and Pacific Oceans are shown in Figure 5. Even though there was both pitting and fouling of specimens in all surface exposures, the corrosion rates decreased with increase in duration of exposure. However, due to the higher average tempera- ture at the Panama Canal Zone, the corrosion rates there were three times as great as those at Port Hueneme, California and at Harbor Island, North Carolina. The corrosion rates at nominal depths of 2,500 and 6,000 feet in the Pacific varied with duration of exposure so that it was not possible to construct smooth curves. This vacillation of the cor- rosion rates is attributed to the pitting and crevice types of corrosion. The pitting of nickel-copper alloy 400 after 1064 days of exposure partially embedded in the bottom sediment at a depth of 5,300 feet is shown in Figure 6. The unpitted portion on the right was embedded in the bottom sediment; the pitted portion extended above the sediments. For this reason the corrosion rates at both depths in sea water are shown as a band in Figure 5 which encompasses all but three of the 17 values. For duration of exposure longer than 400 days this band is between the two curves for surface cor- rosion rates, The low oxygen concentration environment (2,500 foot depth) was of the same aggressiveness as the higher oxygen environ- ment (6,000 foot depth). There was neither pitting nor crevice corrosion of this alloy at a depth of 5,600 feet in the Atlantic Ocean. In fact, there was no visible corrosion after 1050 days of exposure, Figure 5. This excellent resistance to corrosion at a depth of 5,600 feet in the Atlantic Ocean indicates that the environment at this location is different from the environment at a depth of 5,500 feet in the Pacific Ocean. The oxygen concentration in the Atlantic has been reported as 5.7 milliliters per liter (at least as high as at the surface) and no fouling organisms were reported, but, in addition the current must have been high enough to prevent stagnation: all three conditions are usually necessary to prevent pitting. There was a similar variability in corrosion rates of the nickel-copper 400 alloy partially embedded in the bottom sediments which is also attributed to the crevice and pitting types of corro- sion. At the 5,500 foot depths the depths of the pits and the severity of the crevice corrosion increased with increasing duration of exposure. When nickel-copper 400 alloy was welded with filler metal 60 by the inert gas welding process the weld bead both in the sea water and in the bottom sediment after 402 days of exposure at a depth of 2,370 feet was selectively attacked as shown in Figure 7. When welded with electrodes 130 and 180 by the metal-arc welding process the weld beads were not selectively corroded, the corrosion was uniform and no more severe than that on the unwelded sheet. Nickel=-copper alloy 400 was not susceptible to stress corrosion cracking when exposed at stresses equivalent to 50 and 75 percent of its yield strength for 402 days at a depth of 2,370 feet. The mechanical properties of the unwelded nickel-copper 400 alloy were not impaired by exposure at nominal depths of 2,500 and 6,000 feet for periods of time of 402 and 1064 days, respectively except after 751 days at 5,500 feet, Table 7. The 22 percent de- crease in the elongation after 751 days of exposure at a depth of 5,500 feet was due to the deep pits. The percent elongation of the welded specimens decreased with attendant increases in the yield strengths as shown in Table 7. This is not considered significant except for the specimen in the sea water welded with filler metal 60 which broke in a weld defect. Nickel=copper alloys 402, 406, and K-500 behaved much the same as the 400 alloy