Alloy 400 for use in high pressure feedwater heaters Reprinted from Proceedings of materials workshops for the power industry Nickel Development Institute, 1993 = NiDI NICKEL DEVELOPMENT INSTITUTE NiDI Reprint Series N° 14 021 Dennis W. RahoiThe material presented in this publication has been prepared for the general information of the reader and should not be used or relied on for specific applications without first securing competent advice. ‘The Nickel Development Institute, its members, staff and consultants do not represent or warrant its suitability for any general or specific use and assume no liability oF responsibilty of any kind in connection with the information hereinAlloy 400 for use in high pressure feedwater heaters Introduction Alloy 400, UNS NO4400, (67%Ni, 31%Cu) Is one of the ‘most corrosion resistant alloys available for use in high pressure feedwater heaters and has over 40 years of good service life in all conditions of water chemistry. in addition, the stress-relieved temper has excellent me- chanical strength and corresponding allowable stress levels. Table lis a comparison of allowable stress values at 300°F (149°C), 400°F (204°C) and 500°F (260°C), while Table iis a comparison of relative cost, relative surface area, minimum wall and thermal conductivity at 450°F (232°C). As shown, Alloy 400is very cost effective when corrosion resistance and mechanical and thermal properties are taken into account The few failures which have occurred have been equally attributedtofatique/design andto stress-corrosioncrack- ing. Fatigue fractures are transgranular in nature while stress-corrosion cracking failures tendto be intergranular, Itis interesting to note that the most likely heater to fail (by any cause) is the second point heater, ie., the heater that, receives its steam from the first reheat. Thermally in- duced stresses are believed to be highest here because this heater experiences the highest temperature differ- ence between the high pressure water (ID) and the superheated steam (OD). Fatigue/Design Failures Fatigue failures have been few, and where they have occurred were most often due to tube-to-tube or tube-to- Table! baffle vibration; Figures 1 and 2 demonstrate these failure modes. A fracture transverse to the tube is also a {900d indication of fatigue. Other indications are cracked tie rods, twisted baffles and support pieces, and failed welds, Stress-Corrosion Cracking (SCC) ‘Ammonia and caustic are two known media for causing stress-corrosion cracking in Alloy 400. Cold work and high residual stresses from either tube or heater manu- facture are the necessary second components. Although many tubes still in service have high residual stresses present, today’s manufacturing technology consistently produces tubing with residual stress below 10,000 PSI (68.9 MPa). The results of extensive SCC studies with Alloy 400 in ‘a number of liquid and vapor environments have been reported. These studies employed a variety of specimen geometries and stress levels. Tables il and IV list the test media, specimen configuration, test duration, tem- perature and the heat treatment for the specimens. Alloy 400 did not crack in any of the test conditions listed in Tables I!land IV. The liquid phase of 1M NH.OH at pH 6 and 9 also failed to produce cracking in U-bends of Alloy 400 when exposed for 1450 hours at 475°F (246°C). Alloy 400, however, did crack intergranularly at 475°F (246°C) in the vapor phase of 1M NH,OH solutions at pH 9 and 12; the solution pH was periodically adjusted to ‘maintain the original value during the 2160-hrtest. Inthese environments, a stress level of 50,000 PSI (345 MPa) or Design stress* comparison for typical feedwater heater materials Minimum Minimum Maximum allowable stress in tension, ksi specified ¥.S. Maximum metal temperature, °F (°C) Specification Alloy tensile (02%ottset) No. strength 100 200 © 300 © 400» 500600700 ksi ksi 38) ©3149) (204) (260) B16) (B71) 38-163 Seamiess- 70.0 280 75 164 «154 «14814714714 annealed 53°, NO4400 $B-163 Seamless: 85.0 550 12 212 212 210 «210 21.0204 stress relieved Nosaoo A688 Type 304. 