Accepted Manuscript

Microstructure evolution and strengthening mechanisms of pure titanium with nanostructured surface obtained by high energy shot peening
Shijuan Dai, Yuntian Zhu, Zhaowen Huang
PII:

S0042-207X(16)30001-X

DOI:

10.1016/j.vacuum.2016.01.001

Reference:

VAC 6899

To appear in:

Vacuum

Received Date: 27 November 2015

Revised Date:

31 December 2015

Accepted Date: 3 January 2016

Please cite this article as: Dai S, Zhu Y, Huang Z, Microstructure evolution and strengthening
mechanisms of pure titanium with nano-structured surface obtained by high energy shot peening,
Vaccum (2016), doi: 10.1016/j.vacuum.2016.01.001.
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Microstructure evolution and strengthening mechanisms of pure

titanium with nano-structured surface obtained by high energy shot
peening

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Shijuan Dai a, *, Yuntian Zhub, Zhaowen Huang a

Nano Structural Materials Center, Nanjing University of Science and Technology,

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Nanjing 210094, China

College of Engineering, North Carolina State University,

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North Carolina State 27616, USA

Abstract: In this study, the microstructure evolution and strengthening mechanisms

of pure titanium processed by high energy shot peening (HESP) have been studied.
The results show that the deformation layer is formed on the surface and the
microstructure exhibits with the equiaxed 20~40m grains in the matrix after HESP. A

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nanocrystal surface layer is produced by means of HESP on pure titanium. The

formation of nano-grains on the surface can be separated into four steps: (1) the
formation of the dislocations tangles; (2) the occurrence of the intersection of twins;

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(3) appearance of slip band and subgrains; (4) formation of uniformly distributed
nanometer-scale grains. With increasing the holding time, the strength increases and

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the elongation decreases due to the work hardening effect and the formation of the
nanocrystals on the surface.
Key words: Pure titanium; Gradient nanocrystallization; High energy shot peening;
Microstructure; Tensile properties
1.1Introduction

Titanium and its alloys have become excellent metal biomaterials due to their

*Corresponding author. Tel.: +008613814088460.

E-mail address: daishijuan_1982@163.com (Shijuan Dai).
Address: Nano Structural Materials Center, Nanjing University of Science and Technology, 200 Xiao Ling Wei, Nanjing 210094, China.

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lower modulus, superior biocompatibility and enhanced corrosion resistance
compared with stainless steels and cobalt-based alloys [1, 2]. So far, the most widely
used alloy is pure titanium and Ti-6Al-4V alloy for clinical application, but the latter
contains V and Al elements, which exhibit high cytotoxicity [3]. Pure titanium

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without toxic elements is considered as the one of the best implanted materials [4-5].
However, the strength of pure titanium is lower than that of Ti-6Al-4V, leading the
narrower application scope.

The surface nanocrystallization (SNC) is an effective and economical route to

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improve the mechanical properties of metal materials. A variety of severe plastic

deformation processes have been proposed to produce SNC. Shot peening treatment,

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which can produce nano-grains in the surface layer of the metals, is an effective
surface strengthening technology. During the process, the surface of the workpiece is
continuously impacted by a number of shot, which causes the severe plastic
deformation. Unal et al. [6] studied the microstructure and hardness of AISI 304
austenitic stainless steel performed by different types of shot peening, including air

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blast conventional shot peening, severe shot peening and repeening. The results
showed that the deformation layer had nano-grain size distributions with much higher
hardness. Bagherifard et al. [7] studied the microstructure and roughness of cast iron

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specimens treated by severe shot peening and the results indicated the presence of a
highly deformed near surface layer and the surface roughness increases with
increasing the impact energy of shot peening process. The above literatures

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have focused on the microstructure evolution of metal materials after shot peening,
but few investigations about the influences of the microstructure evolution on
mechanical properties after shot peening have been founded.
In this study, a nano-structured grade surface layer was prepared on the surface of

pure titanium by means of HESP technique in order to enhance the strength. The
mechanism of grain refinement was discussed and the effect of the formation of the
nano-grains on the mechanical properties was also studied.
2. Experimental
The material used in this study was a 4mm-thickness plate made of pure titanium
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with the chemical composition in weight percent: 0.10Fe, 0.14O, 0.25Al and balance
Ti. The plate was annealed in argon atmosphere at 1023K for 2h and then air-cooled,
resulting in equiaxed grains averaging 30m in size. The shot velocity was 40m/s and
the stainless steel balls with the 3mm diameter were used as the shots g. Both sides of

holding time was 15, 30, 45 and 60min respectively.

