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Hard Metals and Refractory Alloys

International Conference on

Tun,gsten, Hard'Metals and' Refractory Alloys

EFFECT OF TiC ON THE SINTERING AND WEAR BEHAVIOR OF A MODIFIED WC/Co HARDMETAL

Freddy J. Arenas', Emesto Rujzl, Carmen di Rausso'' and Cristina Grigorescu2

1. Department of Materials Technology, Instituto Universitario de Tecnologia, Km. 8 Carretera Panamericana, P.O. Box 40347, Caracas 1040-A. Venezuela

2. Department of Materials, INTEVEP, S.A. P.O. Box 76343, Caracas 1070-A. Venezuela

ABSTRACT

The microstructure, hardness, toughness and wear properties ofWC- TiC-Co-AI cennets were studied. The compositions followed the relation 90 w/o [(1-x)WC - xTiC] -10 w/o Co-AI where x= 0, 0.1, 0.15 and 0.20. Uniaxially pressed compacts were pressureless vacuum sintered at 13500C, 1400° and 1450°C obtaining a densification higher than 95% in all samples sintered at 14500C. Hardness value decreased with TiC from 87 HRA for the composition without TiC to 85HRA for the 18 w/o TiC composition whereas the fracture toughness was constant between 8.5 - 9.2 MPa""m. The results of the wear tests indicated that the friction coefficient at 298°K was averaged at 0.38 for all cermetsIHSS pair whereas the value for the cennets/WC-Co pair dropped from 0.16 for the material without TiC to 0.12 for the cermet with 18 w/o TiC. An in-depth microstructural development study has also been carried out using MEB and EDX in order to establish a microstructure-properties correlation.

INTRODUCTION

The nature and properties of many transition metal carbides, among them TiC, has been extensively studied [11 because of their interesting properties for high temperature technology applications. The extreme hardness combined with metallic electrical and thermal conductivity has suggested that TiC has a mixed nature bonding [21. The use of TiC in cemented carbides has also been studied and reviewed [31. The striking properties of this material in bulk WC- TiC-Co sintered samples for machining applications led to its use in combination with other materials for CVD coatings on cemented carbide substrates [41 and as a second phase in the first generation of ceramic cutting tools as Ah03- TiC [5,6]. In the case of the later developed ShN4 ceramics, the hardness and flank wear resistance have been improved by TiC addition, despite the decrease in strength [7]. The microstructural development is one of the key factors to attain high performance materials, in the case of WC- TiC-Co cennets a more complex microstructure than WCCo grades is obtained. During sintering a TiC - WC solid state solution process promotes the formation of (Ti, W)C rims surrounding undissolved TiC grains of the structure. This type of structure has been studied in systems where (Ti,Mo)(C,N) rims are surrounding Ti(C,N) grains and it was found that plastic deformation of WC-Co at high temperatures is enhanced when such phases are present in a rim! a- WC ratio close to 1:2 [8]. Though in our work high temperature mechanical properties are not evaluated the aim has been to determine the sintering, microstructure development and wear behavior in cermets where the higher volume fraction corresponds to hard a- WC grains.

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EXPE~NTALPROCEDURE

The starting powders used in the preparation of the cermets were all high-grade purity commercially available materials in the 1-3 micron range size, except the aluminum powder with an average particle size of 5.2 J.UD. Powder mixing according to the compositions given in Table I were made in an attritor with 3/16" WC spheres in acetone media during 1 hour at 500 rpm.

Table I. Compositions of different powder mixtures
Mixture Composition (vol. %) Composition (wt. %)
Hard phase Binder Hard phase Binder
WC TiC Co AI WC TiC Co AI
x=O 77,76 12,19 10,05 90 8 2
x=O.10 59,82 21,17 10,42 8,59 81 9 8 2
x=O.15 53,42 28,72 9,79 8,07 77 13 8 2
x=O.20 46,43 36,97 9,10 7,50 72 18 8 2 The dry mixed powders were uniaxially pressed into cylinders of dimensions 25 mm diameter x 5 mm height Green samples compaction was performed at 350 MPa. Green densities were determined based on physical measurements. For calculations, the theoretical density of each composition was estimated by the rule of mixtures.

The compacts were placed in a graphite box on a loose graphite powder bed and sintered at 1350, 1400 and 1450°C for 60 min. using a heating rate of 5°C/ min. The set of specimens for wear performance study were vacuum pre-sintered at 1100°C, surface ground at 600 SiC grit and then sintered at 1400°C for 60 min. The sintered density was measured according to ASTM B311-93 based on the water displacement method and Archimedes principle to determine the apparent porosity.

