Microstructure and Mechanical Properties of NiTi2-TiB Composite Fabricated by Spark Plasma Sintering


Composites of NiTi2-TiB have been fabricated using spark plasma sintering and mechanical properties have been investigated. Dense specimens of monolithic NiTi2 have been obtained by the sintering at 950?C. By the x-ray diffraction measurements it has been shown that NiTi2 co-exists with TiB in equilibrium at 950?C. The bending strength of NiTi2-TiB composite increases with increasing the volume fraction of TiB2 up to 60 vol%. The maximum bending strength of 730 MPa has been obtained for NiTi2-60vol% TiB2. The Vickers hardness also increases with increasing the volume fraction of TiB up to 70% and the highest Vickers hardness of 1620 Hv has been obtained for NiTi2-70%TiB.

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Yoshida, M. , Shiraishi, H. and Ikki, N. (2015) Microstructure and Mechanical Properties of NiTi2-TiB Composite Fabricated by Spark Plasma Sintering. World Journal of Engineering and Technology, 3, 84-88. doi: 10.4236/wjet.2015.33C013.

1. Introduction

There are three intermetallic compounds in the Ni-Ti system, Ni3Ti, NiTi and NiTi2, among which NiTi has received much interest for its shape memory effect [1]. NiTi2 has favorable properties such as high corrosion resistance and wear resistance and Coating of Ti base alloys by NiTi2 films has been examined [2]-[4]. On the other hand, bulk application of NiTi2 has not been reported probably because of its poor ductility caused by the complicated E93-type lattice structure which contains 96 atoms in a unit cell [5].

The effective method to improve the mechanical properties is adding reinforcement components. Titanium boride (TiB) has many excellent properties such as high hardness (Vickers hardness, Hv, 16 GPa), high strength, high Young modulus (E = 371 GPa), low density (4.54 × 103 kg/m3) and good corrosion resistance [6] [7]. It has needle like shape which is favorable for reinforcement materials [8]-[10].

In the present study we have fabricated monolithic NiTi2 and NiTi2-TiB composite by using Spark Plasma Sintering (SPS) method and investigated the Vickers hardness and bending strength. It has been shown that NiTi2 is brittle and has poor fracture toughness which can be improved by the addition of TiB.

2. Experimental Method

The raw materials were commercially available TiB2, Ti and Ni powders of 99.9% purity (all powders by Furuuchi Chemical Corp.). The diameters of TiB2, Ni, and Ti powder particles were 2 microns, 10 microns and 30 microns, respectively. TiB is formed from TiB2 and Ti during the sintering by the reaction,


A graphite die having an internal diameter of 20 mm and a wall thickness of 10 mm was filled with 5 g of the mixed powders of TiB2, Ni and Ti and sealed by two graphite punches and mounted on the equipment, LABOX- 630, fabricated by Sinter Land Ltd. The sintering temperature is determined as 950˚C since NiTi2 melts peritectically at 984˚C. The mixed powders were heated to 950˚C with the rate of 50˚C/min, kept for 20 minutes, and then furnace cooled to room temperature. The temperature was measured using the infrared radiation thermometer IR-AHS0 fabricated by Chino Corporation. Sintering was performed in a vacuum with a residual pressure of 5 Pa. A uniaxial pressure of 20 MPa was applied during the sintering.

Scanning electron microscope (SEM) observation was performed using a Hitachi H-3300 instrument. X-ray diffraction patterns were measured using Rigaku X-ray diffract meter with Cu-kα radiation source. Vickers hardness was measured using a Shimadzu HMV-2 micro hardness tester with the load of 9.8 N and pressing time of 15 seconds. Five indentations are made to measure the length of indentation diagonals. To perform the bending test, rectangular shape samples with the size of 2 × 3 × 20 mm3 were cut by the electric discharge. Three point bending tests were performed using a Shimadzu AGS-J test machine with the crosshead speed of 0.5 mm/min and the span of 15 mm. Four specimens ware measured for each composition.

3. Results and Discussion

Figure 1 shows the X-ray diffraction pattern of NiTi2, NiTi2-20vol%TiB, NiTi2-40vol%TiB and NiTi2-60volt% TiB specimens sintered at 950˚C. In the X-ray diffraction patterns of NiTi2, peaks from cubic E93 type structure are observed. In the X-ray diffraction pattern of NiTi2-TiB composites, peaks from TiB have been observed as indicated by arrows in addition to peaks from NiTi2 showing that NiTi2 and TiB co-exist in equilibrium at 950˚C. It should be noticed that no peaks from TiB2 is observed indicating that the chemical reaction of TiB2 and Ti have completed during the sintering process at 950˚C.

