Sunteți pe pagina 1din 6

MATERIALS CHARACTERIZATION 60 (2009) 150 155

MATERIALS CHARACTERIZATION 60 (2009) 150 – 155 Microstructural characteristics and corrosion behavior of a super
MATERIALS CHARACTERIZATION 60 (2009) 150 – 155 Microstructural characteristics and corrosion behavior of a super
MATERIALS CHARACTERIZATION 60 (2009) 150 – 155 Microstructural characteristics and corrosion behavior of a super
MATERIALS CHARACTERIZATION 60 (2009) 150 – 155 Microstructural characteristics and corrosion behavior of a super

Microstructural characteristics and corrosion behavior of a super duplex stainless steel casting

Marcelo Martins a, , Luiz Carlos Casteletti b

a Industrial Manager of SULZER BRASIL S/A and Professor of the São Paulo Salesian University Center (UNISAL), Americana Division, SP, Brazil b Department of Materials, Aeronautical and Automotive Engineering, São Carlos School of Engineering, University of São Paulo (USP), São Carlos, SP Brazil

ARTICLE DATA

Article history:

Received 11 December 2007

Received in revised form

10 June 2008

Accepted 8 December 2008

Keywords:

Sigma phase

X-ray diffraction

Corrosion resistance

ABSTRACT

The machining of super duplex stainless steel castings is usually complicated by the

difficulty involved in maintaining the di mensional tolerances required for given

applications. Internal stresses originating from the solidification process and from

subsequent heat treatments reach levels that exceed the material's yield strength,

promoting plastic strain. Stress relief heat treatments at 520 °C for 2 h are an interesting

option to solve this problem, but because these materials present a thermodynamically

metastable condition, a few precautions should be taken.

The main objective of this work was to demonstrate that, after solution annealing at 1130 °C

and water quenching, stress relief at 520 °C for 2 h did not alter the duplex microstructure or

impair the pitting corrosion resistance of ASTM A890/A890M Grade 6A steel. This finding

was confirmed by microstructural characterization techniques, including light optical and

scanning electron microscopy, and X-ray diffraction. Corrosion potential measurements in

synthetic sea water containing 20,000 ppm of chloride ions were also conducted at three

temperatures: 5 °C, 25 °C and 60 °C.

© 2008 Elsevier Inc. All rights reserved.

1.

Introduction

Super duplex stainless steels (SDSS) have a two-phase structure containing ferrite and austenite in almost equal proportions, and a pitting corrosion resistance of over 40. These materials are important for use in offshore platforms in applications that involve pumping of produced water, i.e., sea water containing high concentrations of chloride ions (Cl ), CO 2 , hydrosulfuric gas (H 2 S), and HS and S 2 ions, among others, at temperatures ranging from 40 °C to 80 °C [1]. The production of cast components for centrifugal pumps with wall thicknesses exceeding 125 mm (5 in.) in duplex and super duplex stainless steels has become a complex task due to the low cooling rates during the solidification process.

Precipitation of intermetallic and carbide phases are common and include the sigma phase, which appears in the highest proportion, sometimes reaching values of close to 20% [2,3]. Solution annealing heat tre atments followed by water quenching dissolves these precipitates and keep the alloying elements in solid solutions. Another common problem with these materials is the difficulty of maintaining the dimensional tolerances during and after the machining process of cast components, regard- less of the size and thickness of the components [3]. Stress relief heat treatments at temperatures close to 520 °C allow the dimensional stability to be maintained without promoting precipitation of secondary phases or destroying the meta- stable equilibrium of these SDSS alloys.

Corresponding author. Av. Eng. João Fernandes G. Molina, 905 Distrito Industrial, Jundiaí 13213-080, SP, Brazil. Tel.: +55 11 45892020; fax:

+55 11 45892102. E-mail address: marcelo.martins@sulzer.com (M. Martins).

1044-5803/$ see front matter © 2008 Elsevier Inc. All rights reserved.

MATERIALS CHARACTERIZATION 60 (2009) 150 155

151

MATERIALS CHARACTERIZATION 60 (2009) 150 – 155 151 Fig. 1 – Absorbed energy in impact test

Fig. 1 Absorbed energy in impact test vs volumetric concentration of sigma phase.