For metallographic specimen preparation the sintered samples surface was polished according to conventional procedure down to 1 f.UD. diamond paste and the microstructure was developed using Murakami's reagent following ASTM B657-87. The polished surfaces were then evaluated using a scanning electron microscope (SEM), Philips XL30 coupled with an Energy Dispersive X-ray (EDX) Spectrometer EDAX DX4 with an ultra thin window (UTW) capable of detecting from Boron.

Vickers (using 30 Kg. load) and Rockwell HRA hardness were measured according to ISO 3878 and ASTM B294-92 respectively. The Palmqvist/Vickers fracture toughness was determined by measuring the crack length at the comers of five indentations taken under 30 kg. load on residual stress free polished sample surfaces using SEM in secondary electron (SE) mode. The fracture toughness Krc was calculated using the Shetty et al. [9] model, as per the equation:

Krc (MPa. m 112 ) = 0.0889 (HW)112 (1)

where H is the hardness (MPa) and W is the crack resistance parameter in MNm-1 •

The friction coefficient and dry sliding wear performance was evaluated using a pin on disc apparatus (CSEM tribometer), according to ASTM G99-9O. The experiments were conducted in air atmosphere at room temperature under 10 N load at a sliding speed of 0.1 ms". The pins used were commercially available quenched high speed steel and WC-Co 6 mm. balls. Before the tests, the tribological specimens pairs were cleaned in an ultrasonic bath, weighed and the average surface roughness measured to the disk specimens. Wear tracks and products, both in the pin and disc, were evaluated by SEM and EDX respectively.

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RESULTS AND DISCUSSION

• Densification behavior

The densification values obtained for the different compositions and sintering temperatures used are shown in Table II. It is more significant the increase in the relative density with temperature rather than with the TiC content being practically constant in the samples for the tribological study presintered during 30 min. at 11 OO°C and then sintered at 1400°CI 60 min.

Table II. Relative densities (%) values for 90 w/o [(1-x)WC - xTiC] -10 w/o Co-AI cennets

Sintering temperature eC)
Composition 1350 1400 1450 1100/1400
x=O 90,1 91 93 94,4
x=O.10 69 92 97 96,4
x=O.15 70 91 % 95,8
x=O.20 70,1 91 96 %,4 Fig. 1 shows the variation in sintered density with increasing amounts of TiC, however it also has to be taken into account the effect of the 2 w/o AI added on the theoretical density, i.e. in the case of WC-Co composition its value is approximately 14.6 g.cm".

The linear shrinkage values were between 17-22 % for the composition range from 0 - 18 w/o TiC.

-+- Theoretical density
13 _ 1100/14000c
- -e--14OOOC
'"
E """_13500c
~
C)
-
:11
c:::
G)
"'C 10,12
-
c::: 9,76
e
co 9,2
0- 9
~

7,1
7
0 9 Composition % TIC 19 Fig. 1. Influence of TiC addition on the samples sintered density

• lkficrost.nucture

The SEM microstructures corresponding to compositions pre-sintered at 11000C and then sintered at 14000C are shown in Fig. 2a-2d. EDS analysis has shown the presence of four phases: prismatic shaped

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,shaped we grains, TiC, y- (W,Ti)C and cobalt-aluminum. The Fig. 2g is typical of samples sintered at 14'50aC where it was found needles of the double carbide phase. Fig. 2a and 2b show in SE mode the morphology of the phase obtained where Co and Al are in higher concentration. According to the EDS evaluation and homogeneous appearance it seems that the sintering conditions used allowed the formation of an intermetallic phase but incomplete melting and therefore a homogeneous distribution of this new phase. Fig. 2c-2f are BSE images for 9 and 18 wlo TiC addition, it might be observed the core-rim structure formed between pure TiC and the solid solution y- (W,Ti)C phases, the 0.8 urn average grain size WC phase but it cannot be detected the intermetallic phase clearly observed in the compositions without TiC. Needle-like y- (W,Ti)C grains richer in WC were obtained both at 1400 and 1450°C sintered samples 'being in a higher quantity at the latter case.

Fig. 2e - 2f. Composition with 18%TiC sintered at 1400°C

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Fig. 2g. Composition with 18%TiC sintered at 1450°C • Hardness and toughness

Rockwell hardness values for 60 Kg (lIRA) and toughness values for 30 Kg followed the general trend of antagonistic properties as depicted in Fig. 3. Hardness slightly decrease from 87 to 85 HRA with the TiC addition for the samples sintered in two steps - 1100°/30 min. and 1400°C/60 min. This behavior might be explained by the increase in the general hard phase grain size as the '1- (W,Ti)C phase develops in a heterogeneous morphological form but with a grain size smaller than 5 microns. Regarding K1C values a 40-50% improvement has been achieved with the new microstructure developed where crack-bridging mechanism took place. The proposed criteria for reliable crack measurement of cia 21.3 and O.25S; l/a S; 2.5 for toughness calculations has been satisfied.

