WO2012146626A2 - Constructions super-dures et leurs procédés de réalisation - Google Patents
Constructions super-dures et leurs procédés de réalisation Download PDFInfo
- Publication number
- WO2012146626A2 WO2012146626A2 PCT/EP2012/057584 EP2012057584W WO2012146626A2 WO 2012146626 A2 WO2012146626 A2 WO 2012146626A2 EP 2012057584 W EP2012057584 W EP 2012057584W WO 2012146626 A2 WO2012146626 A2 WO 2012146626A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- projections
- substrate
- interface surface
- superhard construction
- hard material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
- B24D7/00—Bonded abrasive wheels, or wheels with inserted abrasive blocks, designed for acting otherwise than only by their periphery, e.g. by the front face; Bushings or mountings therefor
- B24D7/18—Wheels of special form
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B10/00—Drill bits
- E21B10/46—Drill bits characterised by wear resisting parts, e.g. diamond inserts
- E21B10/56—Button-type inserts
- E21B10/567—Button-type inserts with preformed cutting elements mounted on a distinct support, e.g. polycrystalline inserts
- E21B10/573—Button-type inserts with preformed cutting elements mounted on a distinct support, e.g. polycrystalline inserts characterised by support details, e.g. the substrate construction or the interface between the substrate and the cutting element
- E21B10/5735—Interface between the substrate and the cutting element
Definitions
- This disclosure relates to superhard constructions and methods of making such constructions, particularly but not exclusively to constructions comprising polycrystalline diamond (PCD) structures attached to a substrate and for use as cutter inserts or elements for drill bits for boring into the earth.
- PCD polycrystalline diamond
- Polycrystalline superhard materials such as polycrystalline diamond (PCD) and polycrystalline cubic boron nitride (PCBN) may be 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.
- tool inserts in the form of cutting elements comprising PCD material are widely used in drill bits for boring into the earth to extract oil or gas.
- the working life of superhard tool inserts may be limited by fracture of the superhard material, including by spalling and chipping, or by wear of the tool insert.
- Cutting elements such as those for use in rock drill bits or other cutting tools typically have a body in the form of a substrate which has an interface end/surface and an ultra hard material which forms a cutting layer bonded to the interface surface of the substrate by, for example, a sintering process.
- the substrate is generally formed of a tungsten carbide-cobalt alloy, sometimes referred to as cemented tungsten carbide and the ultra hard material layer is typically polycrystalline diamond (PCD), polycrystalline cubic boron nitride (PCBN) or a thermally stable product TSP material such as thermally stable polycrystalline diamond.
- PCD polycrystalline diamond
- PCBN polycrystalline cubic boron nitride
- TSP material such as thermally stable polycrystalline diamond
- PCD Polycrystalline diamond
- PCD material is an example of a superhard material (also called a superabrasive material) comprising a mass of substantially inter- grown diamond grains, forming a skeletal mass defining interstices between the diamond grains.
- PCD material typically comprises at least about 80 volume % of diamond and is conventionally made by subjecting an aggregated mass of diamond grains to an ultra-high pressure of greater than about 5 GPa, and temperature of at least about 1 ,200°C, for example.
- a material wholly or partly filling the interstices may be referred to as filler or binder material.
- PCD is typically formed in the presence of a sintering aid such as cobalt, which promotes the inter-growth of diamond grains.
- a sintering aid such as cobalt
- Suitable sintering aids for PCD are also commonly referred to as a solvent-catalyst material for diamond, owing to their function of dissolving, to some extent, the diamond and catalysing its re-precipitation.
- a solvent-catalyst for diamond is understood be a material that is capable of promoting the growth of diamond or the direct diamond-to-diamond inter-growth between diamond grains at a pressure and temperature condition at which diamond is thermodynamically stable. Consequently the interstices within the sintered PCD product may be wholly or partially filled with residual solvent-catalyst material.
