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INDIAN INSTITUTE OF TECHNOLOGY, BOMBAY
Department of Metallurgical Engineering and Materials Science ----------------------------------------------------------------------------------SYNOPSIS of the Ph.D. thesis titled MICROSTRUCTURAL AND THE CONSEQUENT LOCALIZED CORROSION RESISTANCE BEHAVIOUR OF HTHAZ OF UNS S32760 SDSS TIG WELDS PREPARED USING NITROGEN ADDITIONS TO ARGON SHIELDING GAS Proposed to be submitted in partial fulfillment of the degree of DOCTOR OF PHILOSOPHY of the INDIAN INSTITUTE OF TECHNOLOGY, BOMBAY By Rahul Khandagale (Roll No. 99411401) Supervisors: Prof. R. Raman and Prof. I. Samajdar July 2006

----------------------------------------------------------------------------------------------------------Second generation duplex stainless steel contains nitrogen as a crucial alloying element specifically added to enhance reaustenitization of the HTHAZ in the limited time available as the weld cools. In the absence of nitrogen a highly ferritized [greater than 80% ferrite] can be obtained in the consequent loss in the expected physico – chemical properties1. During arc welding there is an inevitable dynamic interaction between the molten weld pool/arc atmosphere, molten weld pool/inert gas atmosphere and arc atmosphere/inert gas interfaces leading to exchange of the metallurgically active nitrogen species. The above leads to loss/gain of nitrogen from the metal depending upon the partial pressure of nitrogen [diatomic] in the shielding gas and the monotonic nitrogen in the arc atmosphere. The proposed model is shown in Figure 1.

FZ

PN

PN2

HTHAZ

N

LOSS GAIN (LOSS if PN2 in shielding gas mixture is below a critical value) Figure 1: A schematic indicating the involvement of HTHAZ via FZ in the process of exchange of nitrogen species due to the dynamic interaction between arc plasma/shielding atmosphere and highly convecting molten weld pool (FZ) during arc welding

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The nitrogen plays two contradictory roles during the evolution of HTHAZ microstructure i] Encouragement of reaustenitization which is beneficial ii] Formation of Cr2N which is harmful. Based on the CCT curve for the above two reaction2 it is seen that beyond a particular level of nitrogen in the HTHAZ reaustenitization will dominate leading to efficient trapping of nitrogen as it gets rejected from the ferrite phase, in which the solubility of nitrogen is very low as compared to that in austenite. This leads to non linearity of the effect of nitrogen contain in the HTHAZ on the formation of Cr2N. This has been confirmed by several weld simulation study on super-duplex stainless steels3, 4, 5 in the absence of adequate reaustenitization there is also a good possibility of forming sigma phase in the HTHAZ in SDSS which contain higher levels of Cr and Mo as alloying elements. Formation of both the above deleterious phases can lead to loss of localized corrosion resistance. The success of duplex stainless steel as a material with excellent pitting and SCC resistance relies on i] Maintaining nearly 50 : 50 ferrite (δ): austenite (γ) balanced structure ii] Prevention of deleterious precipitates and phases forming during processing in ferrite. The deviation from optimum performance can also occur due to loss of phase balance either towards ferrite direction or austenite direction. The former occur when effective nitrogen level is below critical level and latter when the level is above a threshold value. The above clearly suggests that while welding second geration DSS it is necessary to maintain adequate nitrogen activity in the arc atmosphere so that an optimum property of HTHAZ is obtained. Note that, in the case of fusion zone the above problem can be offset by choosing a suitable filler metal [Ni rich]. The main objective of the present work is to determine the amount of nitrogen that need to be added to the argon shielding gas while welding super-duplex stainless steels [SDSS] using range of heat input normally required for these materials. Although it is known that nitrogen needs to be added while welding second generation DSS there has been no reported systematic investigation on the effect of nitrogen additions to the shielding gas from the localized corrosion properties of the HTHAZ formed. Most of the reported work on the effect of nitrogen on the response of DSS and SDSS to thermal cycle have been limited to weld thermal simulation studies. However due to practical

