Super Stainless Steel Welded Tubing Solutions: An Alternative To Titanium Welded Tubing For Seawater-Cooled Heat Exchangers ?

Hayde RICHAUD-MINIER and Pascal Grard VALTIMET 27 Avenue du Gnral Leclerc - 92660 Boulogne-Billancourt France Hafida EL-ALAMI and Herv Marchebois Vallourec Research Center Route de Leval - BP 20149, 59620 Aulnoye-Aymeries, FRANCE

ABSTRACT
Thanks to its outstanding resistance to general and localized corrosion attack properties, Titanium has been successfully established as the commonly used material for seawater-cooled heat exchanger tubing, be it for power plants surface condensers, thermal desalination plants heat exchangers or heat exchangers used in the chemical and petrochemical processing industry. In the current material market context in which Titanium price has increased significantly, engineering companies and end-users have shown an increasing interest for more cost-effective alternative solutions using what are called super alloys which are highly alloyed stainless steels showing a far better corrosion resistance than conventional stainless steels. In addition to Titanium, this paper will focus on six different super stainless steel alloys which may be considered alternative solutions to Titanium for seawater-cooled applications: UNS S31254, N08367 and S34565 super austenitic alloys, UNS S44735 and UNS S44660 super-ferritic alloys, and S32750 super-duplex alloy. Taking power plants condensers as an example, the paper reviews both mechanical and corrosion properties for ranking the seven different materials. Both standardized ASTM and electrochemical tests in artificial seawater have been carried out on welded tubes in order to rank the different grade materials according to their pitting and crevice corrosion resistance.

Keywords: titanium, super stainless steel, super austenitic stainless steel, super ferritic stainless steel, super duplex stainless steel, R50400, S44735, S44660, S32750, S31254, N08367, S34565, heat exchanger tubing, welded tubing, condenser tubing, tubing corrosion resistance

INTRODUCTION
Based on titanium immunity to corrosion in marine environments, welded thin-wall titanium tubing have progressively been developed as the best technico-economical solution for seawater service and proved to be the material of choice of those applications. Over the past thirty years, use of titanium tubes has greatly expanded to power plant surface condensers, desalination plants, chemical process and refinery heat exchangers, and auxiliary heat exchangers, with an excellent return of experience indeed. However, given the significant increase in titanium pricing over the past several years, engineering companies and end-users have shown an increasing interest in more cost-effective alternative solutions using highly alloyed stainless steels. These super alloys demonstrate much improved corrosion resistance while maintaining a modest increase in premium pricing when compared to conventional stainless steels. This paper takes the seawater-cooled condenser tubing application as an example to compare titanium with six super alloys alternatives which have been developed on the market: UNS S31254, N08367 and S34565 super austenitic alloys, UNS S44735 and UNS S44660 super-ferritic alloys, and S32750 superduplex alloy. It describes in particular corrosion investigations performed on those alloys used in sea water applications, gathering both electrochemical tests and conventional ASTM tests performed on welded tubes.

MATERIALS FOR CONDENSER AND HEAT EXCHANGER TUBING1

Simply stated, a surface condenser is a shell & tube, steam-to-water heat exchanger, where cooling water (also called circulating water) passes through inside of the tubes and turbine exhaust steam passes over the outside of the tubes. This condensing process or the rejection of heat from the hot steam to the cold water is called the latent heat of vaporization. Within this operating envelop of the surface condenser or BOP heat exchanger, the key properties of power plant surface condenser tubing can be grouped into the following general categories: - Heat transfer properties of the material - O.D. erosion resistance to shell-side steam or fluid flow - I.D. abrasion resistance from suspended solids and turbulent velocities - Corrosion resistance to raw waters Prior to the introduction of stainless tubing materials in the 1960s, condenser and general heat exchanger designers selected copper and copper-alloy materials for their tubing. Materials such as Admiralty Brass, Aluminum, Brass, and Copper Nickel (70/30 or 90/10) were popular and typically supplied in the seamless condition. Wall thicknesses in the 1 1.2 mm range were commonplace. However, when these copper alloys were exposed to highly sensitive and corrosive environments, the overall long-term reliability of condenser tubes equipped with these materials became fragile. The introduction of the first stainless steel welded tubing began in the U.S. with ordinary grades such as UNS S30403 or UNS S31603. These first stainless grades provided good service records in fresh water. S31603 was used for a short period in seawater applications but proved to be susceptible to localized pitting and crevice corrosion in concentrated chloride environments. The titanium development in Europe and Japan in 1970 offered a timely solution. Demonstrating outstanding resistance to general and localized attack in high chloride environments, it has provided nearly forty years of trouble-free seawater service for the power generation and process industries. In the late 70s, due to the titanium market crisis, highly alloyed stainless steels, also called super stainless steels, were developed to offer a lower-cost alternative solution. These new alloys included UNS S31254 and UNS N08367 super austenitic alloys and UNS S44735 and UNS S44660 superferritic alloys.

