CN104507891A

CN104507891A - Superhard constructions and methods of making same

Info

Publication number: CN104507891A
Application number: CN201380040879.6A
Authority: CN
Inventors: 尼德雷特·卡恩; 汉弗莱·萨姆克罗·路基萨尼·希特赫比
Original assignee: Element Six Abrasives SA
Current assignee: Element Six Abrasives SA
Priority date: 2012-06-15
Filing date: 2013-06-14
Publication date: 2015-04-08
Also published as: GB201310668D0; GB2504839A; WO2013186382A1; GB201210658D0; US20150165591A1

Abstract

A superhard polycrystalline construction comprises a body of polycrystalline superhard material having a first region and a second region adjacent to and bonded to the first region by intergrowth of grains of superhard material. The first region comprises a plurality of alternating strata or layers, each having a thickness in the range of around 5 to 300 microns. One or more strata or layers in the second region have a thickness greater than the thicknesses of the individual strata or layers in the first region. The alternating layers or strata in the first region comprise first layers or strata alternating with second layers or strata, the first layers or strata being in a state of residual compressive stress and the second layers or strata being in a state of residual tensile stress. One or more of the layers or strata in the first or second regions comprise a mass of superhard grains exhibiting inter-granular bonding and defining a plurality of interstitial regions therebetween, the superhard grains and a non-superhard phase at least partially filling a plurality of the interstitial regions. The median of the mean free path associated with the non-superhard phase divided by (Q3-Q1) for the non-superhard phase is greater than or equal to 0.50, where Q1 is the first quartile and Q3 is the third quartile; and the median of the mean free path associated with the superhard grains divided by (Q3-Q1) for the superhard grains is less than 0.60.

Description

Superhard construction and manufacture method thereof

Technical field

The present invention relates to the method for superhard construction and this structure of manufacture, special but be not limited to comprise the structure of polycrystalline diamond (PCD) structure being attached to substrate, and relate to the instrument comprising described structure, this instrument is special but be not limited to for rock failure (degradation) or rock drilling (drilling), or drills for the earth's crust.

Background technology

Polycrystalline superhard material such as polycrystalline diamond (PCD) and polycrystal cubic boron nitride (PCBN) can be used to multiple types of tools, and these instruments are used for cutting, mechanical workout, boring or crushing hard or abrasive substance as rock, metal, pottery, matrix material and containing wood material.Particularly, the tool inserts comprising cutting element (cutting element) form of PCD material is widely used in carrying out earth's surface probing with the drill bit of recover petroleum or Sweet natural gas.The working life of sintered carbide tools inserts can comprise by the fracture (fracture) of superhard material peels off (spalling) and cracked (chipping) limit, or limit by the wearing and tearing of tool inserts.

As the cutting element for rock drill bit or other cutting tool typically has the main body of substrate and superhard material form, this substrate has interface edge/surface, and described superhard material forms by such as sintering process the cutting lay being incorporated into the interface surface of substrate.Substrate is made up of the tungsten-cobalt carbide alloy sometimes referred to as cemented tungsten carbide usually, and ultra hard material layer typically is polycrystalline diamond (PCD), polycrystal cubic boron nitride (PCBN) or thermally-stabilised product TSP material as thermally-stabilised polycrystalline diamond.

Polycrystalline diamond (PCD) is an example of superhard material (also referred to as super hard abrasive material), it comprises the diamond particles of a large amount of intergrowth in fact, forms the bone body (skeletal mass) in the gap limited between diamond particles.PCD material typically comprises the diamond at least about 80 volume %, and usually by making the aggregate of diamond particles stand such as to be greater than the hyperpressure of about 5GPa and manufacture at least about the temperature of 1200 DEG C.The material of filling described gap whole or in part can be called as filler or adhesive material.

PCD is typically formed under the existence of sintering aid as cobalt, and sintering aid promotes the intergrowth of diamond particles.The sintering aid be applicable to for PCD dissolves diamond and its reppd function of catalysis to a certain extent due to it, is usually also referred to as adamantine solvent-catalyst material.Be understood to can to promote adamantine growth under diamond thermodynamically stable pressure and temperature condition for adamantine solvent-catalyst or between diamond particles direct diamond to the material of adamantine intergrowth.Therefore remaining solvent-catalyst material can be filled with whole or in part in the gap in the PCD product of sintering.Most typical, PCD is formed in cobalt of being everlasting-cemented tungsten carbide substrate, and this substrate is the source that PCD provides cobalt solvent-catalyst.Do not promote that the material of coherent mutual growths a large amount of between diamond particles itself can form strong combination with diamond particles, but its solvent-catalyst be not applicable to is sintered for PCD.

The cemented tungsten carbide that can be used to form applicable substrate, by the carbide particle be scattered in cobalt matrix, is formed by tungsten carbide particle/particle and cobalt being mixed then to be heating and curing.In order to be formed, there is the cutting element of ultra hard material layer as PCD or PCBN; by diamond particles or particle or CBN particle and cemented tungsten carbide body is contiguous in refractory metal cover (enclosure) is as niobium cover places; and stand high pressure and high temperature; thus occur to combine (inter-grain bonding) between the particle between diamond particles or CBN particle, form polycrystalline ultrahard diamond or polycrystalline CBN layer.

In some cases, substrate fully can be solidified before being attached to ultra hard material layer, and in other cases, substrate can be raw (green), does not namely solidify completely.In the case of the latter, substrate fully can be solidified in HTHP sintering process.Substrate can be powder type, and can be cured in the sintering process for sintering ultra hard material layer.

Constantly increasing the motivating force improving productivity in the drilling field of earth's surface makes the demand to the material for rock cutting constantly increase.Specifically, the PCD material of the wear resistance and shock resistance with improvement is needed to realize rate of cutting and longer life tools faster.

In oil and natural gas probing industry, the cutting element or the tool inserts that comprise PCD material are widely used in drill bit to carry out earth's crust probing.Rock-boring and other manipulation require high-wearing feature and shock resistance.The successful factor of restriction polycrystalline diamond (PCD) emery wheel cutting members is the heat produced due to the friction between PCD and work material.This heat causes the thermal destruction (thermal degradation) of diamond layer.What increase due to PCD layer breaks and peels off and cause the reversal of diamond to graphite of wearing and tearing increase, and thermal destruction adds the wear rate of cutting members.

Method for improving the wearability of PCD matrix material usually causes the shock-resistance of matrix material to reduce.Therefore need the PCS matrix material with wear resistance that is good or that improve, resistance to fracture and shock-resistance, and form the method for this matrix material.

Invention summary

From first aspect, the invention provides a kind of ultrahard polycrystalline structure, it comprises polycrystalline superhard material main body, and described polycrystalline superhard material main body comprises the second area of first area and contiguous first area, and described second area is attached to first area by the intergrowth of superhard material particle; Described first area comprises multiple alternating layer (strata or layer), and the thickness of each layer is in the scope of about 5-300 micron; Described second area comprises multiple layer, and the thickness of one or more layers in second area is greater than the thickness of individual course in first area, wherein:

Alternating layer in first area comprises the first layer replaced with the second layer, and the first layer is in residual compressive stress state, and the second layer is in tensile residual stresses state;

First or second area in one or more layers comprise:

A large amount of superhard particles, it demonstrates intergranular knot and is incorporated between particle and limits multiple gap area, and described superhard particles has relevant mean free path; And

Non-superhard phase, it fills multiple described gap area at least partly, and has relevant mean free path;

Be more than or equal to 0.50 to the intermediate value of described non-superhard mutually relevant mean free path divided by (Q3-Q1) for described non-superhard phase, wherein Q1 is the first quartile, and Q3 is the 3rd quartile; And

The intermediate value of the mean free path relevant to described superhard particles is less than 0.60 divided by (Q3-Q1) for described superhard particles.