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limitations these studies do not properly capture the events which actually occur during arc welding. This is especially true for those materials in which there is a possibility of metallurgical interaction between the arc and the weld pool. In the present work studies on localised corrosion resistance of the HTHAZ formed during TIG welding of UNS S32760 super-duplex stainless steels (12.5mm thick plates in solution annealed followed by water quenched condition) have been carried out. Bead-in-groove welds were prepared using the recommended Ni rich (9%Ni, 2.5mm diameter) filler wire. To vary the effective nitrogen activity in the HTHAZ controlled amount (0 to 5 vol. %) of nitrogen additions to the argon shielding gas was made. To vary the weld cooling rate and hence the HTHAZ cooling rate a range of heat inputs was selected (0.33 to 1.21 kJ/mm). The above heat input corresponded to the HTHAZ cooling rate to, as represented by ∆t12/8 , 0.37 to 4.9 s which is wide enough range to represent the weld cooling rates normally encountered. The HTHAZ of different welds were subjected to different characterization techniques for the purpose of evaluating the evolved microstructure with respect to γ:δ phase balance and presence of deleterious phases such as σ and Cr2N and the consequent localised corrosion behaviour. This thesis consists of eight chapters. Chapter 1 briefly introduces the present project and states the objective and the scope of work. Chapter 2 presents the detailed and critical literature survey related to the evolution, the metallurgy, mechanical properties and corrosion characteristics of wrought duplex stainless steel in general and super duplex stainless steel in particular. Aspects related to formation of various deleterious precipitates and phases such as sigma [σ], Cr2N, secondary austenite (γ’), chi (χ), R, pi (π), carbides etc. have been particularly discussed in greater detail6. A separate section, related to welding metallurgy of these materials to bring about the effect of the weld thermal cycle on the metallurgy of evolution of microstructure of HAZ with particular reference to high temperature heat affected zone [HTHAZ] which is the zone of interest in the present work, conclude this chapter3,4,5. Chapter 3 is related to the important topic of the interaction of the metallurgically active nitrogen with the molten weld pool during arc welding of DSS. The crucial point 4

of increased solubility of nitrogen in the molten metal under arc much above that expected from Severt’s law considerations has been discussed. The chapter concludes with the effect of welding parameters on the nitrogen pick up [or loss] by the molten weld metal during arc welding. Chapter 4 presents the available information on the effect of nitrogen, a strong austenite stabilizer but can also encouraged formation of Cr 2N precipitates in the ferrite phase [in which the solubility of nitrogen is extremely low as compared to austenite phase] on the evolution of HTHAZ microstructure. Conditions favouring ferrite rich unbalanced structure with the attendant deleterious precipitates and phases and those favouring nearly balanced precipitate free balanced structure have been discussed. The importance of suitable combinations weld heat input [which affects the weld cooling rate as represented by ∆t12/8] and the nitrogen content of the material to ensure acceptable HTHAZ microstructure has been brought out. Various electrochemical techniques for evaluating localized corrosion resistance of passive metal/alloys such as cyclic pitting scan, electrochemical reactivation potentiodynamic test[EPR,DLEPR],rapid scratching electrode ,galvanostatic, electrochemical noise analysis [ECNA] and the novel micro-electrochemical Ecorr corrosion potential noise probing technique [a new technique under development in this laboratory]11 have been describe in chapter 5. a discussion on the rescaled range analysis7 [R/S][Hurst analysis], a mathematical tool for appropriately analyzing the essentially non linear Ecorr vs time noise data has also been included in this chapter. Various experimental procedures adopted related to preparation of welds, metallurgical characterization of the HTHAZ of the welds produced by optical and electron microscopy, preparation of appropriate test specimens for different electrochemical corrosion tests to evaluate the localized corrosion resistance of the HTHAZ of the welds have been presented in chapter 6. The chapter also includes brief description of various experimental set ups used for corrosion studies. The results obtained from each of the above experimental procedure are also included in this chapter. For the purpose of convenience results obtained have been presented in the form of tables, figures, micrographs etc. immediately after each type of experiment. Some representative results are shown in Figures 1 to 5 and Tables 1 to 3.