Since the year 2000, material prices for Nickel and Molybdenum have been unstable and fluctuating. As a result, the duplex and lean duplex stainless steels including UNS S31803, UNS S32003, UNS S32304 and UNS S32101 have been developed as a cost-effective alternative to traditional standard austenitic stainless steel alloys for use in mild cooling water service. Recently, super-duplex alloys have also been developed in strip form offering additional material options for brackish and seawater service. Table 1. gives the typical chemical requirements of the seven condenser tubing materials this paper focuses on, including R50400 titanium grade 2 material, super-ferritic alloys S44735 and S44660, super-austenitic alloys N08367, S31254 and S34565, and super-duplex alloy S32750. As indicated in the table below, super stainless steels are highly alloyed stainless steels with high Mo, Cr and N contents, which are the key elements to endow with high corrosion resistance properties. Table 1. Typical chemical requirements in % according to ASTM for commonly used stainless condenser alloys
C Mn P S Si max max max max max
1 5-7 2 1 1 1.2 0.03 0.03 0.04 0.04 0.04 0.01 0.01 0.03 0.03 0.03 0.8 1 1 1 1 0.8

ASTM

UNS

Cr

Ni

Mo
6-6.5 4-5 6-7 3-4 3.6-4.2 3-5

N
0.18-0.25 0.4-0.6 0.18-0.25 0.04 0.045 0.24-0.32

H
-

O
-

Fe
Rem. Rem. Rem.

Others
Cu: 0.5-1 Cb Cu 0.1 0.75

A 249 S31254 0.02 A 249 S34565 0.03 A 249 N08367 0.03 A 268 S44660 0.03 A 268 S44735 0.03 A 789 S32750 0.03 A 790 R50400 B 338 0.08 (Ti Gr.2)

19.5-20.5 17.5-18.5 23-25 20-22 25-28 28-30 24-26 16-18 23.5-25.5 1-3.5 1 6-8

Rem. Ti+Cb: 0.2-1 Ti+Cb Rem. 6(C+N) Rem. Cu 0.5

0.035 0.02

0.03

0.015 0.25

Ti: Rem. Others: 0.3 Each < 0.10 Total < 0.40

HEAT TRANSFER PROPERTIES

Once the mechanical properties are found to be acceptable, condenser designers turn their attention to the tube materials heat transfer properties. The thermal conductivity of the six alternative materials are compared against titanium in Table 2. All six super alloys have reasonable thermal performance in steam condensers, especially when used in thin-wall tube applications. The super-ferritic alloys perform somewhat better than the super-austentic ones, the super-duplex displaying an intermediate thermal performance behaviour. Titanium, due to its little improved thermal conductivity, will still slightly outperform the super alloys under consideration. However, the thermal performance of all seven candidate materials is decidedly less than that of copper alloys. Table 2. Thermal conductivity of the alloys under investigation
Thermal conductivity K in W/ (m C) [ in BTU / (hr ft F) ] UNS N S31254 20C / 68F 13.5 [7.9] S34565 12 [6.9] N08367 11.8 [6.8] S44660 15.9 [9] S44735 17 [9.9] S32750 14 [8.2] R50400 22 [12.7]

Experience in the power generation industry has demonstrated that thermal conductivity is only a small contributor to overall heat transfer. Steam- and water-side film and fouling coefficients have a more

significant influence. Heat transfer performance actually is more closely linked to the corrosion resistance performance of the tubing material. An alloy surface that exhibits low corrosion rates in the heat exchanger environment while remaining relatively clean can provide excellent heat transfer performance over the service life of a heat exchanger. Knowing this, titanium appears therefore as the best alloy regarding heat transfer performance, combining a slightly superior thermal conductivity than super alloys with thin-wall tubing conditions as well as a better corrosion resistance behavior.

MECHANICAL PROPERTIES EROSION RESISTANCE

Two types of erosion damages commonly cause problems for condenser applications: - Abrasion / erosion-corrosion / cavitation caused by the circulating water on the internal surface of the tubes - water droplet / steam impingement erosion on the external surface of the tubes. Regarding impingement attack of condenser tubes due to high water velocities, usually caused by partial blockage by debris or micro- or macro-biological activity, laboratory tests have demonstrated the ability of titanium to handle safely sea water flowing at velocities up to 30 m/s. The presence of sand or other abrasive particles has little effect on the erosion of titanium (see Table 3. ). Titanium is considered one of the best cavitation-resistant materials available for seawater service. Super stainless steel alloys also show an outstanding resistance to cavitation, turbulence and high velocity flow thanks to their high mechanical strengths (see Table 4. ).The commonly accepted maximum water flow rate for erosion-corrosion for those alloys is around 30 m/s. Table 3. Erosion of unalloyed Titanium in seawater containing suspended solids
Seawater at 7 m/s Seawater at 36 m/s Seawater with 40 g/l 60 mesh sand at 2m/s Seawater with 40 g/l 10 mesh emery, 2m/s Seawater with 40% 80 mesh emery, 7.2m/s NO EROSION 0.008 mm/yr 0.003 mm/yr 0.13 mm/yr 1.5 mm/yr

Table 4.

