Hard Coating

ATO100498
782 HM 1 G. Gilleetal.
15" International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
SUBMICRON and ULTRAFINE GRAINED HARDMETALS for

MICRODRILLS and METAL CUTTING INSERTS
G. Gille1), B. Szesny1), K. Dreyer2', H. van den Berg2', J. Schmidt3',

T. Gestrich4', G. Leitner4'
1)
H. C. STARCK GmbH & Co. KG, Goslar, Germany
2)
WIDIA VALENITE GmbH, Essen, Germany
3)
HPTec GmbH, Ravensburg, Germany
4)
FRAUNHOFER INSTITUTE IKTS, Dresden, Germany
Summary
Although round tools as carbide drills and mills are dominating by far the
application of submicron and ultrafine hardmetals the consumption for PCB
microdrills had the strongest growth rate over the last decade. This paper
deals with the latest developments of ultrafine hardmetals and their
application for PCB microdrills and metal cutting inserts. Based on optimized
processing and properties such as hardness, hot hardness, toughness,
strength and wear resistance a new generation of microdrills is presented. In
particular the failure probability of the microdrills could be considerably
reduced and the number of drilling strokes was nearly doubled.
Combining improved pressing behaviour with proper doping and optimized
processing new applications of submicron and ultrafine hardmetals could be
obtained by using complex shaped metal cutting inserts. Apart from these
application examples the paper gives some insight into fundamental
investigations on sintering and properties of ultrafine hardmetals and shows
in particular the influence of milling, doping and sintering on the properties of
ultrafine hardmetals.
The paper also presents a new ultrafine WC grade showing a 0.1 urn WC
intercept of a sintered WC - 10 wt % Co structure and a hardness of HV30 =
2050 for a 1 wt % mixed VC/Cr3C2 doping.
Keywords:
Submicron and ultrafine grained hardmetals, processing and sintering
behaviour, application of submicron hardmetals, PCB microdrills, metal
cutting inserts.
G. Gille et al. HM 1 783
15'" International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
1. Properties of submicron and ultrafine hardmetals

Over the last 20 years and yet more pronounced over the last 10 years, there
has been a strong tendency towards finer und finer grained hardmetals [1],
[2]. Starting with some special applications as wood cutting tools, microdrills
for PCBs and round carbide tools the volume as well as the variety of
applications as tools and wear parts increased continuously for the submicron
hardmetals [3], [4], [5]. The driving force behind this development was the
considerably improved performance of these submicron hardmetals which in
many applications clearly exceeded the performance of hardmetals with WC-
grains greater than 1 urn.
The superiority of the submicron and ulfrafine hardmetals developed in the
80ies and 90ies is mainly based on the fact that very high hardnesses can be
combined with high strengths. This is shown in Fig. 1 for the newest
generation of submicron and ultrafine hardmetals.
ituu • 4500
2200 •
(0.2-0.5) |jm
2000 -
o (0.5-0.8) (im
CO 1800 •
X
1600 •
(0.8-1.3) Mm N
c 1400 -
i—
m
X 1200 -
1000 -
800 - i 1 i—i—i—i— 1500

0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
Weight Percent Co Weight Percent Co
Fig. 1: Hardness and bending strength of ultrafine (0.2 - 0.5 urn WC)
submicron (0.5 - 0.8 urn WC) and fine grain sized (0.8 - 1.3 urn WC)
hardmetals
Up to the seventies the hardmetal industry produced fine grained hardmetals
with high hardnesses but with relativity low bending strengths [6]. A well
known relationship between bending strength and the mean free path of the
784 HM 1 G. Gille et al.
Co binder, as investigated by J. GURLAND in the fifties and sixties [7], was

more or less true up to this time. For submicron hardmetals the GURLAND
relationship predicted an increase of hardness but a decrease of bending
strength for decreasing mean free path and WC intercept. To increase the
strength with decreasing WC grain sizes had prerequisites in a new quality of
powder (in terms of grain size, grain size distribution, purity, homogeneity
etc.) as well as in considerably advanced hardmetal technologies. That
means clean room milling and spray drying and in particular Sinterhip as a
completely new introduced consolidation process in the early eighties [8],
These improvements of raw materials and technologies resulted in fine
grained hardmetals with drastically reduced numbers and sizes of fracture
initiating defects such as pores, inclusions or microcracks. This may easily be
proven by comparing the square of the ratio of fracture toughness Kc and
bending strength a b as a measure of the critical defect size lc for conventional
and the newest generations of submicron and ultrafine hardmetals.
• Medium and coarse grain sized (conventional) WC-Co hardmetals*'
Grade BT10 BT15 BT25 BT30 BT40
12
Kc [MPam" ' ] 12.8 14.7 13.2 13.4 14.1
ob [GPa] 2.50 2.30 2.65 2.90 3.00
2
|(Kc/ab) [urn] 41.2 64.3 39.0 33.6 34.7
• Fine grain sized (conventional) WC-Co hardmetals*'

Grade THF THM THR THA GT30
12
Kc [MPrrT ' ] 9.0 9.6 12.3 12.7 13.8
ab [GPa] 1.60 2.00 2.35 2.45 2.70
2
|(Kc/ab) [urn] 31.6 23.0 27.4 26.9 26.1
• Submicron and ultrafine WC-Co hardmetals*'

Grade THM-U THM-F THR-U THR-S THR-F
12
Kc [MPrrr ' ] 8.6 9.5 9.0 10.8 10.9
[GPa] 3.5 3.0 3.6 3.7 3.2
2
|(Kc/ab) [urn] 9.4 15.7 9.9 13.4 18.1
1
Plain WC-Co hardmetals or hardmetals with additional carbides below 2 wt %
As a measure for the size of the fracture initiating and strength determining
defect, in the lowest line of the table above the diameter of a penny shaped
microcrack l c was calculated due to
lc = 1 * (KJab)2
According to the reduction of numbers and sizes of defects, the strength of
the submicron and ultrafine hardmetals could be considerably increased
without increasing the fracture toughness Kc, as shown in Fig. 2.
O Submicron and Ultrafine

2b00 O Submicron and Ultrafine
Hardmetals Hardmetals
2250 - Conventional Hardmetals - Conventional Hardmetals
2250
^
O
CO
2000
1750
V - \o
\o X
2000
1750 o
o.
o
i ..._
;
\
IS) IS)
% 1500
IS)
0 1500
__ \ n °
c
E —' --|v = -•• Jj5 1250
CD 1250 " \ I '
J
1000 1000 ]\
750 • ; - —
r —• i 750 i • - ;
500 5nn
0 5 10 15 20 25 30 35 1000 2000 3000 4000 5000
1/2n
Fracture Toughness [MPa m ] Bending Strength [MPa]
Fig. 2: Hardness-toughness and hardness-strength combinations for ultra-

fine, submicron and normal grain sized (conventional) hardmetals
The fracture toughness - hardness combinations of submicron and ultrafine
hardmetals rank within the measurement band of the conventional
hardmetals [5]. There is nothing special in this toughness-hardness
combination for submicron and ultrafine hardmetals. As for the coarse and
medium grain sized conventional hardmetals the fracture toughness is a
material constant mainly depending on the properties, the volume fraction vCo
and the dispersity (mean free path pCo) of the binder. Including the submicron
and ultrafine grained hardmetals the measured fracture toughnesses Kc may
be well fitted to p Co / (dwc)1'2 in a broad range of grain size d w c and mean free
path pco [9], [10]. By different doping and optimizing the structure, the fracture
15" International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte {2001), Vol. 2
toughness of submicron and ultrafine hardmetals may be improved within a