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(a)

WZ

(a’)

HTHAZ

σ

HAZ

γ δ
500µm

50µm

(b)
HAZ

WZ

(b’)

HTHAZ

δ

γ
Base metal

σ

Figure 2: Low (25X) and high (250X) magnification optical micrographs respectively showing the composite zone [(a),(b)] and HTHAZ [(a’),(b’)] of welds prepared with 0 vol.% nitrogen additions to the argon shielding gas and ∆t12/8 of 0.41 s [(a),(a’)] and 3.0 vol.% nitrogen additions to the argon shielding gas and ∆t12/8 of 0.37 s [(b),(b’)]{Figure 2 (a): weld 30(W30),(b): weld 48(W48)}.[Note the significant amount of σ phase formation in the ferrite phase in the case of weld prepared with 0 vol.% nitrogen(a’).Cr2N although present can not be revealed by optical microscopy.]

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0 -0.01 -0.02

0.01 0

FZ/HAZ
Ecorr (V) SCE

FZ

-0.01 -0.02 -0.03 -0.04 -0.05

Ecorr(v) SCE

-0.03 -0.04 -0.05 -0.06 -0.07 0 200 400 600 800 1000

HTHAZ FZ

HTHAZ

FZ/HAZ

-0.06 -0.07 0 200 400 600 Time (Sec) 800 1000

Time(Sec)

(a)

(b)

Figure 3: Ecorr vs time noise data obtained with the novel micro-electrochemical corrosion potential noise probing (90 µm diameter probe) technique (under development in this laboratory) on the welds with defective HTHAZ [W30](a) and defect free HTHAZ [W48](b).[The above curves corresponds to the same welds shown in Figure 2. Note the active and negative going trend of the Ecorr vs t noise signal obtained from the defective weld (a).]
0.8
0.8

AR

W48
0.7

W9 W1
E(V,SCE)

0.6 E (V,SCE)

0.4

W30

0.6

AR

0.2

0.5

0

HT

0.4

W30 W33

W48

HT

-0.2 0 100 200 300 Time (Sec) 400 500 600

0.3 0 20 40 60 80 100 Time (sec) 120 140 160 180 200

(a)

(b)

Figure 4: (a) E vs t response anodic galvanostatic current density of 10µamp/cm2 in 0.85 M NaCl solution at 500C for good weld [W 48] and bad weld [W30].The response of as received material [AR] and thermally aged [HT] [8500C+3hrs.] to this test have been included in the Figure (b) E vs t response anodic galvanostatic current density of

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10µamp/cm2 in 0.1 M Na2O3 solution at room temperature of 250C for good weld [W 48], bad weld [W30] and several other welds [W33:Weld No.33, ∆t12/8=0.47s(0.5%nirogen), W1:Weld No.1, ∆t12/8=1.33s(0%nitrogen),W9: Weld No.9, ∆t12/8=1.74s(1%nitrogen), W30:Weld No.30, ∆t12/8=0.41s(0%nitrogen), W48:Weld No.48, ∆

t12/8=0.67s(3%nitrogen)] with different ∆t12/8 / vol.% nitrogen additions combinations [see Table 2]. The response of as received material and thermally aged [8500C+3hrs.] to this test have been included in the figure. [the galvanostatic test is based on the suggestions made by Newman et al 9,10 The test in chloride media [Figure 4 (a)] is a clear indicator of good and bad passive material which has been confirmed with other electrochemical tests [see Table 1] Figure 4 (b) shows the presence of Cr2N [assuming the hypothesis put forward by Newman et al10] shows the non linear behaviour of Cr2N formation with respect to vol.% nitrogen additions to the argon shielding gas and combinations.]
80 70 1.992sec 60 50 % ferrite 40 1.60sec 30 20 10 0 0 1 2 3 4 5 6 Vol.% nitrogen in the shielding gas 4.92sec 3.4sec

∆t12/8
1.33 sec

1.33 sec 1.60 sec 1.992 sec 3.4 sec 4.92 sec

Figure 5: Dependence of vol.% ferrite [estimated by image analyzer] in the HTHAZ on vol.% nitrogen additions to the argon shielding gas and HNet [as represented by ∆t12/8 ].