Mechanical properties minimum values according to ASTM

Yield Strength 0.2% MPa - ksi
310 [45] 415 [60] 310 [45] 450 [65] 415 [60] 550 [80]

ASTM
A 249 A 249 A 249 A 268 A 268 A 789 A 790

UNS
S31254 S34565 N08367 S44660 S44735 S32750

Ultimate Tensile 1 Young Modulus Strength Elongation % 3 GPa ksi x 10 MPa - ksi
675 [98] 795 [115] 690 [100] 585 [85] 515 [75] 800 [116] 35 35 30 20 18 15 200 [29] 190 [28] 195 [28.3] 217 [31.5] 200 [29] 200 [29]

typical values at 20C (68F)

B 338

R50400 Ti GR. 2

275 [40]

345 [50]

20

107 [15.5]

Steam droplet erosion is the second type of erosion damage experienced with condenser tubing immediately adjacent to the turbine exhaust. The problem mainly occurs during winter periods when the condenser cooling water temperature is low, which lowers the condenser back pressure and greatly increases the velocity of wet steam entering the condenser. The condensed water particles (droplets) in the exhaust steam impinging on the condenser tubes eventually removes the metal oxide and metal, and if the condition continues unabated, perforation of the tube eventually takes place. The resistance of this erosion phenomenon is linked to the metal hardness. Higher hardness provides higher erosion resistance. S44660, S44735, S34565 and above all S32750 are therefore particularly resistant to this kind of erosion damage, with a slightly better behavior than S31254, N08367 and Titanium Gr. 2. Thanks to their very high mechanical properties, S44660, S44735, S34565 and above all S32750 are particularly erosion-resistant materials ; in return they are more difficult to mechanically expand and require a greater care during tube-to-tubesheet attachment. The seven alloys under investigation demonstrate excellent resistance to suspended solids (sand) erosion, steam side droplet impingement, cavitation, turbulence and high velocity flow including mechanical damage as a result of flow-assisted corrosion (FAC). Superior mechanical strength associated with these alloys is the principal reason for their excellent resistance to this type of attack.

PITTING AND CREVICE CORROSION RESISTANCE

Titanium is known to offer exceptional resistance to corrosion because of its naturally forming protective oxide film layer. This film layer, which increases over time, provides immunity to general and localized attack in power plant surface condenser applications where high chloride and brackish water conditions exist. Titanium Grade 2 has operated nearly 40 years in condenser power plant service without one reported corrosion incident. Super stainless steel alloys are highly alloyed stainless steels designed to resist mainly pitting and crevice corrosion but also stress corrosion cracking in saline environments. Empiric Formulas Resistance to localised corrosion of stainless steel is closely linked to its chemical composition. The three main elements which have a significant beneficial effect on the resistance of the stainless steels to localized corrosion are chromium (Cr), molybdenum (Mo), and nitrogen (N). The calculated parameter which gives their relative contribution is the Pitting Resistance Equivalent Number (percents are in weight percent of elements in solid solution). Some empiric formulas are commonly used in order to assess the resistance of stainless steels to localized corrosion phenomena. The Pitting Resistance Equivalent Number (PREN), first presented by Herbsled2 in 1982, is a formula indicating the relative resistance of a stainless steel or a similar alloy to pitting and crevice corrosion. The formula is defined as: PREN = (%Cr) + (3.3 %Mo) + (16 %N) For ferritic stainless steels the PREN value is obtained from Cr and Mo only as PREN = %Cr + 3.3 (%Mo) because of the chemical composition of such alloys.

