Nickel in Hardmetals

Eng. Fabio Miranda

UNIWIDIA – Coop. Trab. em Ferr. De Metal Duro
[email protected]

ABSTRACT

Cemented Carbides were first used in Germany in 1925. Although theu

are sometimes called hardmetals, they are not metal but complex materials
consisting of hard particles (WC) and metals (Co). Hardmetals, and the nickel
used in their production, have benefitted industry considerably. The binder
phase was tested analytically and it was found that the tungsten content of
the binder depends on the carbon content of the alloys, on grain size of the
carbide used, on nickel content and on sintering and cooling conditions.
KEY WORDS: CEMENTED CARBIDES, NICKEL BONDED TUNGSTEN-
CARBIDE, NICKEL POWDER and CARBIDE GRAIN SIZE.

INTRODUCTION

Cemented carbides have been used since 1925 and are essentially
carbide particles of a refractory metal cemented by a metal or alloy of the iron
group, cobalt or nickel. There are several reasons why choose a metal as
cement for carbides, for instance Nickel:

a) High melting point (nickel 1453ºC);

b) Form a liquid phase with tungsten-carbide at a suitable temperature

(nickel does at 1310 ºC. This liquid pulls the sintered parts together by
surface tension and eliminates voids;

c) Dissolve WC (nickel forms a eutectic with at ~1310 ºC and dissolves

4% WC at that temperature);

d) On cooling, the binder should reprecipitate WC, leaving a tough

matrix with dispersed carbides (nickel can produce particles around 1-
2µm).

e) No structural defects (pores,etc), and a good surface roughness

showing a mirror appearance.

f) High resistance to corrosion and oxidation;

g) High hardness and strength;

These are the advantages of nickel and explain the paramount

importance it has in cemented carbides. Because of these excellent
mechanical properties, it is effective in applications requiring a high
resistance to corrosion, even under conditions where conventional cemented
carbide tools are used. Grade type with moderate resistance to weak acids

Nickel in cemented carbides - 1

are indicated for seal rings and with good wear resistance. Because WC+Ni
has a microstruture composed of uniformly fine (~3µm max.) carbide grains,
it is possible to polish it as a mirror without the surface topology defects
found in conventional cemented carbides (WC+Co) because of the hardness
difference between the carbide phase and the binder metal phase.

Figure1: Spherical nickel powder.

Spherical nickel powder where all particles larger than 35 µm have been
removed, are shown in figure 1. This product is ideal for making PM moulding
parts where high sintered density and controlled shrinkage are important.
The powder also find application in welding electrodes, thermal spray
formulations, sintered magnets and friction materials. Fine sized spherical
powders are also available and includes -20 µm, + 10 to 20 µm and - 10 µm.

The properties of tungsten carbide-nickel hard metals are determined by

three parameters:

a) Properties of the carbide phase;

b) Properties of the nickel binder phase; and

c) Interaction between carbide and the nickel binder

The present paper is a contribution to the understanding of the binder

metal. It is known that nickel is not present in the hard metal in pure form but
as a solid solution with tungsten and carbon because of is ability to solve
considerable amounts of tungsten carbide at sintering temperature.

Since the solubility if WC in Ni increases substantially with temperature,

the composition of the binder phase at the temperature can be expected to
be determined by many factors such as sintering temperature and time, rate
of cooling, particle size of the carbide used and, consequently, the mean free
path in the binder.

For determination of the composition of the binder phase in WC-Ni

alloys the carbide was electroytically removed so that the remaining binder
could be tested analytically. The chemical analysis can be checked by
determining the lattice constants.

Nickel in cemented carbides - 2

 Moreover, the work is intended as a contribution to the question of the
mecanical properties of nickel-tungsten-carbon alloys. For this purpose, a
number of alloys in the range of compositons of interest were prepared and
mechanically tested. The results, however, must be examined with care
taken into account the conditons of sintered carbides, because the binder in
hard metals is present in very thin layers with considerabele internal thermal
stress. Nevertheless, they give an idea of the excellent mechanical properties
of the binder.

TUNGSTEN CARBIDE-NICKEL ALLOYS

Nickel – bonded tungsten carbide is regarded as the stainless steel of

the sintered carbide family. Indeed, its resistance to oxidation and to a wide
variety of other corrosive media is superior to that of stainless steel or any
other carbide type.

The first commercially available cemented carbides consisted of

tungsten carbide particles bonded with nickel. These are commonly referred
to as normal grades. A typical commercial product has 92 tungsten carbide
and 8 nickel per cent. Abrasion resistance, although rather less than tungsten
Carbide-Cobalt – WC-Co, is clearly greatly superior to that of any normal
corrosion resistant alloy. These alloy exhibt excellent resistance to simple
abrasive wear and thus have many applications in metal cutting. Table 1 lists
the representative properties of severval normal WC-Ni alloys.Uses include
valve components, plungers and other applications combining both corrosive
and abrasive resistance.