10 88
9,5 ____ Fracture toughness, MPam112
s --+- Hardness HRA
9
E
eli 8,5
Q. ~
~
• 8 :t:
ell •
at 7,5 ell 86
c at
~ C
C) "E
:::I 7
S III
:t:
! 6,5
.a
u 6
I!!
II..
5,5
5 84
0 9 13 18
Composition (%TiC) Fig. 3. Hardness and fracture toughness behavior in WC- TiC-CoAl cermets. • Wear behavior

The friction and wear characteristics were determined at 25°C under two different tribological pairs with HSS and WC-Co pins and sliding distances up to 1000 m. The results are shown in Table 3. The mean friction coefficient obtained with the HSS balls was between 0.36-0.41. It decreased to 0.13 - 0.23 for the WC-Co pins. As it can be seen in Fig. 4 the increase in the friction coefficient with sliding distance for the cermetIHSS tribological pair elucidates a wear material transfer mechanism which was evidenced in the SEM and EDS examination. However, in the case with WC-Co the friction coefficient was steady along the 1000 m. sliding distance without any increase and, it is even observed a slight decrease in the test with the 9 w/o TiC composition from 0.2 at the end of the running-in to a 0.15 at the completion of test.

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Table 3a. Friction and wear properties ofWC-TiC-8 w/o Co-2w/o AI materials with high speed steel pin at ambient temperature

~a:ls (%TiC)

Mean Friction. Pin weight Wear rate Disc weight Wear rate

coefficient loss (Ve), mnr' in pin (nun3/N.m) loss (Vd), mnr' in disc (nun3/N.m)

o 9 13 18

0,36 1,345E-02 2,69E-06 1,161E-Ol 2,50E-05

0,39 1,182E-02 2,36E-06 2,750E-Ol 5,50E-05

0,41 1,155E-02 2,31E-06 3,352E-Ol 6,70E-05

0,38 8,760E-03 1,75E-06 3,820E-Ol 7,64E-05

Table 3b. Friction and wear properties of WC- TiC-8 w/o Co-2w/o Al materials with WC-Co pin at ambient temperature

Materials (%TiC)

coefficient

Mean Friction Pin weight Wear rate Disc weight

loss (Ve), mm" in pin (nun3/N.m) loss (Vd), mnr'

o 9 13 18

0,17 0,16 0,23 0,13

1,497E-03 1,49E-07 3,899E-04

1,851E-03 1,85E-07 2,959E-Ol

2,920E-03 2,92E-07 4,703E-02

3, 182E-05 3,18E-09 1,620E-02

4,36E-08 2,95E-05 5,OlE-06 1,72E-06

Wear rate

in disc (nun3/N.m)

0,4 S
0,40
..
.2 0,35
<>
IS
§ 0,30
c 0,25
.9
W CoCo-AI t;
HSS pin ·c 0,20
::.
0,15
0,10
200 400 600 800 1000 0
Distance (m) 0,18
.. 0,16
"
'u 0,14
IS
"
8 0,12
c
0
~ 0,1
0,08
0,06
0
0,5
'5 0,4
'0
E
§ 0,3
§ 0,2
~n
·c
~ 0,1
0
0
0,30
0,25
li
c:; 0,20
IS
8 0,15
o
=
0
'g 0,10
-e
I:r.
0,05
0,00
0 WC-18 w/oTiC-Co-AI HSS pin

200

400 600

Distance (m)

W C-!3 w/oTiC-Co-AI W COCo pin

200 400 600 800 1000 Distance (m)

0,00 +----..,....----..,....------1

0,25
.. 0,20
.,
'u
15 0,15
.,
8
c 0,10
.g
o
-e 0,05
~
0,00
0 W C-9w/oTiC-Co-AI H S Spin

200

400

"5

~ 0,10

8

c:

.g 0,05

o ·c ~

Distance (m)

WC-9 w/oTiC-Co-AI WC-Co pin

200 400 600 800 1000 Distance (m)

WC- 18 w/o TiC-Co-AI WC-Co pin

o

200 400 600

Distance (rn )

Fig. 4. Variation of friction coefficient with sliding distance at ambient temperature, load 10 N, sliding speed 0.1 mls.

