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EffectofThermoPlasticTreatmenton
StructureandCorrosionPropertiesofHigh
NitrogenCrSteels
VeraV.Berezovskaya
Instituteofmaterialscienceandmetallurgy,UralFederalUniversitynamedafterthefirstPresidentofRussiaB.N.
Yeltsin/Professor
ul.Mira,19,Yekaterinburg,620002,Russia
v.v.berezovskaya@urfu.ru
Abstract
Effectofagingonstructureandcorrosionpropertiesinhigh
strength austenitic Crsteels alloying with nitrogen Cr21N1
andCr18Ni2N1hasbeeninvestigated.Structureofthesteels
and kinetics of austenite decomposition during the
treatment was studied by Xray diffraction, TEManalyses
and electric resistance measurements. The highest valuesof
strength, micro hardness, corrosion rate and relative
strength reduction as far as brittle intergranular fracture
wereobservedattheearlystageofaustenitedecomposition
at the aging. The formation of nitrides CrN as well
martensitestressinducedtookplaceinthesteels.According
toresistormeterinvestigationsofnitrogensteelsincompare
withcarbonsteelCr18C1attheearlystageofaging(350C)
the metastable ordered clusters enriched with chromium
and nitrogen were formed. Growths of aging temperature
up to 500C led to dissolve the carbides or nitrides but at
600 C discontinuous precipitations were observed nearby
thegrainboundaries.
Effectofagingcombinedwithcoldplasticdeformation(CPD)
at an 824 % reduction by two schemes, before and after
aging at 350C, on structure and related corrosion
propertiesofsteelCr18Ni2N1hasbeenstudied.CPDatan8
12 % reduction before aging at 350 C was shown to thrice
decreasing of corrosion rate of the steel as compared to the
undeformed state.Athermoplastic treatment by thesecond
scheme with using CPD at an 20% reduction after aging at
350 C is found to be more effective: the corrosion rate
decreased by an order and strength reduction decreased
morethanbyfourfoldascomparedtotheundeformedstate.
Keywords
Austenite Decomposition; Ordered Clusters; StressMartensite;
Lattice Parameter; Stress Corrosion Cracking; Cold Plastic
Deformation.
Introduction
Highnitrogensteels(HNS)duetotheirmorestrength
and corrosion resistant than in other austenitic steels
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Steel
grade
Cr21N1
Contentinthesteel,wt%
C
Mn
Si
Cr
Ni
2.00
Cr18C1
0.920
0.63
30 m
The general corrosion and SCC tests were performed
ina3.5%NaClaqueoussolutionasitdescribedinthe
work [10]. Fractographic studies of fracture surface
after SCC were examined on a JSM35C scanning
electronmicroscopeandmetallographicexamination
onaNeophot32opticalmicroscope.
Theelectricresistancemeasurementswerecarriedout
to investigate the kinetics of solid solution
decomposition [12]. Xray diffraction analysis was
carried out on a DRON3 diffractometer with cobalt
radiation and a radiation filter. The austenite and
martensitecontentsinthesteelswereestimatedusing
the method of homologous pairs by comparing the
integratedintensitiesofthe(110)and(111)lines[13].
The structure of austenite and the type, morphology,
and size of additional phases were investigated by
transmission electron microscopy on an EMV100L
electronmicroscope.
Results and Discussion
Mechanical properties of high nitrogen steels were
following: yield strength (0.2) is 650 and 610 MPa;
specific elongation () is 21 and 18% after quenching
and 0.2=780 and 820 MPa; =5 and 9% in aged state
respectively in Cr21N1 and Cr18Ni2N1 steels. The
highest growth of strength, corrosion rate and
susceptibilitytoSCCin3.5%NaClwasobservedafter
aging at 350 C [14]. The fracture of specimens was
brittle and intergranular in this case (Fig. 1, a) while
the destruction was not associated with nitrides,
located along the grain boundaries. After overaging
the resistance to SCC increased and the intergranular
fracture was replaced to quasicleavage including
20
15 m
FIG.1FRACTURESURFACEAFTERSCCOFCR18NI2N1STEEL
SUBJECTEDOFAGINGAT350(a)AND600C(b)
JournalofMetallurgicalEngineering(ME)Volume2Issue1,January2013www.mejournal.org
TABLEIIPHASECOMPOSITIONANDCORROSIONPROPERTIESOFTHECR18NI2N1STEELAFTERVARIOUSTREATMENT
Contentofphases,%*
CPDafteraging
CPDbeforeaging
AgingwithoutCPD
of
treatment
Schemeoftreatment
Intheinitialstate
Atthesurfaceof
fractureafterSCC
m,
g/m2h
st,%
Quenchingfrom1200
95
62
26
12
2,0
35
1200+350,2h
95
58
22
20
30,0
37
1200+400
95
62
22
16
8,0
34
1200+600
50
44
28
64
1,0
29
1200+700
100
100
0,5
21
1200+8%CPD+350,2h
89
10,0
1200+12%CPD+350,2h
87
11,0
1200+20%CPD+350,2h
50
15
35
40
15
45
55,0
42
1200+24%CPD+350,2h
80
13
50,0
10
1200+20%CPD
95
0,3
11
1200+350,2h+20%CPD
95
95
2,5
10
12
1200+400+20%CPD
95
0,3
13
1200+600+20%CPD
50
50
0,8
14
1200+700+20%CPD
100
0,4
*Withoutexcessphases.
