Journal of Alloys and Compounds 619 (2015) 513519

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Effects of deep cryogenic treatment on the microstructure and

mechanical properties of commercial pure zirconium
Chao Yuan, Yunpeng Wang, Deli Sang, Yijun Li, Lei Jing, Ruidong Fu , Xiangyi Zhang
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, Hebei 066004, PR China
College of Materials Science and Engineering, Yanshan University, Qinhuangdao, Hebei 066004, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The effects of deep cryogenic treatment (DCT) on the microstructure and mechanical properties of com-
Received 25 April 2014 mercial pure zirconium were investigated. Experimental results indicated that DCT induced a change in
Received in revised form 3 August 2014 grain orientation and improved internal stress, which in turn increased dislocation density that led to
Accepted 26 August 2014
improved hardness. Hardness in basal planes was found to be signicantly larger than that in prism
Available online 16 September 2014
planes. Moreover, strength was enhanced in DCT-treated zirconium and the ductility was comparable
to that of as-annealed zirconium. This phenomenon was due to the increase in dislocation density and
Keywords:
the good ductility resulting from the motion of pre-existing dislocations and specic dislocation cong-
Metals and alloys
Deep cryogenic treatment
urations. DCT led to the transformation of tensile fracture mode from mixed-rupture characteristics of
Microstructure quasi-cleavage and dimples to quasi-cleavage, thereby increasing compatible deformation capabilities.
Mechanical properties The possible mechanisms underlying microstructural modication, tensile strength, and hardness
Zirconium improvement were discussed.
2014 Elsevier B.V. All rights reserved.

1. Introduction persed carbides, and removal of residual stresses [6,7,12]. Previous

Cryogenic treatment is a very old process that is widely used for
high-precision components. Shallow cryogenic treatment is set at
low temperatures (about 80 C), whereas deep cryogenic treat-
ment (DCT) is set at near-liquid-nitrogen temperatures (about
196 C). DCT improves certain properties beyond the enhance-
ment obtained by normal cold treatment [13]. DCT is different
from those methods of severe plastic deformation (SPD) processing
at cryogenic conditions, such as cryogenic rolling, pinning and
milling. Instead of nanostructured and ultrane-grains in SPD-pro-
cessed metals, the variation of crystal defect and phase transforma-
tion may play more important role in increasing of the properties
of DCT-treated metals. Over the past few decades, the effects of
various cryogenic treatments on the performance of steel have
received considerable interest. DCT reportedly increases the nor-
mal temperature strength and hardness of steels [4,5], provides
dimensional stability or microstructural stability [6], and improves
wear [79] and fatigue resistance [10,11]. The improvement in
mechanical properties can be ascribed to the complete transforma-
tion of retained austenite into martensite, precipitation of ne dis-
Corresponding author at: State Key Laboratory of Metastable Materials Science
and Technology, Yanshan University, Qinhuangdao, Hebei 066004, PR China. Tel.:
+86 335 858 7046; fax: +86 335 807 4545.
E-mail address: rdfu@ysu.edu.cn (R. Fu).
studies have shown that the hardness and abrasion resistance of
DCT-treated samples evidently improve because of transformation
of abundant retained austenite to martensite, secondary carbide
precipitation [13], and the precipitation of nanosized g-carbides
in primary martensite [14]. In addition, DCT combined with tem-
pering treatment enables the enhancement of fatigue properties
for the precipitation of ne carbides and the reduction in compres-
sive residual stress [15].
Compared with studies on ferrous metals, research on the effect
of DCT on nonferrous metals such as Mg, Al, and Ti alloys are lim-
ited. Asl et al. [2] found that after DCT, tiny laminar b phase parti-
cles almost dissolve, and the coarse divorced eutectic b phase
extends into the neighboring matrix. As a result, the mechanical
properties of AZ91 Mg alloy signicantly improve. Jiang et al.
[16] found that DCT induces the renement of grains to approxi-
mately 0.13.0 lm, thereby improving the strength and elongation
of 3102 Al alloy foil.
As aforementioned, evident changes in microstructure such as
phase transformation or grain renement have been veried for
DCT-treated alloys. However, changes in microstructure and
mechanical properties that can be introduced by DCT if no phase
transformation occurs are worth investigating. In this study,
coarse-grained zirconium (Zr) with a hexagonal close packed
(hcp) structure and higher microstructure stability at cryogenic

