U.S. patent application number 14/026976 was filed with the patent office on 2014-01-09 for techniques and materials for the accelerated removal of catalyst material from diamond bodies.
This patent application is currently assigned to SMITH INTERNATIONAL, INC.. The applicant listed for this patent is Smith International, Inc.. Invention is credited to Yahua Bao, J. Daniel Belnap, Peter Thomas Cariveau, Loel Corbett, Gerald Demenna, Anthony Griffo.
Application Number | 20140007512 14/026976 |
Document ID | / |
Family ID | 41462670 |
Filed Date | 2014-01-09 |
United States Patent
Application |
20140007512 |
Kind Code |
A1 |
Belnap; J. Daniel ; et
al. |
January 9, 2014 |
TECHNIQUES AND MATERIALS FOR THE ACCELERATED REMOVAL OF CATALYST
MATERIAL FROM DIAMOND BODIES
Abstract
A method for making a thermally stable cutting element may
include forming an acid mixture containing two different acid
species by combining an acid solution and at least one acid-forming
compound, wherein the at least one acid-forming compound is
provided in solid form, and wherein the at least one acid-forming
compound produces an acid that is different than the acid solution;
treating at least a portion of a sintered diamond body by placing
the sintered diamond body in the acid mixture, wherein the sintered
diamond body comprises: a matrix phase of bonded-together diamond
grains; a plurality of interstitial regions dispersed within the
matrix phase; and a metal material disposed within a plurality of
the interstitial regions; wherein the treating removes the metal
material from at least a portion of the plurality of interstitial
regions; and removing the sintered diamond body from the acid
mixture after a predetermined length of time, wherein at least a
portion of the diamond body removed from the acid mixture is
substantially free of the metal material and is a thermally stable
diamond body.
Inventors: |
Belnap; J. Daniel; (Lindon,
UT) ; Griffo; Anthony; (The Woodlands, TX) ;
Cariveau; Peter Thomas; (Spring, TX) ; Corbett;
Loel; (Saratoga Springs, UT) ; Bao; Yahua;
(Orem, UT) ; Demenna; Gerald; (Bronx, NY) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Smith International, Inc. |
Houston |
TX |
US |
|
|
Assignee: |
SMITH INTERNATIONAL, INC.
Houston
TX
|
Family ID: |
41462670 |
Appl. No.: |
14/026976 |
Filed: |
September 13, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12581639 |
Oct 19, 2009 |
8535400 |
|
|
14026976 |
|
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|
61106912 |
Oct 20, 2008 |
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Current U.S.
Class: |
51/295 ;
51/309 |
Current CPC
Class: |
C04B 2235/427 20130101;
C04B 35/52 20130101; C04B 2235/386 20130101; E21B 10/567 20130101;
C04B 35/5831 20130101 |
Class at
Publication: |
51/295 ;
51/309 |
International
Class: |
E21B 10/567 20060101
E21B010/567 |
Claims
1. A method for making a thermally stable cutting element
comprising: treating at least a portion of a sintered diamond body
comprising: placing a sintered diamond body in an acid mixture of
HNO.sub.3 at a concentration of 4.5 to 10 mol/liter and HF at a
concentration of 2.5 to 10 mol/liter, the sintered diamond body
having: a matrix phase of bonded-together diamond grains; a
plurality of interstitial regions dispersed within the matrix
phase; and a metal material disposed within a plurality of the
interstitial regions; wherein the treating removes metal material
from at least a portion of the plurality of interstitial regions;
and removing the sintered diamond body from the acid mixture after
a predetermined length of time, wherein the at least a portion of
the diamond body removed from the acid mixture is substantially
free of the metal material and is a thermally stable diamond
body.
2. The method of claim 1, further comprising: forming the acid
mixture by combining an HNO.sub.3 solution and at least one
HF-forming compound, wherein the at least one HF-forming compound
is provided in solid form.
3. The method of claim 1, wherein the treating step further
comprises subjecting the sintered diamond body and acid mixture to
at least one of elevated temperature conditions, elevated pressure
conditions, vibration energy, or ultrasonic energy.
4. The method of claim 1, wherein the sintered diamond body
comprises at least about 80 percent by volume diamond.
5. The method of claim 1, wherein the HF-forming compound is a
fluoride salt.
6. The method of claim 5, wherein the HF-forming compound is
ammonium bifluoride.
7. The method of claim 1, wherein the step of treating further
comprises: subjecting the acid mixture and sintered diamond body to
an elevated temperature; and reducing the temperature of the acid
mixture and sintered diamond body in a controlled manner so as to
form soluble salts within the sintered diamond body.
8. The method of claim 7, wherein the soluble salts are disposed
within the interstitial regions of the sintered diamond body.
9. The method of claim 7, wherein after the step of removing,
further comprising: cleaning the thermally stable diamond body to
remove the soluble salts and/or insoluble oxides therefrom.
10. The method of claim 9, wherein the step of cleaning comprises
placing the thermally stable diamond body into a volume of water
that is at an elevated temperature and pressure.
11. The method of claim 9, wherein after the step of cleaning,
further comprising: reinfiltrating the thermally stable diamond
body by filling at least a plurality of the interstitial regions of
the thermally stable diamond body with an infiltrant material.
12. The method of claim 11, further comprising: a second treating
step, wherein the second treating step comprises: removing the
infiltrant material to a desired depth from a surface of the
thermally stable diamond body.
13. The method of claim 12, wherein the depth is substantially
uniform within the thermally stable diamond body at the center of
the thermally stable diamond body compared to a position along a
circumferential edge of the thermally stable diamond body.
14. The method of claim 1, wherein the metal material is a catalyst
material.
15. The method of claim 1, wherein the metal material is an
infiltrant material.
16. The method of claim 1, further comprising: cleaning the
thermally stable diamond body to remove any residual non-diamond
materials remaining therein.
17. The method of claim 16, wherein the step of cleaning comprises
subjecting the thermally stable diamond body to at least one
process selected from the group consisting of ultrasonic energy,
pressurization, electrolysis and gas-phase leaching.
18. The method of claim 17, wherein the step of cleaning comprises
subjecting the thermally stable diamond body to ultrasonic in a
bath of a solvent.
19. The method as recited in claim 17, wherein during the step of
treating, further comprising elevating the pressure conditions of
the sintered diamond body and the leaching agent to a desired
pressure for a predetermined amount of time.
20. A method for making a thermally stable cutting element
comprising: treating at least a portion of a sintered diamond body
comprising: placing a sintered diamond body in an acid mixture of
HNO.sub.3 at a concentration of 2.5 to 10 mol/liter and HF at a
concentration of 4.0 to 10 mol/liter, the sintered diamond body
having: a matrix phase of bonded-together diamond grains; a
plurality of interstitial regions dispersed within the matrix
phase; and a metal material disposed within a plurality of the
interstitial regions; wherein the treating removes metal material
from at least a portion of the plurality of interstitial regions;
and removing the sintered diamond body from the acid mixture after
a predetermined length of time, wherein the at least a portion of
the diamond body removed from the acid mixture is substantially
free of the metal material and is a thermally stable diamond body.
Description
CROSS-REFERENCE OF RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 12/581,639 filed on Oct. 19, 2009, which
pursuant to 35 U.S.C. .sctn.119, claims the benefit of U.S. Patent
Application No. 61/106,912, filed on Oct. 20, 2008, which is herein
incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of Invention
[0003] Embodiments disclosed herein relate generally to
polycrystalline diamond constructions and cutting structures
comprising the same and, more particularly, to methods and
materials used for improving the thermal stability of
polycrystalline diamond constructions and the polycrystalline
diamond constructions resulting therefrom.
[0004] 2. Background Art
[0005] Polycrystalline diamond compact ("PDC") cutters have been
used in industrial applications including subterranean drilling and
metal machining for many years. In a typical application, a compact
of polycrystalline diamond (PCD) (or other superhard material) is
bonded to a substrate material, which is typically a sintered
metal-carbide to form a cutting structure. PCD comprises a
polycrystalline mass of bonded-together diamond grains or crystals
that form an integral, tough, high-strength mass or lattice. The
resulting PCD structure produces enhanced properties of wear
resistance and hardness, making PCD materials extremely useful in
aggressive wear and cutting applications where high levels of wear
resistance and hardness are desired.
[0006] PCD may be formed by subjecting a volume of diamond grains
to certain high-pressure/high-temperature (HPHT) conditions in the
presence of a sintering aid or binder. Conventionally, the
sintering aid or binder is provided in the form of a solvent metal
catalyst material, such as one or more element from Group VIII of
the Periodic table. The solvent metal catalyst may be added and
mixed with the diamond grains prior to HPHT processing and/or may
be provided during the HPHT process by infiltration from a
substrate comprising the solvent metal catalyst as one of its
constituent materials.
