Accepted Manuscript

Title: Effect of the Holding Time on the Mechanical

Properties of Gradient-Hardened Pure Titanium

Authors: Chang-Lim Kim, Dong-Geun Lee

PII: S0169-4332(18)30596-8
DOI: https://doi.org/10.1016/j.apsusc.2018.02.228
Reference: APSUSC 38686

To appear in: APSUSC

Received date: 28-4-2017

Revised date: 1-2-2018
Accepted date: 23-2-2018

Please cite this article as: Chang-Lim Kim, Dong-Geun Lee, Effect of the Holding Time
on the Mechanical Properties of Gradient-Hardened Pure Titanium, Applied Surface
Science https://doi.org/10.1016/j.apsusc.2018.02.228

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Effect of the Holding Time on the Mechanical Properties of Gradient-Hardened Pure

Titanium

Chang-Lim Kim, Dong-Geun Lee*

Materials Metallurgical Engineering, Sunchon National University, 255, Jungang-ro, Suncheon,

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Jeonnam, 57922, Korea

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* Corresponding author : Dong-Geun Lee

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Tel : +82-61-750-3555, E-mail : leechodg@scnu.ac.kr

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Highlights:

•
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The gradient-hardened inner layers of Ti2N and TiNx produced on titanium surface by
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vacuum rapid nitriding process
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Influences of holding time and nitrogen concentration on the mechanical properties

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• Excellent mechanical properties for the holding time, 1 hour at 800 ℃

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• Hardness of the diffused surface layer was improved up to about four times
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Abstract
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The vacuum rapid nitriding process is a surface modification technique that is used mainly to
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increase the wear resistance and surface hardness of titanium and its alloys. Using this simple

process, the surface of titanium can be hardened within a relatively short time by a continuous
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process. The holding times were controlled to improve the titanium surface and mechanical

properties. The hardened layers consisted of continuous layers with high hardness and deep

thickness, which differed from the conventional discrete over-layer coating. The diffusion

layers were composed of gradient-hardened inner layers of Ti2N, TiNx, and Ti[N].
The thickness and hardness increased with increasing holding time, but the tensile strength

decreased until 1 hour at 800 ℃. The tensile strength was influenced by the relative

combination of the softening effect by the high temperature and the hardening effect by the

hardened area, as a function of the holding times.

Keywords: Titanium, Continuous gradient hardening, Vacuum rapid nitriding process, Inner-

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layer coating

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1. Introduction

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Titanium and its alloys are used widely in the aerospace, chemical, and biomedical industries

owing to their excellent performance, such as specific high strength and good corrosion

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resistance [1]. On the other hand, the applications of titanium and its alloys are limited in some
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specific parts, such as the contact area or the rotation surface of a machine, due to the poor wear
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resistance and low hardness of their surface [2]. To solve this problem, a variety of methods
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have been applied to harden the surface and improve the performance, such as nitriding,

physical vapor deposition (PVD), chemical vapor deposition (CVD), and ion-plasma. These
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methods have been used to form a TiN layer on the titanium surface [3,4]. The layer of TiN
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compound has very high hardness and can improve the wear resistance of the material, so they

can be used in applications, such as cutting tools and some parts requiring a surface coating.
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A compound TiN over-layer cannot improve the surface properties completely. This is
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because these processes have weak adhesive strength of the interface between the surface and

coating layer, and the processing time is quite lengthy. Recently, many studies have been
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performed to control the surface of the compound in a gas atmosphere [5,6]. This process has

been applied in various industries, such as the manufacturing of machine parts, cutting tools,

rolls, and working dies [7].

The vacuum rapid nitriding (VRN) process was introduced to improve the titanium surface
[8]. This method can improve the surface property easily by diffusion and the processing time

is quite short compared to other processes. The VRN method has some advantages, such as the

strong gradient-hardened layers, continuous layers, no limit of a part shape, and no change in

the dimensions of parts after this treatment. Nitrogen atoms were diffused interstitially from the

surface to inside and formed the same compounds on the titanium surface.

In this study, the hardening behaviors of the titanium surface and the variation of the

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mechanical properties were examined by controlling the holding times at 800 ℃ for 30 min,

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1 hour, and 2 hours. The effects of the holding time on the microstructure and hardness

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distribution were analyzed and compared with those of the as-received pure titanium.

