U.S. patent application number 14/440781 was filed with the patent office on 2015-09-17 for polycrystalline super hard construction and a method for making same.
The applicant listed for this patent is ELEMENT SIX ABRASIVES S.A.. Invention is credited to Nedret Can, Habib Saridikmen.
Application Number | 20150259987 14/440781 |
Document ID | / |
Family ID | 47429169 |
Filed Date | 2015-09-17 |
United States Patent
Application |
20150259987 |
Kind Code |
A1 |
Can; Nedret ; et
al. |
September 17, 2015 |
POLYCRYSTALLINE SUPER HARD CONSTRUCTION AND A METHOD FOR MAKING
SAME
Abstract
A polycrystalline super hard construction comprising a body of
polycrystalline diamond (PCD) material and a plurality of
interstitial regions between inter-bonded diamond grains forming
the polycrystalline diamond material; the body of PCD material
comprises a working surface positioned along an outside portion of
the body; a first region substantially free of a solvent/catalysing
material; and a second region remote from the working surface that
includes solvent/catalysing material in a plurality of the
interstitial regions. The first region extends to a depth of at
least about 800 microns from the working surface into the body of
polycrystalline diamond material.
Inventors: |
Can; Nedret; (Oxfordshire,
GB) ; Saridikmen; Habib; (Oxfordshire, GB) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ELEMENT SIX ABRASIVES S.A. |
Luxembourg |
|
LU |
|
|
Family ID: |
47429169 |
Appl. No.: |
14/440781 |
Filed: |
November 5, 2013 |
PCT Filed: |
November 5, 2013 |
PCT NO: |
PCT/EP2013/073007 |
371 Date: |
May 5, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61722688 |
Nov 5, 2012 |
|
|
|
Current U.S.
Class: |
175/426 ;
51/309 |
Current CPC
Class: |
E21B 10/567 20130101;
B22F 2005/001 20130101; B24D 3/06 20130101; B22F 7/06 20130101;
B24D 18/0009 20130101; C22C 26/00 20130101 |
International
Class: |
E21B 10/567 20060101
E21B010/567; B24D 18/00 20060101 B24D018/00; B24D 3/06 20060101
B24D003/06 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 5, 2012 |
GB |
1219877.6 |
Claims
1. A polycrystalline super hard construction comprising a body of
polycrystalline diamond (PCD) material and a plurality of
interstitial regions between inter-bonded diamond grains forming
the polycrystalline diamond material; the body of PCD material
comprising: a working surface positioned along an outside portion
of the body; a first region substantially free of a
solvent/catalysing material; and a second region remote from the
working surface that includes solvent/catalysing material in a
plurality of the interstitial regions; wherein the first region
extends to a depth of at least about 800 microns from the working
surface into the body of polycrystalline diamond material.
2. The polycrystalline super hard construction of claim 1, wherein
a majority of the diamond grains in the body within at least a
depth of 800 microns from the working surface have a surface which
is substantially free of catalyzing material, the remaining grains
contacting catalyzing material.
3.-6. (canceled)
7. The polycrystalline super hard construction of claim 1, wherein
the first region extends from the working surface to a depth of: at
least about 800 microns to about 1000 microns; or at least about
800 microns to about 1400 microns; or at least about 850 microns to
about 1400 microns.
8.-9. (canceled)
10. The polycrystalline super hard construction of claim 1, wherein
the first and/or second regions comprise diamond grains of two or
more diamond grain sizes.
11. The polycrystalline super hard construction of claim 10,
wherein the diamond grains have an associated mean free path; the
solvent/catalyst at least partially filling a plurality of the
interstitial regions in the second region having an associated mean
free path; wherein: the median of the mean free path associated
with the solvent/catalyst divided by (Q3-Q1) for the
solvent/catalyst is greater than or equal to 0.5, where Q1 is the
first quartile and Q3 is the third quartile; and the median of the
mean free path associated with the diamond grains divided by
(Q3-Q1) for the diamond grains is less than 0.6.
12. The polycrystalline super hard construction of claim 11,
wherein the median of the mean free path associated with the
solvent/catalyst divided by (Q3-Q1) for the solvent/catalyst is
greater than or equal to 0.6.
13. The polycrystalline super hard construction of claim 11,
wherein the median of the mean free path associated with the
solvent/catalyst divided by (Q3-Q1) for the solvent/catalyst is
greater than or equal to 0.8.
14. The polycrystalline super hard construction of claim 11,
wherein the median of the mean free path associated with the
solvent/catalyst divided by (Q3-Q1) for the solvent/catalyst is
greater than or equal to 0.83.
15. The polycrystalline super hard construction of claim 11,
wherein the median of the mean free path associated with the
diamond grains divided by (Q3-Q1) for the diamond grains is less
than 0.5.
16. The polycrystalline super hard construction of claim 11,
wherein the median of the mean free path associated with the
diamond grains divided by (Q3-Q1) for the diamond grains is less
than 0.47.
17. The polycrystalline super hard construction of claim 11,
wherein the median of the mean free path associated with the
diamond grains divided by (Q3-Q1) for the diamond grains is less
than 0.4.
18.-20. (canceled)
21. The polycrystalline super hard construction according to claim
1, wherein the catalyst/solvent at least partially filling a
plurality of the interstitial regions forms non-diamond phase
pools, the non-diamond phase pools each having an individual
cross-sectional area, wherein the percentage of catalyst/solvent in
the total area of a cross-section of the body of polycrystalline
diamond material is between around 0 to 12%, and the mean of the
individual cross-sectional areas of the non-diamond phase pools in
an analysed image of a cross-section through the body of
polycrystalline material is less than around 0.7 microns squared
when analysed using an image analysis technique at a magnification
of around 1000 and an image area of 1280 by 960 pixels.
22. The polycrystalline super hard construction according to claim
21, wherein the percentage of catalyst/solvent in the total area of
a cross-section of the body of polycrystalline diamond material is
between around 0 to 10%, and the mean of the individual
cross-sectional areas of the non-diamond phase pools in an analysed
image of a cross-section through the body of polycrystalline
material is less than around 0.7 microns squared when analysed
using an image analysis technique at a magnification of around 1000
and an image area of 1280 by 960 pixels.
23. The polycrystalline super hard construction according to claim
21, wherein the percentage of catalyst/solvent in the total area of
a cross-section of the body of polycrystalline diamond material is
between around 0 to 8%, and the mean of the individual
cross-sectional areas of the non-diamond phase pools in an analysed
image of a cross-section through the body of polycrystalline
material is less than around 0.7 microns squared when analysed
using an image analysis technique at a magnification of around 1000
and an image area of 1280 by 960 pixels.
24. The polycrystalline super hard construction according to claim
21, wherein the mean of the individual cross-sectional areas of the
non-diamond phase pools in an analysed image of a cross-section
through the body of polycrystalline material is less than around
0.5 microns squared when analysed using an image analysis technique
at a magnification of around 1000 and an image area of 1280 by 960
pixels.
25. The polycrystalline super hard construction according to claim
21, wherein the mean of the individual cross-sectional areas of the
non-diamond phase pools in an analysed image of a cross-section
through the body of polycrystalline material is less than around
0.4 microns squared when analysed using an image analysis technique
at a magnification of around 1000 and an image area of 1280 by 960
pixels.
26. The polycrystalline super hard construction according to claim
21, wherein the mean of the individual cross-sectional areas of the
non-diamond phase pools in an analysed image of a cross-section
through the body of polycrystalline material is less than around
0.34 microns squared when analysed using an image analysis
technique at a magnification of around 1000 and an image area of
1280 by 960 pixels.
27.-29. (canceled)
30. A cutter for boring into the earth comprising the
polycrystalline super hard construction according to claim 1.
31.-32. (canceled)
33. A method for making a thermally stable polycrystalline diamond
construction comprising the steps of: treating a polycrystalline
diamond construction comprising a polycrystalline diamond body, the
polycrystalline diamond body comprising a plurality of interbonded
diamond grains and interstitial regions disposed therebetween, to
remove a solvent/catalyst material from a first region of the
diamond body while allowing the solvent/catalyst material to remain
in a second region of the diamond body; further comprising during
the step of treating, controlling the depth of the first region so
that it extends from a working surface of the diamond body to a
depth of not less than about 800 microns.
34.-37. (canceled)
38. The method of claim 33, wherein the step of treating comprises
controlling the depth of the first region so that it extends from a
working surface of the diamond body to a depth of: at least about
800 microns to about 1000 microns; or at least about 800 microns to
about 1200 microns; or at least about 800 microns to about 1400
microns.
39.-42. (canceled)
Description
FIELD
[0001] This disclosure relates to a polycrystalline super hard
construction comprising a body of polycrystalline diamond (PCD)
material and a method of making a thermally stable polycrystalline
diamond construction
BACKGROUND
[0002] Cutter inserts for machining and other tools may comprise a
layer of polycrystalline diamond (PCD) bonded to a cemented carbide
substrate. PCD is an example of a super hard material, also called
super abrasive material.
[0003] Components comprising PCD are used in a wide variety of
tools for cutting, machining, drilling or degrading hard or
abrasive materials such as rock, metal, ceramics, composites and
wood-containing materials. PCD comprises a mass of substantially
inter-grown diamond grains forming a skeletal mass which defines
interstices between the diamond grains. PCD material typically
comprises at least about 80 volume % of diamond and may be made by
subjecting an aggregated mass of diamond grains to an ultra-high
pressure of greater than about 5 GPa, typically about 5.5 GPa, and
temperature of at least about 1200.degree. C., typically about
1440.degree. C., in the presence of a sintering aid, also referred
to as a catalyst material for diamond. Catalyst materials for
diamond are understood to be materials that are capable of
promoting direct inter-growth of diamond grains at a pressure and
temperature condition at which diamond is thermodynamically more
stable than graphite.
[0004] Catalyst materials for diamond typically include any Group
VIII element and common examples are cobalt, iron, nickel and
certain alloys including alloys of any of these elements. PCD may
be formed on a cobalt-cemented tungsten carbide substrate, which
may provide a source of cobalt catalyst material for the PCD.
[0005] During sintering of the body of PCD material, a constituent
of the cemented-carbide substrate, such as cobalt in the case of a
cobalt-cemented tungsten carbide substrate, liquefies and sweeps
from a region adjacent the volume of diamond particles into
interstitial regions between the diamond particles. In this
example, the cobalt acts as a catalyst to facilitate the formation
of bonded diamond grains. Optionally, a metal-solvent catalyst may
be mixed with diamond particles prior to subjecting the diamond
particles and substrate to the HPHT process. The interstices within
PCD material may at least partly be filled with the catalyst
material. The intergrown diamond structure therefore comprises
original diamond grains as well as a newly precipitated or re-grown
diamond phase, which bridges the original grains. In the final
sintered structure, catalyst/solvent material generally remains
present within at least some of the interstices that exist between
the sintered diamond grains.
[0006] A problem known to exist with such conventional PCD compacts
is that they are vulnerable to thermal degradation when exposed to
elevated temperatures during cutting and/or wear applications. It
is believed that this is due, at least in part, to the presence of
residual solvent/catalyst material in the microstructural
interstices which, due to the differential that exists between the
thermal expansion characteristics of the interstitial solvent metal
catalyst material and the thermal expansion characteristics of the
intercrystalline bonded diamond, is thought to have a detrimental
effect on the performance of the PCD compact at high temperatures.
Such differential thermal expansion is known to occur at
temperatures of about 400[deg.] C., and is believed to cause
ruptures to occur in the diamond-to-diamond bonding, and eventually
result in the formation of cracks and chips in the PCD structure.
The chipping or cracking in the PCD table may degrade the
mechanical properties of the cutting element or lead to failure of
the cutting element during drilling or cutting operations thereby
rendering the PCD structure unsuitable for further use.
[0007] Another form of thermal degradation known to exist with
conventional PCD materials is one that is also believed to be
related to the presence of the solvent metal catalyst in the
interstitial regions and the adherence of the solvent metal
catalyst to the diamond crystals. Specifically, at high
temperatures, diamond grains may undergo a chemical breakdown or
back-conversion with the solvent/catalyst. At extremely high
temperatures, the solvent metal catalyst is believed to cause an
undesired catalyzed phase transformation in diamond such that
portions of diamond grains may transform to carbon monoxide, carbon
dioxide, graphite, or combinations thereof, thereby degrading the
mechanical properties of the PCD material and limiting practical
use of the PCD material to about 750[deg.] C.
[0008] Attempts at addressing such unwanted forms of thermal
degradation in conventional PCD materials are known in the art.
Generally, these attempts have focused on the formation of a PCD
body having an improved degree of thermal stability when compared
to the conventional PCD materials discussed above. One known
technique of producing a PCD body having improved thermal stability
involves, after forming the PCD body, removing all or a portion of
the solvent catalyst material therefrom using, for example,
chemical leaching. Removal of the catalyst/binder from the diamond
lattice structure renders the polycrystalline diamond layer more
heat resistant.