Because they are thermodynamically metastable in the solution annealed condition, super duplex stainless steels are subject to microstructural changes when exposed to heat, be it through heat treatments at low temperatures aimed at relieving internal stresses or through the welding process. This is especially the case in the welding repair of cast com- ponents that normally present some type of foundry defect after detection in machining operations. The tendency of these steels to reach a thermodynamically stable condition implies the precipitation of intermetallic and/ or carbide phases rich mainly in chromium and molybdenum. The effect of this precipitation is to form regions adjacent to the particles that are depleted of these elements. Concentra- tion can fall below the minimum 12 wt.% to 13 wt.% of chro- mium required to ensure the passivation process [2]. Regions with quantities below the minimum Cr range undergo active dissolution and usually corrode at rates close to those of carbon steels and pure iron. Stainless steels with high chromium content, as is the case of duplex and super duplex stainless steels, are relatively passive and corrode at much lower rates than do alloys with low chromium content

[4].

In alloys containing chromium, the passive region is initiated at lower potentials than in alloys that do not contain this element, such as carbon steels and pure iron. The trans- passive regions of alloys containing chromium originate from the easy oxidation of the chromium ion from Cr +3 to Cr +6 which forms the passive film [4]. Chloride ions cause aqueous corrosion of stainless steels because they increase the elec trical conductivity of the solution and penetrate easily into the protective oxide film, thereby breaking its passivity. As the concentration of these ions increases, so does the current density, because chloride ions present high charge densities [4]. The best mechanical and chemical characteristics of super duplex stainless steels are ob tained after solution heat treatments, in which all the secondary phases carbide and intermetallic originating from the as cast microstructure are dissolved at high temperatures. Water quenching prevents them from precipitating again, keeping large quantities of solute atoms in solid solution.

Table 1 Composition of the chemical elements in super duplex stainless steel casting (wt.%)

C

0.016

Nb

0.014

Cr

25.69

Ti

0.005

Mo

3.80

Al)

0.016

Ni

7.18

V

0.049

Si

0.74

Zr

0.065

Mn

0.52

Co

0.055

Cu

0.716

Sn

0.007

W

0.736

Pb

0.002

N

0.22

S

0.008

P

0.027

Fe

 

60.16 (by difference)

One of the phases precipitated during solidification cooling is the sigma phase, which contains about 30 wt.% of chro- mium and 8 wt.% of molybdenum [3]. The presence of more than 3% in volume of sigma phase in the microstructure reduces the impact toughness of these materials from 220 J to 20 J at room temperature, Fig. 1 [3]. It is impossible to avoid the precipitation of sigma phase during cooling in the solidification process, in castings with thick sections ( N 75 mm), in regions close to feeder heads and exothermal glovesused for feeding during contraction and for the components that are cooled inside silica sand molds, where thermal conductivity is very low. The volumetric fraction of this precipitate can be minimized by controlling the chemical composition and the cooling rate in the solid state. The solution heat treatment itself introduces a certain level of internal stresses in cast components, because solute atoms such as chromium, nickel and molybdenum are larger than the iron atom. The bcc crystal lattice of ferrite and fcc structure of austenite are slightly deformed and this deformation strains the entire lattice. Another factor that contributes to increase in the level of internal stresses is nitrogen, which lodges in the octahedral and tetrahedral interstices of the austenite, causing micro- deformations in the crystal lattice. The use of this element in super duplex stainless steels is justified because it provides greater pitting corrosion resistance, because it is a strong stabilizer of austenite, contributing to the final equilibrium of the volumetric fraction of austenite in the microstructure.

the volumetric fraction of austenite in the microstructure. Fig. 2 – Micrographs characterizing the as cast

Fig. 2 Micrographs characterizing the as cast state. Murakami reagent. Magnifications: (a) 100× and (b) 200×.

152

MATERIALS CHARACTERIZATION 60 (2009) 150 155

152 MATERIALS CHARACTERIZATION 60 (2009) 150 – 155 Fig. 3 – Micrograph of the material solution

Fig. 3 Micrograph of the material solution annealed at 1130 °C and water quenched. Beraha II reagent. Magnification: 200×.