G. Herbsleb, Werkstoffe und Korrosion, 33 (1982), p. 334

The PREN is accepted to be a rough tool to estimate the pitting and crevice corrosion resistance of different grades such as conventional austenitic stainless steels (e.g. TP 316L) with highly alloyed stainless steels but quite inaccurate to compare highly alloyed stainless steels together. Still it gives an idea of the corrosion behaviour of the alloys. Table 5. gives the average, minimum and maximum PREN of the six super alloys under investigation, according to the chemical composition range as indicated in ASTM standards. Table 5. PREN (average, minimum and maximum) of super alloys under study
UNS N S31254 S34565 N08367 S44660 S44735 S32750 PREN average 44.1 46.9 43.2 38.1 41.9 42.7 PREN min. 42.2 42.6 42.7 34.9 39.9 37.7 PREN max. 46.0 51.1 49.1 41.2 43.9 47.6

The Critical Pitting Temperature (CPT) and the Critical Crevice Temperature (CCT) are defined in ASTM G48 standard in order to assess the temperature below what a material is not susceptible to pitting and crevice corrosion respectively in ferric chloride solution. The way to assess the temperatures is defined in the following formulas: CPT (C) = (2.5 %Cr) + (7.6 %Mo) + (31.9 %N) - 41.0 CCT (C) = (3.2 %Cr) + (7.6 %Mo) + (10.5 %N) - 81.0 Table 6. and Table 7. give respectively the CPT and CCT of the six super alloys under investigation, according to the chemical composition range as indicated in ASTM standards. Table 6. CPT of super alloys under study, as calculated per ASTM G48 formula
UNS N S31254 S34565 N08367 S44660 S44735 S32750 CPT (C) average 63.4 69.2 67.8 52.5 61.9 60.8 CPT (C) min. 59.1 59.7 60.3 44.3 56.4 49.5 CPT (C) max. 67.6 78.6 75.2 60.7 67.4 72.2

Table 7.

CCT of super alloys under study, as calculated per ASTM G48 formula
UNS N S31254 S34565 N08367 S44660 CCT (C) average 32.8 35.5 30.9 30.6 CCT (C) min. 28.9 27.2 30.5 21.8 CCT (C) max. 36.6 43.3 45.2 39.4

S44735 S32750

41.7 32.3

36.0 21.1

47.4 43.6

Attention is to be paid to the minimum values PREN, CPT and CCT can reach due to the tolerances of the different chemical components of the six super alloys under investigation; due to the alloying elements increasing cost, steelmakers generally tend to minimize their content. The empirical values of PREN, CPT, and CCT are typically accepted benchmarks within industry and are employed as tools to estimate the pitting and crevice corrosion resistance of conventional stainless steel grades. Unfortunately, these calculated values are not sufficiently accurate to legitimately compare the members of the same family of highly alloyed stainless. Corrosion investigations performed on super stainless alloys welded tubing used in seawater applications require both electrochemical and conventional ASTM tests to get a clearer picture of the materials performance.

Corrosion Resistance Tests On Welded Condenser Tubing In order to have more reliable data in terms of corrosion resistance than just data coming from raw materials themselves to compare different alloys for condenser tubing use, we have performed corrosion tests on welded tubing made of the different super stainless steel alloys which chemical analysis are indicated in Table 8. Tested samples are 500 mm long. Table 8.
UNS S31254 S34565 N08367 S44660 S44735 S32750 0.5 0.8

Chemical compositions of welded tubing super stainless steel alloys under test
Cr 19.9 24.4 20.5 27 29.3 25.4 Ni 18.1 17.6 24.0 1.7 0.81 7.2 Mo 6.06 4.49 6.2 3.6 3.8 3.9 N 0.205 0.469 0.21 0.024 0.032 0.299 Cu: 0.44 Ti: 0.19 Cb: 0.35 Ti: 0.17 Cb: 0.38 Cu: 0.14 Ti: 0.005 Co: 0.07 Others Cu: 0.67 PREN 43.2 46.7 44.3 38.9 41.8 43.1

OD WT Mn C max P max S max Si max (mm) (mm) max 0.5 1 0.6 0.013 0.022 0.022 0.028 0.018 0.014 0.54 5.58 0.71 0.36 0.27 0.82 0.018 0.001 0.019 0.001 0.42 0.32

0.023 0.0003 0.38 0.031 <0.005 0.51 0.026 0.0003 0.35 0.018 0.001 0.22

In the present paper, different techniques are implemented to rank highly alloyed stainless steels according to their corrosion resistance. First the electrochemical behaviour of stainless steels is recorded in chloride containing solution, within a wide range of electrochemical potentials, by potentiodynamic curves. Then comparative pitting corrosion resistance is measured using ASTM G48 method E. And finally ASTM G48 method F is performed to compare crevice corrosion resistance of the different highly alloyed stainless steels. Electrochemical investigations: In this part highly alloyed stainless steels resistance to general corrosion is evaluated. This evaluation is done through the analysis of their electrochemical behaviour using polarisation curves. The polarisation curves have been recorded using a GAMRY potentiostat PCI4/300 (DC105 software), which allows the measurement of the current developed on the sample as a function of the time and the applied potential. The electrochemical cell is a conventional three electrodes cell, involving the metal surface to be analysed, a platinum counter electrode, and a Saturated Calomel Electrode (SCE) as a

