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Article history: The microstructure and crystallographic features of a semi-austenitic precipitation hardening steel PH
Received 13 November 2015 15-7Mo during solution treatment, roddrawing and aging were investigated by means of optical mi-
Received in revised form croscope, X-ray diffraction analyzer and transmission electron microscope. It was found that the
16 February 2016
microstructure of the steel was consist of dominant austenite, small amount of martensite and 10e15
Accepted 19 February 2016
Available online 23 February 2016
vol.% d-ferrite after solution treatment at 1050 C followed by cooling in water at room temperature. The
austenite transformed into lath martensite during tensile roddrawing about 60% deforming companied
with some coherent ne b-NiAl particles precipitated within martensite. With higher aging temperature
Keywords:
Transition metal alloys and compounds
and longer holding time, tiny carbide M23C6 particles precipitated from martensite, which kept the cubic
Precipitation ecubic orientation relationship (OR) with austenite and G-T OR with martensite which is different with
Phase transitions all the reported orientations. The OR between tiny carbide M23C6 particles G-T OR with martensite was
Transmission electron microscopy, TEM discussed in terms of crystallography of phase transformations.
2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2016.02.172
0925-8388/ 2016 Elsevier B.V. All rights reserved.
H. Liu et al. / Journal of Alloys and Compounds 672 (2016) 386e392 387
strain-induced martensite steel containing Mn or Si is -martensite 5.9 mm with standard deviation 5.5 0.055 mm. The coiled spring
(hexagonal close-packed structure, lattice parameter a 0.254 nm steel was aged at 480 C for 1 h.
and c 0.393 nm) but not a-martensite (face-centered structure, To determine accurately the d-ferrite fraction, the cryothermal
lattice parameter a 0.2866 nm) [12]. Hedstrom reported in situ treatment of the sample was carried out at liquid nitrogen tem-
high-energy X-ray diffraction during tensile loading to investigate perature, so that the metastable austenite completely transformed
strain-induced martensitic transformation in cold-rolled sheets of a into martensite and the microstructure was only composited of
metastable stainless steel [13]. The transformation to a0 -martensite martensite and d-ferrite. Quantitative optical microscopy (OM) and
occurs in stepwise bursts at high strain rate. The stepwise trans- X-ray diffraction (XRD) are used to measure the volume fraction of
formation events were believed to correlate with stepwise inherited ferrite. It is known that area ratio in two-dimensional
increased lattice strains and peak broadening in the austenite image represented volume ratio [17]. On the base of the above
phase. The product martensite with tetragonal structure takes standard of microscopic analysis, ten microstructural images con-
typical three crystallographic equivalent variants. This is because taining inherited ferrite grains were measured in terms of area ratio
that the transformations under consideration are all symmetry of the inherited ferrite followed by statistic calculation. The volume
lowering. That is, the lattice cell of the austenite has higher sym- ratio was also veried by quantitative X-ray diffraction analysis
metry than that of the martensite. Consequently, there are multiple which implies that the intensity ratio between the highest intensity
congurations of the martensite lattice, and these are called vari- peaks from each of the two phases is close to the volume ratio of the
ants [14]. two phases. For determining the effect of austenizing temperature
The current authors have ever investigated the crystallography on the amount of d-ferrite, several solution treatment processes
of strain-induced martensite and reverse austenitic transformation with elevate austenizing temperatures from 1150 C was chosen.
of the semi-austenite stainless steel PH 15-7Mo (chemistry: Afterward the solution treated and water quenched samples were
15Cre7Nie2MoeAl) [15] with comparison of the result reported in cryogenically hold in liquid nitrogen, so that the microstructure of
literature [16]. This work will further investigate the microstruc- the refrigerated samples was composited of only martensite and d-
tural evolution of austenitic heat-resistant cast steel PH 15-7Mo ferrite, and it was easy to determine the ferrite fraction.
