[0001] The present invention generally relates to drilling bits utilized in the oil well
drilling industry and in the mining arts, and more particularly involves a unique
metallic composition for the cutting elements utilized in drilling bits.
[0002] In the conventional drill bit technology, there are generally two kinds of rolling
cutter drill bits, as well as what is termed drag bits having no rolling elements.
The rolling cutter drill bits are generally of the type having cantilevered frusto-conical
cutters such as the tri-cone bit, and there are additionally bits having cutters mounted
transversely on axles supported at each end by saddles, which in turn are affixed
to large cutting heads. This second type of rolling cutter bit primarily is used in
the mining and tunneling industries. In the tri-cone rolling cutter type of bit, there
are generally two kinds of cutter structures utilized, the "milled tooth" cutter,
and the insert cutter. In the milled tooth cutter, a large forging is milled away,
leaving protruding, sharp, wide chisel-shaped teeth as the cutting elements. These
projecting teeth may have a hard. material, such as tungsten carbide, welded to their
faces to increase their erosion resistance. The cutter bodies themselves may be carburized
and hardened to increase their resistance to breakage and wear.
[0003] In addition to the milled tooth cutters, rolling cutter drill bits commonly utilize
insert type cutters wherein a smaller original cutter body is utilized with a minimum
amount of machining, and holes are drilled circumferentially around the cutter body
to receive hard metal cutting inserts which are pressed thereinto. These hard metal
inserts generally are formed of a tungsten carbide composite made in a generally cylindrical
shape with a pointed protruding portion. The insert type cutter bodies generally are
curburized and hardened prior to insertion of the inserts.
[0004] In the mining industry, the saddle type cutters most often used are the milled tooth
variety, although the insert type cutters are becoming more widely used. The formation
of these cutters is similar to that as described above with respect to the tri-cone
drilling bit cutters. In the formation of the rolling cone cutting structures utilized
both in the tri-cone bits and the mining bits, the two types of cutters can generally
be classified as utilizing both gradient techniques and composite techniques, although
none of the conventional cutters have combined these two techniques to arrive at a
gradient composite metallic structure.
[0005] The term "composite" is used in the microstructural sense herein, as is commonly
known in the fields of metallurgy and materials science. It refers to materials having
microstructures composed of at least two individual phases, the volume fraction of
a minor phase being at least 10%, which are bonded together in such a manner that
the average properties of the composite are determined by the individual properties
and morphology of each phase. This usage is distinct from that where an engineering
structure may be referred .to as a "composite" when it is comprised of two or more
distinct, relatively large regions, bonded, coated, welded, or otherwise joined or
internally transformed, forming a heterogeneous unit (See "THE PRINCIPLES OF ENGINEERING
MATERIALS", Barrett, Nix and Tetelman, Prentice-Hall, Inc., 1973, pp. 316 - 317.).
[0006] For example, both the milled tooth cutter and the insert type cutter utilize the
composite structures in that they both have a steel alloy cutter body to which is
added a hard metal cutting surface, or cutting element. In the milled tooth cutter
the composite hard metal element is added as a tungsten carbide alloy weldment which
is fused to the cutting surfaces on the teeth, the gage, and portions of the cutter
body. In the insert type cutter, the composite element is added by the insertion of
the cemented carbide insert into the alloy steel cutter ; shell. The result of these
two types of composite metallurgical construction is a "metallurgical notch", where
a very sharp gradient is formed across the interface between the hard metal and the
alloy steel. In addition to this metallurgical notch, or discontinuity, the composite
formed thereby also suffers from a disadvantage in that a geometrical notch is also
usually formed at the juncture. These metallurgical and geometrical notches serve
to weaken the resulting composite metal component and contribute to earlier failure
of the cutting structure. These discontinuities in elastic moduli, coefficients of
thermal expansion, and yield characteristics limit drilling performance by affecting
the residual stress distributions and applied stress distributions in service. These
characteristics and changes result from all of the different techniques which have
been utilized in . conventional cutter construction for reducing deformation and improving
wear-resistant qualities on drilling equipment.
[0007] The composites utilized in conventional cutters have increased the mechanical strength,
toughness and hardness but have not efficiently optimized these characteristics for
drilling equipment. In addition to the welding of hard metal, such as cemented carbides,
on the cutting structures, other conventional techniques have involved brazing of
the cemented carbides, plasma spraying of cemented carbide coatings, and chemical
and electrical deposition of coatings having high carbide fractions. All of these
techniques suffer from the above-mentioned mechanical and metallurgical discontinuities
at the joint interface. Likewise, the insert cutter construction has been utilized
to improve the mechanical strength, toughness and wear resistance of the cutting structure,
but it still suffers from the elastic strain requirements of the interference fits,
in addition to the limitations of the steel-compos.ite interface on load bearing ability.
[0008] The use of mechanical property gradients in conventional drilling tools has been
known and accepted for many years. For example, gradients are introduced into the
cutting structures by the case hardening, carburizing treatment of steels. The resultant
gradient of a carburized case-hardened steel comprises a hard brittle outer surface
shell with a tapering-off of the hardness and increase in toughness towards the interior
of the part. This has been successful in reducing galling and spalling of bearing
surfaces and other high unit loading contact areas, but offers little improvement
to erosion resistance which is prevalent in rock drilling. Also, this type of gradient
is generally relatively shallow, usually extending no more than 0.050 inches into
the steel component, thus subjecting the surface to cracking or failure by plastic
deformation. Other types of mechanical property gradient-producing processes include
laser and induction hardening, nitriding and boronizing.
[0009] An object of the present invention is to obviate or mitigate the aforesaid disadvantages.
[0010] According to the present invention there is provided a cutter for rock cutting tools
including a cutter body comprising:
an exterior cutter surface region having cutting means thereon; and
an interior cavity having bearing surface means therein; said cutter body having a
portion of substantial thickness comprising a densified powder metallurgical composite
of at least two varying phases, said composite having a substantially continuous mechanical
property gradient through said body portion.
[0011] According to a further aspect of the present invention there is provided a cutting
element for attachment to a rolling cutter which is rotatably mounted on a drill bit,
said cutting element comprising: a root portion adapted for engagement in a bit cutter;
and a cutting portion on said root portion adapted to protrude from a bit cutter in
a cutter orientation; wherein said cutting element comprises a portion of substantial
thickness comprising a densified powder metallurgical composite of at least two varying
phases, said composite having a substantially continuous mechanical property gradient
through said cutting portion.