[0007] A conventional PDC cutter may be formed by placing a
cemented carbide substrate into a HPHT container. A mixture of
diamond grains or diamond grains and catalyst binder is placed atop
the substrate in the container and the container is loaded into a
HPHT device that is configured and operated to subject the
container and its contents to a desired HPHT condition. In doing
so, the solvent metal catalyst material in the substrate melts and
infiltrates into the diamond grain volume to promote
intercrystalline bonding therebetween, thereby forming a sintered
diamond body that is bonded to the substrate. The substrate often
comprises a metal-carbide composite material, such as tungsten
carbide. The deposited diamond body may be provided in the form of
and referred to as a "diamond layer", a "diamond table", or an
"abrasive layer." The solvent metal catalyst material in such
conventional PCD is disposed within interstitial regions that exist
between bonded-together diamond crystals. Conventional PCD includes
85 to 95 percent by volume diamond and a balance binder or catalyst
materials.
[0008] As noted above, PDCs are useful for forming cutting
elements, e.g., PDC cutters, used in applications calling for high
degrees of wear and abrasion resistance, such as drilling
subterranean formations. A significant factor in determining the
longevity of PDC cutters is the generation of heat at the cutter
contact point, specifically at the exposed part of the PCD layer
caused by friction between the PCD and the work material being
engaged. This heat causes thermal damage to the PCD in the form of
cracks (due to differences in thermal expansion coefficients),
which lead to spalling of the PCD body or layer, and/or
delamination between the PCD body and substrate, and/or back
conversion of the diamond to graphite in the PCD body causing rapid
abrasive wear. As a result, the thermal operating range of
conventional PDC cutters is typically less than about 750.degree.
C.
[0009] Conventional PCD is stable at temperatures of up to about
700 to 750.degree. C., after which observed increases in
temperature may result in permanent damage to and structural
failure of PCD. This deterioration in PCD is due to the significant
difference in the coefficient of thermal expansion of the binder or
catalyst material, e.g., as compared to diamond. Upon heating of
PCD during use, the catalyst material and the diamond lattice
expands at different rates, which may cause cracks to form in the
diamond lattice structure and result in deterioration of the PCD.
Damage is also due to the catalyzed formation of graphite at
diamond-diamond necks at high temperatures, leading to loss of
microstructural integrity and strength loss.
[0010] Attempts to address these issues have involved removing the
catalyst or binder material from the diamond body after the PCD has
been formed. Strong acid solutions have been used in some instances
to remove or "leach" the catalyst or binder material from the
diamond lattice structure. This approach has been practiced on the
entire diamond body, where the catalyst material has been removed
form the entire diamond body, or has been practiced on only part of
or a region of the diamond body. Examples of "leaching" processes
may be found, for example, in U.S. Pat. Nos. 4,288,248 and
4,104,344. In these instances, an acid solution, typically nitric
acid or combinations of several acids (such as nitric and
hydrofluoric acid) may be used to treat the diamond table, removing
at least a portion of the catalyst or binder material PCD. By
leaching out the catalyst material from the entire diamond body,
thermally stable polycrystalline (TSP) diamond is formed. In
certain embodiments, only a select portion or region of a diamond
composite is leached, in order to gain thermal stability without
losing impact resistance. As used herein, the term TSP is
understood to include both of the above (i.e., partially and
completely leached) compounds.
[0011] While conventional leaching processes with
nitric/hydrofluoric acid mixtures are somewhat successful in
removing the catalyst or binder material from the PCD, they tend to
be time consuming, e.g., using mixtures of acids may easily take
many weeks in order to leach out the catalyst or binder material.
Further, the use and handling of acid solutions such as
hydrofluoric acid presents potential safety, health, and
environmental dangers. Still further, the use of such conventional
leaching techniques presents certain limitations in the degree of
catalyst and binder material, as well as other unwanted non-diamond
materials, that may be removed from the PCD.
[0012] It is, therefore, desired that a technique and or materials
be developed for the purpose of enhancing the process of removing
unwanted catalyst or binder materials from the PCD. If is further
desired that such technique and/or materials be engineered to also
remove other unwanted non-diamond materials present in the PCD that
may either contribute to undesired PCD performance properties
and/or that may operate to impair subsequent processing of the PCD
body after leaching.
SUMMARY OF INVENTION
[0013] In one aspect, embodiments disclosed herein relate to a
method for making a thermally stable cutting element that includes
forming an acid mixture containing two different acid species by
combining an acid solution and at least one acid-forming compound,
wherein the at least one acid-forming compound is provided in solid
form, and wherein the at least one acid-forming compound produces
an acid that is different than the acid solution; treating at least
a portion of a sintered diamond body by placing the sintered
diamond body in the acid mixture, wherein the sintered diamond body
comprises: a matrix phase of bonded-together diamond grains; a
plurality of interstitial regions dispersed within the matrix
phase; and a metal material disposed within a plurality of the
interstitial regions; wherein the treating removes the metal
material from at least a portion of the plurality of interstitial
regions; and removing the sintered diamond body from the acid
mixture after a predetermined length of time, wherein at least a
portion of the diamond body removed from the acid mixture is
substantially free of the metal material and is a thermally stable
diamond body.
[0014] In another aspect, embodiments disclosed herein relate to a
method of making a thermally stable diamond construction that
includes treating a sintered diamond body, wherein the sintered
diamond body comprises: a matrix phase of bonded together diamond
grains; a plurality of interstitial regions dispersed within the
matrix; and a catalyst material within the plurality of
interstitial regions; wherein the treating step comprises: placing
the sintered diamond body in a leaching agent; and elevating the
temperature of the sintered diamond body and the leaching agent to
a desired leaching temperature for a predetermined amount of time;
wherein after the predetermined amount of time the sintered diamond
body is a thermally stable diamond body and substantially free of
the catalyst material; reducing the temperature of the thermally
stable diamond body and leaching agent in a controlled manner after
the predetermined amount of time has passed; and cleaning the
thermally stable diamond body to remove any residual non-diamond
materials remaining therein.
[0015] In yet another aspect, embodiments disclosed herein relate
to a method for making a thermally stable cutting element that
includes treating at least a portion of a sintered diamond body
comprising: placing a sintered diamond body in an acid mixture of
HNO.sub.3 at a concentration of 2.5 to 10 mol/liter and HF at a
concentration of 4 to 10 mol/liter, the sintered diamond body
having: a matrix phase of bonded-together diamond grains; a
plurality of interstitial regions dispersed within the matrix
phase; and a metal material disposed within a plurality of the
interstitial regions; wherein the treating removes metal material
from at least a portion of the plurality of interstitial regions;
and removing the sintered diamond body from the acid mixture after
a predetermined length of time, wherein the at least a portion of
the diamond body removed from the acid mixture is substantially
free of the metal material and is a thermally stable diamond
body.
[0016] In yet another aspect, embodiments disclosed herein relate
to a polycrystalline diamond construction that includes a diamond
body having a material microstructure comprising a matrix phase of
bonded together diamond crystals formed at high pressure/high
temperature conditions in the presence of a catalyst material, the
diamond body having a surface and including interstitial regions
disposed between the diamond crystals, wherein the interstitial
regions within the diamond body are substantially free of the
catalyst material, wherein the diamond body comprises: a first
region comprising an infiltrant material disposed within the
interstitial regions and that is positioned remote from the
surface; and a second region comprising interstitial regions that
are substantially free of the infiltrant material and that extends
into the body a depth from the surface, wherein the depth is
substantially uniform within the thermally stable diamond body at
the center of the thermally stable diamond body compared to a
position along a circumferential edge of the thermally stable
diamond body.
[0017] Other aspects and advantages of the invention will be
apparent from the following description and the appended
claims.
BRIEF DESCRIPTION OF DRAWINGS
[0018] FIGS. 1A and 1B are perspective view of example PCD
constructions.
[0019] FIG. 2 is a cross-sectional side view of an example of a
pressure vessel that may be used in accordance with a disclosed
embodiment.
[0020] FIG. 3 is a schematic view of an ultrasonic emitter that may
be used in accordance with a disclosed embodiment.
[0021] FIGS. 4A to 4E are perspective views of different example
PCD constructions prepared according to principles of the present
disclosure.
[0022] FIG. 5 is a cross sectional view of a prior art PCD
construction.
[0023] FIG. 6 is a cross sectional view of a PCD construction that
has been treated using a multi-step removal process according to
principles of the present disclosure.
[0024] FIG. 7 is a side view of an example PCD construction
provided in the form of a cutting insert.
[0025] FIG. 8 is a perspective view of a rotary cone drill bit
comprising a number of the cutting elements illustrated in FIG.
5.
[0026] FIG. 9 is a perspective view of a percussion drill bit
comprising a number of the cutting elements illustrated in FIG.
5.
[0027] FIG. 10 is a perspective view of another example PCD
construction provided in the form of a cutting element or shear
cutter.