in that their corrosion rates vacillated between less than 0.1 and 1.5 MPY due to the severity of crevice and pitting corrosion. After 1096 days of exposure at the surface in the Atlantic Ocean, Harbor Island, North Carolina, the corrosion rate of nickel-copper alloy K-500 was 0.8 MPY which compares favorably with its behavior at depth in the Pacific Ocean. Most of the corrosion at the surface was also due to localized corrosion. Cast nickel-copper alloys 410 and K-505 corroded uniformly as shown in Table 6. The corrosion rates of the cast-410, in general, decreased with an increase in the time of exposure at both depths, 2,350 and 5,500 feet as shown in Figure 8, and in both cases the corrosion rates in the bottom sediments were less than those in the sea water at the same depth. After 1064 days of exposure at a depth of 5,300 feet the corrosion rates in the sea water and in the bottom sediment were about the same. The corrosion rates at a depth of 2,350 feet were less than those at a depth of 5,500 feet. Initially the cast nickel-copper K-505 alloy corroded at a greater rate in the bottom sediment than in the sea water but after 1064 days of exposure at a depth of 5,500 feet, it was lower than in sea water as shown in Figure 9. The general trend was for the corrosion rates to decrease as the duration of exposure increased. The corrosion rates at 2,350 feet were lower than those at 5,500 feet. Nickel-copper 60 alloy was attacked by the crevice type of corrosion at both depths, Table 6. In most cases the crevice corro- sion was greater on the specimens exposed in the sea water than on those partially embedded in the bottom sediments. X-ray diffraction, spectrochemical and chemical analyses of corrosion products removed from nickel-copper alloys 400 and K-500 showed that they were composed of cupric oxide (Cu0), nickel oxide (NiO), nickel hydroxide (Ni(OH)5), cupric chloride (CuClj), copper- oxy-chloride (CuClj.3Cu0.4H70), a trace of nickel sulfide (NiS) and phosphate, chloride and sulfate ions. NICKEL ALLOYS The chemical compositions of the nickel alloys are given in Table 8, their corrosion rates and types of corrosion in Table 9, their stress corrosion resistance in Table 10 and changes in mechanical properties in Table ll. There were no significant weight losses or any visible corro- sion on any of the following alloys: a. Ni-Cr-Fe 718, unwelded and welded b. Ni-Cr-Mo #3 c. Ni-Cr-Mo 625 d. Ni-Co-Cr 700 except for 3 specimens with incipient crevice corrosion e. Ni-Cr-Fe-Mo F £. Ni-Cr-Fe-Mo G g. Ni-Cr-Fe-Mo X except for 1 specimen with incipient crevice corrosion h. Ni-Cr-Co 41 Lo NiloMoOaGie |G The U. S. Navy Marine Engineering Laboratory also reported no visible corrosion on nickel-molybdenum-chromium alloy C at depth in the Pacific Ocean.* Nickel-Chromium-Iron Alloys Alloys 600, cast 610, X750 and 88 were attacked chiefly by the crevice type of corrosion with some pitting in a few specimens (see Table 9) both in the sea water and when partially embedded in the bottom sediments. Generally, the crevice corrosion was less severe on the specimens partially embedded in the bottom sediments than on the specimens totally exposed in the sea water. When alloy 600 was welded with electrodes 132, €2 and 82 the weld bead materials were selectively attacked and were perforated after 402 days of exposure in the sea water at a depth of 2,370 feet. In addition, there was line corrosion along the edges of the weld beads made from electrodes 62 and 82. Also, there was severe tunneling corrosion to perforation in the heat-affected zone of alloy 600 adjacent to the weld bead made with electrode 82 as shown in Figure 10. The line corrosion and selective attack of the weld beads indicates