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JournalofMetallurgicalEngineering(ME)Volume2Issue1,January2013www.mejournal.

org

EffectofThermoPlasticTreatmenton
StructureandCorrosionPropertiesofHigh
NitrogenCrSteels
VeraV.Berezovskaya
Instituteofmaterialscienceandmetallurgy,UralFederalUniversitynamedafterthefirstPresidentofRussiaB.N.
Yeltsin/Professor
ul.Mira,19,Yekaterinburg,620002,Russia
v.v.berezovskaya@urfu.ru

Abstract

with carbon are widely used in power machine


building,shipbuildingandotherfieldsofengineering.
In the nearest future [19] after perfecting their
manufacturing technology they are expected will be
applied in a bigger industrial scale. One of the main
directions of investigations to solve these problems is
searching a way to increase their resistance to stress
corrosioncracking(SCC)bothbyefficientalloyingand
optimizationofstrengtheningprocedure.

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.

Well known that nitrogen includes a significant


contribution in hardening of solid solution and grain
boundaries as well as in strain and precipitation
hardening. According to data from work [2],
realization of these factors at appropriate degree of
coldplasticdeformation(CPD)canprovideextremely
high strength for this class of steels up to 3600 MPa.
However in a certain structural state they are
subjectedtoSCCincorrosiveenvironment[10,11]so
inthiscaseexpedienttousethemafterstrengthening
notmorethenupto0.2=1400MPa.

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.

Materials and Procedure


The highstrength lowcarbon steels with high
nitrogen content (0.91.0%) Cr21N1 and Cr18Ni2N1
have been investigated to study mechanism and
kinetics of austenite decomposition and clearing up
CPD influence on structure and corrosion properties
of steels. Kinetics of decomposition of the
oversaturatedsolidsolutioninHNSwascarriedout
as compared with high carbon steel Cr18C1. Their
chemicalcompositionispresentedinTable1,firsttwo
of them were produced by nitrogen pressure casting,
homogenization at 1250 C and rolling with further
quenching in water after being exposed for one and
half an hour at 1200 C. The high carbon steel was

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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manufactured by standard technology and quenched


from the same temperature in oil to put the austenite
structure. The specimens prepared for testing were
agedat300500Cfortwohoursandat600Cforan
hour.
TABLEICHEMICALCOMPOSITIONOFSTEELS

Steel
grade

Cr21N1

Contentinthesteel,wt%
C

Mn

Si

Cr

Ni

0.020 1.021 0.19

0.42 0.015 0.010 21.45

Cr18Ni2N1 0.008 0.899 0.30

0.27 0.020 0.010 17.86

2.00

0.79 0.025 0.023 18.30

Cr18C1

related to colonies of discontinuous decomposition of


solidsolution(Fig.1,b).Theinvestigatedsteelshad
a good passivity in all structural states due to high
contentofchromiuminsolidsolution,howeveratthe
stage of active corrosion the sharp acceleration of
corrosion was observed after aging at 350 C in
investigatedsteels(Table2,line2).

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)

After quenching from 1200 C an austenite and


carbideswithsurfacemartensitewerenotedincarbon
steel as well as in nitrogen steels (Fig. 2, a, b). The
structure of high nitrogen steels varied with rising of
aging temperature identically with some more
stability of austenite in nickelfree steel. The
microstructure of nitrogen steels aged at 350 C was
almost similar to quenched one (Fig. 2, c), but after
agingat600Citwasratherdifferent(Fig.2,d).
Martensitesoftwomorphologieswithdifferentlattice
parameters aT=0.287 nm and a=0.291 nm was
discovered in steel Cr18Ni2N1. As it was shown
earlier [15] it was the thin dispersive martensite (T)
onthegrainboundariesandannealingtwins(Fig.2,b,
c) and lensformed stressinduced martensite () in
the middle of grain (Fig.2, d), which formed
respectively from austenite depleted and enriched
with chromium and nitrogen. The same picture was
found after SCC. The results of Xray diffraction
analysesareshowninTable2.