very limited range [5], [11]. But there may be some possibilities to improve
also the fracture toughness much more as it seems to be realistic up to now,
by specially shaped WC micrograins, by special doping or alloying the binder
[17].
As for conventional hardmetals the hardness declines with increasing
temperature. But up to 800 - 900 °C the submicron and ultrafine hardmetals
show superior hot hardnesses, see Fig. 3.
2500 100
0 200 400 600 800 1000 200 400 600 800 1000
Temperature [°C] Temperature [°C]
Fig. 3: Hardness and thermal conductivity versus temperature for ultrafine,
submicron and fine grain sized hardmetals
This superiority in hot hardness up to 800 - 900 °C provides better

performance not only in cutting wood, plastics and non ferrous metals but
also in cutting operations with higher thermal loading as drilling, milling and
turning of cast iron and steels [4], [12] and [13]. The hot hardness may be
controlled and improved within a limited range by the doping carbides and
their contents, see section 3.1. of this paper and [5].
The diagramm at the right side of Fig. 3 shows the relative strong decrease of
the thermal conductivity with decreasing WC grain size. This lower thermal
conductivity has a positive influence on the thermal loading of the tool,
because the arising heat is transfered in a bigger ratio to the workpiece. An
effect very similar to that of AI2O3/2rO2 coatings on cutting inserts. On the

other hand a lower thermal conductivity A decreases the thermal shock
resistance, which is proportional to
aE
where v is the POISSON ratio, E is the YOUNG-modulus, o b is the bending
strength and a is the coefficient of thermal expansion. Calculations show
however the decrease of A is completely compensated by the higher bending
strength of submicron and ultrafine hardmetals and there are no
disadvantages for these hardmetals concerning thermal shock resistance.
2. Processing of submicron and ultrafine powder and hardmetal
mixtures
To obtain advanced submicron or ultrafine hardmetals with minimal porosity,
defects and discontinuous grain growth the processing of the raw material
mixtures requires appropiate milling and sintering conditions as well as proper
formulations of grain growth inhibitor additives. Sinterhip as an essential
progress in consolidation technique can help a lot to minimize the residual
porosity, but without optimizied milling, granulation and pressing, this
advanced technique is not sufficient to provide high performance ultrafine
hardmetals. Any contamination or inhomogeneity from the raw material or
produced by milling or pressing can not completely be removed by sinterhip
and can be a fracture initiating or wear accelerating defect. To obtain the high
level of the state of the art, high efforts have been made in the past but only a
small part of this work has been published [2], [14], [15]. In particular the
papers of SCHUBERT et al. [2] and CARROLL [14] give good overviews of
the problems connected with the processing of submicron powders and
mixtures. This paper is restricted to two issues selected from the high number
of problems addressed in [2], [14] and elsewhere.
• Pressing behaviour of submicron and ultrafine hardmetal mixtures
• Aspects of doping and sintering
2.1. Pressing behaviour
Some years ago nearly all tools and wear parts made from submicron
hardmetals were extruded materials or were machined as greenware or
finished in the sintered state to provide the final geometry and surface quality.
One reason to restrict submicron hardmetals to this type of tools and parts
was determined by the application as drills, mills, wood cutting tools or other
round carbide tools and construction parts. A second reason for this
restriction arose from the difficulties in pressing parts with complicated
788 HMJ G. Gille et al.
15* International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
geometries and shapes. The finer the powder and their mixtures, the higher
the necessary pressing forces and the greater the problems with
inhomogeneities and intrinsic stresses in pressed parts. In particular these
difficulties prevented the mass production of submicron sintered inserts as
the working horse of the cutting tool industry. To reduce the pressing forces
and to improve the pressing behaviour of fine grained mixtures is therefore of
considerable interest for the hardmetal insert producing industry. In Fig. 4 a
comparison is made between conventional 0.6 and 0.8 urn WC powder (WC
DS 60 and WC DS 80) and WC powder with the same grain size but
improved pressing behaviour (WC DS 60 S and WC DS 80 S). The effect is
shown for the WC powder itself as well as for 24 h ball milled, ungranulated
WC - 6 wt % Co mixtures. The improved pressing behaviour means either a
higher green density may be obtained by the same pressure or the pressure
may be reduced for a given green density. Using the improved WC DS S
grades it is possible to press and sinter sucessfully inserts complicated in
shape and low in tolerances. And based on that progress new application
areas for submicron and ultrafine grained cutting tools could be opened up,
see section 3.
2.2. Aspects of Sintering

Some of the typical features of sintering of submicron and ultrafine
hardmetals were discussed recently in different papers as [2], [15], [16], [17],
[18] and [19].
- The driving force for sintering and densification of WC-Co hardmetals in
general is a reduction of interface energy stored in the WC/gas, Co/gas,
WC/Co, WC/WC and Co/Co interfaces. The finer the WC and Co grain
size the higher the internal interface areas and the stored interface energy
as the driving force for sintering. Therefore densification and sintering of
hardmetals is intensified considerably, and the onset of shrinkage is
shifted to lower temperatures if the WC and Co grain sizes are decreased
to that of submicron (0.5 - 0.8 urn) and ultrafine WC powder (0.2 - 0.5 urn)
[16], [17] and [18], see Fig. 5.
- Although WC-Co hardmetals are typically liquid phase sintering systems,
for normal grain sized hardmetals between 65 and 80 % of the total
shrinkage is realized already before melting of the eutectic binder. For
ultrafine hardmetals the solid state sintering is yet more pronounced and
can contribute up to 90 % of total shrinkage.This first stage of densification
or solid state sintering is driven by the conversion of WC/gas and Co/gas
10 10
A . Ji
,——' ——-^ \
n , <j
o
&
w , '
c
0 0 c
Q Q
c
0 0
CD WC powder CD WC powder
- • • WC DS 60 S
- * - WC DS 80 S
• O WC DS 80 - O WC DS 60
0 100 200 300 400 500 0 100 200 300 400 500
Pressing Pressure [Mpa] Pressing Pressure [Mpa]
8.4 8.4
8.3 8.2
8.2 /
8.0
/
8.1
V %
7.8
v\v
8.0 /
• * - '
" tr\ 7.6

)
/ y
"een Denj
7.9
0 7.4
Q
c
0
7.8
7.7
/
7.2 J y
CD WC-10wt%Co
CD (/ WC-10wt%Co
7.6 / • • • WC DS 80 S 7.0 - * - WC DS 60 S
- O WC DS SO - O WC DS 60
7.5 6.8
0 100 200 300 400 500 0 100 200 300 400 500
Pressing Pressure [MPa] Pressing Pressure [MPa]
Fig. 4: Pressing behaviour of submicron WC powders (above) and WC -

