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Accepted Manuscript

Effects of annealing on hardness and corrosion resistance of 60NiTi film deposited by


magnetron sputtering

Lanhui Zhang, Huabei Peng, Qiuhui Qin, Qichao Fan, Shile Bao, Yuhua Wen

PII: S0925-8388(18)30714-X
DOI: 10.1016/j.jallcom.2018.02.227
Reference: JALCOM 45103

To appear in: Journal of Alloys and Compounds

Received Date: 14 November 2017


Revised Date: 16 January 2018
Accepted Date: 18 February 2018

Please cite this article as: L. Zhang, H. Peng, Q. Qin, Q. Fan, S. Bao, Y. Wen, Effects of annealing on
hardness and corrosion resistance of 60NiTi film deposited by magnetron sputtering, Journal of Alloys
and Compounds (2018), doi: 10.1016/j.jallcom.2018.02.227.

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Effects of annealing on hardness and corrosion resistance of 60NiTi film

deposited by magnetron sputtering

Lanhui Zhang, Huabei Peng*, Qiuhui Qin, Qichao Fan, Shile Bao, Yuhua Wen*

School of Manufacturing Science and Engineering, Sichuan University, Chengdu 610065, PR

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China

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Abstract: Difficulty in shaping and deformation impedes the application of 60NiTi

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alloy showing high hardness and high corrosion resistance. To promote the

application of 60NiTi alloy, a 60NiTi film was deposited on 316 stainless steel

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substrate by magnetron sputtering. The results showed that a 60NiTi film with
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excellent adhesion property and excellent thermal-shock resistance could be prepared
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by sputtering at 1.5 A and then annealing at 500 °C. The hardness of annealed 60NiTi

film was comparable to bulk 60NiTi alloy, and its corrosion resistance was much
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better than that of the bulk 60NiTi alloy.

Keywords: 60NiTi film, Annealing treatment, Hardness, Corrosion resistance


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*Corresponding author: E-mail: penghuabei@scu.edu.cn; wenyh@scu.edu.cn


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1. Introduction

Recent researches showed that 60NiTi alloy (60wt.% Ni) has potential for

applications in navigation, aerospace, and wear-resistance fields due to its high

hardness, high corrosion-resistance, non-magnetic, low elastic modulus, and low

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density [1-5]. DellaCorte et al. reported that the hardness of 60NiTi alloy reached 63

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HRC, which is comparable to the hardness of 440C and M-50 steels. Its friction

coefficient was only 0.06, being 0.02 lower than that of 440C steel. As the result of

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higher hardness and lower friction coefficient, 60NiTi alloy showed better

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wear-resistance than the 440C and M-50 steels [6-8]. The Young’s modulus of 60NiTi
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alloy was about 100 GPa, being half of the ones of 440C and M-50 steels [9]. In

addition, a rust spot appeared in the 60NiTi alloy samples after the salt sprayed for
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3120 h, but it appeared in the 316SS (316 stainless steel) samples after only 1000 h
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[10]. However, although the 60NiTi alloy has the above-mentioned advantages, its
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large-scale applications are impeded by its poor ductility and the difficulty in

hot-working.
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The 60NiTi alloy actually had been reported in 1960s by the US Naval Ordnance
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Laboratory together with 55NiTi alloy, which has been widely studied and utilized so
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far [11]. However, because of its high brittleness and difficulty in shaping as well as

high notch sensitivity, the 60NiTi alloy did not interest people in that time [6, 12].

Recently, Julien had obtained fine-grained 60NiTi plates through pack hot-rolling and

improved the notch sensitivity. Note that the thickness reduction was 0.127 mm per

pass in pack hot-rolling [13]. Therefore, the pack hot-rolling is not cost-effective
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method due to its special requirement for equipment and long working time.

