Formation of (W,V)Cx layers at the WC/Co interfaces in

the VC-doped WC-Co Cemented Carbide

I. Sugiyamaa, Y. Mizumukaib, T. Taniuchic, K. Okadac, F. Shirasec,

T. Tanased, Y. Ikuharab,e, T. Yamamotoa,e,f

aDepartment of Advanced Materials Science, University of Tokyo, 5-1-5,Kashiwanoha,

Kashiwa-shi, Chiba 277-8561, Japan, e-mail : [email protected]
bEngineeringResearch Institute, The University of Tokyo, 2-11-16, Yayoi, Bunkyo-ku,
Tokyo 113-8656, Japan
cTsukuba Plant, Mitsubishi Materials Corp., 1511 Furumagi, Joso-shi, Ibaraki
300-2795 Japan
dJapan New Metals Co., Ltd., 1-6-64, Sen-nari-cho, Toyonaka-shi, Osaka, Japan
eJapan Fine Ceramics Center, 2-4-1, Rokuno, Atsuta-ku, Nagoya 456-8587, Japan
fDepartment of Quantum Engineering, Nagoya University, Furocho, Chikusa-ku,

Nagoya 464-8603, Japan

Abstract

The (W,V)Cx thin layers at the WC/Co interfaces in the oil-quenched

WC-12mass%Co-0.5mass%VC hard metal were investigated by high resolution

transmission electron microscopy. The (W,V)Cx thin layers are formed on the liquid

phase sintering state, because they are observed on the micro-facets and some of them

are included inside the WC grains. The grain growth rate strongly depends on whether

the thickness of the (W,V)Cx layers is more than one layer or less during liquid-phase

sintering.

Keywords

WC-Co, hard metals, cermets, cemented carbides, Transmission Electron

Microscope (TEM), X-ray Energy Dispersive Spectroscopy (EDS)

1. Introduction

WC-Co hard metals are practically important materials widely used for cutting tools,

mining tools, and many other wear parts. The hard metals are generally fabricated by

liquid-phase sintering above the eutectic temperature of a ternary system of W, C, and

Co [1]. After sintered, they show the composite structure of hard WC grains bound with

Co-based phase [2]. In the hard metals, decreasing the WC grain size is one of the

effective ways to improve their mechanical properties [3]. In the purpose of decreasing

the grain size, other carbides are often added as grain growth inhibitors [4]. Especially,

VC remarkably inhibits the WC grain growth during liquid-phase sintering [5]. To

reveal the grain growth inhibition mechanism, there are many reports which observed

the micro structures in other carbides doped hard metals [6-10]. However, so far, the

grain growth inhibition mechanism has not been revealed in detail.

Though atomically scale analysis at the WC/Co interfaces were carried out to reveal

the grain growth inhibition mechanism, contradictory reports about the VC-doped hard

metal have been proposed by several research groups. Yamamoto et al. revealed that the

stairs-like structure called “micro facets” appears at the WC/Co interfaces by doping

VC [11], in contrast to flat interfaces and sharp corners with small diagonal habits in the

_
undoped hard metal [12]. The micro facet structure consists of fine (0001) and {1010}
habit planes of the WC grains. In addition, V-rich layers are formed on the each habit

plane. Lay et al. revealed that the V-rich layers at the WC (0001)/Co interfaces are NaCl

type structure (W,V)Cx [13, 14]. These studies draw the conclusion that the existence of

the (W,V)Cx layers on the sintering state is the key to inhibit the grain growth of the WC

grains. Furthermore, theoretical calculation concerning the thickness of the (W,V)Cx

layers on the sintering state was recently reported by Johansson et al.[15, 16].

According to their calculation, the existence of two layers of the (W,V)Cx is the most

energetically stable on (0001) habit planes of the WC grains. Their calculation results

support the experimental studies mentioned above [11, 13, 14]. In contrast, there are

contradictory results concerning the formation of the thin (W,V)Cx layers. Kawakami et

al. insisted that the (W,V)Cx layers are not formed on the sintering state [17, 18]. By

comparing the thickness of the (W,V)Cx layers in normally and rapidly cooled

specimens after sintering, they found that the (W,V)Cx layers are thinner in the rapidly

cooled specimen. In the consequence, they concluded that the (W,V)C x layers were

formed in the cooling process, not on the sintering state. They insisted that the WC grain

growth inhibition is caused by the adsorption/desorption of doped V atoms at the

WC/Co interfaces without forming the (W,V)Cx layers.

