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Heat Treatment of Precipitation-Hardening Stainless Steels Alloyed With

Niobium

Article in Materials Performance and Characterization · February 2016

DOI: 10.1520/MPC20150039

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Materials Performance and
Characterization
F. E. Mariani,1 G. S. Takeya,1 L. C. Casteletti,1 A. L. Neto,2 and G. E.
Totten3

DOI: 10.1520/MPC20150039

Heat Treatment of
Precipitation-Hardening
Stainless Steels Alloyed
With Niobium
VOL. 5 / NO. 1 / 2016
 Materials Performance and Characterization

doi:10.1520/MPC20150039 / Vol. 5 / No. 1 / 2016 / available online at www.astm.org

F. E. Mariani,1 G. S. Takeya,1 L. C. Casteletti,1 A. L. Neto,2 and G. E. Totten3

Heat Treatment of
Precipitation-Hardening Stainless
Steels Alloyed With Niobium

Reference
Mariani, F. E., Takeya, G. S., Casteletti, L. C., Neto, A. L., and Totten, G. E., “Heat Treatment of
Precipitation-Hardening Stainless Steels Alloyed With Niobium,” Materials Performance
and Characterization, Vol. 5, No. 1, 2016, pp. 38–46, doi:10.1520/MPC20150039. ISSN
2165-3992

ABSTRACT
Manuscript received August 21, Precipitation-hardening stainless steels are iron-nickel-chromium alloys
2015; accepted for publication
containing precipitation hardening elements such as aluminum, titanium,
December 17, 2015; published
online February 26, 2016. niobium, and copper. In this work, heat treatment of a novel precipitation
1 hardening stainless steel using niobium as a forming element for the hardening
Universidade de São Paulo, Escola
de Engenharia de São Carlos, precipitates was carried out in order to increase its hardness. The steel
Departamento de Engenharia de composition was 0.03C - 0.22Si - 17.86Cr - 3.91Ni - 2.19Mo - 1.96Nb (in wt.%).
Materiais, 1100 Avenida João
Dagnone Ave, Santa Angelina, The samples were solution annealed at 1100 C for 2 h. Cooling was done in oil
13563-120 Sao Carlos, Sao Paulo, and the samples were subsequently aged at 500, 550, and 600 C. The
Brazil.
solution annealed samples exhibited an average hardness of 30 Hardness
2
Universidade Tecnológica Federal Rockwell–Scale C and after the aging treatments, the hardness increased to 46
do Paraná, Departamento de
HRC. The hardness increases during the aging treatments were very fast. A
Engenharia de Materiais,
3131 Avenida dos Pioneiros Ave, 5 min treatment achieved hardness levels that were close to the maximum
Jardim Morumbi, 86036-370 obtained for this alloy. Niobium was an efficient precipitation hardeners
Londrina, Parana, Brazil.
forming a Laves phase of the type Fe2Nb.
3
Department of Materials,
Portland State Univ., Portland,
Oregon, 97201. Keywords
stainless steel, precipitation-hardening, niobium, heat treatment, aging

Copyright V
C 2016 by ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-2959 38
 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM 39

Introduction
Substitutional cubic martensite in Fe-Ni steel exhibits a hardness in the range of 25 to
30 Hardness Rockwell–Scale C and good toughness in contrast to the high hardness
and low toughness exhibited by martensites in carbon steels (over 50 HRC). The hard-
ening of Fe-Ni steel martensite to a level that becomes interesting for applications in
engineering, with minimal loss in toughness, depends on the effects of various elements
in solid solution and on their precipitation [1–3]. Many substitutional alloying elements
can produce precipitation hardening in the martensite structure of the Fe-Ni steel with
variations in the aging kinetics or reversal reactions and strong interactions may also
occur between certain combinations of elements. The addition of alloying elements can
be classified roughly as follows: Be and Ti (strong hardeners); Al, Nb, Mn, Mo, Si, Ta,
V, and W (moderate hardeners) and Co, Cu, and Zn (weak hardeners) [2–4].
During the aging treatment, precipitation begins with a very short incubation
period by heterogeneous nucleation on dislocations. Therefore, the initial precipita-
tion rate is very high. Due to the high density of dislocations, a dispersion of very
fine precipitates is obtained. The aging of Fe-based substitutional martensites can be
divided into three stages: (I) the recovery of dislocations in the martensite structure;
(II) precipitation of intermetallic compounds with Guinier-Preston zone formation;
and (III) formation of austenite [4].
The first precipitation hardening stainless steel was martensitic and commer-
cially available in 1946 with the designation W (AISI 635) followed by 17-4 PH
(AISI 630) steel. These steels are easily workable by machining in the solution
annealed state and then hardened by aging. Their chemical compositions are bal-
anced such that at room temperature, after solubilization, they are in the martensitic
state and do not retain austenite in their structure. Among the main types of precipi-
tation hardening martensitic steels, there are the 17-4 PH, 15-5 PH, PH 13-8 Mo
steels, and Custom 455 [2–7]. The temperature range for solubilization varies in the
range 950 C–1100 C. The subsequent aging treatment may be performed between
425 and 600 C, depending on the desired hardness and toughness [2,3,8–11].
Precipitation in niobium hardening stainless steel occurs mainly by the forma-
tion of precipitated Nb (C, N) (carbo-nitrides), Fe2Nb (Laves phases), and Fe3Nb3C
(M6C carbide), with preferential nucleation occurring in the following sequence:
grain boundary, dislocations, and matrix [2,3,10–12]. The nucleation of intermetallic
particles precipitated at the dislocations would be expected, since niobium has a
larger atomic diameter than Fe (15 % higher). The segregation of Nb to the stress
fields of dislocations would decrease the elastic deformation energy of the crystal
lattice. The increase in solute concentration increases the probability of nucleation at
these locations more than in the remaining matrix. Dislocations can also aid nuclea-
tion by providing a shorter route for diffusion. The precipitate nucleation in disloca-
tions explains the acceleration of precipitation produced by localized strain
hardening as dislocation density increases [12].