that the weld bead materials were anodic to the parent sheet material (alloy 600). However, when alloy 600 was weld- ed with electrode 182 the only observable corrosion after 402 days of exposure in the sea water at a depth of 2,370 feet was a slight roughening of weld bead indicating that weld beads made with this composition electrode are compatible (the same corrosion potential in sea water) with the parent metal and is the preferred welding electrode. After 402 days of exposure in the sea water at a depth of 2,370 feet, there was tunnel corrosion in the heat-affected zone and along the edge of the weld bead in alloy X750 which had been welded with electrode 718 by the tungsten electrode inert gas welding process. When alloy X750 was welded with electrode 69 by the tungsten electrode inert gas welding process there was no selective attack of the weld bead material or in the heat affected zone. There was no visible corrosion on alloy 718 unwelded and when welded with electrode 718 by the tungsten electrode inert gas weld- ing process after 402 days of exposure in the sea water at a depth of 2,370 feet, Nickel-Iron-Chromium Alloys There was either no visible corrosion or there was crevice cor- rosion varying from incipient to 35 mils deep on alloys 800, 804, 825, 825 sensitized (heated for 1 hour at 1200°F), 825 Cb, 901 and 902, Table 9. There was crevice corrosion 6 mils deep on alloy 800 after 1064 days of exposure in the bottom sediment at a depth of 5,300 feet; only incipient crevice corrosion on alloys 804, 825 Cb and 901 at both depths, crevice corrosion 22 mils deep on alloy 825 after 751 days of exposure in the sea water at a depth of 5,640 feet; crevice corrosion 4 mils deep on alloy 825 (sensitized) after 1064 days of exposure in the bottom sediment at a depth of 5,300 feet; and crevice corrosion 35 mils deep on alloy 902, after 402 days of exposure in the sea water at a depth of 2,370 feet. The U. S. Navy Marine Engineering Laboratory found essentially the same corrosion behavior of alloy 825 which was exposed on STUs I-3 and I-2 for 123 and 751 days at a depth of 5,640 feet, Reference 8. Grevice corrosion was 63 mils deep (perforated) after 751 days with scattered pitting to 1 mil deep. There was crevice corrosion to 57 mils deep and scattered pitting to a depth of 2 mils after 386 days of exposure of companion specimens at the surface at Harbor Island, North Carolina. These data indicate that the corro- sion of alloy 825 is slightly faster at the surface in the Atlantic than at depth in the Pacific. The corrosion behavior of these alloys was the same both in sea water and in the bottom sediments. After 402 days of exposure in sea water at a depth of 2,370 feet, there was end penetration of the weld bead material when alloy 800 was welded with electrode 82 and line corrosion along the weld bead when alloy 800 was welded with electrode 138. The line corro- sion along the weld bead is indicative of the presence of a line of anodic material along the weld bead. Nickel-Molybdenum-Iron Alloy B Alloy B was corroded uniformly except for a groove about 4 mils deep at the mud line after 403 days at a depth of 6,780 feet and for incipient crevice and pitting corrosion in the bottom sediment after 197 days at a depth of 2,340 feet. The corrosion rates of alloy B are shown in Figure 11. At the 5,500 foot depth in the sea water the corrosion rate increased sharply between 123 and 403 days of exposure and decreased gradually thereafter with increasing duration of exposure. In the bottom sediment at a depth of 5,500 feet, there was generally a decrease in the corrosion rate with increasing duration of exposure and the corrosion rate was lower than in the sea water. The