Some alloying elements have specific functions in super duplex stainless steels, but because they are usually larger than iron atoms, they also cause internal stresses. This phe- nomenon promotes a certain dimensional instability during and after the machining process, especially when large quantities of materials are removed. One way to minimize this effect is through stress relief heat treatments at sufficiently low temperatures to prevent the precipitation of secondary phases. Carrying out this procedure requires good knowledge of the metallurgical aspects of the material. In the solution annealed condition, these steels constitute thermodynamically metastable systems. If the heat input is not well controlled, undesirable phases will appear in the microstructure. In some kinds of duplex and super duplex stainless steels others chemical elements are used to promote specific properties. Among them, tungsten and copper are the most commons. The presence of tungsten in these materials delays precipitation of the sigma phase during the cooling from the solidification process, thereby reducing the tendency for embrittlement [5].

thereby reducing the tendency for embrittlement [5] . Fig. 4 – SEM micrograph after solution annealing

Fig. 4 SEM micrograph after solution annealing heat treatment at 1130 °C and stress relief at 520 °C. Beraha II reagent. Magnification: 3000×.

relief at 520 °C. Beraha II reagent. Magnification: 3000×. Fig. 5 – Diffractogram of the material

Fig. 5 Diffractogram of the material in the solution annealed and stress relieved condition. CuKα1, λ = 1.5406 Å.

On the other hand, copper in solid solution increases erosioncorrosion resistance, especially in components of centrifugal pumps where there are continuous flows of aggressive fluids [6].

where there are continuous flows of aggressive fluids [6] . Fig. 6 – Anodic polarization curves

Fig. 6 Anodic polarization curves of the materials solution annealing heat-treated and solution annealed heat-treated+ stress relieved.

MATERIALS CHARACTERIZATION 60 (2009) 150 155

153

2. Experimental Procedure

The steel studied here was produced in a vacuum induction

furnace with an electric power frequency (60 Hz) and a maxi- mum power of 400 kW. The first step consisted of drawing up the foundry design of the 25 mm diameter, 300 mm long test specimens, followed by simulation of the solidification process using a specific software program. The material's chemical composition was analyzed using an optical emission spectrometer equipped with 47 dif- ferent channels. The solution annealing heat treatments recommended for these materials were carried out in an electric furnace with a heating capacity of up to 1300 °C, and the temperature adopted for this kind of heat treatment was 1130 °C. After the solution heat treatment, several samples were stress relieved at 520 °C for 2 h. X-ray diffraction analyses were conducted in a diffract- ometer coupled to a multipurpose camera, using copper (CuKα 1) radiation at a wavelength of 1.5406 Å, a 50 kV source,

100 mA and a scanning velocity of 1°/min. The pitting potential

was determined in a synthetic sea water solution containing 20,000 ppm of chloride ions, at three different testing

temperatures: 5 °C, 25 °C and 60 °C. The reason for these choices is that the temperatures in deep waters (close to 3000 m) reach 5 °C, and the temperature of 60 °C served to

simulate the pumping of produced sea water, which is the water injected into the oil well to increase its pressure and drag the crude oil from the marine subsoil up to the platform. Because the temperature of petroleum deposits ranges from

140 °C to 160 °C, the water moved up with the oil (which is then

separated from it and reinjected into the well), reaches a temperature of close to 60 °C. To obtain good resolution of the polarization curves, the scanning rate adopted was 1 mV/s, and the immersion time in the open circuit was 1 h prior to initiating the scan [7]. All the

scans were initiated starting from the corrosion potential established during the first hour of immersion and ended when they reached a current density of 1× 10 2 A/cm 2 . The electrochemical cell consisted of a platinum counter electrode. A saturated calomel electrode (SCE) was used as reference. The synthetic sea water was prepared according to

Table 2 Pitting potentials for aerated and CO 2 saturated solutions, for solution annealed at 1130 °C and solution annealed at 1130 °C + stress relieved at 520 °C

Sample

Solution

Test

Pitting

 

temperature

potential

(°C)

(mV)

Solution annealed at 1130 °C

Aerated

5

1070

60

900

 

CO 2 saturated

5

1030

 

60

880

Solution annealed at 1130 °C + stress relieved at 520 °C

Aerated

5

1020

60

910

CO 2 saturated

5

1070

 

60

880

Test temperatures: 5 °C and 60 °C.

 
60 880 Test temperatures: 5 °C and 60 °C.   Fig. 7 – Variation of the

Fig. 7 Variation of the pitting potential as a function of test temperature.

the ASTM D 1141 Standard, using prepared stock solutions for the respective chloride ion concentrations in aerated and CO 2 saturated conditions. The alloying elements that determine the pitting corrosion properties of stainless steels are chromium, molybdenum and nitrogen. To determine quantitatively the effect of these ele- ments on the corrosion resistance of stainless steels, a pit- ting resistance equivalent, PRE N coefficient was introduced. Expression 1 gives the most commonly used formula. Different multiplying factors for the nitrogen contents, vary- ing from 10 to 30, are sometimes used for different types of stainless steels. For duplex stainless steels, for example, the following formula is given in the literature [8]:

PRE N = ½ wt: k Cr + ð3; 3 Þ½ wt: k Mo + ð16Þ½wt : k N

ð1Þ

Other alloying elements such as tungsten are also some- times taken into account [9]:

PRE W = ½ wt : k Cr + ð3; 3Þ½ wt: k Moþð1=2Þwt : k W + ð16Þ½ wt: k N

ð2Þ

In duplex stainless steels, the pitting resistance of the two phases must be considered separately [9].

