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Studies on Hot Corrosion of the Microstructurally Different Regions of 2.25Cr-1Mo (T22) Boiler Tube

Studies on Hot Corrosion of the Microstructurally Different Regions of 2.25Cr-1Mo (T22) Boiler Tube
Studies on Hot Corrosion of the Microstructurally Different Regions of 2.25Cr-1Mo (T22) Boiler Tube

Studies on Hot Corrosion of the Microstructurally Different Regions of 2.25Cr-1Mo (T22)Boiler

Tube Steel Weldment

Ravindra Kumar,V.K.Tewari,and Satya Prakash

(Submitted December 5,2007;in revised form August 27,2008)

This study examines the effect of microstructurally different regions on the hot corrosion of tungsten inert gas weldment in 2.25Cr-1Mo (T22)boiler tube steel.Various regions of weldment were oxidized in molten salt Na 2SO 4-60%V 2O 5environment at 900°C.The base metal was found to oxidize at much higher rates than the weld metal and the heat-affected zone.Oxide scales formed in the three regions were compared by scanning electron microscopy with energy dispersive of X-ray analysis,X-ray diffraction pattern,and electron probe microanalysis.The research investigates the formation of inner scales with free Cr over the HAZ.

Keywords

boiler tube steel,hot corrosion,molten salt,tungsten inert gas (TIG),weldment

1.Introduction

Chromium-molybdenum steels are extensively used in the steam generator circuits of power plants.These components may require welding of the cracks that can develop during fabrication,storage,and transportation stages,or during the service life of the plant.The microstructures of Cr-Mo steels are very susceptible to thermo mechanical treatments.This micro-structural susceptibility is often exploited to develop carbide precipitates of a required chemistry,morphology,and distribu-tion to affect precipitation hardening (Ref 1,2).Welding is by far the most important of the processes to which structural alloy steels are subjected during the different stages of fabrication.When the ferritic steels are fusion welded,sharp changes are caused in the microstructure of the weldment depending upon the welding parameters.Metallurgical transformations that occur during welding result from thermal cycles and wide range of cooling rates experienced by the different regions of the weldments.A strong need,therefore,exists for the simulation of the conditions under which different microstructures could be produced so as to understand the spectrum of microstruc-tures encountered in the specimen,starting from the weld metal through the heat-affected zone (HAZ).Hot corrosion is the accelerated oxidation of materials at elevated temperatures induced by a thin ?lm of fused salt deposit (Ref 3).The failure of boiler tubes due to ?reside corrosion in a waste heat recovery

boiler utilizing the exhaust of a gas turbine ?red with high speed diesel has been analysed by Srikanth et al.(Ref 4).They reported that the corrosion occurs because of the reaction of the sulfur species in the gas phase with metal surfaces.The sulfur present in coal and fuel oils yields SO 2on combustion which is partially oxidized to SO 3.The NaCl (either as impurities in the fuel or in the air)reacts with SO 3and water vapor at combustion temperature to yield Na 2SO 4.Small amount of vanadium may also be present in fuel oils which on combustion forms V 2O 5.This may further react with Na 2SO 4to form low melting sodium vanadate,which are extremely corrosive to high temperature materials used in the combustion system as discussed by Khanna and Jha (Ref 5)and Hwang and Rapp (Ref 6).

The present study has been carried out to asses the hot corrosion behavior of base metal,weld metal,and HAZ regions of TIG weldment in 2.25Cr-1Mo boiler tube steel in Na 2SO 4-60%V 2O 5at 900°C.A SEM back scattered image analysis of the cross section of the oxide scale thickness has been made to measure the oxide scales formed over the regions namely weld metal,HAZ,and base metal.Oxide scale formed over the different regions of TIG weldment have been characterized using X-ray diffraction (XRD),electron probe microanalysis (EPMA),and scanning electron microscopy/energy-dispersive analysis (SEM/EDAX).

2.Experimental Procedure

2.1Materials and Preparation of Weld

SA 2132.25Cr-1Mo (T22)boiler tube steel was procured from thermal power plant Bhatinda (India).This steel tube (10mm thickness 925mm diameter)was machined for mak-ing V-groove with bevel angle 30°,root face of 1mm and root gap 1mm.Tubes were welded together by tungsten inert gas (TIG)welding using 99%pure argon gas as shielded gas with ?ller wire AWS A 5.28ER90S-B3.The nominal chemical

Ravindra Kumar,V .K.Tewari,and Satya Prakash ,Metallurgical and Materials Engineering Department,Indian Institute of Technology Roorkee,Roorkee 247667,India.Contact e-mail:ravirs_2002@rediff https://www.wendangku.net/doc/f619184002.html,.

JMEPEG (2009)18:959–965óASM International DOI:10.1007/s11665-008-9309-21059-9495/$19.00

compositions of the base metal and the deposited?ller wire are given in Table1.The welding parameters were published in an earlier paper by Kumar et al.(Ref7).