More than 80 percent of machine failure results from abrasion and corrosion

occurring in the surface of components. Some studies already clearly revealed that a

film of alloys showing good wear-resistance and corrosion-resistance deposited on the

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surface of the components, such as Ti-Al-V-N coatings, could remarkably elongate the

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machine life [14, 15]. Accordingly, it can be expected that the machine life will

remarkably be elongated by depositing a film of the 60NiTi alloy showing excellent

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wear-resistance and corrosion-resistance. More specific, we will obviate the need for

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shaping 60NiTi alloy. In fact, Abubakar et al. reported that the crystalline Ni rich NiTi
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film after annealed at 550 °C for 60 min in the vacuum furnace with argon gas

environment had a much better wear performance than the as-deposited amorphous Ni
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rich NiTi film on the surface of a 316 stainless steel deposited by a closed field
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unbalanced magnetron sputtering system. In addition, they ascribed the significant


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improvement of wear performance after the annealing to the improved adhesion

bonding and the existence of a TiO2 rutile layer [16, 17]. Note that they only studied
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the effects of annealing at 550 °C and 600 °C for 30 min and 60 min on the adhesion
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properties and wear performance. So far, it is not clear on the effects of annealing at
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higher and lower temperatures. In addition, the comparison of properties between

bulk NiTi alloy and its film should be made to know whether the properties of film is

better or worse as compared to that of bulk NiTi alloy.

In this paper, a NiTi alloy film was deposited on 316SS specimens by magnetron

sputtering a target of 60NiTi alloy, and effects of different annealing temperatures on


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the properties of the deposited film, including the adhesion properties, hardness, and

corrosion resistance, were studies. In addition, the properties of the film were

compared with that of bulk 60NiTi alloy subjected to annealing at different

temperatures. The results showed that the annealed 60NiTi film had excellent

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adhesion properties and thermal-shock resistance. In addition, the annealed 60NiTi

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film showed a hardness comparable to bulk 60NiTi and better corrosion resistance.

2. Materials and methods

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2.1 Experiment materials

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The experimental 60NiTi alloy was melt in water-cooled copper crucible using
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pure nickel and titanium under vacuum atmosphere and then poured into metal mold.

The composition of the ingot was listed in Table 1. Both the targets of 98 mm
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(diameter) ×5 mm (thickness) and bulk samples of 10×10×8 mm3 were cut from the
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ingot by wire electrical discharge machining. All bulk samples were first
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solution-treated at 1050 °C for 4 hours and then annealed in vacuum atmosphere of 3

× 10-2 Pa at different temperatures, followed by a water quenching.


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The substrate material used in the magnetron sputtering was solution-treated


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316SS steel, whose compositions were also listed in Table 1. The samples of
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25×15×1.8 mm3 cut by wire electrical discharge machining were mechanically ground

with different grades of SiC papers (60, 120, 240, 600, and 1200) and then

mechanically polished. All polished samples were ultrasonic cleaned in acetone for 15

min.

Table 1 Compositions of 60NiTi target and substrate material.


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2.2 Magnetron sputtering film and annealing treatment

The 60NiTi film was deposited on 316SS samples by QX-500 magnetron

sputtering. The achieved base pressure was 3.5×10-3 Pa, the deposition pressure was

fixed to 3.0×10-1 Pa by controlling the argon gas (plasma forming gas) flow inside the

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deposition chamber. The deposition current for 60NiTi film was adjusted from 0.5 A

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to 1.5 A, and the sputtering time was 3 hours.

The as-sputtered films were annealed in vacuum atmosphere of 3 × 10-2 Pa at

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different temperatures ranging from 300 °C to 800 °C for different times, followed by

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a water quenching.
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2.3 Properties characterization of 60NiTi film

A Rockwell-A hardness tester was used to assess the adhesion properties of


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60NiTi film [18, 19]. Indentations made by 60 kg load were observed with optical
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microscope. Fig. 1 showed six classes of indentations. A small amount of cracks exists
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in the class HF 1 (HF is the German short form of adhesion strength), and its amount

gradually increases up to the class HF 5. In addition, part detachments of surrounding


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coatings exist in class HF 3 to HF 5. For the class HF 6, all the surrounding coatings
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are completely detached. In other words, the adhesion property of class HF 1 is the
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best, and that of the class HF 6 is the worst.

Fig. 1 Characterization of adhesion property by Rockwell adhesion test.

The hardness of 60NiTi film and bulk samples was tested by HVS-1000 hardness

tester. To determine a proper load which will obviate the impact of the substrate on

the hardness of the film, we first investigated the effect of load on the hardness of the
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film and the substrate, and the results were shown in the Fig. 2. According the results

in the Fig. 2, the load was determined as 25 g. The corrosion-resistance was

characterized by potentiodynamic polarization curve. A three-electrode cell

arrangement was used for the electrochemical measurements, with a saturated calomel

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electrode (SCE) as reference electrode and a platinum plate as auxiliary electrode.