[0012] According to yet another aspect of the present invention there is provided a powder
metallurgical method of constructing a cutter for a rolling cutter drill bit, said
method comprising:
providing a first powder consisting essentially of a mixture comprising a major proportion
by volume of a powdered refractory compound and a minor proportion by volume of a
powdered binder metal or alloy, providing a second powder comprising a powdered binder
metal or .alloy or a mixture comprising a powdered refractory material and a powdered
binder metal or alloy, present in a lesser proportion by volume than in said first
powder, forming said cutter of said first and said second powders; mixing said powders
while forming said cutter and introducing into a first region of said cutter a mixture
having a first preselected proportion of said first powder relative to said second
powder, changing the relative proportions of said powders while mixing to introduce
into a second region of said cutter a mixture having a second preselected proportion
of said first powder relative to said second powder and a continuous gradient in the
relative proportions of said powders between said regions; and powders into a solid
cutter having a gradient in composition and properties from said first region to said
second region.
[0013] According to a still further aspect of the present invention there is provided a
method of forming a drilling bit insert having combined resistance to abrasion and
bending stresses, said method comprising:
providing a first powder consisting essentially of a mixture comprising a major proportion
by volume of a powdered refractory compound and a minor proportion by volume of a
powdered binder metal or alloy, providing a second powder comprising a powdered binder
metal or alloy or a mixture comprising a powdered refractory material and a powdered
binder metal or alloy, present in a lesser proportion by volume than in said first
powder, providing a cutter insert mold, forming said insert of said first and said
second powders; mixing said powders while forming said insert and introducing into
the central portion of said mold a mixture having a first preselected proportion of
said first powder relative to said second powder, changing the relative proportions
of said powders while mixing to introduce into the outer portion of said mold a mixture
having a second preselected proportion of said first powder relative to said second
powder surrounding said central portion and extending to the outer surface of the
insert formed therein and a continuous gradient in the relative proportions of said
powders between said central portion and said outer portion; and densifying said mixtures
of powders into a solid insert having a gradient in composition and properties from
said central portion to the outer surface thereof.
[0014] The present invention provides an optimum cutting structure by the use of gradual
or continuous gradients across the geometry of the cutting structure. This continuous
or gradual gradient substantially eliminates the interface and the resultant geometrical
and metallurgical notches found in the conventional cutter construction. The elimination
of the discontinuities may involve varying several different paramenters to achieve
different desirable techniques. For instance, the composition, the fraction, the shape,
the size and the distribution of phases in a cemented carbide composite may be systematically
varied by powder metallurgy techniques to produce an insert with continuously varying
properties. The gradient through the insert can be arranged so that a hard, stiff,
abrasion-resistant cemented carbide structure exists at the tip of the insert, merging
into a tougher, softer cemented carbide structure in the regions of high bending stress
lower in the insert body. The gradient across the inserts can also be arranged such
that when fused to the normal alloy steel cutter shell, the attachment surface of
the insert can be substantially of the same composition as that of the alloy steel
cutter shell so that the added insert becomes an integral part of the cutting structure
as though originally formed therewith, and a hard metal core extends downwardly along
the central longitudinal axis of the insert.
[0015] In a second embodiment of the invention, the cutting structure is formed in a single
operation rather than by the addition of inserts to a cutter shell. In this embodiment,
the cutter and the teeth structure are formed in a single manufacturing operation
utilizing powder metallurgy techniques. A programmable mixing system for mixing the
alloying components of a powdered metal alloy serves to place the proper concentrates
of the cemented carbides in the locations requiring the properties of cemented carbides
and gradually reducing the cemented carbide fraction as you move geometrically away
from these critical points. The resulting cutting structures therefore has concentrated
fractions of cemented carbide in the high-stress, high-erosion areas with a gradual
decrease in the hard metal component away from these critical areas towards the body
of the cutter. The alloyed powder metallurgy components are then densified into a
single integral cutting structure utilizing conventional powder metallurgy techniques,
such as hot isostatic pressing. Then the completed cutter is removed from the pressing
die and minor machining operations can be performed to create smooth bearing surfaces
and seal surfaces within the cutter where required. Thus, it can be seen that the
resulting drilling bit cutter offers an optimum metallurgical cutting structure in
that it utilizes the desirable effects of the.composites, such as cemented carbides,
in the locations on the cutter where such characteristics are desirable, and the desirable
characteristics of a tough resilient core, such as the alloy steels, for strength
and foundation in the cutter shell itself with a smooth continuous gradient between
the cemented carbide and the alloy steel to greatly reduce or eliminate discontinuities
and their resultant stress risers. In addition, the locations of the gradients and
the gradient rates can be manipulated to provide favorable compressive residual stress
patterns in a finished component, thereby raising the effective fracture resistance
of the resulting cutting structure.
[0016] Embodiments of the present invention will now be described, by way of example, with
reference to the accompanying drawings in which:-
Fig. 1 is a schematic drawing illustrating one embodiment of a pdwder mixing process
suitable for use in the present invention.
Fig. 2 is a cross-sectional schematic drawing illustrating apparatus for manufacturing
a powdered metal cutter.
Fig. 3 is a partial cross-sectional drawing illustrating a rolling cutter manufactured
by the process of Figs. 1 and 2.
Figs. 4, 5 and 6 illustrate cross-sectional partial views of different embodiments
of the present invention utilized in integral tooth cutters.
Figs. 7 and 8 illustrate partial cross-sectional views of inserts made according to
the present invention, and
Figs. 9 to 11 illustrate graphically the relationship between powder feed rates and
time. ,
[0017] Referring now to Fig. 1, which illustrates a schematic diagram indicating one particular
method of forming the gradient composite metal structures of the present invention,
a plurality of powder supply bins feed powder through a closely controlled auger system
into a mixing chamber from whence it flows into a rotating die. In this embodiment,
-a primary supply bin 10 is supplied with a powdered metal A having a high percent
carbide fraction. A secondary supply bin 11 is provided with a powdered metal B having
a low percent carbide fraction, and a tertiary supply bin 12 is supplied with a powdered
metal C comprising a steel alloy having superior bearing qualities. Primary bin 10
is provided with a funnel-shaped wall 13 feeding through a section 14 into a screw
auger tube 15. A rotating screw 16 is rotatably located in channel 15 to accurately
dispense powder A into the mixing chamber 17. The feed auger 16 is preferably microprocessor-controlled
to precisely discharge controlled amounts of powder A at variable rates into chamber
17. Likewise, secondary bin 11 has a funnel-shaped wall section 18 feeding into a
narrowed throat section 19 and thence into auger tube 20 having screw auger 21 rotatably
mounted therein and tightly controlled by a second microprocessor circuit (not shown).