with focusing on mixed phase transformations and multiple The microstructures of the alloy via different treatments were
hardening effects. A detailed comparison between the micro- characterized by means of optical OM, XRD, and transmission
structure of as-aged sample and that of served sample was per- electron microscope (TEM). Specimens for the OM were polished
formed by means of XRD, SEM and TEM in terms of including on diamond sandpapers and etched using chemical reagent with
carbide precipitation, formation and disappearance of precipitation 75% HCl 25% HNO3 (volume percentage, vol. pct). OM specimens
free zone (PFZ) and crystallographic characters of transformation were observed on an Olympus PME3 optical microscope. XRD was
products. We elucidated that the signicant microstructural change performed on a Philips X'pert Pro X ray diffractometer using Cu Ka1
in stainless steel PH 15-7Mo was due to the combined effects of radiation (l 0.15406 nm) and scanning rate 0.2 /min. TEM thin
alloying elements of the steel and service condition. foils were prepared from the ground slices on a Tenupol-2 twin-jet
electropolishing device, using a solution of 6 vol. pct perchloric
acid, 35 vol. pct butanol and 59 vol. pct methanol at 30 C with a
2. Materials and methods
current of 0.12 A. TEM observations were carried out on a JEM-
100CXII transmission electron microscope operated at 120 KV
The chemical weight composition (wt.%) of the steels studied in
and equipped with a high angle double-tilt specimen holder.
the presented work is given in Table 1. The steel ingot was prepared
by vacuum induction melting under 0.001 Pa plus electroslag
remelting (chemical composition C 0.076, Si 0.46, Mn 0.42, Cr 15.04,
Ni 7.23, Mo 2.08, Al 1.46, P 0.01, S 0.003, Fe balance). The weight
percentage composition of the medium is C 0.076, Si 0.47, Mn 0.49,
Cr 14.56, Ni 7.31, Mo 2.14, Al1.28, Fe balance. The testing ingot was
homogenized at 1050 C for 12 h followed by holding at 1150 C for 3. Results and discussion
2 h. It was then drawn to form bar shape with a diameter of F
28 mm at 1000 C and nally cooled in air at room temperature. 3.1. Martensitic transformation start temperature Ms
The hard-drawn at room temperature plus aging treatment
procedure was carried out for preparing the spiral antenna spring. The solution treatment temperature highly affects on the
Specically, the steel rod was austenized at 1050 C for 0.5 h, then Martensitic transformation start temperature (Ms) and ferrite pro-
quenched into water at room temperature, followed by cold portion of semi-austenite precipitation hardening stainless steel
drawing with 60% deformation on a drawbench and spring coiling [18]. According to the composition and a series of experimental
on a spring mold. In order to reach 60% deformation, 5% pre- data of phase proportion-solution temperature relationship, the
deformation was applied before the cold drawing process. The solution treatment temperature was xed in a range of
number of passes during the drawing process is 3. The deformation 1050e1080 C. On the condition that the deformation amount of
amount was controlled by continuous monitoring steel wire the coiled spring steel is up to 60% in length, austenite almost fully
diameter at each pass. In detail, the diameters at the rst stage of transforms into martensite and the steel exhibits high strength and
drawing are 14, 13 and 11.35 mm, those for the second stage are toughness. The aging temperature of the steel is at 510 C for 1 h.
11.35, 9.90, 8.85 and 8.05 mm with standard deviation The Ms temperature of the steel can be calculated as reference
7.5 0.075 mm. At the last stage, the diameters are 8.05, 7.2, 6.5 abd [19]:
Table 1
Chemical composition of the investigated steel PH 15-Mo.
C Cr Ni Mo Al Si Mn P S
Fig. 1. Optical microscopic graphs of the steel PH 15-7Mo, (a)solution treated at 1050 C for 30 min and quenched into water; (b) solution treated and quenched into water, then
roddrawed 60% deformation at room temperature, followed by aged at 510 C for 1 h, cross-sectional view.
H. Liu et al. / Journal of Alloys and Compounds 672 (2016) 386e392 389
Fig. 3. TEM micrographs of PH 15-7Mo solution treated and roddrawned then aged at 480 C for 1 h. A. bright eld TEM image; B. dark eld TEM images of lath martensite variants
C. corresponding SADPs taken from (a), indexed in (D) as B [1 10]f/[001]M1/[1 11]M2; E. bright eld TEM image of d-ferrite. F. EDP of ferrite indexed as zone axis of [111].
conrmed by selected area diffraction pattern as shown in Fig. 3F. crystals [20] while the rest a NeW OR with its austenite matrix in a
The indexed results indicated this particle has BCC structure ac- single slab. The phenomenon of coexistence of mixed KeS and
cording to diffraction extinction rule (The sum of all the three in- NeW ORs between austenite and martensite [21] has been re-
dexes of (hkl) is even only for BCC structure) and lattice parameter ported previously. For instance, Wayman reported that the OR
a 0.288 nm. Ferrite formed on solidication is known as 'delta between martensite and austenite was frequently observed to
ferrite', while ferrite resulting from transformation of austenite change from KeS OR to NeW OR, with the G-T OR as a transition OR
during cooling is termed 'alpha ferrite'. The austenite in martensitic between the KeS and NeW ORs [22]. The Pitsch OR was not
stainless is transformed into martensite, or kept as residual observed. The above mentioned typical ORs and Bain OR [20] are
austenite. The d-ferrite grain primarily presents at the lath summarized in Table 2.