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the annealed samples were high energy shot peened at room temperature and the

The cross-section of each sample was mechanically polished using silicon

carbide paper and a polishing cloth, and finally etched at room temperature in a

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solution of 1 ml HF, 3 ml HNO3 and 7 ml distilled water. Then, the microstructure

close to the treated surface was examined by optical microscope (OM). The phase

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structure of the surface layer was performed using an X-ray diffractometer (XRD, D8
Discover) with Cu K radiation and graphite monochromator operated at 40KV and
40mA. The micro-strains and average grain sizes of all the samples were calculated
according to the XRD pattern using Jade5.0 software. Transmission electron
microscopy (TEM) investigations were carried out on FEI Tecnai 20 microscopes

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operating at 200 KV. The preparation of the TEM foils of the cross-sections was
separated into four steps: (1) polishing the cross-section of the sample mechanically
until it was about 50m thick (Fig. 1(a)); (2) cutting along the dotted line (Fig. 1(b));

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(4) sticking on a copper ring with the butt joint of the two treated surface (Fig. 1(c)
and (d)); (4) electro-polishing the foils using a twin-jet technique in a solution of 6ml
HClO4, 60ml CH3OH and 36ml C4H9OH at a voltage of 30V and a temperature of

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243K. The mechanical properties of the alloys were obtained by an electronic

universal test machine (CMT 5105). The size of the sample was shown in Fig.2 and
the tensile specimens were prepared by using electro-discharging.
3. Results and discussions
3.1 Microstructures
The cross-sectional microstructures of the treated specimens under different
conditions are presented together in Fig. 3. It is seen that the grain boundaries have
not been indentified and it is called the severe deformation layer which is marked in
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dotted line. Also, it is observed that the interior is not affected by the deformation and
the microstructure exhibits with the equiaxed 20~40m grains. From Fig. 3, it is
known that the thickness of the severe deformation layer increases obviously with the
increase of the holding time. When the holding time increases, the accumulation of

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severe deformation causes by the repeated impact of the shots enhanced, leading to
the increase of the thickness of the severe deformation layer [8].
3.2 XRD investigations

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Fig. 4 shows XRD patterns of the samples treated for different holding time.
No new peaks appear after HESP, which shows that there is no obvious phase

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transition after severe plastic deformation. Compared with the specimen before
HESP, the diffraction peaks broaden after HESP and the widening of diffraction line
profile intensifies with the increase of the holding time, which infers the occurrence of
grain refinement and the increasing micro-strain.

The grain size and micro-strain of the samples are calculated from line

10].

cos

tan

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Size=

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broadening of Bragg diffraction peaks by using equation (1) and (2) respectively [9

(1)

(2)

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Where Size means grain size; K means constant, usually K=1; means X ray
wavelength; means the full width at half maximum of the peak; is the Bragg angle
of the [h k l] reflection; means micro-strain. Fig. 5 shows the average grain size and
the micro-strain before and after HESP and it can be seen that the average grain size
of the sample decreases and the micro-strain strengthens with the increase of the
holding time. Average grain size reduction below 100nm can be evaluated after
treating for 60min and the mechanism of the grain refinement will be studied in next
part. After HESP, a lot of defects are introduced into the surface, which causes the
enhancement of the lattice distortion and increased micro-strain.
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3.3 TEM investigations
Fig. 6 shows the TEM images of the sample treated for 15min. The typical
microstructure feature is dislocation tangles, as shown in Fig. 6(a). The irregular
dislocation cells with different sizes (100~500 nm) appear and they are tangled with

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each other in a complex way. As shown in Fig. 6(b), the corresponding selected area
electron diffraction (SAED) shows no disorientations inside the tangles. Meanwhile,
the mechanical twins are not observed, which shows that only the formation of the
dislocations occurs at the beginning of the deformation process.