reference. All experiments are carried out at 50C. Thes samples are cleaned with acetone, with demineralised water, and dried. The solutions used are reconstituted sea water (pH 8.1) and NaCl 100 g/L (pH 6.0), de-aerated with N2. The corresponding curves are represented on Figure 1. Each curve represents the evolution of the current density (j) developed on the steel surface as a function of the applied potential (E). The current density is directly related to the nature and the rate of the electrochemical reactions which occur at the interface between the stainless steel surface and the aggressive solution. Figure 1. shows that the different curves obtained are characteristic of metals that form a passive film at their surface. They present a stable passive state which are more or less similar in the applied conditions: no development of localized corrosion, S31254 steel excepted in 100 g/L NaCl solution. R50400 curve is significantly different from the super stainless steels: current densities developed on R50400 are lower than on the super stainless steels for a given potential, which shows the best global resistance of R50400 to the development of corrosion processes.

1.E-02

sea water 50C

1.E-03

R50400 S34565 S31254

S44735 N08367

S44660 S32750

1.E-04

j (A/cm)

1.E-05

1.E-06

1.E-07

1.E-08 -1200

-1000

-800

-600

-400

-200

200

400

600

800

1000

1200

1400

E (mV/SCE)
1.E-02

(a)

NaCl 100 g/L 50C

1.E-03

R50400 S34565 S31254

S44735 N08367

S44660 S32750

1.E-04

j (A/cm)

1.E-05

1.E-06

1.E-07

1.E-08 -1200

-1000

-800

-600

-400

-200

200

400

600

800

1000

1200

1400

E (mV/SCE)

(b)

Figure 1.

Polarisation curves of highly alloyed stainless steels compared to Ti Gr2, at 50C, in reconstituted seawater (a) and in NaCl 100 g/L (b).

Different parameters have been determined to compare the alloys: the current density developed at the corrosion potential, jcorr, and the corresponding polarisation resistance, Rp. Figure 2. shows that the polarisation resistance Rp is inversely proportional to the corrosion current density jcorr: the higher Rp the lower jcorr, the lower the corrosion rate at the corrosion potential Ecorr. This evolution enables the determination of alloys ranking according to their resistance to global corrosion at the corrosion potential. The sequence of an increasing resistance is as follows: in seawater: S34565 S44660 ~ N08367 S32750 < S44735 << R50400, in 100 g/L NaCl: S34565 N08367 S31254 ~ S32750 < S44660 < S44735 << R50400

As expected, R50400 presents the highest resistance to the development of corrosion processes at Ecorr. Titanium Gr. 2 offers an unmatched corrosion resistance, significantly beyond the super stainless family. From the results it can also be said that super-ferritic stainless steels S44735 and S44660 show a better resistance to general corrosion than the super duplex and super-austenitic alloys, as they present higher Rp and lower jcorr. Super-dupex S32750 is slightly better than the austenitic steels. To evaluate the influence of chemical composition on the resistance of corrosion processes at the corrosion potential, the values of stainless steels polarisation resistance have been represented as a function of the PREN, on Figure 3. It shows that within super austenitic and super duplex stainless steels the modification of chemical composition does not induce significant differences in the behaviour of the corresponding steels, at the corrosion potential in the applied conditions. The lower PREN values of super ferritic stainless steels do not lead to lower corrosion resistance at Ecorr. The difference in microstructure between super ferritic and super austenitic stainless steels seems to lead to an enhancement of the corrosion resistance in favour of super ferritic stainless steels. Within super ferritic group the chemical composition seems to have a significant effect, as it gives to S44735 (higher PREN ferritic steel) better resistance than S44660.
1.E-05

50C seawater
S34565 S44660 1.E-06 S32750 S31254 N0836

j corr (A/cm)

increase of corrosion resistance

S44735

1.E-07 R50400

increase of corrosion resistance corrosionresistance

1.E-08 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07

Rp (ohm cm)

(a)

1.E-05

50C 100 g/L NaCl

S34565 N08367 S31254 S44660

j corr (A/cm)

1.E-06

S32750

increase of corrosion resistance

S44735

1.E-07

increase of corrosion resistance

1.E-08 1.E+03

R50400

1.E+04

1.E+05

1.E+06

1.E+07

Rp (ohm cm)

(b)

Figure 2. Evolution of the corrosion current density jcorr as a function of the polarisation resistance Rp, for the different tested alloys, at 50C, in seawater (a) and in 100 g/L NaCl (b).

6.E+04 S44735 5.E+04 super ferritic 100 g/L NaCl 50C

Rp (ohm cm)

4.E+04 S44660 3.E+04 super austenitic 2.E+04 SS31254 1.E+04 S34565 0.E+00 36 38 40 42 44 46 48 50 N08367 super duplex S32750

PREN

Figure 3.