From second aspect, the invention provides a kind of ultrahard polycrystalline structure, comprise the second area of first area and contiguous described first area, described second area is attached to described first area by the intergrowth of diamond particles; Described first area comprises multiple alternating layer, and the thickness of each layer in described first area is in the scope of about 5-300 micron; One or more layers in described first area and/or second area comprise:

From the 3rd aspect, the invention provides a kind of method forming ultrahard polycrystalline structure, comprising:

A large amount of superhard material particle is provided, and by described a large amount of superhard particles arrangement to form the first area comprising multiple alternating layer, what each layer was independent has first part and second section, first part has the first mean sizes, second section has the second mean sizes, and the superhard material particle providing another a large amount of, to form the second area of contiguous first area, thus form pre-sintered components (pre-sinter assembly); And

Under the hyperpressure of about 5.5GPa or larger and at the described superhard material temperature thermodynamically more stable than graphite, under the existence of the catalyst/solvent material for described superhard particles, process described pre-sintered components, described superhard material particle is sintered to form polycrystalline superhard construction together, described superhard particles demonstrates intergranular knot and is incorporated between described particle and limits multiple gap area, non-ly superhardly fills multiple described gap area at least partly mutually;

Described second area is attached to described first area by the intergrowth of superhard material particle, and the thickness of described first area is in the scope of about 5-300 micron; Wherein:

Alternating layer in described first area comprises the first layer replaced with the second layer, and described the first layer is in residual compressive stress state, and the described second layer is in tensile residual stresses state;

0.50 is more than or equal to divided by (Q3-Q1) for described non-superhard phase to the intermediate value of described non-superhard mutually relevant mean free path, wherein Q1 is the first quartile to described non-superhard mutually relevant mean free path observed value, and Q3 is the 3rd quartile; And

The intermediate value of the mean free path relevant to described superhard particles is less than 0.60 divided by (Q3-Q1) for described superhard particles, and wherein Q1 is the first quartile of the mean free path observed value relevant to described superhard particles, and Q3 is the 3rd quartile.

On the other hand, the invention provides a kind of instrument, it comprises ultrahard polycrystalline as defined above structure, and described instrument is used for cutting, grinding (milling), grinding (grinding), earth's surface probing (earth boring), rock-boring (rock drilling) or other abrasive applications.

Described instrument can comprise, such as earth's surface probing or rock-boring drill bit, for oil and natural gas probing industry rotation fix cut drill or roller cone drill bits, drilling tool, bloat tool (expandable tool), cork drill or other earth's surface boring tool.

From other aspect, the invention provides a kind of drill bit, cutting members or its assembly for it that comprise ultrahard polycrystalline as defined above and construct.

Accompanying drawing explanation

Mode by embodiment is also described with reference to accompanying drawing by the present invention, wherein:

Fig. 1 is the perspective schematic view of an example of the PCD cutting element of drill bit for earth's surface probing;

Fig. 2 shows the schematic cross section of an example of a part for PCD structure;

Fig. 3 shows the schematic longitudinal cross-section figure of an example of PCD element;

Fig. 4 shows the schematic longitudinal cross-section figure of an example of PCD element;

Fig. 5 shows the Some illustrative skeleton view of an example of the drill bit for earth's surface probing;

Fig. 6 A shows the schematic longitudinal cross-section figure of an example of the pre-sintered components for PCD element;

Fig. 6 B shows the schematic longitudinal cross-section figure of an example of PCD element;

Fig. 7 A, 7B, 7C and 7D show the Some illustrative cross-sectional view of the example of PCD structure;

In all the drawings, identical reference marker refers to identical general feature.

Detailed Description Of The Invention

" superhard material " used herein has the material at least about 28GPa Vickers' hardness.Diamond and cubic boron nitride (cBN) material are the examples of superhard material.

" superhard construction " used herein refers to the structure of the main body containing polycrystalline superhard material.In such configuration, described main body can be attached with substrate, or the main body of polycrystalline material can be self-supporting (free-standing) or linerless (unbacked).

As used herein, polycrystalline diamond (PCD) is a class polycrystalline superhard (PCS) material, it comprises a large amount of diamond particles, and major part wherein directly combines each other, and wherein adamantine content be described material at least about 80 volume %.In an embodiment of PCD material, the gap between diamond particles can be filled with the adhesive material comprised for adamantine catalyzer at least in part." gap " used herein or " gap area " are the regions between the diamond particles of PCD material.In the embodiment of PCD material, gap or gap area can be filled with the material beyond diamond substantially or partly, or they can be in fact empty.PCD material can comprise at least one region, and from this region, catalystic material removes from gap, leaves the interstitial void between diamond particles.

As used herein, PCBN (polycrystal cubic boron nitride) material refers to a class superhard material, and it contains cubic boron nitride (cBN) particle be scattered within the matrix comprising metal or pottery.PCBN is an example of superhard material.

" catalystic material " for superhard material can promote growth or the sintering of superhard material.

Term used herein " substrate " refers to any substrate forming ultra hard material layer thereon.Such as, as used herein " substrate " another suprabasil transition layer can be formed in.In addition, term used herein " radial (radial) " and " circumferential (circumferential) " and similar term do not mean that the feature described by restriction is positive round (perfect circle).

As used herein, term " (the integrally formed) that intactly formed " region or part are continuously formed, and can't help different types of material and be separated.

The superhard construction 1 shown in Fig. 1 can be suitable as, such as, for the cutting insert of the drill bit of earth's surface probing.

In all the drawings, identical Ref. No. is for representing identical feature.

In the embodiment shown in figure 1, cutting element 1 comprises substrate 10, and it has formation ultra hard material layer 12 on the substrate 10.Described substrate can by mechanically resistant material as cemented tungsten carbide be formed.Superhard material can be that such as polycrystalline diamond (PCD), polycrystal cubic boron nitride (PCBN) or thermally-stabilised product are as thermally stable P CD (TSP).Cutting element 1 can be installed to frame of the bit as on drag bit body (not shown).With substrate back to the top surface of exposure of superhard material form face of tool 14, this is the surface of in use carrying out cutting together with its edge 16.

Be the interface surface 18 with ultra hard material layer 12 interface cohesion in one end of substrate 10, ultra hard material layer 12 is attached in this interface surface.As shown in the embodiment of Fig. 1, substrate 10 is normally columniform, and has outer surface 20 and periphery upper limb 22.

As used herein, PCD grade is with the volume content of the gap area between the volume content of diamond particles and size, diamond particles and the PCD material consisting of feature that may be present in the material in gap area.The grade of PCD material can be come to obtain by the following method, comprise: the aggregate that the diamond particles with the distribution of sizes being applicable to these level is provided, alternatively catalystic material or additive material are introduced in this aggregate, and under the existence in the source for adamantine catalystic material, make described aggregate stand diamond than the graphite more pressure and temperature that is melted of Thermodynamically stable and catalystic material.Under these conditions, the catalystic material of fusing can penetrate into aggregate from described source, and likely in the process of sintering, promotes that the direct interaction between diamond particles grows, to form PCD structure.The diamond particles that described aggregate can be comprised loose diamond particles or be combined by adhesive material, and described diamond particles can be diamond particles that is natural or synthetic.

Different PCD grades can have different microtextures and different mechanical propertys, if elasticity (or Young) modulus E, Young's modulus, cross-breaking strength (TRS), toughness are (as so-called K ₁c toughness), hardness, density and thermal expansivity (CTE).Different PCD grades also in use may show difference.Such as, the wear rate of different PCD grade also may be different with resistance to fracture.

All PCD grades can comprise the gap area being filled with the material comprising cobalt metal, and it is an example for adamantine catalystic material.

PCD structure 20 comprises one or more PCD grade.

As used herein, term " stressed condition " refers to compressive stress state, unstress state or tension stress state.Compressive stress state and tension stress state are understood to reciprocal stressed condition.In cylindrical geometric system, stressed condition can be axial, radial direction or circumferential, or is net impact state.

An example with reference to Fig. 2, PCD structure 20 comprise at least two isolated be in compressive residual stress state constricted zone 21 and at least one be in the stretch zones 22 of stretching residual stress state.Stretch zones 22 is between constricted zone 21 and engage.

Can to the mechanical properties of PCD material as the various changes in density, Young's modulus, hardness and thermal expansivity (CTE) be selected, to realize the configuration of stretch zones between two constricted zones.Such change can realize by the following method: the change content of diamond particles, the content of packing material and type, the distribution of sizes of PCD particle or median size and be used alone the method that different PCD grades or use comprise the diamond matrix of mixing PCD grade.

With reference to Fig. 3, an example of PCD element 10 comprises the complete PCD structure 20 joining sintered carbide supporter 30 to.Several constricted zones 21 of layer form that PCD structure 20 comprises alternately (or staggered) and several stretch zones 22.This PCD element 10 can be essentially cylindrical in shape, has the PCD structure 20 being positioned at working end and limiting working-surface 24.Described PCD structure 20 can join on supporter 30 in non-planar interface 25.The thickness of constricted zone 21 and stretch zones 22 is about 5 microns to about 200 microns, in some embodiments in the scope of about 5 microns to about 300 microns, and can be set to the working-surface 24 being arranged essentially parallel to PCD structure 20.Substantially annular region 26 can be positioned at around the non-planar parts 31 that stretches out from supporter 30.