- PCD is often formed on a cobalt-cemented tungsten carbide substrate, which provides a source of cobalt solvent-catalyst for the PCD.
- Materials that do not promote substantial coherent intergrowth between the diamond grains may themselves form strong bonds with diamond grains, but are not suitable solvent -catalysts for PCD sintering.
- Cemented tungsten carbide which may be used to form a suitable substrate is formed from carbide particles being dispersed in a cobalt matrix by mixing tungsten carbide particles/grains and cobalt together then heating to solidify.
- an ultra hard material layer such as PCD or PCBN
- diamond particles or grains or CBN grains are placed adjacent the cemented tungsten carbide body in a refractory metal enclosure such as a niobium enclosure and are subjected to high pressure and high temperature so that inter-grain bonding between the diamond grains or CBN grains occurs, forming a polycrystalline ultra hard diamond or polycrystalline CBN layer.
- the substrate may be fully cured prior to attachment to the ultra hard material layer whereas in other cases, the substrate may be green, that is, not fully cured. In the latter case, the substrate may fully cure during the HTHP sintering process.
- the substrate may be in powder form and may solidify during the sintering process used to sinter the ultra hard material layer.
- Cobalt has a significantly different coefficient of thermal expansion from that of diamond and, as such, upon heating of the polycrystalline diamond material during use, the cobalt in the substrate to which the PCD material is attached expands and may cause cracks to form in the PCD material, resulting in the deterioration of the PCD layer.
- interface surfaces on substrates are known to have been formed with a plurality concentric annular rings projecting from the planar interface surface. Due to the difference in the coefficients of thermal expansion of the substrate and the ultra hard material layer, these layers contract at different rates when the cutting element is cooled after HTHP sintering. Tensile stress regions are formed on the upper surfaces of the rings, whereas compressive stress regions are formed on/in the valleys between such rings.
- cutting element substrate interfaces may comprise a plurality of spaced apart projections, the projections having relatively flat upper surfaces projecting from a planar interface surface.
- a superhard construction comprising: a substrate comprising a periphery and an interface surface and a longitudinal axis; and an ultra hard material layer formed over the substrate and having an exposed outer surface, a peripheral surface extending therefrom and an interface surface attached to the interface surface of the substrate; wherein one of the interface surface of the substrate or the interface surface of the ultra hard material layer comprises: a plurality of spaced-apart projections arranged to project from the interface surface, the interface surface between the spaced-apart projections being uneven.
- all or a majority of the interface surface between the spaced-apart projections is non-curved and extends in one or more planes which are not substantially parallel to the plane of the exposed outer surface of the ultra hard material layer.
- all or a majority of the interface surface between the spaced-apart projections extends in one or more planes which are not substantially parallel to a plane through which the central longitudinal axis of the substrate extends.
- one or more of the surfaces of all or a majority of the projections extend in one or more planes which are not substantially parallel to the plane of the exposed outer surface of the ultra hard material layer and/or in one or more planes which are not substantially parallel to a plane through which the central longitudinal axis of the substrate extends.
- the thickness of the ultra hard material layer about the central longitudinal axis of the substrate is substantially the same as the thickness of the ultra hard material layer at the peripheral surface.
- a superhard construction comprising: a substrate comprising a periphery and an interface surface and a longitudinal axis; and an ultra hard material layer formed over the substrate and having an exposed outer surface, a peripheral surface extending therefrom and an interface surface attached to the interface surface of the substrate; wherein one of the interface surface of the substrate or the interface surface of the ultra hard material layer comprises: a plurality of projections arranged to project from the interface surface, the projections abutting one or more adjacent projections along an edge thereof on the surface from which the projections project, and extending over all or a majority of the interface surface; and wherein one or more of the surfaces of all or a majority of the projections extend in one or more planes which are not substantially parallel to the plane of the exposed outer surface of the ultra hard material layer and/or in one or more planes which are not substantially parallel to a plane through which the central longitudinal axis of the substrate extends.