30 m
20 m
30 m
30 m
FIG.2ICROSTRUCTUREOFSTEELSCR18C1(),CR21N1(B)QUENCHEDANDCR18NI2N1(C,D)AGEDAT350AND600C
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22
electricresistanceofthesteels(sharpdecreaseofR/R
preagingstage).
At a longer time of heating it was an increase of
electric resistance most pronounced at 300C. This
stage continued not more than 7 hours at 300 C, 4
hoursat400Cand1hourat500Candassociated
with the separation of the solid solution with
chromium (as well carbon in carbon steel) during
these exposures because of the conductivity electrons
are scattered by these enriched in chromium clusters
[16](sharpincreaseofR/Rstage1).
Longer aging influenced on the curves character
differently depending on the temperature of aging. It
is necessary notice a stabilizing of decomposition of
austenite in carbon steel at 300 and 400 C and in
nitrogensteelsonlyat300C.Itisconnectedwiththe
formingofcarbidesincarbonsteel,butnotcompleting
of nitrides formation in nitrogen steels. It needs to
continue the heatingand further slow increasing of
electric resistance which observed at 400 C in these
steels confirmed it. This process associated with the
orderinginchromiumenrichedclusterswithnitrogen
that was able at an exposure at this temperature or
understresses(nearbytheextinctioncontoursFig.4,
a)ifexposurewasnotenough.Thustheformationof
carbidesornitridescharacterizedwithunchangingor
slowincreasingofR/Rstage2.
Decreasing of electric resistance at 500 C has been
shown in all investigated steels and was connected
with dissolving of clusters enriched in chromium
(slow decreasing of R/R accordingly in carbon and
nitrogensteelsstage3).
Effectofcoldplasticdeformationonthephasecontent
and corrosion properties of the steel Cr18Ni2N1 is
presented inTable2. CPD at an 824%reduction was
combined with aging at 350 C by two ways: before
(lines 610 in Table 2) and after aging (lines 1114) as
compared to the undeformed state (lines 15). It
follows from Tab. 2 that CPD at 812% reduction
before aging at 350 C decreases to thrice a corrosion
rate in spite of some increasing of martensite
content. On the contrary CPD at 20% reduction
increases nearly twice the corrosion rate because of
considerable depleting of austenite and as
consequence increasing of Tmartensite content after
strain aging. Furthermore this treatment condition
negativelyinfluencedontheSCCofthisnitrogensteel
and increased of martensite content if to compare
withundeformedstate(lines2and8).Itisknown[17]
thatalowlevelofstresses(trthresholdstress)
JournalofMetallurgicalEngineering(ME)Volume2Issue1,January2013www.mejournal.org
220
000
133
422
202
331
b
Zone axis [001]Cr2N
10 1 , 200Cr2N
121, 220Cr2N
020
Zone axis [ 1 31 ]
310
211
321
FIG.3STRUCTUREOFQUENCHEDSTEELCR18NI2N1:ASUBGRAINSTRUCTUREOFAUSTENITE;BSELECTEDAREAELECTRON
DIFFRACTIONPATTERNTAKENFROMREGION(A);CKEYPATTERN;DSTRUCTUREOFGRAINBOUNDARY;ESELECTED
AREAELECTRONDIFFRACTIONPATTERNTAKENFROMREGION(D);FKEYPATTERN;GSURFACEMARTENSITE
111
200
200CrN
Zone axis [ 0 11 ]
11 1 rN
CrN
000
CrN
200CrN
200
111 111CrN
11 1 CrN
11 1
311 CrN
311
211
Zone axis [ 1 2 5 ]
000
311
200 110
204
202
121
321
420
Zone axis [ 1 2 5 ]
FIG.4.STRUCTUREOFAGEDAT350STEELCR18NI2N1:AHOMOGENEOUSDECOMPOSITIONOFAUSTENITE;BSELECTED
AREAELECTRONDIFFRACTIONPATTERNTAKENFROMREGION(D);CKEYPATTERN;DEXTINCTIONCONTOURSAND
MARTENSITE;ESELECTEDAREAELECTRONDIFFRACTIONPATTERNTAKENFROMREGION(D);FKEYPATTERN
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20 1
401
000
202
200, 002
11 2
Zone axis
011, 110
211
[ 110 ]
Zone axis [ 01 1 ]
011
000
2 20 ,
220
Zone axis [ 11 8 ]
211
200
Zone axis
711
331
[ 11 6 ]
151
531