[0028] FIG. 11 is a perspective view of a fixed blade drill bit
comprising a number of the cutting elements illustrated in FIG.
8.
DETAILED DESCRIPTION
[0029] In one aspect, embodiments disclosed herein relate to PCD
constructions and cutting elements that have been rendered
thermally stable using methods and materials that are specifically
engineered for both reducing the amount of time required to leach a
PCD body or cutter, and for removing other non-diamond materials
from the PCD body wherein such removal may operate to further
improve the thermal stability of the leached PCD body and/or may
operate to facilitate subsequent processing of the leached PCD
body.
[0030] More specifically, embodiments disclosed herein involve
accelerating techniques and/or the use of new materials used in
conjunction with the treatment process of removing undesired
materials (such as a catalyst, binder, and other non-diamond
materials) used to form PCD or that are created during the process
of removing the catalyst or binder material. The accelerating
techniques that may be used in conjunction with leaching processing
include elevated pressures, elevated temperatures, and/or
ultrasonic energy, and/or controlled processing conditions and/or
specifically sequenced process steps.
[0031] PCD bodies may be formed in a conventional manner, such as
by HPHT sintering of diamond grains in the presence of a suitable
catalyst or binder material as described above to achieve
intercrystalline bonding between the diamond grains or crystals.
"Sintering" typically involves an HPHT process, examples of which
may be found in U.S. Pat. Nos. 4,694,918; 5,370,195; and 4,525,178,
each of which are hereby incorporated by reference. Briefly, to
form a sintered PCD body an unsintered mass or volume of diamond
grains is placed within a metal enclosure of a reaction cell of a
HPHT apparatus. A suitable HPHT apparatus for this process is
described in U.S. Pat. Nos. 2,947,611; 2,941,241; 2,941,248;
3,609,818; 3,767,371; 4,289,503; 4,673,414; and 4,954,139, each of
which are incorporated herein by reference. A metal solvent
catalyst material, such as cobalt or other Group VIII material may
be included with the unsintered mass of crystalline particles to
promote intercrystalline diamond-to-diamond bonding. The catalyst
material may be provided in the form of powder and mixed with the
diamond grains, or may be infiltrated into the diamond grains
during HPHT sintering. Typical HPHT processing is carried out at
elevated pressures of about 55-60 kbar, and at an elevated
temperature of about 1400.degree. C. Those of ordinary skill will
appreciate that a variety of temperatures and pressures may be
used, and the scope of the present invention is not limited to
specifically referenced temperatures and pressures.
[0032] Diamond grains useful for forming a polycrystalline diamond
body may include any type of diamond particle, including natural or
synthetic diamond powders having a wide range of grain sizes. For
example, such diamond powders may have an average grain size in the
range from submicrometer in size to 100 micrometers, and from 1 to
80 micrometers in other embodiments. Further, one skilled in the
art would appreciate that the diamond powder may include grains
having a mono- or multi-modal distribution.
[0033] The diamond powder may be combined with a desired catalyst
material, and the reaction cell is then placed under processing
conditions sufficient to cause the intercrystalline bonding between
the diamond particles. It should be noted that if too much
additional non-diamond material is present in the powdered mass of
crystalline particles, appreciable intercrystalline bonding is
prevented during the sintering process. Such a sintered material
where appreciable intercrystalline bonding has not occurred is not
within the definition of PCD. Following such formation of
intercrystalline bonding, a PCD body may be formed that has, in one
embodiment, at least about 80 percent by volume diamond, with the
remaining balance of the interstitial regions between the diamond
grains occupied by the catalyst material. In other embodiments, the
PCD body may comprise at least 85 percent by volume diamond, and in
another embodiment at least 90 percent by volume diamond. However,
one skilled in the art would appreciate that other diamond
densities may be used in alternative embodiments. Thus, PCD bodies
being treated or leached in accordance with the present disclosure
include what is frequently referred to in the art as "high diamond
density" PCD.
[0034] The PCD body formed during the HPHT process may or may not
include a substrate attached thereto. For example, the diamond
volume may be placed next to a suitable substrate material that
comprises a catalyst or binder material that will melt and
infiltrate into the diamond volume during HPHT processing. The
substrate may be provided in a powder, green, or sintered state,
and may be selected from those substrates conventionally used to
form PCD, that include carbides, nitrides, carbonitrides, ceramics,
metallic materials, cermet materials, and combinations thereof. It
is to be understood that PCD bodies used herein may or may not be
formed using a substrate.
[0035] In an example embodiment, the polycrystalline diamond body
is formed using solvent catalyst material provided as an infiltrant
from a substrate, for example, a WC--Co substrate, during the HPHT
process. In such embodiment, it may be desirable to remove the
resulting PCD body from the substrate prior to leaching to enable
the agents to have unimpaired access to all surfaces of the PCD
body.
[0036] Further, one skilled in the art would appreciate that the
same techniques used with PCD may be applied to polycrystalline
cubic boron nitride (PCBN). Similar to PCD, PCBN may be formed by
sintering boron nitride particles (typically CBN) via a HPHT
process, similar to those for PCD, to sinter "green" or unsintered
grains or particles to create intercrystalline bonding between the
particles. CBN refers to an internal crystal structure of boron
atoms and nitrogen atoms in which the equivalent lattice points are
at the corner of each cell. Boron nitride particles typically have
a diameter of approximately one micron and appear as a white
powder. Boron nitride, when initially formed, has a generally
graphite-like, hexagonal plate structure. When compressed at high
pressures in presence of a suitable solvent catalyst, CBN particles
will be formed with a hardness second only to diamond, and a
stability in air at temperatures of up to 1400.degree. C.
[0037] According to one embodiment of the present disclosure, PCBN
may include a content of boron nitride of at least 50% by volume;
at least 70% by volume in another embodiment; at least 85% by
volume in yet another embodiment. In another embodiment, the cubic
boron nitride content may range from 50 to 80 percent by volume,
and from 80 to 99.9 percent by volume in yet another embodiment.
The residual content of the polycrystalline cubic boron nitride
composite may include at least one of Al, Si, and mixtures thereof,
carbides, nitrides, carbonitrides and borides of Group IVa, Va, and
VIa transition metals of the periodic table. Mixtures and solid
solutions of Al, Si, carbides, nitrides, carbonitrides and borides
of Group IVa, Va, and VIa transition metals of the periodic table
may also be included.
[0038] FIGS. 1A and 1B illustrate different PCD constructions that
may be subjected to the leaching techniques and treatments
disclosed herein. FIG. 1A illustrates a PCD construction 10
comprising a generally cylindrical diamond body 12. The diamond
body has a material microstructure as noted above, comprising a
first matrix phase of bonded-together diamond crystals with a
second phase comprising a plurality or interstitial regions
dispersed within the first matrix phase. The catalyst or binder
material used for forming the PCD body forms the second phase of
the body and is disposed within the interstitial regions. FIG. 1B
illustrates a PCD construction 14 similar to that of FIG. 1A,
except that the diamond body 12 is attached to a substrate 16. In
an example embodiment, the substrate 16 is attached to the diamond
body 12 during the HPHT process when the substrate is provided and
present during the HPHT process as the source of the catalyst or
binder material.
[0039] In various embodiments, a formed PCD body having a catalyst
material in the interstitial spaces between bonded diamond grains
is subjected to a leaching process in conjunction with at least one
accelerating technique, whereby the catalyst material is removed
from the PCD body. As used herein, the term "removed" refers to the
reduced presence of the catalyst material in the PCD body that was
used to initially sinter the PCD body, and is understood to mean
that a substantial portion of the catalyst material no longer
resides in the PCD body. However, one skilled in the art would
appreciate that trace amounts of the catalyst material may still
remain in the microstructure of the PCD body within the
interstitial regions and/or adhered to the surface of the diamond
grains.
[0040] The quantity of the catalyst material remaining in the PCD
material microstructure after the PCD body has been subjected to a
leaching treatment may vary, for example, on factors such as the
composition of the PCD body, e.g., the diamond volume content
and/or the diamond grain size, and the treatment conditions, e.g.,
the leaching agents that are used and/or the treatment time.
Further, one skilled in the art would appreciate that it may be
desired in certain applications to allow a small amount of the
catalyst material to stay in the PCD body. In a particular
embodiment, the PCD body may include up to about 1 to 2 percent by
weight of the catalyst material. However, one skilled in the art
would appreciate that the amount of residual catalyst present in a
leached PCD body may depend on such factors as the diamond density
of the material, the diamond grain size, and/or the diamond body
thickness. Residual solvent catalysts are in many instances trapped
as inclusions within the microstructure, within regions of neck
growth between diamond crystals
[0041] As described above, a conventional leaching process involves
the exposure of an object to be leached with a leaching agent, such
as described in U.S. Pat. No. 4,224,380, which is herein
incorporated by reference in its entirety. In select embodiments,
the leaching agent may be a weak acid, a strong acid, or mixtures
of different acids. In other embodiments, the leaching agent may be
a caustic material such as NaOH or KOH. Suitable acids may include,
for example, nitric acid, hydrofluoric acid, hydrochloric acid,
sulfuric acid, phosphoric acid, or perchloric acid, or combinations
of these acids. In addition, caustic materials, such as sodium
hydroxide and potassium hydroxide, have been used by the carbide
industry to digest metallic elements from carbide composites. In
addition, other acidic and basic leaching agents may be used as
desired. Those having ordinary skill in the art will appreciate
that the molarity of the leaching agent may be adjusted depending
on the time desired to leach, concerns about hazards, handling
issues, and the like.