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Samples were tested in a naturally aerated 3.5% NaCl solution at room temperature,

leaving areas of 1 cm2 for exposure to the electrolyte.

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Fig. 2 Effects of load on hardness of as-deposited film and 316 stainless steel.

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The potentiodynamic polarization curves were obtained at 2 mV/s in the
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potential range of Eop ± 1 V. The corrosion potential (Eo), corrosion current (Io) and

corrosion rate can be obtained using Tafel traditional method in CorrView


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electrochemical analysis software.


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A grazing angle X-ray diffractometer (GAXRD) was used to identify the phases
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of 60NiTi film with 3 °/min scanning rate at a grazing angle of 2°. A general X-ray

diffractometer (XRD) was used to determine phases of bulk 60NiTi alloy with 2 °/min
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scanning rate. A Co target was used, and the diffraction angle (2θ) was from 40° to
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105°. A TESCAN VEGA3 XMU scan electron microscopy was used to characterize
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the film including its surface and phase.

3. Results

3.1 Effect of sputtering current on adhesion properties of film

The HRA indentations of 60NiTi film prepared at different sputtering currents

were shown in Fig. 3. Based on the comparison with Fig. 1, the adhesion properties of
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film sputtered at 1.5 A was determined as the class HF 1, the ones of film sputtered at

0.9 A and 0.6 A as class HF 4 and HF 5, respectively. It seems that the adhesion

properties increased as increasing the current. Because a higher current would result

in some damage to the equipment, only the 60NiTi film sputtered at 1.5 A were

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further studied.

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Fig. 3 Adhesion property of 60NiTi film sputtered at different currents.

The cross-sectional SEM image revealed that the film sputtered at 1.5 A was

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compact, and its thickness was about 6.5 µm (Fig. 4). In addition, the interface

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between the film and 316SS was continuous.
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Fig. 4 Cross-sectional SEM image of 60NiTi film sputtered at 1.5 A for 3 h.

3.2 Effects of annealing on adhesion properties and hardness of film


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Fig. 5 shows the HRA indentations of 60NiTi film sputtered at 1.5 A for 3 h after
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annealed at 300 °C to 800 °C for 0.5 h. As compared to the as-deposited film, the
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annealing at 300 °C slightly deteriorated the adhesion properties, but the annealing at

higher temperatures further improved the adhesion properties. When annealing


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temperature was increased to 700 °C or 800 °C, the cracks were not observed in the
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indentation. Especially note that a water quenching treatment was used after the
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annealing. Therefore, the present annealed 60NiTi film deposited on the 316SS

substrate showed not only excellent adhesion properties but also excellent

thermal-shock resistance.

Fig. 5 Effects of annealing at 300 °C to 800 °C for 0.5 h on adhesion properties of

60NiTi film sputtered at 1.5 A for 3 h.


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Fig. 6 shows the hardness of 60NiTi film sputtered at 1.5 A for 3 h after annealed

at 300 °C to 800 °C for 0.5 h. The hardness of 60NiTi film increased rapidly as

increasing the annealing temperature and reached a peak value of 747 HV at 500 °C.

When the annealing temperature exceeded 500 °C, it decreased rapidly with further

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rise in the annealing temperature. It is worth pointing out that the hardness of 60NiTi

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film was 521 HV after annealing at 800 °C, which was 190 HV higher than that of

as-deposited film.

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The hardness of solution-treated bulk 60NiTi alloy (the black curve) were also

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shown Fig. 6 after annealing at 300 °C to 800 °C for 0.5 h. The hardness of
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solution-treated 60NiTi alloy was 722 HV, which was comparable to that of 60NiTi

film annealed at 500 °C. The annealing at 300 °C to 600 °C had little effect on its
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hardness, but the annealing at 700 °C significantly lower the hardness to 473 HV.
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Interestingly, the hardness increased to 520 HV after the annealing at 800 °C.
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Fig. 6 Effects of annealing at 300 °C to 800 °C for 0.5 h on hardness of 60NiTi film

sputtered at 1.5 A for 3 h and solution-treated 60NiTi bulk alloy.