[0009] Due to the hostile environment that cutting elements
typically operate, cutting elements having cutting layers with
improved abrasion resistance, strength and fracture toughness are
desired. However, as PCD material is made more wear resistant, for
example by removal of the residual catalyst material from
interstices in the diamond matrix, it typically becomes more
brittle and prone to fracture and therefore tends to have
compromised or reduced resistance to spalling.
[0010] There is therefore a need to overcome or substantially
ameliorate the above-mentioned problems to provide a PCD material
having increased resistance to spalling and chipping.
SUMMARY
[0011] Viewed from a first aspect there is provided a
polycrystalline super hard construction comprising a body of
polycrystalline diamond (PCD) material and a plurality of
interstitial regions between inter-bonded diamond grains forming
the polycrystalline diamond material; the body of PCD material
comprising: [0012] a working surface positioned along an outside
portion of the body; [0013] a first region substantially free of a
solvent/catalysing material; and [0014] a second region remote from
the working surface that includes solvent/catalysing material in a
plurality of the interstitial regions; [0015] wherein the first
region extends to a depth of at least about 800 microns from the
working surface into the body of polycrystalline diamond
material.
[0016] Viewed from a second aspect there is provided a method for
making a thermally stable polycrystalline diamond construction
comprising the steps of: [0017] treating a polycrystalline diamond
construction comprising a polycrystalline diamond body, the
polycrystalline diamond body comprising a plurality of interbonded
diamond grains and interstitial regions disposed therebetween, to
remove a solvent/catalyst material from a first region of the
diamond body while allowing the solvent/catalyst material to remain
in a second region of the diamond body; [0018] further comprising
during the step of treating, controlling the depth of the first
region so that it extends from a working surface of the diamond
body to a depth of not less than about 800 microns.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Various embodiments will now be described in more detail, by
way of example only, and with reference to the accompanying figures
in which:
[0020] FIG. 1 is a schematic drawing of the microstructure of a
body of PCD material;
[0021] FIG. 2 is a schematic drawing of a PCD compact comprising a
PCD structure bonded to a substrate;
[0022] FIGS. 3a to 3c are schematic cross-sections through a
portion of the PCD structure of FIG. 2 according to an embodiment
showing progressive wear in application;
[0023] FIG. 4 is a schematic side view of an example assembly
comprising first and second structures;
[0024] FIG. 5 is a schematic diagram of part of an example pressure
and temperature cycle for making a super-hard construction;
[0025] FIGS. 6 to 10 are schematic diagrams of parts of example
pressure and temperature cycles for making a PCD construction;
[0026] FIGS. 11a and 11b are processed images of a micrograph
(shown in negative) of a polished section of an embodiment of a
body of PCD material at different diamond densities;
[0027] FIG. 12 is a plot of wear scar area against cutting length
in a vertical borer test for an embodiment; and
[0028] FIG. 13 is a plot of wear scar area against cutting length
in a vertical borer test for another embodiment.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0029] With reference to FIG. 1, a body of PCD material 10
comprises a skeletal mass of directly inter-bonded diamond grains
12 and interstices 14 between the diamond grains 12, which may be
at least partly filled with filler or binder material. The filler
material may comprise, for example, cobalt, nickel or iron and also
or in place of may include one or more other non-diamond phase
additions such as for example, Titanium, Tungsten, Niobium,
Tantalum, Zirconium, Molybdenum, Chromium, or Vanadium, the content
of one or more of these within the filler material being, for
example about 1 weight % of the filler material in the case of Ti,
and, in the case of V, the content of V within the filler material
being about 2 weight % of the filler material, and, in the case of
W, the content of W within the filler material being about 20
weight % of the filler material.
[0030] PCT application publication number WO2008/096314 discloses a
method of coating diamond particles, to enable the formation of
polycrystalline super hard abrasive elements or composites,
including polycrystalline super hard abrasive elements comprising
diamond in a matrix selected from materials selected from a group
including VN, VC, HfC, NbC, TaC, Mo.sub.2C, WC. PCT application
publication number WO2011/141898 also discloses PCD and methods of
forming PCD containing additions such as vanadium carbide to
improve, inter alia, wear resistance.
[0031] Whilst wishing not to be bound by any particular theory, the
combination of metal additives within the filler material may be
considered to have the effect of better dispersing the energy of
cracks arising and propagating within the PCD material in use,
resulting in altered wear behaviour of the PCD material and
enhanced resistance to impact and fracture, and consequently
extended working life in some applications.
[0032] In accordance with some embodiments, a sintered body of PCD
material is created having diamond to diamond bonding and having a
second phase comprising catalyst/solvent and WC (tungsten carbide)
dispersed through its microstructure together with or instead of a
further non-diamond phase carbide such as VC. The body of PCD
material may be formed according to standard methods, for example
as described in PCT application publication number WO2011/141898,
using HpHT conditions to produce a sintered PCD table.
[0033] FIGS. 2 and 3a to 3c show an embodiment of a polycrystalline
composite construction 20 for use as a cutter insert for a drill
bit (not shown) for boring into the earth. The polycrystalline
composite compact or construction 20 comprises a body of super hard
material 22 such as PCD material, integrally bonded at an interface
24 to a substrate 30. The substrate 30 may be formed of a hard
material such as a cemented carbide material and may be, for
example, cemented tungsten carbide, cemented tantalum carbide,
cemented titanium carbide, cemented molybdenum carbide or mixtures
thereof. The binder metal for such carbides may be, for example,
nickel, cobalt, iron or an alloy containing one or more of these
metals. Typically, this binder will be present in an amount of 10
to 20 mass %, but this may be as low as 6 mass % or less. Some of
the binder metal may infiltrate the body of polycrystalline diamond
material 22 during formation of the compact 20.
[0034] The super hard material may be, for example, polycrystalline
diamond (PCD).
[0035] The cutting element 20 may be mounted in use into a bit body
such as a drag bit body (not shown). The exposed top surface of the
super hard material 22 opposite the substrate 30 forms the working
surface 34, which is the surface which, along with its edge 36,
performs the cutting in use.
[0036] The substrate 30 may be, for example, generally cylindrical
and has a peripheral surface and a peripheral top edge.
[0037] The exposed surface of the cutter element 20 comprises the
working surface 34 which also acts as a rake face in use. A chamfer
44 extends between the working surface 34 and the cutting edge 36,
and at least a part of a flank or barrel 42 of the cutter, the
cutting edge 36 being defined by the edge of the chamfer 44 and the
flank 42.
[0038] The working surface or "rake face" 34 of the cutter is the
surface or surfaces over which the chips of material being cut flow
when the cutter is used to cut material from a body, the rake face
34 directing the flow of newly formed chips. This face 34 is
commonly referred to as the top face or working surface of the
cutter. As used herein, "chips" are the pieces of a body removed
from the work surface of the body by the cutter in use.
[0039] As used herein, the "flank" 42 of the cutter is the surface
or surfaces of the cutter that passes over the surface produced on
the body of material being cut by the cutter and is commonly
referred to as the side or barrel of the cutter. The flank 42 may
provide a clearance from the body and may comprise more than one
flank face.
[0040] As used herein, a "cutting edge" 36 is intended to perform
cutting of a body in use.
[0041] As used herein, a "wear scar" is a surface of a cutter
formed in use by the removal of a volume of cutter material due to
wear of the cutter. A flank face may comprise a wear scar. As a
cutter wears in use, material may be progressively removed from
proximate the cutting edge, thereby continually redefining the
position and shape of the cutting edge, rake face and flank as the
wear scar forms. As used herein, it is understood that the term
"cutting edge" refers to the actual cutting edge, defined
functionally as above, at any particular stage or at more than one
stage of the cutter wear progression up to failure of the cutter,
including but not limited to the cutter in a substantially unworn
or unused state.
[0042] With reference to FIGS. 3a to 3c, the chamfer 44 is formed
in the structure adjacent the cutting edge 36 and flank 42. The
rake face 34 is therefore joined to the flank 42 by the chamfer 44
which extends from the cutting edge 36 to the rake face 34, and
lies in a plane at a predetermined angle 8 to the plane
perpendicular to the plane in which the longitudinal axis of the
cutter extends. In some embodiments, this chamfer angle is up to
around 45 degrees. The vertical height of the chamfer 44 may be,
for example, between 350 .mu.m and 450 .mu.m, such as around 400
.mu.m.
[0043] FIGS. 3a to 3c, are schematic representations of the PCD
construction 20 which has been treated to remove residual
solvent/catalyst from interstitial spaces between the diamond
grains using the techniques described in detail below. The depth D
in the PCD layer 22 from the working surface 34 towards the
interface 24 with the substrate 30 from which the solvent/catalyst
has been substantially removed is known as the leach depth.
According to embodiments, this depth D is at least around 800
microns. In some embodiments it is between around 800 and around
1400 microns, in other embodiments, it is between around 850
microns and around 1400 microns, in other embodiments it is between
around 800 microns to around 1200 microns or 1300 microns, and in
other embodiments it is greater than 1000 microns.
[0044] The first point of contact 36 in FIG. 3a is the first
position of the cutting edge at first use. As the cutter wears, the
wear on the cutter is shown by a shift in the dashed line 45 to the
position denoted by the second dashed line 46, as shown in FIGS. 3a
to 3c, together with the shift in cutting edge denoted by reference
numerals 36a and 36b. FIG. 3b shows the first stage with the first
dashed line 45 showing the start of the cut and the second hashed
line 46 showing the progressive wear of the super hard
material.
[0045] FIG. 3c shows further wear of the cutter after additional
use and shows the progression of the wear scar through the PCD
material. The wear has therefore progressed in the leached region
only of the PCD.
[0046] Whilst not wishing to be bound by theory, it has been
appreciated that cracks have a tendency to propagate in the PCD
along the interface between leached and unleached regions of the
PCD. Ordinarily, once the wear reaches the top of the chamfer 20,
this could lead to spalling, however, as the wear scar is
maintained in the leached region of PCD at this point, as shown
schematically in FIG. 3c, spalling is less likely to occur as the
interface between the leached and unleached regions of the PCD
along which the cracks tend to propagate initiating spalling has
yet to be reached by the wear scar.
[0047] The cutter of FIGS. 1 to 3c may be fabricated, for example,
as follows.
[0048] As used herein, a "green body" is a body comprising grains
to be sintered and a means of holding the grains together, such as
a binder, for example an organic binder.
[0049] Embodiments of super hard constructions may be made by a
method of preparing a green body comprising grains of super hard
material and a binder, such as an organic binder. The green body
may also comprise catalyst material for promoting the sintering of
the super hard grains. The green body may be made by combining the
grains with the binder and forming them into a body having
substantially the same general shape as that of the intended
sintered body, and drying the binder. At least some of the binder
material may be removed by, for example, burning it off. The green
body may be formed by a method including a compaction process,
injection or other methods such as molding, extrusion, deposition
modelling methods. The green body may be formed from components
comprising the grains and a binder, the components being in the
form of sheets, blocks or discs, for example, and the green body
may itself be formed from green bodies.
[0050] One embodiment of a method for making a green body includes
providing tape cast sheets, each sheet comprising, for example, a
plurality of diamond grains bonded together by a binder, such as a
water-based organic binder, and stacking the sheets on top of one
another and on top of a support body. Different sheets comprising
diamond grains having different size distributions, diamond content
or additives may be selectively stacked to achieve a desired
structure. The sheets may be made by a method known in the art,
such as extrusion or tape casting methods, wherein slurry
comprising diamond grains and a binder material is laid onto a
surface and allowed to dry. Other methods for making
diamond-bearing sheets may also be used, such as described in U.S.
Pat. Nos. 5,766,394 and 6,446,740. Alternative methods for
depositing diamond-bearing layers include spraying methods, such as
thermal spraying.
[0051] A green body for the super hard construction may be placed
onto a substrate, such as a cemented carbide substrate to form a
pre-sinter assembly, which may be encapsulated in a capsule for an
ultra-high pressure furnace, as is known in the art. The substrate
may provide a source of catalyst material for promoting the
sintering of the super hard grains. In some embodiments, the super
hard grains may be diamond grains and the substrate may be
cobalt-cemented tungsten carbide, the cobalt in the substrate being
a source of catalyst for sintering the diamond grains. The
pre-sinter assembly may comprise an additional source of catalyst
material.
[0052] In one version, the method may include loading the capsule
comprising a pre-sinter assembly into a press and subjecting the
green body to an ultra-high pressure and a temperature at which the
super hard material is thermodynamically stable to sinter the super
hard grains. In some embodiments, the green body comprises diamond
grains and the pressure to which the assembly is subjected is at
least about 5 GPa and the temperature is at least about 1,300
degrees centigrade.