700 250 109 9993, A688 Type304L* 70.0 250 130125123 SA68B Type 304LN* 75.0 300 41138135 SAG8B Type 304 75.0 300 20 110 = 104 A688 Type 304 75.0 300 141198135, A688 Type304N’ 80.0 350 1420128118 A688 Type 304N' 80.0 350 161156 151 SAS56-A2 LCsteei 47.0 260 8 118 118 SAS56-B2 LCStee 60.0 370 150 150150 SAS56-C2 LCSteei 700 400 75 175175 SA803 44660 85.0 65.0 480178 177 a ASE” Bae andes ese Coe, 182 Sion Pat. Sane peting aye ce N Srdopen ed be stoaton anes 011002 wt‘more was required to produce cracking. Similar cracking was also produced by exposure of U-bends to the liquid and vapor of a pH 12 solution containing hydrazine (N;H,) for 2160 hours. In all the above cases, O, was not ‘excluded from the vapor space in the autoclave, Experi- ence suggests that no cracking occurs when O2 is ex: cluded by deaeration. The cracking of highly stressed Alloy 400 in ammoniacal environments under laboratory conditions also was cited by Reynolds and Pement. ‘Sato and Nagata" were able to produce intergranular SCC up to 75mm deep in highly stressed (372 MPa) Alloy 400 specimens exposed in oxygenated water and steam at 572°F (300°C) for 1200 hrs. The intergranular SCC occurred only when NH, and O, both were present in the steam; pH 10, 6-8 ppm Oz, Intergranular attack, 0.01 mm deep, was observed by Faber and Joynt® on Alloy 400 specimens exposed 100 hours in autoclaves at 707°F (375°C) with 95 percent NaOH in the presence of ©. The intergranular attack occurred over most of the std i . Figure 1 Photograph shows both primary and secondary failures from fatigue under a baffle, Note chafing in area under baffle. Tubes are lined up as they were within the heater. The top two are primary failures; the cracking is transgranular in nature. The lowest tube shows high pressure water erosion as it shot down the baffle. specimen surfaces and thus the attack was not consid- ered to be SCC. No attack occurred on specimens of Alloy 400 when O, was excluded from the NaOH environment ‘and NH, was present. Operating experience with Alloy 400 also shows that SCC ‘can occuronly underavery specific combination of conditions and thatitis notadversely affected by ammonia, ammonium hydroxide, and the various amines used in typical power- plant water treatment. This combination usually occurs in the desuperheating and condensing zone on the shell side ofthe tubes as a result of: localized high pH, unmeasurable butabove 11; high ammonia content; some oxygen present; and high stress in the tubes. The stress in the tubes can, result from operating conditions, plus residual stresses. Tubes produced many years ago with a residual stress component on the order of 35,000 PSI (241 MPa) have still given excellent service life, however, current production practice should keep the residual stresses very low; less than 10,000 PSI (68.9 MPa). Figure 2 Photograph shows a fatigue fracture. The cracking is transgranular. In this case, the tubes were vibrating against one another along their length. The tube-to-tube contact and abraded area is clearly visible. Table Il Approximate relative cost for feedwater heater tubes" (Design Conditions: 450°F (282°C), 2350 psi, tube diameter 0.75 in.) ‘Allowable Minimum Thermal FWH FWH Relative Relative Tubing Stress Wall Conductivity Surface Linear Surface Cost Material (si) Thickness (BTUihr/ Area Area hh) f°F) (sq. ft) (ft) NeCu 44750 067 166 5085 25650 1.08 342 ‘Alloy 400 Annealed ‘Alloy 400 21000 048 166 4649 29683 1.00 209 ‘Stess-relieved Type 304, 16000 062 105 8507 28054 1418 2.28 Seamless Type 304, 13600 072 105 5683 28976 1.22 4.00 Welded Carbon 11800 083 278 aT0T 23979 101 0.63 Steel 7o!30 CUNi 9900 099 220 sit 28074 1.19 1.85 80/20 CwNi 9600 100 260 5261 26801 143 174 2Table Ill ‘Summary of vapor-phase test conditions that failed to produce scc of monel alloy 400” Specimen Test Temperature M Configuration Condition Duration,hr °F (0) Cyclohexylamine, Stenciled ‘Annealed 840" “400 (204) 1-100% Reciprocal U-Bend Morphine, Standard U-Bend Annealed 960" 350 (17) 1-100% Hagamine, Stenciied Annealed 840" 400 (208) 10-100% Reciprocal U-Bend Cup (4 Tests) Annealed 4000 400 (204) Cup (4 Tess) Annealed 2000 400 (204) Feedwater Standard U-Bend ‘Annealed 960" 350 (17) Solution Sodium Sulphite, Standard U-Bend ‘Annealed 960" 350 (177) 40% Cyclohexylamine, Stenciled Tube Full Hard 7200 500 (260) 40% ‘Stencled Tube Stress-Relieved 7200 500 (260), Standard U-Bend Annealed 7200" 500 (260) Standard U-Bend 50% Cold-Worked 7200" 500 (260) “eg aoa wae Oxygen, Peaking Service and Copper Carry-Over Exfoliation Widersum and Tice’ tested a series of Cu-Ni alloys, Ni- Cu Alloy 400, and some other alloys in a pilot heat exchanger which operated under load peaking condi- tions in parallel with other feedwater heaters in a power plant. The plantused continuous morpholine and Na,SO, injection for pH control and O, scavenging, respectively; the pH at the feedwater pump was maintained at 8.8 to, 9.2 and the Na,SO, concentration was 15 to 20 g/ms (ppm). Some NaOH and phosphate were added to the ‘drum boiler. No corrosion or exfoliation was observed on Alloy 400 surfaces in almost three years of plant opera- tion. On the other hand, 70Cu-0Ni alloys were severely damaged by exfoliation and other Cu-Ni alloys were mildly scaled in the above tests. Castle, et al’ investigated the exfoliation corrosion of ‘some Cu-Ni alloys including Alloy 400 at elevated tem- peratures and pressures. The alloys were tested under the following conditions: a) Deaerated steam at 300°F (149°C) and 10,000 PSI (8.69 MPa); b) Saturated steam at 527°F (275°C) containing O,; ©) Dry superheated steam with O,; and 4) (0) plus thermal cycling to produce condensation, Exfoliation attack occurred on some Cu-Ni alloys, but minimal attack was observed on Alloy 400. Hopkinson reported good exfoliation resistance of Al- loy 400in autoclave tests at500°F (260°C) in O,saturated, ammoniated water of pH 10.5and 10.7. Thealloy showed equally good resistance in distilled water and in steam, Which contained no NH,, but was oxygenated with 0.35 MPa O, overpressure, Copper has some solubility in high pressure water and once in the system, can be carried over to the boiler and further, to the turbine blading, where it often “plates” out causing a severe imbalance in the turbine rotor and plugging. This could result in a loss of efficiency or in the worst case, derating. The problem is also related to the turbine design, whether it is impact or reaction (vane spacing is different). The problem is severe in once- through units and most severe in supercritical plants. Because Alloy 400 contains about 33% copper, it has sometimes been unfairly removed from service (all cop- per containing alloys in the condenser and feedwater train have been suggested for replacement when copper carryover occurs). Note that oxygen has a pronounced effect on the corrosion of copper-base alloys. In one study by Orville Smith’, a utility did a test to consider which low-solids treatment using amines would give the best result compared to their current method which used coordinated phosphate water treatment. They did their analysis by extracting water from the system after each stage in the condenser and feedwater train, meas- lured the copper content of the water, and used this analysis as a measure of the amount of copper corrosion product put into the system. In this system the condenser ‘was Admiralty metal. Two low-pressure heaters were 90/, 10CulNi; twolow-pressure heaters were 70/30 CuNI; and all of the high-pressure heaters were Alloy 400. The water temperature went from 311°F (155°C) in the first HP heater to 540°F (282°C) outlet in the last HP heater. ‘The condenser, with the largest surface area, contrib- tuted significant copper content to the water. The copper content increased incrementally going through the low. pressure heaters, then dropped after the first HP heaterTable IV ‘Summary of liquid-phase test conditions that failed to produce SCC of Monel Alloy 400" Specimen Test Temperature Media Configuration Condition Duration,hr SFC) Gyciohexylamine, Sienciled Reciprocal U-Bend “Annealed 3650" “Ambient 4-100% Standard