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The effects of annealing time on the hardness of 60NiTi film and bulk 60NiTi
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alloy were shown in Fig. 7 when annealing at 500 °C. The annealing time had a
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marginal effect on the hardness of solution-treated bulk 60NiTi alloy. Interestingly, a

short time annealing of 0.5 h remarkably increased the hardness of the film, but its

hardness gradually and slightly dropped as further increasing the time.

Fig. 7 Effects of annealing time on hardness of 60NiTi film and bulk alloy when

annealed at 500 °C.


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3.3 Effect of annealing on microstructural evolution

The XRD patterns of 60NiTi film sputtered at 1.5 A after annealed at different

temperatures for 0.5 h were shown in Fig. 8(a). Only a broad peak at around 2θ=51°

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except the sharp peaks of 316SS substrate appeared in the as-deposited film and the

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one annealed at 300 °C, indicating that both the structure of as-deposited film and the

one annealed at 300 °C were amorphous [20]. When the annealing temperature was

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higher than 400 °C, the broad peak and peaks of 316SS substrate disappeared while

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the peaks of NiTi, Ni4Ti3 and Ni3Ti appeared. In addition, the intensity of NiTi and
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Ni4Ti3 peaks decreased gradually as increasing the annealing temperature from 500 °C

to 800 °C, but the intensity of Ni3Ti peaks increased gradually. The XRD patterns of
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60NiTi film after annealed at 500 °C for various times were shown in Fig. 8(b). The
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peaks intensity of Ni3Ti phase increased as increasing annealing time, indicating the
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increase in the amount of Ni3Ti phase.

The XRD patterns of bulk 60NiTi alloy annealed at different temperatures for 0.5
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h were shown in Fig. 8(c). As for the solution-treated 60NiTi alloy, the peaks of NiTi,
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Ni4Ti3, Ni3Ti2, and Ni3Ti were observed. When annealing temperature was 700 °C, the
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peaks of Ni4Ti3 phase disappeared, and the peaks intensity of Ni3Ti phase increased.

In addition, some new peaks of Ni3Ti phase. In other words, the amount of Ni4Ti3

phase significantly reduced after annealined at 700 °C, but the amount of Ni3Ti phase

increased.

Fig. 8(d) shows the effect of annealing time on phase evolution in the
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solution-treated 60NiTi alloy when annealed at 500 °C. The intensity of Ni4Ti3 peaks

increased as increasing annealing time. That is, the amount of Ni4Ti3 phase increased

with time. Table 2 lists the second phase evolution of 60NiTi film and bulk alloy after

annealed. Interestingly, Ni3Ti2 phase existed in both the bulk solution-treated 60NiTi

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alloy and the annealed ones, but it did not appear in the 60NiTi film including the

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as-deposited and annealed ones. In addition, the Ni4Ti3 phase of 60NiTi disappeared

in the film and bulk alloy after annealed at above 500 °C and 600 °C, respectively.

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Fig. 8 XRD patterns of 60NiTi film sputtered at 1.5 A for 3 h and bulk 60NiTi alloy

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after annealed at different temperatures. (a) and (b) 60NiTi film; (c) and (d) bulk
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60NiTi alloy.

Table 2 Second phase evolution of 60NiTi film and bulk alloy with annealing
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temperature.
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SEM observation (Fig. 9) showed that after annealed at 500 °C for 0.5 h, a great
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many islands and plenty of channels on the surface of as-deposited 60NiTi film fused

with each other and disappeared. EDS analysis confirmed that Ni3Ti phase existed in
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the 60NiTi film after annealed over 400 °C (Fig. 9 and Table 3). Moreover, lots of
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Ni3Ti particles were distributed in the 60NiTi film annealed at 500 °C for 0.5 h (Fig.
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9(c)), but coarser Ni3Ti phase were observed after annealed at 500 °C for 2 h (Fig.

9(d)). The submicron Ni3Ti phase was uniformly distributed in the film annealed at

800 °C for 0.5 h (Fig. 9(e) and (f)). In addition, EDS analysis also confirmed that

some Ni3Ti phase existed in the bulk solution-treated 60NiTi alloy, the white bulk

phase in Fig. 9(g).