10 wt % Co hardmetal mixtures (below)
interfaces into WC/Co interfaces with around one fifth of interface energy.
The lower the grain size and the higher the internal interface areas, the
higher the solid state sintering intensity, as can be obtained from the right
part of Fig. 5 (ARRHENIUS plot of T_(shrinkage rate) versus inverse
temperature 1/T).
- Besides the very low grain sizes of the submicron and ultrafine hardmetals
the always necessary doping with grain growth inhibitors has a strong
influence on the sintering and densification [16], [18]. As shown in Figs. 6
and 7 the composition and content of grain growth inhibitors as VC, Cr3C2,
TaC etc. shifts the onset of shrinkage to higher temperatures, decreases
the shrinkage rate (at least within the solid state sintering range) and
reduces the melting point of the eutectic binder.
- The solid state sintering is subdivided into two stages, see Figs. 5, 7 and
8. The first stage at lower temperatures strongly depends on the
processing before sintering and depends only slightly on grain size. The
second stage with a higher slope rate of the straight ARRHENIUS fit line
only weakly depends on processing but is correlated to the grain size, see
Figs. 5, 7 and 8. Some of the most important factors bearing influence on
the first stage of solid state densification are:
• Milling conditions: Ball or attritor mill, mill media, milling time etc.
• Pressing additives: Content and composition of organic binder
(paraffine, PEG etc.)
• Granulation and pressing conditions (hardness of granules, pressure
etc.)
• Atmosphere, heating rate and holding times during debinding, out-
gassing and sintering.
All these effects are more pronounced if the grain sizes of WC and WC-
Co mixtures are decreased to submicron and ultrafine grain sizes.
- Coming to ultrafine hardmetals the elementary mechanism behind the
solid state sintering seems to be yet more complicated and the process is
subdivided into more than two stages, see Figs. 7 and 23 in section 4.
With increasing temperature T the shrinkage rate versus 1/T shows again
the upward tendency with increasing T, but the curve may be
approximated by one or two straight lines only very roughly.
In cases of submicron and ultrafine hardmetals in particular the solid state
sintering, the discontinuous as well as the continuous grain growth and the
residual porosity are of interest.
th
15 International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
60 100.0
A - 0 . 4 5 Mm WC,
no doping
B - 2.0 urn WC
40
<D A - 0.45 Mm WC,

-t—•
CO no doping
B - 2.0 urn WC
a: 20
CD
0*0.02
x
CO
-0.03
500 1000 1500
Temperature [°C] (1/T)-1 cf [1/K]

Fig. 5: DSC-siqnal and shrinkage rate of ultrafine (0.45 [jm WC) and medium
grain sized (2 urn WC) WC -10 wt % Co hardmetais
40 •
o-
/ no doping 1374°C
i
1/min
TaC1367 °C
A\ \B / 30-
o Cr 3 C 2 1355 c
'—i
\ / CO
X
pin
S \\ 0 VC1346°C
or
CO
o
w\v
\\
M
o
o
"O
c CO
20 • VC/Cr 3 C 2
1328 °C • ii
Tl I
CO c
c A - no doping I // A° 10 "
)/O/
• ^ -0.01 •
<~
B-VC/Cr 3 C 2 CO
CO
V 6
CO
500 1000 1500 Q 1200 1300 1400 1500

Fig. 6: Influence of doping on the shrinkage rate and eutectic melting
temperature for 0.45 urn WC - 10 wt % Co hardmetais

1300 1100 900 800 1300 1100 900 800
100.0 "3 T I I 100.0-5
1 - 0.45 p m W C , no doping
2 - 0.45 ^ m W C , 1 - Attritor Mill
c V C / C r 3 C 2 doping 2 - Ball Mill
3-Ball Mill,
"E high organic
io.oi binder content
Fig. 7: Influence of doping on the shrinkage rates of 0.45 urn WC-10 wt % Co

hardmetals (left). ARRHENIUS-plot for 0.8 urn WC-10 wt % Co hardmetals
with different milling conditions.
Solid state sintering: Elementary mechanism
As already discussed in [20], [21] but more detailed investigated in [17], [18]
at temperatures above 0.5 Toting (which is about 650 - 710 °C for fine
grained hardmetals) the highly dispersed binder particles behave like a
viscous mass spreading by wetting onto the surrounding WC surfaces. This
wetting reduces the internal energy but otherwise it is connected with
microscopic LAPLACE forces acting along the wetting front line between WC
and the viscous binder. These microscopic forces and moments rearrange
WC particles and reduce the mean distances between neighboured WC
particles which means effective shrinkage of the pressed WC-Co-pore
specimen [17]. The plot of T -(shrinkage rate) versus 1/T of Figs. 5, 7 and 8
demonstrates the solid state densification may be interpreted as a thermal
activated process with an activation energy Qv and an effective viscosity rj
driven by the stress a.
d/dt (Al/Io) = a /T) and 1 lr\ = 1 / (kT • r\0) • exp (- Qv I kT)
The driving force a is the sum of the LAPLACE stress a L ~ ycJdwc and an
intrinsic stress aiNT arising from mechanical activation during milling and
pressing [17]. Going into more details the question arises about the
G. Gille et al. HMJ 793^
mechanism behind the two stages of solid state densification. The

experimental results suggest the following explanation. The first stage is
determined by the spreading of the viscous Co binder and the wetting
between binder and WC surfaces. The speed limiting mechanism is the rate
of wetting or the rate of changing from WC/gas and Co/gas to WC/Co
surfaces. It is easy to understand that the wetting rate and therefore the
shrinkage rate is strongly influenced by the processing before sintering and
the sintering conditions such as heating rate and atmosphere during
debinding, degassing and heating. By physical reasons the wetting rate is
determined by
• Area, curvature, chemistry and structure of WC particle surfaces
• Content, particle size and dispersion of Co-binder
• Composition (W and C content, dopants) and intrinsic, microscopic
properties of the Co-binder such as densities of dislocations, stacking
faults, vacancies and internal stresses etc.
This explains the experimental results shown in Fig. 7 and may be related to
some results found and discussed by SCHUBERT et al. in [18] and CARROL
in [14]:
• Using the same fine grained hardmetal mixture (WC grade, dopants, Co
content) but milling either by a ball or an attritor mill influences
considerably the rate and intensity of shrinkage in the low temperature
stage, see Fig. 7. In case of attritor milling the activation energy is Qv = 50
kj/mol and for ball milling it is Qv = 100 kJ/mol, see Fig. 8.
• Staying with the same ball milling conditions but using a high percentage
of organic binder (5 - 6 wt %) and realize debinding and sintering in one
cycle, the result of Fig. 7 is obtained. In this case the first stage of solid
state sintering is nearly completely depressed. And as shown in curve 3 of
Fig. 7 the densification rate seems to be determined by only one
mechanism between 950 to 1200 °C. This result is surprising but may be
explained by the impact of the organic binder on the particle
rearrangement during the pressing already. Due to the 40 - 50 vol % of
organic binder nearly all pores will be filled with binder and nearly no gas is
enclosed in the pressed specimen. And in the latest stage of pressing the
external force is transformed into hydrostatic pressure acting through the
organic binder. During pressing the viscous organic binder has therefore
two effects:
1. Supporting the rearrangement of particles by easy gliding of
neighboured particles.
15" International Piansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
2. Transforming the pressing forces into an internal hydrostatic pressure

