Sie sind auf Seite 1von 16

Engineering Failure Analysis 70 (2016) 141–156

Contents lists available at ScienceDirect

Engineering Failure Analysis


journal homepage: www.elsevier.com/locate/engfailanal

Failure of a nickel aluminium bronze (NAB) canned motor pump


impeller working under polluted sea water – Influence of
material selection, section thickness dependent microstructure
and temper annealing heat treatment
Mrityunjoy Hazra ⁎, K.P. Balan
Defence Metallurgical Research Laboratory (DMRL), P.O. – Kanchanbagh, Hyderabad 500 058, India

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, a damaged pump impeller working under highly polluted sea water was
Received 19 June 2015 taken up for investigation on probable cause(s) for its failure. Major steps in the investigation
Received in revised form 28 June 2016 were visual examination, thorough microstructural observation of the affected (surface and
Accepted 29 July 2016
sub-surface) and unaffected portions of the base material at different locations on the impeller
Available online 30 July 2016
having varying section thickness. An effort has been made for correlating unaffected micro-
structural attributes to corroded features with respect to various section thicknesses. Failure
Keywords: of the impeller is found to be due to combined effect of a corrosion susceptible microstructure
Impeller
and highly polluted corroding medium that resulted in selective phase corrosion (SPC) of cer-
Nickel aluminium bronze (NAB)
tain phases in the microstructure leading to surface roughening and perforation, predominantly
Selective Phase Corrosion (SPC)
Microstructure through pitting mechanism governed by dealuminification initiated at phase interfaces.
Temper annealing Networked alpha plus kappaIII eutectoids, Cu-O type of precipitates, dendritic Cu-Al phase
Sulphide attack and retained beta have been found to be corrosion susceptible microstructure. Principle corrod-
ing features in thick sections were found to be kappaII and alpha plus kappaIII eutectoids,
while that in thin sections include severe cracking involving Cu-S-O rich coarse precipitate
(of 15 μm approx size), corrosion along interfaces of dendritic Cu-Al phase and retained beta
with alpha matrix. Presence of alpha plus kappaIII eutectoids and retained beta has been the
result of combined effect of improper selection of material (aluminium) composition, complex
cast shape of the impeller and ineffective temper annealing treatment, while dendritic Cu-Al
phase and high level of porosity are casting defects.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction

Canned motor centrifugal pump is a single centrifugal vertical inline and overhung impeller type pump having double safety
feature incorporated in it. Material of the pump is so selected that it can be used in sea water and can withstand shock loading of
48 g. Impeller of the sea water pump was found to be corroded during inspection of the pump after 3500 h of operation onboard.
Inlet and outlet of the pumps fitted on sea water system are of Ti alloy which were oxidized prior to installation. It is also

⁎ Corresponding author.
E-mail addresses: mhazra@dmrl.drdo.in, hazra.mrityunjoy@gmail.com (M. Hazra).

http://dx.doi.org/10.1016/j.engfailanal.2016.07.010
1350-6307/© 2016 Elsevier Ltd. All rights reserved.
142 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

Table 1
Specification of the pump.

Item nomenclature Details

Pump model HDV65-160/15H2/SPL


Type Vertical
Capacity 100 TPH
Power 15 kW
Synchronous speed 3000 rpm
Design temperature 65 °C
Design pressure 30 bar
Casing NAB (NES 747 part 2)
Shaft ASTM A 336 TP F316L
Impeller NAB (NES 747 part 2)
Materials of main components Bearing Bush Carbon Graphite
Bearing sleeve Tungsten Carbide
Circulation piping SS 316
Impeller key SS 316
Impeller washer ASTM A 240 TP 316L

reported that the sea water circulated through the pump is contaminated and almost stagnant. General specification and materials
used in the main components of the pump are listed in Table 1.
Composition, heat treatment and microstructure have most important role in controlling mechanical properties and corrosion
resistance of the nickel aluminium bronze (NAB). Therefore, in the present study, an effort is put to correlate failure evidences of
the corroded impeller to its composition, heat treatment, microstructure and hardness properties so as to establish the probable
root cause(s) of the failure.
To the best of our knowledge, there has been one study so far, on corrosion damage of NAB impeller [1]. In that, significant
findings include corrosion response of α and β phases. However, in that, there was no report on the corrosion response of
alpha plus gamma-2 and alpha plus kappaIII eutectoid phases, kappa intermetallics and casting and/or heat treatment defects.
Also, there was no information on microstructure and corrosion response of NAB material with respect to section thickness of im-
peller. Therefore, in the present study, a detailed failure investigation has been carried out which include thorough microstructural
characterization of the affected and unaffected regions with respect to section thickness of the impeller.

2. Results

2.1. Visual examination

Corroded impeller in the as-received condition is shown in Fig. 1. Some portion of the impeller was badly corroded leading to
formation of holes (Figs. 1c–f), giving an impression of pitting corrosion. Corrosion of the blades resulted in surface roughening,

Fig. 1. The damaged impeller in the as-received condition – (a) complete view of suction side, (b,c) close-up view of the surface roughening and perforation on
suction side, (d) view of pressure (discharge) side, (e,f) close-up view of holes on pressure side.
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156 143

Fig. 2. Another photograph of the damaged impeller showing red coloration (a–d), greenish coloration (c).

giving an impression of erosion corrosion (Figs. 1a–c). Five areas were marked as 1 to 5 on the damaged impeller with decreasing
corrosion experience for the higher numbers (Figs. 1a and d). Fig. 2 shows some additional views of the component showing
greenish and/or reddish coloration of the surface.