FIG. 5 STRUCTURE OF AGED AT 500 STEEL CR18NI2N1: A GRAIN BOUNDARY; B SELECTED-AREA ELECTRON DIFFRACTION
PATTERN TAKEN FROM REGION (A); C KEY PATTERN; D MARTENSITE ; E SELECTED-AREA ELECTRON DIFFRACTION PATTERN
TAKEN FROM REGION (D); F KEY PATTERN
Zone axis [ 11 0 ]
110
222, 404Cr2N
000
011
2 01
200
211
FIG. 6 STRUCTURE OF AGED AT 600 STEEL CR18NI2N1: GRAIN BOUNDARY; B SELECTED-AREA ELECTRON DIFFRACTION
PATTERN TAKEN FROM REGION (A); C KEY PATTERN
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FIG.7.KINETICSOFELECTRICRESISTANCECHANGEININVESTIGATEDSTEELSCR21N1(1),CR18NI2N1(2)CR18C1(3)DURING
THEAGINGAT:A300;B400;C500
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Zone axis [ 1 03 ]
110, 020
3 11
200
000
002
220
311
310
Zone axis [ 11 0 ]
222
FIG.10STRUCTUREOFDEFORMEDATAN8%REDUCTIONBEFOREAGINGAT350STEELCR18NI2N1:MARTENSITE;B
SELECTEDAREAELECTRONDIFFRACTIONPATTERNTAKENFROMREGION(A);CKEYPATTERN
-Fe/Fe2+
x2
C
2 - tr
B
-H+/H
Conclusion
1 - tr
-O2
i2
i1
500
450
HV100
400
350
300
250
200
0
11
20
, %
24
FIG.9DEPENDENCEOFTHEMICROHARDNESSONTHE
DEGREEOFCPDPRECEDEDTHEAGINGAT350INSTEEL
CR18NI2N1
26
Coldplasticdeformationat812%reductionpreceding
the aging at 350 C is shown to decrease three times
thecorrosionrateofthesteelCr18Ni2N1ascompared
to the undeformed state. The role of CPD at this
degree consists of accelerating of nitrides CrN
precipitation without intermediate stage of ordering
JournalofMetallurgicalEngineering(ME)Volume2Issue1,January2013www.mejournal.org
clusters.Athermoplastictreatmentby20%CPDafter
agingat350Cismoreeffectivebecauseofdestroying
already formed ordered clusters, which are the main
reasonofhighsusceptibilitytoSCC.
ACKNOWLEDGMENT
TheauthorwishestothankMansurS.Khadyevforhis
helpinexperimentalprocedure.
This work was carried out and is running now with
the financial support of Russian Foundation for Basic
Research,grantsN070300062aandN110300065.
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[15] BerezovskayaV.V.,GolyakovI.V.,BannykhO.A.etal.
EffectofColdPlasticDeformationontheStructureand
Corrosion Resistance of Austenitic Aging 0Kh18N2A
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[RussianMetallurgy(Metally),2006,5:390393].
[16] LivshitsB.G.,KraposhinV.S.,LinetskiyYa.L.Physical
PropertiesofMetals.Moscow:Metallurgiya,1980.320
pp.
[17] Isaev N. I. Theory of corrosion processes. Moscow:
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[18] Nelson H. G., Williams D. P. Stress Corrosion and
[19] BerezovskayaV.V.DelayedFailureofMaragingSteels
PhD,MetalScienceandHeatTreatment,
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UralPolytechnicInstitute,1985;
Assoc. of Prof., Metallurgical Department of Ural State
Technical University, Yekaterinburg (former Ural
PolytechnicInstitute,Sverdlovsk),1996;
Doctorofscience,MetalScienceandHeatTreatment,Baikov
Institute of Metallurgy and Materials Science, Russian
AcademyofScience,Moscow,Russia,2004;
Professor, Metallurgical Department of Ural State Technical
University,Yekaterinburg,2005;
Currently Professor, Institute of Metal Science and
Metallurgy of Ural Federal University named after the first
PresidentofRussiaB.N.Yeltsin.
The main area of scientific interest is relationship between
structureandfractureofstainlessandhighstrengthsteelsat
cavitations,delayedfailureandstresscorrosioncracking.
She is a LECTURER at the Ural Federal University on
following subjects: Material Science; Theory of corrosion,
corrosionresistant materials and coatings, from 1991 and
Advanced Materials and Technologies from 2010. She has
about200publications,themainofthemare:
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