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Furthermore, the correlation between the percentage of hardened area and the mechanical

tensile properties was also evaluated.

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2. Experimental
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The material used in this study was commercially pure titanium (Grade 2); the chemical
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composition is listed in Table 1. Rectangular samples (10 × 12 × 10 mm3) and plate-type tensile
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specimens were treated by a vacuum rapid nitriding (VRN) process using nitrogen gas as the

heat treatment atmosphere. The tensile specimens were machined in accordance with ASTM
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E8 standard (Fig. 1).

The samples were heat treated at 800 ℃ (below the beta transformation temperature of
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Commercially Pure Ti, 883℃) for 30 min, 1 hour, and 2 hours by the gas controlled vacuum

furnace (GCVF) system, and by controlling the pressure in the chamber to 2.5×10-3 Pa. Nitrogen
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gas injection was maintained at a certain level of 50 cc/min. Consequently, the inner-hardened

layer was formed by diffusing nitrogen atoms into the titanium surface.

After cutting the heat treated samples and polishing with SiC abrasive paper and colloidal silica

(SiO2), they were etched with a solution containing 20% HNO3, 3% HF, and 77% distilled
water. To analyze the diffused inner-hardened layer, the microstructures of the cross-sectioned

samples were observed by optical microscopy and scanning electron microscopy (SEM). Micro

Vickers hardness measurements were carried out from the surface of the hardened layer to the

matrix with an applied load of 10 g for 10 seconds. A tensile test was conducted using a 250

kN universal testing machine (SHIMADZU, AG-250KNXPLUS) at room temperature at a

strain rate of 1.5 mm/minute. The depth of the hardened area was analyzed at different holding

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times to determine its effects on the tensile properties, assuming that the diffusion of nitrogen

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occurs equally on all sides.

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3. Results and discussion

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Microstructural analysis of the surface and the hardened layer was carried out, as shown in
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Fig. 2, which was thermo-chemically diffused by nitrogen at 800 ℃ for 30 min, 1 hour, and 2
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hours. The microstructures of all samples consisted of the equiaxed alpha-Ti crystals due to the
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heat treatment at 800 ℃, which is below the beta transformation temperature. The average
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grain size of the matrix was measured to confirm the occurrence of grain growth at high

temperatures. As the holding time was increased, the mean grain size of the matrix increased
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slightly. The grain size of the samples heat treated for 30 min, 1 hour, and 2 hours was 46 ㎛,

48 ㎛, and 51 ㎛, respectively.
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On the other hand, the grain size of the surface was similar in all heat-treated samples. The

grain size for 30 min, 1 hour, and 2 hours was 27 ㎛, 28 ㎛, and 30 ㎛, respectively. As the
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pinning effect by the diffusion of nitrogen atoms into the interstitial sites of the HCP structure

occurred, grain growth of the alpha phase was suppressed in this diffusion layer. The diffusion

layers of the treated samples consisted of continuous inner-layers of Ti2N, TiNx, and Ti[N].

Table 2 lists the thickness of the diffusion layer as a function of the holding time at 800 ℃.
The thickness of the compound layer (Ti2N + TiNx) increased from 9.2 ㎛ to 12.6 ㎛ with

increasing holding time from 30 min to 2 hours.

The Vickers hardness was measured to determine the hardness distribution and confirm the

hardened depth from the surface according to the VRN process time. As a result, the surface

hardness of the samples heat treated for 30 min, 1 hour, and 2 hours was 520 Hv, 675 Hv, and

704 Hv, respectively, and improved 3~4 fold compared to the surface hardness of pure titanium

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(180 Hv).

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During the VRN process for forming the continuous gradient-hardened layer from the surface,

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nitrogen atoms can penetrate the interstitial sites of the alpha HCP lattice. The depth of the

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hardened layer is affected by the diffusion coefficient and process time in accordance with the

equation, 𝑥 ≈ √𝐷𝑡. The diffusion coefficient (D) is related to the temperature by the Arrhenius

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equation, D = Do exp (-Q/RT). On the other hand, the depth (x) changed as a function of the
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holding time (t) due to heat treatment at a constant temperature of 800 ℃.
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The differential equation of Fick’s second law for diffusion is as follows:

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𝜕𝐶 𝜕2 𝐶
= 𝐷 (𝜕𝑥 2 ) (1)
𝜕𝑡
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If the nitrogen concentration of the surface is constant, the concentration profile can be

calculated using the following equation:

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𝑐𝑠 −𝑐𝑥 𝑥
= erf⁡(2√𝐷𝑡) (2)
𝑐𝑠 −𝑐0
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where cs is the constant concentration of nitrogen at the titanium surface; c0 is the initial
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concentration (the constant concentration of matrix); and cx is the concentration of nitrogen

atom at a distance (x) from the surface after the holding time (t). C.J. Rosa [9] reported the
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relationship between the diffusion coefficient and the hardness distribution at a certain distance

using equation (3).