Tertiary bin 12 has a funnel-shaped wall section 22, throat section 23, screw auger
tube 24, and feed auger 25, which is also microprocessor-controlled for precise metering
of powdered metal C into mixing chamber 17. Powder dispensed in mixing chamber 17
flows through a vibratable discharge chute 26 into a rotating die 27 whenceforth it
is moved by centrifugal force outward into the outer cavities of die 27. A vibrator
48 is located on chute 26 to facilitate the flow of powder therethrough. Fig. 9 illustrates
a schematic graph showing the feed rates of the various powders A, B and C into die
27 in a typical process embodying the present invention. The vertical axis of the
graph shown in Fig. 9 represents the rate of powder flow into the mixing chamber 17
and the horizontal axis indicates the time continuum. It can be seen from Fig. 9 that
by means of the microprocessor system (not shown), which system is well known in the
art, the volume of powder flow initially is heavy in component A and light in component
B, with no component C being introduced. The volume feed rate of component A decreases
with time at about the same rate component B increases with time until a point where
component B peaks out slightly before component A is completely shut off. Component
B then begins to decrease in volume feed rate, and at the time component A is terminated,
component C begins feeding into chamber 17. Component B decreases to a point where
only component C is being introduced into the rotating die and component C is introduced
therein until the die cavity is completely filled.
[0018] By the use of the present system, the high percent carbide fraction A ends up in
the outer extremities and surface portions of the product being formed in the rotating
die 27. Then moving inward towards the inner portion of the component being built,
the percent of high carbide fraction component A gradually reduces as the percent
of component B increases, resulting in a gradual continuum of high carbide fraction
to low carbide fraction. Then towards the inner portion and center of the component
is the final component C comprising a powdered metal of an alloy-steel having superior
bearing surface qualities.
[0019] It should be noted that, in powder metallurgy processes, the powdered metal constituents
of the part being manufactured must be compressed to remove the gas voids and heated
to solidify and strengthen the part. This is normally done in one of several ways.
One method uses a pre-compaction of the powder into a "green" part and then sintering
at a temperature above the liquidus temperature of the binder metal to fuse the powder.
The sintering usually occurs in a vacuum or inert gas atmosphere. An alternative process
comprises Hot Isostatic Pressing, commonly termed, "HIPing". Other processes such
as hot forging are also used. For convenience, all such processes will be occasionally
referred to herein as "densification".
[0020] Referring now to Fig. 2, the rotating die 27 is illustrated in close-up cross-sectional
view. The inner configuration of die 27 is adapted for manufacturing a typical integral
tooth rolling cutter for a tri-cone drilling bit. In this particular embodiment, die
27 comprises a tough metal outer shell 28 made of a material such as steel and a disposable
material 29, such as castable ceramic, molded by a conventional process such as a
lost-wax or investment casting process. Ceramic material 29 is formed in the shell
28 with an internal cavity 30 shaped to correspond to the external dimensions of an
integral tooth cutter body for use in the aforementioned drilling bit. This cavity
generally has a body section 31 which has radially outwardly projecting tooth sections
32. Above the cutter cavity is a generally cylindrical filler neck 33 with a funnel-shaped
top 34, During the powder-filling stage of forming the cutter, powder A is first fed
into the rotating die 27 such that it forms around the surface of the teeth and cutter
body as indicated at 35. The distribution of powdered metal along the irregular surface
of the die cavity may be controlled by the rotary die speed, orientation of the die
rotational axis with respect to the vertical, and/or the geometric configuration of
discharge chute 26. This configuration may be selected to provide a stream of any
desirable width or may be adapted to produce a uniform or non-uniform "curtain" of
powder. Powder A is heavy in the cemented carbide component of the final cutter metallurgical
content. Because of the rich feed rate of component A during the initial filling of
cavity-30, the outer extremities of cavity 30, such as indicated at 35, have an extremely
high percentage content of the cemented carbide component moving inwardly from the
outer surface of the cavity. A gradually decreasing amount of cemented carbide and
increasing amount of matrix material is encountered in the area 36. This corresponds
to the decreasing feed rate of component A and the increasing feed rate of component
B, as shown in Fig. 7. Near the center of cavity 30 is relatively pure component C
corresponding to the far right-hand portion of the graph in Fig. 9. This is indicated
at 37 in Fig. 2. A phantom line 38 is disclosed showing the desired final outline
of the internal portion of the cutter after it has been densified into the final product,
and machined to create internal bearing areas.
[0021] After the varying gradients of the powdered metals have been added to cavity 30,
the die shell is closed by steel cap 40 which is welded across the top, and the gas
content is evacuated through pipe 50. The die is then placed in a HIPing chamber where
a pressurized inert gas such as argon is introduced. The hydrostatic pressure of the
inert gas is increased and the temperature in the chamber is simultaneously increased
until cap 40 is deformed inwardly. The powdered metal is thus compressed radially
outward into cavity 30 to form the final sintered metal part having the external shape
shown in Fig. 3. After a sufficient period-of time, pressure, and temperature to completely
solidify the powdered metal in cavity 30, cap 40 is removed and the ceramic material
29 is fractured to remove the completed, solidified cutter.
[0022] Referring to Fig. 3, the cutter 41 is shown after removal from the centrifugal die.
Cutter 41 may then be machined,to provide bearing surfaces 42 and 43 and a seal cavity
44. Cutter 41 in its final state is a single integral body member having protruding
teeth 45,'with the' body 41 and teeth 45 exhibiting a gradual metallurgical gradient
beginning with a high tungsten carbide surface and thickness 46, and ending in a low
carbide, high steel bearing area 47 for superior bearing surfaces 42 and 43. The gradient
from the extremely high carbide content area 46 to the extremely low carbide content
47 is almost uniform and gradual across this thickness. This resulting cutter has
no metallurgical notches, as mentioned with respect to the prior art, and as a result,
offers extreme hardness and erosion resistance
Jat the outer surfaces and along the cutting members 45 while the inner area 47 provides
extreme toughness and hardenable surface material for bearings and seals. Also, the
cutter exhibits a surface greatly freed of pores and defects.