boundaries and is enclosed by the different lath martensite packets. The metastable austenite transformed into martensite after the
Based on the indexing result (shown in Fig. 3D) of the cold drawing processing. Meanwhile, the d-ferrite kept its original
composited EDPs, some martensite laths were conrmed to keep a volume fraction. The proper amount of ferrite is benet to defor-
typical KeS orientation relationship (OR) about 10 away from Bain mation because that the harmonized deformation of martensite,
OR of Bain strain lattice correspondence between FCC and BCC residual austenite and retained d-ferrite can impede the extending
390 H. Liu et al. / Journal of Alloys and Compounds 672 (2016) 386e392
Table 2
The observed KeS, G-T and NeW ORs in martensitic phase transformations.
No OR Expression Ref.
or growth of fracture and cleavage and so eliminate the volume martensite, both M1 and M2, keep a G-T OR with austenite, and thus
expansion dilution caused by the martensite transformation. It was all the three martensite variants keep a unique G-T OR with
found that the appropriate ferrite kept the high toughness and the austenite in a single packet [15,23]. Fig. 5 indicates that all the three
metastable austenite is benet to deformation ability (ductility). martensite lath variants kept a unique G-T OR with austenite. It
This procedure induced both the deforming hardening and trans- should be noted that i) M1 and M2 are not really {112} twin related,
formation hardening. Furthermore, aging treatment contributed ii) no genuine {112} twin plane is formed between them, and hence
more toughness and strength of spring. retained austenite akes are frequently embedded between them.
Thus this could be named as pseudo twinning relationship.
3.2.3. Precipitations in martensite matrix It is noticed that the crystallography of martensite to retained
Aging of the martensite steel causes recovery of martensite, austenite is the same as the crystallography of martensite to
precipitation hardening, and reversed austenite. Reversed austenite reversed austenite. It is known that retained austenite thin akes
(conrmed by XRD pattern shown in Fig. 2) also kept the G-T OR (not shown) are presented between any two adjacent laths. The
with martensite revealed by TEM. remarkable microstructure of this type steel PH 15-7Mo is relevant
The nanoscale ne particles precipitating within the martensite to its good comprehensive toughness.
lath were veried by extensive TEM observation. However they The martensite fraction could be controlled by deformation
were too small in size to show complete electron diffraction pattern amount in the strain-induced martensite transformation. The
as the diffraction intensity from nanoparticles is much weaker than retained austenite akes embedded between the martensite laths
that from martensite matrix. are benet to absorb the strain energy, passivate the crack, hinder
In order to determine the phase nature of the observed pre- the crack expansion and increase the toughness. Furthermore the
cipitates, high temperature aging (803 K for 3 h) was conducted to followed aging treatment strengthens the martensite. It is much
obtain the precipitate particles with larger size suitable for TEM appropriated for this type of process to produce steel spring ber as
analysis. The corresponding results are shown in Fig. 4. Fig. 4A and the both high mechanical properties and simple process can be
B shows the TEM BF and dark eld images of a martensite variant attained in a single process.
using diffraction vector g (002)M2. The dark eld TEM image of OR between b-NiAl and martensite. We also nd the b-NiAl
the reversed austenite was obtained with diffraction vector phase keeps the cubic-parallel OR with the martensite because they
g (202)f. The M23C6 carbide also formed at high aging tempera- present the similar crystal structure and there is very small mist
ture. However, the dark eld TEM image of carbide M23C6 was very under the cubic-to-cubic OR [9]. b-NiAl phase has an ordered BCC
weak by using diffraction vector g (202)M23C6. It is capable to structure (B2) with lattice spacing a 0.2887 nm. While the a0 -
acquire the dark eld image with better intensity by systematically matensite is BCC structure which lattice constant a 0.2866 nm [9].
tilting to ideal or near double-beam condition. The composited Erlach reported the same OR between precipitate b-NiAl and BCC
EDPs corresponding to panel A consist ve different phases, i.e., a0 -martensite [24] and that the strengthening effect was attributed
austenite, martensite lath variants 1 to 3, carbide and b-NiAl which to multiphase precipitation process of secondary hardening car-
could be indexed as B [1 10]M1/[1 10]M2/[11 3]M3/[1 10]NiAl/[1 bides and an intermetallic b-NiAl phase.