For the bottom-up design of the hard metals, it is very important to clarify the grain
growth inhibition mechanism due to VC doping. In this purpose, it must be revealed

whether the (W,V)Cx thin layers are formed or not on the sintering state. However, there

is no report which shows direct evidence for the existence or not of the (W,V)Cx layers

on the sintering state. In this study, the existence of the (W,V)Cx layers at the WC/Co

interfaces during the liquid-phase sintering are revealed by the high resolution

transmission electron microscopy (HRTEM) and the X-ray energy dispersive

spectroscopy (EDS).

2. Experimental procedure

The composition of the hard metals used in this study was

WC-12mass%Co-0.5mass%VC. The carbon content was controlled close to the lower

limit of three phase region of WC, Co based phase, and Co3W3C [19]. The hard metals

were prepared from the raw powder of WC (Japan New Metals Co. Ltd., nominal grain

size of 0.8m), Co (Umicore Co. Ltd., 1.4m) and VC (Starck Co. Ltd., 1.6m) by an

ordinary liquid-phase sintering method. All powder including VC were weighed to be

aimed composition. After that, they were attritor-milled, dried and pressed into a shape

of 10x10x8mm3 under a pressure of 150MPa. After that, the green compacts were

liquid-phase sintered at 1653K for 1h in a vacuum, and then, quenched by dropping it

into oil. The cooling rate is estimated to be higher than 100K/sec. The carbon content

was checked by the saturated magnetization measurement and the microstructure,

whether there are Co3W3C phase and free carbon or not, was checked by the scanning

electron microscope (SEM, S-800, Hitachi Co. Ltd., Japan). The microstructure was

investigated by HRTEM (JEM-2010F, JEOL Co. Ltd., Japan), and the compositional

analysis was performed by EDS equipped on the JEM-2010F. Thin foils for TEM

observation were prepared by the conventional ion-milling technique with Ar ion beam,

in addition to mechanical grinding and polishing.

3. Results

Figure 1 shows a TEM bright field image of the typical WC grain in a VC-doped hard

_
metal, which was taken from [1210] of the WC grain. The micro facets are also

observed in the oil-quenched hard metals. The micro facets consist of fine (0001) and

_
{1010} habits, and a lump of (W,V)Cx is observed at a corner of the two habits, which is

the same result to the previous studies [11, 13, 14]. Fig. 2 and 3 are magnified HRTEM

_
images of the (0001) and {1010} habits, respectively. In the images, W atomic columns

are indicated by the circles. There are very thin atomic layers at the WC/Co interfaces

showing a different crystal structure from that of the WC grain. These layers show the
same structure to the NaCl type structure of (W,V)Cx, which was observed by Lay et al.

[13, 14]. The thickness is one or two layers at the (0001) habits and less than one layer

_
at the {1010} habits, which are almost the same to the observation results by Kawakami

et al. [17]. As their results, the layers are confirmed to be thicker at the (0001) habit than

_ _
at the {1010} habit. The (W,V)Cx thin layers are not formed continuously on the {1010}

habit whereas they fully covers the interface of (0001) habit.

Figure 4(a) shows a HRTEM image at a corner of the two habit planes of a

micro-facet. It is noticeable that the line contrast as shown by the arrow is observed at

the interiors of the WC grains. It is often observed in the VC-doped hard metal. The line

contrast starts at the WC/Co interface and ends at the interiors of the WC grains. Fig.

4(b) shows a magnified HRTEM image of the area around the line contrast as shown by

the square in Fig. 4(a). W atomic columns are indicated by the black dots. There are one

or two layers of the structure different from the WC grain as shown by the white dots.

The EDS analysis results are shown in Fig. 4(c). Each profile was taken at the each

point shown in Fig. 4(a), respectively. The electron probe diameter used for the analysis

is less than 1nm and the distances between each point are 2nm. The V-Kα line is clearly

detected only on the line contrast. These results show that the line contrast is due to

NaCl type structure (W,V)Cx. The fact indicates that the (W,V)Cx is already formed at
the sintering temperature because the cooling rate during the oil-quenching is too high

to form the (W,V)Cx layers inside the WC grains.

4. Discussions

Two possibilities can be considered concerning the formation of the (W,V)Cx thin

layers inside the WC grains. One is the incorporation by the grain growth of the WC

grains. The micro facet starts to form at the initial state of the sintering process, even at

the solid state [11], which accompanies the formation of the (W,V)Cx layers at the

WC/Co interfaces. Step migration proceeds on the two habit planes of the WC grains

during the liquid-phase sintering. Even in the VC-doped hard metals, the slow grain

ripening occurs during the liquid phase sintering [4]. The step migration proceeds over

the (W,V)Cx layers which are already formed on the habit plane. This results in the

incorporation of the (W,V)Cx layers into the WC grains. The other possibility is that a

WC grain axially aligned and attached on another WC grain, where micro facet is

already formed. This case also results in incorporating the (W,V)Cx layers into the WC

grains. In both case, the (W,V)Cx layers are included inside WC grains. The important

point is that forming the (W,V)Cx layers on the cooling state is impossible because the

time required for cooling is much shorter than that for the grain growth or the aligning
and attaching [4]. Consequently, the (W,V)Cx layers exist at WC/Co interfaces during

liquid-phase sintering temperature.