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When the holding time increases to 30min, a larger number of parallel twins can
be observed (Fig. 7(a)) and the SAED patterns are given in Fig. 7(b). It is concluded

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that they are the twins with respect to (0 5 -5 12) plane by analyzing Fig. 7(c). It was
reported that the twins on {1 0 -1 2}, {1 1 -2 1}, and {1 1 -2 2} planes had formed
during deformation at room temperatures for -Ti [11-14]. For example, Zhu et al [15]
founded that the twins with respect to (1 0 -1 2) plane appeared after surface
mechanical attrition treatment. However, the mechanical twins with respect to (0 5 -5

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12) plane have not founded in other literatures and the detailed mechanisms have not
been clear until now. Also, the intersection of strip twins is observed beside the
parallel twins (Fig. 7(e)). One twin might end at the other one (such as T1 and T3) or

process.

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go across the other one (such as T3 and T4), as a result of a shear accommodation
Maybe it is because a large number of dislocations generates at the

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beginning of the deformation and then the dislocation density increases dramatically.
When the dislocation density increases to a certain extent, the deformation process is
difficult to continue. At this time, the formation of the mechanical twins, which can
often change the hard orientation into soft orientation, are believed to accommodate
the increasing strain during deformation so that the subsequent sliding deformation
occurs more easily [16-18].
Fig. 8 shows TEM images of the sample treated for 45min. Thereby causing
greater strain, a larger number of parallel slip bands can be observed (Fig. 8(a)). Their
boundaries are not as straight as those of the twins (the site of white arrows in Fig.
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8(a)) and a lot of dislocation pile-ups are present in the bands. Meanwhile, it can be
seen that the typical microstructure in the slip band are subgrains with the size of
about 200nm (the site of white arrows in Fig. 8(b)). It is proved that high angle
misorientations among the subgrains appear and the misorientation between the

angle gain boundary at this step (seen Fig. 8(c)).

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subgrains and surrounding is about 22, suggesting the transition from low to high

When the holding time increases to 60min, the microstructure is characterized by

uniformly distributed nanometer-scale grains (seen Fig. 9(a)) and the corresponding

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SAED patterns (Fig. 9(b)) exhibits the formation of finer grains with a more random
orientation on the top treated surface. With the increase of the strain, the defect

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density and the stored energy increase, leading to the lower recrystallization
temperature and dynamic recrystallization. Then the nano-grains with randomly
orientation on the surface layer are formed [19, 20].
3.4 Mechanical properties

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Fig. 10 shows the mechanical properties of the samples before and after
HESP. The ultimate tensile strength (UTS) and the yield strength of the sample before
HESP and after HESP for 60min are 545MPa and 637MPa, 405MPa and 540MPa,
and they increases by 17% and 33%, respectively (seen Fig. 10(a)). The increase in

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strength after HESP can be attributed to two primary factors. On one hand, the
introduction of the defects on the surface leads to the increase of the strength. During

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shot peening process, the severe deformation occurs on the surface of the sample and
a large number of dislocations and twins are formed, resulting in the work hardening
[21, 22]. The thickness of the deformation layer increases with prolonging the holding
time, leading to the increase of the strength. On the other hand, the grain refinement
of the surface also contributes to the variety of the mechanical properties with the
increase of the holding time. The average grain size of the sample before HESP is
30m and it is gradually refined to nano-scale after HESP for 60min.
In addition, it is seen that the elongation before and after HESP for 60min was 31%
and 18% and it decreased by 40% after treatment from Fig. 10(a). However, the
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elongation of the sample treated for 60min is still far larger than 8%, which meets
the requirements of biomedical metal materials [23-25]. Work hardening is a factor
for the decrease of the elongation with the increase of the holding time. The
introduction of a large number of defects results in the difficulty of the deformation.

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The information of nano-grains is another factor for the worse of the elongation.
Some researchers reported that the deformation occurred by grain boundary sliding
and grain rotation instead of dislocation sliding for nano-grains [26-28].There is no
space for the dislocation gliding of nano-grains due to the small grain size and the

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macroscopic measurable deformation cannot be accumulated, resulting the wore

ductility.