http://dx.doi.org/10.1016/j.jallcom.2014.08.201
0925-8388/ 2014 Elsevier B.V. All rights reserved.
514 C. Yuan et al. / Journal of Alloys and Compounds 619 (2015) 513519

temperature was chosen as a model metal because of the limited

deformation capability that results in easily saturated dislocation
density [17]. Some unusual changes in mechanical properties were
found in DCT-treated Zr, and the possible mechanisms in terms of
microstructural modication were discussed.

2. Experimental

The material used in this study was commercial pure Zr plate (chemical
composition summarized in Table 1). The plate was annealed in a vacuum at
1123 K for 4 h to obtain a homogeneous polycrystalline structure. The average grain
size of the as-annealed sample was approximately 3050 lm. The samples cut from
the as-annealed plate were placed in a liquid nitrogen environment at 77 K for 24 h.
Afterwards, the samples were taken out and cooled to room temperature.
X-ray diffraction (XRD) patterns of the as-annealed and DCT-treated samples
were measured using a Rigaku D/max 2500 X-ray diffractometer (18 kW) with Cu
Ka radiation (wavelength k = 1.54 ) in continuous-scanning mode over 2h = 30
80 at a step of 0.02. Differential scanning calorimetry (DSC) was conducted on a
Diamond DSC (PerkinElmer Inc., UK). For dynamic scans, samples were subjected
to temperatures ranging from 20 C to 160 C at a cooling rate of 20 C/min.
Microstructure features before and after DCT were observed by optical microscopy
(OM), electron backscatter diffraction (EBSD), and transmission electron micros-
copy (TEM). EBSD analysis was performed using a HITACHI S-4800 scanning elec-
tron microscopy (SEM) system, whereas TEM observations were carried out with
a JEOL-2010 TEM system at a voltage of 200 kV.
A FM-ARS9000 Vickers microhardness tester was used to measure the hardness
of samples. Indentations were carried out with a given load of 200 g and a dwell
time of 10 s. Hardness distributions over a square area of 4.5  4.5 mm2, with a
space between adjacent indentations of 0.5 mm were obtained. The tensile samples
were machined with a gauge length of 30 mm and a cross-section of 10  1.5 mm2.
Four repeated tensile tests were performed on a MTS test system at a strain rate of
1  104 s1 at room temperature under extensometer-measured strain control.
Fracture surfaces after the tensile test were observed by SEM, and microstructures
near the fracture surfaces were observed by TEM.