[0042] While conventional leaching techniques may require many
weeks for sufficient removal of catalyst material from a PCD body
to occur, in accordance with the present disclosure, accelerating
techniques may be applied to the leaching process to decrease the
amount of treatment time required to reach the same or an improved
level of catalyst removal.
[0043] In an example embodiment, the results obtained from leaching
a PCD body may be improved upon by increasing the strength of the
leaching agent beyond that possible using conventional leaching
agents, e.g., provided in the form of acid solutions. As noted
above, the conventional leaching agents that are used are acids, or
a combination of two or more acids, such as nitric acid (HNO.sub.3)
and hydrofluoric acid (HF). An issue that exists with using such
leaching agent formed from the combination of HNO.sub.3 and HF is
the dilution effect that is known to result from the combination. A
typical HNO.sub.3 solution comprises about 70 percent acid and the
remainder water. A typical HF solution comprises only about 47
percent acid, and the remainder water, due to the unique handling
and safety issues inherent with HF. Thus, upon combining these acid
solutions the water content of the HF acts to effectively dilute
the active molecular species of the HNO.sub.3, thereby reducing the
oxidation potential and leaching capability of the leaching
mixture.
[0044] Thus, in an example embodiment, the strength and leaching
effectiveness of the leaching agent may be improved upon by
eliminating this dilution effect. This is done by, instead of using
a first acid solution and combining it with a second acid solution,
using a solid chemical compound capable of forming a desired acid
and combining this with an acid solution. Alternatively, a leaching
agent may be formed by using two solid chemical compounds and then
combining them with a desired amount of water to form the desired
mixture of acid species. The benefit of providing at least one of
the acid constituents in solid form is that you are able to reduce,
control or eliminate the dilution effect that would otherwise exist
if it was provided in the form of a solution, thereby producing a
more effective or stronger leaching mixture.
[0045] In an example embodiment, the solid chemical compound may be
provided in the form of a salt that is capable of forming a desired
acid when combined with an acid solution or with water. In an
example embodiment, it is desired that the salt be a fluoride salt,
and more particularly one that is capable of forming HF, as HF is
useful for facilitating the removal of tungsten found within the
PCD body. Thus, a further advantage of providing the acid forming
ingredient in the form of a solid or salt is that it avoids or
eliminates the safety, health, and/or environmental precautions
that must otherwise be taken in raw material storage if such
ingredient was provided in the form of an acid solution.
[0046] In an example embodiment, the fluoride salt is combined with
a HNO.sub.3 solution to form a leaching mixture comprising
HNO.sub.3 and HF. A preferred fluoride salt useful for this purpose
is ammonium bifluoride (NH.sub.4F--HF). NH.sub.4F--HF is a solid at
room temperature and is soluble in HNO.sub.3. The advantage of
using such a salt is that it may be added to an oxidizing acid
without dilution to thereby provide an improved degree of metal
removal from the PCD body. Another potential advantage of using
ammonium bifluoride, and obtaining ammonium bifluoride in solution,
is the potential of the resulting ammonium ion to form complexes
with the reaction product (cobalt nitrate) produced during the
removal or leaching process. The formation of such complexes may be
desirable because they may operate to increase the solubility of
the cobalt nitrate in a strong acid environment, thereby allowing
for enhanced reaction kinetics and possibly a higher number of
parts that may be treated in a reaction chamber. While the use of a
particular salt with a particular acid solution is described
herein, it is to be understood that the example provided is
representative of one combination of chemical species that may be
used, and that combinations of other types of salts or solids from
chemical compounds capable of forming acids when combined with an
acid solution, water, or other water-containing solutions may be
used to form improved leaching agents according to principles
disclosed herein.
[0047] In another embodiment, it may be desirable to use a diluted
leaching agent. For example, a solution which has been found to
work satisfactorily in leaching PCD material is made from reagent
grade acids, diluted with water. Thus, while reagent grade
HNO.sub.3 is 15.9 mol/liter, and reagent grade HF is 28.9 mol/liter
and a 1:1 mixture of reagent grade HNO.sub.3 and reagent grade HF
produces 8.0 mol/liter HNO.sub.3 and 14.5 mol/liter HF, a preferred
mixture may comprise a concentration of approximately 5.3 mol/liter
HNO.sub.3 and approximately 9.6 mol/liter HF (ratio of 1:1:1 by
volume of HNO.sub.3--15.9 mol/liter: HF--28.9 mol/liter: and
water). This was found to remove solvent catalyst material faster
than a solution with a concentration of 8.0 mol/liter HNO.sub.3 and
14.5 mol/liter HF (1:1 ratio by volume of HNO.sub.3--15.9
mol/liter: HF--28.9 mol/liter). This gives indications that
mobility and diffusion of the reacted species (in this case cobalt
reacting to form cobalt nitrate) may be, in some cases, a
rate-limiting step, and that reaction rates may be improved by
decreasing the concentration of the acids. In other embodiments,
more or less amounts of water may be used, and would thus effect
the concentration of the acid components accordingly. In another
particular embodiment, a fluoride salt such as NH.sub.4F--HF may be
combined with HNO.sub.3 (70 percent solution--15.9 M (mol/liter)),
and may optionally be diluted with water, as described above, to
provide greater mobility and diffusion of the reacted species. In
an example embodiment, the resulting leaching mixture comprises
concentrations equivalent to the standard solution disclosed above.
In another example, the concentration of the HF is in the range of
from about 2.5 --10 mol/liter, and from 2.5 to 7 mol/liter in
another embodiment, and the concentration of the HNO.sub.3 is in
the range of from about 4.0 --10 mol/liter. Use of the
above-described leaching mixture may be used alone or in
combination with any other of the techniques or methods described
herein to provide accelerated leaching.
[0048] Accelerated leaching of a PCD body may be achieved by
subjecting the leaching environment and thus the PCD body to
different pressure conditions. This may involve subjecting the PCD
body during the leaching process to pressures that are greater than
atmospheric pressure, i.e., wherein the PCD body is subjected to an
elevated pressure that facilitates the leaching process. This may
also involve subjecting the PCD body during the leaching process to
differential pressures, e.g., where a pressure at one location or
surface of the PCD body is different than the pressure at another
location or surface of the PCD body and that facilitates the
leaching process.
[0049] As used herein, the term "elevated pressure" refers to
pressures greater than atmospheric pressure. Suitable pressure
levels may include elevated pressure levels ranging from about 5 to
345 bar, and ranging from about 5 to 100 bar in another embodiment.
However, one skilled in the art would appreciate that the
particular pressure may be dependent, for example, on the
particular equipment used, the temperature selected, amount (and
type) of leaching agent present, and total system volume.
[0050] Elevated pressure conditions may be obtained, for example,
by conducting a leaching process in a pressure vessel. Suitable
pressure vessels include any type of closed environment or
container in which a leaching process may be performed with
application of elevated pressure levels. One of ordinary skill in
the art would appreciate that depending on the various combinations
of accelerating techniques, the leaching may be performed for
example, in an open container placed within a closed container,
where the closed container is pressurized, or in a closed
pressurized container (optionally within a second closed
container). For example, one skilled in the art would appreciate
that when using a closed container, the elevated pressures may be
derived from (and thus dependent on) vapor pressures contained
within the container at elevated temperatures. Thus, the extent of
the pressure elevation may be a function of the temperature, amount
of leaching agent present, and total system volume.
[0051] Differential pressures may be exerted onto the PCD body for
example through the use of a fixture or an assembly that is
configured to engage the PCD body in such a manner so as to exert a
differential pressure onto or along one or more surfaces of the PCD
body. When used in conjunction with a desired leaching agent, the
presence of such differential pressure may operate to facilitate
migration of the leaching agent through the desired region of the
PCD body.
[0052] Accelerated leaching may also be achieved by using elevated
temperatures alone or in combination with any other of the
techniques, methods or leaching agents described herein. As used
herein, the term "elevated temperature" refers to a temperature
that is close to or above the room pressure boiling point of the
liquid or agent in which the PCD body to be leached is submersed or
subjected to. Suitable temperature levels may range from the
boiling point to three times the boiling point of the leaching
agent solution at room pressure, for example, from about 90 to
350.degree. C. in one embodiment and from about 175 to 225.degree.