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Fig. 9 SEM photographs of 60NiTi film and bulk alloy. (a) as-deposited 60NiTi film in

secondary electron mode; 60NiTi film annealed at 500 °C for 0.5 h in secondary

electron mode (b) and in back scattered electron mode (c); (d) 60NiTi film annealed at

500 °C for 2 h in back scattered electron mode; (e) and (f) 60NiTi film annealed at

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800 °C for 0.5 h in back scattered electron mode; (g) solution-treated bulk 60NiTi

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alloy in back scattered electron mode.

Table 3 The elements content of secondary phase in 60NiTi bulk and film tested by

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EDS.

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3.3 Electrochemical performance of 60NiTi film and bulk alloy
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Fig. 10 shows the potentiodynamic polarization curves of 60NiTi film annealed

at 500 °C for 0.5 h, solution-treated bulk 60NiTi alloy, and 316SS. The fitting values
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of corrosion potential (Eo), corrosion current (Io) and corrosion rate were listed in
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Table 4. The corrosion current of 60NiTi film was 5.812E-8 Amp/cm2, which was
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lower than the ones of bulk 60NiTi (8.29E-7 Amp/cm2) and 316SS (7.55E-6

Amp/cm2). In addition, the annual corrosion rate of 60NiTi film was 0.00077 mm/a,
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which was significantly lower than the ones of bulk 60NiTi alloy (0.00940 mm/a) and
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316SS (0.08876 mm/a). The above results indicated that the corrosion resistance of
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60NiTi film is significantly higher than the ones of bulk 60NiTi alloy and 316SS.

Fig. 10 Potentiodynamic polarization curves in aerated 3.5% NaCl of 60NiTi film

annealed at 500 °C for 0.5 h, solution-treated bulk 60NiTi alloy and 316SS.

Table 4 Polarization fitting values in aerated 3.5% NaCl of 60NiTi film annealed at

500 °C for 0.5 h, solution-treated bulk 60NiTi alloy and 316SS.


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After the electrochemical performance test, many corrosion pits whose diameter

was about 200 µm were observed on the surfaces of 316SS (Fig. 11(a)) and bulk

60NiTi alloy (Fig. 11(c)), while only a few tiny pits were observed on the surface of

60NiTi film (Fig. 11(b)). These results also indicated that the corrosion resistance of

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60NiTi film is significantly better than the ones of bulk 60NiTi alloy and 316SS.

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Fig. 11 Surface photographs after electrochemical performance test. (a) 316SS; (b)

60NiTi film annealed at 500 °C for 0.5 h; (c) solution-treated bulk 60NiTi.

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4. Discussion

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4.1 Effect of annealing on the hardness of 60NiTi film and bulk alloy
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The results by Qin et al. showed that the hardness at room temperature depended

on only the Ms temperature (the starting temperature of martensite transformation) of


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B19’ martensitic transformation in highly Ni-rich NiTi alloys undergoing only B19’
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martensitic transformation. The higher Ms temperature was, the lower hardness was at
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room temperature [21]. Besides, the Ms temperature will significantly increase when

more high Ni-rich phases Ni3Ti2 and Ni3Ti precipitate [22-26]. In present experiment,
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after annealed at 700 °C, many Ni3Ti2 and Ni3Ti phases precipitated in bulk 60NiTi
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alloy due to the decomposition of the Ni4Ti3 phase. As a result, the Ms temperature
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significantly rose. This explains why the hardness of solution-treated bulk 60NiTi

alloy significantly dropped. However, as compared to 700 °C, the hardness of bulk

60NiTi alloy increased slightly after annealed at 800 °C because of the reduction of

Ni3Ti2 and Ni3Ti phases.

The present 60NiTi film was still amorphous after annealed at 300 °C, but its
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hardness was improved to 497 HV from 330 HV at as-deposited state. In fact, the

similar results were reported in amorphous Fe40Ni40P14B6 alloy, amorphous Zr-Cu-Ti

films, and amorphous Y-Mo films, and the authors ascribed the increase of hardness to

structural relaxation or atomic rearrangement in the amorphous induced by the

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low-temperature annealing [27-30]. The true reasons need further investigation. The

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crystallization in the present deposited 60NiTi alloy film occurred and finished after

annealed at 400 °C. In the crystallization, high-strength NiTi parent phase was formed

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gradually and hard superfine Ni4Ti3 intermetallic compound precipitated [31]. Besides,

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the defects like channels disappeared gradually in the crystallization (Fig. 9(b)).
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Therefore, the hardness of as-deposited 60NiTi film increased as increasing annealing

temperature, and reached the peak value of 747 HV when the annealing temperature
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was 500 °C.