- an earth boring drill bit comprising a body having any of the aforementioned superhard constructions mounted thereon as a cutter element.
- FIG. 1 is a perspective view of a cutting element
- FIG. 2a is a perspective view of the plurality of projections of FIG. 1 in free space
- FIG. 2b is a schematic plan view of the substrate of the cutting element of FIG. 1 ;
- FIG. 2c is a schematic cross-sectional view of the substrate along the axis A- A shown in FIG. 2b;
- FIG. 2d is a schematic perspective view of the substrate of the cutting element of FIG. 1 ;
- FIG. 3 is a perspective view of a cutting element according to an embodiment
- FIG. 4 is a perspective view of a substrate according to a further embodiment
- FIG. 5a is a perspective view of a substrate of a cutting element according to a further embodiment
- FIG. 5b is a schematic plan view of the substrate of the cutting element of FIG 5a.
- FIG. 5c is a schematic cross-sectional view of the substrate along the axis A- A shown in FIG. 5b.
- a "superhard material” is a material having a Vickers hardness of at least about 28 GPa.
- Diamond and cubic boron nitride (cBN) material are examples of superhard materials.
- a "superhard construction” means a construction comprising a body of polycrystalline superhard material and a substrate attached thereto.
- polycrystalline diamond is a type of polycrystalline superhard material (PCS) material comprising a mass of diamond grains, a substantial portion of which are directly inter-bonded with each other and in which the content of diamond is at least about 80 volume percent of the material.
- interstices between the diamond grains may be at least partly filled with a binder material comprising a catalyst for diamond.
- interstices or "interstitial regions” are regions between the diamond grains of PCD material .
- interstices or interstitial regions may be substantially or partially filled with a material other than diamond, or they may be substantially empty.
- PCD material may comprise at least a region from which catalyst material has been removed from the interstices, leaving interstitial voids between the diamond grains.
- PCBN polycrystalline cubic boron nitride
- cBN cubic boron nitride
- PCBN is an example of a superhard material.
- a "catalyst material" for a superhard material is capable of promoting the growth or sintering of the superhard material.
- substrate as used herein means any substrate over which the ultra hard material layer is formed.
- a “substrate” as used herein may be a transition layer formed over another substrate.
- the terms “radial” and “circumferential” and like terms are not meant to limit the feature being described to a perfect circle.
- the superhard construction 1 shown in the attached figures may be suitable, for example, for use as a cutter insert for a drill bit for boring into the earth.
- a cutting element 1 includes a substrate 10 with a layer of ultra-hard material 12 formed on the substrate 10.
- the substrate may be formed of a hard material such as cemented tungsten carbide.
- the ultra-hard material may be, for example, polycrystalline diamond (PCD), polycrystalline cubic boron nitride (PCBN), or a thermally stable product such as thermally stable PCD (TSP).
- the cutting element 1 may be mounted into a bit body such as a drag bit body (not shown).
- the exposed top surface of the ultra-hard material opposite the substrate forms the cutting face 14, which is the surface which, along with its edge 16, performs the cutting in use.
- the substrate 10 is an interface surface 18 that interfaces with the ultra-hard material layer 12 which is attached thereto at this interface surface.
- the substrate 10 is generally cylindrical and has a peripheral surface 20 and a peripheral top edge 22.
- the interface surface 18 includes a plurality of spaced-apart projections 24 that are arranged in a substantially annular first array and are spaced from the peripheral edge 22, and a second or inner substantially annular array of projections 26 that are radially within the first array 24.
- the spaced-apart projections 24, 26 are arranged in two arrays which are disposed in two substantially circular paths around a central longitudinal axis of the substrate 10.
- the invention is not limited to this geometry, as, for example, the placement of the projections 24, 26 may be in an ordered non-annular array on the interface surface 18 or the projections may be randomly distributed thereon rather than in a substantially circular or other ordered array.
- the projections are arranged in annular arrays, these may be elliptical or asymmetrical, or may be offset from the central longitudinal axis of the substrate 10.