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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According to comparison of SCC tests and Xray


diffractionresultsthecorrelationbetweenthevalueof
relative strength reduction (/K) and quantity of
stressinduced martensite, formed directly during the
tests, is observed in high nitrogen steels. The biggest
portionofmartensiteinstructureofsteelwasnoted
afteragingat350C.
By transmission electron microscopy of thin foils the
evolution of structure in steel Cr18Ni2N1 under the
aging was studied. The structure of quenching steel
consisted of austenite (Fig. 3, ac), rather big particles
ofnitridesCr2Nretainedafterheatingalongthegrain
boundaries and not more than 5% of Tphase as a
result of martensitic transformation in depleted
austenite near the nitrides (Fig. 3, df). The nitride
Cr2Nhasahexagonalcrystallinestructurewithlattice
parametersa=0.4805nm,c=0.4480nm.Thecrystalsof
surface martensite formed at electrolytic polishing of
foilcouldbeseenaswell(Fig.3,g).
After aging at 350 and 400 C besides and phase
ultra dispersive nitrides CrN with FCC crystalline
orderedstructureandlatticeparameteraCrN=0.415nm
formed from a supersaturated solid solution due to
homogeneous isomorphic decomposition were
observed (Fig.4,ac). The crystals of martensite
were found as well. Both phases CrN and were
noticednearbytheextinctioncontoursintheplacesof
foilbending(Fig.4,df).After2houragingat500C
besides Tphase in the settlement of discontinuous
decompositiononthegrainboundaries(Fig.5,ac)the
singlecrystalsofmartensitewerediscovered(Fig.5,
d). At temperature 600 C fresh portions of
discontinuousdecompositionsettlementsconsistingof
nitridesCr2NandTmartensitewasobserved(Fig.6).
The electric resistance of the steels Cr21N1,
Cr18Ni2N1 and Cr18C1 has been measured
depending on time of aging in isothermal conditions
at 300, 400 and 500 C (Fig. 7). These dependences
wereshowntobethesameforhighnitrogenandhigh
carbonsteels.Attheinitialstagesofprocess(36h)we
can see a sharp electric resistance decrease which
becomes bigger as the temperature of aging grows.
The effect of aging depends on a super saturation
degreebyinterstitialatomsofaustenitequenchedbut
at the same content of carbon and nitrogen (about
0.9%) its displayed stronger in high nitrogen steels.
Withtheincreasingofthetemperatureatthisstageof
aging a difference between the curves reduced and
they practically coincided at 500 C. The stress
recoveryattheheatingwasresponsiblefordecreaseof

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)

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220

Zone axis [ 111]

000

133

422

Zone axis [ 343 ]

202

331

b
Zone axis [001]Cr2N

10 1 , 200Cr2N

121, 220Cr2N

020

Zone axis [ 1 31 ]
310

211

321

Zone axis [ 012 ]

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 Zone axis [ 011 ]

000

CrN

200CrN
200

111 111CrN

11 1 CrN

11 1

311 CrN

311

211

Zone axis [113]

004 Zone axis [ 010 ]Cr2N

Zone axis [ 1 2 5 ]
000

311

200 110

204

202

Zone axis [ 111 ]


131

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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Zone axis [010]Cr2N

20 1

401

000

202
200, 002

11 2

Zone axis

011, 110

Zone axis [ 011 ]

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

Zone axis [ 0 1 0 ]Cr2N 203Cr2N, 112

2 01

200

211

Zone axis [ 011 ]

FIG. 6 STRUCTURE OF AGED AT 600 STEEL CR18NI2N1: GRAIN BOUNDARY; B SELECTED-AREA ELECTRON DIFFRACTION
PATTERN TAKEN FROM REGION (A); C KEY PATTERN

does not considerably increase the corrosion current


atSCCofironbutahighlevelofthem(tr)causes
a significant growth of this one (Fig. 8). And taking
intoconsiderationthesametodelayedfailure[18,19]
mechanism of SCC, when the main depolarization
process is hydrogen ions (H+) discharge on the
ordered clusters to atoms (H), they become the
effective sub micro cathodes in electrochemical
process on the surface of the steel. The atoms of
hydrogen can join to molecules (H2) significantly

24

increasing their size and level of stresses in the


clusters. That is why the stressmartensite can be
formedfromthoselocalareasofstructure.
After 24% reduction the austenite has more stability
than after 20% reduction because of strain recovery,
thats confirmed by dependence of micro hardness
from deformation degree (Fig.9). Fig. 10 shows the
structure of deformed before aging at 350 C steel
with the electron diffraction pattern where
martensitecanbenoted.

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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 [ 001 ]

Zone axis [ 11 0 ]

222

FIG.10STRUCTUREOFDEFORMEDATAN8%REDUCTIONBEFOREAGINGAT350STEELCR18NI2N1:MARTENSITE;B
SELECTEDAREAELECTRONDIFFRACTIONPATTERNTAKENFROMREGION(A);CKEYPATTERN

-Fe/Fe2+
x2

Treatment with CPD at 20% reduction after aging at


350Cisfoundtobemoreeffective:thecorrosionrate
decreasedbyanorderandthereductionofstrengthat
SCC was about a quarter of magnitudes of
undeformed state. This positive influence of CPD is
probably connected with breaking the order in
metastable clusters which could be acceptors of
discharged hydrogen and nucleus of stressinduced
martensiteatSCC.