With reference to Fig. 4, an example of PCD element 10 is included in the complete PCD structure 20 joining sintered carbide supporter 30 in non-planar interface 25 place relative with the working-surface 24 of PCD structure 20.PCD structure 20 can comprise constricted zone 21 and the stretch zones 22 of the extended layer form that about 10-20 replaces.Region 26 in this embodiment not containing layer can abutment 25 be arranged.Layer 21,22 can be bending or arc, but usually aligns with interface 25, and can be crossing with the side surface 27 of PCD structure.Some layers can be crossing with working-surface 24.

In some embodiments, region 26 can have the thickness larger in fact than single layer 21,22, in some embodiments, the thickness that the thickness comprising the region of alternating layer 21,22 neighbour near can form the region 26 of the sintered carbide supporter 30 of PCD material substrate is larger.

In some embodiments, the region 26 of contiguous supporter 30 can comprise multiple layers of (not shown), the thickness of the layer 21,22 that the Thickness Ratio of these layers is independent is larger in fact, such as layer 21,22 can have the thickness in about 5 to 200 micrometer ranges, and the thickness of layer in the region 26 of contiguous supporter 30 exceedes about 200 microns.

In some embodiments, as shown in Fig. 1 to Fig. 4, the thickness of alternating layer 21,22 can in about 5-300 micrometer range, and diamond is formed by the mixture of PCD of PCD such as two or more grades with two or more different average diamond particle diameters.Such as, layer 21 can be formed by the diamond matrix of the gathering with average diamond particle diameter A and B, and layer 22 also can by having average diamond particle diameter A with B but the diamond matrix different from the ratio of layer 21 is formed.In an optional embodiment, layer 21 can be formed by the diamond matrix with average diamond particle diameter A and B, and layer 22 can be formed by the diamond matrix with average diamond particle diameter C.Should be understood that other order/mixing any of two or more diamond particle diameter can be used for forming alternating layer 21,22.In these embodiments, the region 26 adjacent with supporter 30 can by thicker in fact than single layer 21,22, and the individual layer being such as greater than about 200 microns is formed.Optionally; region 26 can by comprising as the formation of the diamond matrix of layer 21,22 or the median size A of other material and B, and/or the diamond particles of C or have multiple layer of diamond particles of the diamond particle diameter that can be used for the layer formed in this region 26 of contiguous supporter 30 or single layer is formed.

In some embodiments, diamond layer 21,22 and/or the layer formed in the region 26 of contiguous supporter 30 (not shown) can comprise: such as Nano diamond powder is up to the Nano diamond additive of 20wt% form, salt system, boride, one or more in the metallic carbide of any one of Ti, V, Nb or metal Pd or Ni.

In some embodiments, layer 21,22 and/or the layer that formed in the region 26 of contiguous supporter 30 can be positioned at the plane of the plane perpendicular that the longitudinal axis that constructs 10 with diamond extends through.

Such as the result standing hyperpressure in sintering process, this layer can be plane, bending, arc, hemispheric or distortion.Alternatively, the planar registration that the longitudinal axis that alternating layer 21,22 can construct 10 with predetermined angle and diamond extends through, to pass through crack propagation control effect performance.

With reference to Fig. 5, show an example of the drill bit 60 for rock-boring, it comprises the exemplary PCD element 10 be installed on frame of the bit 62.Arrange PCD element 10, each PCD structure 20 is stretched out, for rock cutting from frame of the bit 62.

Can be such as diamond particles or particle for forming the superhard material particle of one or more layers in region described in any one or more.In starting mixt before sintering, these superhard material particles can be such as bimodulus (bimodal), that is, charging comprises the mixture of diamond particles coarse fraction for the formation of one or more alternating layer and diamond particles fine fraction.In some embodiments, coarse fraction can have the averaged particles/particle size range of such as about 10 to 60 microns." averaged particles or particle size " refers to that single particle/particle has a size range, and this size range has expression " average " averaged particles/particle size.Averaged particles/the particle size of fine fraction is less than this size of coarse fraction, such as, between about 1/10 to 6/10 of the size of coarse fraction, and is such as about 0.1 to 20 microns in some embodiments.

In some embodiments, brait part is for the weight ratio of fine diamond part in the scope of about 50% to about 97%, and the weight ratio of fine diamond part can be about 3% to about 50%.In other embodiments, coarse fraction for fine fraction weight ratio by about 70:30 to about 90:10 scope in.

In other embodiments, coarse fraction can in the scope of such as about 60:40 to about 80:20 for the weight ratio of fine fraction.

In some embodiments, the size-grade distribution of coarse grain and fine fraction is not overlapping, and in some embodiments, and an order of magnitude between the independent particle size fraction that the composition of the different size of material block (compact) is distributed by composition multimodal separates.

Described embodiment is included at least one the wide bimodal size distribution between the coarse grain of superhard material and fine fraction, but some embodiments can comprise the size pattern of three or even four or more, it is an order of magnitude that these patterns such as can separate dimensionally, and such as median size is 20 microns, 2 microns, the mixing of the size of particles of 200 nanometers and 20 nanometers.

The size of diamond particles/particle is included fine fraction, coarse fraction or other size in-between in and is pulverized to have come compared with king kong stone granulate and similar method as sprayed by currently known methods.

Be in the embodiment of polycrystalline diamond abrasive compact at superhard material, the diamond particles for the formation of polycrystalline diamond abrasive compact can be natural or synthetic.

In some embodiments, binder catalyst/solvent can comprise cobalt or some other iron family element ting, as iron or nickel or its alloy.The carbide of the group IV-VI metal in the periodic table of elements, nitride, boride and oxide compound are other examples of the non-diamond materials that be introduced in sintering mix.In some embodiments, binder/catalyst/sintering aid can be Co.

Cemented metal carbide substrate can be conventional on composition, and thus, can comprise any IVB race, the metal of VB race or group vib, it is pressed and sinters under the existence of the tackiness agent of cobalt, nickel, iron or its alloy.In some embodiments, metallic carbide are wolfram varbides.

In some embodiments, the main body of such as diamond and carbide material adds that sintering aid/binder/catalyst is used in powder form, and sinters in single UHP/HT process simultaneously.The formation diamond of substrate and the alternating layer of a large amount of carbide are positioned in HP/HT reaction tank assembly, and carry out HP/HT process.The HP/HT treatment condition selected are enough to the intergranular realized between the adjacent particle of abrasive particle and combine, and the combination of optional sintering particle and cemented metal carbide supporter.In one embodiment, these treatment condition generally include and apply to be about 3-120 minute at least about the temperature of 1200 DEG C and the hyperpressure that exceedes about 5GPa.

In some embodiments, in the sintering process of superhard polycrystalline material, presintering substrate in a separate step before substrate can be to combine in HP/HT compacting.

In another embodiment, the main body of substrate and polycrystalline superhard material all carries out premolding.Such as; the bimodulus of superhard particles/particle or multimode charging with optional be also powder type carbonate tackiness agent-catalyst mix together with; and this mixture is filled into the tank (canister) of suitable shape with alternating layer, then in compacting, stand extremely high pressure and temperature.Typically, this pressure is at least 5GPa, and temperature is at least about 1200 DEG C.Then the preform of polycrystalline superhard material is positioned over the appropriate location on the upper surface of premolding carbide substrate (containing binder catalyst), and assembly is positioned in the tank of suitable shape.Then make assembly stand high temperature and high pressure in compacting, the rank of temperature and pressure is still respectively at least about 1200 DEG C and 5GPa.In the process, solvent/catalyst to move to the main body of superhard material from substrate and serves as tackiness agent-catalyzer to realize the intergrowth in layer, and for polycrystalline superhard material layer is attached to substrate.Sintering process is also for being incorporated into substrate by the body junction of superhard polycrystalline material.

Present description is for the manufacture of another case method of PCD element.The aggregate of sheet (sheet) form containing the diamond particles combined by adhesive material can be provided.Described can by the currently known methods preparation in this area; such as extrusion molding or doctor-blade casting process; wherein comprise and there is the independent slip being applicable to be formed the diamond particles of the distribution of sizes of independent bimodulus or the multimode PCD grade expected, and adhesive material is distributed on the surface and makes it dry.Also the additive method for the preparation of diamantiferous can be used, as the method described in U.S. Patent number 5766394 and 6446740.Spraying method is comprised, such as thermospray for the optional method deposited containing diamond layer.Adhesive material can comprise water base organic binder bond, as methylcellulose gum or polyoxyethylene glycol (PEG), and can provide the different sheet comprising diamond particles, diamond content or the additive with different size distribution.Such as, can providing package containing adamantine at least two sheets with different mean sizes, and first group and second group of dish (disc) can be cut from independent first and second.This sheet can also contain for adamantine catalystic material, as cobalt and/or for suppressing the misgrowth of diamond particles or strengthening the additive of PCD material character.Such as, described can containing have an appointment 0.5 % by weight to about 5 % by weight vanadium carbide, chromium carbide or wolfram varbide.In an example, each group can comprise about 10 to 20 dishes.