Success in observing microstructure at sintering temperature enabled us to discuss the

grain growth mechanism. The layers are fully formed on (0001) habits with one or two

_
layers while partially formed on {1010} habits. Considering the grain growth inhibition

due to VC doping, it must be noted that the grain growth inhibition mechanism is

_
different between (0001) and {1010} habit planes. There are one or two layers of the

(W,V)Cx on (0001) habit planes on the sintering state as shown in Fig. 2. Namely, as for

(0001) habits, the formation of the (W,V)Cx layers inhibits the WC grain ripening as

_
reported by Yamamoto et al.[11] and Lay et al.[13]. In contrast, as for {1010} habit

planes, the (W,V)Cx layers are partially formed as shown in Fig. 3. A part of this habit

planes directly contact to the liquid-phase on the sintering state. Therefore, the grain

_
growth inhibition mechanism on {1010} habit planes is adhesion process of V atoms, as

Kawakami et al. suggested [17].

Considering the grain growth inhibition mechanisms described above, step migration

_
of WC grains should be slower on (0001) than on {1010} habit planes. According to the

_
previous reports, step migration at the WC/Co interfaces is faster at {1010} than at

(0001) habit planes of WC grains in undoped WC-Co hard metals [20, 21]. The growth
rate inhomogeneity of each habit becomes larger in other carbides doped hard metals

[22]. Hence, the difference of the growth rate between the two habits predicted from the

grain growth inhibition mechanisms corresponds to the experimental results about the

WC grains growth rate inhomogeneity.

_
The difference of the thicknesses of the (W,V)Cx layers of (0001) and {1010} habit

planes possibly concerns to the lattice coherency difference between (W,V)Cx and WC,

whose structures are fcc and hcp, respectively. Although the lattice constant of (W,V)Cx

changes with carbon content, (W,V)Cx exhibits the higher lattice coherency in

_ _
[111](W,V)Cx/[0001]WC with (111)(W,V)Cx/(0001)WC than in [11 0](W,V)Cx/[101

_ _
0]WC with (110)(W,V)Cx/{1010}WC. The difference in the coherency between WC

grains and the (W,V)Cx layers is closely related to the grain growth rate in each habits.

5. Conclusion

In this study, the formation behaviors of the (W,V)Cx layers at the micro facets were

investigated by high-resolution transmission electron microscopy in the oil-quenched

VC-doped WC-Co hard metals. The thickness of the (W,V)Cx layers decreases to be one

_
or two layers at the WC (0001)/Co interfaces and one or less at the WC {1010}/Co

interfaces by oil-quenching. The layers also exist in the WC grains. This is the evidence
that the (W,V)Cx layers exist at the WC (0001)/Co interfaces during the liquid-phase

sintering state. The grain growth inhibition due to VC doping is closely related to the

formation of the (W,V)Cx layers.

Acknowledgement

This study was supported by a grant-in-aid for scientific research for the

priority area ‘‘Nano Materials science for atomic scale modification 474’’ 19053001

from the Ministry of Education, Culture, Sports, Science and Technology of Japan.
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Figure Caption

Fig. 1 TEM bright field image of a micro facet at the corner of a typical WC grain in

_
VC-doped hard metal. The image is taken from [1210] of the WC grain.

Fig. 2 The magnified HRTEM image of the WC(0001)/Co interface at the area as shown

_
by the black box in Fig. 1. The image is taken from [1210] of the WC grain. The black

dots show the W columns of WC, and the white dots show the W columns of the

(W,V)Cx layers.

_
Fig. 3 The magnified HRTEM image of the WC{1010}/Co interface at the area as

_
shown by the white box in Fig. 1. The image is taken from [1210] of the WC grain. The

black dots show the W columns of WC, and the white dots show the W columns of the

(W,V)Cx layers.

Fig. 4 (color online) (a) HRTEM image of a micro facet with the line contrast inside a

_
WC grain taken from [1210] of the WC grain. (b) A magnified HRTEM image at the

white box in Fig. 4(a). (c) EDS profile taken at A, B, and C indicated in Fig. 4(a),

respectively.