- the projections 26 of the inner array are shown to be closer to the outer array 24 than to the longitudinal central axis of the substrate, in other embodiments the projections 26 of the inner array may be closer to the longitudinal central axis.
- the projections 26 in the second array may be positioned to radially align with the spaces between the projections 24 in the first array.
- the projections 24, 26 and spaces may be staggered, with projections in one array overlapping spaces in the next array. This staggered or mis-aligned distribution of three- dimensional features on the interface surface may assist in distributing compressive and tensile stresses and/or reducing the magnitude of the stress fields and/or arresting crack growth by preventing an uninterrupted path for crack growth.
- all or a majority of the projections 24, 26 are shaped such that all or a majority of the surfaces of the projections are not substantially parallel to the cutting face 14 of the ultra hard material 12 or to the plane through which the longitudinal axis of the substrate extends.
- the interface surface 18 in the spaces between projections is uneven. This may be interpreted as, but not limited to, covering one or more of these spaces being non-uniform, varying, irregular, rugged, not level, and/or not smooth, with peaks and troughs.
- This arrangement is thought to act to inhibit uninterrupted crack propagation along the interface surface 18 and to increase the contact surface area between the interface of the substrate 10 and the interface of the ultra hard material layer 12. Furthermore, it is believed that such a configuration acts to disturb 'elastic' wave formation in the material and deflect cracks at the interface. These spaces or uneven valleys separating each projection 24, 26 from the adjacent projections may be uniform in some embodiments and non-uniform in other embodiments.
- the projections 24, 26 may have a smoothly curving upper surface or may have a sloping upper surface. In some embodiments, the projections 24, 26 may be slightly trapezoidal or tapered in shape, being widest nearer the interface surface from which they project.
- the projections 24, 26 are spaced substantially equally in/round the respective substantially annular array, with each projection 24, 26 within a given array having the same dimension.
- the projections 24, 26 may be formed in any desired shape, as described above, and spaced apart from each other in a uniform or non-uniform manner to alter the stress fields over the interface surface 18.
- the projections 24 in the outer array are, as shown in the embodiment of Figures 1 and 2, larger in size than those in the inner array. However, these relative sizes may be reversed, or the projections 24, 26 in both arrays could be approximately of uniform size, or a mixture of sizes.
- the outer array includes double the number of projections 24 than the inner layer, for example ten and five projections respectively.
- the projections 24, 26 are positioned and shaped in such a way that they inhibit one or more continuous paths along which cracks could propagate across the interface surface 18. Also, in some embodiments, all or the majority of the projections and/or spaces therebetween do not have any surfaces which are substantially normal or parallel to any loads expected to be applied to the cutter element 1 in use, and nor which are substantially normal or parallel to any exterior surfaces thereof.
- the arrangement and shape of the projections 24, 26 and spaces therebetween may affect the stress distributions in the cutting element 1 and may act to improve the cutting element's resistance to crack growth, in particular crack growth along the interface surface 18, for example by arresting or diverting crack growth across the stress zones in, around and above the projections 24, 26.
- the depth of ultra hard material in the region around the central longitudinal axis of the substrate 10 may be substantially the same depth as the depth of the ultra hard material at the periphery of the ultra hard material layer 12. This may enable the volume and area of ultra hard material exposed to the work surface in use not to decrease significantly with wear progression thereby improving the lifespan of the cutter element 1 . It may also assist in stiffening the cutter element 1 when loaded in the axial direction. Furthermore, it may assist in decreasing or substantially eliminating the possibility of grooving wear formation during use.
- the interface surface 51 of the substrate 50 includes a plurality of adjacent rows of projections 54, each being substantially pyramidal in shape and abutting one or more adjacent projections along one side of its base along the surface 50 from which the projections 54 project.
- all or a majority of the projections 54 do not have any surface substantially parallel to either the cutting face of the ultra hard layer (not shown) which will be attached thereto, or the plane through which the longitudinal axis of the substrate 50 extends.