Experimental Methods
Samples with dimensions 30 by 20 by 4 mm of a specially developed
precipitation hardening stainless steel, with the chemical composition (in wt.%)

Materials Performance and Characterization

40 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM

0.03C - 0.22Si - 17.86Cr- 3.91Ni - 2.14Mo - 1.96Nb - balance Fe, were cut from bars
forged at 1200 C, with cross sections 20 by 30 mm, obtained from an ingot with
dimensions 70 by 70 by 200 mm. To obtain the aging curves, the samples were sub-
jected to solubilization treatment for 30 min at 1100 C, followed by cooling in oil.
Aging temperatures of 500, 550, and 600 C were used with treatment times of 5, 10,
15, 20, 40, 60, 90, 120, and 240 min. The samples were characterized by Rockwell C
hardness testing, optical microscopy (OM), scanning electron microscopy (SEM),
chemical mapping, and energy dispersive spectroscopy for punctual X-rays (EDX).

Results and Discussion

presents optical micrographs obtained in the center of the bar of precipitation
Fig. 1
hardenable stainless steel in the as-forged and solution annealed conditions.
The presence of a continuous phase precipitate along the grain boundaries is
observed in the as-forged sample. In the solution annealed sample, that phase was
almost completely dissolved in the newly formed martensitic matrix.

FIG. 1
Precipitation hardening
niobium stainless steel (a)
as-forged condition and (b)
solution annealed for 30 min
at 1100 C followed by cooling
in oil.

Materials Performance and Characterization

 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM 41

FIG. 2
Precipitation hardening
niobium stainless steel aged at
(a) 500, (b) 550, and (c)
600 C.

Materials Performance and Characterization

42 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM

Fig. 2 presents the optical micrographs of the precipitation hardening niobium

stainless steel aged at 500, 550, and 600 C for 40, 15, and 5 min, respectively (maxi-
mum hardness).
Fig. 3 shows the scanning electron microscopy results of grain boundaries from
samples aged at 500, 550, and 600 C for 40, 15, and 5 min, respectively.
As seen in Figs. 2 and 3, the thermal treatment did not influence the
morphology and quantity of pre-existing precipitates in the grain boundaries.
Figs. 4 and 5 show the chemical mapping results of the sample in the
as-forged condition and after ageing at 500 C for 40 min (maximum hardness),
respectively.
These results show that the grain boundaries precipitates are likely a complex
type of intermetallic Laves phase produced during solidification, mainly containing
Mo and Nb, and Fe, Cr, Ni and Si, in lower contents, as indicated by Ikeda et al. [13]
and Yamamoto et al. [14].
These results show that the solubilizing treatment prior to the aging dissolved a
fraction of the precipitates present in the grain boundaries. The nickel was almost

FIG. 3 Grain boundaries of precipitation hardening Nb stainless steel. Aged at (a) 500, (b) 550, and (c) 600 C.

Materials Performance and Characterization

 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM 43

FIG. 4 Compositional mapping of precipitation hardening niobium stainless steel in the as-forged condition.

fully dissolved. Normally, it is not possible to detect variations in compositional

maps between samples in solution annealed and aged state since the precipitation
treatment involves atomic diffusion that occurs in a very short range (small precipi-
tates), and thus do not alter significantly the composition of the matrix.

Materials Performance and Characterization

44 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM

FIG. 5 Compositional mapping of precipitation hardening niobium stainless steel in the aged condition at 500 C for 40 min.

In previous work [15], the Nb precipitation hardening effect on Fe-Ni alloys

was validated, where the addition of 1 % of Nb resulted in hardness peak of about 30
HRC. Since the addition of 2 % of Nb resulted in hardness peaks in the range from
40 to 50 HRC, it indirectly confirmed again the effect of hardening due to the Nb.
Fig. 6 shows the aging curves for stainless steel aged at 500, 550, and 600 C.

Materials Performance and Characterization

 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM 45

FIG. 6
Stainless steel aging curves for
the three temperatures of
treatment used.

It is observed that the solution annealed sample exhibited an average hardness

of 30.3 HRC. The aging treatment at 500 and 550 C provided an increase in hard-
ness, achieving a maximum of 43.0 HRC and 41.8 HRC for 40 and 15 min of treat-
ment, respectively. After this period of aging for both treatment temperatures, the
hardness remained stable for up to 240 min, the longest aging time studied. The
aging conducted at 600 C showed a maximum peak hardness of 40.7 HRC for 5 min
of treatment.

Conclusions
The stainless steel alloy specially developed for this work, using Nb as a precipitates
forming element, based on previous work that we conducted with similar alloys,
showed a good response to aging treatment.
The precipitation hardening process occurred rather rapidly during the aging
treatment.
At the higher aging temperature (600 C), the peak hardness was reached in less
time, but with lower hardness levels than those obtained with the same steel aged
at lower temperatures (from 500 to 550 C), as it occurs with most precipitation
hardening alloys.

ACKNOWLEDGMENTS
The writers thank the Conselho Nacional de Desenvolvimento Cientı́fico e Tecnoló-
gico (CNPq), Brazil, for the financial support under the process no. 305789/2012-0.

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Materials Performance and Characterization

 46 MARIANI ET AL. ON HEAT TREATMENT WITH NIOBIUM

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Materials Performance and Characterization

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