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When annealed at 500 °C to 800 °C, the second phases in present 60NiTi film
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precipitated in the sequence of NiTi → Ni3Ti and Ni4Ti3 → Ni3Ti (Table 2), which

was similar to the research results of Adharapurapu et al. [32]. Besides, there are
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many vacancies and other defects in the film, and the crystallized film also has very
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small grain size and a large number of grain boundaries [33, 34]. Therefore, it is
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easier for atoms to diffuse, and the precipitation process is faster [35]. As a result,

metastable Ni4Ti3 phase decomposed completely, and more Ni3Ti phase precipitated

in present 60NiTi film at 600 °C, lower than the 700 °C at which metastable Ni4Ti3

phase decomposed completely in the bulk 60NiTi alloy. Accordingly, the hardness of

60NiTi film deceased rapidly after annealed at 600 °C. However, after annealed at
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800 °C, the hardness of 60NiTi film declined further due to more Ni3Ti phase

precipitated. The reason why more Ni3Ti phase precipitated in the film after annealed

at 800 °C need further investigation.

With the increase of annealing time at 500 °C, the intensity of Ni3Ti diffraction

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peak (Fig. 8(b)) increased gradually, that is, more Ni3Ti second phase precipitated in

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60NiTi film. Consequently, the Ms increased due to the decrease of the Ni content in

the NiTi parent. As a result, the hardness variation of 60NiTi film showed a declining

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trend with annealing time increasing.

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4.2 Comparison of corrosion resistance between 60NiTi film and bulk alloy
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In general, titanium has a stronger formation ability of passive film due to its

much lower standard electrode potential (-1.63 V, compared with SHE). Therefore,
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titanium and titanium alloys have better corrosion resistance due to the compact TiO2
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film [36, 37]. In addition, a new TiO2 passive film can form once the preexisting TiO2
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film is destroyed [38]. Therefore, the present 60NiTi film and bulk 60NiTi alloy had a

better corrosion resistance than 316SS due to its high Ti content (39.01 wt.%).
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The present 60NiTi film had better corrosion resistance than the bulk 60NiTi
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alloy. The results were similar to the literature reported by Blawert et al. [39].
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According to their mechanism and our results, the presence of coarse precipitates is

detrimental for the corrosion resistance. The coarse precipitates are the sources of

localised or pitting corrosion caused most likely by defects in the passive film (TiO2).

Strong variations of the elemental distribution weaken the passive films, thus leading

to their earlier breakthrough and the starting of localised corrosion. As shown in Fig. 9,
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many coarse Ni3Ti phase can be observed in bulk 60NiTi. Oppositely, in 60NiTi film,

the secondary phases were submicron and uniformly distributed. Accordingly, the

uniform distribution of alloying elements in 60NiTi film leads to uniform corrosion

mechanisms without any localized corrosion or microgalvanic effects. As a result, the

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corrosion resistance of bulk 60NiTi lowered than 60NiTi film.

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5. Conclusions

1). A 60NiTi film with excellent adhesion property, thermal-shock resistance,

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high hardness, and high corrosion resistance can be prepared by magnetron sputtering

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and annealing treatment. The adhesion property of annealed 60NiTi films were better
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than the class HF 1 because less or no cracks were observed in the indentations. And

the hardness of as-deposited 60NiTi film reached 330 HV and improved to 747 HV
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after annealed at 500 °C.


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2). The hardness of 60NiTi film annealed at 500 °C was comparable to that of
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solution-treated bulk 60NiTi alloy, and corrosion resistance of 60NiTi film annealed

at 500 °C was significantly higher than that of solution-treated bulk 60NiTi alloy. The
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hardness of 60NiTi film annealed at 500 °C reached 747 HV, being 25 HV higher than
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that of solution-treated bulk 60NiTi alloy. As compared to solution-treated bulk


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60NiTi alloy, 60NiTi film annealed at 500 °C had much lower annual corrosion rate

(0.00077 mm/a) and tinier corrosion pits after electrochemical performance test.
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Table 1 Compositions of 60NiTi target and substrate material

Chemical elements Fe Ni Cr Mo Ti

Content(wt.%) Target material / 60.99 / / 39.01

316SS Bal. 11.0 16.7 2.45 /

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Table 2 Second phase evolution of 60NiTi film and bulk alloy with annealing
temperature.

