706

ISSN 1392 -1207. MECHANIKA. 2013 Volume 19(6): 706-710

The structure and mechanical properties of the high chromium and

nickel content cast alloy after long duration work in high temperature
R. Skindaras*, A. V. Valiulis**, W. L. Spychalski***
*AB ORLENLietuva, Juodeikiai, 89467 Mazeikiai District, E-mail: r.skindaras@gmailcom.
**Department of Materials Science and Welding, VGTU, J. Basanaviciaus str. 28, 03224, Vilnius, Lithuania,
E-mail: algirdas. vaclovas@vgtu. It.
***Materials Engineers Group Ltd, Woloska 141, 00-732 Warsaw, Poland, E-mail: [email protected]
http://dx.doi.org/10.5755/j01 .mech. 19.6.5986

1. Introduction superalloys.
Of particular importance is 35Cr45NiNb Micro
The technological development of materials is es- (Steloy 1.4889 MA) alloy. The major applications for these
sential in the manufacturing of equipment operating in alloys are reformer and catalyst tubes. Various internation-
extreme conditions by incorporating more quality, enabling al companies are currently producing micro-alloyed HP45.
a longer service life, and lower production costs [1]. Heat These alloys must be regarded as one of the most signifi-
resistant alloys have widespread uses in the petrochemical cant alloy developments for the petrochemical industry.
industry in pyrolysis and reformer furnaces. These alloys Microscopic structure and operational conditions are pa-
have replaced the traditional nickel based superalloys and rameters which affect the fracture of the alloy [10]. The
have equivalent properties under conditions of creep, with failure mechanisms generaly encauntered are fatique, stress
excellent resistances to high temperature oxidation. In corrosion cracking and ductile fracture [11].
most cases, these complex alloys are used in their as-cast Most literature sources pointed out that the cause
condition but, during service, ageing and phase transfor- of alloy failure is exposure to an excessively high tempera-
mations occur. The typical microstructure of as-cast alloys ture [12, 13]. Exposure to an excessively high temperature
is an austenite matrix with intergranular eutectic-like pri- could have two detrimental effects. First, the creep rate can
mary chromium-rich carbides (M7C3 and/or M23C6 types) lead to the accelerated formation of grain boundary voids.
and niobium carbides (MC type). During service at tem- Furthermore, creep deformation can lead to cracking of the
peratures of 850-1050°C, all the primary chromium car- protective oxide scale causing an accelerated carburization
bides eventually transform into M23C6; intragranular sec- attack. Secondly, a bigher temperature accelerates the rate
ondary M23C(, carbides also precipitate [2, 3]. For the ex- of carburization attack. It is very likely that the effect of
treme applications of the petrochemical industry the range creep is compounded by the presence of a continuous net-
of advanced alloys, that reflects the evolution which has work of grain boundary carbides [14]. Thirdly, the changes
taken place in high-temperature materials, are produced. in mechanical properties are cormected with the evolution
The operation range of these alloys are 533 to 1150°C. of intermetallic phases and other intermetallic compounds
High heat transfer coefficient, mechanical strength at ele- arising in service [15]. The carburization behaviour of the
vated temperatures, creep resistance, microstructural stabil- tubes used under the conditions of petrochemical cracking
ity, carburization resistance, oxidation resistance, and eco- processes depends in a flrst line on the temperature. Up to
nomic considerations are various criteria that should be 1000°C carbon pickup is low, but above 1050°C heavy
considered for the appropriate selection of materials for carbon pickup and increasing carburization depth must be
equipment structures [4-6]. For alloys are produced for the counted with. This temperature dependence is due to the
petrochemical industry, two requirements are of paramount fact that at 1050°C equilibrium is attained between cbro-
importance: corrosion resistance and heat resistance. mium oxide and carbide, so tbat the oxide is no longer sta-
The demand for higher creep strengths at higher ble and the original protective effect of the oxide layer is
temperatures, with ever diminishing wall or section thick- lost. Carburization of a surface layer may set in at tempera-
ness, has been the major driving force behind these materi- tures as low as 800°C. Carburization is delayed by high Cr
al developments [7, 8]. and Ni contents.
It should be noted that creep resistant alloys also
contain a signiflcant quantity of carbon, required for solid 2. Material and analysis methods
solution strengthening as well as carbide formation. Of
further importance of carbon is the secondary carbide for- The research was carried out on high chromium
mation, where carbides precipitate during operation at high and nickel GX40NiCrNb45-35 steel with its chemical
temperatures. Precipitation takes place at operating tem- composition given in Table 1. Test pieces for research
perature, within the austenite grains, contributing to were taken out from a section of a fractured structure. Ex-
strength and creep resistance [9]. In general, they have an amination of chemical composition were carried out using
austenitic (y-phase) matrix and contain a wide variety of a wavelength dispersive x-ray fluorescence spectrometer
secondary phases. The most common second phases are Bruker S4 EXPLORER (WDXRF). Areas of examination
metal carbides (MC, M23C6, MéC, and M7C3) and y', the were cleaned with a sand (abrasive) paper grade 60. The
ordered face-centered cubic strengthening phase [NÍ3(A1, examination with light microscope Keyens VHX-100
Ti)] found in age-hardenable Fe-Ni-Cr and nickel-base (used with magniflcation from 500x to lOOOx) was carried
 707

out on cross section of the tube coil sheet. In order to ex- was carried out with a Hitachi S-2600N scanning electron
amine microstructure elements in more detail, especially microscope.
the morphology of precipitations, additional observation