3. Results and discussion

3.1. XRD and DSC analyses

Fig. 1(a) shows the XRD patterns of as-annealed and DCT-
treated samples. No phase transformation was observed in DCT-
treated Zr compared with as-annealed Zr. However, the intensities
of the diffraction peaks of DCT-treated Zr were slightly enhanced,
which can be attributed to the variation in lattice constants caused
by DCT. Changes in lattice constants were also observed in DCT-
treated Mg [18,19]. To further conrm the microstructure stability
of Zr at cryogenic temperature, a cryogenic DSC curve was obtained
and is shown in Fig. 1(b). The smooth feature of the DSC curve indi-
cated that no transformation occurred during DCT.
3.2. EBSD analysis
To gain deep insight into microstructural changes, EBSD analy-
sis was performed. In this analysis, orientation imaging microscopy
(OIM) maps, inverse pole gure (IPF) maps, and boundary misori-
entation angle distributions were obtained before and after DCT,
as shown in Fig. 2. Fig. 2(a) and (b) shows the OIM maps of Zr
before and after DCT, with high-angle (HAGBs; grain boundary
misorientations P 15) and low-angle (LAGBs; grain boundary
misorientations < 15) grain boundaries depicted by black and
white lines, respectively. The crystallographic directions corre-
sponding to various colors can be inferred from the IPF triangle
shown at the bottom right corner of Fig. 2(a) and (b). The micro-
structure was characterized by equiaxed grains and a higher
Fig. 1. XRD patterns of as-annealed and DCT-treated samples (a), and the cryogenic
DSC curve of Zr (b).
fraction of HAGBs. No phase transformation and precipitation
occurred during DCT, consistent with the XRD and DSC results.
Fig. 2(c) and (d) shows the IPF maps of Zr before and after DCT,
respectively. The maximum intensity indicated the number of ran-
dom orientations. A strong preference was observed toward the
(0 0 0 1) orientation, which was corroborated by the OIM maps in
Fig. 2(a) and (b). Furthermore, the intensity of prism planes was
lower and the grain orientations were much closer to the (0 0 0 1)
basal plane orientation after DCT. This nding can be attributed
to the ordered arrangement of atoms resulting from the small
changes in lattice constants [18,19]. The misorientation angle dis-
tributions in Fig. 2(e) and (f) shows that the crystallite boundaries
were mainly high angle in nature. The HAGB fractions of Zr before
and after DCT were about 81.2% and 85.3% of the total grain bound-
ary length, respectively. Thus, DCT improved the formation of
HAGBs. The increase in HAGB fractions may be related to the
extrinsic dislocations formed during DCT (Fig. 3). The extrinsic dis-
locations were probably easier to react with the dislocations in
LAGBs [20,21]. Therefore, the accumulation and rearrangement of
dislocations resulted in the transformation of LAGBs to HAGBs,
leading to increased HAGB and decreased LAGB fractions.

3.3. TEM observations

Table 1
Chemical composition (in wt%) of the investigated pure Zr. The TEM images of the samples before and after DCT are pre-
Fe + Cr C N H O Hf Zr sented in Fig. 3. The dislocation density of the DCT-treated sample
was apparently higher than that of the as-annealed sample. When
0.2 0.05 0.01 0.005 0.16 4.5 Balance
the temperature dropped from room temperature to cryogenic
 C. Yuan et al. / Journal of Alloys and Compounds 619 (2015) 513519 515

Fig. 2. Representative OIM maps of (a) as-annealed and (b) DCT-treated samples. IPF maps of (c) as-annealed and (d) DCT-treated samples. Distribution of boundary
misorientation angle of (e) as-annealed and (f) DCT-treated samples.