3. Results and Discusssion

The chemical composition of the material used, ASTM A890/ A890M Grade 6A [10] , determined by means of optical emission spectrometry, is described in Table 1. The volumetric concentrations of the phases, determined experimentally by

hand counting on a grid of points following the ASTM E562 standard [11], were 43% and 57%, respectively, for the ferrite

and the austenite. The concentration of ferrite can be

increased by up to 10% with the same chemical composition only by increasing the temperature of the solution annealing

heat treatment. Fig. 2 illustrates the microstructure of the material in the as cast state, after solidification in a silica sand mold

154

MATERIALS CHARACTERIZATION 60 (2009) 150 155

agglomerated with organic urethane-phenol resin. The sigma phase nucleates at the ferrite/austenite interfaces and grows towards the ferrite phase, which is the phase that supplies it with stabilizing elements (Cr and Mo). During cooling inside the silica sand mold, the solubility of alloying elements such as chromium and molybdenum diminishes in the ferrite, favoring high concentrations at the interfaces, which are also regions of high energy, promoting the subsequent nucleation of the sigma phase and secondary austenite. Precipitation of the sigma phase during cooling in the solidification process is difficult to avoid in this kind of material (SDSS), because the chemical composition fa- vors its formation. However, the quantity of precipitated sigma phase can be minimized by controlling the chemi- cal composition itself. This is achieved by limiting the concentration range of each element, and by controlling the cooling rate in the solidification process, maximizing it by means of forced air or water. Once it is formed, the sigma phase can only be dissolved by means of heat treatment at a high temperature of approximately 1060 °C followed by water quenching [3]. The soak dwell time at this temperature must be sufficient to allow the entire material to reach an isothermal condition. Fig. 3 depicts the microstructure of the material in the solution annealing condition (1130 °C, followed by water quenching). The matrix contains the precipitated austenite phase, with rounded and elongated morphologies. Note the absence of intermetallic or carbide phases precipitated at the ferrite/austenite interfaces or precipitated intergranularly in the ferrite. The black spots indicate inclusions originating from the deoxidation process. The heat treatment promoted the total dissolution of the sigma phase that had precipitated during solidification cool- ing, leaving the microstructure composed solely of ferrite and austenite. After solution annealing and water quenching, some of the samples were stress relieved at 520 °C for 2 h. The material's microstructure shows only the two constituent phases of the super duplex structure, i.e. ferrite and austenite, as shown in Fig. 4 . Although the material was in a thermodynamic condition of metastability after the solution annealing heat treatment, the heat input from the stress relief was not enough to overcome the energy gap between the metastable and stable conditions in which intermetallic phases, mainly sigma phase, would nucleate and grow in the microstructure. The ferrite/austenite interfaces, as well as the inside of the ferrite grains are devoid of precipit ates, and confirm that the material is still in the metastable condition. The phases in the samples that were solution annealed at 1130 °C, water quenched, and stress relieved at 520 °C were characterized by X-ray diffraction, producing a diffractogram shown in Fig. 5 . The figure shows only a few peaks corresponding to reflections of atomic planes belonging to ferrite and austenite, and no reflections of crystalline planes of any intermetallic phase, indicating that the stress relief heat treatment at 520 °C did not cause the precipitation of undesirable secondary phases. The anodic polarization curves of the samples solution annealed at 1130 °C and for the samples treated at the same temperature and then stress relieved at 520 °C for 2 h are