C. in another embodiment. Further, one skilled in the art would
appreciate that the selection of an elevated temperature may be
dependent, for example, on the type of leaching agent selected, so
that, for example, the boiling point may be reached while still
avoiding boiling of the leaching agent. Further, the source of the
elevated temperatures is not a limitation of the scope of the
present disclosure. Thus, one skilled in the art would appreciate
that such heating may be provided, for example, by conventional
resistance-based heating such as conventional oven or furnace
heating or by volumetric-based heating such as microwave
heating.
[0053] In various embodiments, a PCD object to be leached may be
disposed in a pressure vessel with leaching agent(s), and the
pressure vessel and its contents be exposed to elevated
temperatures. Such vessels may include those known in the art as
acid digestion bombs. Vessels suitable for use in embodiments of
the present disclosure include those described, for example, in
U.S. Pat. Nos. 5,369,034, 4,933,529, 4,882,128, and 6,744,024,
which are all herein incorporated by reference in their entirety.
Alternative types of vessels may include autoclaves. Various
vessels are commercially available, for example, from Parr
Instrument Company (Moline, Ill.) and Berghof/America (Coral
Springs, Fla.).
[0054] FIG. 2 illustrates an example a pressure vessel constructed
according to one embodiment of the present disclosure. The pressure
vessel 20 includes a container body 22 (which may be comprised of
two parts, body 24 and liner 26) having an opening 28 at the top
end thereof. The container body 22 is closed by closure 30, which
includes closure portion 32 and holding collar 34 that threadably
engages with body 24. Closure portion 32 includes sealing section
36 and boss 38. Body 24 is constructed from a material having
sufficient strength (tensile strength) and other physical
characteristics, including dimensions, so that it may withstand
internal pressures in ranges likely to be encountered in various
heating and digestion operations in which the container may be
employed. Such pressure ranges may range, for example, up to 5000
psi. However, a venting means 40 is provided for the container 20
so that if pressures generated within the container 20 exceed the
limits for which the container is designed, the generated pressures
will vent from the container to the external environment. Such
venting means 40 may include a rupturable diaphragm (not shown
separately), which under normal pressures seals the interior of the
container 20 from passageways 42 leading to the exterior
environment
[0055] Most suitable synthetic organic polymeric plastic materials
for such body 22 are any of the polyether imides, such as those
sold under the ULTEM.RTM. trademark by General Electric
Corporation, but others of the "engineering plastics," fiber
reinforced plastics, such as glass fiber reinforced polyesters or
polyethers, or other polymers known to be of good strengths and/or
transmissive of microwaves (when microwave heating is used) may
also be used. Further, one skilled in the art would appreciate that
any configuration of a sealed, but ventable container may be used
for forming a pressure vessel, such as the one shown in FIG. 2, to
leach PCD bodies in accordance with the present disclosure.
[0056] Inside the body 24, as a part of the container body 22, is
the liner 26, which is essentially or completely transparent to
microwave radiation and is also resistant to damage from chemical
attacks by strong chemicals, such as strong acids, often employed
as leaching agents. Materials of construction suitable for
manufacture of such liners, such as fluorinated alkylenes or
perfluorocarbons, e.g., polytetrafluoroethylene and other polymers
of this type sold under the tradename TEFLON.RTM. or other
tradenames may be employed, with the preferred materials being
TEFLON PFA and TEFLON FEP, but other chemically resistant plastics,
such as chloroprene, silicone, ethylene, propylene and other
suitable polymers, under the proper circumstances, may also be
used. However, at elevated temperature such polymers and others
which are satisfactorily resistant to chemical reactions with the
materials being heated or by the digestion mixes are not usually
sufficiently strong to resist pressures that may be developed in
the container and therefore such are normally employed only as
liners within strengthening body members which are made of other,
stronger materials.
[0057] Further, one skilled in the art would appreciate that, in
alternative embodiments, the liner and body of the vessel may be
made of a single material, without the need for a separate liner.
For example, when using microwave heating, if microwave and other
radiant energy-transmissive materials that are available or may
become available are satisfactorily resistant to chemical damage
from the contained materials and are strong enough to resist
pressures developed during the heatings of such materials in the
closed container, the container body means may be made of one piece
of one material without the need for a separate liner.
[0058] While the above description references microwave transparent
materials for use in the pressure vessel, one of ordinary skill in
the art would appreciate that should a pressure vessel be used
without microwave energy, the material requirements for liner
and/or body container may vary accordingly. Further, while the
above description has described one particular type of pressure
vessel in obtaining elevated pressures, no limitation is intended
on the scope of the present invention. One of ordinary skill in the
art would recognize that the elevated pressure may be achieved
directly or indirectly. That is, it is specifically within the
scope of the present invention that the elevated pressure may
result as a by-product of one or more other applied conditions.
[0059] Accelerated leaching may also be achieved through the use of
vibration or ultrasonic energy alone or in combination with any of
the other techniques, methods and/or materials described herein. In
an example embodiment, the application of pressure may be coupled
with the application of ultrasonic energy to accelerate the
leaching process. Ultrasonic energy is mechanical, vibratory energy
in the form of sound that operates at frequencies beyond audible
sound (18,000 cycles per second and greater). An ultrasonic stack
is generally formed of a converter or piezoelectric transducer, an
optional booster and a sonotrode (also called a horn).
[0060] In a typical arrangement, the piezoelectric transducer is
formed of a piezoelectric crystal connected to an electrical energy
source, such as a battery, through a wire. Piezoelectric crystals
may be used to convert electrical energy into mechanical energy or
be used to convert mechanical energy into electrical energy. For
example, in one embodiment, electrical charges may be sent from the
electrical energy source through the wire to the piezoelectric
crystal.
[0061] The electrical charges may then be converted by the
piezoelectric crystal into acoustic energy (e.g. mechanical energy)
such that an acoustic signal may be produced. The piezoelectric
crystal may be comprised of many materials, ceramics and quartz
crystals being most common. Specifically, in one embodiment, the
piezoelectric crystal may be comprised of Kezite K600, available
from Keramos of Piezo Technologies, which is a modified lead
zirconate titanate piezoelectric ceramic.
[0062] The material of the piezoelectric crystal may then be
modified in various ways to produce different wave modes of the
acoustic signal. For example, the overall shape of the
piezoelectric crystal determines a sound field of the acoustic
signal produced from the piezoelectric crystal.
[0063] Further, the thickness of the piezoelectric crystal may
determine the frequency of the acoustic energy produced by the
piezoelectric crystal. Specifically, the piezoelectric crystal
produces a wavelength about twice its thickness.
[0064] Boosters may be used to modify the amplitude of the
mechanical vibration. A sontotrode, or horn, may be used to apply
the vibration. All three elements of the stack may be specifically
tuned to resonate at the same exact ultrasonic frequency (typically
20, 30, 35 or 40 kHz)
[0065] As noted above, a power supply (also known as an electronic
ultrasonic generator) may be used to deliver a high-power AC signal
with frequency matching the resonance frequency of the
piezoelectric crystal.
[0066] FIG. 3 illustrates a schematic example of an ultrasonic
apparatus 50 for use in disclosed embodiments. Desired
high-frequency electrical energy is delivered, via a power supply
52, to a piezoelectric crystal (shown as converter 54) where the
high-frequency electrical energy is converted to high-frequency
ultrasonic mechanical energy. That energy is then sent to a booster
56, and finally is transferred to a horn 58.
[0067] The effect of applying ultrasonic energy to a leaching
process may have the effect of providing up to an 80 percent
increase in leaching depth after 2 hours, when compared to a
leaching process without ultrasonic energy, and up to a 90 percent
increase in leaching depth after 4 hours, again when compared to a
leaching process without ultrasonic energy. This is for leaching a
PCD body using a leaching agent comprising a 1:1 mixture of HF and
HNO.sub.3 where each is provided in solution form. In a test using
the 1:1:1 ratio of nitric acid, hydrofluoric acid, and water
described earlier it was found that the use of ultrasonic energy in
combination with elevated pressure was able to increase the amount
of solvent catalyst removal by approximately 35%, despite the fact
that the temperature of the pressure vessel equipped with
ultrasonics was maintained at 140.degree. C. and the pressure
vessel without ultrasonics was maintained between 200-210.degree.
C.
[0068] While the use of vibration energy has been disclosed, it is
to be understood that agitation may be used to accelerate the
removal process. For example, such agitation may be caused by
moving the leaching agent relative to the object being leached in a
desired manner. Alternatively, such agitation may be caused by
moving the object being leached relative to the leaching agent. The
agitation movement may have a controlled or random character.