acting as a driving force for particle rearrangement.
In combination of these two effects considerable particle rearrangement
can start already during pressing the WC-Co-organic binder composite.
Independent of the organic binder content the pressed specimen has
nearly the same density or porosity after debinding. But the densification
of clusters of hundreds or thousands of particles is the higher, the higher
the organic binder content of the WC-Co-binder mixture. During pressing
a high organic binder content acts like the external gas pressure at
Sinterhip. The second stage normally found in solid state sintering starts
at a characteristic temperature T ^ and shows a steeper slope of the
ARRHENIUS plot that is a higher activation energy, see Figs. 5, 7 and 8.
At this temperature T 1j2 a certain level of particle rearrangement results in
locally dense areas comprising tens or hundreds or thousands of
particles. But these completely densified areas are formed in parallel and
to the disadvantage of some micropores or pores. Any inhomogeneity of
Co binder distribution or local fluctuations of green density, WC surface
area or grain size causes local fluctuating densification and results in
micropores or pores, see left sided pictures in Fig. 8. For temperatures T
> T 1l2 densification means creep of WC-Co composite material areas into
the micropores and pores, see Fig. 8, below.The effective surface tension
a* acting perpendicular to the pore surface is driving this creep process
a* = 4y */ddpp
where d p is the pore diameter and y* the effective surface energy which is
a mean value of Co/Gas and WC/gas surface energies. According to
intensive creep and annealing in the first stage the intrinsic stresses am
are relaxed and may be neglected as driving forces. The effective
viscosity rf. relating the shrinkage rate d/dt (Al/Io) to the driving force a*, is
determined by the properties of the binder as well as by constraints
arising from the rigid WC grains. As in the low temperature stage thermal
activated processes in the viscous Co binder are causing the materials
creep. But in difference to the nearly free creep of Co binder in the early
densification stage, during the second stage all microscopic
mechanisms are influenced by
• the high content of WC/Co interfaces enclosing all Co binder areas and
• the annealed Co binder microstructure, at the higher temperatures.
The heat treatment and spreading during the first stage of densification
has considerably changed the microstructure of the Co particles.
G. Gilleetal. HM 1 795
Temperature [°C]
1300 1100 900 800
100.0 i
10.0
33
104[1/K]
Micropores due to inhomogeneities
Macropore / Pressing hole
Temperature [°C]
1300 1100 900 800
100.0 ^
10.0
o
0.1 "f
- 104[1/K]
Fig. 8: Stages 1 and 2 of solid state sintering. Experimental curves (right

side) for 0.8 urn WC - 10 wt % Co hardmetals.
The highly disordered microstructure of the milled Co binder is annealed at

this stage. And creep due to dislocation climbing and vacancy diffusion is
intensified by the increased temperature on one hand, but decreased by the
reduced disorder of the microstructure on the other hand.
Effectively this results in a higher effective viscosity n* and a higher
activation energy Qv* ruling the shrinkage rate d/dt (Al/Io) in the second stage
of solid state sintering
e H U ~ d p r l - M " " T 1 - - L i + 3vwcJfoo.*T)~lH kT

where vWc is the volume fraction of rigid WC grains. In difference to the
activation energy of the low temperature stage Qv the energy Qv* is a material
constant depending on properties of the annealed Co binder and WC/Co
interfaces. This is clearly indicated in Figs. 7 and 8 where all ARRHENIUS
plots show the same activation energy Qv* = 250 kJ/mol for higher
temperatures although the Qv values are different at the low temperature
stage (Q v = 50 - 100 kJ/mol), that means they depend on processing
conditions.
WC grain growth
As in the case of densification the minimization of the internal energy is
driving the WC grain growth. In difference to densification however the
reduction of the total WC/Co interface area is the driving force of WC
coarsening. In practice "continuous" as well as "discontinuous" (local or
exaggerated) grain growth must be considered and suppressed as much as
possible. Good overviews discussing the phenomenons as well as critical
parameters of grain growth are given in [2], [14], [15], [18].
Continuous grain growth during liquid phase sintering may be considered as
an Ostwald ripening process. Smaller WC particles dissolve due to their
higher dissolution potential and reprecipitate after diffusion through the binder
at coarser WC grains. The intensity of this dissolution - reprecipitation
process and therefore the WC growth rate is increased by high carbon
content and essentially decreased by a proper addition of grain growth
inhibitors such as VC, Cr3C2, Ta/NbC etc. All these grain growth additives
are soluble in the Co binder and can segregate at the WC/Co interfaces or as
separate particles during sintering. Most probably the additives alter the
WC/Co interfaces by forming mixed crystals or new phases reducing the
interface energy and therefore the driving force of grain growth. As
densification, WC grain growth is not restricted to liquid phase sintering but
comes to a remarkably extent during solid state sintering [2], [18]. This is one
G. Gilleetal. HMJ 797^
th
15 International Plansee Seminar, Eds. G. Kneringer, P. Rddnammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
of the reasons to admix the grain growth inhibitors as early and as

homogeneously as possible to the WC-Co mixture or to the WC powder or
co-carburize the WC with the additives. Another reason for co-carburizing the
WC with the additive carbides is based on the grain growth inhibiting effect of
VC, Cr3C2, (Ta,Nb)C on the WC grains during their synthesis at 1350 to
1450 °C. But there are different findings and evalutions as for example
CARROLL [14] has found that admixed VC provides the same degree of
grain growth control as a co-carburized WCA/C carbide. In the case of Cr3C2,
a significant difference however was found between the admixed and co-
carburized inhibitor. For a mixed VC/Cr3C2 doping, admixed additives were
just as effective as their co-carburized counterparts when the VC content was
greater than 0.3 w t % [14].
In case of discontinuous grain growth the variety of reasons is enormous and
the understanding much more complex as in case of continuous grain growth
[15]. But nevertheless to suppress discontinuous grain growth and
exaggerated WC grains is a fundamental prerequisite to obtain high strength
and high performance submicron and ultrafine hardmetals. Apart from
impurities or inhomogeneities arising from the raw materials or the processing
one reason for discontinuous grain growth is the difference of interface
energies on basal (001) and prismatic (100) WC planes [15]. Although the
face-oriented grain growth may be used successfully for toughening of coarse
grained hardmetals with platelet structures, in submicron and ultrafine
hardmetals it may cause exaggerated platelet shaped WC grains too and
degrades strength, wear resistance and other performance related properties.
Additionally to well known facts from the literature it should be mentioned that
the microstructure of the carbide can remarkably influence the grain growth
behaviour too. Microstructural features such as densities of stacking faults,
dislocations and vacancies are determined by the carburizing as well as the
processing conditions of hardmetal fabrication. In particular the temperature
of carburization and the milling intensity have a strong influence on the
microstructure, see section 4. Recently UNGAR et al. [31] proposed a
sophisticated method to measure the dislocation density as well as the
crystallite size distribution on nanocrystalline WC. This may be an useful tool
to enlighten the grain growth behaviour of WC powder. In particular the higher
grain growth rate of low temperature carburized WC may find their
explanation by such sophisticated X-ray analysis.
Finally Fig. 9 shows structures of ultrafine grained hardmetals with
discontinuous WC grain growth or WC agglomerates in comparison to a
perfect structure which is free of defects or exaggerated WC grains and
completely homogeneous. It is evident, this type of structural defects reduce
strength and other properties such as wear resistance, which is probably

degraded. And this type of defects can't be removed by Sinterhip at all.
Discontinuous WC agglomerates Homogeneous and

WC grain growth I 1 10 pm defect free uitrafine
structure
Fig. 9: Structures of uitrafine hardmetals
3. Application of submicron and uitrafine hardmetals

In 2000 between 11.500 and 12.500 tons of submicron hardmetals were
produced worldwide excluding PR China. This are around 40 % of the total
hardmetal production.
Submicron and uitrafine hardmetals 1 60 % Round tools (Carbide drills
subdivided due to their applications and mills)
13 % Tools for the electronics
industry (Microdrills etc.)
18 % Wear parts, Circular
shearing and cutting
blades for paper,
plastics etc., Chipless
forming tools, Dental tools,
etc.
Total production of submicron and 4% Wood cutting tools
uitrafine hardmetals in 2000:
11.500 to 12.500 tons r^'7, 5 o/o |\/|eta| cutting inserts
Fig. 10: Submicron and uitrafine hardmetals subdivided due to their