2.2. Morphology and corrosion product on damaged surface

Images of severely and lightly corroded surfaces were captured with scanning electron microscope (SEM). One representative
image from severely corroded region is shown in Fig. 3a in which a thick layer of corrosion product can be seen. EDS pattern
taken on the product under SEM indicates presence of chlorine, sulphur and oxygen in addition to the alloying elements of the
base material (Fig. 3b). Examination of the surface morphology of severely and lightly corroded areas did not reveal any features
typical of erosion, such as shear lip formation or their fracture etc.

Fig. 3. Scanning Electron Microscope (SEM) image of the corroded surface in SE mode (a) and EDS pattern taken on that surface (b).
144 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

Table 2
Elemental composition of the material of the impeller under study with respect to that is specified in NES 747-part II.

Element Content (wt%)

As in analysed impeller As-specified in NES


of the present study 747-part II

Al 11.25 8.90–9.60
Ni 4.70 4.50–5.50
Fe 4.50 4.00–5.00
Mn 1.00 1.00–1.40
Cu Rem Rem

Table 3
Composition of sea water to which impeller was exposed.

Elements Cl− F− NO−


2 Br− SO2−
4 Na Ca K Mg Fe SiO2 Dissolved O2 Free Cl

Content (ppm) 15,055 1.5 0.008 310 4.7 3697 175 123 354 N0.16 0.7 20.26 0.38

Table 4
Hardness readings on the impeller.

Area HV

Severely corroded area 220


Lightly corroded area 190
Dark phase (β) 205
Bright phase (α) 171

2.3. Chemical analysis

Elemental bulk compositional analysis of the impeller material was obtained using wet chemical analysis method, after com-
plete removal of visually observed corrosion products through grinding. The measured composition of the investigated material
and the composition as specified by NES 747-partII standard are given in Table 2 for ready comparison purpose.
Sea water composition is given in Table 3. Standard ASTM test methods were adopted for analysis of element groups (Cl−, F−,
NO− − 2−
2 , Br ), (SO4 , Na, K, Ca, Mg), Fe, silica, dissolved oxygen and free chlorine [2].

2.4. Hardness

Average Vickers hardness of the component in unaffected region was measured at 5 kg load. Micro hardness of the two major
phases α and β of the microstructure was measured at 50 g load. The hardness values are presented in Table 4.

Fig. 4. Optical micrograph of cross-section of one of the thickest sections in impeller (area 1), unetched.
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156
Fig. 5. SEM images of the cross-sections in one of the thickest sections (area 1) of the impeller component showing distribution of various phases.

145
146 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

2.5. Microstructure and corroding phases

Sections of the corroded impeller taken from severely and lightly corroded regions were prepared for metallography and ob-
served under optical microscope and SEM. Total five samples, each from one representative corroded areas 1–5 (as marked in
Fig. 1) with varying cross-sectional thickness were extracted perpendicular to the corroded surface, in order to investigate the
damaged microstructure on the sub-surface. Here, general microstructure and corroding phases for areas 1, 3 and 5 have been
briefly discussed, taking into account of the corresponding section thickness. Microstructure of the unaffected base material was
revealed after removing sufficient material from each of the said areas on the impeller, in consideration with the fact that corro-
sion depth in NAB under sea water can be as high as 6 mm [3]. Acidified potassium dichromate with composition 5 g FeCl3
+ 5 mL HCl + 100 mL H2O was used as etchant for revealing the microstructural details. Optical micrographs taken on all the
sections in unetched condition reveal high volume fraction of pores, as shown in Fig. 4, for area 1. Here, SEM images of etched
samples of sufficient magnifications were found relevant for presentation and so only those and no optical images are presented.

2.5.1. Area 1
Micrograph of the unaffected base material is shown in Fig. 5. Microstructure primarily consists of light etched alpha (α)
phase, small amount of relatively dark etched retained beta (β) phase along with partially temper transformed β [i.e. partially
developed (α + γ2)], as-cast alpha plus gamma-2 (α + γ2) and a series of deeply dark etched kappa (κ) intermetallic phases,
distributed throughout the structure. Compositions of the observed phases in base material are given in Table 5. Basically,
[κII+(α + κIII) + (α + κIV) + (α + γ2) + retained β] aggregates of various phase morphologies are obtained [4,5], as marked
in Fig. 5. κI of coarse rosette shape was observed occasionally. As-cast κII is found to be of star fish-like or rosette shape, while
temper refined one is of modified rosette shape. Some distinct κIII precipitates with spheroidal morphology and coming from
two sources, viz. parent retained β and tempered (α + κIII) and with subsequent coarsening seem to be present [6]. These κIII
precipitates have some kind of similarity in shape to that of temper refined κII, although each of them reveals different phase con-
trast and compositions. It is to be noted that principle type of distinct κ phase is κII precipitates. κIV has a spheroidal or cruciform
morphology. Here, α has been found to exist as matrix with fine distribution of κIV precipitates within it. Table 5 does not include
composition of κIV, whose detail cannot be determined clearly by SEM [4–6]. Retained β seems to exist in two forms, namely
martensitic β and partially tempered retained β (in form of partially developed α + γ2 eutectoid with little bit of retained
beta) with distinct κIII precipitates distributed over those phases. Both of α + κIII and α + γ2 eutectoids have a lamellar mor-
phology with lower aspect ratio and higher networking of the later. Eutectoid (α + κIII) also seems to appear in two forms,
viz. fully tempered and insignificantly tempered ones.
Fig. 6 shows images of the corroded sections of area 1. Corrosion product with Ni-rich Fe-Al composition, similar to that of
κII at both usual star-shaped and temper refined κII feature was found. Each of the interfaces of α-κII and α-κIII in eutectoid
(α + κIII) was found corroded in some locations (regions 1 and 2). κII followed by (α + κIII) has been found to corrode most
frequently in this area. Additionally, fluorine (F) containing Fe-Al-Ni-rich corroded constituent (marked as 3) have been noticed
and found often to be dislodged out of the structure (marked as 3/). EDS compositional analyses on marked unusual corrosion
products in areas 1–3 are presented in Table 6.