[0053] A version of the method may include making a diamond
composite structure by means of a method disclosed, for example, in
PCT application publication number WO2009/128034 for making a
super-hard enhanced hard-metal material. A powder blend comprising
diamond particles, and a metal binder material, such as cobalt may
be prepared by combining these particles and blending them
together. An effective powder preparation technology may be used to
blend the powders, such as wet or dry multi-directional mixing,
planetary ball milling and high shear mixing with a homogenizer. In
one embodiment, the mean size of the diamond particles may be at
least about 50 microns and they may be combined with other
particles by mixing the powders or, in some cases, stirring the
powders together by hand. In one version of the method, precursor
materials suitable for subsequent conversion into binder material
may be included in the powder blend, and in one version of the
method, metal binder material may be introduced in a form suitable
for infiltration into a green body. The powder blend may be
deposited in a die or mold and compacted to form a green body, for
example by uni-axial compaction or other compaction method, such as
cold isostatic pressing (CIP). The green body may be subjected to a
sintering process known in the art to form a sintered article. In
one version, the method may include loading the capsule comprising
a pre-sinter assembly into a press and subjecting the green body to
an ultra-high pressure and a temperature at which the super hard
material is thermodynamically stable to sinter the super hard
grains.
[0054] After sintering, the polycrystalline super hard
constructions may be ground to size and may include, if desired, a
45.degree. chamfer of approximately 0.4 mm height on the body of
polycrystalline super hard material so produced.
[0055] The sintered article may be subjected to a subsequent
treatment at a pressure and temperature at which diamond is
thermally stable to convert some or all of the non-diamond carbon
back into diamond and produce a diamond composite structure. An
ultra-high pressure furnace well known in the art of diamond
synthesis may be used and the pressure may be at least about 5.5
GPa and the temperature may be at least about 1,250 degrees
centigrade for the second sintering process.
[0056] A further embodiment of a super hard construction may be
made by a method including providing a PCD structure and a
precursor structure for a diamond composite structure, forming each
structure into the respective complementary shapes, assembling the
PCD structure and the diamond composite structure onto a cemented
carbide substrate to form an unjoined assembly, and subjecting the
unjoined assembly to a pressure of at least about 5.5 GPa and a
temperature of at least about 1,250 degrees centigrade to form a
PCD construction. The precursor structure may comprise carbide
particles and diamond or non-diamond carbon material, such as
graphite, and a binder material comprising a metal, such as cobalt.
The precursor structure may be a green body formed by compacting a
powder blend comprising particles of diamond or non-diamond carbon
and particles of carbide material and compacting the powder
blend.
[0057] The present disclosure may be further illustrated by the
following examples which are not intended to be limiting.
[0058] The grains of super hard material, such as diamond grains or
particles in the starting mixture prior to sintering may be, for
example, bimodal, that is, the feed comprises a mixture of a coarse
fraction of diamond grains and a fine fraction of diamond grains.
In some embodiments, the coarse fraction may have, for example, an
average particle/grain size ranging from about 10 to 60 microns. By
"average particle or grain size" it is meant that the individual
particles/grains have a range of sizes with the mean particle/grain
size representing the "average". The average particle/grain size of
the fine fraction is less than the size of the coarse fraction, for
example between around 1/10 to 6/10 of the size of the coarse
fraction, and may, in some embodiments, range for example between
about 0.1 to 20 microns.
[0059] In some embodiments, the weight ratio of the coarse diamond
fraction to the fine diamond fraction ranges from about 50% to
about 97% coarse diamond and the weight ratio of the fine diamond
fraction may be from about 3% to about 50%. In other embodiments,
the weight ratio of the coarse fraction to the fine fraction will
range from about 70:30 to about 90:10.
[0060] In further embodiments, the weight ratio of the coarse
fraction to the fine fraction may range for example from about
60:40 to about 80:20.
[0061] In some embodiments, the particle size distributions of the
coarse and fine fractions do not overlap and in some embodiments
the different size components of the compact are separated by an
order of magnitude between the separate size fractions making up
the multimodal distribution.
[0062] The embodiments consists of at least a wide bi-modal size
distribution between the coarse and fine fractions of super hard
material, but some embodiments may include three or even four or
more size modes which may, for example, be separated in size by an
order of magnitude, for example, a blend of particle sizes whose
average particle size is 20 microns, 2 microns, 200 nm and 20
nm.
[0063] Sizing of diamond particles/grains into fine fraction,
coarse fraction, or other sizes in between, may be through known
processes such as jet-milling of larger diamond grains and the
like.
[0064] In embodiments where the super hard material is
polycrystalline diamond material, the diamond grains used to form
the polycrystalline diamond material may be natural or
synthetic.
[0065] In some embodiments, the binder catalyst/solvent may
comprise cobalt or some other iron group elements, such as iron or
nickel, or an alloy thereof. Carbides, nitrides, borides, and
oxides of the metals of Groups IV-VI in the periodic table are
other examples of non-diamond material that might be added to the
sinter mix. In some embodiments, the binder/catalyst/sintering aid
may be Co.
[0066] The cemented metal carbide substrate may be conventional in
composition and, thus, may be include any of the Group IVB, VB, or
VIB metals, which are pressed and sintered in the presence of a
binder of cobalt, nickel or iron, or alloys thereof. In some
embodiments, the metal carbide is tungsten carbide.
[0067] In some embodiments, both the bodies of, for example,
diamond and carbide material plus sintering aid/binder/catalyst are
applied as powders and sintered simultaneously in a single UHP/HT
process. The mixture of diamond grains and mass of carbide are
placed in an HP/HT reaction cell assembly and subjected to HP/HT
processing. The HP/HT processing conditions selected are sufficient
to effect intercrystalline bonding between adjacent grains of
abrasive particles and, optionally, the joining of sintered
particles to the cemented metal carbide support. In one embodiment,
the processing conditions generally involve the imposition for
about 3 to 120 minutes of a temperature of at least about 1200
degrees C. and an ultra-high pressure of greater than about 5
GPa.
[0068] In another embodiment, the substrate may be pre-sintered in
a separate process before being bonded together in the HP/HT press
during sintering of the super hard polycrystalline material.
[0069] In a further embodiment, both the substrate and a body of
polycrystalline super hard material are pre-formed. For example,
the bimodal feed of super hard grains/particles with optional
carbonate binder-catalyst also in powdered form are mixed together,
and the mixture is packed into an appropriately shaped canister and
is then subjected to extremely high pressure and temperature in a
press. Typically, the pressure is at least 5 GPa and the
temperature is at least around 1200 degrees C. The preformed body
of polycrystalline super hard material is then placed in the
appropriate position on the upper surface of the preform carbide
substrate (incorporating a binder catalyst), and the assembly is
located in a suitably shaped canister. The assembly is then
subjected to high temperature and pressure in a press, the order of
temperature and pressure being again, at least around 1200 degrees
C. and 5 GPa respectively. During this process the solvent/catalyst
migrates from the substrate into the body of super hard material
and acts as a binder-catalyst to effect intergrowth in the layer
and also serves to bond the layer of polycrystalline super hard
material to the substrate. The sintering process also serves to
bond the body of super hard polycrystalline material to the
substrate.
[0070] The practical use of cemented carbide grades with
substantially lower cobalt content as substrates for PCD inserts is
limited by the fact that some of the Co is required to migrate from
the substrate into the PCD layer during the sintering process in
order to catalyse the formation of the PCD. For this reason, it is
more difficult to make PCD on substrate materials comprising lower
Co contents, even though this may be desirable.
[0071] An embodiment of a super hard construction may be made by a
method including providing a cemented carbide substrate, contacting
an aggregated, substantially unbonded mass of diamond particles
against a surface of the substrate to form an pre-sinter assembly,
encapsulating the pre-sinter assembly in a capsule for an
ultra-high pressure furnace and subjecting the pre-sinter assembly
to a pressure of at least about 5.5 GPa and a temperature of at
least about 1,250 degrees centigrade, and sintering the diamond
particles to form a PCD composite compact element comprising a PCD
structure integrally formed on and joined to the cemented carbide
substrate. In some embodiments of the invention, the pre-sinter
assembly may be subjected to a pressure of at least about 6 GPa, at
least about 6.5 GPa, at least about 7 GPa or even at least about
7.5 GPa.
[0072] The hardness of cemented tungsten carbide substrate may be
enhanced by subjecting the substrate to an ultra-high pressure and
high temperature, particularly at a pressure and temperature at
which diamond is thermodynamically stable. The magnitude of the
enhancement of the hardness may depend on the pressure and
temperature conditions. In particular, the hardness enhancement may
increase the higher the pressure. Whilst not wishing to be bound by
a particular theory, this is considered to be related to the Co
drift from the substrate into the PCD during press sintering, as
the extent of the hardness increase is directly dependent on the
decrease of Co content in the substrate.
[0073] In embodiments where the cemented carbide substrate does not
contain sufficient solvent/catalyst for diamond, and where the PCD
structure is integrally formed onto the substrate during sintering
at an ultra-high pressure, solvent/catalyst material may be
included or introduced into the aggregated mass of diamond grains
from a source of the material other than the cemented carbide
substrate. The solvent/catalyst material may comprise cobalt that
infiltrates from the substrate in to the aggregated mass of diamond
grains just prior to and during the sintering step at an ultra-high
pressure. However, in embodiments where the content of cobalt or
other solvent/catalyst material in the substrate is low,
particularly when it is less than about 11 weight percent of the
cemented carbide material, then an alternative source may need to
be provided in order to ensure good sintering of the aggregated
mass to form PCD.
[0074] Solvent/catalyst for diamond may be introduced into the
aggregated mass of diamond grains by various methods, including
blending solvent/catalyst material in powder form with the diamond
grains, depositing solvent/catalyst material onto surfaces of the
diamond grains, or infiltrating solvent/catalyst material into the
aggregated mass from a source of the material other than the
substrate, either prior to the sintering step or as part of the
sintering step. Methods of depositing solvent/catalyst for diamond,
such as cobalt, onto surfaces of diamond grains are well known in
the art, and include chemical vapour deposition (CVD), physical
vapour deposition (PVD), sputter coating, electrochemical methods,
electroless coating methods and atomic layer deposition (ALD). It
will be appreciated that the advantages and disadvantages of each
depend on the nature of the sintering aid material and coating
structure to be deposited, and on characteristics of the grain.
[0075] In one embodiment of a method of the invention, cobalt may
be deposited onto surfaces of the diamond grains by first
depositing a pre-cursor material and then converting the precursor
material to a material that comprises elemental metallic cobalt.
For example, in the first step cobalt carbonate may be deposited on
the diamond grain surfaces using the following reaction:
Co(NO.sub.3).sub.2+Na.sub.2CO.sub.3.fwdarw.CoCO.sub.3+2NaNO.sub.3
[0076] The deposition of the carbonate or other precursor for
cobalt or other solvent/catalyst for diamond may be achieved by
means of a method described in PCT patent publication number
WO/2006/032982. The cobalt carbonate may then be converted into
cobalt and water, for example, by means of pyrolysis reactions such
as the following:
CoCO.sub.3.fwdarw.CoO+CO.sub.2
CoO+H.sub.2.fwdarw.Co+H.sub.2O
[0077] In another embodiment of the method of the invention, cobalt
powder or precursor to cobalt, such as cobalt carbonate, may be
blended with the diamond grains. Where a precursor to a
solvent/catalyst such as cobalt is used, it may be necessary to
heat treat the material in order to effect a reaction to produce
the solvent/catalyst material in elemental form before sintering
the aggregated mass.
[0078] In some embodiments, the cemented carbide substrate may be
formed of tungsten carbide particles bonded together by the binder
material, the binder material comprising an alloy of Co, Ni and Cr.
The tungsten carbide particles may form at least 70 weight percent
and at most 95 weight percent of the substrate. The binder material
may comprise between about 10 to 50 wt. % Ni, between about 0.1 to
10 wt. % Cr, and the remainder weight percent comprises Co. The
size distribution of the tungsten carbide particles in the cemented
carbide substrate ion some embodiments has the following
characteristics: [0079] fewer than 17 percent of the carbide
particles have a grain size of equal to or less than about 0.3
microns; [0080] between about 20 to 28 percent of the tungsten
carbide particles have a grain size of between about 0.3 to 0.5
microns; [0081] between about 42 to 56 percent of the tungsten
carbide particles have a grain size of between about 0.5 to 1
microns; [0082] less than about 12 percent of the tungsten carbide
particles are greater than 1 micron; and [0083] the mean grain size
of the tungsten carbide particles is about 0.6.+-.0.2 microns.
[0084] In some embodiments, the binder additionally comprises
between about 2 to 20 wt. % tungsten and between about 0.1 to 2 wt.
% carbon
[0085] A layer of the substrate adjacent to the interface with the
body of polycrystalline diamond material may have a thickness of,
for example, around 100 microns and may comprise tungsten carbide
grains, and a binder phase. This layer may be characterised by the
following elemental composition measured by means of
Energy-Dispersive X-Ray Microanalysis (EDX): [0086] between about
0.5 to 2.0 wt % cobalt; [0087] between about 0.05 to 0.5 wt. %
nickel; [0088] between about 0.05 to 0.2 wt. % chromium; and [0089]
tungsten and carbon.
[0090] In a further embodiment, in the layer described above in
which the elemental composition includes between about 0.5 to 2.0
wt % cobalt, between about 0.05 to 0.5 wt. % nickel and between
about 0.05 to 0.2 wt. % chromium, the remainder is tungsten and
carbon.