corrosion rates at the 2,350 foot depth increased between 200 and 400 days of exposure the increase being greater in the sea water than in the bottom sediment. Nickel-Tin-Zine Alloy 23 Alloy 23 was susceptible to severe crevice corrosion (56 mils in 751 days) and to pitting corrosion (35 mils in 1064 days). Nickel-Beryllium Alloy The nickel=beryllium alloy specimens were in the form of bars 0.94 inch diameter which were pitted on the ends to depths of 17 mils in the sea water and 8 mils in the bottom sediment. The cor- rosion rate in the sea water was greater than that in the bottom sediment. Nickei-Chromium Alloys Alloys 65-35, 75 and 80-20 were attacked by crevice corrosion which varied in severity from incipient to perforation (50 mils) both in the sea water and in the bottom sediment. The corrosion rates usually were less than 0.1 mils penetration per year; in one case, after 751 days of exposure at a depth of 5,640 feet in sea water the rate was 0.5 mils penetration per year. Because of the localized nature of the corrosion, low corrosion rates are mis- leading if considered by themselves. Nickel-Molybdenum Alloy 2 Alloy 2 was attacked by general corrosion; therefore, corro- sion rates calculated from weight losses are meaningful and signifi- cant. The corrosion rates of alloy 2 are shown in Figure 12. At both depths, 5,500 and 2,350 feet, the corrosion rates increased with increasing duration of exposure. No explanation is offered at this time for the exceptionally high corrosion rate in sea water after 751 days of exposure at a depth of 5,640 feet. The corrosion rates were less in the bottom sediments than in the sea water at both depths. Nickel=Silicon Alloy D Alloy D was attacked by the crevice and pitting types of cor- rosion. The most severe attack was after 1064 days of exposure in the sea water at a depth of 5,300 feet; crevice corrosion extended to a depth of 42 mils and pitting corrosion to a depth of 38 mils. STRESS CORRCSION Nickel-iron-chromium alloy 825 and nickel-molybdenum-chromium alloy C were exposed in the stressed condition at stresses equiva- lent to 35, 50 and 75 percent of their yield strengths, as shown in Table 10. Alloy 825 was not susceptible to stress corrosion cracking after 402 days of exposure at a depth of 2,370 feet. Alloy C was not susceptible to stress corrosion cracking for periods of exposure as long as 751 days at a depth of 5,640 feet. MECHANICAL PROPERTIES The changes in the mechanical properties of the nickel alloys are given in Table 11. The mechanical properties of nickel-iron- chromium alloy 825 and nickei-molybdenum-chromium alloy C were not impaired by exposure to sea water or in the bottom sediments for periods of time of 751 and 1064 days at the nominal depth of 5,500 10 feet. There was considerable decrease (49 percent) in the percent elongation of nickel-iron-chromium alloy 902 after 402 days of exposure at a depth of 2,370 feet. Since there was no visible corrosion, especially pitting, on the surfaces of the specimens, this decrease cannot justifiably be attributed to corrosion. No reason can be given for this at this time. SUMMARY AND CONCLUSIONS The purpose of this investigation was to determine the effects of deep ocean environments on the corrosion of nickel and nickel alloys. To accomplish this a total of 635 specimens of 75 different alloys were exposed at nominal depths of 2,350 and 5,500 feet for periods of time varying from 123 to 1064 days. There was no significant weight loss or any visible corrosion on the fellowing alloys: nickel-chromium-iron alloy 718, nickel- chromium-molybdenum alloys 3 and 625, nickel-cobalt-chromium alloy 700, nickel-chromium-iron-molybdenum alloys F, G and X, nickel- chromium-cobalt