2.5.2. Area 3
Fig. 7 shows images of the base material. Usual NAB phases and varieties of intermetallic κ phases, like that was found in area
1, are observed. However, there is refinement of the structure than that was found in area 1. It should be noted that presence of
as-cast α + γ2 eutectoid was in as significant quantity as that of (α + κIII) eutectoid, unlike to what was observed in area 1.
Additionally, volume fraction of retained β was comparable to what was observed in area 1. Also, formation of fine dendritic
Cu-Al phase (with high aspect ratio) was observed here. It should be noted that there is a presence of three usually uncommon
constituents – (i) lengthy dendritic rosette shaped κI phase with composition similar to that of κII, (ii) fine dendritic Cu-Al phase,
(iii) Cu-Al-O- and Cu-S-O-rich phases.
Corroded micrographs are presented in Fig. 8. Significant amount of corroded retained β phase and often their dislodgement
from the structure was noticed in some locations (marked as 5 and 5/ in Fig. 8a). Fig. 8b shows interfacial corrosion along

Table 5
Compositions of observed phases in unaffected base material of the present study.

Phase/constituent EDS compositional analysis (at%)

Al Si Mn Fe Ni Cu O

Common NAB phases Alpha (α) 20.52 0.00 1.41 2.53 3.36 72.18 0.00
Retained beta (β) 30.58 0.00 1.62 5.44 6.65 55.71 0.00
Partially developed (α + γ2) 29.26 0.61 1.63 2.47 6.05 59.97 0.00
KappaII (κII) 32.58 1.51 2.46 42.64 10.26 10.55 0.00
Distinct KappaIII (κIII) precipitates 39.45 0.63 1.37 5.64 11.00 41.91 0.00
κIII precipitates in eutectoid (α + κIII) 36.25 0.00 1.49 0.00 7.89 54.37 0.00
Uncommon NAB phases KappaI (κI) 24.04 2.78 1.97 56.85 6.63 7.72 0.00
Dendritic Cu-Al precipitate 22.18 0.00 1.31 5.37 4.02 67.12 0.00
Cu-Al-O-rich phase 21.53 0.00 1.76 1.18 1.80 33.84 39.89
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156
Fig. 6. SEM images of the cross-sections in most severely corroded area (area 1) of the impeller, indicating preferential corrosion on different phases.

147
148 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

Table 6
Details of the unusual corrosion products with feature no (as marked in all figures), their site of occurrence (w.r.t. impeller), EDS compositional analyses and their struc-
tural identification.

Corroding phase/constituent Site of occurrence Elemental composition of the Identified phase/constituent


no (as in Figs. 6, 8 and 9)* (w.r.t. location in impeller) phase/constituent/corrosion product,
as obtained from SEM EDS analysis (in at%)

3, 3/ Area 1 21.31 F, 24.88 Al, 2.02 Mn, 32.60 Fe, F enriched Fe-Al-Ni-type precipitate (3) and
9.48 Ni, 9.72 Cu their dislodgement (3/)
6, 6/ Area 3 14.10 F, 32.20 Al, 1.47 Mn, 16.40 Fe, F-Fe-Ni enriched interfacial corrosion product
12.86 Ni, 22.77 Cu between dendritic Cu-Al and α matrix (6) and
their cracking (6/)
8 Area 3, area 5 15.16 O, 1.38 Si, 24.53 S, 58.93 Cu Cu-S-O-type precipitate
9 Area 3 31.94 O, 17.37 Al, 1.74 Mn, 2.21 Fe, Modified dislodged pure Cu (α) and dendritic
2.5 0 Ni, 44.24 Cu Cu-Al phases
10 Area 3 100 Cu Pure Cu phase surrounding cracks
11 Area 3 22.55 Al, 2.80 Fe, 3.92 Ni, 70.74 Cu Cu-Al type phase surrounding cracks
12,13 Area 5 – Dislodgement of Ni-deposited кII of as-cast and
temper refined type
*
A phase/constituent no followed by a dash indicates corrosion modified and/or dislodged parent phase/constituent.

interface of earlier mentioned dendritic Cu-Al phase with matrix (α), resulting in Cu-Al phase with F-Fe-Ni enriched interface
(marked as 6). The said F-Fe-Ni enriched interface was frequently found to be cracked (marked as 6/). Dendritic Cu-Al phase
was also often found to have been dislodged (marked as 7) out of the structure, when its all interfaces with the matrix got
cracked. It is to be noted that major fraction of corroded surface contains Cu-S-O-rich (marked as 8) and Cu-Al-O-rich flower-
like (marked as 9) corrosion products along with plenty of cracks, as in Fig. 8c. This type of extensive cracking was observed
only in this area in the whole impeller component. Cracking was found to be involved with and/or initiated at Cu-Al-O- and

Fig. 7. SEM images of the cross-sections in one of the thinnest sections (area 3) of the impeller component showing distribution of various phases.
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156 149

Fig. 8. SEM images of the cross-sections in moderately corroded area (area 3) of the impeller, indicating preferential corrosion on different phases.

Cu-S-O-rich product, especially the latter one. Fig. 8d shows presence of corrosion products of pure Cu (marked as 10) and Cu-Al-
rich phase (marked as 11) surrounding some of those cracks. It is noteworthy that corrosion on (α + κIII) eutectoid was very
rare, unlike that was found in area 1.

2.5.3. Area 5
Microstructure of base material in this area is similar to that was observed in almost equally thick area 1, except presence of
ample of lamellar networked eutectoid (α + κIII) structure at and near to the surface.
Eutectoid (α + κIII) constituent, followed by κII of usual as well as temper refined variety were found to corrode most
frequently, as is shown in images in Figs. 9a–f. Similar form of corrosion was also observed in area 1, as was mentioned earlier.
Besides, presence of ample amount of Cu-S-O-rich precipitates had been observed. It is to be noted that there was dislodgement of
both types of κII like feature, as shown by markings 12 and 13 in Figs. 9b,c.