[0091] The layer of substrate may further comprise free carbon.
[0092] The magnetic properties of the cemented carbide material may
be related to important structural and compositional
characteristics. The most common technique for measuring the carbon
content in cemented carbides is indirectly, by measuring the
concentration of tungsten dissolved in the binder to which it is
indirectly proportional: the higher the content of carbon dissolved
in the binder the lower the concentration of tungsten dissolved in
the binder. The tungsten content within the binder may be
determined from a measurement of the magnetic moment, .sigma., or
magnetic saturation, M.sub.s=4.pi..sigma., these values having an
inverse relationship with the tungsten content (Roebuck (1996),
"Magnetic moment (saturation) measurements on cemented carbide
materials", Int. J. Refractory Met., Vol. 14, pp. 419-424.). The
following formula may be used to relate magnetic saturation, Ms, to
the concentrations of W and C in the binder:
M.sub.s.varies.[C]/[W].times.wt. % Co.times.201.9 in units of
.mu.Tm.sup.3/kg
[0093] The binder cobalt content within a cemented carbide material
may be measured by various methods well known in the art, including
indirect methods such as such as the magnetic properties of the
cemented carbide material or more directly by means of
energy-dispersive X-ray spectroscopy (EDX), or a method based on
chemical leaching of Co.
[0094] The mean grain size of carbide grains, such as WC grains,
may be determined by examination of micrographs obtained using a
scanning electron microscope (SEM) or light microscopy images of
metallurgically prepared cross-sections of a cemented carbide
material body, applying the mean linear intercept technique, for
example. Alternatively, the mean size of the WC grains may be
estimated indirectly by measuring the magnetic coercivity of the
cemented carbide material, which indicates the mean free path of Co
intermediate the grains, from which the WC grain size may be
calculated using a simple formula well known in the art. This
formula quantifies the inverse relationship between magnetic
coercivity of a Co-cemented WC cemented carbide material and the Co
mean free path, and consequently the mean WC grain size. Magnetic
coercivity has an inverse relationship with MFP.
[0095] As used herein, the "mean free path" (MFP) of a composite
material such as cemented carbide is a measure of the mean distance
between the aggregate carbide grains cemented within the binder
material. The mean free path characteristic of a cemented carbide
material may be measured using a micrograph of a polished section
of the material. For example, the micrograph may have a
magnification of about 1000.times.. The MFP may be determined by
measuring the distance between each intersection of a line and a
grain boundary on a uniform grid. The matrix line segments, Lm, are
summed and the grain line segments, Lg, are summed. The mean matrix
segment length using both axes is the "mean free path". Mixtures of
multiple distributions of tungsten carbide particle sizes may
result in a wide distribution of MFP values for the same matrix
content. This is explained in more detail below.
[0096] The concentration of W in the Co binder depends on the C
content. For example, the W concentration at low C contents is
significantly higher. The W concentration and the C content within
the Co binder of a Co-cemented WC (WC--Co) material may be
determined from the value of the magnetic saturation. The magnetic
saturation 4.pi..sigma. or magnetic moment .sigma. of a hard metal,
of which cemented tungsten carbide is an example, is defined as the
magnetic moment or magnetic saturation per unit weight. The
magnetic moment, .sigma., of pure Co is 16.1 micro-Tesla times
cubic metre per kilogram (.mu.m.sup.3/kg), and the induction of
saturation, also referred to as the magnetic saturation,
4.pi..sigma., of pure Co is 201.9 .mu.Tm.sup.3/kg.
[0097] In some embodiments, the cemented carbide substrate may have
a mean magnetic coercivity of at least about 100 Oe and at most
about 145 Oe, and a magnetic moment of specific magnetic saturation
with respect to that of pure Co of at least about 89 percent to at
most about 97 percent.
[0098] A desired MFP characteristic in the substrate may be
accomplished several ways known in the art. For example, a lower
MFP value may be achieved by using a lower metal binder content. A
practical lower limit of about 3 weight percent cobalt applies for
cemented carbide and conventional liquid phase sintering. In an
embodiment where the cemented carbide substrate is subjected to an
ultra-high pressure, for example a pressure greater than about 5
GPa and a high temperature (greater than about 1,400.degree. C. for
example), lower contents of metal binder, such as cobalt, may be
achieved. For example, where the cobalt content is about 3 weight
percent and the mean size of the WC grains is about 0.5 micron, the
MFP would be about 0.1 micron, and where the mean size of the WC
grains is about 2 microns, the MFP would be about 0.35 microns, and
where the mean size of the WC grains is about 3 microns, the MFP
would be about 0.7 microns. These mean grain sizes correspond to a
single powder class obtained by natural comminution processes that
generate a log normal distribution of particles. Higher matrix
(binder) contents would result in higher MFP values.
[0099] Changing grain size by mixing different powder classes and
altering the distributions may achieve a whole spectrum of MFP
values for the substrate depending on the particulars of powder
processing and mixing. The exact values would have to be determined
empirically.
[0100] In some embodiments, the substrate comprises Co, Ni and
Cr.
[0101] The binder material for the substrate may include at least
about 0.1 weight percent to at most about 5 weight percent one or
more of V, Ta, Ti, Mo, Zr, Nb and Hf in solid solution.
[0102] In further embodiments, the polycrystalline diamond (PCD)
composite compact element may include at least about 0.01 weight
percent and at most about 2 weight percent of one or more of Re,
Ru, Rh, Pd, Re, Os, Ir and Pt.
[0103] Some embodiments of a cemented carbide body may be formed by
providing tungsten carbide powder having a mean equivalent circle
diameter (ECD) size in the range from about 0.2 microns to about
0.6 microns, the ECD size distribution having the further
characteristic that fewer than 45 percent of the carbide particles
have a mean size of less than 0.3 microns; 30 to 40 percent of the
carbide particles have a mean size of at least 0.3 microns and at
most 0.5 microns; 18 to 25 percent of the carbide particles have a
mean size of greater than 0.5 microns and at most 1 micron; fewer
than 3 percent of the carbide particles have a mean size of greater
than 1 micron. The tungsten carbide powder is milled with binder
material comprising Co, Ni and Cr or chromium carbides, the
equivalent total carbon comprised in the blended powder being, for
example, about 6 percent with respect to the tungsten carbide. The
blended powder is then compacted to form a green body and the green
body is sintered to produce the cemented carbide body.
[0104] The sintering the green body may take place at a temperature
of, for example, at least 1,400 degrees centigrade and at most
1,440 degrees centigrade for a period of at least 65 minutes and at
most 85 minutes.
[0105] In some embodiments, the equivalent total carbon (ETC)
comprised in the cemented carbide material is about 6.12 percent
with respect to the tungsten carbide.
[0106] The size distribution of the tungsten carbide powder may, in
some embodiments, have the characteristic of a mean ECD of 0.4
microns and a standard deviation of 0.1 microns.
[0107] Embodiments are described in more detail below with
reference to the following examples which are provided herein by
way of illustration only and are not intended to be limiting.
Example 1
[0108] A quantity of sub-micron cobalt powder sufficient to obtain
2 mass % in the final diamond mixture was initially de-agglomerated
in a methanol slurry in a ball mill with WC milling media for 1
hour. A fine fraction of diamond powder with an average grain size
of 2 microns was then added to the slurry in an amount to obtain 10
mass % in the final mixture. Additional milling media was
introduced and further methanol was added to obtain suitable
slurry; and this was milled for a further hour. A coarse fraction
of diamond, with an average grain size of approximately 20 microns
was then added in an amount to obtain 88 mass % in the final
mixture. The slurry was again supplemented with further methanol
and milling media, and then milled for a further 2 hours. The
slurry was removed from the ball mill and dried to obtain the
diamond powder mixture.
[0109] The diamond powder mixture was then placed into a suitable
HpHT vessel, adjacent to a tungsten carbide substrate and sintered
at a pressure of around 6.8 GPa and a temperature of about 1500
deg. C.
Example 2
[0110] A quantity of sub-micron cobalt powder sufficient to obtain
2.4 mass % in the final diamond mixture was initially
de-agglomerated in a methanol slurry in a ball mill with WC milling
media for 1 hour. A fine fraction of diamond powder with an average
grain size of 2 microns was then added to the slurry in an amount
to obtain 29.3 mass % in the final mixture. Additional milling
media was introduced and further methanol was added to obtain a
suitable slurry; and this was milled for a further hour. A coarse
fraction of diamond, with an average grain size of approximately 20
microns was then added in an amount to obtain 68.3 mass % in the
final mixture. The slurry was again supplemented with further
methanol and milling media, and then milled for a further 2 hours.
The slurry was removed from the ball mill and dried to obtain the
diamond powder mixture.
[0111] The diamond powder mixture was then placed into a suitable
HpHT vessel, adjacent to a tungsten carbide substrate and sintered
at a pressure of around 6.8 GPa and a temperature of about 1500
deg. C.
[0112] The diamond content of the sintered diamond structure is
greater than 90 vol % and the coarsest fraction of the distribution
is greater than 60 weight % and preferably greater than weight
70%.
[0113] In polycrystalline diamond material, individual diamond
particles/grains are, to a large extent, bonded to adjacent
particles/grains through diamond bridges or necks. The individual
diamond particles/grains retain their identity, or generally have
different orientations. The average grain/particle size of these
individual diamond grains/particles may be determined using image
analysis techniques. Images are collected on a scanning electron
microscope and are analysed using standard image analysis
techniques. From these images, it is possible to extract a
representative diamond particle/grain size distribution.
[0114] Generally, the body of polycrystalline diamond material will
be produced and bonded to the cemented carbide substrate in a HPHT
process. In so doing, it is advantageous for the binder phase and
diamond particles to be arranged such that the binder phase is
distributed homogeneously and is of a fine scale.
[0115] The homogeneity or uniformity of the sintered structure is
defined by conducting a statistical evaluation of a large number of
collected images. The distribution of the binder phase, which is
easily distinguishable from that of the diamond phase using
electron microscopy, can then be measured in a method similar to
that disclosed in EP 0974566. This method allows a statistical
evaluation of the average thicknesses of the binder phase along
several arbitrarily drawn lines through the microstructure. This
binder thickness measurement is also referred to as the "mean free
path" by those skilled in the art. For two materials of similar
overall composition or binder content and average diamond grain
size, the material which has the smaller average thickness will
tend to be more homogenous, as this implies a "finer scale"
distribution of the binder in the diamond phase. In addition, the
smaller the standard deviation of this measurement, the more
homogenous is the structure. A large standard deviation implies
that the binder thickness varies widely over the microstructure,
i.e. that the structure is not even, but contains widely dissimilar
structure types.
[0116] The binder and diamond mean free path measurements were
obtained for various samples formed according to embodiments in the
manner set out below. Unless otherwise stated herein, dimensions of
mean free path within the body of PCD material refer to the
dimensions as measured on a surface of, or a section through, a
body comprising PCD material and no stereographic correction has
been applied. For example, the measurements are made by means of
image analysis carried out on a polished surface, and a Saltykov
correction has not been applied in the data stated herein.
[0117] In measuring the mean value of a quantity or other
statistical parameter measured by means of image analysis, several
images of different parts of a surface or section (hereinafter
referred to as samples) are used to enhance the reliability and
accuracy of the statistics. The number of images used to measure a
given quantity or parameter may be, for example between 10 to 30.
If the analysed sample is uniform, which is the case for PCD,
depending on magnification, 10 to 20 images may be considered to
represent that sample sufficiently well.
[0118] The resolution of the images needs to be sufficiently high
for the inter-grain and inter-phase boundaries to be clearly made
out and, for the measurements stated herein an image area of 1280
by 960 pixels was used. Images used for the image analysis were
obtained by means of scanning electron micrographs (SEM) taken
using a backscattered electron signal. The back-scatter mode was
chosen so as to provide high contrast based on different atomic
numbers and to reduce sensitivity to surface damage (as compared
with the secondary electron imaging mode). [0119] 1. A sample piece
of the PCD sintered body is cut using wire EDM and polished. At
least 10 back scatter electron images of the surface of the sample
are taken using a Scanning Electron Microscope at 1000 times
magnifications. [0120] 2. The original image was converted to a
greyscale image. The image contrast level was set by ensuring the
diamond peak intensity in the grey scale histogram image occurred
between 10 and 20. [0121] 3. An auto threshold feature was used to
binarise the image and specifically to obtain clear resolution of
the diamond and binder phases. [0122] 4. The software, having the
trade name analySIS Pro from Soft Imaging System.RTM. GmbH (a
trademark of Olympus Soft Imaging Solutions GmbH) was used and
excluded from the analysis any particles which touched the
boundaries of the image. This required appropriate choice of the
image magnification: [0123] a. If too low then resolution of fine
particles is reduced. [0124] b. If too high then: [0125] i.
Efficiency of coarse grain separation is reduced. [0126] ii. High
numbers of coarse grains are cut by the boarders of the image and
hence less of these grains are analysed. [0127] iii. Thus more
images must be analysed to get a statistically-meaningful result.