Can providing package containing the supporter of sintered carbide, wherein, sintering or adhesive material comprise for adamantine catalystic material, as cobalt.Supporter can have the on-plane surface end that will form PCD structure thereon or the near-end being essentially plane, this formation interface, end.The molded non-planar of end can be configured to reduce undesirable unrelieved stress between described PCD structure and supporter.Cup (cup) can be provided for being assembled into supporter by diamantiferous.First group and second group of dish can enter the bottom of cup with the sequence stack replaced.In a form of the method, the layer of substantially loose diamond particles can be filled in the superiors of dish.Then supporter can be embedded in cup, and near-end is introduced into, and pushes it against substantially loose diamond particles, causes these particles to move a little, and locates it according to the shape of the on-plane surface end of described supporter, to form pre-sintered components.

Pre-sintered components can put into the capsule (capsule) for ultra-high voltage compacting, and stand the hyperpressure at least about 5.5GPa and the high temperature at least about 1300 DEG C with sintered diamond particles and form PCD element, this PCD element comprises the complete PCD structure joined on supporter.In a form of the method, when pre-sintered components processes under ultra-high voltage and high temperature, the adhesive material in supporter melts and infiltrates the layer of diamond particles.The existence carrying out the catalystic material of the fusing of self-supporter by diamond particles intergrowth to each other to promote the sintering of diamond particles, thus can form PCD structure that is complete, layering.

In some forms of the method, aggregate can comprise substantially loose diamond particles, or the diamond particles combined by adhesive material.The aggregate of multimode particle can be particle, dish, the form of disk or sheet, and can contain such as adamantine catalystic material and/or the additive for reducing Abnormal diamond grain growth, or aggregate can essentially no catalystic material or additive.In some embodiments, aggregate can be assembled on sintered carbide supporter.

In some embodiments, pre-sintered components can stand at least about 6GPa, at least about 6.5GPa, at least about 7GPa or even at least about the pressure of 7.5GPa.

With reference to figure 6A, an example for the manufacture of the pre-sintered components 40 of PCD element can comprise supporter 30, comprise the region 46 to the stacking diamond particles of the on-plane surface end of supporter 30, and be stacked on the multiple diamantiferous aggregates replaced on region 46 with dish or the general type of disk 41,42.In some forms, aggregate can be loose diamond particles (grains) or grain (granules) form.Pre-sintered components can be heated to remove the adhesive material be included in stacked dish.

With reference to figure 6B, an example of PCD element 10 comprises PCD structure 20, and it contains the multiple alternating layers 21,22 formed by the PCD material of different independent multimode grades and the part 26 not comprising layer.Part 26 can be formed according to the form fit of the on-plane surface end of supporter 30, and in the process of uhp treatment, part 26 is intactly bonded to supporter 30.The alternating layer 21,22 of the mixture of the PCD of different grades or diamond particle size or grade is combined to adamantine intergrowth by direct diamond, with form complete a, solid with the PCD structure 20 of layering.The shape of PCD layer 21,22 can be bending, arc or distortion as the result standing hyperpressure to a certain extent.In some forms of the method, consider and arrange and may be out of shape in ultra-high voltage and high-temperature process, aggregate can be disposed in presintering body assembly, to realize other the layer configuration various in PCD structure.

Layer 21,22 can comprise the different independent PCD grade of the result of the different average diamond particle diameters as layer.The catalystic material of different amount may penetrate in the dissimilar dish 41,42 be included in presintering body assembly, because they comprise the diamond particles with different mean sizes, and causes the space of the different sizes between diamond particles thus.Thus corresponding alternative P CD layer 21,22 can comprise different, alternately amount for adamantine catalystic material.By volume percentages, the content of the filler material in stretch zones can be greater than the content in each constricted zone.

In an example, the layer of compression can comprise the diamond particles that median size is greater than the median size of the diamond particles of the layer of stretching.

When not wishing the constraint being subject to particular theory, when making the PCD structure of layering get off from the high temperature cooling formed at that time, the alternating layer of the Metal catalyst materials containing different amount can shrink with different speed.This may be that metal shrinks in fact much bigger than diamond because when it gets off from high temperature cooling.This shrinking percentage difference may cause adjacent layers mutually to be pullled, thus causes relative stress therebetween.

Can be undertaken processing to adjust its shape by grinding with reference to the PCD element 10 described by Fig. 6 B, thus form PCD element in fact as described in Figure 4.This may relate to a part for some buckled layer of removing, to form the working-surface that is essentially plane and to be essentially columniform side surface.Catalystic material can remove from the region of the PCD structure of adjacent working-surface or side surface or adjacent working-surface and side surface.This can pass through by this PCD structure of acid treatment to leach catalystic material between diamond particles, or has been come by other method such as electrochemical method.Can provide thermally-stabilised region thus, it can be porous in fact, extends at least about 50 microns or at least about the degree of depth of 100 microns from the surface of PCD structure.Some embodiments (wherein leaching the degree of depth is about 250 microns) with the layer of 50-80 micron thickness have been proved to be the performance demonstrating and improve in fact, and such as, relative to the PCD product do not leached, the product after leaching is double in performance.In an example, the region of porous can comprise the catalystic material of at the most 2 % by weight in fact.

When to PCD structure 10 application Ore Leaching, especially for the wherein tackiness agent embodiment containing V and/or Ti, the use by the difference on such as binder content with the alternating layer of different-grain diameter can controllably provide different structures.In the process of HCl Ore Leaching, such structure can be formed due to residual tungsten different in each layer.In fact, probably in each layer all different (except non-usage contains the acid of HF), this can make particularly can preferentially leach on the edge of PCD material leaching yield.For the layer of thickness more than 120 microns, this situation may be more obvious.If to PCD material application HF Ore Leaching, then this situation unlikely occurs.Its reason is, in the process, HCl acid is removed Co and leaves tungsten, and HF Ore Leaching can remove the whole compositions in binder composition.

A variation instance with reference to figure 7A, PCD structure 20 comprises with alternating structure arrangement and is arranged essentially parallel to the working-surface 24 of PCD structure 20 and at least three crossing with the side surface 27 of the PCD structure layers 21,22 being essentially plane.

A variation instance with reference to figure 7B, PCD structure 20 comprises with at least three layers 21,22 of alternating structure arrangement, and described layer has bending or bowed shape, described layer trend towards working-surface 24 away from PCD structure and and cutting edge 28 at least partly.

A variation instance with reference to figure 7C, PCD structure 20 comprises with at least three layers 21,22 of alternating structure arrangement, described layer trend towards working-surface 24 away from PCD structure at least partly and the usual cutting edge 28 towards PCD structure extends.

With reference to figure 7D, a variation instance of PCD structure 20 comprises with at least three layers 21,22 of alternating structure arrangement, working-surface 24 substantial alignment of at least part of and PCD structure of some layers, and at least part of of some layers aligns with the side surface 27 of PCD structure usually.Layer usually can be annular section annular and in fact with PCD structure 20 to be essentially columniform side surface 27 coaxial.

PCD structure can have the surf zone close to working-surface, and this region comprises the PCD material with about 1050MPa at the most or the Young's modulus of about 1000MPa at the most.Surf zone can comprise heat-staple PCD material.

Some examples of PCD structure can have at least 3, at least 5, at least 7, at least 10 or even at least 15 constricted zones, and stretch zones is therebetween.

In some embodiments, the thickness of each layer can be at least about 5 microns, in other embodiments, this thickness is at least about 30 microns, and in other embodiments, this thickness is at least about 100 microns, or in other embodiments, this thickness is at least about 200 microns.In some embodiments, the thickness of each layer can be about 300 microns or about 500 microns at the most at the most.In some example embodiments, by by the working-surface of one end a bit to the thickness of the point measurement layer on apparent surface, the thickness of each layer can be PCD structural thickness at least about 0.05%, at least about 0.5%, at least about 1% or at least about 2%.In some embodiments, the thickness of each layer can be at the most about 5% of PCD structural thickness.