The microstructure of WC-Ni alloys should exhibit only two phases:

angular WC grains – phase α and Ni binder – phase γ. Representative
microstructures of normal WC-Ni alloys are shown in Fig. 2 and Fig 3. The
carbon content must be controlled within narrow limits. Too high carbon
content results in the presence of free and finely divided graphite, which in
small amounts has no adverse effects in machining applications.

STRUCTURAL CHARACTERIZATION
The metallographic structure of polished samples can be revealed using
reactants such as: Murakami´s solution, to reveal tungsten carbides, and
Nital 2% reagent or aqueous solution of FeCl3, to reveal the metallic phase.
In all samples, diffusion between carbides and the metallic phase during
the sintering process, was observed:

a) There are only two phases present: WC - α1 or α2, and γ phase of Ni

solid solution;
b) α – phase has simple hexagonal structure with stoichiometric structure
1:1 (W) in all alloys;
c) the highest concentration of W occurs in the centre of α – phase
carbides and gradually decreases to the carbide surface;
d) some of W is found inside the metallic phase;

Nickel in cemented carbides - 3

 e) Nickel diffuse into the α – phase and is found in the carbide surface; and
f) The structural characterization shows that in all the alloys, the matrix
phase has a face centred cubic structure. This give the alloy
considerably improved properties compared to the conventional
hardmetal (WC+Co) in which a hexagonal structure is found. The fcc
structure, which has four slipping compact planes, has the ability to
undergo plastic strain and so a high toughness.

Fig. 2 - 94WC+6Ni alloy, coarse grain. Etched with Murakami’s reagent

form 10 sec. (5V). Type of sintered carbide was WC+Ni, whose structure is
characterise by the irregular of the WC grain – phase α1. (x1500).
PROPERTIES CEMENTED CARBIDE
Many national and ISO standards have been developed for determining
the selected properties of cemented carbides (Table 2).
Table 2 Test methods for dtermining the properties of cemented carbides.

TEST METHOD
PROPERTY
ASTM ISO

ABRASIVE WEAR RESISTANCE B 611 ---------

APPARENT GRAIN SIZE B 390 ---------

APPARENT POROSITY B 276 4505

COERCIVE FORCE --------- 3326

COMPRESSIVE STRENGTH --------- 4506

DENSITY B 311 3369

FRACTURE TOUGHNESS --------- ---------

HARDNESS, HRA B 294 3738

HARDNESS, HV --------- 3878

LINEAR THERMAL EXPANSION B 095 ---------

Nickel in cemented carbides - 4

 MAGNETIC PERMEABILITY --------- ---------

MICROSTRUCTURE B 657 4499

POISSON’S RATIO --------- ---------

TRANSVERSE RUPTURE STRENGTH B 406 3327

YOUNG’S MODULUS --------- 3312

TYPICAL PHYSICAL PROPERTIES CEMENTED CARBIDE

Hardmetals grade G6Ni, G8Ni and G10Ni composite have 3-4µm

carbide particle size and 6%,8% and 10% nickel binder. The microstructure
shows fine-grained ‘pellets’ in the coarser matrix. Typical physical properties
are shown in table 1.

Table 1 properties of representative nickel-bonded cemented carbide.

Nominal Grain Size Hardness Hra Density Transverse POROSITY

3
composition ASTM 294 (g/cm ) Strength ASTM B276
ASTM B390 ASTM B311 (N/mm2)

Type 6 F 90,0 14,92 1600

94WC+6Ni Type 6 M 88,8 14,85 1760 A03

Type 6 C 87,0 14,80 2000

Type 8 F 89,0 14,85 1950

92WC+8Ni Type 8 M 88,0 14,75 2200 A02

Type 8 C 87,0 14,69 2500

Type 10 F 88,5 14,56 2040

90WC+10Ni Type 10 M 87,5 14,45 2300 A02

Type 10 C 86,5 14,39 2700

Fig 3- Photomicrographs of various grades of WC+Ni

|---10 µm---| |---10 µm---| |---10 µm---|

a) α - Fine, type 6 - F b) α - Medium, type 8 - M c) α - Coarse, type 10 - C

a) 6% Ni – fine grain b) 8% Ni – medium grain c) 10% Ni – Coarse grain

Nickel in cemented carbides - 5

 Microstructures of normal WC-Ni alloys. a) 94WC+6Ni alloy, fine grain size. b) 92WC+8Ni
alloy, medium grain and c) 90WC+10Ni alloy, coarse grain. All etched with Murakami’s
reagent form 10 sec. (5V). Type of sintered carbide was WC+Ni, whose structure is
characterise by the angularity of the WC grain – phase α2. (x1500)

HARDNESS determine the resistance of a material to abrasion and

wear. It is affected not only by composition but also by the level of porosity
and microstructure. For normal WC-Ni alloys of comparable WC grain size,
hardness decreases with increasing nickel content (fig.4). However, because
both composition and microstrucure affect hardness, nickel content and grain
size must be considered. At a given nickel level, hardness improves with
decreasing WC grain size.
In Hardmetal WC+Ni, hardness is measured by the Rockwell A (Hra or
Ra), 60 kg, scale diamond cone (∠120º) identation test (Hra) or by the
Vickers diamond pyramid indentation test (HV). Hardmetal WC+Ni used in
machining applications hardness values range from 86 to 90 Hra.