[0128] 5. Each particle was finally represented by the number of
continuous pixels of which it is formed. [0129] 6. The AnalySIS
software programme proceeded to detect and analyse each particle in
the image. This was automatically repeated for several images.
[0130] 7. Ten SEM images were analyzed using the grey-scale to
identify the binder pools as distinct from the other phases within
the sample. The threshold value for the SEM was then determined by
selecting a maximum value for binder pools content which only
identifies binder pools and excludes all other phases (whether grey
or white). Once this threshold value is identified it is used to
binarize the SEM image.) [0131] 8. One pixel thick lines were
superimposed across the width of the binarized image, with each
line being five pixels apart (to ensure the measurement is
sufficiently representative in statistical terms). Binder phase
that are cut by image boundaries were excluded in these
measurements. [0132] 9. The distance between the binder pools along
the superimposed lines were measured and recorded--at least 10,000
measurements were made per material being analysed. Median values
were reported for both the non-diamond phase mean free paths and
diamond phase mean free paths.
[0133] Also recorded were the mean free path measurements at Q1 and
Q3 for both the diamond and non-diamond phases.
[0134] Q1 is typically referred to as the first quartile (also
called the lower quartile) and is the number below which lies the
25 percent of the bottom data. Q3 is typically referred to as the
third quartile (also called the upper quartile) has 75 percent of
the data below it and the top 25 percent of the data above it.
[0135] From this, it was determined that embodiments have:
[0136] alpha is >=0.50 and <1.5, and beta<0.60,
[0137] where
[0138] alpha is the non-diamond phase MFP median/(Q3-Q1), which
gives a measure of "uniform binder pool size"; and
[0139] beta=diamond MFP median/(Q3-Q1) which gives a measure of
"wide grain size distribution"
[0140] In some embodiments, it was determined that alpha>=0.60
and <1.5, or alpha>=0.80 and <1.5, or alpha>=0.83 and
<1.5.
[0141] In some embodiments, beta<0.60, or <0.50, or <0.47,
or <0.4.
[0142] Additional methods for producing the PCD compact 20
comprising the body of PCD material 22, as shown in FIGS. 1 to 3c,
are illustrated with reference to FIGS. 4 to 10. As shown in FIG.
4, a PCD structure (the second structure) 200 is disposed adjacent
a cemented carbide substrate (the first structure) 300, a thin
layer or film 400 of binder material comprising Co connecting
opposite major surfaces of the PCD structure 200 and the substrate
300 to comprise an assembly encased in a housing 100 for an
ultra-high pressure, high temperature press (not shown). The CTE of
the PCD material comprised in the PCD structure 200 is in the range
from about 2.5.times.10-6 per degree Celsius to about 4.times.10-6
per degree Celsius and the CTE of the cobalt-cemented tungsten
carbide material comprised in the substrate 300 is in the range
from about 5.4.times.10-6 per degree Celsius to about 6.times.10-6
per degree Celsius (the CTE values are for 25 degrees Celsius). In
this example, the substrate 300 and the PCD structure 200 contain
binder material comprising Co. It is estimated that PCD material
would have a Young's modulus from about 900 gigapascals to about
1,400 gigapascals depending on the grade of PCD and that the
substrate would have a Young's modulus from about 500 gigapascals
to about 650 gigapascals depending largely on the content and
composition of the binder material.
[0143] FIG. 5 shows a schematic phase diagram of carbon in terms of
pressure p and temperature T axes, showing the line D-G of
thermodynamic equilibrium between diamond and graphite allotropes,
diamond being the more thermally stable in region D and graphite
being the more thermally stable in region G of the diagram. The
line S-L shows schematically the temperature at which the binder
material melts or solidifies at various pressures, this temperature
tending to increase with increasing pressure. Note that this
temperature is likely to be different from that for the binder
material in a pure form because the presence of carbon from the
diamond and or some dissolved WC is expected to reduce this
temperature, since the presence of carbon in solution is expected
to reduce the melting point of cobalt and other metals. The
assembly described with reference to FIG. 4 may be under a first
pressure P1 of about 7.5 gigapascals to about 8 gigapascal and at a
temperature of about 1,450 degrees Celsius to about 1,800 degrees
Celsius, at a condition at which the PCD material has been formed
by sintering an aggregation of diamond grains disposed adjacent the
substrate. There may be no substantial interruption between the
formation of the PCD in situ at the sinter pressure and sinter
temperature on the one hand and subjecting the assembly to the
first pressure P1 on the other; it is the subsequent relationship
between the reduction of the pressure and the temperature at stages
I and II that is the more relevant aspect of the method. At the
sinter temperature, the Co binder material will be molten and
expected to promote the direct inter-growth sintering of the
diamond grains to form the PCD material, the diamond comprised in
the PCD material being thermodynamically substantially more stable
than graphite at the sinter temperature and sinter pressure.
[0144] With further reference to FIG. 5, the pressure and
temperature of the assembly may be reduced to ambient levels in
stages I, II and III. In a particular example, the pressure may be
reduced in stage I from the first pressure P1 to a second pressure
P2 of about 5.5 gigapascals to about 6 gigapascals while reducing
the temperature to about 1,350 degrees Celsius to about 1,500
degrees Celsius to ensure that the pressure-temperature condition
remains such that diamond is more thermodynamically stable than
graphite and that the binder material remains substantially molten.
In stage II, the temperature may then be reduced to about 1,100
degrees Celsius to a temperature in the range of about 1,200
degrees Celsius while maintaining the pressure above the line D-G
in the diamond-stable region D to solidify the binder material; and
in stage III the pressure and temperature may be reduced to ambient
levels in various ways. The PCD construction can then be removed
from the press apparatus. Note that the stages I, II and III are
used merely to explain FIG. 6 and there may not be clear
distinction between these stages in practice. For example these
stages may flow smoothly into one another with no substantial
period of maintaining pressure and temperature conditions at the
end of a stage. Alternatively, some or all of the stages may be
distinct and the pressure and temperature condition at the end of a
stage may be maintained for a period.
[0145] In some examples, a pre-sinter assembly for making a PCD
construction, for example, may be prepared and provided in situ at
the first pressure P1 as follows. A cup may be provided into which
an aggregation comprising a plurality of diamond grains and a
substrate may be assembled, the interior shape of the cup being
generally that of the desired shape of the PCD structure (having
regard to likely distortion during the sintering step). The
aggregation may comprise substantially loose diamond grains or
diamond-containing pre-cursor structures such as granules, discs,
wafers or sheets. The aggregation may also include catalyst
material for diamond, or pre-cursor material for catalyst material,
which may be admixed with the diamond grains and or deposited on
the surfaces of the diamond grains. The diamond grains may have a
mean size of at least about 0.1 micron and or at most about 75
microns and may be substantially mono-modal or multi-modal. The
aggregation may also contain additives for reducing abnormal
diamond or grain growth or the aggregation may be substantially
free of catalyst material or additives. Alternatively or
additionally, another source of catalyst or matrix material such as
cobalt may be provided, such as the binder material in a cemented
carbide substrate. A sufficient quantity of the aggregation may be
placed into the cup and then the substrate may inserted into the
cup with a proximate end pushed against the aggregation. The
pre-sinter assembly comprising the aggregation and the substrate
may be encased within a metal jacket comprising the cup, subjected
to a heat treatment to burn off organic binder that may be
comprised in the aggregation, and encapsulated within a housing
(which may be referred to as a capsule) suitable for an ultra-high
pressure press. The housing may be placed in a suitable ultra-high
pressure press apparatus and subjected to a sinter pressure and
sinter temperature to form the assembly comprising a PCD structure
adjacent the substrate, connected by a thin film of molten binder
comprising cobalt. In examples such as these, the sinter pressure
may be regarded as the first pressure P1.
[0146] In an example arrangement, a pre-sinter assembly for making
a PCD construction may be prepared and provided in a press
apparatus at the first pressure P1 as follows. A PCD structure may
be provided pre-sintered in a previous ultra-high pressure, high
temperature process. The PCD structure may contain binder material
comprising cobalt, located in interstitial regions between the
diamond grains comprised in the PCD material. In the case of PCD
material, the PCD structure may have at least a region
substantially free of binder material. For example, the PCD
structure may have been treated in acid to remove binder material
from the interstices at least adjacent a surface of the PCD
structure or throughout substantially the entire volume of the PCD
structure (or variations between these possibilities), leaving at
least a region that may contain pores or voids. In some examples,
voids thus created may be filled with a filler material that may or
may not comprise binder material. The PCD structure may be placed
against a substrate and the resulting pre-construction assembly may
be encased within a housing suitable for an ultra-high pressure
press. The housing may be placed in a suitable ultra-high pressure
press apparatus and the subjected to the first pressure P1 at a
temperature at which the binder material is in the liquid state (at
a condition in region D of FIG. 5).
[0147] Example methods for making an example PCD construction will
be described below with reference to FIGS. 6 to 10. In each figure,
only part of the pressure and temperature cycle is shown, the part
beginning at respective first pressures P1, at which the PCD
material comprised in the construction becomes formed by sintering,
and ending after the temperature has been reduced sufficiently to
solidify the binder material and the pressure has been reduced from
the second pressure P2.
[0148] In some examples, a pre-sinter assembly may be provided,
comprising an aggregation of a plurality of diamond grains located
adjacent a surface of a substrate comprising cobalt-cemented
tungsten carbide. The diamond grains may have a mean size in the
range of about 0.1 to about 40 microns. The pre-sinter assembly may
be encapsulated within a capsule for an ultra-high pressure press
apparatus, into which the capsule may be loaded. The capsule may be
pressurised at ambient temperature to a pressure of at least about
6.5 gigapascals and heated to a temperature in the range of about
1,500 to about 1,600 degrees Celsius, substantially greater than
the melting point (at the pressure) of the cobalt-based binder
material comprised in the substrate and causing the cobalt material
to melt. At this temperature the pre-sinter assembly may be at a
first pressure P1 in the range from about 7.5 to about 10
gigapascals (P1 may be somewhat higher than 7 gigapascals at least
partly as a result of the increase in temperature). The first
pressure P1 and the temperature may be substantially maintained for
at least about 1 minute, or in any event sufficiently long to
sinter together the diamond grains (in these examples, the sinter
pressure will be substantially P1). The pressure may then be
reduced from first pressure P1 through a second pressure P2 in the
range from about 5.5 to about 8.5 gigapascals. The second pressure
may be the pressure at which the binder material begins to solidify
as the temperature is reduced through its solidification
temperature.
[0149] The temperature of the pre-sinter assembly may be reduced
simultaneously with pressure, provided that it remains greater than
the temperature at which the cobalt-based binder material will have
completely solidified. As the pressure is reduced from P2, the
temperature may also be reduced through the solidification line of
the cobalt-based binder material, resulting in the solidification
of the binder material. In these particular examples, the pressure
is substantially continuously reduced from the first pressure P1,
through the second pressure P2 and through the pressure(s) at which
the binder material solidifies, without substantial pause. The rate
of reduction of the pressure and or temperature may be varied or
the rate of the reduction of either or both may be substantially
constant, at least until the cobalt-based binder material has
solidified. The temperature may also be reduced substantially
continuously at least until it is sufficiently low for
substantially all the cobalt-based binder material to have
solidified. The temperature and pressure may then be reduced to
ambient conditions, the capsule removed from the ultra-high
pressure press apparatus and the construction removed from the
capsule. The construction may comprise a sintered PCD structure
formed joined to the substrate, the PCD structure having become
joined to the substrate in the same general step in which the PCD
material was formed by the sintering together of the plurality of
diamond grains. A thin layer rich in cobalt will be present between
the PCD structure and the substrate, joining together these
structures.
[0150] In a particular example method illustrated in FIG. 6, the
first pressure P1 is about 7.6 gigapascals, the temperature at the
first pressure being in the range of about 1,500 to about 1,600
degrees Celsius, and an example second pressure P2 is about 6.8
gigapascals.
[0151] In a particular example method illustrated in FIG. 7, the
first pressure P1 is about 7.7 gigapascals, the temperature at the
first pressure being in the range of about 1,500 to about 1,600
degrees Celsius, and an example second pressure P2 is about 6.9
gigapascals.
[0152] In a particular example method illustrated in FIG. 8, the
first pressure P1 is about 7.8 gigapascals, the temperature at the
first pressure being in the range of about 1,500 to about 1,600
degrees Celsius, and an example second pressure P2 is about 6.9
gigapascals.
[0153] In a particular example method illustrated in FIG. 9, the
first pressure P1 is about 7.9 gigapascals, the temperature at the
first pressure being in the range of about 1,500 to about 1,600
degrees Celsius, and an example second pressure P2 is about 5.5
gigapascals.
[0154] In the example method illustrated in FIG. 10, the first
pressure P1 is about 9.9 gigapascals, the temperature at the first
pressure being about 2,000 degrees Celsius, and an example second
pressure P2 may be about 8.1 gigapascals.
[0155] Note that the line S-L in FIGS. 6 to 10, indicating the
melting and solidification temperatures of cobalt-based binder
material in the presence of carbon, was estimated based on a
calculation using available data. In practice, it may be advisable
not to rely completely on calculated values lying on S-L but to
carry out trial and error experiments to discover the melting and
solidification temperatures for the particular binder material and
pressure being used.