C
2 - tr

B
-H+/H

Conclusion

1 - tr

-O2

i2

i1

FIG. 8 POLARIZATION DIAGRAM OF CORROSION AT SCC:


O2ABC CATHODE CURVE; FE/FE2+X11 AND FE/FE2+X22
ANODECURVESATADIFFERENTSTRESS

The structure of quenched steels Cr21N1, Cr18Ni2N1


andCr18C1withhighcontentofnitrogenandcarbon,
respectively 1.021, 0.899 and 0.920% consists of
metastable austenite with nitrides or carbides settled
downthegrainboundaries.Alsoasmallcontentof
phase takes place near the nitrides/carbides or as a
resultofpolishing.
Twostagesofdecompositionofausteniteattempering
were shown to be in nitrogen steels by electric
resistance: separation of the solid solution with
chromiumfollowedbyorderingoftheseclusterswith
nitrogenwhichinducedbytimeexposureorstresses.

500
450

HV100

400

The highest hardness, corrosion rate and stress


corrosion cracking susceptibility in HNS were
observed at the second stage of aging. This structural
state characterized of ordered enriched with
chromium and nitrogen clusters which had an ability
totransformintoastressinducedmartensite.

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.

Akad. Nauk, Ser. Met., 2008, 1: 3641. [Russian


Metallurgy(Metally),2008,1:2933].
[11] Kostina M. V., Bannykh O. A., Blinov V. M.,

Berezovskaya V. V., et al. Effect of Chemical


Composition and Heat Treatment on the Corrosion
Properties in High Nitrigen IronBased Alloys
Containing1524%Cr.Izv.Ross.Akad.Nauk,Ser.Met.,
2001, 3: 2634. [Russian Metallurgy (Metally), 2001, 3:
243250].

ACKNOWLEDGMENT

TheauthorwishestothankMansurS.Khadyevforhis
helpinexperimentalprocedure.
This work was carried out and is running now with
the financial support of Russian Foundation for Basic
Research,grantsN070300062aandN110300065.

[12] Bannykh O. A., Berezovskaya V. V., Effect of heat

treatment conditions on the structure and


physicomechanical and chemical properties of an Ni
CrCuTi maraging steel. Izv. Ross. Akad. Nauk, Ser.
Met.,2007,3:4047.[RussianMetallurgy(Metally),vol.
2007,3:201208].

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[19] BerezovskayaV.V.DelayedFailureofMaragingSteels

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Volume 6. Editors: James C. Taylor.Chapter 7. N.Y.,
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Vera. V. Berezovskaya was born


04.04.1949.

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Alloyed Austenitic Stainless Steels for Wire and Cable
Applications.InthesamebookHNS2003:199210.

Engineer, Physics of Metals, Ural


Polytechnic Institute (Sverdlovsk,
USSR),1971;

[10] Berezovskaya V. V., Kostina M. V., Blinov E. V., et al.

Corrosion Properties of Austenitic CrMnNiN Steels


with Various Manganese Concentration. Izv. Ross.

PhD,MetalScienceandHeatTreatment,

27

www.mejournal.orgJournalofMetallurgicalEngineering(ME)Volume2Issue1,January2013

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:

Berezovskaya V. V. Delayed Failure of Maraging Steels in


Environment. Advances in Chemistry Research. Volume 6.
Editors: James C. Taylor. Chapter 7. N.Y., USA, Nova
SciencePublishersInc.2011.219244.
Berezovskaya V. V., Savrai R. A., Merkushkin E. A.,
Makarov A. V. Structure and Mechanical Properties of new
highnitrogen CrMn Steels Containing Molybdenum. Izv.
Ross. Akad. Nauk, Ser. Met., 2012, 3: 3139. [Russian
Metallurgy(Metally),2012,5:380388].
Her current research interests lie in the area of High
Nitrogen Steels, their structure, mechanical, physical and
chemicalproperties.
Dr. Berezovskaya supervises the contracts and grants,
preparedtwoMasters(2010,2011)andthePhD(2002).Sheis
Member of New York Academy of Sciences (New York,
USA,1996);
Member of Association of Russian Metallurgists (Moscow,
Russia2002).
Shehas

Berezovskaya V. V. Structural Factors Governing Steel


ResistanceduringOperationinCorrosiveMediaunder

Honorary title Hero of Labor of regional importance


(Sverdlovskayaarea,Russia,2003);

Cavitation Conditions. Metallovedenie i Termicheskaya


ObrabotkaMetallov,1987,11:5056[MetalScienceandHeat
Treatment.1987.V.29,I.1112:863869].

Diploma of the Ministry of Education and Science for her


significant contribution to the training of highly qualified
specialists(Russia,2011).

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