[0023] Referring now to Figs. 4 to 6, various constructions for cutter teeth are disclosed
in fragmentary, partial cross-sectional illustrations. Fig. 4 illustrates the teeth
32 as shown in Figs. 2 and 3. In tooth 32, the entire outer surface comprises the
tungsten carbide-rich component A with a gradual decrease in carbide in area B and
a relatiyely pure alloy steel in area C. Although tooth 32 is disclosed as part of
the integral cutter member 41, an alternative method of manufacturing cutter 41 is
to form the teeth in a separate operation. Each tooth could be precompacted in green
form utilizing powder metallurgy techniques, and then inserted into their proper cavities
in die 27. Then the remainder of powder to form the cutter body is added to the die
and the entire cutter is then densified by Hot Isostatic Pressing. Alternatively,
the teeth and cutter can be densified separately and then fused together by means
such as electron beam welding.
[0024] Fig. 5 illustrates a different gradient concept embodied in a'tooth member 132. In
this embodiment, a carbide-rich fraction A is disclosed running longitudinally through
the center of a tooth member 132 and downward into the root section 133. The rich
carbide section comprises a generally planar shape running transversely through tooth
member 132. A gradient is established with material B on both sides of the carbide-rich
plane A. The remainder of root section 133 is made up of primarily steel C. The high-modulus
core of this structure is particularly adapted to carry drilling stress into the cutter
body by an internal route rather than across defect-prone surfaces.
[0025] Fig. 6 illustrates in a fragmentary, partial cross-sectional isometric view a third
embodiment 232 of cutting teeth for cutter body 41. In tooth 232, a carbide-rich area
is formed along the surface of the tooth and the root section, and also a carbide-rich
area is formed down through the center of the tooth in a planar shape similar to that
of Fig. 5. Actually, the cutting tooth 232 is a combination of the structure 32 and
132. The remainder of the tooth and a portion of the root section 233 comprise_the
mixed component B, and the remainder of root portion 233 is made up of pure steel
alloy C. As previously mentioned, manufacturing techniques to form the cutting teeth
32, 132 and 232 can be utilized in the process of Fig. 1 to form an integral cutter
assembly or alternatively, the individual cutting teeth may be formed separately in
a gradient forming process and then densified as a unit with the body or may be separately
densified and then added to the cutter body preferably along isopleths of composition
by means such as welding or fusion.
[0026] Although not shown in the drawings, one such procedure for manufacturing these teeth
separately would be cold isostatic pressing in polymeric molds shaped like the final
tooth configuration desired. The mold would be identical for the three embodiments
of cutting teeth, but the introduction of the various powder fractions would be different
for each tooth. The process for tooth 32 would involve spraying the carbide-rich fraction
A with a carrier fluid into the tooth mold initially, then gradually changing to fraction
B and ending up with fraction C. After evacuating the residual carrier vehicle, pressure
would be applied to the mold to form the cutting tooth 32. The resulting green compact
would then be densified by sintering or HIPing.
[0027] Figs. 7 and 8 are partial cross-sectional views of tungsten carbide cutting elements
commonly termed, "inserts". In Fig. 7 insert 110 is formed in the conventional insert
shape but exhibiting the gradient composite concept of the present invention. For
example, insert
'110 comprises a generally truncated conical protrusion 112 extending upward from a
generally cylindrical base portion 113. A central axial core section is made up of
the carbide-rich material A extending throughout the length of insert 110. The mixed
component B is located radially outward from A, and the basic matrix - metal C is
located around the surface of the insert..The carbide-rich fraction extends from the
very tip of truncated portion 11 to the very base of portion 112.
[0028] Conversely, in Fig. 8, insert 111 has a conical base portion 115 and a truncated
conical protruding portion 114. Protruding portions 114 and 112 could alternatively
be formed in another geometrical shape, such as hemispherical, pyramidal, ogive, compound
conical, or any combination of these. Also base portions 113 and 115 could be formed
of any geometrical shape which lends itself to easy fusion into the cutter shell.
The base portion 115 is made conical.for easy welding by a beam welder such as an
electron beam, which can be easily rotated to form the conical weld line along the
surface of base 115. Other surface configurations could be used on base 115 for other
types of welding. For example, for friction or inertia welding, any easily formed
surface of revolution, such as spherical or parabolic, could be employed.
[0029] Insert 111 has a carbide-rich material extending all the way across the top surface
of the truncated portion 114 of the insert. The carbide-rich material A basically
comprises the top end or the cutting end of the insert, and the composite gradient
extends downward towards the lower end of the insert. The process for manufacturing
the inserts shown in Figs. 7 and 8 is very similar to that described above with respect
to Figs. 4 to 6, i.e., filling the die cavity of a stationery or rotating die, followed
by compaction and/or encapsulation, and then sintering or HIPing.
[0030] This results in the gradient composite structures illustrated in Figs. 7 and 8 for
the insert type cutting elements, which inserts exhibit localized tungsten carbide-
enriched areas gradually changing to an almost pure steel alloy, cobalt alloy, or
other matrix metal area such as indicated at C. The finished inserts are then inserted
into openings in the conventional cutter bodies by interference fitting or fusion
techniques.
[0031] In the above-described process, various alloys and elements may be utilized and substituted
in the makeup of components A, B and C. For example, when manufacturing complete cutters
such as illustrated in Figs. 2 and 3, the components A, B and C are selected to provide
a gradient ranging from tungsten carbide to a bearing steel. For example, component
A would comprise a powdered tungsten carbide-cobalt mixture having about 14 to 14.5%
cobalt and the remainder tungsten carbide, with a tungsten carbide grain size of 1.5
to 2 microns. Component B would be a powdered metal comprising about 18 to 19% cobalt
and the remainder powdered tungsten carbide, with the tungsten carbide grain size
being about-1 to 1.5 microns. Component C would be a prealloyed atomized powder of
a bearing steel such as AISI 52100. '
[0032] The rate of powder feed with respect to time for this particular example is illustrated
in the graph of Fig. 10. The initial powder feed would be substantially all of the
A component, with the feed-rate decreasing at a non-linear rate. Concurrently, the
feed-rate of B would begin at zero and increase at a non-linear rate to a maximum
level at approximately the same time the A powder feed-rate ceases. The B feed-rate.
would continue for a short period of time and then be abruptly stopped while the feed-rate
of-C is abruptly initiated at substantially the same time that the B rate is stopped,
and at substantially the same level. .