[0156] The method used to measure the pressure and temperature
cycles as illustrated in FIGS. 6 to 10 is measured using so-called
K-type thermocouples and knowledge of the melting temperatures of
copper (Cu) and silver (Ag). Data for the melting points of Cu and
Ag measured using K-type thermocouples up at 60 kilobars was
published by P. W. Mirwald and G. C. Kennedy in an article entitled
"The melting curve of gold, silver and copper to 60-Kbar
pressure--a reinvestigation", published on 10 Nov. 1979 in the
Journal of Geophysical Research volume 84, number B12, pages 6750
to 6756, by The American Geophysical Union. A K-type thermocouple
may also be referred to as a "chromel-alumel" thermocouple, in
which the "chromel" component comprises 90 percent nickel and 10
percent chromium, and the "alumel" component comprises 95 percent
nickel, 2 percent manganese, 2 percent aluminium and 1 percent
silicon. The method includes inserting the junction of a first
K-type thermocouple into a body consisting essentially of Cu and
the junction of a second K-type thermocouple into a body consisting
essentially of Ag, and positioning the two bodies proximate the
pre-sinter assembly within the capsule. The readings from both
thermocouples are recorded throughout at least a part of the
pressure and temperature cycle and the readings processed and
converted to pressure and temperature values according to the
published data.
[0157] Various kinds of ultra-high pressure presses may be used,
including belt-type, tetrahedral multi-anvil, cubic multi-anvil,
walker-type or torroidal presses. The choice of press type is
likely to depend on the volume of the super-hard construction to be
made and the pressure and temperature desired for sintering the
super-hard material. For example, tetrahedral and cubic presses may
be suitable for sintering commercially viable volumes of PCD
material at pressures of at least about 7 gigapascals or at least
about 7.7 gigapascals.
[0158] Some example methods may include subjecting a PCD
construction to a heat treatment at a temperature of at least about
500 degrees Celsius, at least about 600 degrees Celsius or at least
about 650 degrees Celsius for at least about 5 minutes, at least
about 15 minutes or at least about 30 minutes. In some embodiments,
the temperature may be at most about 850 degrees Celsius, at most
about 800 degrees Celsius or at most about 750 degrees Celsius. In
some embodiments, the PCD structure may be subjected to the heat
treatment for at most about 120 minutes or at most about 60
minutes. In one embodiment, the PCD structure may be subjected to
the heat treatment in a vacuum. For example, U.S. Pat. No.
6,517,902 discloses a form of heat treatment for pre-form elements
having a facing table of PCD bonded to a substrate of cemented
tungsten carbide with a cobalt binder. The substrate includes an
interface zone with at least 30 percent by volume of the cobalt
binder in a hexagonal close packed crystal structure.
[0159] While wishing not to be bound by a particular theory, the
method may result in a reduced likelihood or frequency of cracking
of super-hard constructions because the residual stress within the
construction is reduced.
[0160] Further non-limiting examples are described in more detail
below.
Example 3
[0161] A PCD insert for a rock-boring drill bit was made as
described below.
[0162] A pre-sinter assembly was prepared, comprising an
aggregation of a plurality of diamond grains disposed against a
proximate end of a generally cylindrical cemented carbide
substrate. The aggregation comprised a plurality of wafers
comprising diamond grains dispersed within an organic binder
material, the diamond grains having a mean size of at least about
15 microns and at most about 30 microns. The substrate comprised
about 90 weight percent WC grains cemented together by a binder
material comprising Co. The pre-sinter assembly was enclosed in a
metal jacket and heated to burn off the organic binder comprised in
the wafers, and the jacketed, pre-sinter assembly was encapsulated
in a capsule for an ultra-high pressure, high temperature
multi-anvil press apparatus.
[0163] The pre-sinter assembly was subjected to a pressure of about
7.7 gigapascals and a temperature of about 1,550 degrees Celsius to
sinter the diamond grains directly to each other to form a layer of
PCD material connected to the proximate end of the substrate by a
film of molten binder material comprising cobalt from the
substrate. The pressure was reduced to about 5.5 gigapascals and
the temperature was reduced to about 1,450 degrees Celsius,
maintaining conditions at which the diamond comprised in the PCD is
thermodynamically stable (in relation to graphite, a softer
allotrope of carbon) and at which the binder material is in the
liquid phase. The temperature was then reduced to about 1,000
degrees Celsius to solidify the binder material and form a
construction comprising the layer of PCD bonded to the substrate by
the solidified binder material, and the pressure and temperature
were then reduced to ambient conditions.
[0164] The construction was subjected to a heat treatment at 660
degrees Celsius for about 2 hours at substantially ambient pressure
in a substantially non-oxidising atmosphere, and then cooled to
ambient temperature. No cracks were evident in the PCD layer after
the heat treatment.
[0165] The construction was processed by grinding and polishing to
provide an insert for a rock-boring drill bit.
[0166] For comparison, a reference construction was made as
follows. A pre-sinter assembly was prepared as described above in
relation to the example pre-sinter assembly. The pre-sinter
assembly was subjected to a pressure of about 7.7 gigapascal and a
temperature of about 1,550 degrees Celsius to sinter the diamond
grains directly to each other to form a layer of PCD material
connected to the proximate end of the substrate by a film of molten
binder material comprising cobalt from the substrate. The
temperature was reduced to about 1,000 degrees Celsius to solidify
the binder material and form a construction comprising the layer of
PCD bonded to the substrate by the solidified binder material, and
then the pressure and temperature were reduced to ambient
conditions. The construction was subjected to a heat treatment at
660 degrees Celsius for about 2 hours at substantially ambient
pressure in a substantially non-oxidising atmosphere, and then
cooled to ambient temperature. Severe cracks were evident at the
side of the PCD layer after the heat treatment.
Example 4
[0167] A PCD insert for a rock-boring drill bit was made as
described below.
[0168] A pre-sinter assembly was prepared, comprising a PCD
structure having a generally disc-like shape disposed against a
proximate end of a generally cylindrical cemented carbide
substrate. PCD structure had been made in a previous step involving
sintering together an aggregation of a plurality of diamond grains
at an ultra-high pressure of less than about 7 gigapascals and a
high temperature (at which the diamond was thermodynamically more
stable than graphite). The substrate comprised about 90 weight
percent WC grains cemented together by a binder material comprising
Co. The pre-sinter assembly was enclosed in a metal jacket and
heated to burn off the organic binder comprised in the wafers, and
the jacketed, pre-sinter assembly was encapsulated in a capsule for
an ultra-high pressure, high temperature multi-anvil press
apparatus.
[0169] The pre-sinter assembly was subjected to a pressure of about
7.7 gigapascals and a temperature of about 1,550 degrees Celsius to
modify the microstructure of the PCD structure. The pressure was
reduced to about 5.5 gigapascals and the temperature was reduced to
about 1,450 degrees Celsius, maintaining conditions at which the
diamond comprised in the PCD is thermodynamically stable (in
relation to graphite, a softer allotrope of carbon) and at which
the binder material is in the liquid phase. The temperature was
then reduced to about 1,000 degrees Celsius to solidify the binder
material and form a construction comprising the layer of PCD bonded
to the substrate by the solidified binder material, and the
pressure and temperature were then reduced to ambient
conditions.
[0170] The construction was subjected to a heat treatment at 660
degrees Celsius for about 2 hours at substantially ambient pressure
in a substantially non-oxidising atmosphere, and then cooled to
ambient temperature. No cracks were evident in the PCD layer after
the heat treatment.
[0171] The construction was processed by grinding and polishing to
provide an insert for a rock-boring drill bit.
[0172] As used herein, the thickness of the PCD structure 22, 200
or the substrate 30, 300, or some part of the PCD structure or the
substrate is the thickness measured substantially perpendicularly
to the interface 24. In some embodiments, the PCD structure, or
body of PCD material 22, 200 may have a generally wafer, disc or
disc-like shape, or be in the general form of a layer. In some
embodiments, the PCD structure 22, 200 may have a thickness of at
least about 0.3 mm, at least about 0.5 mm, at least about 0.7 mm,
at least about 1 mm, at least about 1.3 mm or at least about 2 mm.
In one embodiment, the PCD structure 22, 200 may have a thickness
in the range from about 2 mm to about 3 mm.
[0173] In some embodiments, the substrate 30, 300 may have the
general shape of a wafer, disc or post, and may be generally
cylindrical in shape. The substrate 30, 300 may have, for example,
an axial thickness at least equal to or greater than the axial
thickness of the body of PCD material 22, 200, and may be for
example at least about 1 mm, at least about 2.5 mm, at least about
3 mm, at least about 5 mm or even at least about 10 mm in
thickness. In one embodiment, the substrate 30, 300 may have a
thickness of at least 2 cm.
[0174] The PCD structure 22, 200 may be joined to the substrate 30,
300 for example only on one side thereof, the opposite side of the
PCD structure not being bonded to the substrate 30, 300.
[0175] In some embodiments, the largest dimension of the body of
PCD material 22, 200 is around 6 mm or greater, for example in
embodiments where the body of PCD material is cylindrical in shape,
the diameter of the body is around 6 mm or greater.
[0176] In some versions of the method, prior to sintering, the
aggregated mass of diamond particles/grains may be disposed against
the surface of the substrate generally in the form of a layer
having a thickness of least about 0.6 mm, at least about 1 mm, at
least about 1.5 mm or even at least about 2 mm. The thickness of
the mass of diamond grains may reduce significantly when the grains
are sintered at an ultra-high pressure.
[0177] The super hard particles used in the present process may be
of natural or synthetic origin. The mixture of super hard particles
may be multimodal, that it is may comprise a mixture of fractions
of diamond particles or grains that differ from one another
discernibly in their average particle size. Typically the number of
fractions may be: [0178] a specific case of two fractions [0179]
three or more fractions.
[0180] By "average particle/grain size" it is meant that the
individual particles/grains have a range of sizes with the mean
particle/grain size representing the "average". Hence the major
amount of the particles/grains will be close to the average size,
although there will be a limited number of particles/grains above
and below the specified size. The peak in the distribution of the
particles will therefore be at the specified size. The size
distribution for each super hard particle/grain size fraction is
typically itself monomodal, but may in certain circumstances be
multimodal. In the sintered compact, the term "average particle
grain size" is to be interpreted in a similar manner.
[0181] As shown in FIG. 1, the bodies of polycrystalline diamond
material produced by an embodiment additionally have a binder phase
present. This binder material is preferably a catalyst/solvent for
the super hard abrasive particles used. Catalyst/solvents for
diamond are well known in the art. In the case of diamond, the
binder is preferably cobalt, nickel, iron or an alloy containing
one or more of these metals. This binder may be introduced either
by infiltration into the mass of abrasive particles during the
sintering treatment, or in particulate form as a mixture within the
mass of abrasive particles. Infiltration may occur from either a
supplied shim or layer of the binder metal or from the carbide
support. Typically a combination of the admixing and infiltration
approaches is used.
[0182] During the high pressure, high temperature treatment, the
catalyst/solvent material melts and migrates through the compact
layer, acting as a catalyst/solvent and causing the super hard
particles to bond to one another. Once manufactured, the PCD
construction therefore comprises a coherent matrix of super hard
(diamond) particles bonded to one another, thereby forming an super
hard polycrystalline composite material with many interstices or
pools containing binder material as described above. In essence,
the final PCD construction therefore comprises a two-phase
composite, where the super hard abrasive diamond material comprises
one phase and the binder (non-diamond phase), the other.
[0183] In one form, the super hard phase, which is typically
diamond, constitutes between 80% and 95% by volume and the
solvent/catalyst material the other 5% to 20%.
[0184] The relative distribution of the binder phase, and the
number of voids or pools filled with this phase, is largely defined
by the size and shape of the diamond grains.
[0185] The binder (non-diamond) phase can help to improve the
impact resistance of the more brittle abrasive phase, but as the
binder phase typically represents a far weaker and less abrasion
resistant fraction of the structure, and high quantities will tend
to adversely affect wear resistance. Additionally, where the binder
phase is also an active solvent/catalyst material, its increased
presence in the structure can compromise the thermal stability of
the compact.
[0186] FIGS. 11a and 11b are an example of a processed SEM image of
a polished section of a PCD material, shown in negative, for a
diamond intensity of 0 (FIG. 11a) and a diamond intensity of 15
(FIG. 11b) showing the boundaries between diamond grains. These
boundary lines were provided by image analysis software and were
used to measure the total non-diamond phase (eg binder) surface
area in a cross-section through the body of PCD material and
surface area of the individual non-diamond phase (interstitial)
regions which are indicated as dark areas in the actual SEM images
but are shown in the negative (ie as light areas) in FIGS. 11a and
11b. The cross-section through the body of PCD material may be at
any orientation through the body of PCD material for the following
analysis to be conducted and results to be achieved. The image
analysis technique is described in more detail below.
[0187] As a non-limiting example, the cross section shown in FIGS.