As used herein, term " residual stress state " refers to when not having the outside loading force applied, the stressed condition of a part for main body or main body.The residual stress state that PCD structure comprises Rotating fields is by strain gage and successively progressively remove material and measure.In some examples of PCD element, the compressive residual stress of at least one constricted zone can be at least about 50MPa, at least about 100MPa, at least about 200MPa, at least about 400MPa or even at least about 600MPa.Difference between adjacent layers unrelieved stress size can be at least about 50MPa, at least about 100MPa, at least about 200MPa, at least about 400MPa, at least about 600MPa, at least about 800MPa or even at least about 1000MPa.In an example, two continuous print constricted zones or stretch zones is had at least can to have different unrelieved stresss.PCD structure can comprise at least three compressions or stretch zones, and each region has different compressive residual stresses, and this region is respectively with compression or the ascending order of tensile stress size or descending sort.

In an example, each region can have the average tenacities of 16MPa.m1/2 at the most.In some embodiments, the average hardness in each region can be at least about 50GPa or at least about 60GPa.The average Young's modulus in each region can be at least about 900MPa, at least about 950MPa, at least about 1000MPa or even at least about 1050MPa.

As used herein, " cross-breaking strength " (TRS) stands to measure at the load of three positions applyings by making the sample of rod (bar) form with width W and thickness T, wherein two positions are in the side of sample, a position is at opposite side, and increase load, until sample ruptures at load P with a loading rate.Then calculate TRS based on load P, sample size and span L, wherein span L is the distance between the load position of two, side.This measurement can also be called as three-point bend test, and be described in " pottery; mechanical property; fault behavior, Material selec-tion (Ceramics, mechanical properties; failurebehaviour; materials selection) " (1999, Springer Verlag, Berlin) by D.Munz and T.Fett.Corresponding to the measurement of the TRS of specific grade PCD material, realized by the TRS measuring the PCD sample be made up of this grade.

And have alternate compression and tensile stress state PCD layer PCD structure the effective toughness of entirety being tending towards increasing PCD structure is provided, this may have the impact of the Potential feasibility increasing division delamination (its middle level is tending towards breaking).When not wishing the constraint being subject to particular theory, if PCD layer is not enough firm in the unrelieved stress maintained between them, then divides delamination and can be easy to occur.This impact by selecting PCD grade, and can particularly form the PCD grade of stretch zones, to have sufficiently high TRS to improve.The TRS forming the PCD grade of stretch zones should be greater than its tensile residual stresses that may stand.A method of the stress intensity that range of influence may be stood is the relative thickness by selecting adjacent area.Such as, by the thickness selecting thickness to be greater than the stretch zones of adjacent constricted zone, the size of tension stress in stretch zones is probably reduced.

The residual stress state in region can change with temperature.In use, the temperature of PCD structure may be significantly different between the point near cutting edge and the point away from cutting edge.In some purposes, the temperature near cutting edge can reach hundreds of degree Celsius.If temperature exceedes about 750 degrees Celsius, under the existence of catalystic material as cobalt, diamond is probably converted into graphite material, and this is undesirable.Therefore, in some purposes, when temperatures as high about 750 degrees Celsius, the alternating stress state in adjacent area as described herein should be considered.

The K1C toughness of PCD dish is measured by split test (diametral compression test), it is described in Lammer (" Mechanical properties of polycrystalline diamonds ", Materials Science and Technology, volume 4, 1988, and Miess (Miess p.23.), D.and Rai, G., " Fracture toughness and thermal resistances of polycrystallinediamond compacts ", Materials Science and Engineering, 1996, volume A209, number 1to 2, pp.270-276).

Young's modulus is a class Young's modulus, and is show in elastic stress range at material, in response to the measuring of uniaxial strain of uniaxial stress.Measuring the preferred method of Young's modulus E is by according to equation E=2 ρ .C _t ²(1+ υ), measures the horizontal and vertical component of the velocity of sound by this material, wherein υ=(1 – 2 (C _t/ C _l) ²)/(2 – 2 (C _t/ C _l) ²), C _land C _tbe the vertical and horizontal speed of the sound by it measured respectively, and ρ is the density of this material.As known in the art, the vertical and horizontal speed of sound can use ultrasonic wave to measure.When a kind of material is the matrix material of differing materials, average Young's modulus is by one of following three formula, and namely the harmonic wave (harmonic) of mixed formulation, geometry (geometric) and law (rule) are estimated:

E=1/ (f ₁/ E ₁+ f ₂/ E ₂)); E=E ₁ ^f1+ E ₁ ^f2; And E=f ₁e ₁+ f ₂e ₂;

Wherein different materials is divided into and has respective volume fractiion f ₁and f ₂two parts, f ₁and f ₂and be 1.

As used herein, word " by ... formed " refer to " by ... composition, do not consider the little or immaterial difference that may exist in composition or microtexture ".

The hardness of cemented tungsten carbide substrate by standing ultra-high voltage especially by this substrate and high temperature strengthens under diamond is thermodynamically stable pressure and temperature.The amplitude that hardness strengthens can be depending on pressure and temperature condition.Particularly, hardness strengthens and can increase higher pressure.When not wishing the constraint by particular theory, it is relevant that this is considered in compacting sintering process, to enter PCD with Co from basement migrate, because the degree that hardness increases directly depends on the reduction of Co content in substrate.

In cemented carbide substrate containing enough for adamantine solvent/catalyst, and PCD structure is intactly formed in suprabasil embodiment in ultra-high pressure sintering process, solvent/catalyst material can be included in or be introduced in the aggregate from the diamond particles of the material source being different from cemented carbide substrate.This solvent/catalyst material can comprise the cobalt only penetrated into before ultra-high pressure sintering step and in ultra-high pressure sintering process from substrate the aggregate of diamond particles.But, in cobalt or the lower embodiment of other solvent/catalyst material content in the substrate, particularly when its lower than cemented carbide material about 11 % by weight time, then may need to provide other source to guarantee the good sintering of aggregate, to form PCD.

Can be incorporated in the aggregate of diamond particles by various method for adamantine solvent/catalyst, comprise solvent/catalyst material and the diamond particles of mixed powder form, in the deposited on silicon solvent/catalyst material of diamond particles, or solvent/catalyst material is infiltrated through aggregate by the material source being different from substrate by the part before the sintering step or as sintering step.The method deposited on the surface of diamond particles as cobalt for adamantine solvent/catalyst be well known in the art, it comprises chemical vapour deposition (CVD), physical vapor deposition (PVD), sputter coating, electrochemical method, chemical coating method and ald (ALD).It should be understood that the merits and demerits of often kind of method depends on the character of sintering aid and coated structure to be deposited, and the characteristic of particle.

In one embodiment, by following methods, cobalt is deposited on the surface of diamond particles: first depositing precursor materials, then precursor material is converted into the material of containing element cobalt metal.Such as, in a first step, following reaction can be used to be deposited on the surface of diamond particles by cobaltous carbonate:

Co(NO ₃) ₂+Na ₂CO ₃→CoCO ₃+2NaNO ₃

For the carbonate of adamantine cobalt or other solvent/catalyst or other precursor or deposition can be realized by the method described in PCT patent publication No. WO2006/032982.Then such as by pyrolysis as described below, cobaltous carbonate is converted into cobalt and water:

CoCO ₃→CoO+CO ₂

CoO+H ₂→Co+H ₂O

In another embodiment, the precursor of cobalt powder or cobalt, as cobaltous carbonate, can mix with diamond particles.When the precursor using solvent/catalyst as cobalt, material described in thermal treatment may be necessary, with before sintering aggregate, carry out reacting the solvent/catalyst material with generting element form.

In fact the sintered carbide grade that cobalt contents is lower is subject to following truth as the practical application of the substrate for PCD inserts and limits, and namely in sintering process, a part of Co needs to enter PCD layer to promote the formation of PCD from substrate migration.For this reason, although it may be desired, the base material comprising lower Co content manufactures PCD more difficult.

In some embodiments, cemented carbide substrate may be formed by the tungsten carbide particle be bonded together by adhesive material, and this adhesive material comprises the alloy of Co, Ni and Cr.This tungsten carbide particle can form at least 70 % by weight and at the most 95 % by weight of substrate.Adhesive material can comprise the Cr between the Ni, about 0.1 to 10 % by weight between about 10 ~ 50 % by weight, and all the other weight percents comprise Co.In some embodiments, the distribution of sizes of the tungsten carbide particle in cemented carbide substrate has following characteristics:

-the particle diameter that is less than the carbide particle of 17% is equal to or less than about 0.3 micron;

The particle diameter of the tungsten carbide particle between-Yue 20-28% is between about 0.3-0.5 micron;

The particle diameter of the tungsten carbide particle between-Yue 42-56% is between about 0.5-1 micron;

-the tungsten carbide particle that is less than about 12% is greater than 1 micron; And

The median size of-tungsten carbide particle is about 0.6 ± 0.2 micron.