[0033] As a result of this component feed-rate matrix, a large amount of the tungsten carbide-rich
powder A will be placed in the outer regions of the mold cavity, and then the immediately-inward
regions receive primarily the B material having an increased percentage of the cobalt
matrix and a decreased percentage of tungsten carbide, with the interior portion of
the mold cavity having substantially pure alloy steel. It should be noted that this
feed diagram illustrated in Fig. 10 appears to initiate the discontinuity or gradient
between materials B and C, but this is not detrimental because of several factors.
The elastic and plastic behaviours of materials B and C are very similar, as well
as the temperature coefficients of expansion for these two materials. Likewise, a
certain amount of migration and diffusion between the two materials will occur during
the densification process.
[0034] In addition to this example of forming the cutters of Fig. 2, a second example could
be utilized to obtain different material properties with the gradient composites.
For instance, the A material would comprise a powder having 10% cobalt and 90% tungsten
carbide, with a tungsten carbide grain size of 2 to 3 microns. The B component would
comprise approximately 18 to 19% cobalt powder, with the remainder being tungsten
carbide having a grain size of 1 to 1.5 microns. Component C would comprise a powdered
mixture with 60% of the powder comprising an iron/nickel/carbon alloy, with the remainder
being tungsten carbide of sub-micron particle size.
[0035] Fig. 11 illustrates a feed rate graph for use with this set of powder components.
As in the other examples, powder component A is first introduced into the cavity in
large quantities, and the introduction of powder A decreases in a non-linear fashion
with time. Component B begins introduction and incnases non-linearly as A decreases.
The feed rate of component B peaks and begins decreasing, with component C being introduced
at a point approximately coinciding with the peak of component B and increasing at
a non-linear rate to a point where component C is abruptly terminated. Component A
and component B are both terminated during the increase in feed rate of component
C. Although the aforementioned example is stated as being particularly useful in manufacturing
the cutters of Figs. 2 and 3, it should be noted that this system of component compositions
and feed rates would similarly be advantageous for manufacturing the inserted cutting
teeth, as shown in Figs. 4 to 8.
[0036] Another example of compositions which would be particularly useful for manufacturing
the cutter of Fig. 3 and/or the inserted cutting elements of Figs. 4 to 8 would consist
of component A having about 14.5 to 15% iron/nickel/carbon alloy and the remainder
a tungsten carbide having a grain size of 1.5 to 2 microns. Component B would be a
powder having about 25% of the iron/nickel/carbon alloy, with the remainder a tungsten
carbide having a grain size below 1 micron. Component C would comprise about 60% of
the iron/nickel/carbon alloy, with the remainder being sub-micron sized tungsten carbide
powder. The time-feed-rate relationship of this example would be similar to that of
the immediately preceding example, as illustrated in Fig. 11. As previously mentioned,
this set of components and the associated time-feed-rate relationship would be useful
in manufacturing both integral cutters and replaceable cutting teeth.
[0037] A fourth example of the component feed-rate
;relationship, which is particularly useful in manufacturing the inserts illustrated
in Figs. 7 and 8, would be one utilizing about 10 to 10.5% cobalt and about 90% tungsten
carbide, with a grain size of 2 to 3 microns for component A. Component B would comprise
about 14 to 14.5% cobalt and the remainder tungsten carbide with a grain size of about
1.5 to 2 microns. Component C would comprise about 18 to 19% cobalt and the remainder
a tungsten carbide having a grain size of about 1 to 1.5 microns. The materials of
this example would be utilized in a feed-rate-time relationship similar to that disclosed
in Fig. 9. An insert manufactured according to this example would be placed in a cutter
shell very similarly to the placement of conventional inserts. The cutter shell would
be drilled with holes, and the inserts would be press-fit into the drilled holes.
[0038] The inserts, or cutting teeth, formed by the third example above, preferably would
be welded into the cutter shell, or might be fusion-bonded in the cutter. The inserts
or cutters formed according to the second example differ from the components manufactured
by the last two examples in that in addition to the gradient in hard metal fractions,
an additional gradient is introduced -that being the chemical gradient between the
tungsten carbide material and the iron/nickel/carbon alloy. Likewise, the first example
introduces the additional chemical gradient between the tungsten carbide hard metal
fraction and the iron/nickel/carbon alloy.
[0039] Although the examples and descriptions given above relating to the processes and
products formed by the present invention deal entirely with the use of three component
systems, i.e., A, B and C, it can be seen that a simpler system utilizing only two
components, i.e., A and B , could be utilized, although the results obtained might
not be as desirable as the three-component system. The two-component system might
comprise a first component A, which is a powdered binder metal or binder metal alloy,
and a second component B, which is a pure powdered tungsten carbide. This two-component
system would be particularly advantageous in manufacturing the insertable cutting
elements such as those disclosed in - Figs. 7 and 8. Conversely, a system could be
utilized to implement the present invention wherein more than three components are
added together to form a more complex gradient within the cutting structure. For example,
a four-component system can be visualized in which the A component may comprise a
pure binder metal or binder alloy powder; the B component may comprise a pure powdered
tungsten carbide; the C component may comprise a mixture of a binder metal and the
tungsten carbide, or the tungsten carbide and a bearing steel alloy; and the D component
may comprise a pure bearing steel alloy. Even further visualizations can foresee five-
and six- component systems for manufacturing the cutting structures, or even more.
[0040] Thus, it can be seen from the description given above that this invention reveals
methods for manufacturing unique, gradient composite cutting structures particularly
advantageous for use in underground drilling tools. These unique methods and the novel
articles manufactured thereby provide cutting structures which have greatly reduced,
and in some cases eliminated, the previously mentioned undesirable metallic and geometric
notches which lead to- early failure in conventional drilling equipment. Primarily
these notches are eliminated by the provision of a gradually changing composite material
which goes from an almost pure cemented tungsten carbide fraction to an almost pure
alloy steel or matrix metal fraction, with the tungsten carbide fraction being located
in the areas of high point contact loading and high erosion, and the matrix metal
or alloy steel being in areas requiring toughness and strength as well as areas requiring
machineability and hardenability suitable for bearing and seal surfaces. Between the
points of high tungsten carbide content and high alloy steel content, the change from
one fraction to the other is gradual rather than abrupt, and as a -result, regions
of high stress normally occurring at metallic and geometric notches have been reduced
or eliminated. In addition to this location of gradual gradients and elimination of
notches and discontinuities, the properties of the cutting structures can also be
varied desirably by changing the rate of gradient utilized in the entire cutting structure
and/or changing the rate of gradients in particular regions of unusual high stress
and/or erosion occurrences. Furthermore, the gradients can be utilized to provide
residual compressive stresses in favourable locations in a finished component to increase
the effective fracture resistance of that element. Other parameters can be closely
controlled and varied by utilizing the present invention, i.e., the grain size of
the tungsten carbide material can be varied to obtain advantages in the different
sized grain structures, the amounts of matrix material in the tungsten carbide fraction
can be varied to obtain varying hardnesses in the resulting cutting elements, and
the alloy content of the C fraction can likewise be varied to obtain particular hardenability
in the bearing surface areas.