[0069] While particular treatment conditions, processes and/or
materials have been described above for purposes of removing the
catalyst material from a PCD body, it is to be understood that
treatment conditions, processes and/or materials processes other
than those described above may be used alone or in combination with
such afore-described treatment conditions, processes and/or
materials. These include but are not limited to electrical
discharge or other electrical or galvanic processes, e.g.,
electrolytic process and the like, and/or gaseous phase removal or
reduction. Gaseous phase removal involves subjecting the PCD body
to a halogen gas or gaseous environment containing a source of
halide ions at a desired elevated temperature. The gaseous phase
material contacts and reacts with the catalyst material within the
PCD body at elevated temperature to react with and/or volatize the
catalyst material and other metals or metal compounds that may be
present to thereby facilitate their removal from the PCD body.
[0070] The gaseous compound may comprise a halogen gas, an inert
gas, an acid gas, and/or a mixture thereof. In an example
embodiment, the gaseous environment comprises some amount of
chlorine, and may also include some amount of another gas such as
argon gas or the like. Hydrogen may also be used and the source may
be hydrogen chloride gas, or an ammonium halide salt, which in the
case of ammonium chloride decomposes at temperature to form
nitrogen gas, hydrogen gas and chlorine gas, wherein the hydrogen
gas and chlorine gas may react in situ to form hydrogen chlorine
gas.
[0071] Further, as mentioned above, while the above discussion has
applied to PCD cutting elements, those having ordinary skill in the
art will appreciate that these techniques may be more generally
applied to any material that requires the leaching of a material
(such as a catalyst or binder agent) from its surrounding matrix.
In particular, embodiments disclosed herein apply to
"free-standing" PCD bodies, such as, PCD wafers having no carbide
substrate. Such PCD bodies may have been formed "free-standing" or
may have been detached from a carbide substrate prior to leaching.
In a particular embodiment, the PCD bodies may be at least 1 mm
thick, and at least 1.5 or 2 mm thick in alternate embodiments.
However, in other particular embodiments, where leaching of the
entire PCD is not desired, the PCD bodies may be attached to a
carbide substrate.
[0072] Accelerated leaching may be achieved during a single step
using one or more of the techniques, processes and/or materials
disclosed herein, or may be achieved by using more than one step.
In a single step process, the accelerated leaching of the PCD body
is achieved by simply subjecting the PCD body to the desired
leaching agent and any additional conditions, e.g., elevated
pressure, pressure differential, elevated temperature, and/or
vibration energy. The product resulting from the process is then
taken and used to form a desired cutting or wear product.
[0073] Alternatively, if a leached PCD body having a greater degree
of purity is desired, a multi-step process may be used. As used
herein, the term "purity" is used to refer the relatively improved
diamond content in the PCD body and the reduced content of any
non-diamond materials. It has been discovered that a higher purity
leached PCD diamond body may be provided through the use of a
multi-step treatment process.
[0074] In an example embodiment, during a first treatment step the
PCD body is exposed to a desired leaching agent or mixture. The
leaching agent or mixture may be one of those described above. In
an example embodiment, the first treatment step is conducted at an
elevated temperature as described above. Additionally, the first
treatment step may be conducted under conditions of both heat and
pressure as described above. During this first treatment step, the
PCD body is subjected to the leaching agent for a desired duration
of time desired to obtain the finally leached PCD diamond body,
i.e., the catalyst material is removed from the entire PCD diamond
body.
[0075] During a conventional single step leaching process, once the
PCD body has been leached, it is rapidly cooled down with a forced
cooling and then taken for subsequent processing and/or forming
into the desired cutting or wear element. It has been discovered
that during this rapid cool down, certain unwanted by-products from
the leaching process, in the form of oxides, are formed. These
oxides are insoluble, and thus remain in the leached PCD or TSP
body and are present during any subsequent processing. The presence
of such insoluble oxides or contaminates within the TSP body may be
undesired as they may impair any subsequent processing of the TSP
body that may involve introducing an infiltrant material therein,
e.g., when used to attached the TSP body to a substrate by
infiltration of an intermediate material or a constituent material
of a substrate therein for the purpose of forming an attachment
bond therebetween. Additionally, the presence of such contaminates
within the TSP body may operate to degrade the diamond bonding
within the body.
[0076] It has been discovered that the formation and presence of
such unwanted oxides in the TSP body may be avoided by carefully
controlling the first treatment process and, more specifically, by
carefully controlling the cooling rate of the TSP body and leaching
agents after the leaching process has been completed. A slow
reduction of the TSP body and leaching agent temperature during the
first treatment step after leaching has been shown to avoid or
reduce the extent that unwanted oxides are formed, and promote the
preferential formation of soluble salt. In a particular embodiment,
cooling rates may be no faster than about 75 degrees/hour, no
faster than about 60 degrees per hour in another embodiment, and no
faster than about 45 degrees in yet another embodiment. These
soluble salt form in the interstitial regions of the TSP body. The
exact types of soluble salts that are formed will depend on the
type of catalyst or binder material that is used, whether the
source of the catalyst material is a substrate, and the types of
leaching agents that are used.
[0077] In an example embodiment where the catalyst material is
cobalt, and tungsten is present in the diamond body, e.g., provided
from a substrate used as a source of the catalyst material, and the
leaching agent includes HNO.sub.3, the salt present in the diamond
PCD body will be nitrite salts of cobalt and tungsten. Again,
unlike the oxides, such salts are soluble and may be removed from
the TSP body during a further or subsequent treatment step.
[0078] In an example embodiment second treatment or "clean up"
step, the TSP body that now includes the soluble salts is placed
into water that is at an elevated temperature, e.g., boiling water.
This treatment may be conducted at atmospheric pressure or at
elevated pressure via use of a pressurized container as described
above. During this second treatment step, the soluble salts are
removed from the TSP body to produce a TSP body having a high level
of purity with little or no contaminate or by-product materials
disposed therein that will interfere with any subsequent
infiltration process, or that will operate to degrade diamond
bonding within the TSP body.
[0079] In a particular embodiment, the cleaning process may involve
multiple rinses and/or involve multiple types of treatments. For
example, following a cool-down from leaching (such as described
above), the thermally stable diamond body having byproducts present
in the interstitial regions may be placed in a bath of water
subjected to ultrasonic energy. The ultrasonic energy may aid the
water (or other solvent) to infiltrate through the pores of the
diamond body. Alternative solvents that may also optionally be used
to clean the TSP body may include alcohols and/or acetone, which
may be used to aid in solubilizing and/or transporting any
by-products that are less compatible in water than these solvents.
Once water (or other solvent) occupies the pore space, the water
provides a medium through which the vibrational waves may travel to
reach the byproducts residing in the pores. The waves create
microscopic gas pockets during periods of positive pressure, which
implode and release a burst of energy during periods of negative
pressure, disrupting weak molecular binding forces in the
by-products, including insoluble oxides such as complex cobalt
and/or tungsten oxides, as well as soluble salts. Thus, the
imploding bubbles and bond disruption occurs wherever the solution
goes. Once the bonds are disrupted (forming smaller pieces of
by-products and/or disrupting bonds between the by-products and the
surrounding diamond network), the solvent may transport the
by-products out of the diamond body.
[0080] Exemplary conditions may include a power of at least 500
watts (and at least 800 watts in a particular embodiment), a
frequency ranging from 5 to 50 kHz (and from 15-35 kHz in a
particular embodiment), and an exposure time of at least one hour
(and at least two hours in a particular embodiment. However, other
conditions are envisioned as also being within the scope of the
present disclosure, depending, for example, on the level of
byproduct formation and desired purity level. For example, the
exposure time may be as low as 15 minutes, and energy levels of
less than 500 watts may be used Further, one skilled in the art
should appreciate after reading the teachings of the present
application that if a lower energy is used, for example, it may be
desirable to vary other conditions to counterbalance the change in
energy.
[0081] Following an ultrasonic treatment, the diamond part may be
transferred to a pressure vessel, such as those described above
that are used in the leaching process, with fresh water. The
pressure vessel (and its contents) may be heated, such as to a
temperature ranging from about 130.degree. F. to 230.degree. F., or
160.degree. F. to 200.degree. F. in a particular embodiment. Such
pressurizations may last at least 4 hours in one embodiment, at
least 6 or 8 hours in another embodiment, or at least 10 hours or
12 hours in yet another embodiment. When the temperature is
elevated, pressure is generated within the pressure vessel. This
increase in pressure may allow for the water to be forced into the
diamond body, and soluble byproducts present in the diamond body be
allowed to diffuse out until an equilibrium is reached. Following
the pressurization, the ultrasonic treatment may be repeated.
Further, additional pressurizations and ultrasonic treatments may
also be repeated. In a particular embodiment, at least two
ultrasonic treatments and at least one pressurization may be
performed. In an even more particular embodiment, at least three
ultrasonic treatments and at least two pressurizations may be
performed. The number of treatments may depend on the amount of
material removed after each stage (which may be determined by
measuring the weight percentage reduction in the diamond body after
each stage) and the expected amount of material to be removed.