3. Discussion

3.1. Material's suitability

Chemical [7], microstructural [4–7] and hardness [7] analyses suggest that the impeller was made of cast nickel aluminium
bronze (NAB). The material forms phase constituent consisting of [κII+(α + κIII) + (α + κIV) + (α + γ2) + retained β] at
room temperature, like that is obtained in a slowly cooled NAB alloy of present composition and as is shown in Fig. 10 [4,5]. κI
phase was found occasionally in some locations. It is reported to form in an alloy containing Fe content exceeding 5 wt%
[4,5,8]. Therefore, formation of κI phase is a localized event where local Fe content at those κI nucleation sites became in excess
of 5 wt%, whereas bulk Fe content was around 4.5 wt%.
150
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156
Fig. 9. SEM images for the cross-sections in least affected corroded area (area 5) of the impeller, indicating preferential corrosion on different phases.
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156 151

Fig. 10. Phase diagram of Cu-5Fe-5Ni-xAl (in wt%) type of NAB alloy with varying Al contents.

In NAB consisting of above 10 wt% Al, chances of presence of β phase and/or its partial/complete decomposition to eutectoid
(α + γ2) phase is large even with the addition of Ni and Fe [4–6,9,10]. Impeller of the present study contains around 11.25 wt%
Al, which is much above the specified (8.9–9.6 wt%) Al level [11]. This is the primary reason behind obtaining significant amount
of as-cast (α + γ2) eutectoid and retained β in final structure, beside complex shape of the impeller component and associated
differences in cooling rate at different locations during casting [7,9,10]. Retained β in the cast and temper annealed material
consisted of temper transformed partially developed eutectoid product (α + γ2) and/or martensitic β constituent [6]. Further,
Cu-Al-O rich phase in unaffected material and Cu-S-O rich precipitates in corroded areas seem to be inclusion type of casting de-
fect and corrosion product respectively [7]. It is to be noted that Cu-S-O rich precipitates formed as a result of reaction between
surface oxide films (made of aluminium and copper) of the unaffected material part with sulphur coming from sulphides of sea
water. However, it could not be observed in unaffected material part, probably due to their similar etching contrast as that of the
common NAB phase/constituents.
Heat treatment recommended for the material in British naval standard NES747-part II is temper annealing, that results in
stress relieving, homogenisation of microstructure, transformation of retained β to α and various κ-phases, so as to improve me-
chanical properties as well as corrosion resistance [11]. Although the material has undergone the required temper annealing heat
treatment, according to the user's saying, volume fraction of retained and/or partially developed eutectoid α + γ2 (temper trans-
formed β) was too much in certain regions for the intended application, like that was found in area 3. Similarly, ample amount of
networked lamellar eutectoid (α + κIII) was often observed. An extreme example of exceptionally inadequate tempering is evi-
dent by presence of lamellar eutectoid (α + κIII) at and near to the surface in area 5. However, moderate tempering related re-
finement was nevertheless evident by presence of distinct κIII precipitates of appreciable size in temper transformed product of
lamellar eutectoid (α + κIII) [4,5,7,8,10]. This is also true for refinement of κII precipitates, resulting in finer and modified shaped
features, earlier mentioned as temper refined κII. Heterogeneity observed in microstructure is quite usual in sand-cast and temper
annealed complex components like impeller [3,6,9–12]. This is due to the varying section thicknesses in the component, leading to
structural heterogeneity across most parts of the impeller, based on cooling rate during casting and/or tempering and the
sufficiency of soaking (holding) time during tempering. Section thickness related varying microstructural refinement was ob-
served to follow quite logical trend in thick (1,5) as well as thin (3) areas in terms of relative volume fraction of as-cast eutectoids
(α + κIII) and (α + γ2), as was mentioned earlier [12]. For example, as-cast α + κIII could not form in that quantity in area 3
as it could in area 1 because of the faster cooling rate in former than that in later; although it did not effect in quantity of as-cast
α + γ2 that way leading to almost comparable volume fraction of the two eutectoid features in area 3 unlike that in area 1 (refer
to Fig. 10). However, in the present case, tempering seems to be sufficiently ineffective in some sense, leading to ample of unin-
tended networked (α + κIII) structure at and near to the surface in thick area 5 and untransformed retained β in thin area 3. This
kind of insufficient tempering effect in some sections of the impeller may have arisen out of the combined effect of complex shape
of impeller and placement of the impeller within heat treatment (furnace) equipment.

3.2. Corrosion evidences and probable associated macro-mechanism(s)

EDS results showed that corrosion products were highly enriched with oxidizing agents such as sulphur, chlorine and oxygen,
providing the evidence for contamination of the sea water with potential corrodents. SEM examination of surface morphology of
severely and lightly corroded area did not reveal any gross features of erosion like shear lip, their fracture etc. Thus, failure due to
152 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

erosion is not the cause. Further, evidences of galvanic corrosion are also absent here, as usually is found in form of uniform cor-
rosion of a material system at the interface between the corroding part and its nobler counterpart [13–15]. Highly corrosive fluid
that came in contact with the component, contained appreciable dissolved oxygen and chlorine, thus extremely minimizing the
chance of galvanic corrosion [7]. Crevice corrosion is most likely to be present in the hub-shaft hole junctions and adjacent to
those areas [13–16], although in a scattered and insignificant way. It is evidenced by presence of trench like appearance of the
region (marked A in Fig. 1) along with reddish deposits. There was extensive presence of pitting mechanism, as is strongly evi-
denced by fine pores and holes, when examined visually and microscopically. This is further supported by presence of sulphur
on as-received corroded surface, as part of the highly polluted sea water [13,14,17], Cu-S-O rich precipitates at sub-surface, exis-
tence of high level of macro- and micro-porosity in structure, overall blackish appearance of the impeller and stagnant nature of
water [13,14,17–19].