In some embodiments, tackiness agent comprises the tungsten about between 2-20wt% and the carbon about between 0.1-2wt% in addition.

The layer of the substrate adjacent with the interface with polycrystalline diamond abrasive compact main body can have the thickness of such as about 100 microns, and can comprise tungsten carbide particle and tackiness agent phase.The feature of this layer can be the following essentially consist having and measured by energy dispersion X-ray microscopic analysis (EDX):

Cobalt between-Yue 0.5-2.0wt%;

Nickel between-Yue 0.05-0.5wt%;

Chromium between-Yue 0.05-0.2wt%; And

-tungsten and carbon.

In another embodiment, comprise in the above-mentioned layer of the cobalt about between 0.5-2.0wt%, the nickel about between 0.05-0.5wt% and the chromium about between 0.05-0.2wt% in essentially consist, remainder is tungsten and carbon.

The layer of substrate can comprise free carbon further.

As used herein, matrix material " mean free path " (MFP) as sintered carbide is the measuring of mean distance between the gathering carbide particle that congeals in adhesive material.The mean free path feature of cemented carbide material can use the Photomicrograph of the polished section of this material to measure.Such as, this Photomicrograph can have the ratio of enlargement of about 1000 times.This MFP can be determined by the distance measured between each point of crossing that uniform grid is reached the standard grade and crystal boundary.Matrix (matrix) line segment Lm is sued for peace, and particle (grain) line segment Lg is sued for peace.The mean matrix line segment length adopting diaxon is " mean free path ".The mixture of multiple distributions of tungsten carbide particle size may cause MFP value for the wide distribution of same matrix content.Below this is explained in more detail.

In some embodiments, substrate comprises Co, Ni and Cr.

Adhesive material for substrate can to comprise in sosoloid at least about 0.1 % by weight to one or more in the highest V, Ta, Ti, Mo, Zr, Nb and Hf of about 5 % by weight.

For assisting the thermostability improving sintering structure, can be close to from polycrystal layer in the region of its exposed surface and removing catalytic material.Usually, this surface is in the polycrystal layer side relative with substrate, and the working-surface that will provide for polycrystalline diamond layer.The removal of catalytic material can use methods known in the art such as electrolytically etching, acidleach and evaporation technique to carry out.Find that the multimode distribution of some embodiments can contribute to realizing the diamond intergrowth of very high level, still kept enough open porosity to realize effective leaching simultaneously.

Be explained in more detail embodiment of the present invention below with reference to the following example, these embodiments only provide by way of illustration, and are not intended to limit the scope of the invention.

Embodiment 1

Carry out carrying out first depolymerization in 1 hour with WC grinding medium by the methyl alcohol slurry of the submicron cobalt powder being enough to obtain the amount of 2 quality % in the final diamond matrix of the layer for the formation of a type in ball milling.Then be that the thin fraction of the diamond powder of 2 μm joins in described slurry with the amount obtaining 10 quality % in final mixture by median size.Introduce extra grinding medium and add other methyl alcohol to obtain applicable slurry; Gains are ground one hour again.Then the adamantine thick fraction of median size about 20 μm is added with the amount obtaining 88 quality % in the final mixture of the layer for the formation of a type.Again other methyl alcohol and grinding medium are supplemented to slurry, and then grind 2 hours.Slurry is removed from ball milling and drying, to obtain diamond powder mixture.

Then diamond powder mixture is placed in suitable HPHT container with alternating layer, make it and may replace by maybe can't help another diamond matrix that the mixture of multimode diamond grades formed, above-mentioned layer is adjacent with tungsten carbide substrate and sinter under the pressure of about 6.8GPa and at the temperature of about 1500 DEG C.

Embodiment 2

Carry out carrying out first depolymerization in 1 hour with WC grinding medium by the methyl alcohol slurry of the submicron cobalt powder being enough to obtain the amount of 2.4 quality % in the final diamond matrix of the layer for the formation of a type in ball milling.Then be that the thin fraction of the diamond powder of 2 μm joins in described slurry with the amount obtaining 29.3 quality % in the final mixture of the layer for the formation of a type by median size.Introduce extra grinding medium and add other methyl alcohol to obtain applicable slurry; Gains are ground one hour again.Then the adamantine thick fraction of median size about 20 μm is added with the amount obtaining 68.3 quality % in the final mixture of the layer for the formation of a type.Again other methyl alcohol and grinding medium are supplemented to slurry, and then grind 2 hours.Slurry is removed from ball milling and drying, to obtain the diamond powder mixture of the layer for the formation of a type.

Then diamond powder mixture is placed in suitable HPHT container with alternating layer, make it and may replace by maybe can't help another diamond matrix that the mixture of multimode diamond grades formed, above-mentioned layer is adjacent with tungsten carbide substrate and sinter under the pressure of about 6.8GPa and at the temperature of about 1500 DEG C.Particularly, each is containing having different mean sizes and the first and second sheet materials of the diamond particles combined by organic binder bond, and it is by the manufacture of flow casting molding (tapecasting) method.The method comprises provides diamond particles to be suspended in independent slurry in liquid adhesive, pours into a mould this slurry slabbing, and make its drying with formed can self-supporting containing diamond sheet material.Cup will be put into, the alternately stacking dish from staggered first group and second group above each other containing diamond disk.To there is the top that about 18 microns of layers to the loose diamond particles of the mean sizes in about 25 micrometer ranges are placed on the Bei Zhong disk the superiors upward for the formation of the second area that wherein there is not alternating layer, embedded by supporter in cup, its on-plane surface end is pushed to this layer.

The diamond content of sintered diamond structure is greater than 90 volume %, and in some embodiments, and the thick fraction of this distribution can be greater than 60 % by weight or be greater than 70 % by weight.

In polycrystalline diamond abrasive compact, independent diamond particles/particle is attached on adjacent particle/particle by Buddha's warrior attendant stone bridge or diamond neck (neck) to a considerable extent.This independent diamond particles/particle keeps its consistence (identity), or usually has different orientations.Average grain/the size of particles of these other diamond particles/particles can utilize image analysis technology to determine.Scanning electronic microscope collects image and uses standard image analysis technology to analyze.From these images, representational diamond particles/particle size distribution can be extracted.

Usually, the main body of polycrystalline diamond abrasive compact will produce and be attached in cemented carbide substrate in high temperature high pressure process (HPHL) process.In doing so, arrange the tackiness agent phase in every layer and diamond particles, to make tackiness agent be uniformly distributed mutually and have small scale, this is favourable.

By grinding and polishing, PCD element is processed, to be formed, there is the working-surface of plane and the cutting element of cylindrical sides substantially.Then scanning electronic microscope (SEM) is carried out in microtexture inspection to the cross section by PCD structure is used.

The homogeneity of sintering structure or homogeneity are by carrying out statistical evaluation to define to the image collected in a large number.The distribution of tackiness agent phase is easily distinguished with the distribution of diamond phase by using electron microscope, then can measure the distribution of tackiness agent phase by the method similar with method disclosed in EP0974566.This method can carry out statistical evaluation by microtexture line to the mean thickness of tackiness agent phase to what draw arbitrarily along several.To those skilled in the art, the observed value of this adhesive thickness is also referred to as " mean free path ".For entirety composition or binder content and the similar bi-material of average diamond particle diameter, the material that mean thickness is less will be tending towards evenly, because this means the distribution of " more the small scale " of tackiness agent in the layer of diamond phase.In addition, the standard deviation of this measurement is less, and structure is more even.Large standard deviation shows that adhesive thickness alters a great deal in microtexture, and namely this structure uneven (even), extensively comprises different structure types.

Tackiness agent and the diamond mean free path observed value of various sample is obtained below in the mode listed.Unless otherwise indicated herein, on the surface that the mean free path size in PCD material main body refers to the main body comprising PCD material or by the cross section of this main body is measured and do not carry out the size of three-dimensional correction.Such as, obtain observed value by the image analysis carried out on a polished surface, and in data described in this article, do not carry out Sa Ertekefu (Sltykov) correction.

In the mean value of measuring vol or other statistical parameter of being measured by image analysis, the reliability and accuracy that use multiple images of the different piece of surface or cross section (hereinafter referred to sample) to increase to improve statistic data.Can be such as 10 to 30 for measuring the picture number of a given amount or parameter.If the sample analyzed is uniform, the situation for PCD depends on ratio of enlargement, can think that 10 to 20 width images represent this sample enough fully.