While it may be difficult to quantify the amount of material
expected to be contained within a diamond body (and recognizing
that the amount may vary depending, for example, on the cooling
conditions following the leaching step), several optimizing tests
varying time, power, frequency, etc. may be performed for a given
leached sample lot to determine the particular combination of
parameters that may cumulatively result in the greatest relative
reduction in diamond weight. While a preferred embodiment may
provide for alternating ultrasonic treatments and pressurizations,
it is also within the scope of the present disclosure that only
ultrasonic treatments and/or pressurizations may be used, depending
on the level of byproduct formation and desired purity level.
[0082] Shown in Table 1 below are several examples of cleaning
steps that may be carried out in accordance with embodiments of the
present disclosure, and the resulting percent weight reductions in
the diamond body. Each ultrasonic (US) treatment was performed in
water for 3 hours at the indicated energy and at a frequency of 25
kHz. Between two ultrasonic treatments, the diamond body was placed
with water in a pressure vessel, and the temperature was increased
to 180.degree. F. for 12 hours, and then allowed to cool to ambient
temperatures in 5 hours. The diamond body was weighed following
each ultrasonic treatment to calculate the percent weight reduction
in the diamond body due to the removal of byproducts therefrom. In
particular embodiments, the cleaning may result in a cumulative
percent weight reduction of at least 1.5 wt %, or at least 2.5 wt %
or at least 3 or 3.5 wt % in other embodiments. Further cessation
of the cleaning treatments may be based on the amount removed
within each subsequent step. For example, a reduction of less than
0.1 wt % (such as in a 3 hour interval) for a given step may
indicate a sufficient level of cleaning and/or be representative of
diminishing effectiveness of the washing process when undergoing
subsequent wash cycles.
TABLE-US-00001 TABLE 1 Reduction Sample Diamond amount Percent
weight No. Energy Schedule Body (g) (g) reduction 1 400 W Initial
16.718 post 1st US 16.511 0.207 1.24 post 2nd US 16.46 0.051 0.31
post 3rd US 16.418 0.042 0.25 2 1000 W Start 16.802 post 1st US
16.28 0.522 3.11 post 2nd US 16.217 0.063 0.37 post 3rd US 16.203
0.014 0.08 3 400 W Start 16.59 post 1st US 16.379 0.211 1.27 post
2nd US 16.317 0.062 0.37 post 3rd US 16.281 0.036 0.22 post 4th US
16.273 0.008 0.05 4 1000 W Start 16.772 post 1st US 16.272 0.5 2.98
post 2nd US 16.23 0.042 0.25 post 3rd US 16.208 0.022 0.13 post 4th
US 16.188 0.02 0.12
[0083] While a particular technique has been described above for
carrying out the second treatment or "clean up" step, other
techniques or subsequent follow up treatment steps, may be used.
For example, any oxides, additional catalyst material, or
by-product may be removed from the TSP body by conducting an
additional reduction process, such as by electrolysis process or
gaseous halogen phase reduction as noted above.
[0084] By first controlling the first treatment step to
preferentially form soluble salts as leaching by-products rather
than insoluble oxides, and then by performing the second treatment
"clean up" step, the resulting TSP body may have a material
microstructure that does not have clogged or filled interstitial
regions. In certain PCD constructions where a reinfiltration of the
TSP body is desired, the TSP body produced in such manner
facilitates a more thorough and uniform infiltration process. The
uniform infiltration of a material into the TSP body is desired to
facilitate distribution of the extreme pressures applied to the TSP
body, e.g., when such infiltration is conducted during an HPHT
process, to all internal pore surfaces and keeps the TSP body in
the diamond stable range during such infiltration and any
attachment to a substrate. Additionally, removing the contaminates
from the TSP body may create the highest bond strength between the
infiltrant material and the TSP body in both the pore surfaces and
at the interface region.
[0085] Additionally, removing the contaminates from the TSP body
may greatly reduce any unwanted degradation of the
diamond-to-diamond bonds within the TSP body.
[0086] Once the PCD body is leached, the resulting material
microstructure comprises a first matrix phase of the
bonded-together diamond grains and a second phase comprising a
plurality of empty interstitial regions dispersed within the matrix
phase. The resulting TSP body is substantially free of the catalyst
material used to initially form or sinter the diamond body. Thus,
at the end of the leaching process, the interstitial regions are
substantially empty so that the second phase may be described as a
plurality of voids or empty regions dispersed throughout the
diamond-bonded matrix phase.
[0087] Further when such "free-standing" PCD bodies are leached, in
particular embodiments, the leached PCD bodies may be attached (or
reattached) to a substrate, to facilitate attachment to a bit,
cutting tool, or other end use application or device. Such methods
of reattachment may include sintering a leached PCD body with a
substrate in a second HPHT sintering step, such as discussed in
U.S. patent application Ser. No. 12/026,398, filed on Feb. 5, 2008,
which is assigned to the present assignee and which is incorporated
herein by reference in its entirety. Further, as discussed in U.S.
patent application Ser. No. 12/026,398, the interstitial regions
(or at least a portion thereof) previously occupied by the
catalyzing material used to initially form the diamond body that
has been removed by the leaching process may optionally be filled
with a variety of infiltrants or replacement materials using any
number of techniques, including liquid-phase sintering under HPHT
conditions.
[0088] The type of infiltrant or replacement material is not a
limitation on the scope of the present disclosure. Rather any type
of infiltrant or replacement materials may be used, including, for
example, non-refractory metals such as copper or other Group IB
metals or alloys thereof, Group VIII metals such as cobalt, nickel,
and iron, ceramics, silicon, and silicon-containing compounds,
ultra-hard materials such as diamond and cBN, and combinations
thereof. In a particular embodiment, the source of infiltrant or
replacement material may be a substrate that is attached to the
leached PCD body during an HPHT process. Substrates useful in this
regard may include those substrates that are used to form
conventional PCD, including those formed from metals, ceramics,
and/or cermet materials that contain a desired infiltrant, such as
a substrate formed from WC--Co. Further, in specific embodiments,
the substrate may be formed of a cermet such as WC and a binder
material including Group IB metals or alloys thereof such as Cu,
Ag, Au, Cu--W, Cu--Ti, Cu--Nb, or the like.
[0089] In an embodiment where it is preferred that a material such
as cobalt does not infiltrate into the leached PCD during substrate
attachment by HPHT process, it may be desirable to use a substrate
having at least one infiltrant material with a melting temperature
below about 1,200.degree. C., and limiting the HPHT sintering
temperatures accordingly so that such the replacement material
infiltrates into the PCD body without causing any catalyst material
present in the substrate to melt and enter the PCD body.
[0090] Additionally, although a substrate may be attached to the
leached PCD body during the introduction of the replacement
infiltrant material, it is also understood that the substrate may
alternatively be attached to the PCD body after the desired
infiltrant has been introduced into the PCD diamond body. In such
an embodiment, the infiltrant material may be introduced, for
example, by an HPHT process that does not use the substrate
material as an infiltrant source, and the desired substrate may be
attached to the diamond body by a separate HPHT process or by other
method, such as by brazing, welding, or the like.
[0091] Further, one skilled in the art would also appreciate that,
as described in U.S. patent application Ser. No. 12/026,398, an
intermediate material may be attached between the PCD body and a
substrate to facilitate attachment between the substrate and PCD
body and/or that may act as a barrier to minimize, control or
prevent the migration of a particular constituent material within
the substrate into the PCD body. Alternatively, if such constituent
material does migrate or infiltrate into the PCD body during
reattachment, it is within the scope of the present disclosure that
the PCD body filled with the infiltrant material may be
subsequently treated to remove a portion of the infiltrant material
therefrom. Techniques useful for removing the infiltrant material
include chemical treatment such as acid leaching or aqua regia
bath, electrochemical treatment, such an electrolytic process,
liquid metal solubility techniques, liquid metal infiltration
techniques, those techniques, methods and using those materials
described above, or combinations thereof. For example, in a
particular embodiment, the infiltrant material may be removing
using a leaching agent such as the acid mixture of two different
acid species formed by combining an acid solution and at least one
acid-forming compound. Alternatively, the an acid mixture of
HNO.sub.3 at a concentration of 2.5 to 10 mol/liter and HF at a
concentration of 4 to 10 mol/liter may be used to remove the
infiltrant material from a portion of the diamond body.
[0092] FIGS. 4A to 4E illustrate an example PCD construction at
different steps of being processed. FIG. 4A illustrates a PCD
construction 60 comprising a PCD body 62 having a catalyzing or
binder material found in the interstitial regions between the
diamond-bonded grains. In this particular embodiment, the PCD body
was formed using a substrate 64 as a source of the catalyzing
material, which substrate 64 is attached thereto. As illustrated in
FIG. 4B and discussed above, the PCD body 62 may be formed without
the use of a substrate 64, or any substrate may be removed from the
PCD body prior to treatment of the PCD body 62 to remove the
catalyzing material using the techniques, methods, and/or materials
disclosed herein.