depicted in Fig. 6. Note that the test temperature was 25 °C, but tests for 5 °C and 60 °C were also made and the results are showed at Table 2 . All these temperatures tried to simulate the conditions as close as possible to the situations of pumping on offshore platforms. The polarization curves resulting from the aerated solution and the CO 2 saturated solution were very similar, without major deviations in shape or position in relation to the Cartesian E × I system. The samples solution annealed at 1130 °C and stress relieved at 520 °C generally presented more positive pitting potentials than the samples only solution annealed at 1130 °C. The region of passivation on the curve corresponding to the solution annealed and stress relieved samples was found to shift to higher currents only at two of the test temperatures (5 °C and 60 °C, for CO 2 saturated solutions), with the curves appearing practically superim- posed in the other conditions. The anodic current oscillations (serratedregions of the E × I curve) observed below the pitting potential are related to the formation and repassivation of microscopic pits, or micropits [12] . These metastable pits, are very small, growing and repassivating in a few seconds below the pitting potential and during the induction time for the formation of stable pits. Fig. 7 illustrates the behavior of the pitting potential as a function of the test temperature for aerated solution (the CO 2 saturated solution presented the same values). Generally speaking, the stress relief heat treatment at 520 °C for 2 h did not significantly alter the pitting potential at any of the temperatures tested here, in view of the fact that curves for all practical purposes were superimposed. The pitting potential decreased linearly as the test tem- perature increased, in both the solution annealed samples and the solution annealed and stress relieved samples. Indepen- dent of the test solution (aerated or CO 2 saturated), the behavior of the straight lines was quite similar. The values of the pitting potentials in both aerated and CO 2 saturated solutions were practically identical at the different test temperatures, indicating that the stress relief heat treatment did not produce differences in this variable.

4.

Conclusions

The sigma phase is always present in the as cast micro- structure of super duplex stainless steels. It precipitates at the ferrite/austenite interfaces, occupying a major part of the ferritic phase. The quantity of sigma phase can be minimized in the as cast microstructure only by controlling the chemical composition and the cooling process. The solution annealing heat treatment followed by water quenching dissolved the sigma phase that precipitated during the solidification process, leaving the microstructure com- posed solely of ferrite and austenite. The stress relief heat treatment at 520 °C for 2 h did not alter the material's microstructure, i.e., it did not promote the precipitation of any intermetallic phase. From the standpoint of corrosion, the stress relief heat treatment hardly altered the pitting potential at all, at any of the tested temperatures in either the aerated or CO 2 saturated solutions.

MATERIALS CHARACTERIZATION 60 (2009) 150 155

155

REFERENCES

[1] Weber, J. Materials for sea water pumps and related systems. SULZER Brothers Limited; Winterthur; Switzerland, p. 1 11. [2] Maehara Y, Ohmori Y, Murayama J, Fujino N, Kunitake T. Effects of alloying elements on σ phase precipitation in δγ duplex stainless steels. Met Sci November 1983;17:541 7. [3] Martins, M. Caracterização microestrutural-mecânica e resistência à corrosão do aço inoxidável super duplex ASTM A890/A890M Grau 6A, Doctoral Thesis, Universidade de São Paulo, Interunidades EESC-IFSC-IQSC. [4] Laycock NJ, Newman RC. Localized dissolution kinetics, salt films and pitting potentials. Corros Sci 1997;39(10 11):1771 9. [5] Kim SB, Paik KW, Kim YG. Effect of Mo substitution by W on high temperature embrittlement characteristics in duplex stainless steels. Mater Sci Eng 1998;A247:67 74. [6] Garfias-Messias LF, Sykes JM. Effect of copper on active dissolution and pitting corrosion of 25% Cr duplex stainless steels. Corros Sci 1998;54(1):40 7. [7] Alonso, N. Análise do método potenciodinâmico de determinação do potencial de pite. Doctoral Thesis (Materials

Science and Engineering) Escola Politécnica da Universidade de São Paulo USP São Paulo, 1992. [8] Nilsson JO. Overview: super duplex stainless steel. Mater Sci Technol 1992;8:685700. [9] Okamoto H. The effect of tungsten and molybdenum on the performance of super duplex stainless steels, applications of stainless steels. In: Nordberg H, Björklund J, editors. Proceeding of international conference on stainless steels. Kristianstad Boktryckeri ABSweden: Stockholm; 1992. p. 3609. [10] American Society For Testing and Materials ASTM A890/ A890M-91. Standard practice for castings, iron chromium nickel molybdenum corrosion resistant, duplex (austenitic/ferritic) for general application. Annual book of ASTM standards. V.01.02. Ferrous castings; ferroalloys; 1999. p. 55669. [11] American Society for Testing and Materials ASTM E 562. Standard practice for determining volume fraction by systematic manual point count. Annual book of ASTM standards. V.03.01; 1988. p. 575 9. [12] Szklarska-Smialowska Z. Mechanism of pit nucleation by electrical breakdown of the passive film. Corros Sci 2002;44:1143 9.