Table 1
Chemical composifion of GX40NiCrNb45-35 steel, %
Ó
' mass
c Si Mn Cr Ni Nb Fe
0.35-0.45 1.76 1.25 34.20 44.33 1.858 16.56

Images were recorded with secondary electron The crack was start in the region of stress concen-
(SE) and backscattered electrons (BSE) detectors. Magni- tration - the comers of the element (Fig. 2). The fracture
fication from 500x to 2000x were applied. on the entire surface has brittle character.
For characterisation of material structures the High performance (HP) alloys are complex mate-
Scanning Electron Microscopy (SEM) with Energy Dis- rials, since they can contain different phases (austenite,
persive X-Ray Analysis (EDX) was applied (Fig. 1). M7C3, M23C6, MC), with high temperature phase transfor-
Hardness measurement of samples from the tube mations. In the present work have been studied work aged
coil sheet was carried out using Zwick ZHU 2.5. The sur- alloy. Different phases with various stoichiometries are
face before measurement was cleaned with a sand (abra- present in these alloys: chromium rich-phases (M23C6 and
sive) paper grade 320. M7C3) and niobium carbides (MC). Microstructure of two
The impact toughness examinations were carried different regions specimen is shown in Fig. 3.
out at room temperature, 300°C, 600°C and 900°C.
Visual inspection of fractures of samples afrer
impact resistance testing was carried out using Hitachi \f-
2600N scanning electron microscope (SEM). Images were
recorded with secondary electron (SE) detector. Magnifica-
tion from 250x to 4000x were applied. The examinations
were aimed at determination of fracture character and
morphology.
In order to determine resistance properties of the
examined material, measurements of uniaxial tension test
were carried out with the use of Zwick Z250 static re-
sistance machine. The samples were subjected to tension
with initial velocity 5x10""*, s"' at room temperature and
900°C operating temperature.

1000- Cr
f 80«-
Î "'',1
*¡ ^ cnA Cr Ni
Ni
J|400-
5.20O- il ^ MAA
II Fe \

0-
4 5
keV

Fig. 1 EDX analysis of the structure (from Fig. 7, point 1)

2. Test results and discussion

Fracturing of tube coil sheet. During the visual

testing the origins of crack of tube coil sheet were speci-
fied.

Fig. 3 Structure of the tube coil sheet materials after etch-

ing: a - light microscope microstructure observation,
magnification 200x; b - SEM microscope image of
material microstructure, magnification lOOOx

As it can be seen in Fig. 3, primary precipitates

are well-visible in the fully austenitic matrix and dendritic
boundaries. Different environmental conditions, particular-
ly the effect of temperature and carbon diffusion, influence
the microstructural and property changes in the service-
exposed specimens. Working at high temperatures may
Fig. 2 Tube coil sheet fractures result in re-dissolution of primary carbides and re-
arrangement of secondary carbides in supersaturated ma-
 708
room temperature
trix[6, 15, 16].
Cracks are going between dendrites along car-
bides (Fig. 4). The visual examination shown that the
cracks were start in the regions of stress concentration -
the comers of the element. The facture on the entire sur-
face has brittle character.

Fig. 5 Morphology of fractures surface of samples after

impact resistance testing at room and at 900°C tem-
perature: a - magniflcation 500x; b - magnification
2000X

Microstructure on Scanning Electron Microscopy.