Evolution of polarisation resistance Rp, for the different tested alloys, at 50C, in 100 g/L NaCl as a function of PREN.

From these results it can be said that the super-ferritic stainless steels S44735 (in both solutions) and S44660 (in 100 g/L NaCl) show a better resistance to general corrosion than the super-austenitic alloys, the super-duplex S32750 being slightly better than the austenitic steels. Titanium Gr. 2 offers an unmatched corrosion resistance in both solutions, significantly beyond the super stainless family. Pitting resistance: In this part highly alloyed stainless steels resistance to pitting corrosion is evaluated. This evaluation is done through ASTM G48 E corrosion tests. These tests allow the determination of the temperature at which pits are initiated on the metal, by exposing 50 mm length tubes in a solution containing 6% FeCl3 acidified by 1% HCl (pH around 0.6) at a constant temperature during a standard test period of 24 h. Before exposed to the aggressive solution, the specimens are cleaned in acetone, in demineralised water, and dried. As indicated by the standard just one specimen is placed in one test container.

The results are presented in terms of critical pitting temperature CPT of the welded zone and of the base metal, for the different steels (Figure 4. ). It can be noticed that method C could also be applied to estimate the pitting corrosion resistance. The only difference between method E and method C is the test period respectively 24 h and 72 h. As 24 h is enough to detect pitting on the stainless steels under investigation, and as method E presents better repeatability standard deviation than method C (results of interlaboratories tests described in ASTM G48), method E seems to be the most appropriate test to conduct a comparative evaluation of pitting resistance of stainless steels. ASTM G48 test allows the determination of the temperature at which pits are developed on the metal. Usually, this temperature, also called Critical Pitting Temperature or CPT, corresponds to the minimum temperature at which a pit can be seen. However, this criterion does not take into account the severity of the damage generated. This is why we have decided to define an additional parameter which is considered more appropriate to characterize the reliability of condenser tubing alloys in terms of corrosion resistance: the temperature of critical damage formation. This parameter corresponds to the minimum temperature at which a pit has sufficiently developed to induce a hole in the tube. Then the damage (pit or crevice) will be considered as initiating if its depth is between 25 m and 50 m. It will be considered as a critical damage if its depth is over 50 m. This critical value of 50 m has been chosen according to the wall thicknesses of the tested tubes, which are from 0.5 mm to 1.0 mm: the damage is considered as critical if it overpasses 5% of the tube thickness. In this approach, we have in particular focused when possible on the tubing internal surface which is the one in contact with the cooling water and therefore the surface where corrosion may be prone to develop first in the case of condenser tubing. For tests carried out to only characterize the internal surface of the tubes, the external surface was protected by a varnish. Pitting resistance of external surface of tubes: the results are presented in terms of Critical Pitting Temperature CPT of the welded zone and of the base metal, for the different alloys (Figure 4. ). Table 9. indicates the maximum pit depth measured on the tested alloys at specific temperatures. Based on the lowest CPT, i.e. the minimum temperature at which a pit of at least 25 m depth is observed, Table 9. and Figure 4. show that the sequence of increasing resistance to the initiation of pitting, on the welded tubes, is as follows: S32750 < S44660 < S44735 << R50400 The ranking is the same as the one achieved when using electrochemical techniques and looking at the resistance to corrosion in high content chloride solution at the corrosion potential. This suggests that the initiation of pits is closely linked to the corrosion rate at the corrosion potential. In other words, pits seem to be preferentially formed on alloys surfaces which present a high dissolution rate at the corrosion potential.
90 85 80 75 base metal weld > 85C

CPT (C)

70 65 60 55 50 45 40 S32750 S44660 S44735 R50400

Figure 4.

Critical Pitting Temperature (CPT) values for the welded tube, according to ASTM G48 Method E corrosion test

Table 9.

Values of pit maximal depth of welded tubing super stainless steel alloys tested at different temperatures
T (C) 70 75 80 65 70 60 65 85 tube thickness (mm) 0.7 0.7 0.7 0.7 0.7 0.8 0.8 0.6 pit max. depth (m) no pit 25 180 no pit 700 no pit 150 no pit pit max. depth (% thickness) 0 4 26 0 100 0 19 0

steel S44735 S44735 S44735 S44660 S44660 S32750 S32750 R50400

Table 10. and Figure 5. show the resulls when looking at the critical damage temperature, which is the temperature at which a critical damage is developed on the tube surface (damage depth over 5% of its thickness). The rankling of the alloys under test in welded tubing condition is as follows: S32750 < S44660 < S44735 << R50400 This ranking is more or less related to the propagation of pits. As expected, it shows that R50400 presents the best resistance to pitting, as no pitting is observed for the tested temperatures. Super duplex S32750 first pits appear at 65C, and the propagation of these pits lead to a critical damage (depth: 19% of the tube thickness) at 65C. For super ferritic S44660, at 70C first pits appear and they are critical for the tube integrity as they immediately form holes. For super ferritic S44735 first pits appear at 75C, but critical damage is formed at 80C (depth: 26% of the tube thickness).