11a and 11b may be exposed for viewing by cutting a section of the
PCD composite compact by means of a wire EDM. The cross section may
be polished in preparation for viewing by a microscope, such as a
scanning electron microscope (SEM) and a series of micrographic
images may be taken. Each of the images may be analysed by means of
image analysis software to determine the total binder area and
individual binder areas between the diamond grains. The values of
the total binder area and individual binder area are determined by
conducting a statistical evaluation on a large number of collected
images taken on the scanning electron microscope.
[0188] The magnification selected for the microstructural analysis
has a significant effect on the accuracy of the data obtained.
Imaging at lower magnifications offers an opportunity to sample,
representatively, larger particles or features in a microstructure
but may tend to under-represent smaller particles or features as
they are not necessarily sufficiently resolved at that
magnification. By contrast, higher magnifications allow resolution
and hence detailed measurement of fine-scale features but can tend
to sample larger features such that they intersect the boundaries
of the images and hence are not adequately measured. It has been
appreciated that it is therefore important to select an appropriate
magnification for any quantitative microstructural analysis
technique. The appropriateness is therefore determined by the size
of the features that are being characterised. The magnifications
selected for the various measurements described herein are
discussed in more detail below.
[0189] Unless otherwise stated herein, dimensions of total binder
area and individual binder area within the body of PCD material
refer to the dimensions as measured on a surface of, or a section
through, a body comprising PCD material and no stereographic
correction has been applied. For example, the measurements are made
by means of image analysis carried out on a polished surface, and a
Saltykov correction has not been applied in the data stated
herein.
[0190] In measuring the mean value of a quantity or other
statistical parameter measured by means of image analysis, several
images of different parts of a surface or section (hereinafter
referred to as samples) are used to enhance the reliability and
accuracy of the statistics. The number of images used to measure a
given quantity or parameter may be, for example between 10 to 30.
If the analysed sample is uniform, which is the case for PCD,
depending on magnification, 10 to 20 images may be considered to
represent that sample sufficiently well.
[0191] The resolution of the images needs to be sufficiently high
for the inter-grain and inter-phase boundaries to be clearly made
out and, for the measurements stated herein an image area of 1280
by 960 pixels was used.
[0192] In the statistical analysis, 15 images were taken of
different areas on a surface of a body comprising the PCD material,
and statistical analysis was carried out on each image.
[0193] Images used for the image analysis were obtained by means of
scanning electron micrographs (SEM) taken using a backscattered
electron signal. The back-scatter mode was chosen so as to provide
high contrast based on different atomic numbers and to reduce
sensitivity to surface damage (as compared with the secondary
electron imaging mode).
[0194] A number of factors have been identified as being important
for image capturing. These are: [0195] SEM Voltage which, for the
purposes of the measurements stated herein remained constant and
was around 15 kV; [0196] working distance which also remained
constant and was around 8 mm [0197] image sharpness [0198] sample
polishing quality, [0199] image contrast levels which were selected
to provide clear separation of the microstructural features; [0200]
magnification (should be varied according to different diamond
grain size and is as stated below), [0201] number of images
taken.
[0202] Given the above conditions, the image analysis software used
was able to separate distinguishably the diamond and binder phases
and the back-scatter images were taken at approximately 45.degree.
to the edge of the samples.
[0203] The magnification used in the image analysis should be
selected in such a way that the feature of interest is adequately
resolved and described by the available number of pixels. In PCD
image analysis various features of different size and distribution
are measured simultaneously and it is not practical to use a
separate magnification for each feature of interest.
[0204] It is difficult to identify the optimum magnification for
each feature measurement in the absence of a reference measurement
result. It could vary from one operator to another. Therefore, a
procedure is proposed for the selection of the magnification.
[0205] The size of a statistically significant number of diamond
grains in the microstructure is measured and the average value
taken.
[0206] As used herein in relation to grains or particles and unless
otherwise stated or implied, the term "size" refers to the length
of the grain viewed from the side or in cross section using image
analysis techniques.
[0207] The number of pixels that describe this average length is
determined and a range of pixel values are established to fix the
magnification.
[0208] In the image analysis technique, the original image was
converted to a greyscale image. The image contrast level was set by
ensuring the diamond peak intensity in the grey scale histogram
image occurred between 15 and 20.
[0209] As mentioned above, several images of different parts of a
surface or section were taken to enhance the reliability and
accuracy of the statistics. For measurements of total non-diamond
phase (eg binder) area, the greater the number of images, the more
accurate the results are perceived to be. For example, about 15000
measurements were taken, 1000 per image with 15 images.
[0210] The steps taken by the image analysis programme may be
summarised in general as follows: [0211] 1. The original image was
converted to a greyscale image. The image contrast level was set by
ensuring the diamond peak intensity in the grey scale histogram
image occurred between 10 and 20. [0212] 2. An auto threshold
feature was used to binarise the image and specifically to obtain
clear resolution of the diamond and binder phases. [0213] 3. The
binder was the primary phase of interest in the current analysis.
[0214] 4. The software, having the trade name analySIS Pro from
Soft Imaging System.RTM. GmbH (a trademark of Olympus Soft Imaging
Solutions GmbH) was used and excluded from the analysis any
particles which touched the boundaries of the image. This required
appropriate choice of the image magnification: [0215] a. If too low
then resolution of fine particles is reduced. [0216] b. If too high
then: [0217] i. Efficiency of coarse grain separation is reduced.
[0218] ii. High numbers of coarse grains are cut by the boarders of
the image and hence less of these grains are analysed. [0219] iii.
Thus more images must be analysed to get a statistically-meaningful
result. [0220] 5. Each particle was finally represented by the
number of continuous pixels of which it is formed. [0221] 6. The
AnalySIS software programme proceeded to detect and analyse each
particle in the image. This can be automatically repeated for
several images. [0222] 7. A large number of outputs was available.
The outputs may be post-processed further, for example using
statistical analysis software and/or carrying out further feature
analysis, for example the analysis described below for determining
the mean of the total binder area for all images and the means of
the individual binder areas.
[0223] If appropriate thresholding is used, the image analysis
technique is unlikely to introduce further errors in measurements
which would have a practical effect on the accuracy of those
measurements, with the exception of small errors related to the
rounding of numbers. In the current analysis, the statistical mean
values of the total binder area and individual binder areas were
used as, according to the Central Limitation Theorem, the
distribution of an average tends to be normal as the sample size
increases, regardless of the distribution from which the average is
taken except when the moments of the parent distribution do not
exist. All practical distributions in statistical engineering have
defined moments, and thus the Central Limitation Theorem applies in
the present case. It was therefore deemed appropriate to use the
statistical mean values.
[0224] The individual non-diamond (eg binder or catalyst/solvent)
phase areas or pools, which are easily distinguishable from that of
the super hard phase using electron microscopy, were identified
using the above-mentioned standard image analysis tools. The total
non-diamond phase areas (in square microns) in the analysed
cross-sectional images were determined by summing the individual
binder pool areas within the entire microstructural image area that
was analysed.
[0225] The collected distributions of this data were then evaluated
statistically and an arithmetic average was then determined. Hence
the mean total binder pool area in the surface of the
microstructure being analysed was calculated
[0226] It is anticipated that microstructural parameters may alter
slightly from one area of an abrasive compact to another, depending
on formation conditions. Hence the microstructural imaging is
carried out so as to representatively sample the bulk of the super
hard composite portion of the compact.
[0227] Additional non-limiting examples are now described. Three
sets of samples were produced as follows: a multimodal (trimodal)
diamond powder mix with average diamond grain size of approximately
13 .mu.m and 1 weight percent cobalt admix was prepared, in
sufficient quantity to provide approximately 2 g admix per sample.
The admix for each sample was then poured into or otherwise
arranged in a Niobium inner cup. A cemented carbide substrate of
approximately 13 weight percent cobalt content and having a
non-planar interface was placed in each inner cup on the powder
mix. A titanium cup was placed in turn over this structure and the
assembly sealed to produce a canister. The canisters were
pre-treated by vacuum outgassing at approximately 1050.degree. C.,
and divided into three sets which were sintered at three distinct
ultrahigh pressure and temperature conditions in the diamond-stable
region, namely at approximately 5.5 GPa (Set 1), 6.8 GPa (Set 2),
and 7.7 GPa (Set 3). Specifically the canisters were sintered at
temperatures sufficient to melt the cobalt so as to produce PCD
constructions with well-sintered PCD tables and well-bonded
substrates. The technique described above in connection with FIGS.
3 to 9 was applied for the sintering of the canisters at 7.7 GPa
(set 3). The resulting super hard constructions were not subjected
to any post-synthesis leaching treatment.
[0228] Image analysis was then conducted on each of these super
hard constructions using the techniques described above and in
particular the determination of appropriate magnification described
above to determine the mean total binder area in a polished
cross-section and mean cross-sectional binder area for each
sample.
[0229] The experiments may be repeated for different diamond grain
size compositions and the results are set out in Table 1.
TABLE-US-00001 TABLE 1 Grain Total Size Binder Binder microns Area
Area Mean Std Dev % micron{circumflex over ( )}20.01 Magnification
13.4600 2.2750 8.0699 0.4446 1000x 12.5755 3.1707 8.0223 0.2802
1000x 10.8800 1.8440 6.4004 0.2638 1000x 3.9700 0.7990 10.3135
0.1528 3000x
[0230] It was determined from the above experiments that, for a
total non-diamond phase area (for example binder area) in the range
of around 0 to 12%, it is possible to achieve an associated
individual non-diamond area of less than around 0.7 micron.sup.2,
as determined using an image analysis technique applying a
magnification of around 1000 and analysing an image area of
1280.times.960 pixels, with the largest dimension of the body of
PCD material being around 6 mm or greater. The thickness of the
body of PCD material in these embodiments may be, for example,
around 0.3 mm or greater.
[0231] Furthermore, in some embodiments, for a total non-diamond
phase area (for example binder area) in the range of around 0 to
12%, such as less than 12%, or less than 10% or less than 8%, it is
possible to achieve an associated individual non-diamond area of
less than around 0.7 micron.sup.2, or less than around 0.5
micron.sup.2, or less than around 0.4 micron.sup.2, or less than
around 0.34 micron.sup.2, as determined using an image analysis
technique applying a magnification of between around 1000 and
analysing an image area of 1280.times.960 pixels, with the largest
dimension of the body of PCD material being around 6 mm or greater.
The thickness of the body of PCD material in these embodiments may
be, for example, around 0.3 mm or greater.
[0232] To assist in improving thermal stability of the sintered
structure, the catalysing material is removed from a region of the
polycrystalline layer adjacent an exposed surface thereof, namely
the working surface opposite the substrate. Removal of the
catalysing material may be carried out using methods known in the
art such as electrolytic etching, and acid leaching and evaporation
techniques.
[0233] The polycrystalline super hard layer 22 to be leached by
embodiments of the method may, but not exclusively, have a
thickness of about 1.5 mm to about 3.5 mm.
[0234] It has been found that the removal of non-binder phase from
within the PCD table, conventionally referred to as leaching, is
desirable in various applications. The residual presence of
solvent/catalyst material in the microstructural interstices is
believed to have a detrimental effect on the performance of PCD
compacts at high temperatures as it is believed that the presence
of the solvent/catalyst in the diamond table reduces the thermal
stability of the diamond table at these elevated temperatures.
Therefore leaching is desired to enhance thermal stability of the
PCD body. However, leaching solvent/catalyst material from a PCD
structure is known to reduce its fracture toughness and strength by
between 20 to 30%. The present applicants have surprisingly
determined that, contrary to conventional expectations, leaching to
a deeper leach depth and, in particular, leaching to a depth into
the PCD body greater than 800 microns from the working surface,
actually significantly increases the strength of the PCD body in
terms of the pure mechanical strength in cutting applications and
in strength in response to loading thereby retarding the likelihood
of spalling. This is explained and illustrated with examples
below.
[0235] In acid leaching, the reaction rate regarding leaching is
considered to be dominated by the chemical rate initially as acid
contacts a surface of the PCD table and later by the diffusion rate
as the acid diffuses through the pores of the PCD table.
[0236] Conventionally, HF--HNO.sub.3 has been shown to be the most
effective media for the removal of tungsten carbide (WC) from the
sintered PCD table. The problem with HF--HNO.sub.3 is that it is
volatile and, when heating this acid, specific technology, for
example, gas sealing technology, is required. If such technology is
not provided then the application of temperature will reduce the
efficacy of HF--HNO.sub.3 due to evaporation of the HF (which is
poisonous) and formation of NO species, which are usually gaseous,
and thus frequent replenishment of the acid media is required.
Furthermore, heat would ordinarily be required to accelerate the
leaching process in order to render the process commercially
feasible. Another problem is that HF--HNO.sub.3 is corrosive to
most containment vessels making the reaction difficult to
perform.
[0237] HCl and other similar mineral acids are easier to work with
at high temperatures than HF--HNO.sub.3 and are aggressive towards
the catalyst/solvent, particularly cobalt (Co). HCl, for example,
may remove the bulk of the catalyst/solvent from the PCD table in a
reasonable time period, depending on the temperature, typically in
the region of 80 hours, although it does not remove WC and it has
been appreciated by the present applicant that HCl alone is not
suitable for removing any non-diamond phase additions, such as VC
from the PCD table.