alloy 41 and nickel-molybdenum-chromium alloy C. Four alloys, cast nickel-copper alloys 410 and K-505, nickel- molybdenum-iron alloy B and nickel-molybdenum alloy 2 were attacked by uniform or general corrosion. Their corrosion rates were lower in the bottom sediments than in sea water at both depths, 2,350 and 5,500 feet. The corrosion rates of cast nickel-copper alloys 410 and K-505 at both depths and of nickel-molybdenum-iron alloy B at the 5,500 foot depth, decreased with increasing duration of exposure. The corrosion rates of nickel-molybdenum alloy 2 at both depths and of nickel-molybdenum-iron alloy B at the 2,370 foot depth increased with increasing duration of exposure. Some alloys were uncorroded except for isolated instances of erevice corrosion. They were nickel-iron~chromium alloys 800, 804, 825, sensitized 825, 825 Cb and 901. The remaining alloys were attacked either by crevice or pit- ting corrosion or by both types of corrosion. These alloys were: electrolytic nickel, nickel 200, 201, 211, 270, cast 210 and 301; nickel-copper alloys 400, 402, 406, K-500 and 60; nickel-chromium- iron alloys 600, cast 610, X750 and 88; nickel-iron-chromium alloy 902; nickel-tin-zine alloy 23, nickel-beryllium; nickel-chromium alloys 65-35, 75 and 80-20; and nickel-silicon alloy D. There was attack of the weld beads, at the edge of the weld bead or in the heat-affected zone of the following: nickel 200 welded with electrodes 61 and 141; nickel-copper alloy 400 welded with electrode 60; nickel-chromium-iron alloy 600 welded with iit electrodes 62, 82 and 132; nickel-chromium-iron alloy X750 welded with electrode 718; nickel-iron-chromium alloy 800 welded with electrodes 82 and 138; and nickel-iron-chromium alloy 825 welded with electrode 135. There was no selective attack when nickel-copper alloy 400 was welded with electrodes 130 and 180; when nickel-chromium-iron alloy 600 was welded with electrode 182; when nickel-chromium-iron alloy X750 was welded with electrode 69; when nickel-iron-chromium alloy 825 was welded with electrode 65; and when nickel-chromium- iron alloy 718 was welded with electrode 718. Nickel 200, nickel-copper 400, nickel-molybdenum-chromium alloy C and nickel-iron-chromium alloy 825 were immune to stress corro- sion cracking. Corrosion products from the nickel-copper alloys contained cupric oxide (Cu0), nickel oxide (NiO), nickel hydroxide (Ni(OH),), cupric chloride (CuCl5), trace nickel sulfide (NiS), copper oxy-— chloride (CuCl9.3Cu0.4H,0) and phosphate, chloride and sulfate ions. The mechanical properties of nickel and the nickel alloys were unaffected by exposure at depths in the Pacific Ocean except for decrease in percent elongation of nickel-iron-chromium alloy 902. ACKNOWLEDGMENTS The author wishes to acknowledge the generosity of Dr. T. P. May, Manager, Harbor Island (Kure Beach) Corrosion Laboratory, International Nickel Company, Incorporated for granting permission to include his deep ocean corrosion data in this report. 12 REFERENCES 1. U.S. Naval Civil Engineering Laboratory Technical Note N-900: Corrosion of materials in hydrospace - Part I. Irons, steels, cast irons and steel products, by Fred M. Reinhart. Port Hueneme, Calif., July 1967. 2 . Technical Report R-504: Corrosion of materials in hydrospace, by Fred M. Reinhart. Port Hueneme, Calif., Dec. 1966. Bo . Technical Note N-605; Preliminary examination of materials exposed on STU I-3 in the deep ocean - (5,640 feet of depth for 123 days), by Fred M. Reinhart. Port Hueneme, Calif., June 1964. by . Technical Note N-695: Examples of corrosion of materials exposed on STU II-1l in the deep ocean - (2,340 feet of depth for 197 days), by Fred M. Reinhart. Port Hueneme, Calif., Feb. 1965. 