3.3. Corrosion sequence of popular NAB phases in the present study

Selection of the phases to be attacked during corrosion mainly depends on the availability (volume percent), inherent corro-
sion susceptibility and microstructural attributes (size, shape, morphology and distribution) of the phases at the subject location.

3.3.1. Based on availability, inherent corrosion susceptibility and microstructural attributes of the phases

3.3.1.1. Availability. In the present study, there are three types of principally corroding phases, namely κII intermetallic precipitates,
(α + κIII) eutectoids and retained β, beside dendritic F-Fe-Ni rich Cu-Al and Cu-S-O-rich corrosion products. Microstructural ev-
idence confirmed selective phase corrosion (SPC) of the retained β phase and its subsequent dislodgement (marked as 5 and 5/ in
Fig. 8) in preference to α phase and negligible effect on the κ intermetallics in occasionally observed predominantly α-β rich and
κ phase deficient regions. It is frequently reported that retained β in any of its probable forms is worse than α in terms of cor-
rosion resistance in an NAB alloy [9,13,14,16,17]. Distinct κII and lamellar (α + κIII) eutectoids have been found to corrode in
other major fraction of regions.

3.3.1.2. Inherent corrosion susceptibility. Phase γ2 has been found to possess a potential of − 0.5 V w.r.t. SCE [9,13,20,21], while
Konamori et al. [22] reported that potential of all other phases in NAB fell in the range of − 0.24 to − 0.26 V. Therefore,
electro-chemical potential of the phases in NAB ranks from anodic to cathodic in the order of γ2 → κ → β → α, based on alumin-
ium content and dealuminification tendency. This is also well supported by the published literature on relative corrosion damage
on phases in NAB system under sea water, although in a scattered way. However, the detailed sequence, as is proposed by the
present investigators and supported by evidence in the present case, is in the order of κIII → κII/κIV → γ2 → β → α. This indicates
that micro-galvanic couple (α-κIII) of eutectoid (α + κIII) experienced the most severe corrosion, through preferential
dealuminification along α-κIII interface and subsequently consumption of whole κIII phase. Next moderately susceptible phase
couples are (α-κII), (α-γ2) and (α-β) in the decreasing order of severity. In those systems, κII, γ2 and β act as anode respectively
and corrodes selectively through dealuminification with respect to α. Thus, in the present study, severe corrosion was observed
on κ phases. Presence of γ2 (Cu9Al14) makes the eutectoid (α + γ2) extremely corrosion prone through dealuminification, while
α (Cu-rich phase with negligible Al) is known to have an excellent corrosion resistance. Similar logic also holds true for much
lower corrosion resistance of α/κII, α/various types of κIII and eutectoid (α + κIII) than that of α. The shift from the expected
order of preferential corrosion of κ and γ2 phases in present study may have arisen out of availability and size factors for
those said phases.

3.3.1.3. Microstructural attributes. Structural heterogeneity in terms of size, shape, morphology and distribution of α and κ phases is
observed, depending on the varying thermal history arising out of complex casting and critical heat treatment procedure, as has
already been pointed out. For example, various shapes and sizes of κII and κIII are observed. Usually, too sharp shaped (i.e. of high
aspect ratio) and too coarse sized distribution of any phase in a corroding structure is extremely dangerous [9,13,20–22]. There-
fore, based on this logic, severity of corrosion on κ phases is coarser κII to finer tempered κII, in the decreasing order, when each
of them is distinct precipitate type. This was evident in the present findings.
Morphology and distribution (like isolated, networked/continuous etc.) of the phases also plays significant role in determining
the degree of corrosion. Among the (α-κIII) eutectoid families, lamellar types of networked couple corroded most severely due to
its high aspect ratio and networked nature [9,13,20–22]. This corrosion of eutectoid κIII propagated deep into the structure to re-
sult in corrosion depth of approximately 30 μm in area 5. This is due to generation of huge corrosion current and also propagation
of the same, deep into the structure, unlike the frequently observed mild and superficial corrosion of β and/or κ phase(s)
[9,13,22].
It is to be noted that each of as-cast κII, temper refined κII, tempered κIII and eutectoid κIII phases have been found to corrode
initially along their corresponding interface with the α matrix and their total consumption rate is very slow and often incomplete,
except their dislodgement frequent dislodgement from the structure. However, κIII in eutectoid mass seems to be totally con-
sumed in many locations, unlike the interfacial corrosion at precipitate-matrix interfaces for distinct tempered κIII precipitates,
because of the existence of much higher corrosion current due to very fine lamellar nature of the eutectoid unlike in other cases.
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156 153

It is quite well established that, in NAB system under sea water, each of crevice and pitting corrosions takes place in form of
dealuminification [13–15,17,23]. In the present case, the predominant mechanism appears to be the dealloying or selective phase
corrosion (through dealuminification) governed pitting corrosion.