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600

Fig. 5a-5e swnmarize different aspects of the wear tracks on the discs evaluated with the HSS ball. It can clearly be observed that no modification of the microstructure of the materials evaluated occurred, being in some cases for the samples tested with WC-Co very difficult to even evaluate the wear track width and detect some grooving. No pull-out of the grains of the different phases present was detected. SEM micrographs shown in Fig. 5b and 5d revealed iron debris being 14 w/o and 17 w/o the average values respectively, obtained by EDS in five different zones on the wear track. Since the wear characteristics are contradictory to this increase in Fe, it could rather be associated to the formation of a thin adhesive smearing layer or patches of iron oxide by the increase in friction with sliding distance. This oxide layer being mechanically unstable breaks apart and promotes the cermet wear. Due to the increase in friction with distance and as the tests were carried out in air the Qresence of aluminum in the materials composition could also promote the formation of aluminum oxide which is highly abrasive. This last assumption is supported by the wear behavior in the tribological pair with the WC-6Co because in these cases as the friction even decreased with the sliding distance the wear rates obtained were 1-2 orders of magnitude lower.

(c)

(a)

18 w/o TiC

(b)

9 w/o TiC

(d)

e) Typical HSS pin wear track left after test on 9 w/o TiC cermet. Iron oxide formation detail.

Fig. 5. SEM migrographs of wear tracks in WC-TiC-Co-AI cermets and HSS pin

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It is shown in Fig. 6a-6c a view in the outer limit of the wear track developed with a WC-6Co pin on a 18 w/o TiC material, a topographical image (Fig. 6b) of tracks made with WC-Co (left) and HSS (right) on the material without TiC, such pattern was followed by all the other materials evaluated and a magnified image where it is detailed the fracture pattern due to the abrasive wear mechanism observed (Fig.6c).

Fig. 6. (a) SElof a wear traCk se~tion in 18 w/o TiC where it can hardly be seen the groove formed (marked). It is appreciated the Imaltere<J: microstructure by the wear test. (b) Couple of characteristic wear tracks where it is elucidated the diffe~llit wear meQbanism acting. (c) SEI showing a topographic detail in the track.

CONCLUSIONS

• Lower density highly densified materials with rather acceptable mechanical properties might be produced by low cost controlled pressureless sintering. The addition of TiC has lead to an increase in the order of 40-50% in toughness with a decrease of only 2% in the hardness.

• Wear rate values of 10-6 mm3/(N.m) were measured for compositions with TiC dry sliding against WC-6Co in laboratory pin-on-disk measurements. Such results allow to consider the materials manufactured and tested in this work wear resistant.

REFERENCES

1. G. S. Upadhyaya, Nature and Properties of Refractory Carbides, Nova Science Publishers, Inc., New York, NY, 1996, p. 1

2. P.T. Jochym , K. Parlinski and M. Stemik, "TiC lattice dynamics from ab initio calculations", Eur. Phys. J. , B 10, 1999, pp. 9-13.

3.H.E. Exner, "Physical and chemical nature of cemented carbides", Int. Met Rev. 4, 1979, pp. 149-173.

4. S. Ruppi, B. Hogrelius, M. Muhtiranta, "Wear characteristics of TiC, Ti(C,N), TiN and Ah03 coatings in the turning of conventional and Ca-treated steels", Int. J. of Hard Met. & Refractory Mat., 16, 1998, pp. 353-368.

S.A. Krell, P. Blank, L.-M. Berger, V. Richter, "Sub-micrometer alumina cutting ceramics for continuous and discontinuous machining of hard materials", Ceramic Forum Int. cfilBer. 76, 4, 1999, pp. 23-29

6. T. Takahashi, Y. Katsumura, H. Suzuki, "Cutting performance of white ceramic tools having high strength, J. Japan Soc. Of Powder and Powder Metall. ", 41,1,1994, pp.33-37.

7.H.z. Miao, L.H. Qi, Z.Q. Zeng, X.Q. Hu, D.l. Ma, "SijNa-based and Ti CxN1•x - based ceramic cutting tools", Ceramics: Getting into the 2000's Part D, compiled by P. Vincenzini, Techna srl., Faenza, 1999, p.l65.

8. T. Viatte, S. Bolognini, T. Cutard, G. Feusier, D. Marl, W. Benoit, "Investigation into the potencial of a composite combining toughness and plastic deformation resistance", Int. J. of Hard Met. & Refractory Mat., 17, 1999, pp 79-89 9. D. K. Shetty, I. G. Wright, P. N. Mincer, A. H. Calver, "Indentation fracture toughness of WC-Co cermets", J. Mat. Sci., 20,1985, pp. 1873-1882.

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