[0041] Thus, the present invention embodies the use of intentional variation in the fraction,
composition, shape, size and/or distribution of phases in a cemented carbide/alloy
steel composite to produce an insert or onsert with continuously varying properties.
The property gradients can be designed to accommodate stress field variations resulting
from geometry and loading characteristics.
[0042] Although certain preferred embodiments of the present invention have been herein
described in order to provide an understanding of the general principles of the invention,
it will be appreciated that various changes and innovations can be effected in the
desired composite gradient-structure without departure from these principles. For
example, various residual stresses may be introduced strategically within the cutting
element to increase resistance to failure from cracking and/or erosion. Similarly,
the present invention can be utilized to reduce discontinuities and notches in composite
elements manufactured from metallic fractions other than cemented carbides and alloy
steels. In any event, whatever fractions present in the cutting structure, the present
invention allows one to vary the composite gradient so that the hard phase may possess
orientational variation with respect to location, a changing volume fraction, and
aspect ratio, and the element may also possess a varying metallurgical chemistry.
The binder phase metallurgy could be structured to evidence compatible variation.
Additional phases can be utilized in the composite to result in a greater number of
potential variations which, in light of this invention, would be known to those skilled
in the art of metallurgy. It is also clear that, whereas this invetnion is illustrated
and described in relation to drilling and cutting tools, that it should not be limited
thereto, and can be applied by those skilled in the art to any structural metal component,
given the inventive steps disclosed herein. All modifications and changes of this
type are deemed to be embraced by the spirit and scope of the invention except as
the same may be necessarily limited by the appended claims or reasonable equivalents
thereof.
1. A cutter for rock cutting tools including a cutter body (41) comprising: an exterior
cutter surface region having cutting means (110,111,32,45,132,232) thereon; and an
interior cavity having bearing surface means (42,43) therein- said cutter body (41)
having a portion of substantial thickness comprising a densified powder metallurgical
composite of at least two varying phases, said composite having a substantially continuous
mechanical property gradient through said body portion.
2. A cutter as claimed in claim 1, in which at least one of said phases is a refractory
compound and at least one other phase is a binder metal or alloy.
3. A cutter as claimed in claim 2, in which said refractory compound is a transition
metal carbide.
4. A cutter as claimed in claim 3, in which said metal carbide is tungsten carbide
and said binder metal or alloy is iron, cobalt, nickel or copper.
5. A cutter as claimed in any of claims 1 to 4, in which said composite gradient varies
from one mixture of said phases having wear and deformation resistant properties at
one point ot another mixture of said phases having toughness properties at another
point.
6. A cutter as claimed in any of claims 1 to 4, in which said composite gradient varies
from one mixture of said phases having wear and deformation resistant properties at
one surface of at least part of said cutter body (41) to another mixture of said phases
having toughness properties in another portion pf said cutter body.
7. A cutter as claimed in any of claims 1 to 4, in which said composite gradient varies
from one mixture of said phases having wear and deformation resistant properties at
the exterior surface of said cutting means (110,111,32,45,132,232) to another mixture
of said phases having toughness properties in another part of said cutting means.
8. A cutter as claimed in any of claims 1 to 4, in which said composite gradient varies
from one mixture of said phases having wear and deformation resistant properties at
an exterior surface including the exterior surface of said cutting means (110,111,32,45,132,232)
and the exterior surface of said cutter body.(41).to another mixture of said phases
having toughness properties in another part of said cutter body (41) around said cavity.
9. A cutting member having high surface resistance to galling and spalling and a tough
strong core, said member comprising a body having substantial thickness; said body
further comprising a densified powder metallurgical composite of at least two varying
phases, said composite having a substantially continuous mechanical property gradient
therethrough varying from one mixture of said phases having wear and deformation resistant
properties at the exterior surface of said body to another mixture of said phases
having toughness properties in the core of said body.
-10. A cutting member as claimed in claim 9, in which at least one of said phases
is a refractory compound and at least one other phase is a binder metal or alloy..
11. A cutting member as claimed in claim 10, in which said refractory compound is
a transition metal carbide.
12. A cutting member as claimed in claim 11, in which said metal carbide is tungsten
carbide and said binder metal or alloy is iron, cobalt, nickel or copper.
13. A member as claimed in claim 12, wherein said exterior surface comprises one phase
of binder metal of about 5 to 20 volume percent and another phase of tungsten carbide
particles of about 95 to 80 volume percent, and said core comprises one phase of tungsten
carbide particles of about O to 60 volume percent and another phase of binder metal
of about 100 to 40 volume percent.
14. A member as claimed in claim 13, further comprising a bearing steel alloy in said
core; and wherein said tungsten carbide particles comprise about 70 to 95 volume percent
of said exterior surface and less than about 20 volume percent of said core.
15. A rolling cutter drill bit of the type having at least one generally frusto-conical
cutter rotatably mounted on a bearing shaft, characterized in that said cutter has
at least one cutting element.(32,132,232). protruding from an external surface thereof;
bearing surface means.(42,43).are provided in the interior of said cutter adapted
for co-action with said bearing shaft; and said cutter comprises a densified powder
metallurgical composite of at least two varying phases, said composite having a substantially
continuous mechanical property gradient therethrough varying from one mixture of said
phases having wear and deformation resistant properties at the exterior surface of
said cutter to another mixture of said phases having toughness properties in the bearing
surface means of said cutter.
16. A drill bit as claimed in claim 15 wherein said exterior surface comprises one
phase of binder metal of about 5 to 30 volume percent and another phase of metal carbide
particles of about 95 to 70 volume percent, and said core comprises one phase of metal
carbide particles of about O to 60 volume percent and another phase-of binder metal
of about 100 to 40 volume percent.