3.4. Corrosion involving unusual features and characteristics

It is noteworthy that corrosion effect on both readily detectable shaped and temper refined modified shaped κII precipitate
with Ni-rich Fe-Al composition is majorly revealed by crystal clear evidence of interfacial discontinuity and/or dislodgement
of the phase from the structure. It was predominantly found in thick areas 1 and 5. Here, it is proposed that corrosion of
(α + κIII) eutectoid mass through dealuminification leads to avalanche of Ni species to redistribute within certain regions in
areas 1 and 5. The said κII precipitates with Ni-rich Fe-Al composition is likely to be the result of that re-distribution. It is also
noteworthy that the newly formed Ni-rich κII precipitates were frequently existing in halves and one-fourths (marked in the
text), probably as a result of corrosion and/or polishing. Phenomenon of dislodgement has been observed for F enriched Fe-Al-
Ni precipitates found in area 1 of the impeller. It is to be noted that corrosion has been observed at interface of Cu-S-O-rich pre-
cipitates with α matrix. Area 3 has been found to exhibit varieties of unusual and unique features among all corroding features in
the impeller like (i) extensive cracking involving (≈10 μm sized) coarse Cu-S-O rich precipitates which is quite evident from the
visually observed perforated and holed regions, (ii) corrosion of fine dendritic Cu-Al precipitate along its interface with α matrix
with F-Fe-Ni rich Cu-Al as corrosion product, cracking along interface(s) and their often dislodgement, (iii) presence of pure Cu
and Cu-Al- rich and Cu-Al-O rich flower like phases surrounding both types of cracks. Cu-Al-O-rich flower like phase in area 3
seems to be a corrosion product, which is very likely to be a modified version of previously mentioned pure Cu and/or Cu-Al
type of phases over a period. Similarly, pure Cu also seems to be a modified version of dislodged α phase. This is supported
by similar whitish type of appearance as that of pure Cu and Cu-Al phase, apparently looking superficial residence of those fea-
tures on the surface and non-involvement of this phase with any kind of cracking unlike Cu-S-O-rich precipitate. Extensive crack-
ing may have arisen out of a combined effect of presence of ample amount of Cu-S-O-rich coarse precipitates in thinnest section
of the impeller and high level of exposure to the sea water. On the other hand, existence and corrosion of (α + κIII) eutectoid
phase constituent was rarely observed in area 3 unlike that in case of areas 1 and 5. Details of the unusual corrosion features
and/or corroding phase(s) in all areas of the impeller are given in Table 6.
Interfaces of the above said dislodged precipitates with matrix seem to loss their mass and sufficient strength as a result of
dealuminification, and consequently those precipitates come out of the structure when dealuminification followed by cracking
takes place along all interfaces surrounding the precipitates.

3.5. Comparative corrosion effect on different areas with varying sectional thickness

Table 7 gives an account of the comparative section thickness of areas 1, 3 and 5 along with the visually observed level of cor-
rosion and corrosion depth, level of exposure to sea water and most frequently affected corroding features of the corresponding
areas. It is to be noted that level of exposure of different areas to sea water seems to have played the most crucial role in deter-
mining the extent of damage and thus visible corrosion severity of the corresponding areas. Thus, area 1 in suction side with
higher level of exposure to sea water experienced more corrosion attack than area 5 in the reverse side, in spite of the comparable
section thickness of those areas and much unintended (networked α + κIII eutectoid) microstructure at and adjacent to surface
in later. Here, one should note that eutectoid α + κIII in area 5 was found to be concentrated in network form at and adjacent to
surface, as a result of almost nil temper annealing effect unlike its low volume fraction with quite uniform distribution in area 1;
thus, resulting in reduced chance of deepening the corrosion damage in area 5 in addition to its reduced chance coming from fac-
tor of low level of sea water exposure. κII has been found to corrode the most in area 1, while α + κIII was the principally cor-
roding phase in area 5. Presence of Cu-S-O type of precipitates of appreciable size (≈ 15 μm) in addition to corrosion along
interface of dendritic Cu-Al phase and α matrix leads to severe cracking and hole (as was shown in Fig. 1) in thinnest section
area 3 under high level of sea water exposure in service. Cracking along dendritic Cu-Al-matrix interface seems to be much local-
ized event, while that involving Cu-S-O-rich precipitate led to lengthy cracks and thus impairing integrity of the material severely.
However, Cu-S-O-rich precipitates seem to prevail prior to usual corrosion activity came into action. In corroded area (marked as
A), principle deteriorating mechanism seems to be uniform corrosion along with plenty of lengthy cracks involving Cu-S-O-rich

Table 7
Corrosion severity on selected impeller areas w.r.t. corresponding section thickness (refer to Figs. 1,2,6,8,9).

Section Level of section Most frequently affected corroding features Level of Level of visually observed corrosion attack
no thickness exposure (corrosion depth, μm)

1 Highest κII followed by (α + κIII) lamellar eutectoid High Severest (100)


3 Least Extensive cracking involving Cu-S-O rich precipitates High Moderate
at precipitate-matrix interface, corrosion along interface (40)
of dendritic Cu-Al phase and α matrix, corrosion at
α-retained β interface
5 Comparable to that (α + κIII) lamellar eutectoid Low Least (30)
of 1 (≈highest)
154 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

precipitates, corrosion at interface of Cu-Al phase with α matrix, occasional cracking along those interfaces and dislodgement of
Cu-Al phase from matrix. It should be noted that extensive cracking at Cu-Al phase-α matrix interface and subsequent dislodge-
ment of both the phases have been observed at the boundary between uniformly corroded (region A) and uncorroded regions.
Thus, fresh masses of pure Cu (as modified α) and Cu-Al-rich phase were found in significant quantity in this area, as were
marked as 10 and 11 in Fig. 8. Therefore, it is clear from the above discussion that cracking involving the Cu-Al phase is playing
a crucial role in maintaining integrity of the uniformly corroded and borderline uncorroded regions, and as a whole the integrity
of the impeller, irrespective of the existence of cracking involving Cu-S-O-rich precipitates. It is noteworthy that development of
dendritic Cu-Al features, their corrosion and subsequent cracking at their interfaces with α matrix and dislodgement of both the
phases are so far not reported in the literature, to the best of our knowledge.