Annealing temperature Phases

60NiTi film 60NiTi bulk

As-deposited/solution-treated Amorphous NiTi Ni4Ti3 Ni3Ti Ni3Ti2

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300 °C Amorphous Undetermined

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400 °C NiTi Ni4Ti3 Undetermined

500 °C NiTi Ni4Ti3↑ Ni3Ti NiTi Ni4Ti3↓ Ni3Ti↑ Ni3Ti2↑

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600 °C NiTi Ni3Ti↑ NiTi Ni4Ti3↓ Ni3Ti↑ Ni3Ti2↑

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700 °C NiTi Ni3Ti↑
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800 °C NiTi Ni3Ti↑ NiTi Ni3Ti↓ Ni3Ti2↓

Note: “↑” means the increase in the amount of phases, “↓” is opposite.
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Table 3 The elements content of secondary phase in 60NiTi bulk and film tested by
EDS.

Ni (at.%) Ti (at.%)

60NiTi bulk White phase 72.78 27.22

60NiTi film White phase 73.13 26.87

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Table 4 Polarization fitting values in aerated 3.5% NaCl of 60NiTi film annealed
at 500 °C for 0.5h, solution-treated bulk 60NiTi alloy and 316SS.

Samples Ba Bc Eo Io Corrosion Rate

(mV) (mV) (Volts) (Amp/cm2) (mm/a)

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316SS 553.36 -330.13 -0.28 7.55E-6 0.08876

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Bulk 60NiTi 437.90 234.75 -0.33 8.29E-7 0.00940

60NiTi film aged at 544.39 -34.47 -0.21 5.812E-8 0.00077

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500 °C

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Fig. 1 Characterization of adhesion properties by Rockwell adhesion test.
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Fig. 2 Effects of load on hardness of as-deposited film and 316 stainless steel.
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Fig. 3 Adhesion properties of 60NiTi film sputtered at different currents.
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Fig. 4 Cross-sectional SEM image of 60NiTi film sputtered at 1.5 A for 3 h.

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Fig. 5 Effects of annealing at 300 °C to 800 °C for 0.5 h on adhesion properties of


60NiTi film sputtered at 1.5 A for 3 h.
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Fig. 6 Effects of annealing at 300 °C to 800 °C for 0.5 h on hardness of 60NiTi film
sputtered at 1.5 A for 3 h and solution-treated bulk 60NiTi alloy.
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Fig. 7 Effects of annealing time on hardness of 60NiTi film and bulk alloy when
annealed at 500 °C.
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Fig. 8 XRD patterns of 60NiTi film sputtered at 1.5 A for 3 h and 60NiTi bulk alloy

after annealed at different temperatures. (a) and (b) 60NiTi film; (c) and (d) bulk
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60NiTi alloy.
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Fig. 9 SEM photographs of 60NiTi film and bulk alloy. (a) as-deposited 60NiTi film
in secondary electron mode; 60NiTi film annealed at 500 °C for 0.5 h in secondary
electron mode (b) and in back scattered electron mode (c); (d) 60NiTi film annealed at
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500 °C for 2 h in back scattered electron mode; (e) and (f) 60NiTi film annealed at
800 °C for 0.5 h in back scattered electron mode; (g) solution-treated bulk 60NiTi
alloy in back scattered electron mode.

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Fig. 10 Potentiodynamic polarization curves in aerated 3.5% NaCl of 60NiTi film
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Fig. 11 Surface photographs after electrochemical performance test. (a) 316SS; (b)
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60NiTi film annealed at 500 °C for 0.5 h; (c) solution-treated bulk 60NiTi.
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Highlights

 A 60NiTi film with excellent adhesion can be prepared by magnetron sputtering.

 Annealing treatment improved the hardness of as-deposited 60NiTi film.

 The hardness of annealed 60NiTi film was comparable to that of bulk 60NiTi

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alloy.

 Annealed 60NiTi film had better corrosion resistance than bulk 60NiTi alloy.

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