applications in 2000
G. Gilleetal. HM_1 799
1
The carbide round tools have, with around 60 % or 7.000 to 7.500 tons,
by far the biggest share of submicron and ultrafine hardmetals application. In
particular the carbide drills and mills with and without internal coolant
channels are a rapidly growing segment of the carbide tool industry. Together
with threaders, reamers, routers and other round tools they substitute more
and more the HSS tools. Based on the advanced technology of producing
twisted coolant channels, there is a steady tendency to carbide drills and mills
with greater tool diameters and higher Co binder content over the last 10
years [26]. The carbide drills, mills, threaders, reamers etc. are nearly
completely based on 0.8 to 0.5 urn WC with a strong tendency to 0.3 urn WC.
The enormous progress of extrusion technology and Sinterhip together with
the excellent performance of the submicron carbide tools make these tools
more and more attractive for the metal machining industry. Besides coolant
channels coating can also prevent the tool from too high temperatures that
facilitate thermal degradation of the fine grained tool material. Coating
therefore additionally accelerates the application of submicron carbide tools in
particular for drilling and milling steels.
A good overview on applications of submicron hardmetals as wear parts,
circular shearing and cutting blades for paper, magnetic video tapes etc.,
chipless forming tools and dental tools is given in [3]. In many applications the
performance of such tools was improved by decreasing the WC grain size
from 1 — 0.7 |jm in 1995 to 0.6 — 0.4 pm in 2000. Together with the improved
finishing of the tools and wear parts the step from submicron to ultrafine
carbides could fulfill the increasing demands on such high precision tools as
video tape and paper cutters. Although wood cutting tools are one of the first
application of fine grained carbides, and the carbide tonnages used for them
are further increasing, their share of total consumption of submicron
hardmetals is decreasing. Otherwise the submicron wood cutting tools are in
tough competition to diamond tools. Besides the round tools the tools for the
electronics industry are the most rapidly growing application of submicron and
ultrafine carbide. Together with the metal cutting inserts they will be
discussed in more detail below.
3.1. Microdrills
Microdrills and other tools for machining PCBs (Printed Circuit Boards) are
one of the first und most demanding application for submicron hardmetals.
And as shown in Fig. 11 the number of produced microdrills and the
demanded tonnage of submicron and ultrafine hardmetals applied for these
tools is strongly growing up to now.
500 1.4 200 0.6

to
O „— 180
.£ 400 \
-- 1 . 2
r-.
o
21 160
\ Ac.
\ E a) E
1700 tons! 1 3 15 ,40
T3
O N ^
o 300 \ 120
/ ^ W "Z
0.8 c ©
T3
CD \
/ ' 'ro = 100 0.3 £
CD
O
\ 1 a6
-D200 S I 80 E
E -•0.2
b
570 tons 1 M / 0 4 c | 60
CD o
"5 CD £
E
CD 1 0 0 ^ ^ 40
.Q /
0.2 5 WC Grain Size in M m + 0.1 '.£
E ons HM
20
^-
< 14( tons HM
£ 0.8 0.6
\
0 0
1985 1990 1995 2000 1985 1990 1995 2000
Year Year
Fig. 11: Market development and technical trends for PCB microdrills
Fig. 11 shows also some technical trends of microdrill application and

production. Over the last 15 to 20 years the revolutions per minute were
increased from 80 • 103 min'1 in 1985 to 180 • 103 min"1 in 2000 and in parallel
to this the diameter of microdrills was reduced from 500 urn to 200 urn. As
shown in Fig. 12 the smallest microdrill produced today in a pilot stage has a
diameter of 70 urn which is in the range of a diameter of a human hair. The
tendeny to smaller and smaller drill diameters has to be accompanied by
finer and finer structured hardmetals. State of the art microdrills have only
some hundreds of WC grains at the cutting edge. With an ultrafine hardmetal
showing a mean WC intercept of 0.2 urn and a mean free Co path of 0.03
urn, around 300 WC grains are cutting at the edge of a 70 urn microdrill (see
also Fig. 11 in [17]). To follow the demanding needs of a rapid, progressive
miniaturization of microelectronics the performance of microdrills has to be
continuousely improved by:
• Increase of the reliability of microdrills. That means reducing the failure
probability during drilling thousands of holes in PCBs.
Fig. 12: Submicron carbide tools for PCB machining (left) and the latest
generation of microdrills in comparison to a paper clip and a lead refill (right)
• Reduction of wear at the cutting egde and increase of the lifetime of
microdrills.
• Improvement of the precision of drilling by reducing the bending deviation
of microdrills.
• Increase of productivity of hole drilling by higher cutting speeds and feeds.
For the powder and hardmetal producer this means to supply not only finer
and finer powder but also to improve the quality of powder and hardmetals.
Already ten years ago A. EGAMI et al. [22] and T. FUKATSU et al. [23]
reported on their efforts to optimize submicron hardmetals by proper choise of
dopants, using high purity raw materials with Ca, Al, Mg, C < 5 ppm.Si < 10
ppm and by clean room processing.
This paper reports on the newest generation of microdrills with diameters
down to 70 urn and on microdrills based on optimized ulfrafine grained
hardmetals with 0.2 - 0.3 urn WC intercepts [24]. Doping with VC, Cr3C2 and
(Ta,Nb)C restricts the WC grain growth and increases the room temperature
hardness but also influences the toughness and high temperature properties
such as hot hardness and creep restistance. While VC is the strongest grain
growth inhibitor showing the highest hardness, Cr3C2 has a more positiv
influence on toughness as shown in Fig. 13.
19
17
CD
Q.
15
co
CO 13
CD
c
11
CD
O
CO
1100 1300 1500 1700 1900 2100 2300 2500

Hardness HV30
Fig. 13: _Fracture toughness versus hardness for submicron, ultrafine and fine
grained hardmetals with different doping
1.05
E
>
X
1.00
« 0.95
CD
c
•o
X 0.90
T3
<D
N
"TO 0.85
E
0.80
0 10 20 30 40 50 60 70 80 90 100
VC Fraction of Total Doping [%]
Fig. 14 Normalized hot hardness versus VC fraction of doping for ultrafine

grained hardmetals
15" International Plansee Seminar, Eds. G. Kneringer, P. Rddhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
Therefore a mixed VC/Cr3C2(TaC) doping can result in an optimized

hardness-toughness combination [17], [24]. The relationship between hot
hardness and mixed VC/Cr3C2 doping is shown in Fig. 14. At room and low
temperatures (^ 300 °C) the highest hardness values are found with pure VC
or VC rich doping. Increasing the temperatures to values between 450 und
650 °C for Cr3C2 rich doped 0.6 urn WC hardmetals the highest hardnesses
may be obtained. This corresponds well with the findings of S. INADA and H.
YOSHIMURA [25]. But at temperatures higher than 700 °C the mixed doped
hardmetals with a well balanced VC and Cr3C2 content have the highest
hardnesses. Therefore a hardmetal with a mixed and well balanced VC/Cr3C2
ratio has not only an optimized hardness-toughness combination but also an
excellent hardness for high temperatures (> 650 °C). Based on this a new
ultrafine hardmetal grade THR-D was developed for microdrills. Some
performance features are shown in Figs. 15 and 16. First of all the reliability
of the microdrills could considerably be improved by applying the new grade
THR-D instead of the standard grade THR-U. The tool life tests as shown in
Fig. 15 are made with 300 urn drills by drilling a 2.75 mm thick multilayer
board with 14 layers of Copper each 35 urn thick and 12 layers of glass fibre
reinforced plastics each 188 urn thick.
All of the tested 10 microdrills with the new THR-D hardmetal grade had a
tool life greater than 5.000 strokes. In comparison 5 of the 10 tested
microdrills made from the THR-U standard grade hardmetal were broken
within 2.250 and 5.000 drilling strokes. The mean value of the life time was
4.035 and the standard deviation was 1.110 drilling strokes, see. Fig. 15. The
reduced failure probabilities of the new microdrill generation is essential for
improving the productivity of PCB drilling. Every failure of a microdrill by
fracture means a non-cutting dead time for changing the drill by a new one
from a magazine. This non-cutting time is around 100 times longer than the
time necessary to drill one hole which is between 250 and 400 ms. Due to
productivity and cost reasons the PCB industry accepts at the moment a
failure rate of 1/1000 for drill fracture, but is demanding lower rates for the
future. To avoid drill fracture as life time limiting incident the drilling conditions
are adjusted to the lower fracture limit of drilling strokes typical for a tested lot
of microdrills. Under these drilling conditions (cutting speed, feed, etc.) the
continuousely increasing wear at the cutting edge is life time limiting. Fig. 16
shows how the wear of the cutting edge could be reduced by using microdrills
with the new THR-D ultrafine hardmetal grade. This means the lifetime of the
new generation of microdrills could be increased by reduced fracture failure
as well as by improved wear resistance.
1 Optimized Grade THR-D Drilling Conditions