90 85 80 75
T (C)

critical damage

> 85C

70 65 60 55 50 45 40 S32750 S44660 S44735 R50400

Figure 5.

Temperature of critical damage due to pitting corrosion of the welded tube, according to ASTM G48 Method E corrosion test

The evolution of the weight loss associated to each test is represented on Figure 7. Weight losses are representative of the metal quantity which is dissolved during the test. Then Figure 7. also gives an idea of the severity of the damages generated on the tubes. It can be observed that when the weight loss exceeds around 10 mg/m the damage generated at the tube is critical for the tube integrity. The corresponding ranking is in line with the previous ranking related to the propagation of pits and the depth of critical damage.

1000

100
mass loss (g/m)

10 g/m 10 S44660 1 S32750 S44735 0.1 50 55 60 65 70 75 80 85 90 temperature (C)

Figure 6.

Weight losses due to pitting corrosion of the welded tube, as a function of temperature of tests according to ASTM G48 E corrosion test

Internal pitting resistance of tubes: Internal pitting resistance is analysed following ASTM G48 method E. Internal surface of tubes have been exposed to the solution test. The results are presented in terms of Critical Pitting Temperature CPT of the welded zone and of the base metal, for the different alloys (Figure 7. ). It has to be underlined that the seam weld corrosion resistance is as good as the parent metals one; the seam weld of welded tubing is not a weak point in terms of corrosion resistance. Based on the lowest CPT, i.e. the minimum temperature at which a pit of at least 25 m depth is observed, Table 10. and Figure 8. show that the sequence of increasing resistance to the initiation of pitting, on the welded tubes, is as follows: S44660 < S44735 < S32750 < R50400 CPT values show that internal surfaces of tubes are slightly more resistant to the initiation of pits than the external surfaces, for super ferritic stainless steels. This effect is much more pronounced for super duplex S32750, as its CPT is translated over 85C. This is most probably linked to the laser weld seam of this tube as S32750 alloy was the only one of the alloys under test which has been welded using the laser technology whereas all other tubes have been TIG welded. S44725 CPT is still higher than S44660 one. Table 10. Values of pit maximal depth of internal surfaces of welded tubing super stainless steel alloys tested at different temperatures
T (C) 70 75 80 75 80 85 85 tube thickness (mm) 0.7 0.7 0.7 0.7 0.7 0.8 0.6 pit max. depth (m) no pit 70 700 no pit 350 no pit no pit pit max. depth (% thickness) 0 10 100 0 50 0 0

steel S44660 S44660 S44660 S44735 S44735 S32750 R50400

90 85 80 75
CPT (C)

weld base metal

> 85C

70 65 60 55 50 45 40 S44660 S44735 S32750 R50400

Figure 7.

Critical Pitting Temperature (CPT) values for internal surfaces of the welded tube, according to ASTM G48 Method E corrosion test

Based on the temperature at which a critical pitting is developed on the internal tube surface (damage depth over 5% of its thickness), to take into account the severity of the damage generated on the tube, Figure 8. shows that the sequence of increasing resistance to the development of pits, on the welded tubes, is the following: S44660 < S44735 < S32750 << R50400 No pitting is observed on S32750 and R50400 for the tested temperatures.
90 85 80 75 70
T (C)

> 85C critical damage

65 60 55 50 45 40 S44660 S44735 S32750 R50400

Figure 8.

Temperature of critical damage due to pitting corrosion on the internal surface of the welded tube, according to ASTM G48 Method E corrosion test

The results for the tubing internal surface are similar to those achieved for the external surface, except the exceptional behaviour of the S32750 material tubing which was the only welded tube with a laser seam weld, whereas all other tubing have been TIG-welded.

Crevice corrosion resistance: The aim of the present part is to evaluate the resistance of different highly alloyed stainless steels to crevice corrosion. This evaluation is assessed thanks to corrosion tests according to ASTM G48 F standard, on the external surfaces of the tubes for practical testing reasons. ASTM G48 method F is used to determine the Critical Crevice Temperature CCT at which crevice corrosion is generated at the surface of tubes. The steels analysed are: super ferritic S44735 and S44660, super austenitic N08367 and S34565, and super duplex S32750, with respect to R50400. The solution is composed of FeCl3 6% acidified by 1% HCl. The pH is around 0.6.