𝐻−𝐻0 𝑥
𝐻𝑠 −𝐻0
∝ 1 − erf⁡(2√𝐷𝑡) (3)
 where H is the hardness; H0 is the hardness in a matrix of titanium; and Hs is the hardness at

the surface. Using equation (3), H0 was substituted for the matrix 180 Hv hardness of pure

titanium, and Hs was substituted for the outermost surface hardness.

From equations (2) and (3), it is possible to predict the hardness distribution at a set

temperature, concentration, time, and distance, because the hardness is related strongly to the

concentration of interstitial atoms. According to E. Metin [10], the diffusion coefficient (D) of

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alpha titanium can be calculated using the following equation:

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−35,760±2530
D = 2.7(±1.05) × 10−3 exp( ) (4)
𝑅𝑇

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The diffusion coefficient was calculated to be 1.3775×10-14 m2/s by inserting the temperature

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(800℃) and ideal gas constant (R). By substituting this diffusion coefficient for equation (3),

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the hardness distribution can be calculated and determined as a function of distance (penetration
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depth). The actually measured hardness of the various samples and the hardness calculated
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using this equation were compared as a function of holding time and depth at 800℃, as shown
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in Fig. 3. The thickness of the hardened layer increased with increasing holding time in both

the actual measurement and theoretical calculation. A small difference of approximately 2 ~ 5

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㎛ depth was observed in both, but the trend was similar.

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At a particular depth (x= 10 ㎛), the actual measured hardness increased with increasing

holding time (Fig. 4). On the other hand, only a slight increasing in hardness occurred when the
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holding times were increased from 1 hour to 2 hours. This is because the amounts of interstitial
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nitrogen atoms, which can diffuse into and reside at the titanium lattice, are limited [11-13].
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Therefore, despite the longer holding time, the increase in cross-sectional hardness was not high.

In the case of another depth (x= 30 ㎛), a similar phenomenon in hardness was observed.

Fig. 5 shows the tensile stress-strain curves for the specimens heat-treated at 800 ℃ for

various holding times. The measured yield strength (YS) and ultimate tensile strength (UTS) of

the as-received pure titanium were 345 MPa and 449 MPa, respectively. For the 30 min VRN-
ed specimens, the YS and UTS were 318 MPa and 412 MPa, respectively, which were slightly

lower than the as-received titanium (Table 3). This is basically due to the softening effect caused

by the heat treatment at a relatively high temperature of 800 ℃.

On the other hand, for the 1 hour VRN-ed specimens, the YS and UTS increased to 336 MPa

and 435 MPa, respectively. In contrast, for the 2 hours VRN-ed specimens, the YS and UTS

decreased slightly to 335 MPa and 424 MPa, compared to the 1 hour VRN-ed specimens, even

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though the holding time was doubled. To analyze this phenomenon, the fraction of the hardened

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area at a certain hardness was measured and calculated for the three specimens, as shown in

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Fig. 6, assuming that the penetration of nitrogen atoms occurred equally in all sides of the tensile

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specimen. As the holding time was increased, the percentage of the hardened area increased in

each hardness value. The difference in the percentage between the 1 hour VRN-ed specimens

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and 2 hours VRN-ed specimens was not large. This is because the hardened layer, such as Ti2N,
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TiNx, can prevent the penetration of nitrogen into the matrix. The concentration of the diffused
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nitrogen and the depth increase with increasing longer holding time, but the concentration of
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nitrogen atoms in the titanium matrix was limited and converged.

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From this graph, the percentage of the hardened area of the 1 hour VRN-ed specimens

increased abruptly compared to the 30 min VRN-ed specimens, which caused an increase in
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tensile strength. This hardening effect can be stronger than the softening effect at high

temperature, as explained above. In the case of the 2 hours VRN-ed specimens, as the holding
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time was increased, the softening effect of the matrix was applied to the specimens. On the
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other hand, the percentage of the hardened area was similar to the 1 hour VRN-ed specimens

shown in Fig. 6. Therefore, the tensile strength can be decreased slightly by the combination of
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a higher softening effect and relatively low hardening effect.