5) . Technical Note N-781: Effects of deep ocean environments on the corrosion of selected alloys, by Fred M. Reinhart. Port Hueneme, Calif., Oct. 1965. 6. . Technical Note N-793: Visual observations of corrosion of materials on STU I-l1 after 1064 days of exposure at a depth of 5,300 feet in the Pacific Ocean, by Fred M. Reinhart. Port Hueneme, Calif., Nov. 1965. 7. Dr. T. P. May, unpublished data, International Nickel Company, Inc., Wrightsville Beach, North Carolina. 8. W. L. Wheatfall. ''Metal Corrosion in Deep-Ocean Environments," MEL R&D Phase Report 429/66, U. S. Navy Marine Engineering Laboratory, Annapolis, Maryland, Jan. 1967. 9. U. S. Naval Civil Engineering Laboratory Technical Note N-859: Corrosion rates of selected alloys in the deep ocean, by J. B. Crilly and W. S. Haynes, PhD. Port Hueneme, Calif., Nov. 1966. 13 10. Ihibe Wo 13. 14. B. F. Brown, et. al. "'Marine corrosion studies: Stress corrosion cracking, deep ocean technology, cathodic protection, and corrosion fatigue. Third interim report of progress," Technical Memorandum 1634, U. S. Naval Research Laboratory, Washington, ID, Go, swihy Soa, E. Fischer and S. Finger. ‘"'Corrosion at 4,500 foot depth in Tongue-of-the-Ocean,'’ Technical Memorandum 3, Laboratory Project 9400-72, U. S. Naval Applied Science Laboratory, Brooklyn, New York, Mar. 1966. A, Anastasio and A. Macander. "'Retrieval, examination and evaluation of materials exposed for 199 days on NASL deep sea materials exposure mooring No. 1," Technical Memorandum 5, Laboratory Project 9300-6, U. S. Naval Applied Science Laboratory, Brooklyn, New York, July 1966. F. L. La Que. "Behavior of Metals and Alloys in Sea Water," Corrosion Handbook, 1948 ed., Edited by H. H. Uhlig, Wiley, New York, pp. 394-400. C. V. Brouillette. ''Corrosion Rates in Port Hueneme Harbor," Corrosion, Vol. 14, No. 8, Aug. 1958, pp. 352t-356t. C. R. 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BOQ Ooo oe © uoTSOTIO) VW, WW) WAN Wh PN WING NS NYS. ZNBNZENENENEN BNEBENENENEN quo —-UOATAUY HAL *aansodxq (p,3u09) sXkoT Ty TexoTN JO UoTsorr0D Jo sedA], pue savy UoTsoii10p AOTLV "6 eTdeL 45 sqUOUTpes WORIOq UT peppequis ATTeTj1ed ‘NIS Jo eseq ut pasodxa susuitoads Ei fea! /POONt ZOONT / OONT ») /jOONz 9) Pont woz o4 d 5 /POONt wg¢E 03 d 7JOONt d /TOONI eee! OONT d /j00Nt Pont pTONt /JOONt 7pOont Pont FONT /7OONE 7pooNt 7 OONt /Toont = 901Nn0S uUoOTSOLAC) /€ —jo ody, OUOVOUOVUVVOOHHYD Et ougovvuyFevuaA ZoqeM ves UL ATS FO septs uo pasodxa oe) ° e ° ° ° ° ° ° ZSNENENBENENEN yas nw noAtnTtOnNn HANA oF O;O ° NZENENENEN MOONWADNOM oonFnwHtHOTO shed Ssansodxy quo —- UO ITAUY /T ST TW © a0TAer) WOTSOLIOD (p,3uc2) sAOT TY TexXoTN FO UCTsOAt0D Fo sad], pue saqzey WOTsoist0D suoutoods PFAaANgAAaananaaaaA NNNNNNN NSN val ie) rt re Dj1NnS anne yy ite entoway eK {len Figure 4. Corrosion of weld bead on nickel made with electrode 61 exposed in sea water for 402 days at a depth of 2,370 feet. Hy Ned, 1, oan ; "hp By ve Pil. f 7p ; Dvn MN oie! MURANO i Tales et 4, i t ' Ni i Nleeerdventt lf i " he (f on i i i ia y 7 i ‘ y wee) ‘ iit i i t d (ye ay, \ \ bap i) 009 ‘1 "J2JDM DAS Ul QOP AO]}0 seddoo-; o> SIU JO UOISOIIO“) (shoq) ainsodxy 00r “I 00Z ‘I 000 “I ( )s G ainbi4 jOONI "UDBIQ IINf19Dq ‘4994 QGE'Z TAN ‘U08I0 F14!90q ‘4994 QGE'Z , 1YN ‘uD82Q DU_|IY 4924 0099'S g 1SaW ‘UD@IQ FNVIIDg “4994 O0G'S 6 1SON "UD99Q F1}!20q ‘4894 Q0S'S OONI ‘UD8I0 F1}19Dq “4994 Q0G'S TAON ‘¥U0890 F14!90q “4995 00'S “plpoD ‘ewauany Jog ‘UD85Q dJIyI3Dq ‘adD4INS g2 “N ‘y2Daq s4Ny ‘UDS5DQ JIJU_]JW ‘BDDjINS z12 "N ‘y2D28g a4nNy ‘UDaDQ JIJU_] IW ‘a2Dj4NS Pe}}O1 404 ‘au0Z ;DUD>D DWDUDY ‘UDSIQOH JIjIDDq ‘ADDjINS 0 el Al mt Ppjo> ‘eu0Z jpuD> DWDUDY ‘UDeDH 351j19Dq ‘aaDy1NS 4994 0SE'7 ‘sUSWIPasS 4984 QSE'Z ‘1940M 4994 