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Fig. 10(b) depicts the stress-strain curves of the samples and it can see that the
climbing rate at the hardening stage of the curves enhances with the increase of the
holding time, which means that the work hardening effect strengthened. In addition,
the local plastic deformation stages are observed in the curves for all the samples. It
shows that the facture has gone through a process and it cannot rupture immediately

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when it reaches the peak of the strength, which infers that the samples have
undergone the process of necking and the fracture behavior belongs to ductile
fracture.

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4. Conclusions

1. After HESP, the deformation layer was formed on the surface and the
microstructure exhibited with the equiaxed 20~40m grains in the matrix. With

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prolonging the holding time, the thickness of the deformation layer increased.
2. A nanocrystal surface layer was produced on pure titanium by HESP. The

microstructures evolution could be separated into four steps: (1) the formation of the
dislocations tangles; (2) the occurrence of the intersection of twins; (3) appearance of
the slip band and subgrains; (4) formation of uniformly distributed nanometer-scale
grains.
3. With the increase of the holding time, the strength increased and the elongation

decreased due to the work hardening effect and the formation of the nano-grains on
the surface.
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Acknowledgement
This work was partly supported by Jiangsu Planned Projects for Postdoctoral
Research Funds (grant of 1402008A).

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Figure Captions
Fig. 1 Preparation process of TEM foils

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Fig.2 Size of tensile test specimen

Fig.3 Cross-sectional optical micrographs close to the treated surfaces for different

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holding time: (a) 15min; (b) 30min; (c) 45min; (d) 60min

Fig.4 XRD patterns of the samples before and after HESP

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Fig. 5 Average grain sizes and micro-strains of the samples before and after HESP

Fig.6 TEM images of the sample treated for 15min (a) bright field image; (b) SAED

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pattern of (a)

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Fig.7 TEM images of the sample treated for 30min (a) parallel twins; (b) SAED
pattern of (a); (c) sketch map of (b); (d) intersection of the twins; (e) SAED pattern of
(d)

Fig.8 TEM images of the sample treated for 45min: (a) slip bands; (b) subgrains;(c)
SAED pattern of (b)

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Fig.9 TEM images of the sample treated for 60min: (a)bright field image; (b)SAED
pattern of (a)

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Fig. 10 (a) Mechanical properties and (b) stress-strain curves of the samples before

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and after HESP

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Fig. 1

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Fig. 1 Preparation process of TEM foils

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Fig.2 Size of tensile test specimen

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Fig.2

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Fig. 3

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Fig.3 Cross-sectional optical micrographs close to the treated surfaces for different holding
time: (a) 15min; (b) 30min; (c) 45min; (d) 60min

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3000
2000
1000
0

Treated for 45min

3000
2000
1000
0

Treated for 60min

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Treated for 30min

40

60

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3000
2000
1000
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(103)
(112)

Treated for 15min

(110)

3000
2000
1000
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(102)

Before HESP

(100)
(002)
(101)

3000
2000
1000
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80

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Intensity

Fig. 4

100

2theta/deg

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Fig.4 XRD patterns of the samples before and after HESP

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Fig. 5
0.4
Micro-strain

Average grain size/nm

20000

Grain size

0.3

Micro-strain/%

15000

10000

5000

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0.2

0.1

0
10

20

30

Time/min

40

50

60

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Fig. 5 Average grain sizes and micro-strains of the samples before and after HESP

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Fig. 6

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Fig.6 TEM images of the sample treated for 15min (a) bright field image; (b) SAED pattern
of (a)

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Fig. 7

Fig.7 TEM images of the sample treated for 30min (a) parallel twins; (b) SAED pattern of
(a); (c) sketch map of (b); (d) intersection of the twins; (e) SAED pattern of (d)

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Fig. 8

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Fig.8 TEM images of the sample treated for 45min: (a) slip bands; (b) subgrains;(c) SAED
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Fig. 9

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Fig. 9 TEM images of the sample treated for 60min: (a)bright field image; (b)SAED pattern
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Fig. 10

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Fig. 10 (a) Mechanical properties and (b) stress-strain curves of the samples before and
after HESP

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A nanocrystalline surface layer was produced by HESP on pure titanium.

The formation of nano-grains on the surface can be separated into four steps.
With increasing the holding time, the strength increased due to work hardening.

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