For will be clear that the object made from alternate boundary between particle, the resolving power of image needs enough high, for described observed value, employs the image area of 1280 × 960 pixels herein.The image for image analysis is obtained by the mode of the scanning electron photomicrograph (SEM) captured by use backscattered electron signal.Select backscatter mode to provide the high-contrast based on different atomicity, and reduce the susceptibility (compared with secondary electron imaging pattern) of surface damage.

1. use EDM line to cut the exemplar of PCD sintered compact and polishing.Use scanning electronic microscope with at least 10 width backscattered electron image of 1000 times of magnification shooting sample surfaces.

2. original image is converted to gray level image.By guaranteeing that diamond peak intensity appears at the contrast level setting image between 10 to 20 in grey scale histogram.

3. automatic threshold characteristic is used for binary image, especially for acquisition diamond and tackiness agent phase resolving power clearly.

4. use from Soft Imaging the software of the trade(brand)name analySIS Pro of GmbH (trade mark of Olympus Soft ImagingSolutions GmbH), and any particle getting rid of contact image border from analyze.This needs suitably to select image magnification ratio:

If a. too low, the resolving power of fine particle reduces.

If b. too Gao Ze:

I. the efficiency that coarse particles is separated reduces.

Ii. the coarse particles of comparatively high amts is excised by the border of image, analyzes these less particles thus.

Iii must analyze more images thus to obtain the result having statistical significance.

5. each particle represents eventually through the quantity of the contiguous pixels forming it.

6.AnalySIS software program carry out detect and analysis image in each particle.This process is repeated automatically to multiple image.

7. use grey scale to analyze ten width SEM images, to determine the binder pool (binder pool) distinguished out with other in sample.Then by selecting only to identify binder pool and the maximum value getting rid of the binder pool content of other phases all (no matter grey or white) determines the threshold value of SEM.Once determine this threshold value, this threshold value is used to carry out binaryzation SEM image.

8. be superimposed upon on the width of whole binary image by line thick for pixel, every root line at a distance of 5 pixels (having enough representativenesses to guarantee to measure) on angle of statistics.Be excluded mutually outside these are measured by the tackiness agent that image boundary is excised.

9. to measure and the analyzed material of distance-often kind recorded between the binder pool along superposition line at least carries out 10,000 time measures.Calculate the intermediate value of non-diamond phase average free path and diamond phase average free path.In this article, term " intermediate value " is considered to have its conventional sense, by the Lower Half of data and upper part from numerical value.

Also record the mean free path observed value at Q1 and Q3 for both diamond phase and non-diamond phase.

Q1 is commonly called the first quartile (also referred to as lower quartile), and for there being the numerical value of the data of the bottom of 25% under it.Q3 is commonly called the 3rd quartile (also referred to as upper quartile), and has the data of 75% under it, and the data of 25% thereon.

Thus, determine that embodiment has:

α >=0.50 and β <0.60,

Wherein

α is non-diamond phase MFP intermediate value/(Q3-Q1), which show the observed value of " uniform adhesive pool size "; And

β=diamond MFP intermediate value/(Q3-Q1), which show the observed value of " wide particle diameter distribution ".

Following item lists some the possible combinations dreamed up by content of the present invention:

1. comprise the PCD structure of the first layer, the second layer and third layer; The second layer is placed between the first layer and third layer and by the intergrowth second layer of diamond particles and is bonded to the first layer and third layer; Each layer is formed by independent PCD grade or the grade with at least 1200MPa or at least TRS of 1600MPa; The PCD grade comprised in the second layer has higher thermal expansivity (CTE) than the independent PCD grade of the first layer and third layer.The second layer can comprise and has at least 4 × 10 ^-6millimeter/DEG C the PCD grade of CTE.

2. comprise every one deck to be in the first layer of respective residual compressive stress state and third layer and to comprise and be in tensile residual stresses state and the PCD structure of the second layer between the first layer and third layer; Every one deck of the first layer, the second layer and third layer is formed by one or more independent PCD grade and is directly bonded to each other by the intergrowth of diamond particles; PCD grade has the cross-breaking strength (TRS) of at least 1200MPa.

3. comprise the PCD structure of the first layer, the second layer and third layer; The second layer is placed between the first layer and third layer and by the intergrowth second layer of diamond particles and is bonded to the first layer and third layer; What each region formed by one or more independent PCD grade comprised at least 85 volume % has at least 0.1 micron and the diamond particles of 30 microns of median sizes at the most; Comprise the metal content contained in each independent PCD grade that PCD grade in the second layer comprises than in the first layer and third layer high.The PCD grade comprised in the second layer can contain the metal of at least 9 volume %.

4. comprise the PCD structure of the first layer, the second layer and third layer; The second layer is placed between the first layer and third layer and by the intergrowth second layer of diamond particles and is bonded to the first layer and third layer; Each layer is formed by the one or more independent PCD grade of the TRS with at least 1200MPa; The each independent PCD grade that the PCD grade comprised in the second layer comprises than in the first layer and third layer contains more metal.The PCD grade comprised in the second layer can contain the metal of at least 9 volume %.

5. more than all numbering 1 to 4 combination in, described PCD structure can comprise the thermally-stabilised district extending at least 50 micrometer depth from the surface of PCD structure; Wherein, this thermally-stabilised district comprise at the most 2 % by weight for adamantine catalystic material.

6. more than all numbering 1 to 5 combination in, described layer can be the form of the layer of alternately configured arrangement, to form PCD structure that is complete, layering.The thickness of described layer can be at least about 10 microns and about 500 microns at the most, and described layer can be general plane, bending, arc or hemispheric.

7. more than all numbering 1 to 6 combination in, described layer can be crossing with the working-surface of PCD structure or side surface.Being included in the first layer can be different from the median size of the diamond particles comprised in the second layer with the diamond particles of the PCD grade in third layer.

8. more than all numbering 1 to 7 combination in, the volume of the second layer or thickness can be greater than the volume of the first layer or the volume of thickness and third layer or thickness.

The PCD element comprising the PCD structure be attached on sintered carbide supporter can be provided.This PCD element can be columniform substantially, and has the working-surface being essentially plane, or roughly hemispheric, sharp, conical or Frusto-conical working-surface.This PCD element may be used for rotational shear (or cutting) drill bit for earth's surface probing, for percussion bit or for being used for the hoe of digging up mine or pitch is degraded.

Although be described various embodiment with reference to some embodiments, but one skilled in the art should appreciate that, can make various change for element wherein and can be replaced by equivalent, and these embodiments are not intended to be limited to disclosed specific embodiments.Such as, although the subsequent disposal having described PCD element 10 with reference to the embodiment shown in Fig. 6 B is as leached with from wherein removing catalystic material, such treatment technology can be applied in any embodiment.

Claims

1. a ultrahard polycrystalline structure, comprise polycrystalline superhard material main body, described polycrystalline superhard material main body comprises the second area of first area and contiguous described first area, and described second area is attached on described first area by the intergrowth of superhard material particle; Described first area comprises multiple alternating layer, and the thickness of each layer is in the scope of about 5-300 micron; Described second area comprises multiple layer, and the thickness of one or more layers in described second area is greater than the thickness of layer independent in described first area, wherein:

Described first or second area in one or more described layer comprise:

2. ultrahard polycrystalline structure according to claim 1, wherein said superhard particles comprises diamond particles that is natural and/or synthetic, described ultrahard polycrystalline formation of structure polycrystalline diamond stone construction.

3. the ultrahard polycrystalline structure according to aforementioned any one claim, wherein saidly non-ly superhardly comprises tackiness agent phase mutually.

4. ultrahard polycrystalline structure according to claim 3, wherein said tackiness agent comprises cobalt mutually, and/or one or more other iron family element tings, as iron or nickel or its alloy, and/or one or more carbide of group IV-VI metal, nitride, boride and oxide compound in the periodic table of elements.

5. the ultrahard polycrystalline structure according to aforementioned any one claim, comprises further along interface cohesion to the cemented carbide substrate in described polycrystalline material main body.

6. ultrahard polycrystalline structure according to claim 5, wherein said cemented carbide substrate comprises the tungsten carbide particle combined by adhesive material, and described adhesive material comprises the alloy of Co, Ni and Cr.

