ScriptaMaterialia,

Vol.37,No,12,pp.1843-1849, 1997
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GRAIN BOUNDARY NIOBIUM CARBIDESIN INCONEL 718

Ming Gao and Robert P. Wei
Departmentof MechanicalEngineeringand Mechanics,LehighUniversity
Bethlehem,PA 18015USA
(ReceivedAugust27, 1996)
(AcceptedOctober22, 1996)

Introduction

A coordinated,multidisciplinaryinvestigationwas conductedto determinethe mechanismsand rate

controllingprocesses for environmentallyassisted crack growth under sustained(static) loading in
Inconel718 at elevatedtemperatures[1-3].Theresultsshowedthat oxygenhad a significantinfluence
on crack growth, increasingthe crack growthrate, for example,by nearly four orders of magnitude
(i.e., by 104times) at 973 K. Based on resultsffomthe companionsurfacechemicaland metallurgical
studies,it was suggestedthat the mechanismfor crackgrowthenhancementby oxygenwas the format-
ion and fractureof a brittleniobiumoxide(NbZO@pe)filmon the grainboundarysurfaces[1-3].The
Nb came principallyfrom the oxidationand decompositionof NbC (or Nb-rich carbides)at the grain
boundaries,and crack growthwas controlledby the rate of oxidationand decompositionof these car-
bides [1-3].Becausethere was extensiveoxidationof the primaryNbC, these carbideswere implicitly
consideredto be the primary source of Nb [1-3]. Althoughthese carbideswere large and contained
substantialamountsof Nb, they were too few and spacedtoo far apartto be of concern(averagingone
NbC for two grain boundaryfacetsand spacedabout25~m apart).To wit, whetherthe freed Nb could
diffuse over such a large distance and be oxidizedto supportthe postulated mechanism for crack
growth? Thepresenceof otherNb-richcarbideselsewhereon the grainboundaries,or othersourcesfor
Nb, therefore,needsto be re-examinedand is the focusof this study.
Two typesof niobiumcarbides(namely,primaryand secondarycarbides)havebeen reportedin the
literaturefor Inconel718 [4-8].The primaryNbC were formedduringsolidificationand are large and
stable. They do not residepreferentiallyat grainboundaries,and often appear in chainsalignedin the
rolling direction.The secondaryniobiumcarbides,on the otherhand, were formed during aging and
precipitated at the grain boundaries[6-8]. This type of carbide may re-dissolve or be replaced by
cr23c6tit temperatureshigherthan 973 K [6,7]. Becausethese studies[4-8]were focused on the pre-

cipitationof y’,y“ and 5 phases,Nb-richcarbidesat the grainboundarieswere not fullycharacterized.

In this paper, the results of a study of grain boundaryniobium carbides and their distributionin
Inconel718 are reported,and are discussedin termsof theircontributionto crackgrowth.

1843
1844 GRAIN BOUNDARY Vol. 37, No. 12

Material and Experimental Work

The same Inconel718utilizedin the crackgrowthstudies(compositionin weightpercent:Ni 53.68,Cr

18.12,Fe 18.04,Nb 4.85,Mo 2.93, Ti 0.98,Al 0.42,C 0.066)was used for this study [1-3]. Specimen
blankswere heat treated using the standardcommercialtwo-stepprocedure:solutiontreat at 1255K,
1 h, air cool (AC)+ 1005K, 8 h, t%rnacecool(FC),andthen age at 894K, 8 h, AC.
Two scanning electronmicroscopes(namely,ETEC and JEOL 6300), both equippedwith an en-
ergy-dispersive spectroscopy(EDS) system and operated at 20 kV, were used. The JEOL 6300,
equippedwith a field-emissiongun, was mainlyused for high magnificationexaminations.Two types
of surfaceswere examined:(1) fracturesurfacesproducedby crack growthin oxygen,and (2) fi-acture
surfacesof hydrogenchargedspecimensbrokenat liquidnitrogentemperature.The llacture surfaces
producedby eithermethodwere intergranular.The grainboundaryfacetsexposedby crack growth in
oxygenwere oxidized,and providedinformationon reactionsof the particleswith oxygenduringhigh
temperatureexposure.Thoseproducedby fractureof hydrogenchargedspecimens,on the otherhand,
were “clean”,beingonlylightlyoxidizedby exposureto air afterfracture.
Specimensfor transmissionelectronmicroscopy(TEM)were preparedby electrochemicalthinning
in a TENUPOL-3jet polisher at 20V and 263 K using a solutionof 10°/0perchloric acid and 90°/0
methanolby volume. TEM observationswere periiormedusing a Philips400T electron microscope
operatedat 120kV. In additionto selected-areadiffraction(SAD)and dark-fieldimagingtechniques,a
convergentbeam diffraction(CBED)techniquewas used to identi~ the fine grain boundaryprecipi-
tates. The chemicalinformationon grain boundaryprecipitateswas obtainedusing EDS operated in
the scanningtransmissionelectronmicroscope(STEM)mode.