Fig 4- Variation of Rockwell Hardness of WC-Ni

alloys with composition and grain size of WC

91,5

91
6%
90,5
Hardness, Hra

90
8%
89,5

89

88,5 10%
88

87,5

87

86,5
2 2,5 3 3,5 4 4,5 5 5,5 6

Grain Size of WC, microns

Nickel in cemented carbides - 6

 Variation in Hardness

Fine Grain Medium grain Coarse Grain

90,5

90

89,5
Hardness, Hra

89

88,5

88

87,5

87

86,5

86
5 6 7 8 9 10 11
Nickel content, wt%

DENSITY, or specify gravity, of WC+Ni, is very sensitive to composition

and porosity in the sample and is widely used as a quality control test.
Density values of WC+Ni range from 14,97g/cm3 for low-nickel WC-Ni alloy
to about 10 or 12 g/m3 for highly alloyed carbide grades (Fig 5).

Fig 5- Variation in Density

Fine Grain Medium Grain Coarse Grain
15

14,9
Density, g/cm3

14,8

14,7

14,6

14,5

14,4

14,3
5,5 6 6,5 7 7,5 8 8,5 9 9,5 10 10,5

Nickel content, wt%

POROSITY - The properties of a WC+Ni, hardmetal, are dependent on its

density, which in turn is critically dependent on composition and porosity.
Porosity is evaluated on the as polished material. The American Society for
testing and materials (ASTM) has established a standard procedure (B276)
that rates three types of porosity:
a) type A, covering pore diameters less than 10 µm;
b) type B, covering pore diameters between 10 and 25 µm;

Nickel in cemented carbides - 7

 c) type C, covering porosity developed by the presence of free carbon.
Type A porosity is rated at a magnification of 200X, while types B and C
porosity are rated at 100X. The degree of porosity is given by four numbers
ranging in value from 02 to 08. The number provides a measure of pore
volume as a percentage of total volume of the sample. Example is shown ifn
Fig 6.

Apparent porosity (200X) - type A03 (0.02 vol%)

REFERENCES:

1. K. J. A Brookes – Cemented Carbides for Engineers and Tool Users–

International Carbide Data 1983 .
2. K. J. A Brookes – World Directory and Handbook of Hardmetals, 4th ed.,
International Carbide Data 1987;.
3. ASM Engineering Bookshelf- Source Book On Cold Forming- Pág. 255 –
257;
4. An American National Standard – ASTM;
5. Metal Powder Industries Federation – MPIF – Standard Test Methods for
Metal Powders and Powder Metallurgy Products;
6. Ädvance Sintering Technology – Preprint of a Seminar held at the 1988
International Powder Metallurgy Conference Orlando, Florida, June 7,
1988 – Metal Powder Industries Federation – MPIF;
7. T.E. Chung; D.S. Colemand - Recent Advances in Hardmetal Production,
September 1979 – Vol.2 – Dept. of Materials Eng. & Design
Loughborough University of Technology and Metal Powder Report;
8. Chiaverini, V. - Metalurgia Do Pó – Técnicas e Produtos; 4 ed. –São
Paulo – Associação Brasileira de Metalurgia e Materiais, 2001.
9. ISO3 – 3RD International Conference on Isostatic Pressing, Vol.2 – Metal
Powder Report, London – November 10-12,1986;
10. Coutinho, Telmo de Azevedo – Análise e Prática Metalografica de Não-
Ferrosos- São Paulo -Ed. Edgard Blucher Ltda.-1980;
11. Gurland,J. and Norton,J.T.: Role of the Binder phase in Cemented
Tungsten Carbide – Cobalt and alloys, Trans. Amer. Inst. Min. Met. Eng.,
1956;
12. Dawihl, W.: A Handbook of Hard Metals, Her Majesty’s Stationery Office,
London,1955;

Nickel in cemented carbides - 8

13. Sandford, E.J., and Trent, E. M.: The Physical Metallurgy of Sintered
Carbides; in “Symposium on Powder Metallurgy”, Iron and Steel Institute
Spec. Rep. Nº.38, London, 1947;
14. “Properties of Carboloy Cemented Carbides” Eng. Bull. Carboloy Dept.,
General Electric Co.,Detroit, April, 1951;
15. G. Schneider, Jr., Principles of Tungsten Carbide Engineering, 2nd ed.,
Society of Carbide andt Tool Engineers, 1989;
16. BRASIMET – Com. e Industria S/A, Processos e equipamentos a vácuo
para a sinterização sob pressão de metais e cerâmicas – São Paulo,
1987.
17. I. Sanchiz – Estructura y Propiedades de Nuevas Aleaciones Tenaces de
Metal Duro, Tesis de Licenciatura (Facultad de Química-Universidad de
Barcelona. Febrero 1991;
18. R.J. Kendrick -Nickel powders – The latest developments, INCO SSP
Company - Canada
19. OMG Group, Inc – Innovative Metal Technology – Nickel Products Group,
Producers of Metal-Based Specialty Products – Harjavalta, Finland.

Nickel in cemented carbides - 9