17. A drill bit as claimed in claim 16, further comprising a bearing steel alloy in
the region of said bearing surface means.(42,43), said bearing steel having substantially
none of said metal carbide phase therein.
18. A drill bit as claimed in claim 16 or 17,wherein said metal carbide phase comprises
tungsten carbide, said binder metal phase is cobalt, and said cutting element (32,132,232).is
integrally formed on said cutter.
19. A drill bit as claimed in claim 16 or 17, wherein said metal carbide phase comprises
tungsten carbide, said binder metal phase is cobalt, and said cutting element (110,111)
is formed separately from said cutter - and attached thereto.
20. A rolling cutter tool of the type having at least one rotatable cutter.(41).mounted
on a bearing shaft, said cutter having a plurality of cutting teeth.(110,111, 32,
132,232).protruding from the surface thereof and an internal bearing surface in close
proximity to said shaft; characterized in that: said cutter (41) comprises a densified
powder metallurgical composite of at least two varying phases, said composite having
a substantially continuous mechanical property gradient therethrough varying from
one mixture of said phases having wear and deformation resistant properties at the
exterior surface of at least the teeth of said cutter to another mixture of said phases
having toughness properties in another portion of said cutter.
21. A rolling cutter tool as claimed in claim 20, in which the powder metallurgical
composite cutter.(41). comprises at least one phase of a metal carbide and at least
one other phase of a tough binder metal or alloy, said wear and deformation resistant
mixture on the exterior surface comprising a large volume percent of said metal carbide
and a small volume percent of said binder metal or alloy, and said tough mixture in
another portion of said cutter comprising a small volume percent of said metal carbide
and a large volume percent of said binder metal or alloy.
22. A cutting element.(110,111).for attachment to a rolling cutter which is rotatably
mounted on a drill bit, said cutting element comprising: a root portion.(113,115).
adapted for engagement in a bit cutter; and a cutting portion.(112,114).on said root
portion adapted;to protrude from a bit cutter in a cutting orientation; wherein said
cutting element comprises a portion of substantial thickness comprising a densified
powder metallurgical composite of at least two varying phases, said composite having
a substantially continuous mechanical property gradient through said cutting portion.
23. A cutting element as claimed in claim 22, wherein at least one of said phases
is a refractory compound and at least one other phase is a binder metal or alloy.
24. A cutting element as claimed in claim 23, wherein said refractory compound is
a transition metal carbide and said binder metal or alloy is iron, cobalt, mickel
or copper.
25. A cutting element as claimed in any of claims 22 to 24, in which said composite
gradient varies from one mixture of said phases having wear and deformation resistant
properties at one point to another mixture of said phases having toughness properties
at another point.
26. A cutting element as claimed in any of claims 22 to 24, in which said composite
gradient varies from one mixture of said phases having wear and deformation resistant
properties at one surface of at least part of said cutting portion to another mixture
of said phases having toughness properties in another portion thereof.
27. A cutting element as claimed in any of claims 22 to 24, in which said composite
gradient varies from one mixture of said phases having wear and deformation resistant
properties at the exterior surface of said cutting portion to another mixture of said
phases having toughness properties in another part thereof. 28. A cutting element
as claimed in claim 24, wherein said transition metal carbide comprises tungsten carbide
with the volume fraction of tungsten carbide comprising said one phase ranging from
about O percent to about 95 percent and the volume fraction of said binder metal or
alloy comprising said other phase being from about 100 percent to about 5 percent,
at least part of the surface of said cutting portion comprising a large volume fraction
of said tungsten carbide and a small volume fraction of said binder metal or alloy
and another portion of said cutting portion comprising a-substantially lesser volume
fraction of said tungsten carbide and a substantially greater volume fraction of said
binder metal or alloy than on said surface portion, with a continuous composition
gradient therebetween.
29. - A cutting element-as claimed in claim 23,24 or 28, wherein the cutting portion
of said cutting element is chisel-shaped, said one phase is concentrated relative
to said other phase at the surface of said cutting portion, and said other phase is
more concentrated relative to said one phase in the interior of said cutting element.
30. A cutting element as claimed in claim 29, comprising in addition a vertical planar
region comprising a large volume fraction of said one phase and small volume fraction
of said other phase extending transversely through the interior of said element.
31. A cutting element as claimed in claim 23, 24 or 27, wherein said one phase is
concentrated relative to said other phase at the outermost end of said cutting portion.
32. A cutting element as claimed in claim 23,24 or 27, wherein said one phase is concentrated
relative to said other phase along the central longitudinal axis of said cutting element.
33. An insert for use in an insert-type rolling cutter drill bit, said insert comprising:
a geometric base portion.(113,115).for insertion into a matching hole in a drill bit
cutter; and, a tapered,.geometrical cutter portion.(112,114).formed on said base portion
and adapted to protrude from said hole in a drill bit cutter; wherein said insert
cutter portion comprises a densified powder metallurgical composite of at least two
varying phases, said composite having one portion in which one phase is present in
a large volume fraction relative to the other phase, another portion in which said
other phase is. present in larger volume fraction relative to said one phase and having
a substantially continuous mechanical property gradient therebetween.
34.. An insert as claimed in claim 33, wherein said base portion.(115).is substantially
conical and said one phase comprises a transition metal carbide and said other phase
comprises a binder metal or alloy.
35. An insert as claimed in claim 33, wherein said base portion.(113).is substantially
cylindrical and said one phase comprises a transition metal carbide and said other
phase comprises a binder metal or alloy.
36. Ah insert as claimed in claims 34 or 35, wherein said transition metal carbide
comprises tungsten carbide and said binder metal or alloy is iron, nickel, cobalt
or copper.
37. An insert as claimed in any of claims 33 to 35, wherein said one phase of said
powder metallurgical composite is concentrated relative to said other phase along
the central longitudinal axis of said insert and said other phase is concentrated
relative to said one phase near the outer surface of said insert, with a radially
oriented gradient therebetween.
38. An insert as claimed in any of claims 33 to 35, wherein the outermost end of said
protruding portion of said insert has one phase concentrated relative to the other
phase, and the base portion has the other phase concentrated relative to said one
phase, with a longitudinal gradient therebetween.