6- • Standard Grade THR-U
Number of
VI \ / revolutions n : 3
110- 10 min"
1
0 5
o Mean
Cutting Speed vc: 104 m/min
-i—<
4 Value
CO
en -, Feed per
3- revolution : 9 urn/rev
-i
Minimal
Q - - - - • •
Feed per minute f: 1 m/min
2
-1 Value
o '
Contact time of
0
.Q 1- drilling stroke t c : 279 ms
1 2 3 4 5 6 7 8 9 10
Number of tested Microdrills
Fig. 15: Failure of microdrills by fracture during drilling in dependence on the

uitrafine hardmetai grade applied for the drills
Cutting Speed Vc = 90 m/min Cutting Speed Vc = 118 m/min
Competitor THR-U THR-D Competitor THR-U THR-D
Fig. 16: Improved wear resistance and lifetime of microdrills based on the
new uitrafine hardmetai grade THR-D
3.2. Metal cutting inserts

Nowadays metall cutting inserts comprise only a small share of the total
consumption of submicron and ultrafine carbides although conventional fine
grain sized (0.8 - 1.3 urn WC) inserts are the working horse of the metal
machining industry. Besides the high price pressure, difficulties in pressing
and defect free vacuum sintering prevented submicron carbides up to now
from stronger penetration into the insert market. But based on improved
pressing and sintering behaviour of the submicron and ultrafine carbides (see
sections 2.1. and 2.2.) the tendencies to dry machining, high speed cutting
and the dramatic changes in workpiece materials make the submicron and
ultrafine carbide inserts a fast growing application now.
3.2.1. Machining cast steel and iron
Up to now coated inserts are mainly applied to prevent the submicron
hardmetals from thermal overloading and degrading performance. Fig. 17
however shows the impressive cutting performance of uncoated ulfrafine
carbide milling inserts. Cast iron engine blocks (GG 26 Cr) are first milled by
roughing with a conventional coated K15 grade HC-K15-M. The finishing
operation is done with a conventional coated K05 grade, HC-K05-M, and in
comparison to that with an ultrafine uncoated grade THM-U. For the cutting
conditions specified in Fig. 17 the number of finished engine units increases
from 3.200 to more than 8.000 by using the ulfrafine carbide grade THM-U
instead of the coated K05 grade.
3.2.2. Milling of aluminium alloys
To reduce the weight and to increase the mass specific power of cars more
and more light alloys are applied for motors and gears. In particular AISiMg-
alloys substitute cast iron as standard materials for motor blocks. Only five
years ago around 80 % of all motor and gear blocks are made from cast iron
and only 20 % were made from light alloys. Today the ratio has strongly
shifted towards aluminium alloys, although vermicular cast iron (VGG) has
brought some improvements compared to conventional cast iron. To develop
and produce cutting tools for light alloys is therefore of increasing importance.
Submicron and ultrafine hardmetals have a big potential to meet the
requirements necessary for this fast growing tool market. The thermal
loadings and temperatures during turning, milling and drilling of aluminium
and magnesium alloys are in a range where the advantageous properties of
submicron and ultrafine hardmetals can be exploited successfully. For cutting
edge temperatures below 700 - 800 °C the high hardness, abrasive and
thermal wear resistance and cutting edge stability of submicron and ultrafine
hardmetals result in higher lifetimes and allow higher cutting speeds and
feeds compared to conventional hardmetals. Also the surface quality
(roughness) may be improved by using ulfrafine hardmetals with sharp and
specially designed cutting edges. To demonstrate the excellent performance
of ultrafine hardmetals Figs. 18 and 19 show results of milling operations on
gearbox and valve cases of AlSiCu and AISiMg alloys.
Workpiece: GG 26 Cr Tool: Hexacut M 750 (for roughing and

Engine Units finishing)
finishing excess length = 0.04 mm
Roughing: • 39 Inserts HNGF 090520-MM
•Grade: HC-K15-M
Finishing: • 13 Inserts HNGF 090512-MF
8000 • Grade: 1. Coated HC-K05-M
2. Ultrafine THM-U
Cutting
conditions: vc = 125.3 m/min
= 0.361 mm/t
= 0.50 mm
Coated Grade Ultrafine HM

HC-K05-M THM-U
Fig. 17: Tool life advantages for ultrafine, uncoated milling inserts THM-U.
Comparison is made with coated HC-K05-M insert in milling GG 26 Cr engine
blocks (oil sump side)
In Fig. 18 a two step milling operation - roughing with conventional K10 grade
and finishing with a PCD insert - is compared with a one step roughing
/finishing operation using an ultrafine carbide grade THM-U for both
operations. Using THM-U inserts the number of machined GK-AISi18Cu3
gearbox cases can be increased from 400 to 1200 per tool and the cutting
time per workpiece can be reduced from 4 to 2.7 min. In Fig. 19 the lifetime
and productivity improvement for machining AISi10Mg(Cu) valve cases are
shown if ultrafine carbide grade THM-U inserts are used instead of submicron
grade THM-F milling inserts.
15'" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
Workpiece: GK-AISi 18 Cu3

Gearbox Cases
1500
4 1200
•£ 1200 4 .g
c
CO
900 3 Inserts :XPHT160404 ALP
2,7 Tool : M 680 Square shoulder mill
.03
Roughing/
O) Roughing Finishing Finishing
"o 600 2 .E HM-K10 PKD THM-U
O -4—>
400 ^ H 4—1
z [St] 3 2 5
300 i
by ^^B
• I O
I
a
p
ae [mm]
n
[mm]
[U/min]
3-4
9-46
4200
0.3
M6
5500
3-4/0.3
9-46
5500
K10/PKD
il
THM-U
vf
fz
[mm/min]
[mm/z]
v c [m/min]
1500
0.12
830
2500
0.23
1088
2000
0.07
1088
Fig. 18: Enhanced tool life and reduced cutting time by using ulfrafine milling
inserts THM-U for milling GK-AISi18Cu3 gearbox cases
Workpiece: AISMOMg (Cu) 2000
w
Valve Cases 1800
CO
Cutting Conditions: CL
vc = 1820 m/min, ap = 2 - 4.5 mm 1600
TJ
ae = 4 - 20 mm 0 1400
fz = 0.13 mm/Z-0.2 mm/Z
O 1200
CO
1000
o 800
600
E 400
200
0
Competitor THM-F THM-U
(*) Milling Tool, D = 40 mm,
z = 5 XCKX13T304R-ME10
(**) M680-Milling Tool, D = 40 mm,
z = 4XPHT160404-ALP
Fig. 19: Increased productivity in milling AISi10Mg(Cu) valve case by using

ulfrafine THM-U inserts
3.2.3. HSC milling of crankshafts

Compared to the established machining operations as turn-turn broaching
and internal milling the dry HSC (High Speed Cutting) external milling of
crankshafts offers some technological and ecological advantages. However,
the tool for this dry HSC milling has to meet extremly high demands
concerning
• high temperature wear resistance
• high mechanical stability of the cutting edge
• excellent thermoshock resistance and fatigue strength.
Only a very fine grained hardmetal as the underlying substrate in combination
with an optimized multilayer coating and a well adjusted micro- and
macrogeometry of the cutting edge and tool can meet the heavy demands on
the tool, see Fig. 20. The high hardness, mechanical stability, stiffness and
wear resistance maybe exploited only if the thermal loading during the dry
HSC milling can be limited. To restrict the thermal loading of the fine grained
m
O
Diameter 700 mm
Workpiec 9:GGG60
W Insert: 180
zeff: 45
ap: 22 mm
1b - ae: 3 mm
CD
i 1,
o2 10 •
Fine grained
hardmetal
* ,
* i1
Q
i
5
Conventional
hardmetal
(D i "*
New developed HSC milling inserts * • *
• 3 special fine grained hardmetals E 0