21]f/[1 21]M23C6 as shown in Panels G to J of Fig. 4 respectively. It OR between M23C6 carbide, austenite and martensite. The
was noticed that the martensite lath boundaries were still clear precipitate M23C6 carbide has some difference compared with
even aged at 803 K for 3 h. Meanwhile the reversed austenite could precipitate b-NiAl. M23C6 likely precipitates with tempered
be conrmed from dark eld image in Fig. 4C and corresponding martensite and keeps the typical G-T OR with the martensite and
EDP in Fig. 4G. However the b-NiAl particles were too small to cubic-to-cubic OR with the retained austenite. This is exactly the
highlight by dark led image using the EDP of b-NiAl in Fig. 4J, same as the G-T OR between reversed austenite and martensite.
though which was present the complete diffraction pattern. While a recent work revealed a phenomenon of multiple orienta-
tion relationships of M23C6 precipitate in BCC martensite in a
3.2.4. Orientation relationship between precipitates b-NiAl, M23C6, martensitic creep resistant steel (9 wt% Cr) [25]. The OR between
martensite and austenite M23C6 and martensite obeyed the Kurdjumov-Sachs (KeS),
OR between austenite and martensite. The orientation rela- Nishiyama-Wassermann (NeW), and Pitsch orientation relation-
tionship of martensite lath and austenite lm was schematically ships as well as two new orientation relationships with a-Fe matrix
illustrated in Fig. 5. Composited stereographic projections pre- (BCC martensite) at the same time in the same sample. The current
sented the ORs among M23C6 carbide, b-NiAl, three martensite OR reported in this work is different with the above reported ORs.
variants, and austenite. The pole centre is parallel to [111] austenite, It is well known that such multiple orientation relationship
[110] carbide, [110] martensite and [110] b-NiAl simultaneously. phenomenon is very common for FCC-Fe and BCC-Fe, i.e., g-
The pole A in the stereographic projection in Fig. 5 is equivalent to austenite and a0 -martensite [25]. This is very sensible as the
the composited EDPs shown in Fig. 3C, and the Pole B to EDPs in structural similarity between M23C6 and austenite. They are both
Fig. 4 (0 f0 stands for FCC-structured austenite, and 0 M00 , 0 M10 and FCC structure with the same space group Fm-3m while the lattice
0 M 0 denote the three martensite lath variants). The two variants of parameter is 1.065 nm for the former and 0.3654 nm for the latter.
2
H. Liu et al. / Journal of Alloys and Compounds 672 (2016) 386e392 391
Fig. 4. TEM micrographs of the steel aged at 530 C for 3 h: A. bright eld TEM image showing the martensite laths and ne carbide particles precipitated within in it; B. dark eld
TEM image of a martensite variant, g (002)M2; C. dark eld TEM image of the reversed austenite, g (202)f; D. dark eld TEM image of carbide M23C6, g (202)M23C6; E. composite
SADP corresponding to (a); F. EDP sketch corresponding (e), indexed as B [1 10]M2/[11 3]M3/[1 10]NiAl/[1 21]f/[1 21]M23C6; G to I, Index results for austenite, martensite 2,
martensite 3 & carbide and NiAl precipitate, respectively. J. Index result oe EDP for beta-NiAl phase. The zone axis is parallel to [110].
More interesting is that the lattice parameter of M23C6 is exactly martensite has been extensively studied [26,27]. However, such
three times of that of austenite. In terms of coincidence site lattice multiple orientation relationship phenomena in martensite and
(CSL), M23C6 is a super-lattice of austenite and can be regarded as semi-austenite stainless steel is valuable to draw more concern as
austenite when considering phase transformation. It is then there must be some competition between KeS, NeS, G-T and Pitsch
expectable to reach the same G-T OR between M23C6 and a0 - ORs. The morphology and crystallography of a transformation
martensite. The crystallography of M23C6 precipitate formed in BCC product might vary with different ORs. If the OR could be
392 H. Liu et al. / Journal of Alloys and Compounds 672 (2016) 386e392
Acknowledgments
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