Q0G'G ‘sueWIpas 4994 00S'S ‘1910M OPN! DIU 4SDD JO UOISOIIO“) (shoq) easnsodx3 "6 ainBi4 007 002 0 | / / 1SO1J0> P a}DYy UO = 3 < ( icv; ooh peas “it Gini Mba fy 7a arid ea rN Lyn pabiniwmr ame omen ce Ha ymca el ttf el ny oes llr cima, ey rink i \ i} i r { i ya tdaoihe dbl Serr nel agra at rk : oe i Fm iy Seana tether > oman Nl he tz; Uaserterenkormartie 0 Uniddr tc@uraiae a { ( H id { | i , i } i , ‘i ih ‘ j ane snl ori le ebb wt teem iga pay ibn Aor ty ie nal Al ee id og w i 19 i om aR ne a re vrboriehy lahat nth th ig dim fe i el “ | agree Cit) yey Ail ya Figure 10. Nickel-chromium-iron alloy 600 welded with electrode 82. Corrosion at edge of heat affected zone and of weld bead. INE) pees LAI NT by ilar a iio ( in *g Ao}jD Uosl—uinuapqdjowj-|ax91U yo UoIsOMOy “|| eunBi4 (shoq) eansodx3 007 ‘L 002 ‘I 000 ‘L 008 009 O0v 002 0 sUBWIPSS WO40G Vv 12}0M DAG 7 4934 QS¢'Z juewipas woyjog @® 4840M D28AS_ = CE 4924 00S'S LOONI 1SQJ4107) (Adw) ayoy uo 8 xptts eras =Aeinand vishh« Mibllecynisteedaentem i Sweooxd liloin te rerio! 4 vane mea memset enti aA 2 ian) iv HI a) Bi) itty Uae oem iwelinde tratando rinthy te her te Die Corrosion Rate (mpy) INCO” 5,500 Feet ©. Sea water @ Bottom sediment 2,350 Feet 4& Sea water & Bottom sediment Exposure (Days) Figure 12. Corrosion of rnickel-molybdenum alloy 2. ee et we Sealy IES A nn , bibs cei iigivn Yala diem Hr Se rt tere Lf Votliteedt | vee (ad nck hall es ae wet Oke Ae | eek gal Pury webs. wea a ye . sees sha i ne Pa Besant OR... (oo Hate at Stee ee Covel) epee) a ‘ ue > y COS ULERY Fee UNCLASSIFIED Security Classification a ; i DOCUMENT CONTROL DATA - R&D F (Security classification of title, body of abstract and indexing annotation must be entered when the overall report ia classified) H 1. ORIGINATING ACTIVITY (Corporate author) 2a. REPORT SECURITY CLASSIFICATION Unclassified U. S. Naval Civil Rue tneceene Laboratory it 2b. GROUP 4 Port Hueneme, California 930 | 3. REPORT TITLE Corrosion of Materials in Hydrospace. Part II - Nickel and Nickel Alloys 4. DESCRIPTIVE NOTES (Type of report and inclusive dates) ; 5. AUTHOR(S) (Last name, first name, initial) Reinhart, Fred M. 6. REPORT DATE 7a. TOTAL NO. OF PAGES 7b. NO. OF REFS August 1967 65 14 Ba. CONTRACT OR GRANT NO. 9a. ORIGINATOR’S REPORT NUMBER(S) . PROJECT NO. Y-F015-01-05-002A Technical Note N-915 8b. OTHER REPORT NO(S) (Any other numbere that may be assigned this pes - AVAILABILITY/LIMITATION NOTICES Each transmittal of this document outside the agencies of the U. S. Government must have prior approval of the U. S. Naval Civil Engineering Laborator . SUPPL EMENTARY NOTES 12. SPONSORING MILITARY ACTIVITY Naval Facilities Engineering Command Washington, D. C. 20390 13. ABSTRACT A total of 635 specimens of 75 different nickel alloys were exposed at two different depths in the Pacific Ocean for periods of time varying from 123 to 1064 days to determine the effects of deep ocean environments on their corrosion resistance. Corrosion rates, types of corrosion, pit depths, effects of welding, stress corrosion cracking resistance, changes in mechanical properties and analyses of corrosion products of the alloys are presented. Of those alloys tested, the following were practically immune to corrosion; nickel-chromium-iron alloy 718; nickel-iron-chromium alloys, except 902; nickel- chromium-molybdenum alloys; nickel = cobalt-chromium alloy; nickel-chromium-iron= molybdenum alloys; nickel-chromium-cobalt alloy; and nickel-molybdenum-chromium alloy. Alloys attacked by uniform or general corrosion were the cast nickel- copper alloys; nickel-molybdenum-iron alloy; and nickel-molybdenum alloy. Alloys attacked by crevice or pitting corrosion were the nickels; wrought nickel-copper alloys; nickel-chromium-iron