• 2 new coating systems 150 250 300 350 400 450 500 550
• Optimized tool geometry
• Optimized cutting edge Cutting Speed V c [m/min]
Fig. 20: HSC milling of GGG 60 crankshafts. By using ultrafine grained

inserts the number of milled crankshaft pins can be doubled.
G. Gille et al. HMJ 809^
15" International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding A 6 , Reutte (2001), Vol. 2
hardmetal a newly developed Ti(C,N)/AI203/Zr(C,N) coating with a strong

<111>-texture is necessary. This special coating reduces the heat
production and regulates the heat transport preferable to the workpiece. In
Fig. 20 those improvements are shown which can be obtained in dry HSC
milling of GGG 60 crankshafts by using the very fine grained hardmetal as
the heart of the tool.
4. New ultrafine (nano) hardmetal with 0.1 [im WC intercept

To meet future requirements of the hardmetal industry and to follow their
trends towards finer and finer grain sized tools, a new WC powder was
developed using a completely new carburization process [27], [28]. Powder
characteristics and the resulting hardmetal properties are shown in Fig. 21.
By considering powder properties such as FSSS-value or particle size
distribution alone, some misunderstandings may result because these
properties are influenced by the powder treatment before measurement and
by the insufficient discrimination of the measuring method itself. The best and
most realistic way to characterize the powder is to measure the hardmetal
properties, such as hardness and coercivity, as well as hardmetal structure
[28], [29]. Particle size distribution of the structure, as measured by the linear
intercept or point counting method, are most closely connected to hardness
and other hardmetal properties [17], [28].
The comparison between the new WC 0.1 L grade and the finest,
commercially available WC DS 40 and DS 60 grades from H. C. STARCK is
therefore made on the basis of the hardmetal structure and properties, see
Fig. 21. For the first time, an arithmetic mean linear intercept of 0.1 urn = 100
nm for a WC - 10 wt % Co hardmetal could be measured and the hardness
HV30 clearly surpasses 2000. This nano sized structure and high hardness
was obtained with a mixed VC/Cr3C2 doping content of only 1 wt % in total.
Producing a nano sized, homogeneous and pure WC powder is only the first
step to end up successfully with the wanted, very fine grained hardmetal, see
chapt. 2.1. and 2.2. of this paper. Besides optimized milling and sintering
conditions a possible explanation and reason for the successful
transformation of the ultrafine WC 0.1 L powder into a 0.1 u m hardmetals is
shown in Fig. 22.
For all lots of WC 0.1 L powder the combination of crystallite size and lattice
distortion, both measured by X-ray diffraction, is within the marked area in
Fig. 22 . Investigations on commercially available, ultrafine WC powder show
that the combinations of crystallite size and lattice distortion are outside the
marked area. This means that the combination of low crystallite size and low
5" International Plansee Seminar, Eds. G. Kneringer, P. Rödhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
100
90
80
70
60
.O
WC DS 60 •
o 50 - i . , M
• WCDS40 ! '. ' •
40 ® WC0,1L
30
E
20
ü
10
„ -;-•'
0,01 0,1 1 10
WC Intercept [um]
Powder di o 1 ) d50 1 ) d9 0 1 ) Ad2) dFSSS dso 3 )

WC DS 60 0. 34 0 .57 1.36 1.02 0 .55 0 .22
WC DS 40 0.23 0 .44 1.02 0.79 0 .48 0 .17
WC 0.1 L 0. 14 0 .26 0 .56 0.42 0 .33 0 .10
1) 1
All values in |jm SEDIGRAPH 5000 D Ad = d 90 - d
3)
d 5 0 = 50 % value of intercept distribution
Hardmetal P , Hc 4TTOS HV30 Kc

Composition [g/cm3] [kA/m] [MTm3/kg] at 20 °C [N/mm]
WC 0.1 L- 6wt%Co 14.83 53.3 10.2 2280 370
WC 0.1 L-10wt%Co 14.46 45.4 17.2 2043 530
WCDS 40-10 wt% Co 14.43 35.8 19.0 1870 810
WC 0.1 L-12wt%Co 14.30 41.8 21.9 1910 570
WC 0.1 L-15wt%Co 13.95 35.8 27.7 1700 725
Fig. 21: Properties of submicron (0.6 pm WC) and ultrafine (0.45 um WC)
grained WC powder and hardmetals in comparison with a new WC 0.1 L
grade
lattice distortion is typical for the new WC 0.1 L WC grade. The lattice
distortion measured by X-ray diffraction is a measure of stacking fault and
dislocation densities within the closed packed hexagonal (cph) lattice of WC.
The higher these densities, the higher the lattice distortion. A highly distorted
lattice however, shows a tendency to stronger grain growth in the solid state
as well as in the stage of liquid phase sintering. The low lattice distortion of
the WC 0.1 L powder explains some of the advantageous features such as
stable sintering, structure fineness and homogeneity without strong
continuous and discontinuous grain growth.
0.12
0.11 • WC0.1L powder
O Conventional ultrafine WC-powder

0.1
* -
0.09
c
— —
-—-^
o
•
0.08
a
CD
0.07
O w W
ifci \
TO 0.06 \ I
V w
0.05 \
P
W
0.04 \
0 20 40 60 80 100 120 140 160 180 200 220 240 260
Crystallite size [nm]

Fig. 22: Lattice distortion versus crystallite size for conventional ulfrafine WC
and the new WC 0.1 L powder
Looking at the shrinkage rate or the ARRHENIUS plot of sintering curves the
tendency towards a wavy shaped curve as already typical for a 0.45 urn WC
is yet more pronounced for the new WC 0.1 L grade (0.30 um FSSS value),
see Fig. 23. Although the shrinkage rates may be very roughly approximated
by straight lines a subdivision into four or five steps seems to be more
appropriate to the experimental results obtained for the 0.45 and 0.30 um WC
hardmetals. It seems there are some "stick and slip" mechanisms behind the
local particle rearrangements. The higher the temperature the higher the
number of particles in a cluster which are able to a coordinated move or

rearrangement. After some localized rearrangements the densified cluster
may easily fill up the surrounding pores or "diluted areas". That means a
steep increase of shrinkage rate is followed by a flat curve for the fill up
process, see Fig. 23. The next steep increase is related to a higher number of
particles moving correlated in a bigger cluster comprising some of the smaller
clusters one step before. Finally the diameter of the cluster or the "correlation
length" (in terms of phase transformation) is in the order of the specimen
diameter itself.
1300 1100 900 800 1300 1100 900 800
100.0 100.0
QA= 290 kJ/mol Qc= 185 kj/mol
= 20 kJ/mol QD= 330 kj/mol
0.1
(1/T)- 104 [K/min] (1/T)- 104 [K/min]
Fig. 23: ARRHENIUS plots of WC - 10 wt % Co hardmetals with 0.45 urn