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[ the Figure clearly brings out the complex interdependence of the reaustenitization process which depends on the effective nitrogen available in the HTHAZ [which in turn depends on vol.% nitrogen additions to the argon shielding gas and HNet latter of which decides the weld pool size and weld pool/arc/inert atmosphere interface area] and ∆t12/8 which depends only on the HNet for a given plate thickness and if preheat temperature if any. This result also brings about an important fact of inadequacy of results obtained in weld simulation studies on materials which are capable of metallurgically interacting with the arc during welding.] Chapter 7 is the penultimate chapter of the present thesis. Discussion of the various results related to HTHAZ of different welds prepared namely degree of ferritization, formation of sigma, Cr2N and localized corrosion resistance is presented in this chapter. Before analyzing the actual results basis for expected variation in different microstructural features of the HTHAZ and its consequent localized corrosion resistance in response to the experimental input of HNet [hence ∆t12/8]8 combinations has been formulated. Due recognition is given to the fact that the kinetics of evolution of HTHAZ microstructure is far different from that associated with CCT diagram determination and weld thermal simulation study the latter of which has limitation with respect to maximum temperature, heating and cooling rates that can be simulated. The final chapter 8 of the thesis presents conclusions related to a] the localized corrosion resistance of HTHAZ of the various welds depending upon the combination of the heat input HNet [which determines the ∆t12/8] and vol.% nitrogen addition to the argon shielding gas [which together with HNet decides the effective nitrogen activity in the HTHAZ] combination. b] The evolution of HTHAZ microstructure with respect to alpha gamma balance and presence of deleterious precipitates such as sigma and Cr 2N. c] The satisfactory performance of the novel micro-electrochemical corrosion potential noise probing technique [under development in this laboratory] for evaluating local localized corrosion resistance [the exposed area limited to 90 micrometer diameter] of passive surfaces and encouraging results using galvanostatic technique suggested by Newman9, 10. The chapter also includes practical suggestions levels of nitrogen additions to be made to argon shielding gas while TIG welding of UNS S32760 super duplex stainless steels 9

using a range of heat input normally used. While making this suggestion it is kept in mind that not only has good localized corrosion resistance but also has reasonably balanced microstructure with respect to alpha (δ) and gamma (γ).

Table 1: Basis for evaluation of HTHAZ of different welds using various electrochemical tests Sr. No. 1 Corrosion Test DLEPR (2M H2SO4 + 0.01M KSCN + 0.5M NaCl, RT) Rapid scratching electrode (3.5% NaCl, RT) Basis for evaluation of localized corrosion resistance  Based on ir / if ratio.  Acceptable : < 10 X 10-3  Unacceptable : >10 X 10-3  Based on repassivation tendency ∆Erepass =Emax – (Ecorr+ 50mV)  Acceptable : >800 mV  Unacceptable : < 800 mV  Based on E vs Time curve  Acceptable: rapidly attaining noble potential without significant noise towards active potential.  Unacceptable: noisy and tendency to attain active potential.  Based on E vs Time curve  Has been used for precipitate phase identification only because transpassive dissolution in mild alkaline solution is not stable because of formation of stable Fe+++ oxide or oxyhydroxide.  Cr2N starts dissolving at lower potential (hence earlier) than χ than σ.  Based on Hurst exponent (H) along with whether the Ecorr vs t tends to go +ve or –ve.  Acceptable: H > 0.8 with +ve going tendency. Unacceptable : H > 0.6 with –ve going tendency

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3 Galvanostatic (0.85 M NaCl, 500C )9

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Galvanostatic (0.1M Na2CO3, RT )10

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Micro-electrochemical corrosion potential noise probing (3.5% NaCl, RT) [Under development in this laboratory]11

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Table 2: Consolidated localized corrosion resistance test results of HTHAZ of various welds [42 in all]
[AR: As received UNS S32760, HT: Thermally aged UNS S32760 at 8500C +3hours, Gal-Nacl: Galvanostatic studies in 0.85 M NaCl] [Results of pitting scan have not been included]