temperature, the volume of the material contracted. This volume
contraction released great compression deformation energy that
served as the driving force for the formation and movement of dis-
locations [18]. The improvement in dislocation density played a
signicant role in enhancing mechanical properties and deforma-
tion behavior, as discussed in the following sections.
3.4. Hardness measurements
To better understand the variation in hardness of Zr, contour
maps of the spatial distribution of the Vickers hardness (Hv) over
a 4.5  4.5 mm2 square area before and after DCT are shown in
Fig. 4(a) and (b), respectively. The hardness of as-annealed Zr
substantially varied from approximately 140190 Hv, with an average
value of 159.5 Hv. By contrast, the hardness of DCT-treated Zr gen-
erally changed from approximately 160220 Hv, with an average
value of 197.5 Hv. Evidently, the average hardness signicantly
increased after DCT. The difference between the two average hard-
ness values reached 23.8%. Although the spatial distribution of
hardness was not uniform from one area to another, the increase
in hardness of the DCT-treated sample was a holistic rather than
localized phenomenon, as can also be conrmed by the hardness
evolution characterized by the color maps in Fig. 4. The inhomoge-
neity of hardness distribution may be closely related to the grain
orientation. An in situ comparison between the OIM map and
OM image of hardness indentation of DCT-treated Zr is presented
516 C. Yuan et al. / Journal of Alloys and Compounds 619 (2015) 513519
Fig. 3. TEM images of (a) as-annealed and (b) DCT-treated samples.
Fig. 4. Spatial distributions of the hardness values of Zr: (a) before and (b) after
DCT.
in Fig. 5. The letters in Fig. 5(a) correspond to those in Fig. 5(b), and
grain M indicates the reference grain. The hardness values of grains
AD in Fig. 5(b) were 211.65, 259.54, 199.35, and 233.57 Hv,
respectively. The hardness values varied with the orientation
between basal and prism planes. Planes close to the (0 0 0 1) basal
plane orientation were signicantly harder than planes close to
the prism 1 0 1  0 and 2 1 1
 0 planes. The hardness difference
among different grain orientations reached up to 30.2%. The depen-
dency of hardness values on orientation has also been observed in
previous reports [2224].
For hcp Zr, the axial ratio c/a was 1.593, which was less than
that of the ideal value (i.e., <1.633). Consequently, the lattice resis-
tance for prism planes was lower than that for basal or pyramidal
planes; thus, slip preferred to occur on prism planes [25]. In other
words, plastic deformation more easily occurred on prism planes
than on basal planes. Consequently, the hardness in basal planes
was much larger than that in prism planes. Therefore, the overall
improvement of hardness may be closely related to both changes
in grain orientation and dislocation density. After DCT, the grain
orientation tended to be more consistent, resulting in ordered
strengthening [18]. Meanwhile, the increase in dislocation density
increased the force to overcome the resistance of dislocation
motion. Thus, the improvement in plastic deformation resistance
resulted in increased hardness.
3.5. Tensile properties
The tensile engineering and true stressstrain curves of
as-annealed and DCT-treated Zr are presented in Fig. 6. For
as-annealed Zr, the yield strength (0.2% offset, r0.2) and ultimate
tensile strength (rUTS) were 288 and 393 MPa, respectively. The
elongation to fracture reached 28.7%. Correspondingly, r0.2 and
rUTS of DCT-treated Zr increased by about 60% and 40%, respec-
tively, compared with as-annealed Zr. Meanwhile, the elongation
to fracture reached 26.5%, which was similar to that of as-annealed
Zr. This nding indicated that DCT was a better route to improving
the strength and keeping a good ductility of Zr.
As depicted in Fig. 6(b), DCT-treated Zr also exhibited high
strain hardening capabilities relative to as-annealed Zr. The strain
hardening exponent (n) is dened by [26]
r K en 1
where r is the true stress, e is the true strain, and K is a constant.
The n values for as-annealed and DCT-treated Zr were 0.09 and
0.11, respectively. The enhancement in strain hardening capabilities
of DCT-treated Zr was further conrmed by an improved strain
hardening rate (H) dened by [26]
 
1 @r
H 2
r @e
Variations in H with e before and after DCT are displayed in
Fig. 7. The variation trends were consistent with continuous strain
hardening to signicant strains, but the strain hardening rate of the
DCT-treated sample was larger than that of the as-annealed
sample.
 C. Yuan et al. / Journal of Alloys and Compounds 619 (2015) 513519
M (a)
A
D
B C
Fig. 5. (a) OIM map and (b) corresponding OM image of hardness indentation of the DCT-treated Zr.
Fig. 6. Tensile (a) engineering and (b) true stressstrain curves of as-annealed and
DCT-treated samples.
DCT-treated Zr exhibited enhancement of strength and main-
tained the good ductility compared with as-annealed Zr. The vari-
ation in mechanical properties can be attributed to the difference
in dislocation density and dislocation congurations produced dur-
ing deformation [17,27,28]. To reveal the mechanism underlying
the increase in strength and maintain the good ductility in DCT-
treated Zr, TEM observations of the fractured tensile samples were
performed (Fig. 8). As shown in Fig. 8(a), for as-annealed Zr after
tensile deformation, the grains were apparently distorted and elon-
gated, and masses of dislocations were found in the grains. How-
ever, the deformation of DCT-treated Zr was more uniform and
517
(b)
B C
D
A M
Fig. 7. Normalized strain hardening rate (H) against the true strain of as-annealed
and DCT-treated samples.
compatible than that of as-annealed Zr. Many dislocations were
also observed within the grains, which were divided into smaller
blocks (Fig. 8(b)). During DCT, a large number of pre-existing dislo-
cations were introduced into the grains (Fig. 3(b)), and these grains
were movable during tensile deformation [2732]. At the initial
stage of deformation, more dislocations and dislocation tangles
formed. The increase in dislocation density and resistance of
dislocation motion resulted in improved strength. With increased
strain, many irregular dislocation tangles changed into parallel dis-
location lamellas along with the tensile direction. With further
increased strain, dislocation accumulation and rearrangement
occurred to form dislocation cells, dense dislocation walls, and
nanoscale subgrains and grains. As a result, the coarse grains were
divided into smaller blocks. These blocks made the plastic
deformation of DCT-treated Zr more uniform and compatible,
thereby resulting in the ductility being comparable to that of
as-annealed Zr.
3.6. Fracture behavior
The fracture surfaces of the as-annealed and DCT-treated Zr
sample are shown in Fig. 9. As shown in Fig. 9(a), the fracture sur-
face of edge regions of the as-annealed sample exhibited mixed
characteristics with dimples and a small amount of quasi-cleavage
facets, whereas the fracture surface in the middle region as shown
in Fig. 9(b) mainly contained many quasi-cleavage facets. The
dimples in the edge of fracture surface of as-annealed sample
were related to the noticeable necking caused by severe strain
518 C. Yuan et al. / Journal of Alloys and Compounds 619 (2015) 513519