2.2Metallography and Specimen Preparation

The cross section of the weldment portion was polished, etched with2%nital for20s and then examined by optical microscopy.Microsturucturally different regions,i.e.,base metal,weld metal,and HAZ were identi?ed.The structures of these regions are shown in https://www.wendangku.net/doc/f619184002.html,ing a diamond precision wafering blade specimens of weld metal,HAZ and base metal were cut out from the weldment in the approximate size 159592mm3and polished with220grades of SiC paper and emery paper and then wheel polished before corrosion test. 2.3Hot Corrosion Test

The cyclic oxidation studies for weld metal,HAZ and base metal regions of TIG weldment were conducted in Na2SO4-60%V2O5at900°C for50cycles.Each cycle consisted of1h heating at a given temperature in a silicon carbide tube furnace followed by20min cooling at ambient conditions.The specimens were kept in alumina boats and then the boats were inserted in the furnace.The aim of cyclic hot corrosion is to create accelerated conditions for testing.The specimens were wheel cloth polishing before corrosion test.The coating of uniform thickness with3-5mg/cm2of Na2SO4-60%V2O5was applied with a camel hair brush on the preheated sample (250°C).The samples were examined at the end of each cycle and subjected to weight change measurements.The electronic balance machine Model06120(Contech,India)with a sensitivity of1mg was used to measure the weight change values.The spalled scale was also included at the time of measurements of weight change to determine total rate of oxidation.The samples after oxidation were analyzed by SEM/ EDAX and XRD for surface analysis.The samples were then cut and mounted for the cross-sectional oxide scale thickness measurement and EPMA.

3.Results and Discussion

3.1Microstructure

The microstructures of the base metal,weld metal,and HAZ regions of the weldment are different.The weld metal shows a combination of widmanstatten type ferrite,pearlite,and bainite. The presence of Cr and Mo in the alloy enhances hardenability and promotes bainite formation even on relatively slow cooling

Table1Chemical composition(wt.%)for2.25Cr-1Mo boiler tube steel and?ller wire used in the present study

Materials

Chemical composition,wt.%

C Mn Si S P Cr Mo Fe

Base metal0.150.3-0.60.50.030.03 1.9-2.60.87Balance

Filler wire0.100.620.480.0060.009 2.55 1.08

Balance

Fig.1Optical micrographs of the etched microstructures in the different region of the weldment of2.25Cr-1Mo steel(a)base metal,2509, (b)weld metal,1009,and(c)coarse grain bainite in HAZ,1009

(Fig.1b)as also suggested by Natarajan and Babu(Ref8).The HAZ region showed coarse grain bainite(Fig.1c).The microstructures of base metal show ferrite(white constituent) and pearlite(dark constituent);those could be resolved at certain locations showing alternate lamellas of ferrite and cementite(Fig.1a).

3.2Cyclic Oxidation in Molten Salt

Cumulative weight change(mg/cm2)variation as a function of time expressed in number of cycles for different regions of TIG weldment is shown in Fig.2.Intense spalling was observed through out the experimentation on base metal.As soon as subscale forms the top layer of scale breaks away from it and the separated multiple layers overlapping each other were seen.It was observed that for weld metal,the color of the surface scale turned black during the?rst cycle.Spalling of oxide scale was observed during the third cycle.Even little cracks appeared on the scale at13th cycles,after that there was increase in the number and width of these cracks and protrusion of oxides from these cracks was observed.The color of the scale was dark gray after the50th cycle.In case of HAZ black gray color was observed on this region during?rst cycle.A thin layer of oxide scale got spalled during17th cycle.The scale of HAZ specimen started cracking during32nd cycle.The scale was protruded out at the edges in subsequent cycles.In base metal intense spalling and cracking was observed up to50th cycle.

It can be inferred from Fig.2that the weight gain for base metal is much larger as compared to weld metal.The total weight gain after50cycles for base metal is around1.78times that of weld metal.All the regions of TIG weldment followed the parabolic behavior as can be inferred from the square of weight change(mg2/cm4)plotted with number of cycles in Fig.3.The parabolic rate constants values are shown in Table2.

3.3Measurements of Oxide Scale Thicknesses

The thickness of the oxide scale formed on the base metal, weld metal,and HAZ was measured from the BSEI,along the cross section of the mounted samples.Images for all the samples are shown in Fig.4.The thicknesses of the different regions of TIG weldment,as measured from the BSE images, are shown in Table2.

3.4X-ray Diffraction Analysis

The XRD patterns of the high temperature corroded specimens after50cycles have been shown in Fig.5.These diffractograms reveal almost similar phases for all the steels.As obvious from the composition all the steels exhibited the formation of iron oxide(Fe2O3)as main phase along with weak peaks of Cr2O3.The XRD patterns for the oxidized sections of the base metal are different in intensity peak as compared to weld metal and the HAZ.