39. A powder metallurgical method of constructing a cutter.(41).for a rolling cutter
drill bit, said method comprising: providing a first powder consisting essentially
of a mixture comprising a major proportion by volume of a powdered refractory compound
and a minor proportion, by volume of a powdered binder metal or alloy, providing a
second powder comprising a powdered binder metal or alloy or a mixture comprising
a powdered refractory material and a powdered binder metal or alloy, present in a
lesser proportion by volume than in said 'first powder, forming said cutter of said
first and said second powders; mixing said powders while forming said cutter and introducing
into a first region of said cutter a mixture having a first preselected proportion
of said first powder relative to said second powder, changing the relative proportions
of said powders while mixing to introduce into a second region of said cutter a mixture
having a second preselected proportion of said first powder relative to said second
powder and a continuous gradient in the relative proportions of said powders between
said regions; and densifying said powders into a solid cutter having a gradient in
composition and properties from said first region to said second region.
40. A cutter constructing method as claimed in claim 39, wherein said first-named
mixture of powders is located along at least a portion of the cutting surface of said
cutter.(41).and said second-named mixture of powders is located around at least a
portion of the interior surface of said cutter.
41. A cutter construction method as claimed in claim 39 or 40 wherein said mixture
of powders formed into the shape of said cutter is densified by hot isostatic pressing.
42. A cutter constructing method as claimed in any of claims 39'to 41, further comprising
machining a bearing surface (42, 43) in said interior surface of the densified cutter.
43. A method of constructing an abrasion and fracture resistant cutter for rock and
underground formation cutting, said method comprising: securing a mould having a cavity.(30).substantially conforming to the desired exterior shape of said cutter; forming
a cutter.(41).in said mould by the steps defined in claim 1, and separating said densified
cutter from said mould.
44. A cutter construction method as claimed in claim 43, further comprising: forming
at least one powdered metal cutting element into a precompacted form having at least
two different regions with mixtures of metallic phases with a gradient therebetween;
and placing at least one said cutting element into said mould cavity immediately prior
to introducing said mixtures of powders into said mould.
45. A method of forming a drilling bit insert.(110,111). having combined resistance
to abrasion and bending stresses, said method comprising: providing a first powder
consisting essentially of a mixture comprising a major proportion by volume of a powdered
refractory compound and a minor proportion by volume of a powdered binder metal or
alloy, providing a second powder comprising a powdered binder metal or alloy or a
mixture comprising a powdered refractory material and a powdered binder metal or alloy,
present in a lesser proportion by volume than in said first powder, providing a cutter
insert mould, forming said insert.(110,111).of said first and said second powders;
mixing said powders while forming said insert and introducing into the central portion
of said mould a mixture having a first preselected proportion of said first powder
relative to said second powder, changing the relative proportions of said powders
while mixing to introduce into the outer portion of said mould a mixture having a
second preselected proportion of said first powder relative to said second powder,
surrounding said central portion and extending to the outer surface of the insert
formed. therein and a continuous gradient in the relative proportions of said powders
between said central portion and said outer portion; and densifying said mixtures
of powders into a solid insert having a gradient in composition and properties from
said central portion to the outer surface thereof.
46. A method as claimed in claim 45, wherein said central portion comprises a large
volume fraction of said refractory compound and a small volume fraction of said binder
metal or alloy, and said outer portion comprises a smaller volume fraction of said
refractory compound and a larger volume fraction of said binder metal or alloy.
47. A method as claimed in claim 45, wherein said central portion comprises a smaller
volume fraction of said refractory compound and a larger volume fraction of said binder
metal or alloy, and said outer portion comprises a large volume fraction of said refractory
compound and a small volume fraction of said binder metal or alloy.
48. A method as claimed in any of claims 45 to 47, wherein said refractory compound
comprises a transition metal carbide, and said binder metal or alloy comprises a metal
selected from iron, nickel cobalt, or copper.
49. A method as claimed in any of claims 45 to 47, wherein said refractory compound
comprises tungsten carbide, and said binder metal or alloy comprises a metal selected
from iron, nickel cobalt, or copper.
50. A method of forming a drilling bit insert.(110,111). haying combined resistance
to abrasion and bending stresses, said method comprising: providing a first powder
consisting essentially of a mixture comprising a major proportion by volume of a powdered
refractory compound and a minor proportion by volume of a powdered binder metal or
alloy, providing a second powder comprising a powdered binder metal or alloy or a
mixture comprising a powdered refractory material and a powdered binder metal or alloy,
present in a lesser proportion by volume than in said first powder, providing a cutter
insert mould, forming said insert.(110,111).of said first and said second powders;
mixing said powders while forming said insert and introducing into the tip portion
of said mould a mixture having a first preselected proportion of said first powder
relative to said second powder, changing the relative proportions of said powders
while mixing to introduce into the base portion of said mould a mixture having a second
preselected proportion of said first powder relative to said second powder and a continuous
gradient in the relative proportions of said powders between said tip portion and
said base portion; and densifying said mixtures of powders into a solid insert having
a gradient in composition and properties from said tip portion to the base thereof.
51. A method as claimed in claim 50, wherein said tip portion comprises a large volume
fraction of said refractory compound and a small volume fraction of said binder metal
or alloy, and said base portion comprises a smaller volume fraction of said refractory
compound and a larger volume fraction of said binder metal or alloy.
52. A method as claimed in claim 50 or 51, wherein said refractory compound comprises
a transition metal carbide, and said binder metal or alloy comprises a metal selected
from iron, nickel cobalt, or copper.
53. A method as claimed in claim 50 or 51,'wherein said refractory compound comprises
tungsten carbide, and said binder metal or alloy comprises a metal selected from iron,
nickel cobalt, or copper.
54. A method according to any of claims 39, 45 or 50 in which said powders are admixed
with a fluid carrier to form at least one slurry prior to introduction into said mould
cavity and said slurry sprayed into said mould cavity.
55 A method according to any of claims 39, 45 or 50 in which the powders are mixed
and the composition selectively changed during introduction into the mould cavity,
and said mixing and changing of composition is controlled by a microprocessor.
56. A method according to any of claims 39, 45 or 50 in which said second powder comprises
a mixture comprising a powdered refractory material and a powdered binder metal or
alloy, present in a lesser proportion by volume than in said first powder, additionally
providing a third powder comprising a binder metal or alloy, and said powders being
formed or introduced into a mould in compositions ranging from a mixture comprising
said first powder in one region through intermediate mixtures comprising at least
two of said powders in an intermediate region to a composition comprising said third
powder in another region.