4. Summary

Failure of the impeller was due to combined effect of a susceptible microstructure of the casting and severity of corroding (pol-
luted sea water) medium that resulted in selective phase corrosion (SPC) of certain phases in the microstructure leading to sur-
face roughening and perforation, predominantly through pitting mechanism governed by dealuminification at phase interfaces.
Following findings from the present investigation are noteworthy:

a) Aluminium content (11.25 wt%) of out of specified composition (8.9–9.6 wt%) along with complex shape of the impeller and
associated differences in cooling rate resulted in appreciable volume fraction of networked alpha plus kappaIII eutectoid struc-
ture, retained beta and extreme structural heterogeneity in microstructure of the impeller material. Various oxides of copper
and aluminium and dendritic Cu-Al phase were found to be crucially important heterogeneities controlling corrosion resis-
tance of the failed component.
b) Inadequate temper annealing treatment resulting from ineffective soaking time for varying section thicknesses was unable to
break the retained beta and alpha plus kappaIII eutectoid network sufficiently in microstructure of the impeller material.
c) Highly polluted sea water typified by presence of sulphur along with above mentioned unintended microstructure led to im-
peller failure predominantly through pitting mechanism governed by dealuminification initiated along interfaces of different
phases. Initiation of dealuminification at different interfaces between various phases and its consumption followed by propa-
gation into more susceptible phase in a phase couple and subsequent consumption of the as-cast kappaII and kappaIII phase
has been found to be the principle deteriorating mechanism for corrosion of alpha plus kappaII and alpha plus kappaIII con-
stituents respectively. On the other hand, for alpha-retained beta and alpha-temper refined kappaII constituents, dislodgement
of retained beta and temper refined kappaII through interfacial corrosion and subsequent cracking along all of their interfaces
with alpha matrix was observed.
d) In (≈12 mm) thick sections, most frequently affected corroding features was found to be interface of alpha with kappaII
followed by that of alpha with kappaIII, and subsequent consumption and/or dislodgement of kappaII and kappaIII respective-
ly. In (≈3 mm) thin sections, most frequently affected corroding features appears to be interface of dendritic Cu-Al phase with
alpha followed by Cu-O-type phase (resulting in Cu-S-O rich corrosion product) and often interfacial cracking and dislodge-
ment of the said phases.
e) Level of exposure of different sections of the failed impeller component to sea water was found to affect the extent of corro-
sion damage directly.
f) F-rich Fe-Al-Ni phase, F-Fe-Ni-rich dendritic Cu-Al phase, Ni-deposited kappa II phases as corrosion products are some uncom-
mon findings in this type of investigation of corrosion of NAB in sea water.

5. Recommendations

5.1. Proper selection of composition and structural modification

Use of an as-specified alloy with b10 wt% aluminium would definitely be a better choice with respect to the reduced chance of
obtaining retained beta in any form like parent bcc beta and/or martensitic beta and/or transformed beta (alpha plus gamma-2)
[11]. Therefore, associated corrosion problem arising out of presence of retained beta in the structure would be lower in that case,
than that in the present scenario.

5.2. Casting process related

Casting practice should be carefully controlled so as to forbid presence of any Cu-Al-O type of inclusion as well as heteroge-
neities in various grain morphologies and associated segregation effects that deteriorate corrosion resistance of the material [7].
This along with prediction on very minute variation in local microstructure may be achieved through effective flow modeling
and finite element simulation as well as adoption of improved casting process such as centrifugal casting [7,24–26]. Blending
and/or repair welding should be applied for minimization and/or removal of pores like surface and sub-surface casting defects,
as guided by NES 747 part-II specification [11]. Thorough radiographic and ultrasonic inspections should be taken up for each
casting for detection of various casting defects and taking action for their removal [7,11].
M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156 155

5.3. Temper annealing heat treatment

Impeller component for sea water use should be given a temper annealing treatment. This consists of soaking the component
for 2–6 h at 650–675 °C, depending on the composition and different section thicknesses of the impeller [11,17]. This treatment,
when optimized, usually eliminates and/or minimizes the deleterious retained beta as well as eutectoid alpha plus kappaIII and
results in a transformation product of discrete alpha plus kappa. However, heat treatment play different role in the mechanical
properties and the corrosion resistance of NAB. Therefore, a tradeoff should be considered in heat treatment process design,
with an aim for optimization of those properties, as required for sea water use.

5.4. Need of periodic inspection

There should be sufficient periodic inspection for measuring section thickness and detecting corrosion product in this type of
corrosion of NAB material under sea water. This may be routinely and easily carried out through methods like ultrasonic caliper
test [27], silver nitrate test [3] etc.

5.5. Caution for severe environment

For polluted sea water, extra care should be taken in minimizing the effect of sulphide pollution and corrosion arising out of
that, esp. the localized phenomenon of pitting [18,19]. Extended use of the impeller in stagnant or quiet condition is not at all
recommended in terms of active participation of already present sulphides and also sulfate reducing bacterias (SRBs) to cause ac-
celerated pitting, and so, sufficient periodic cleaning is required. Also, ferrous sulfate dosing may be employed for additional safe-
ty, as a precaution for cases of deficiency in dissolved oxygen in the system [28].
In case of nil possibility of avoidance of sulphide attack, NAB material may be replaced with super duplex or super austenitic
stainless steel [7]. Method of overcoming pitting problems in stainless steel is to make the static parts of the pumps of stress relief
heat treated (for a few hours at 650–675 °C and furnace cooled) Ni-Resist Type D-2 W which gives cathodic protection to stainless
steels at shutdowns [29]. This combination can also control pitting and crevice corrosion under static conditions. However, it is
essential to apply the said stress relief heat treatment before service and after any weld repairs.

Acknowledgement

Authors are extremely grateful to Dr. Amol A Gokhale, distinguished scientist and director, DMRL for his constant encourage-
ment to work on the present field. Financial support from DRDO is deeply acknowledged.