4. Conclusions

Vacuum rapid nitriding at 800 ℃ for various holding times was introduced to improve the
titanium surface. The thickness and hardness of the gradient-hardened layer increased with

increasing holding time. The diffusion layers were composed of inner-layers of Ti2N, TiNx, and

Ti[N], and increased with increasing holding time. Although the holding time increased at

800 ℃, grain growth of the alpha phase was suppressed in this diffusion layer, which was

attributed to the pinning effect by the diffusion of nitrogen atoms. This diffused layer can

suppress the penetration of nitrogen atoms into the matrix inside and increase the tensile

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strength under certain conditions.

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The hardness distribution according to the various holding times could be calculated and

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predicted as a function of the holding time and depth, which was compared with the actual

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measured hardness and in accordance with each other. The surface hardness of the VRN-ed

samples was improved 3~4 fold compared to pure titanium. The tensile properties of the VRN-

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ed samples were analyzed in terms of the relationship of the softening effect by high
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temperature and the hardening effect by the amount of hardened area. In addition, the tensile
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properties were excellent when they were treated thermo-chemically at 800 ℃ for the holding
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time of 1 hour.
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Acknowledgements
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This study was supported by the Korean government MSIP (the Ministry of Science, ICT and
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Future Planning), MOTIE (the Ministry of Trade, Industry & Energy), and Sunchon National
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University Research Fund in 2017.

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Figure captions

Fig. 1. Schematic diagram of tensile specimen referred to ASTM E8 (mm).

Fig. 2. OM and SEM microstructures of the pure titanium treated at 800℃ for (a) 30 min, (b)

1 hour, and (c) 2 hours.

Fig. 3. Comparison of the measured and the calculated hardness profiles in pure titanium treated

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at 800℃ for 30 min, 1 hour, and 2 hours.

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Fig. 4. Vickers hardness and the depth profiles for various holding times; 30 min, 1 hour, and

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2 hours.

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Fig. 5. Tensile stress-strain curves of the as-received pure titanium and the VRN-ed titanium

for various holding times.

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Fig. 6. Variations of the percent of hardened area as a function of the holding times at a certain
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hardness.
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100
R6
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6 10
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25

30 32 30 1.5
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Fig. 1.
 Optical Microscope Scanning Electron Microscope

(a)

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(b)
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N
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(c)
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Fig. 2.
 800
30min (calc)
30min (exp)

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1hr (calc)

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600
1hr (exp)
Vickers Hardness (Hv)

2hr (calc)
2hr (exp)

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400

200
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N
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0
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0 20 40 60 80 100

Depth(㎛)
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Fig. 3.
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 70 600
calc
exp
60 x=10㎛
500
x=30㎛

Vickers Hardness (Hv)

50

T
400

40

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Depth (㎛)

300
30

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20 200

10 100

0 U
N
0.5 1.0 1.5 2.0

Time (h)
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Fig. 4.
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 500
pure Ti
30 min
1 hr
2 hr
400

T
IP
stress (MPa)

300

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200

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100

0 U
N
0 10 20 30
strain (%)
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Fig. 5.
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 10
500Hv
450Hv

T
400Hv
Percent of hardened area (%)

8 350Hv
300Hv

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250Hv

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4

U
N
0
0.0 0.5 1.0 1.5 2.0 2.5
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Treatment time (h)
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Fig. 6.
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Table 1.
Chemical compositions of pure titanium.

Elements C Fe H N O Ti
wt. % 0.05 0.3 0.008 0.02 0.2 Bal.

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Table 2.

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Thickness of the diffusion layer of titanium samples treated under various holding times.

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Treatment parameters Thickness (㎛)
T (℃) t (h) Ti2N TiNx

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0.5 2.6 6.6
800 1 2.9 7.2
2 3.9
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Table 3.
Tensile properties of the VRN-ed samples as a functions of various holding times.
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Holding time As-received 30 min 1 hour 2 hours

YS (MPa) 345 318 336 335
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UTS (MPa) 449 412 435 424

EI (%) 32 29 28 25
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