Results and Discussion

SEM Observations

The fracture surfacemorphologyproducedby crack growthin pure oxygenat 973 K is illustratedin

Fig. 1Aand showstypicalintergranularseparationwith well definedgrain boundaryfacets. AIthough
the fi-acturesurfaceswere exposedat 973 K for more thanthree hours,the grainboundaryfacetswere
not severelyoxidizedbecauseof the superioroxidationresistanceof Inconel718. Many fine features
of the facets could still be clearly identified.The large feathery clusters, accompaniedby adjacent
holes or holes beneath, were observedand identifiedpreviously[1-3]. In the re-examination,small
particlesand holes, withwell definedshapes,were alsonoted,Fig. la. The smallerparticlesand holes
were always seen as particle-holepairs, with each hole or particle on one of the fracture surfaces
matchedby a particleor hole on the matingsurface.
The EDS spectrumof the featherycluster(Fig. la and lb) showedthat the clusterscontainedprinci-
pally Nb, with a smallamountof Ti, whichsuggestedthat the clusterswere formed from the primary
NbC. The featheryappearancereflecteda strongreactionbetweenthe carbidesand oxygenduringhigh
temperatureexposure,and the clusterswere essentiallyniobiumoxidesthat formed during and subse-
quentto crack growth.The EDS spectrum(Fig. Ic) from one of the smallparticles (Fig. la) showed
that these particleswere also rich in Nb, but containedappreciableamountsof Cr, Fe, and Ni in addi-
tion to Ti. The presence of Cr, Fe and Ni in the EDS spectrummay be associatedwith oxides that
formed from the matrix elements,or couldbe attributedto the nature of the secondarycarbides.Fur-
ther confirmationof the primaryand secondarycarbides,therefore,was neededand was carriedout by
SEMexaminationsof hydrogenchargedspecimensand TEM studiesof grainboundarycarbides.
Vol. 37, No. 12 GRAIN BOUNDARY 1845

Figure 1. (a) FeatheryNbC clusters and smallerNb-richcarbideson the grain boundaryfacets producedby crack growth in
oxygenat 973K, (b) and(c) EDSspectrafromA andB in (a),respectively.

Typicalmicrofi-autographs taken fromthe hydrogenchargedspecimens(fi-acturedin liquidnitrogen)

are shown in Fig. 2, along with EDS spectra fi-omselected particles.The presence of two types of
particles were confirmed; namely, (1) large particles, or clusters of particles, principally at grain
boundarytriple points,with adjacentholesor holesbeneaththe particles(Fig. 2a), and (2) smallparti-
cles and holeswith well definedshapeson the grainboundaryfacets(Fig.2b). An EDS spectrum(Fig.
2c) fi-oma typical, large particle showed that this type of particle containedprincipallyNb, with a
small amount of Ti, which is consistentwith that observedon the fracture surface exposed by crack
growth in oxygen.EDS (Fig. 2d) results fromthe smallerparticlesagain showedthe presence of ap-
preciableamountsof Cr, Fe and Ni alongwith Nb and Ti. The resultsconfirmedthat the triple-point
particlesare associatedwith primaryNbC that formedduringsolidification.The smallerparticles,on
the otherhand,are most likelyniobiumcarbidesin whichNb is substitutedby Cr, Fe, Ni and Ti.

TEM Observations

In conformancewith the SEMfindings,two typesof grainboundary@b-rich) carbideswere observed

by TEM. The first type is usuallylargeand of irregularshape,and is most oftenfoundat grain bound-
ary triplepoints.The secondtypetendsto be smaller,and is foundalongthe grainboundaries.A small
grain boundarycarbideof the firsttype is shownin Fig. 3, alongwith a SAD patternfrom the particle
and its surroundingmatrix.The particlecontainedprincipallyNb, with a small amountof Ti. It had a
cubic structurewith latticeparametera = 0.444nm, which matchedwell with the NbC-typecarbides
(a= 0.447nm) reportedby Wilsonand Burke[9]. There is no crystallographicorientationrelationship
between the particleand the matrix on eitherside of the grain boundruy.Theseparticleswere stable,
with no detectabledissolutionupon specimenheatingup to 1373K. Similarlargeparticleswere often
observedwithin the grains;there is, therefore,no preferencefor the grain boundariesin their forma-
tion. Theseobservationsindicatethatthe particlesare associatedwith primaryNbC that formedduring
solidification,and confm their identificationby SEManalyses.
A typicalarray of the secondtypeof grainboundaryparticlesis shownin Fig. 4, alongwith a CBED
pattern (under Kossl-Mollentedtconditions)tlom one of these particles. The CBED shows that the
1846 GRAIN BOUNDARY Vol. 37, No. 12