and 0.30 urn WC (WC 0.1 L). The experimental curves are approximated by
one or some straight lines with indications of the corresponding activation
energies.
In comparison to the state of the art, the marked area and points of Fig. 24
finally show the hardness values which may be obtained for different Co
binder contents by using the new WC 0.1 L grade, in ultrafine hardmetals.
th
15 International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
3500
3000
2500
I 2000
w
w
CD 1500
c
CO
I 1000
1 10 100
FSSS Grain Size of WC Powder [urn]
Fig. 24: Hardness values which may be obtained by using the WC 0.1 L
powder with varying Co contents
5. Conclusions
Within the hardmetal industry submicron and ultrafine hardmetals are the
most demanding but also the fastest growing grades in production and
application. Nowadays these grades have a share of around 40 % of the total
hardmetal production and consumption. The further growth of the already well
established applications as round tools, wear parts, wood cutting tools and
microdrills will be stronger than that of the total hardmetal industry and will be
accompanied by increasingly new applications as metal cutting inserts for
HSC or dry cutting or cutting Al, Mg-alloys. To follow these unbroken trends
towards finer and finer hardmetal grades the raw material producers as well
as the hardmetal industry are confronted with demanding challenges:
• With the fabrication of 0.3 - 0.4 urn WC powder the conventional
technology seems to achieve a limit. New technologies as direct or gas
phase carburization, RCR (Rapid Carburization Reaction) or entrainment
process, CVR (Chemical Vapor Reaction) and spray conversion seem to
be necessary to produce WC powder below 0.3 - 0.2 urn as
homogeneous, high quality raw materials in big quantities and at
15L" International Plansee Seminar, Eds. G. Kneringer, P. Rodhammer and H. Wildner, Plansee Holding AG, Reutte (2001), Vol. 2
reasonable costs, see Fig. 25. But also the qualities of the Co metal binder
and other carbide additives as e. g. grain growth inhibitors have to be
further improved to optimize milling and sintering as well as the hardmetal
properties.
Apart from improved raw materials the optimization of processing in
particular milling, pressing and sintering will have a big effect on new
applications and improved performances of ultrafine hardmetals. With
decreasing grain size the share of solid state sintering increases and
therefore all processing steps prior to sintering are increasingly important
for final hardmetal properties.
Further progress more and more needs a closer cooperation between the
raw material producers and the hardmetal industry as well as more
fundamental research and sophisticated methods instead of mainly
empirical investigations, up to now.
3500
- ~P I I I
^mmm Experimental values
and fit curve
3000
* WC0.1L
N
2500
>
X
co 2000
w %k
CD
c
Hard
CVF
1500
/ 11e lative tt ichn DlO jy
ionven ona te ch Ic y
1000- N a Ddyne process
E n r ginment process
Menst 'uun pr ac S
n t carburization
500 p as Tia proce
I
0.01 0.1 1 10
FSSS grain size of WC powder [1 urn]
Fig. 25: New powder producing technologies to follow the trends towards WC
powder < 0.2 urn
1
Literature
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Refractory Alloys, Annapolis/USA, Sept. 2000
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[17] G. Gille, B. Szesny and G. Leitner, Proc. of 14th Int. Plansee Seminar,
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P. Wilhartiz, Innsbruck 1997
[18] W. D. Schubert, A. Bock and B. Lux, Adv. in Powder Met. and
Particulare Mat., Vol. 3 (1999), 10-23, Eds. Ch. L. Rose and M. H.
Thibodeau, Princeton 1999
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AG, Kulmbach 1996
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European Conf. on Advances in Hard Materials Production, Turin Nov.
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ATO100498

SUBMICRON and ULTRAFINE GRAINED HARDMETALS for

G. Gille1), B. Szesny1), K. Dreyer2', H. van den Berg2', J. Schmidt3',

1. Properties of submicron and ultrafine hardmetals

800 - i 1 i—i—i—i— 1500

Co binder, as investigated by J. GURLAND in the fifties and sixties [7], was

• Fine grain sized (conventional) WC-Co hardmetals*'

• Submicron and ultrafine WC-Co hardmetals*'

O Submicron and Ultrafine

Fig. 2: Hardness-toughness and hardness-strength combinations for ultra-

toughness of submicron and ultrafine hardmetals may be improved within a

This superiority in hot hardness up to 800 - 900 °C provides better

effect very similar to that of AI2O3/2rO2 coatings on cutting inserts. On the

2.2. Aspects of Sintering

Pressing Pressure [Mpa] Pressing Pressure [Mpa]

" tr\ 7.6

Pressing Pressure [MPa] Pressing Pressure [MPa]

Fig. 4: Pressing behaviour of submicron WC powders (above) and WC -

<D A - 0.45 Mm WC,

Temperature [°C] (1/T)-1 cf [1/K]

Temperature [°C] Temperature [°C]

Temperature [°C] Temperature [°C]

Fig. 7: Influence of doping on the shrinkage rates of 0.45 urn WC-10 wt % Co

mechanism behind the two stages of solid state densification. The

2. Transforming the pressing forces into an internal hydrostatic pressure

Fig. 8: Stages 1 and 2 of solid state sintering. Experimental curves (right

The highly disordered microstructure of the milled Co binder is annealed at

e H U ~ d p r l - M " " T 1 - - L i + 3vwcJfoo.*T)~lH kT

of the reasons to admix the grain growth inhibitors as early and as

strength and other properties such as wear resistance, which is probably

Discontinuous WC agglomerates Homogeneous and

3. Application of submicron and uitrafine hardmetals

Fig. 10: Submicron and uitrafine hardmetals subdivided due to their

500 1.4 200 0.6

Fig. 11 shows also some technical trends of microdrill application and

1100 1300 1500 1700 1900 2100 2300 2500

Fig. 14 Normalized hot hardness versus VC fraction of doping for ultrafine

Therefore a mixed VC/Cr3C2(TaC) doping can result in an optimized

1 Optimized Grade THR-D Drilling Conditions

Number of tested Microdrills

Fig. 15: Failure of microdrills by fracture during drilling in dependence on the

Cutting Speed Vc = 90 m/min Cutting Speed Vc = 118 m/min

Competitor THR-U THR-D Competitor THR-U THR-D

3.2. Metal cutting inserts

Workpiece: GG 26 Cr Tool: Hexacut M 750 (for roughing and

Coated Grade Ultrafine HM

Workpiece: GK-AISi 18 Cu3

Fig. 19: Increased productivity in milling AISi10Mg(Cu) valve case by using

3.2.3. HSC milling of crankshafts

• 3 special fine grained hardmetals E 0

Fig. 20: HSC milling of GGG 60 crankshafts. By using ultrafine grained

hardmetal a newly developed Ti(C,N)/AI203/Zr(C,N) coating with a strong

4. New ultrafine (nano) hardmetal with 0.1 [im WC intercept

Powder di o 1 ) d50 1 ) d9 0 1 ) Ad2) dFSSS dso 3 )

Hardmetal P , Hc 4TTOS HV30 Kc

0.11 • WC0.1L powder

O Conventional ultrafine WC-powder

Crystallite size [nm]

number of particles in a cluster which are able to a coordinated move or

(1/T)- 104 [K/min] (1/T)- 104 [K/min]

Fig. 23: ARRHENIUS plots of WC - 10 wt % Co hardmetals with 0.45 urn

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