[0093] Treating of the PCD body 62 removes at least a substantial
portion of the catalyzing material used to initially form the
diamond body from the interstitial regions, leaving a PCD body or
TSP body 32 as illustrated in FIG. 4C having a plurality of voids
distributed therein. At this stage, the interstitial regions within
the leached PCD body or TSP body are substantially empty. As noted
above, if desired, the so-formed TSP body may be treated to
introduce a desired material into all or part of the empty
interstitial regions. FIG. 4D illustrates the treated PCD body 66
as attached to a substrate 68, e.g., by HPHT sintering or other
technique.
[0094] FIG. 4E illustrates the PCD construction 400 at a further
stage of processing where the reinfiltrated PCD body 410 has been
treated to remove the infiltrant material from a desired depth 414
extending from an outer surface 416 of the PCD body 410.
Accordingly, the resulting PCD body 410 comprises a first region
418 extending from the outer surface to the depth 414 that is
substantially free of the infiltrant material, and a second region
420 extending from the depth 414 to the substrate 412. It is to be
understood that the outer surface 416 may be any surface of the PCD
body that may or may not be a working surface. In an example
embodiment, the infiltrant material may be removed from the outer
surface extending along a top and/or side of the PCD body.
[0095] A feature of using the multi-step catalyst removal process
described above is that it may provide a high-purity treated PCD
body, i.e., one that is substantially free of unwanted oxides
and/or other leaching byproducts. While the absence of these oxides
may operate to facilitate reinfiltration of the PCD body with a
desired infiltrant material, such absence may also facilitate the
subsequent removal or releaching of the infiltrant material from a
desired region of the PCD body. Specifically, the absence of such
oxides provides for greater consistency/uniformity, and reduced
degree of variability, in the infiltrant material removal
depth.
[0096] FIG. 5 illustrates in cross section a prior art PCD
construction 500 comprising a PCD body 502 that has had the
catalyst material removed therefrom by a conventional single-step
leaching process, that was subsequently reinfiltrated by an
infiltrant material and attached to a desired substrate 504.
Further, the PCD body 502 has been treated or leached to remove the
infiltrant material from a desired depth 506, creating a PCD body
first region 508 that is substantially free of the infiltrant
material, and a PCD body second region 510 that includes the
infiltrant material. As illustrated in FIG. 5, the depth of the
infiltrant material removal is not uniform moving from a position
at the center 512 of the body to a position along an edge 514 of
the body adjacent a bevel or chamfer 516, but rather varies greatly
depending on position within the body. This is believed to be a
result of the oxides and other leaching byproducts left in the PCD
body during the initial step of removing the catalyst material
therefrom. FIG. 6 illustrates in cross section a PCD construction
600 comprising a PCD body 602 that has been treated using the
multi-step catalyst removal process described above. The PCD body
602 was further reinfiltrated with a desired infiltrant material
and attached to a desired substrate 604. The PCD body 602 was
treated or leached to remove the infiltrant material from a desired
depth 606, creating a PCD body first region 608 that is
substantially free of the infiltrant material, and a PCD body
second region 610 that includes the infiltrant material. As
illustrated in FIG. 6, the depth of the infiltrant material removal
is substantially uniform within the PCD body moving from a position
at the center 612 of the body to a position along an edge 614 of
the body adjacent a bevel or chamfer 616. Such uniformity may be
quantified by a variation of the depth within the construction
being less than about 5 percent. Following all processing and
treatment steps, the cutting elements of the present disclosure may
have a PCD body having diamond grains with an average grain size of
less than 20 microns, and ranging from about 5 to 15 microns in a
particular embodiment. Such average grain sizes after treatment may
be estimated by using electron backscatter diffraction of
cross-sections of multiple PCD bodies with a scanning electron
microscope, and using a mean linear intercept method.
[0097] Further, while many of the embodiments described herein
involve leaching a PCD wafer so that substantially all of the
catalyst material is removed therefrom, some embodiments may also
relate to partial leaching of a PCD body that may be unattached or
attached to a carbide substrate. Specifically, the leaching agents
described herein may be used to partially leach a PCD body so as to
create a first region extending a given depth from a surface of the
PCD body having the interstitial regions substantially empty of the
catalyst material, and a second region adjacent the first region
having the interstitial regions occupied by the catalyst material.
The resulting leach profile may be similar to that shown in FIG. 6,
with the exception that a catalyst material, and not an infiltrant
material is being removed. Further, following a partial leaching,
whether using the leaching agents described herein or other
leaching agents, it also may be desirable to use the cleaning
processes described herein on such partially leached PCD body.
[0098] Advantageously, embodiments disclosed herein may provide a
reduced treatment time and/or an increased level of diamond purity
as compared to prior art techniques. In addition, some embodiments
may allow the use of weaker acids, which may reduce the likelihood
of injury during the manufacturing process, while some embodiments
may allow the use of stronger acids while at the same time reducing
any health, safety and/or environmental issues associated with the
same. Additionally, some embodiments provide a leached product
having a high level of purity for the purpose of both providing
improved performance properties of thermal stability, and
facilitating any subsequent infiltration processes that may be
used.
[0099] PCD constructions formed as described herein may be used in
a number of different applications, such as tools for mining,
cutting, machining and construction applications, where the
combined properties of thermal stability, wear and abrasion
resistance, and strength and toughness are highly desired. Such PCD
constructions are particularly well suited for forming working,
wear and/or cutting components in machine tools and drill and
mining bits such as roller cone rock bits, percussion or hammer
bits, diamond bits, and shear cutters.
[0100] FIG. 7 illustrates an embodiment of a PCD construction
prepared as disclosed herein provided in the form of an insert 70
used in a wear or cutting application in a roller cone drill bit or
percussion or hammer drill bit. For example, such inserts 70 are
constructed having a substrate portion 72, formed from one or more
of the substrate materials disclosed above, that is attached to a
PCD body 74 that is thermally stable. In this particular
embodiment, the insert comprises a domed working surface 76 that is
thermally stable. The insert may be pressed or machined into the
desired shape or configuration prior to the treatment for rendering
the selected region thermally stable. It is to be understood that
such PCD constructions may be used with inserts having geometries
other than that specifically described above and illustrated in
FIG. 7.
[0101] FIG. 8 illustrates a rotary or roller cone drill bit in the
form of a rock bit 80 comprising a number of the wear or cutting
inserts 82 disclosed above and illustrated in FIG. 7. The rock bit
80 comprises a body 84 having three legs 86 extending therefrom,
and a roller cutter cone 88 mounted on a lower end of each leg. The
inserts 82 are the same as those described above comprising the PCD
construction that is thermally stable, and are provided in the
surfaces of each cutter cone 88 for bearing on a rock formation
being drilled.
[0102] FIG. 9 illustrates the cutting insert described above and
illustrated in FIG. 7 as used with a percussion or hammer bit 90.
The hammer bit generally comprises a hollow steel body 92 having a
threaded pin 94 on an end of the body for assembling the bit onto a
drill string (not shown) for drilling oil wells and the like. A
plurality of the inserts 96 are provided in the surface of a head
98 of the body 92 for bearing on the subterranean formation being
drilled.
[0103] FIG. 10 illustrates a PCD construction prepared as disclosed
herein embodied in the form of a shear cutter 100 used, for
example, with a drag bit or fixed blade bit for drilling
subterranean formations. The PCD shear cutter comprises a PCD body
102 that is sintered or otherwise attached to a cutter substrate
104 as described above. The PCD body includes a working or cutting
surface 106 that is thermally stable. The shear cutter working or
cutting surface may include the upper surface and a beveled surface
defining a circumferential edge of the upper surface. It is to be
understood that PCD constructions may be used with shear cutters
having geometries other than that specifically described above and
illustrated in FIG. 10.
[0104] FIG. 11 illustrates a drag bit 180 comprising a plurality of
the shear cutters 200 described above and illustrated in FIG. 10.
The shear cutters are each attached to blades 202 that extend from
a head 204 of the drag bit for cutting against the subterranean
formation being drilled. Because the PCD shear cutters of this
disclosure include a metallic substrate, they are attached to the
blades by conventional method, such as by brazing or welding.
[0105] Other modifications and variations of PCD constructions and
methods, techniques and/or materials for making the same as
described and illustrated herein will be apparent to those skilled
in the art. Further, it is also intended that PCBN constructions or
any other sintered ultrahard matrial may be used in all of such
embodiments as a diamond-like material. It is, therefore, to be
understood that within the scope of the appended claims, this
invention may be practiced otherwise than as specifically
described.
[0106] While the invention has been described with respect to a
limited number of embodiments, those skilled in the art, having
benefit of this disclosure, will appreciate that other embodiments
can be devised which do not depart from the scope of the invention
as disclosed herein. Accordingly, the scope of the invention should
be limited only by the attached claims.
* * * * *