In Figure 2 is shown the SEM images of the polished surface of (a) NiTi2-40vol%TiB and (b) NiTi2-70vol%TiB. In Figure 2(a), it has been observed that dense samples are obtained with TiB grains of needle like shape dispersed in NiTi2 matrix by the sintering at 950˚C. On the other hand, in Figure 2(b), some cracks have been observed as indicated by arrows probably because of the thermal mismatch between TiB and NiTi2.

We have performed the 3-point bending test and the Vickers hardness test to measure the mechanical properties of NiTi2-TiB composites. In Figure 3 is shown the dependence of the bending strength of NiTi2-TiB com- posites on the amount of TiB. The bending strength of NiTi2-10vol%TiB is 290 MPa, which increases as the amount of TiB increases up to 60% and the highest bending strength of 730 MPa has been obtained. The bending strength decreases as the amount of TiB increases above 60vol%. We could not measure the bending

Figure 1. X-ray diffraction pattern from NiTi2-TiB composites sintered at 950˚C.

(a) (b)

Figure 2. SEM image of (a) NiTi2-40vol%TiB and; (b) NiTi2-70vol%TiB.

Figure 3. Bending strength of NiTi2-TiB composites.

strength of monolithic NiTi2 because NiTi2 specimens have been cracked during the cutting procedure by using electric discharge. This decrease of the bending strength may be caused by the cracks as observed in Figure 2(b).

Figure 4 shows the dependence of the Vickers hardness of NiTi2-TiB composites on the amount of TiB. The Vickers hardness of NiTi2 is 650 Hv. The Vickers hardness of NiTi2 increases as the amount of TiB increases up to 70 vol% and decreases above 70%. The largest Hy value is 1620 Hv for NiTi2-70vol%TiB specimen. .

Zhang et al. have fabricated Ti-TiB composite and investigated the bending strength and the Vickers hardness [11]. They have obtained the bending strength of 608 MPa and Vickers hardness of 18.3 GPa. The bending strength of NiTi2-TiB, 730 MPa, is higher than that of Ti-TiB composite while the Vickers hardness of NiTi2-TiB, 1620 Hv (15.9 GPa) is lower than that of Ti-TiB composite. This fact indicates that composites of intermetallics and ceramics are promising as well as metal-ceramics composites.

In Figure 5 is shown the SEM images of the fracture surface of (a) NiTi2, (b) NiTi2-20vol%TiB and (c) NiTi2-60vol%TiB and (d) NiTi2-80vol%TiB. In Figure 5(a) it is shown that the fracture surface of NiTi2 is composed by a few flat steps indicating that NiTi2 has low fracture toughness. The fracture surface of NiTi2-20wt%TiB contains several flat surface separated by TiB grains. It seems that the crack propagation is impeded by TiB grains. The dimension of the flat surface becomes smaller in the NiTi2-60wt%TiB specimen in comparison with that of NiTi2-20wt%TiB specimen, which may cause the improvement of the bending strength. In the fracture surface of NiTi2-80vol% TiB specimen is observed granular regions where bonding between grains seems to be weak. The amount of NiTi2 is not sufficient to fill the space between TiB grains in NiTi2-80vol%TiB specimen.

4. Conclusion

Dense NiTi2 and NiTi2-TiB composite specimens have been fabricated using spark plasma sintering at 950˚C. The bending strength of NiTi2-TiB increases as the amount of TiB increases up to 60% and the highest value of

Figure 4. Vickers hardness of NiTi2-TiB composites.

(a) (b)(c) (d)

Figure 5. Fracture surface of (a) NiTi2; (b) NiTi2-20%TiB; (c)NiTi2-60%TiB and (d) NiTi2-80%TiB.

730 MPa is obtained for NiTi2-60vol%TiB. The Vickers hardness of monolithic NiTi2 is 650 Hv, which increases up to 1620 for NiTi2-60%TiB. In NiTi2-TiB composite, crack propagation is observed to be impeded by TiB grains. Those values are nearly the same as those obtained for Ti-TiB composite and it has been shown that composites of intermetallics and ceramics are promising as well as metal-ceramics composites.


This work is supported by the Grant-in-Aid for Science Research from Japan Society for the promotion of Science (Kakenhi 25420739).


*Corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.


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