U-Bend Annealed 336 Boiing Standard U-Bend ‘Annealed 720 Ambient Seal Tube Annealed 9500 Boling Unistee! Test Jig Annealed 720 Boling Cup Annealed +000" 300 (149) Cup Annealed 1000" 300 (149) Stenciled Tube Annealed 500 Boling Stenciled Reciprocal U-Bend Annealed a0 400 (204) Stencled Tube Annealed 720 Boiling Stenciled Tube Annealed 720 Boiing Standard U-Bend Annealed 720 Boiling Stencled Tube Ful-Hard 720 500 (260) Stenciled Tube Stress Relieved 70 500 (260) ‘Standard U-Bend Annealed 720" 500 (260), Standard U-Bend 50% Cold-Worked 720" 500 (260) Morphaline, ‘Standard Reciprocal U-Bend Annealed 3650" Ambient 1-100% ‘Standard U-Bend Annealed 336 Boiling ‘Standard U-Bend Annealed 720 Ambient Unisteel Test Jig Annealed 720 Boiling ‘Standard U-Bend Annealed 960" 350 (177) Stenciled Tube Annealed 500 Boiing Stenciled Tube Annealed 720 Boling Stenciled Tube Annealed 720 Boiling Standard U-Bend Annealed 720 Boiing Hagamine, Standard U-Bend Annealed 336 Boling 10-10% Standard U-Bend Annealed 720 Ambient Sealed Tube Annealed 9500 Boling Unisteel Test Jig Annealed 720 Boiing Cup Annealed +000" 300 (149) Cup Annealed 1000+ 300 (149) Stencled Tube ‘Annealed 500 Boling Stencled Reciprocal U-Bend Annealed a0" 400 (204) Standard U-Bend Annealed 720 Boiing Sealed Tube Annealed 4920 Boiing Cup (4 Tests) ‘Annealed 1000+ 400 (204) Cup (4 Tests) Annealed 2000" +400 (204) Din-butytamine Standard U-Bend Annealed 396 Boiling Standard U-Bend ‘Annealed 720 Ambient Unistee! Test Jig ‘Annealed 720 Boiing ‘Stenciled Tube Annealed 500 Boiling (CuCLNH,C), Stenciled Annealed 3650 ‘Ambient 2H Opa Reciprocal U-Bend ‘Ammonium Stenciled Reciprocal U-Bend ‘Annealed 3650 “Ambient Hydroxide, Standard U-Bend Annealed 396 Boiing 10-58% Standard U-Bend Annealed 720 Ambient Unistee! Test Jig Annealed 720 Boiing Stenciied Tube ‘Annealed 720 Boiing Stencileg Tube Annealed 720 Boling Standard U-Bend Annealed 720 Boling Copper Standard U-Bend ‘Annealed 720 Ambient Sealed Tube Annealed 9500 Boling Unite! Test dig Annealed 720 Boiing Cup Annealed 1000" 300 (149) Standard U-Bend Annealed 720 Boiing Sealed Tube Annealed 1920 Boling Feedwater Solution Standard U-Bend Annealed 60" 960 (177) Sodium Hydroxide ‘Sealed Tube Annealed 1920 Boiing Sodium Sulphite Sealed Tube Annealed 9500 Boling Standard U-Bend Annealed 960 662 (950) Tire ae aoeHp turbine J With layup water and chemical feed \ — Air intake ‘co Mechanical deaeration Chemical reaction Thermal decomposition, ‘oxidation, reduction (hep hrs) soavengin Sample MetaiO,reaction, Scavenger Makeup 4 Rupture gises Cond, storage — 7 Bats Tohotwell 47 or deaerator Fp turbine Lp Horizontal Joint turbine Air eject or Joint vacuum pump Tube leaks Condenser—.]_f— With makeup Shaft seal Scavenger — |_— Cond. pump 1 testa 7 | Ene Deaerator Scavenger 9 (Hp hrs) Scavenger D*P PUMP Figure 3 Air ingress is a concern both for O, and CO, chemical and mechanical removal. and again after the second HP heater. The Alloy 400 was ‘not contributing to the corrosion product release. In fact, the opposite was happening, ie, a “plating” of copper was occuring in the HP heater. This deposithas been seen in many HP heaters of Alloy 400. We have coined it snake skin because it can be pealed-off the inside-diameter surface intact as ifit were asnake’s skin. The composition of this deposit is 90-95% Cu/Cu0 with some iron present. Inthe same study, only under start-up conditions where the oxygen content in the water was higher, the opposite. analysis was obtained, ie, the highest copper content in the test was after the first HP heater where the plated copper was redissolving. Perhaps the following example illustrates how resistant Alloy 400 is to corrosion. The Eddystone One Station of, Philadelphia Electric is a 1960-vintage, 325 MW base loaded unit of an advanced design with double reheat at 4400 psig, 1145°F/1050°F (618°C/566°C), It had an arsenical copper condenser, 90/10 CulNi in the low- content, This diagram shows sources and points of pressure heaters, 70/30 Cu/Niin the intermediate pres- sure heaters and Alloy 400 in the high pressure heaters. Upon