- the projections 54 may be all the same height or some may be of a greater height than others.
- FIG. 5a to 5c A further embodiment of a substrate 100 is shown in Figures 5a to 5c.
- This embodiment differs from that shown in Figures 1 to 2d in that the shape of the projections 24, 26 extending from the interface surface 18 are of a differing shape and the number of projections 24 in the outer array are fewer than that shown in Figure 1 .
- these projections 24, 26 have a peripheral shape having one or more non-planar faces.
- the features of the interface surfaces 18, 51 may be formed integrally whilst the substrate is being formed through use of an appropriately shaped mold into which the particles of material to form the substrate are placed.
- the projections and uneven surfaces of the interface surface 18, 51 may be created after the substrate has been created or part way through the creation process, for example by a conventional machining process. Similar procedures may be applied to the ultra hard material layer 12 to create the corresponding shaped interface surface for forming a matching fit with that of the substrate.
- the ultra hard material layer 12 may be attached to the substrate by, for example, conventional brazing techniques or by sintering using a conventional high pressure and high temperature technique.
- the durability of the cutter product including the substrate and ultra hard material layer with the aforementioned interface features and/or the mitigation of elastic stress waves therein may be further enhanced if the ultra hard material layer 12 is leached of catalyst material, either partially or fully, in subsequent processing, or subjected to a further high pressure high temperature sintering process.
- the leaching may be performed whilst the ultra hard material layer 12 is attached to the substrate or, for example, by detaching the ultra hard material layer 12 from the substrate, and leaching the detached ultra hard material layer 12. In the latter case, after leaching has taken place, the ultra hard material layer 12 may be reattached to the substrate using, for example, brazing techniques or by resintering using a high pressure and high temperature technique.
- the substrate described herein has been identified by way of example.
- the ultra-hard material may be attached to other carbide substrates besides tungsten carbide substrates, such as substrates made of carbides of W, Ti, Mo, Nb, V, Hf, Ta, and Cr.
- the embodiments shown in FIGS 1 to 5c are depicted in these drawings as comprising PCD structures having sharp edges and corners, embodiments may comprise PCD structures having rounded, bevelled or chamfered edges or corners. Such embodiments may reduce internal stress and consequently extend working life through improving the resistance to cracking, chipping, and fracturing of cutting elements through the interface of the substrate or the ultra hard material layer having unique geometries.
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- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Earth Drilling (AREA)
- Golf Clubs (AREA)
- Laminated Bodies (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1317530.2A GB2505575B (en) | 2011-04-26 | 2012-04-25 | Superhard constructions & methods of making same |
| US14/009,890 US20140087640A1 (en) | 2011-04-26 | 2012-04-25 | Superhard constructions and methods of making same |
| CN201280025859.7A CN103748310B (zh) | 2011-04-26 | 2012-04-25 | 超硬结构 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161479248P | 2011-04-26 | 2011-04-26 | |
| US61/479,248 | 2011-04-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2012146626A2 true WO2012146626A2 (fr) | 2012-11-01 |
| WO2012146626A3 WO2012146626A3 (fr) | 2013-11-14 |
Family
ID=46044661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2012/057584 Ceased WO2012146626A2 (fr) | 2011-04-26 | 2012-04-25 | Constructions super-dures et leurs procédés de réalisation |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20140087640A1 (fr) |