[0238] To improve the performance and heat resistance of a surface
of the body of PCD material 22, at least a portion of the
metal-solvent catalyst, such as cobalt, and at least a portion of
the additions to the PCD, such as carbide additions, may be removed
from the interstices 14 of at least a portion of the PCD material
22. Additionally, tungsten and/or tungsten carbide may be removed
from at least a portion of the body of PCD material 22.
[0239] Chemical leaching is used to remove the metal-solvent
catalyst and the additions from the body of PCD material 22 up to a
desired depth from the working surface 34 of the body of PCD
material. Following leaching, the body of PCD material 22 comprises
a first volume that is substantially free of a metal-solvent
catalyst. However, small amounts of catalyst may remain within
interstices that are inaccessible to the leaching process.
Following leaching, the body of PCD material 22 also comprises a
volume that contains a metal-solvent catalyst. In some embodiments,
this further volume may be remote from one or more exposed surfaces
of the body of PCD material 22.
[0240] The interstitial material which may include, for example,
the metal-solvent/catalyst and one or more additions in the form of
carbide additions, may be leached from the interstices 14 in the
body of PCD material 22 by exposing the PCD material to a suitable
leaching solution.
[0241] According to some embodiments, the leaching solution may
comprise one or more mineral acids and diluted nitric acid. The
body of PCD material may be exposed to such a leaching solution in
any suitable manner, including, for example, by immersing at least
a portion of the body of PCD material 22 in the leaching solution
for a period of time.
[0242] According to some embodiments, the body of PCD material may
be exposed to the leaching solution at an elevated temperature, for
example to a temperature at which the acid leaching mixture is
boiling. Exposing the body of PCD material to an elevated
temperature during leaching may increase the depth to which the PCD
material may be leached and reduce the leaching time necessary to
reach the desired leach depth.
[0243] When only a portion of the body of PCD material is to be
leached, the body, and if it is still attached to the substrate,
the substrate may be at least partially surrounded by a protective
layer to prevent the leaching solution from chemically damaging
certain portions of the body of PCD material and/or the substrate
attached thereto during leaching. Such a configuration may provide
selective leaching of the body of PCD material, which may be
beneficial. Following leaching, the protective layer or mask may be
removed.
[0244] Additionally, in some embodiments, at least a portion of the
body of PCD material and the leaching solution may be exposed to at
least one of an electric current, microwave radiation, and/or
ultrasonic energy to increase the rate at which the body of PCD
material is leached.
[0245] Examples of suitable mineral acids may include, for example,
hydrochloric acid, phosphoric acid, sulphuric acid, hydrofluoric
acid, and/or any combination of the foregoing mineral acids.
[0246] In some embodiments, nitric acid may be present in the
leaching mixture of some embodiments in an amount of, for example,
between 2 to 5 wt % and/or a molar concentration of up to around
1.3M. In some embodiments, one or more mineral acids may be present
in the leaching solution at a molar concentration of up to around,
for example, 7M.
[0247] In some embodiments, the PCD table was leached using a
solution comprising hydrochloric acid and nitric acid diluted in
water. The PCD table was leached for between around 30 to 300
hours, depending on desired leach depth and composition of the PCD
material, at a temperature at which the acid leaching mixture was
boiling and ultrasound was applied after a period of leaching to
remove remnant reactants.
[0248] After leaching, leached depths of the PCD table were
determined for various portions of the PCD table, through
conventional x-ray analysis.
[0249] In order to test the wear resistance of the sintered
polycrystalline products formed according to the above methods and
leached to various leach depths, a first example product (Example
1) comprising a bimodal mixture of 70 weight percent of diamond
grains having an average grain size of 17 microns, and 30 weight
percent of diamond grains having an average grain size of 1.7
microns was sintered at a sintering pressure of 6.8 GPa. The
sintered products were leached for a sufficient leach time (from
around 40 hours for a leach depth of around 250 microns and around
100 hours for a leach depth of around 1000 microns) to produce, for
comparison, a leached product having a leach depth from the working
surface of 256 microns, a further product having a leach depth of
572 microns and a further product having a leach depth of 947
microns.
[0250] The diamond layers were then polished and a subjected to a
vertical boring mill test. In this test, the wear flat area was
measured as a function of the number of passes of the cutter
element boring into the workpiece. The results obtained are
illustrated graphically in FIG. 12. The results provide an
indication of the total wear scar area plotted against cutting
length.
[0251] It will be seen that the PCD compacts formed according to
Example 1 were able to achieve a significantly greater cutting
length and smaller wear scar area at leach depths of 572 microns
and 947 microns than that leached to 256 microns.
[0252] A further example set of polycrystalline compacts were
produced according to the above described methods and form Example
2, these compacts were comprised of a trimodal mixture of 40 weight
percent of diamond grains having an average grain size of 17
microns, 30 weight percent of diamond grains having an average
grain size of 10 microns and 30 weight percent of diamond grains
having an average grain size of 1.7 microns. The sintering pressure
was 7.1 GPa.
[0253] The sintered products were leached for a sufficient leach
time (from around 230 hours for a leach depth of around 700 microns
and around 250 hours for a leach depth of around 900 microns) to
produce, for comparison, a leached product having a leach depth
from the working surface of 971 microns, and a further product
having a leach depth of 770 microns.
[0254] The diamond layers were then polished and a subjected to a
vertical boring mill test. The results obtained are illustrated
graphically in FIG. 13.
[0255] It will be seen that the PCD compacts formed according to
Example 2 were able to achieve a significantly greater cutting
length and smaller wear scar area at leach depths of 971 microns
than that leached to 770 microns.
[0256] Whilst not wishing to be bound by a particular theory, using
the conditions described herein it was determined possible to
achieve a mechanically stronger and more wear-resistant body of PCD
material which, when used as a cutter, may significantly enhance
the durability of the cutter produced according to some embodiments
described herein.
[0257] Indeed, in particular, whilst leaching is desired to enhance
thermal stability of the PCD body it is known that leaching
solvent/catalyst material from a PCD structure reduces its fracture
toughness and strength by between 20 to 30%. The present applicants
have appreciated that, contrary to conventional expectations,
leaching to a deeper leach depth and, in particular, leaching to a
depth into the PCD body greater than 800 microns from the working
surface, actually significantly increases the strength of the PCD
body in terms of the pure mechanical strength in cutting
applications and in strength in response to loading thereby
retarding the likelihood of spalling when compared to PCD bodies
leached to depths of less than 800 microns. This may be assisted by
maintaining the wear scar in use in the leached PCD layer thereby
inhibiting the effects of cracks propagating along the interface
between the leached and unleached regions of PCD. These serve to
reduce the likelihood or frequency of spalling and therefore
increasing the useful working life of the PCD construction.
[0258] It has also been found that the multimodal distributions of
some embodiments may assist in achieving a very high degree
(density) of diamond intergrowth while still maintaining sufficient
open porosity to enable efficient leaching.
[0259] While various embodiments have been described with reference
to a number of examples, those skilled in the art will understand
that various changes may be made and equivalents may be substituted
for elements thereof and that these examples are not intended to
limit the particular embodiments disclosed.
[0260] In addition, various arrangements and combinations are
envisaged for the method by the disclosure, and examples of the
method may further include one or more of the following
non-exhaustive and non-limiting aspects in various
combinations.
[0261] There may be provided a method for making a super-hard
construction comprising:
[0262] a first structure joined to a second structure, the first
structure comprising first material having a first coefficient of
thermal expansion (CTE) and a first Young's modulus, and the second
structure comprising second material having a second CTE and a
second Young's modulus; the first CTE and the second CTE being
substantially different from each other and the first Young's
modulus and the second Young's modulus being substantially
different from each other; at least one of the first or second
materials comprising super-hard material; the method including:
[0263] forming an assembly comprising the first material, the
second material and a binder material arranged to be capable of
bonding the first and second materials together, the binder
material comprising metal; subjecting the assembly to a
sufficiently high temperature for the binder material to be in the
liquid state and to a first pressure at which the super-hard
material is thermodynamically stable; reducing the pressure to a
second pressure at which the super-hard material is
thermodynamically stable, the temperature being maintained
sufficiently high to maintain the binder material in the liquid
state; reducing the temperature to solidify the binder material;
and reducing the pressure and the temperature to an ambient
condition to provide the super-hard construction.
[0264] In some embodiments, the CTE of one of the first or second
materials is at least about 2.5.times.10-6 per degree Celsius and
at most about 5.0.times.10-6 per degree Celsius and the CTE of the
other of the first or second materials is at least about
3.5.times.10-6 per degree Celsius and at most about 6.5.times.10-6
per degree Celsius, at about 25 degrees Celsius.
[0265] In some embodiments, the Young's modulus of one of the first
or second materials is at least about 500 gigapascals and at most
about 1,300 gigapascals and the Young's modulus of the other of the
first and second materials is at least about 800 gigapascals and at
most about 1,600 gigapascals.
[0266] The Young's moduli of the first and second materials may,
for example, differ by at least about 10%.
[0267] In some embodiments, the CTE of the first and second
materials may, for example, differ by at least about 10%.
[0268] The method may further include sintering an aggregation of a
plurality of grains of the super-hard material in the presence of
sinter catalyst material at a sinter pressure and a sinter
temperature to form the second structure.
[0269] The method may include disposing an aggregation of grains of
super-hard material adjacent the first structure and in the
presence of the binder material to form a pre-sinter assembly;
subjecting the pre-sinter assembly to a sinter pressure and a
sinter temperature to melt the binder material and sinter the
grains of super-hard materials and form the second structure
comprising polycrystalline super-hard material connected to the
first structure by the binder material in the molten state.
[0270] In some embodiments, the first pressure is substantially the
sinter pressure.
[0271] The method may further include providing the first
structure, providing the second structure comprising
polycrystalline super-hard material, disposing the first structure
adjacent the second structure and forming a pre-construction
assembly, and applying a pressure to the pre-construction assembly,
increasing the pressure from ambient pressure to the first
pressure.
[0272] The method may, for example, include subjecting an
aggregation of a plurality of grains of super-hard material to a
sinter pressure and a sinter temperature at which the super-hard
material is capable of being sintered to form the second material,
and reducing the pressure and temperature to an ambient condition
to provide the second structure; the first pressure being
substantially greater than the sinter pressure.
[0273] The second structure may comprise diamond material and the
binder material comprises catalyst material for diamond.
[0274] The first and second structures may each comprise diamond
material and the binder material comprises catalyst material for
diamond.
[0275] In some embodiments, the difference between the second
pressure and the first pressure is at least about 0.5
gigapascal.
[0276] The method may further include subjecting the super-hard
construction to further heat treatment at a treatment temperature
and a treatment pressure at which the super-hard material is
thermodynamically meta-stable.
[0277] The super-hard material may comprise diamond material and
the treatment temperature is at least about 500 degrees Celsius and
the treatment pressure is less than about 1 gigapascal.
[0278] The method may include the step of reducing the pressure
from the first pressure to an intermediate pressure for an holding
period, and then further reducing the pressure from the
intermediate pressure to the second pressure.
[0279] The first pressure may, for example, be at least about 7
gigapascal, the intermediate pressure may be, for example, at least
about 5.5 gigapascals and less than about 10 gigapascals, the
holding period may, for example, be at least about 1 minute and the
second pressure may, for example, be at least about 5.5 gigapascals
and at most about 7 gigapascals.
[0280] The pressure at which the binder material begins to solidify
responsive to the reduction in temperature may, for example, be
substantially equal to the second pressure in some embodiments.
[0281] In other embodiments, the pressure at which the binder
material begins to solidify responsive to the reduction in
temperature may be substantially less than the second pressure.
[0282] In some embodiments, the first structure comprises
cobalt-cemented tungsten carbide material and the second material
comprises PCD material, the CTE of the cemented carbide material
being in the range of about 4.5.times.10-6 to about 6.5.times.10-6
per degree Celsius, the CTE of the PCD material being in the range
of about 3.0.times.10-6 to about 5.0.times.10-6 per degree Celsius;
the Young's modulus of the cemented carbide material being in the
range of about 500 to about 1,000 gigapascals, and the Young's
modulus of the PCD material being in the range of about 800 to
about 1,600 gigapascals; the first pressure being in the range of
about 6 to about 10 gigapascals, and the second pressure being in
the range of about 5.5 to about 8 gigapascals.
[0283] In some embodiments, the pressure at which the cobalt-based
binder material comprised in the cemented carbide material begins
to solidify is equal to the second pressure.
[0284] The second pressure may, for example, be in the range of
about 6.5 to about 7.5 gigapascals.
[0285] In some embodiments, the second structure comprises PCD
material and the method includes subjecting the super-hard
construction to further heat treatment for a treatment period in
the range of about 30 to about 90 minutes at a treatment
temperature in the range of about 550 to about 650 degrees
Celsius.
* * * * *