start-up, severe copper plating problems occurred ‘on the turbine blades. To remedy the situation, three changes were executed at the same time: 1. The Alloy 400 was replaced with carbon steel; 2. A filter was put in just before the high pressure feed pump; and 3. The turbine seals were replaced. The copper plating problem was solved! However, in two months the carbon steel heater had eroded tofailure atthe inlets. The Alloy 400 heaters were stillin the station lot and were put back into service. They are still there today with no problems. The conclusion is that the combination of new turbine seals to prevent oxygen leakage into the system and the fiter to remove the copper after the water passes through the condens- ers, low pressure andintermediate pressure heaters was sufficient to prevent copper plating in the turbine. Arecent article by Otaker Jonas? on controlling oxygen in steam generating systems describes water treatments and in-leakage areas. Figure 3is a copy of his diagram showing both O, and CO; sources. Conclusion Analysis of HP feedwater heater service and tubing failures indicates that Alloy 400 is highly resistant to all forms of corrosion under the operating conditions found, in utility service. Service experience in 1800 and 2400 PSI systems with drum type boilers has proven conclu- sively that Alloy 400 does not contribute to copper ‘carryover in the system. When made to strict specifica- tions and used in feedwater heaters that are properly fabricated and operated, Alloy 400 has been shown tobe. resistant to stress-corrosion cracking. References 1. Rahoi, D., etal, "Performance of MonelF Alloy 400 in feedwater heaters", ASME Journal of Engineering for Power, Vol. 95, p. 27, 1973. 2, Reynolds, Jr., S. D. and Pement, F. W., “Reduce stress-corrosion cracking in feedwater heaters”, Power, Vol. 115, (4), pp. 83-84, 1971. 3. Sato, S. and Nagata, K., “Stress-corrosion cracking of cupro-nickel and Monel* metal tubes in high pressure feedwater heaters", Sumitomo Light Metal Technical Reports, 15, (4), p. 269, 1974. 4, Sato, S. and Nagata, K., “Stress-corrosion cracking of copper alloys in pure steam and water at high temperatures", Boshoku Gijutsu, Vol. 23, (3), p. 125, 1974, 5. Faber, G. and Joynt, G. A., “influence of the partial pressure of oxygen and the corrosion mechanism of Copper-nickel alloys in the presence of caustic soda’, Brown Boveri Review, Vol. 54, p. 704, 1967. 6. Wiedersum, G. C. and Tice, E. A., “Corrosion of feedwater heater tubing alloys in peaking service”, ASME Journal of Engineering for Power, Vol. 87, (3), p. 324, 1965, 7. Castle, J. E., Harrison, J.T., and Masterson, G.,"The exfoliation corrosion of cupro-nickel feedwater heater tubes’, British Corrosion Journal, Vol. 1, (4), p. 143, 1966. 8. Hopkinson, B.E., “Copper-nickel alloys for feedwater heater service, Corrosion, Vol. 20, p. 80t, 1964. 9. Smith, 0. A.,"A program to locate copper pickup ina high pressure utility system’, Proceedings of the ‘American Power Conference, Vol. XXIX, pp. 731- 787, 1967. 10, Jonas, O., “Controlling oxygen in steam generating systems", Power, p. 43, May, 1990. 11. Reynolds, Jt. S., Richter, Dr. H., and Lawson, F. E., “Nicorros™ Alloy 400tubing for high-reliabilty feedwater heaters’, VOM Report No. 8, p. 3, July 1964, 12, ASME Boiler and Pressure Vessel Code, Section Il, Part D, 1992 ed. Monel isa registered trademark ofthe INCO family of companies. * Nicorros isa registered trademark of Krupp VM GmbhThe Nickel Development Institute is an international nonprofit organization serving the needs of people interested in the application of nickel and nickel-containing materials. Members of NiDI ‘Companhia Niquel Tocantins Empresa de Desenvolvimento de Recursos Minerals "CODEMIN’ S.A Falconbridge Limited Inco Limited Morro do Niquel S.A, Nippon Yakin Kogyo Co., Ltd. NRNQ (a limited partnership) (Outokumpu Oy P-T. International Nickel Indonesia Pacific Metals Co.., Ltd. QNI Limited Sherritt Gordon Limited Shimura Kako Company, Ltd ‘Sumitomo Metal Mining Co., Ltd. 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