| CN (1) | CN103748310B (fr) |
| GB (1) | GB2505575B (fr) |
| WO (1) | WO2012146626A2 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015091672A3 (fr) * | 2013-12-17 | 2015-11-19 | Element Six Limited | Structures superdures et leurs procédés de fabrication |
| GB2528728A (en) * | 2013-12-17 | 2016-02-03 | Element Six Abrasives Sa | Super hard constructions & methods of making same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130081882A1 (en) * | 2011-09-30 | 2013-04-04 | Diamond Innovations, Inc. | Method of characterizing a material using three dimensional reconstruction of spatially referenced characteristics and use of such information |
| US9970249B2 (en) * | 2014-12-05 | 2018-05-15 | Baker Hughes, A Ge Company, Llc | Degradable anchor device with granular material |
| WO2017106388A1 (fr) * | 2015-12-14 | 2017-06-22 | Smith International, Inc. | Coulée directe d'insert ultra-dur dans un corps de trépan |
| GB201523149D0 (en) * | 2015-12-31 | 2016-02-17 | Element Six Uk Ltd | Super hard constructions & methods of making same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69131846T2 (de) * | 1990-10-05 | 2000-05-18 | Sumitomo Electric Industries, Ltd. | Hartmaterial mit diamant bekleidet, wegwerfeinsatz, und methode zum herstellen dieses materials und einsatzes |
| CA2060823C (fr) * | 1991-02-08 | 2002-09-10 | Naoya Omori | Materiaux rigides carbones et diamantes ou de type diamantes |
| GB2273306B (en) * | 1992-12-10 | 1996-12-18 | Camco Drilling Group Ltd | Improvements in or relating to cutting elements for rotary drill bits |
| EP0655548B1 (fr) * | 1993-11-10 | 1999-02-03 | Camco Drilling Group Limited | Améliorations à ou concernant des éléments couverts d'un matériau superdur |
| US6082474A (en) * | 1997-07-26 | 2000-07-04 | Camco International Limited | Elements faced with superhard material |
| US6068913A (en) * | 1997-09-18 | 2000-05-30 | Sid Co., Ltd. | Supported PCD/PCBN tool with arched intermediate layer |
| JP2000054007A (ja) * | 1998-07-31 | 2000-02-22 | Sumitomo Electric Ind Ltd | ダイヤモンド焼結体及びその製造方法 |
| CN101427000A (zh) * | 2006-02-23 | 2009-05-06 | 贝克休斯公司 | 旋转钻头中备用切削件插入件 |
| US7604074B2 (en) * | 2007-06-11 | 2009-10-20 | Smith International, Inc. | Cutting elements and bits incorporating the same |
| US7909121B2 (en) * | 2008-01-09 | 2011-03-22 | Smith International, Inc. | Polycrystalline ultra-hard compact constructions |
| US8627905B2 (en) * | 2009-08-17 | 2014-01-14 | Smith International, Inc. | Non-planar interface construction |
-
2012
- 2012-04-25 WO PCT/EP2012/057584 patent/WO2012146626A2/fr not_active Ceased
- 2012-04-25 CN CN201280025859.7A patent/CN103748310B/zh active Active
- 2012-04-25 GB GB1317530.2A patent/GB2505575B/en active Active
- 2012-04-25 US US14/009,890 patent/US20140087640A1/en not_active Abandoned
Non-Patent Citations (1)
| Title |
|---|
| None |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015091672A3 (fr) * | 2013-12-17 | 2015-11-19 | Element Six Limited | Structures superdures et leurs procédés de fabrication |
| GB2528728A (en) * | 2013-12-17 | 2016-02-03 | Element Six Abrasives Sa | Super hard constructions & methods of making same |
| CN106068362A (zh) * | 2013-12-17 | 2016-11-02 | 第六元素有限公司 | 超硬构件及其制造方法 |
| US20190366442A1 (en) * | 2013-12-17 | 2019-12-05 | Element Six Limited | Superhard constructions & methods of making same |
| US20220144646A1 (en) * | 2013-12-17 | 2022-05-12 | Element Six Limited | Superhard constructions & methods of making same |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201317530D0 (en) | 2013-11-20 |
| CN103748310A (zh) | 2014-04-23 |
| US20140087640A1 (en) | 2014-03-27 |
| CN103748310B (zh) | 2017-09-01 |
| WO2012146626A3 (fr) | 2013-11-14 |
| GB2505575A (en) | 2014-03-05 |
| GB2505575B (en) | 2018-12-19 |
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