∆t12/8 Ir/If X (s) 3
AR HT 0.365 0.387 0.411 0.435 0.459 0.592 0.680 0.711 1.054 1.170 1.289 1.334 1.377 1.420 1.600 1.644 1.742 1.941 1.992 2.041 2.598 2.778 3.360 3.428 3.635 4.368 4.445 4.921

0 vol.% nitrogen Hurst Gal(H) NaCl 10 1.3 100 15.0 30.6 0.7Bad 20.0 0.820.5 0.623.2 0.727.6 24.3 Bad 11.3 21.5 0.7Bad 24.4 -

0.5 vol.% nitrogen Ir/If Hurst GalX (H) NaCl 103 24.2 0.7-0.6Bad -1.22 0.618.2 0.721.4 0.5+ 20.7 0.814.2 0.8+ Good 12.2 0.7Bad 25.9 0.8Bad -

1.0 vol.% nitrogen Ir/If Hurst GalX (H) NaCl 103 60 0.8+ Bad 23 12.9 0.711.1 0.78 0.54 0.7Bad 1.05 0.8+ Good 0.85 0.8+ Good 0.48 0.8-

3.0 vol.% nitrogen Ir/If Hurst GalX (H) NaCl 103 2.65 0.6+ 0.26 0.9+ Good 0.82 0.64.52 0.8+ 3.92 5.5 0.6+ 1.96 0.6+ Good 0.12 0.5Good -

5.0 vol.% nitrogen Ir/If Hurst GalX (H) NaCl 103 -4.69 1.0+ Good 1.63 1.0+ 2.79 1.0+ Good 1.29 1.0+ Good 1.96 1.0+ 3.04 0.7+ 1.66 1.0+ Good 12

It is seen from the result [Table 2] that welds prepared with 0, 0.5 and 1 vol. % nitrogen addition to the argon shielding gas have been associated with poor localized corrosion of the HTHAZ. This can be ascribed to the formation of sigma phase and Cr 2N which precipitate ferrite phase leading to Cr/Mo depleted regions. The non linear behaviour of formation of Cr2N with respect to the input parameters namely vol.% nitrogen additions to the argon shielding gas and HNet [which determines the ∆t12/8 ] as well as weld pool /arc/atmosphere interface area and interaction time has also been observed. Limited TEM studies have been done on the HTHAZ with respect to Cr2N formation. The extent of Cr2N formation has been assessed on the basis of galvanostatic studies in 0.1 M Na2CO3 has recommended by Newman et al9, 10. It is seen from the result that the HTHAZ of the welds prepared with 3.0 and 5.0 vol. % nitrogen additions to the shielding gas too contain Cr2N. However the HTHAZ of these weld shave shown good localized corrosion resistance. This means that Cr2N by itself need not lead to drop in localized corrosion resistance. Hence the loss of localized corrosion resistance of HTHAZ should be ascribed mainly to formation of sigma phase with Cr2N formation enhancing this effect. This has been the case welds prepared with none or zero addition of nitrogen in the argon shielding gas and low heat input. It is thus advisable to keep the nitrogen additions to around 3.0 vol. % in welding UNS S32760 super duplex stainless steels [SDSS]. Also, to ensure adequate effective nitrogen activity in the HTHAZ higher values of nitrogen addition [but still around 3.0 vol. %] should be used with higher heat inputs. Too higher value of nitrogen additions will lead to the problem of loss of phase balance in the HTHAZ towards austenite side that should be avoided. Finally reference to be made to the Table 3 which gives conditions for obtaining welds acceptable both with respect to localized corrosion resistance of HTHAZ and its phase balance while welding UNS S32760 SDSS. Before concluding it is interesting to note that the novel micro-electrochemical corrosion potential noise probing technique [under development in this laboratory]11 appears to be quiet efficient in assessing local localized corrosion resistance of the passive materials. Galvanostatic technique suggested by Newman et al potentiostats.
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appear to be very promising and can found a good

economic alternative to the normally employed electrochemical techniques involving

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Table 3: Acceptable HNet range and vol. % nitrogen additions to the argon shielding gas while TIG welding UNS S32760 (12.5mm thick, without preheat)

Sr. No.