Fig. 8. TEM images of (a) as-annealed and (b) DCT-treated samples after tensile tests.

(a) (b)

500 m 500 m

(c) (d)

500 m 500 m

Fig. 9. SEM images showing the fracture surfaces of as-annealed and DCT-treated Zr tensile samples. (a) and (b) are the edge and middle region of as-annealed Zr sample; (c)
and (d) are the edge and middle region of DCT-treated Zr sample.

localization during tensile test. For comparison, the fracture
surfaces of DCT-treated Zr in the same regions are presented in
Fig. 9(c) and (d), respectively. The fracture characteristics of two
regions were mainly consisted of quasi-cleavage facets. No obvious
necking was observed in the edge and middle regions of the
fracture surfaces.
The above ndings indicated that DCT restricted strain localiza-
tion occurring in the edge regions of tensile samples. For as-
annealed Zr, plastic instability (i.e., necking) occurred in the edge
region of tensile samples before ultimate fracture. Moreover,
Fig. 2(e) and (f) shows that the fraction of LAGBs before DCT was
slightly larger than that after DCT. LAGBs are reportedly associated
with the early onset of plastic instability during tensile testing
[3335]. The plastic instability accounted for the different fracture
characteristics in the edge and middle region exhibited by as-
annealed Zr. By contrast, the motion of pre-existing dislocations
and specic dislocation congurations effectively enhanced the
compatible deformation capability, resulting in the same fracture
characteristics in both regions of the DCT-treated sample.
4. Conclusion
Based on the above-described investigations, the following con-
clusions were drawn.
(1) The grain orientations were much closer to the (0 0 0 1) basal
plane orientation after DCT. DCT increased HAGB fractions
and dislocation density.
 C. Yuan et al. / Journal of Alloys and Compounds 619 (2015) 513519
(2) Hardness was closely related to grain orientations and dislo-
cation density. The hardness in basal planes was much
higher than that in prism planes. After DCT, dislocation den-
sity increased the resistance of dislocation motion, thereby
improving hardness.
(3) Strength levels were high and good ductility could still be
achieved after DCT. The enhancement in strength was due
to the increase in dislocation density, and the maintenance
of good ductility resulted from the motion of pre-existing
dislocations and specic dislocation congurations.
(4) The fracture surfaces exhibited mixed features with quasi-
cleavage facets and dimples for as-annealed Zr and quasi-
cleavage facets for DCT-treated Zr. The grains were divided
into smaller blocks because of the interaction of dislocations
during the tensile process of DCT-treated Zr. Consequently,
the compatible deformation capability of materials was
enhanced and good ductility could still be achieved.
Acknowledgment
Financial support from the National Basic Research Program of
China (Grant No. 2010CB731606) is greatly acknowledged.
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