EG-M93 Masoud JahanbakhshJavid 2233898

1200 Word essay

Introduction
Crystal structure of Zirconium in temperature room is HCP which changes as the temperature increases by
1136°K to BCC in zero pressure [1]. The melting point of Zirconium is at 2128°K [1]. As we are considering
a Ni based superalloy (IN713c), it is required to investigate the solubility of Zr in Ni, so we should
implement the Hume-Rothery rules; Zr and Ni have different crystal structures which is FCC for Nickel
and HCP and BCC for Zirconium, the atomic radius of Zr is 0.159 nm which is 28% higher than Ni with
an atomic radius of 0.124 nm which represent the tendency of Zr to place in grain boundries, the valency
of Zr is +4 and for Ni is +2, and electronegativity of Ni is 1.8 which is 1.2 for Zr. By considering these data,
we cannot expect a high solubility of Zr in Ni as some of Hume-Rothery rules do not meet our criteria. The
density of Ni is 8.9 g/cm3 and for Zr is 6.51 g/cm3[]. The price of Zirconium is about $29 per kilogram
which is comparable with the Nickel price of $23.8 per kilogram. Zirconium role in superalloys is used for
strengthening of grain boundaries…., which IN713C consist of 0.06 Zr in compare with IN738C and IN792
with 0.1, and Rene80, IN100, and Mar M246 with 0.03, 0.04, and 0.05 of Zr respectively []. The solubility
of Zr in Ni reported in some works which is 1.047 wt-% in 1200°C, and 0.591 wt-% 900°C [4*]. This essay
will evaluate the role and recommend some changes in range of Zr to increase mechanical properties of
IN713C (creep, fatigue, stress rupture properties) to reach the same level as Mar M246 with the minimum
changes in cost and density.

Role of Zirconium and interaction with other elements in superalloys

Minor proportion of Zirconium used in superalloys which is between 0.01 to 0.1 []. As Zr can have multiple
roles and influences in superalloys, we will discuss each in separate paragraphs.
It is observed that the Boron and Zirconium with certain proportion (0.0059 wt-% B, 0.042 wt-% Zr), will
have positive effect on mechanical properties of IN718, they help to increase segregation of Mo and Nb
which both have great positive influence on mechanical properties, and they reduce segregation of Ti which
has highly effect on corrosion resistance [3*]. As the B and Zr increase the grain boundaries cohesion, by
adding more B and Zr to IN718, the GB strengthen and better YS and UTS achieved. The influence of Zr
and some other elements on two alloys produced in vacuum condition investigated in a paper which
revealed that by increasing the volume of Zr from 0.005 to 0.076 wt-%, Titanium from 0.69 to 3.42 wt-%,
and C from 0.08 to 0.15 wt-%, higher mechanical properties can be observed [5*]. This may happen as a
result of carbide formation which was four times higher than previous version and happened by the effect
of Ti and C, and as an effect of Zr and B, the amount of porosity is significantly reduced which led to twice
harder alloy.
High temperature oxidation resistance of Ni base superalloys must be considered, as the working
temperature of their products is high. Several factors have an influence on oxidation resistance, one of the
main factors is Alumina (Al2O3). Elements like Y, Hf, Zr, Ce, La with proportion of 0.01-0.1 wt-% can
increase alumina scale adhesion [7*]. As the alumina layer can create a barrier between oxygen and
underlying alloying elements, it can increase the oxidation and corrosion resistance. In new generation
superalloys the amount of Al kept between 3-6.6 wt-%, as the heat treatment window will be lost beyond
this proportion [7*]. Oxygen reactive elements (Y, Hf, La, Sc, Ce, and Zr) may change the alumina growth
mechanism and stabilize it, and segregate at interface which lead to better oxidation resistance [6*].