7. ultrahard polycrystalline structure according to claim 6, wherein said tungsten carbide particle forms at least 70 % by weight and at the most 95 % by weight of described substrate; Described adhesive material comprises the Ni of about 10-50 % by weight, the Cr of about 0.1-10 % by weight, and all the other weight percents comprise Co; And the distribution of sizes of tungsten carbide particle has following characteristics described in wherein said cemented carbide substrate:

The particle diameter being less than the described tungsten carbide particle of 17% is equal to or less than about 0.3 micron;

The particle diameter of the described tungsten carbide particle of about 20-28% is about 0.3-0.5 micron;

The particle diameter of the described tungsten carbide particle of about 42-56% is about 0.5-1 micron;

The described tungsten carbide particle being less than about 12% is greater than 1 micron; And

The median size of described tungsten carbide particle is about 0.6 ± 0.2 micron.

8. ultrahard polycrystalline structure according to claim 7, wherein said tackiness agent also comprises the tungsten of about 2-20wt% and the carbon of about 0.1-2wt%.

9. the ultrahard polycrystalline structure according to aforementioned any one claim, the thickness of each layer in wherein said first area at about 30-300 micron, or in the scope of about 30-200 micron.

10. the ultrahard polycrystalline structure according to aforementioned any one claim, the thickness of the described layer in wherein said second area is greater than about 200 microns.

11. according to aforementioned any one claim ultrahard polycrystalline structure, the described layer in wherein said first area comprises two or more different average diamond particle diameters.

12. 1 kinds of ultrahard polycrystalline structures, comprise the second area of first area and contiguous described first area, described second area is attached to described first area by the intergrowth of diamond particles; Described first area comprises multiple alternating layer, and the thickness of each layer in described first area is in the scope of about 5-300 micron; One or more layers in described first area and/or second area comprise:

13. according to aforementioned any one claim ultrahard polycrystalline structure, wherein said first area comprise in use formed described ultrahard polycrystalline structure virgin work surface operate outside surface.

14. according to claim 12 or 13 ultrahard polycrystalline structure, the thickness of wherein said second area is greater than the thickness of layer independent in described first area.

15. according to any one of claim 12-14 ultrahard polycrystalline structure, wherein said second area comprises multiple layer.

16. according to any one of claim 12-15 ultrahard polycrystalline structure, wherein said alternating layer comprises the first layer replaced with the second layer, and described the first layer is in residual compressive stress state, and the described second layer is in tensile residual stresses state.

17. ultrahard polycrystalline structures according to aforementioned any one claim, the layer in wherein said first area and/or described second area comprise following in one or more:

Up to the Nano diamond additive of the Nano diamond particle-shaped formula of 20wt%;

Salt system;

The boride of at least one in Ti, V or Nb or metallic carbide; Or

At least one in metal Pd or Ni.

18. according to aforementioned any one claim ultrahard polycrystalline structure, wherein said ultrahard polycrystalline there is the longitudinal axis, and the described layer in described first area and/or described second area is in the plane of the plane perpendicular that the longitudinal axis that constructs with described ultrahard polycrystalline extends through.

19. ultrahard polycrystalline structures according to aforementioned any one claim, wherein said layer is essentially plane, bending, arc or hemispheric.

20. according to any one of claim 1-17 ultrahard polycrystalline structure, wherein said ultrahard polycrystalline there is the longitudinal axis, and the described layer in described first area and/or described second area is in the angled plane of plane that extends through with the longitudinal axis of described PCD structure.

21. according to aforementioned any one claim ultrahard polycrystalline structure, the volume of wherein said first area is greater than the volume of described second area.

22. according to aforementioned any one claim ultrahard polycrystalline structure, layer described in wherein one or more is crossing with the working-surface that described ultrahard polycrystalline constructs or side surface.

23. according to aforementioned any one claim ultrahard polycrystalline structure, the respective PCD grade that wherein each layer is at least 1000MPa by one or more TRS is formed; Described PCD grade in adjacent layers has different thermal expansivity (CTE).

24. ultrahard polycrystalline structures according to claim 23, it is at least 3 × 10 that layer described in wherein one or more comprises CTE ^-6the PCD grade of mm/ DEG C.

25. according to aforementioned any one claim ultrahard polycrystalline structure, wherein said first area there is no that, for adamantine catalystic material, described part forms thermally-stabilised region at least partially.

26. ultrahard polycrystalline structures according to claim 25, wherein said thermally-stabilised region extends the degree of depth of at least 50 microns from the surface that described ultrahard polycrystalline constructs.

27. according to claim 25 or 26 ultrahard polycrystalline structure, wherein said thermally-stabilised region comprise maximum 2 % by weight for adamantine catalystic material.

28. 1 kinds for be used for earth's crust probing rotational shear drill bit or construct for the ultrahard polycrystalline of percussion bit, comprise and be attached to the ultrahard polycrystalline described in aforementioned any one claim on sintered carbide supporter and construct.

29. 1 kinds of methods forming ultrahard polycrystalline and construct, comprising:

A large amount of superhard material particle is provided, and by described a large amount of superhard particles arrangement to form the first area comprising multiple alternating layer, what each layer was independent has first part and second section, described first part has the first mean sizes, described second section has the second mean sizes, and the superhard material particle providing another a large amount of, to form the second area of contiguous described first area, thus form pre-sintered components (pre-sinter assembly); And

Under the hyperpressure of about 5.5GPa or larger and at the described superhard material temperature thermodynamically more stable than graphite, under the existence of the catalyst/solvent material for described superhard particles, process described pre-sintered components, described superhard material particle is sintered together to form polycrystalline superhard construction, described superhard particles demonstrates intergranular knot and is incorporated between described particle and limits multiple gap area, non-ly superhardly fills multiple described gap area at least partly mutually;

Described second area is attached on described first area by the intergrowth of superhard material particle, and the thickness of described first area is in the scope of about 5-300 micron; Wherein:

30. methods according to claim 29, wherein provide the described step of a large amount of superhard material particle to comprise and a large amount of diamond particles is provided, it has first part and second section, described first part has the first mean sizes, described second section has the second mean sizes, the median size of described first part is in the scope of about 10-60 micron, and the median size of described second section is less than the median size of described first part.

31. methods according to claim 30, the median size of wherein said second section is about 1/10 to 6/10 of the median size of described first part.

32. methods according to any one of claim 29-31, the median size of wherein said first part is about 10-60 micron, and the median size of described second section is about 0.1-20 micron.

33. methods according to any one of claim 29-32, wherein said first part relative to the weight ratio of described second section in the scope of about 50% to about 97%, described second section % by weight in the scope of about 3 % by weight to about 50 % by weight.

34. methods according to claim 33, wherein said first part is about 60:40 for the ratio of the weight percent of described second section.

35. methods according to claim 33, wherein said first part is about 70:30 for the ratio of the weight percent of described second section.

36. methods according to claim 33, wherein said first part is about 90:10 for the ratio of the weight percent of described second section.

37. methods according to claim 33, wherein said first part is about 80:20 for the ratio of the weight percent of described second section.

38. methods according to any one of claim 29-37, wherein saidly provide the step of a large amount of superhard material particle to comprise to provide the nonoverlapping particle of size distribution of a large amount of described first part and second section.

39. methods according to any one of claim 29-37, wherein saidly provide the step of a large amount of superhard material particle to comprise to provide three kinds or more kind granularity pattern to form the multimodulus particle comprising the particle diameter mixing with relevant median size.

40. methods according to any one of claim 29-39, it is an order of magnitude that the median size of wherein said part separates.

41. methods as described in claim 39 or 40, wherein said a large amount of superhard particles comprises the first part with about 20 microns of median sizes, the second section with about 2 microns of median sizes, has the Part III of about 200nm median size and have the Part IV of about 20nm median size.

42. 1 kinds of instruments, comprise the ultrahard polycrystalline structure according to any one of claim 1-28, and described instrument is used for cutting, grinding, grinding, boring, earth's crust probing, rock drilling or other abrasive applications.

43. instruments according to claim 42, wherein said tool kit is containing the drill bit for earth's crust spy or rock drilling.

44. instruments according to claim 42, wherein said tool kit fixes cut drill containing the rotation for oil and natural gas probing.

45. instruments according to claim 42, wherein said instrument is roller cone drill bits, drilling tool, bloat tool, cork drill or other earth's crust boring tool.

46. drill bit or cutting members or its assemblies comprising the ultrahard polycrystalline structure according to any one of claim 1-28.

47. 1 kinds of foregoing in fact structures of the ultrahard polycrystalline with reference to any one embodiment illustrated in the accompanying drawings.

The manufacture method of 48. 1 kinds of foregoing in fact structures of the ultrahard polycrystalline with reference to any one embodiment illustrated in the accompanying drawings.