Figure2. (a) A largeNbC (C-1)with an adjacenthole;(b) Nb-richcarbides;(c) and(d) EDSspectrafromC-I in (a) and C-2 in
(b), respectively.Specimenhydrogenchargedandthctured in LN,.

particlehas a tetragonalstructure,with latticeparametersa = 0.504 and c = 0.635 nm. The crystallo-

graphicorientationof the particlesappearsto be related to that of the matrix on one side of the grain
boundary.Based on the diffractionfromthe particleand its surroundingmatrix,the followingmatrix-
Partic]e relationships were obtained: (020)7//(220)PmiC1.and IOO1]Y // [oOl]particle. The EDS spectra
showedthe particlesto be rich in Nb, but also containedappreciableamountsof Cr, Fe and Ni. The
results are consistentwith those observedby SEM (c~Fig.2). Althoughthe chemicalcompositionof
these particles is similarto that of Laves phase in Inconel718, their crystal structures,however, are
completelydifferent [9-11]. The particles are identified,therefore, as niobium-rich(MC) carbides
similarto a type of niobiumcarbideobservedin niobium-containingstainlesssteels[12,13].

Discussion

With two types of Fib-richcarbidesidentified,their coverage(densityand distribution)of the grain

boundarieswas assessedfromthe SEMand TEM micrographs.For SEM, fracturesurfaceareas incor-
porating 122 grain boundaryfacets (taken at an originalmagnificationof 500X) were analyzed. The
smallestparticlethat couldbe resolvedat this magnificationwas about 1 pm in diameter.Sixty-three
large primary NbC (>1 pm) were observed,with estimatedaverage areal density and inter-particle
spacingof 0.5 particlesper bounday facetand 25 pm, respectively.Many secondaryNb-richcarbides
Vol. 37, No. 12 GRAIN BOUNDARY 1847

Figure3. Brightand dark fieldTEMimagesof a primaryNbCon the grainboundaries.The SADPS(see insert) showno crys-
tallographicrelationshipsbetweenthe particleandthe matrix. B// [111]W.

(001)7/1(()()l)xbc , [0201# [220]NbC

Figure4. Bright and dark field TEMimagesshowingfine precipitateson a grain boundary,rdongwith CBEDpatternsfrom
TheEDSspectra
AreaA, B// IOOl]Wfi~I,. showthePmicletoberichinNb.
1848 GRAINBOUNDARY Vol. 37, No. 12

were also foundon thesefacets.The densityand averagespacingof the secondarycarbides(largerthan

0.3 pm) were estimatedto be about 0.1 carbideper ~mz and 3 ~m, respectively,using SEM micro-
graphsof21 randomlyselectedfacets fromthe same specimenat 3,000to 5,000X, The particle den-
sity and averagespacingon the individualfacetsrangedfromabout0.3 to 0.03per pmzand 2 to 6 pm,
respectively. Other SEM observations(not shown) suggest,however, that the density might be an
orderof magnitudehigher,with an averageparticlespacingon the orderof 0.5 ~m.
Particle coverage was also determinedfrom 12 grain boundarysegments(with a total length of
about2,250mm at 28,000X,or about80 ~m) selectedrandomlyfromtwo TEM specimens.Se ondary
Nb-rich carbideswere identifiedon only three of the 12 boundaries.Lineal (fractional)coJ erage of
carbidesover these three boundarieswas about 350A,and was reducedto 7.2°Aby consideringall 12
boundaries.Using an estimatedparticle size (interceptlength)of 0.2 pm, the average inter-particle
spacing was estimated to be 0.6 and 3 ym, respectivelyfor 35°/0and 7.2°/0coverages, with corre-
sponding densities of 3 and 0.1 carbidesper pmz of grain boundary surface. The estimated inter-
particlespacingand densityare consistentwiththoseobtainedfrom SEM.
The presence of these finer secondaryNb-rich carbides allayed the original concern regarding
carbidespacing.Even thoughthey containlessNb, they are importantto the proposedNbC decompo-
sitionl’Nboxidationmechanismfor crackgrowthenhancement[1-3]. Becauseof the lack of difisivity
data, however,an estimateof the appropriatespacingcouldnot be made. Other sourcesof embrittle-
ment (e.g., grain boundariesy“ [1-3])remainto be identifiedand studiedto better establisha mecha-
nism for environmentallyassistedcrackgrowthin Inconel718.

Summary

Two types of grain boundarycarbidesthat are believedto be responsiblefor oxygen assisted crack
growth in Inconel 718 have been identified;namely,primaryNbC and secondaryNb-rich carbides.
The secondaryNb-rich carbidesserve as a more attractive,additionalsource of embrittlingNb and
ensureits ready diffision over the grain boundaries.The possiblecontributionof ‘y”and the applica-
bility of the proposedembrittlementmechanismto other nickel-basealloys are being examined and
will be reported.

Acknowledgment

Work supportedby National Science Foundation,Divisionof MaterialsResearch, under Grant No.

DMR-9102O93.

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