Based on the lowest CCT, minimum temperature at which a crevice of at least 25 m depth is observed, Table 11. and Figure 9. show that the sequence of increasing resistance to the initiation of crevice, on the welded tubes, is as follows: N08367 < S34565 = S32750 = S44735 < S44660 << R50400 Super austenitic stainless steel N08367 is slightly less resistant to crevice initiation than super austenitic S34565 and than super duplex and super ferritic steels. Super ferritic S44660 has a better resistance to crevice initiation than super ferritic S44735. R50400 always presents the best resistance to crevice initiation. It has here again to be noticed that the seam weld displays the same corrosion resistance as the parent metal. Table 11. Values of crevice maximal depth of internal surfaces of welded tubing super stainless steel alloys tested at different temperatures
tube thickness (mm) 0.7 0.7 0.7 0.7 0.7 0.8 0.8 0.8 1.0 1.0 1.0 0.6 0.6 0.6 0.6 crevice max. depth (m) crevice max. depth (% thickness) no crevice 0 30 4 65 9 no crevice 0 100 14 no crevice 0 40 5 100 13 no crevice 0 40 4 100 10 no crevice 0 30 5 60 10 no crevice 0

steel S44735 S44735 S44735 S44660 S44660 S32750 S32750 S32750 S34565 S34565 S34565 N08367 N08367 N08367 R50400

T (C) 30 35 40 40 45 30 35 40 30 35 40 25 30 35 85

70 65 60 55 50
CCT (C)

> 85C base metal weld

45 40 35 30 25 20 15 10 N08367 S34565 S32750 S44735 S44660 R50400

Figure 9.

Critical Crevice Temperatures (CCT) values for the external surface of the welded tube, according to ASTM G48 Method F corrosion test

Based on the temperature at which a critical damage is developed on tube surface (crevice depth over 5% of its thickness), to take into account the severity of the damage generated on the tube, Figure 10.

shows that the sequence of increasing resistance to the development of crevice, on the welded tubes, is as follows: N08367 <= S34565 = S32750 = S44735 <= S44660 << R50400
70 65 60 55 50 45 40 35 30 25 20 15 10 N08367 S34565 S32750 S44735 S44660 R50400 critical damage > 85C

Figure 10. Temperature of critical damage due to crevice embrittlement on the external surface of the welded tube, according to ASTM G48 Method F corrosion test

ASTM G48 tests confirm the electrochemical test results, with the high corrosion resistance of super stainless alloys, in particular super-ferritic S44735 and S44660 and super-duplex S32750 alloys, but the superiority of titanium grade 2 material over the super stainless family.

T (C)

CONCLUSION
Depending on the quality of the circulating water, many tube material options can be selected for the steam surface condenser. Despite claims that certain super stainless alloys are the same as titanium, this paper again documents titanium tubing for condenser and heat exchanger service as the uncontested, superior technical solution. Titanium, as it is recognized since a long time ago by the corrosion specialists as the premium and the safest solution, demonstrates general corrosion immunity in sea and brackish water. Titanium also has better heat transfer performance than the stainless family, has very good erosion and excellent corrosion resistances, and has an installation track record approaching 40 years of operation without one reported corrosion event. In addition, titanium can be utilized in very thin-wall gauges (down to 0.4mm/0.016) enabling savings in both first cost and weight. Following decades of power generation and desalination service, its superiority is incontestable and its flawless corrosion-free record intact. Employing a variety of corrosion measurement techniques for evaluating welded stainless steel tubing including electrochemical assessment and ASTM standardized investigations, the paper also presented significant data in support of the use of super stainless tubing in sea water service. However, a careful analysis of the water chemistry, of the operating conditions and the maintenance program has to be done in order to make the most appropriate alloys selection. In order to complete all the laboratory corrosion tests performed on super stainless steels and get as close as possible of the operating conditions of condenser tubing in service, additional tests in natural seawater with fit-for-purpose conditions and addition of chlorine for example have been launched. Admittedly, the family of super alloy stainless steels is not as corrosion resistant as titanium and therefore can be less reliable in terms of lifetime costing. However, when utilized properly and employing regular maintenance programs, super alloys can provide a positive return on the investment. TM3 Consider the excellent experience of bright annealed, ValBrite welded tubing made from UNS S44735 strip. A successful 15 to 25 year European installation experience has proven this super alloy
3

ValBriteTM is a trademark of VALTIMET

tubing, produced in a protected environment during the heat treating process, can demonstrate a high degree of operational success.

References
1

Titanium and Super Stainless Steel Welded Tubing Solutions For Seawater Cooled Heat Exchangers, by Hayde Richaud-Minier, Pascal Grard and Herv Marchebois, Stainless Steel World 2007 Conference