HNet range (kJ/mm)
0.30-0.40

0 vol.% N2 LCR
N.A

0.5 vol.% N2 LCR
N.A

1 vol.% N2 LCR
N.A

3 vol.% N2 LCR
A

5 vol.%N2 LCR
A

BM
N.A

BM
N.A

BM
MOD

BM
A

BM
A

1

2 3 4 5

0.41-0.50 0.51-0.65 0.66-0.80 0.80-1.21

N.A N.A MOD N.A

N.A N.A N.A N.A

N.A N.A N.A N.A

N.A N.A N.A N.A

N.A MOD A A

A N.A MOD MOD

A A A A

A A A A

A A A A

A N.A N.A N.A

( LCR: Localised corrosion resistance of HTHAZ ; BM : Balanced microstructure ; N.A : Not Acceptable ; MOD : Moderate ; A : Acceptable.)

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REFERENCES
1. J. O. Nilsson, “Super duplex stainless steels-Overview”, Material Science and Technology, vol.8, pp. 685-700 (1992). 2. B.Joseffsson, J.O.Nilsson, and A.Wilson, “Phase transformation in duplex steels and the relation between continuous cooling and isothermal heat treatment”, Proc.Conf. “Duplex stainless steels’91”, p.67, Les Ulis, France, Les Editions de Physique (1991). 3. A.J.Ramirez, J.C.Lippold, S.D.Brandi, Metallurgical and Materials transactions A, vol.34A, p.1575 (2003). 4. H. Hoffmeister and G.Lothongkum, “Quantitative effects of nitrogen contents and cooling cycles on δ → γ transformation, chromium nitride precipitation and pitting corrosion resistance after weld simulation of duplex stainless steels.” Vol.2, paper 55, Jacques Charles, Welding in the World, vol.36, pp.43-54(1995). 5. E.I. Kivineva and N.E.Hannerz: “The properties of Gleeble simulated heat affected zone of SAF 2205 and SAF 2507 duplex stainless steels.” .Vol.2 paper 7, Proc. Conf. Duplex 94, Glasgow, 1994. 6. J.O Nilsson and P.Liu, Mater. Sci. Technol., 7,(9), pp.853-862 (1991 7. J.Feder, “Fractals”, Plenum, New York, 1988. 8. Bjorn E. S. Lindblom, Berthold Lundqvist and Nils Erick Hannerz, Scandinavian Journal of Metallurgy, 20, pp.305-315 (1991). 9. M.A. Domninguez-Aguilar, R.C.Newman, Corrosion Science (2005) (article in press). 10. M.A. Domninguez-Aguilar, R.C.Newman, Corrosion Science (2005) (article in press). 11. R.Raman, DRDO sponsored project on “The development of micro-electrochemical corrosion potential noise probing technique for evaluating local localized corrosion resistance of passive materials in aqueous solution” (June2003 to August 2006). Being carried out in the Department of Metallurgical Engg. and Material Science, I.I.T. Bombay (India).

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Publication resulting from the Ph.D work: 1) Ramesh P , R.Khandagale, R.Dalvi, Depashree Nage, R.Raman “Repassivation Studies by Rapid Scratch Technique on Super Duplex Stainless Steel, Steel Welds in non-deaerated 3.5% NaCl Solution”, published in NACE India, conference held in Goa(India), from 28th – 30th November 2002. 2) R.Raman, R.Khandagale, “Development of micro electrochemical Ecorr noise probing system to study degradation or enhancement of localized corrosion resistance of passive materials.”, published in NACE India, conference held in Goa (India), from 28th – 30th November 2002. R.Raman, R.Khandagale, “GTAW of UNS S32760 Super Duplex Stainless Steel using Nitrogen additions in the shielding gas – microsturctural and localized corrosion resistance aspects of fusion zone / heat affected interface”, one day seminar on ‘Advance in Welded Fabrication’, held in BARC, Mumbai (India)on 18” January 2003. R.Raman, P.Raju, P.J.Antony, R.Khandagale, “Analysis of corrosion potential noise by R/S analysis and wavelet transform methods” International conference on corrosion (CORCON2003) in Mumbai(India), Dec. 1 to 4, 2003. ………………………………….

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