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EG-M93 Masoud JahanbakhshJavid 2233898

The effect of Zr in increasing the adhesion of Al2O3 or Cr2O3 were investigated in some papers, but Zr can
be replaced by Yttrium in case of density reduction as the Zr density is 6.52 g/cm3 and Y density is 4.47
g/cm3, which can be a good explanation of why in the state-of-the-art Ni-base superalloys, Zr element is
eliminated from composition or has minor amount (≈0.01 wt-%). In some textbooks it is observed that the
most effective element for hot corrosion resistance in Ni-base superalloys is Cr, which can be dissolved in
several valence states as proactive Chromia, and this may lead to positive interaction with other elements
in case of corrosion resistance, but the effect cannot be seen in Al2O3 [6*].
Alloying elements in superalloys tend to make groups such as GCP (intermetallic phases) and TCP groups
[8*]. The formation of topologically closed-packed can be caused by precipitation of many elements such
as W, Re, Cr, Co, and Mo which some of them participate in intermetallic phases, 𝛾/𝛾’, but higher amount
of them can increase TCP phases [9*]. Deterioration of mechanical properties of Ni-base superalloys caused
by TCP phases is mostly reported as they are brittle and suitable for crack initiation, but in some cases, it is
seen that small amount of σ phase can raise creep-rupture strength [8*]. As the poor mechanical properties
caused by TCP phases were mostly attributed to Cr, its proportion in superalloys new generations decreased
to 2-3 wt-% [7*], but in some papers the range of 4-4.2 wt-% suggested for Cr [10*]. On the other hand, Cr
has significant effect on environmental resistance and superalloys needs sufficient amount of it, in some
applications like discs as they are not commonly coated, environmental effect would be observed [11*].
The effect of Zr in TCP phases is not reported in papers, as it may have no specific effect.
Finally, as mentioned Zirconium tend to place in grain boundaries, but Arthur Després et al found that the
heat treatment will help Zr to move from GB and reduce alumina to be replaced by zirconia, and
considerable amount of Zr will precipitates in 𝛾’ which remove Zr from grain boundaries [1*]. IN713C is
generally used in as-cast condition, and heat treatment can improve 1000h rupture life [2*]. Therefore, with
conducting heat treatment two purposes will be reached.
Conclusion

References

[1] Schnell I & Albers RC (January 2006). "Zirconium under pressure: phase transitions and
thermodynamics". Journal of Physics: Condensed Matter. 18 (5): 16. Bibcode:2006JPCM...18.1483S.
doi:10.1088/0953-8984/18/5/001. S2CID 56557217.

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EG-M93 Masoud JahanbakhshJavid 2233898

[1*] Revealing the true partitioning character of zirconium in additively manufactured polycrystalline
superalloys
[2*] alloys-713c_337
[3*] Effects of boron and zirconium additions on the fluidity, microstructure and mechanical properties of
IN718C superalloy
[4*] Analysis of γ′ Precipitates, Carbides and Nano-Borides in Heat-Treated Ni-Based Superalloy Using
SEM, STEM-EDX, and HRSTEM
[5*] Role of Titanium, Carbon, Boron, and Zirconium in Carbide and Porosity Formation during
Equiaxed Solidification of Nickel-Based Superalloys
[6*] Bose, Sudhangshu. (2007). High Temperature Coatings - 5.3.4 Tungsten and Molybdenum. Elsevier.
Retrieved from https://app.knovel.com/hotlink/pdf/id:kt009FROS6/high-temperature-coatings/tungsten-
molybdenum
[7*] R. Darolia (2018): Development of strong, oxidation and corrosion resistant nickel-based
superalloys: critical review of challenges, progress and prospects, International Materials Reviews, DOI:
10.1080/09506608.2018.1516713
[8*] GCP and TCP phases presented in nickel-base superalloys
[9*] M., J., Donachie, S., J., Donachie, Superalloys – A technical guide, 2nd ed. ASM International, USA,
2002
[10*] Kawagishi, Kyoko & Yeh, An-Chou & Yokokawa, Tadaharu & Kobayashi, Toshiharu & Koizumi,
Yutaka & Harada, Hiroshi. (2012). Development of an Oxidation-Resistant High-Strength Sixth-
Generation Single-Crystal Superalloy TMS-238. 10.1002/9781118516430.ch21.
[11*] A. S. Wilson (2017) Formation and effect of topologically close-packed phases in nickel-base
superalloys, Materials Science and Technology, 33:9, 1108-1118, DOI: 10.1080/02670836.2016.1187335