The microstructure of tube coil sheet materials obtained by
Fig. 4 The character of crack of tube coil sheet (after scanning electron microscope are shown on Fig. 6. The
etching, magniflcation lOOx) results of microstructure observation are shown typical
microstructure in this type of the Fe-Cr-Ni-Nb alloy cast
The microstructure of this alloys is composed of
steel. There was no evidence of advance materials micro-
primary austenite dendrites with various eutectic cons
structure degradation process as a result of the exploitation
composed of primary austenite dendrites with various eu-
in the high temperature. The complex precipitations were
tectic constituents in interdendritic regions - Y/M23C6 and
not found.
y/NbC. Cracks are going between dendrites along the
chromium carbides. The complex precipitations, consist of
different carbides, were not found. The results shown also
that transient temperature appear in high temperature at
about 900°C. In this coincidence material will have ten-
dency to cracks in low temperature.
Impact resistance testing. Test was performed to
establish Facture Appearance Transient Temperature of
steel. There is no data for GX40NiCrNb45-35 (1.4889)
steel about impact resistance at EN 10295 standards and
literature of the subject. Comparison with other Fe-Cr-Ni
cast steel alloy shown that impact resistance much lower
than the other [17]. The microscope examinations of im-
pact test morphology (Fig. 5) and impact strength test (Ta-
ble 2) lead to the conclusion that the fracture were exam-
ined, in room and elevated temperature, material has brittle
character. Fig. 6 SEM microscope image of material microstructure
(secondary electron detectors, magniflcation lOOOx)
Table 2
Impact strength in different temperatures Micro-chemical analysis. During examinations
phases rich in chromium (Fig. 1) and niobium (Fig. 7, b)
Sample Temperature, Impact Impact strength, were found. The chemical composition of these phases
°C work, J J/cm" [16] are following: chromium carbides - M7C3.07 and
1-3 RT 4 M23C6.41, niobium carbides - M0.55C0.45-
4 300 3 4 Tensile test. The samples were subjected to ten-
5-6 600 3 4 sion with initial velocity 5x10"'*, s'' at room temperature
7-9 900 11-18 14-23 and 900°C operating temperature.The results of the tests
Room temperature - 17°C are shown in Table 2. It can be noted, from the stress-strain
curves obtained at room temperature shown in Fig. 8 that
However, it has to be emphasized that some areas of the total elongation measured for samples exceeds 0.7%.
plastic fracture were observed in sample tested in 900°C. According to EN 10292 standard material
These observations can explain the lowered impact re- GX40NiCrNb45-35 should have minimum total elongation
sistance of the materials tested in room temperature. 3% [17].
 709
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 710

n.Superaustenitic alloys. [Retrieved November 03 2011] R. Skindaras, A. V. Valiulis, W. L. Spyehalski

Available from: <http://www.fondinox.com/
superausteniticalloys.htm>. THE STRUCTURE AND MECHANICAL PROPERTIES
OF THE HIGH CHROMIUM AND NICKEL ALLOY
AFTER HIGH TEMPERATURE AGEING
R. Skindaras, A. V. Valiulis, W. L. Spychalski
Summary
SENDINTO AUKSTOJE TEMPERATÜROJE
CHROMO IR NIKELIO LYDINIO S T R U K T O R A IR In the petrochemical industries cast steel tube coil
MECHANINÈS SAVYBÉS sheets with high chromium and nickel content are used.
The operation range of these alloys are 533 to 1150°C. A
R e zi u m è paramount for these alloys are: - corrosion and scaling re-
sistance at high temperatures; - dimensional stability, i.e.
Naftos chemijos pramonèje vamzdyn^ rinkliij pa- resistance to warping, cracking and thermal fatigue; - re-
laikymui naudojami lieti lakstiniai elementai, pagaminti is sistance to plastic flow, i.e. creep strength. Tube coil sheet
daug chromo ir nikelio turinciij lydinii}. Lydiniij darbo of fumace resulting in aggregate failures have been con-
temperatura yra 533-1150°C. Lydiniai turi bOti atsparüs sidered. Life span of the studied specimens obtained from
korozijai ir oksidacijai aukstoje temperatûroje, pasizymèti tube coil sheet was 3 years. After a few years of exploita-
matmeni} stabilumu (t.y., atsparumu matmenij ir geometri- tion several hollow cracks on the heater tube-sheet were
jos iskraipymams) ir atsparumu auksta temperatOriniam identiñed. Pre-oxidation of the tubes surface are possible
valksnumui. Darbe pateikti si^ lydinii} konstrukciniij ele- and it has not only favourable effects: during cooling
mentii jrimo tyrimai. Tirtij elementij medziaga dirbo tik 3 cracks may form in the oxide layer. The aim of the per-
metus, taciau juose buvo pastebeti dideli konstrukcinii} formed research was to characterize the microstructure and
elementi} supleisèjimai. Darbo metu vyksta intensyvi mechanical properties of the investigated alloy after ageing
konstrukcinii} elementij pavirsiaus oksidacija. Siij elementij at the temperature of 900°C. The high temperature deter-
ausimo iki aplinkos temperatûros metu, oksidij sluoksnyje mine elements diffusion in the structure, emergence of
gali susidaryti mikrojtrükiai. Pristatomoje tyrimij medzia- chromium and niobium carbides and other precipitates and
goje nustatyti ir jvertinti lydinio, sendinto 900°C tempera- cause the changes in the mechanical properties.
tûroje, mikrostruktûros ir mechaniniij savybii} pokyciai,
chromo, niobio ir kompleksiniij karbidij susidarymas ir ji} Keywords: high chromium-nickel alloys, mechanical
poveikis lydinio eksploataeinèms savybèms. properties, fractures, precipitation phases, carbides.

Reeeived December 06, 2011

Accepted October 10, 2013
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