Reference

[1] A.M. Olszewski, Dealloying of a nickel–aluminum bronze impeller, J. Fail. Anal. Prev. 8 (6) (2008) 505.
[2] https://www.astm.org/Standards/water-testing-standards.html, last accessed on 25.06.2016.
[3] R.J. Ferrara, T.E. Caton, Review of dealloying of cast bronze and nickel-aluminum bronze in sea water service, Mater. Perform. 21 (2) (1982) 30.
[4] P. Brezina, Heat treatment of complex aluminium bronzes, Int. Met. Rev. 27 (1982) 77.
[5] M. Cook, W.P. Fentiman, E. Davis, Observations on the structure and properties of wrought cooper-aluminium-nickel-iron alloys, J. Inst. Met. 80 (1951) 419.
[6] F. Hasan, A. Jahanafrooz, G.W. Lorimer, N. Ridley, The morphology, crystallography, and chemistry of phases in as-cast nickel-aluminum bronze, Metall. Trans. A
13A (1982) 1337.
[7] I. Richardson, Guide to Nickel Aluminium Bronze for Engineers, in: Carol Powell (Eds.), Copper Development Association (CDA) Publication no 222, January 2016.
[8] C.V. Hyatt, K.H. Magee, Laser surface melting and cladding of nickel aluminum bronzes, Proceedings of Advanced Methods of Joining NeW Materials II, The Amer-
ican Welding Society, Miami, Florida 1994, pp. 111–126.
[9] P.J. Macken, A.A. Smith, The Aluminium Bronzes: Properties and Production Processes. CDA Publication No. 31, second ed., 1966.
[10] H.I. Meigh, Cast and Wrought Aluminium Bronzes—Properties, Processes and Structure, Institute of Materials, London, 2000.
[11] Requirements for Nickel Aluminium Bronze Castings and Ingots. Defence Standard 02-747 (NES 747). Issue 1. Publication Date, 01 April 2000.
[12] A.H. Khan, P.K. Singh, Influence of heat treatment on microstructure and mechanical properties of aluminum bronze, Int. J. Metall. Mater. Science Eng. (IJMMSE) 3
(1) (2013) 57.
[13] J.A. Wharton, R.C. Barik, G. Kear, R.J.K. Wood, K.R. Stokes, F.C. Walsh, The corrosion of nickel–aluminium bronze in seawater, Corros. Sci. 47 (2005) 3336.
[14] D. Nazeran, S.T. Talebian, I. Sadr, Corrosion behavior of copper alloys in seawater with emphasis on UNC C95700, Tech. J. Eng. App. Sci. 3 (4) (2013) 286.
[15] J.R.C. Strang, Shipham Valves. Cast Valve Materials for Seawater Service: Nickel-aluminium Bronze and its Rivals (Paper P0607), Valve World 2006 Conference,
MECC Maastricht, Netherlands, November 2006 7–9.
[16] J.A. Wharton, K.R. Stokes, The influence of nickel–aluminium bronze microstructure and crevice solution on the initiation of crevice corrosion, Electrochim. Acta
53 (2008) 2463.
[17] H.S. Campbell, Aluminum Bronze Corrosion Resistance Guide. Publication 80, Copper Development Association, U.K. July 1981 1–27.
[18] H. Le Guyader, A.M. Grolleau, V. Debout, Corrosion Behaviour of Copper Alloys in Natural Sea Water and Polluted Sea Water, dcns Cherbourg-Cetec - Code 0981
bp 440 50 104 Cherbourg Octeville, France.
[19] A. H. Tuthill, Guidelines for the Use of Copper Alloys in Seawater, Jointly Published by Nickel Development Institute (NiDI) and Copper Development Association
(CDA).
[20] A. Al-Hashem, W. Raid, The role of microstructure of nickel–aluminium–bronze alloy on its cavitation corrosion behavior in natural seawater, Mater. Charact. 48
(2002) 37.
[21] S. Fonlupt, B. Bayle, D. Delafosse, J. Heuze, Role of second phases in the stress corrosion cracking of a nickel–aluminium bronze in saline water, Corros. Sci. 47
(2005) 2792.
[22] M. Kanamori, S. Ueda, S. Matsuo, On the corrosion behaviour of copper-aluminum-nickel-iron cast alloys in sea water, Nippon Kinzoku Gakkai 24 (5) (1960) 268.
[23] C.J. Czajkowski, Dealloying in Aluminum Bronze Components, in: K.A. Esakul (Ed.), Handbook of Case Histories in Failure Analysis, Vol 2, 1992 (ASM
International).
156 M. Hazra, K.P. Balan / Engineering Failure Analysis 70 (2016) 141–156

[24] J. Olofsson, I.L. Svensson, P. Lava, D. Debruyne, Characterisation and investigation of local variations in mechanical behaviour in cast aluminium using gradient
solidification, digital image correlation and finite element simulation, Mater. Des. 56 (2014) 755.
[25] V. Bijagare, V. Deulgaonkar, Modeling and finite element analysis for a casting defect in thin-wall structures, Int. J. Emerg. Eng. Res. Technol. 3 (5) (2015) 77.
[26] W. Junqing, S. Xun, G. Yang, W. Penghua, L. Hailan, B. Limei, S. Xinzhi, Numerical simulation and process optimization for producing large-sized castings, China
Foundry 5 (3) (2008) 179.
[27] S.C. Jirapure, A.B. Borade, Naval corrosion–causes and prevention, Int. J. Eng. Sci. Res. Technol. 3 (7) (2014) 263.
[28] C. Powell, P. Webster, Copper alloys for marine environments, Copper Development Association (CDA) Publication no 206, December 2002.
[29] Industrial corrosion and corrosion control technology, in: H.M. Shalaby, A. Al-Hashem, M. Lowther, J. Al-Besharah (Eds.),Proceedings of the 2nd Arabian Corrosion
Conference Kuwait, October 12–15, 1996.