alloys except 718; nickel-iron-chromium alloy 902; nickel-tin-zine alloy; nickel-beryllium alloy; nickel-chromium alloys; and nickel- silicon alloy. Corrosion resistance of welds in the nickel alloys, depends upon the selec- tion of the proper welding electrodes. The nickel alloys were not susceptible to stress corrosion cracking. Corrosion products consisted of oxides, hydroxides, chlorides and oxychlorides. Mechanical properties of the alloys were not adversely affected in a significant way. 0) oR 1 4 73 0101-807-6800 UNCLASS IF IED at ‘Security Classification UNCLASSIF LED _ Security Classification KEY WORDS Nickel Nickel Alloys Corrosion Corrosion resistance Hydrospace Ocean environments Stress corrosion resistance Welding electrodes INSTRUCTIONS 1, ORIGINATING ACTIVITY: Enter the name and address of the contractor, subcontractor, grantee, Department of De fense activity or other organization (corporate author) issuing the report. 2a. REPORT SECURITY CLASSIFICATION: Enter the over- all security classification of the report. Indicate whether “Restricted Data’’ is included. Marking is to be in accord ance with appropriate security regulations. 2b. GROUP: Automatic downgrading is specified in DoD Di- rective 5200.10 and Armed Forces Industrial Manual. Enter the group number. Also, when applicable, show that optional markings have been used for Group 3 and Group 4 as author- ized. 3. REPORT TITLE: Enter the complete report title in all capital letters. Titles in all cases should be unclassified. If a meaningful title cannot be selected without classifica- tion, show title classification in all capitals in parenthesis immediately following the title. 4 DESCRIPTIVE NOTES: If appropriate, enter the type of report, e.g., interim, progress, summary, annual, or final. Give the inclusive dates when a specific reporting period is covered, 5. AUTHOR(S): Enter the name(s) of author(s) as shown on or inthe report. Ente: last name, first name, middle initial. If military, show rank and branch of service. The name of the principal author is an ahsolute minimum requirement. 6, REPORT DATE: Enter the date of the report as day, month, year; or month, year. If more than one date appears on the report, use date of publication. 7a. TOTAL NUMBER OF PAGES: The total page count should follow normal pagination procedures, i.e., enter the number of pages containing information 7b. 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Each paragraph of the abstract shall end with | an indication of the military security classification of the in- formation in the paragraph, represented as (TS), (S), (C), or (U). There is no limitation on the length of the abstract. How- ever, the suggested length is from 150 to 225 words. 14. KEY WORDS: or short phrases that characterize a report and may be used as index entries for cataloging the report. Key words must be selected so that no security classification is required. Identi- fiers, such as equipment model designation, trade name, military] project code name, geographic location, may be used as key words but will be followed by an indication of technical con- text. The assignment of links, rales, and weights ie optional. UNCLASSIFIED a —----— i Securitv Classification If additional space is required, a continuation sheet shal] | Key words are technically meaningful terms | ) i } if i} 1 i} UNCLASSIFIED - continuation of Abstract (DD Form 1473) The bottom sediments were less aggressive than sea water environments and the lower oxygen content sea water was less aggressive than the higher oxygen content sea water. UNCLASSIFIED jj i) HETEO) On Pe ‘* “ J ¥ r j i ee Gila i RIT rn vst shh ga ie a a aa a mC eS eh Moe p apt i ny dy ih i ii ii a tp i