3.5SEM/EDAX Analysis

The surface SEM/EDAX morphology of different regions of TIG weldment in2.25Cr-1Mo boiler steel is shown in Fig.6. EDAX analysis indicates that the top scale of weld metal consists of mainly Fe2O3(96.57%)with MnO(2.85%)whereas inner scale contain SiO2(3.17%),Cr2O3(1.24%),and MnO (1.88%)along with main phase Fe2O3(92.83%).The SEM micrographs of HAZ region show more corrosion of grain boundary(Fig.6b).The upper oxide scale mainly consists of MnO(4.59%)and Fe2O3(94.64%).The inner scale along the boundary contains small amounts of SiO2(9.87%)and MnO (3.80%)with iron oxide Fe2O3(85.63%)(point1,Fig.6b).

3.6EPMA Analysis

The cross-sectional EPMA analysis of oxide scale of weld metal of TIG weldment in2.25Cr-1Mo steel shown in Fig.7 indicates mainly the presence of iron in the whole oxide scale. EPMA analysis of weld metal revealed chromium as a layer in the lower part of scale.Vanadium is also distributed in small concentration in the bottom scale.At some places

small Table2Average scale thickness(mm)and parabolic rate constants(K p)

Materials Scale thickness,mm K p,1028g2cm4s21 Base metal???76.233

Weld metal 1.323.098

HAZ 1.17065.408

concentration of Na is also indicated in the upper and lower parts of the scale.EPMA shows (Fig.8)that for HAZ where iron is the main element present throughout the scale sodium and vanadium are distributed in the whole scale equally.A small concentration of Cr is also indicated in the upper scale.Manganese is present in the upper layer of oxide scale.

The base metal showed intense spalling,peeling of scale,and enormous weight gain.The higher corrosion rate during initial hours of study,which might be attributed to the rapid oxygen pick up by diffusion of oxygen through the molten salt

layer,is identical to the results reported by Sidhu and Prakash (Ref 9),Tiwari and Prakash (Ref 10),and Kumar et al.(Ref 7).The identi?cation of Fe 2O 3in the scales of base metal after hot corrosion experiments indicated that nonprotective conditions were established when Na 2SO 4-60%V 2O 5molten salt was present on the surface.The formation of mainly Fe 2O 3in the upper scale has also been reported to be nonprotective by Raman and Muddle (Ref 11).The base metal showed more weight gain than HAZ and weld metal and the reason may be the intense spalling and cracking of the oxide scale.The BSE image of the corroded HAZ shows that the scale has detached from the metal and cracked.From the scale thickness measurement (BSEI),it can be concluded that the multilayer scale on the HAZ specimen was thicker as compared to scale on the weld metal.Generally,thicker scales are more prone to spallation.It is important to note that even though the

weld

Fig.4B SEI micrographs showing cross section oxide scale morphology of different regions of TIG weldment (a)weld metal and (b)

HAZ

Fig.6Surface morphology and EDAX analysis for different regions of TIG weldment in T22steel exposed to cyclic hot corro-sion in Na 2SO 4-60%V 2O 5at 900°C for 50cycles (a)weld metal,10009and (b)HAZ,10009

metal oxidized at lower rates and formed a scale of lower thickness than the HAZ,it is the former that indicated a tendency for spallation after 17th cycle that became more prone to corrosion.

Further,it is con?rmed by EPMA that the scale mainly contained oxide of iron with small concentration of chromium as shown in case of the scale on weld metal (Fig.7).The higher weight gain of the HAZ and the formation of a thicker scale as compared to weld metal have been attributed to the absence of a protective inner scale of Fe-Cr oxides,due to the nonavailabil-ity of free Cr in this region (Fig.8)as also discussed by Raman and Gnanamoorthy (Ref 12).The debonding at the metal/oxide interface for HAZ specimen might be contributed by formation and evaporation of MoO 3.This might have led to the acidic ?uxing of the protective oxide scale.Identical results have been reported by Peters et al.(Ref 13),Fryburg et al.(Ref 14),and Pettit and Meier (Ref 15).

4.Conclusions

From the present studies,the following points are con-cluded.

1The weld metal shows a combination of widmanstatten type ferrite,pearlite,and bainite.HAZ region showed coarse grain bainite.

2When the base metal,weld metal,and the HAZ are oxi-dized in the molten salt environment;all of them follow parabolic kinetics.The weight gain of the base metal and HAZ were greater than that of weld metal.Even weld metal shows a little tendency for spallation and cracks during hot corrosion test.Fe 2O 3was identi?ed as the major phase by XRD,EDAX,and EPMA analysis in the scale of base metal,weld metal,and

HAZ.

Fig.7B SEI and X-ray mapping of the cross section of weld metal of TIG weldment in T22steel subjected to cyclic oxidation in Na 2SO 4-60%V 2O 5at 900°C for 50cycles,2009

3

The thicker oxide scale over HAZ was due to the for-mation of inner scales with free Cr than that of weld metal.4The corrosion rate (in terms of weight gain)of base metal,weld metal,and HAZ regions has been found in the following order base metal >HAZ >weld

metal.

Fig.8B SEI and X-ray mapping of the cross section of HAZ of TIG weldment in T22steel subjected to cyclic oxidation in Na 2SO 4-60%V 2O 5at 900°C for 50cycles,2009

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