CN103813872A

CN103813872A - Polycrystalline diamond construction and method for making same

Info

Publication number: CN103813872A
Application number: CN201280045436.1A
Authority: CN
Inventors: 奈德瑞·堪; 迈克尔·莱斯特·费史
Original assignee: Element Six Ltd; Element Six Abrasives SA
Current assignee: Element Six Ltd; Element Six Abrasives SA
Priority date: 2011-08-02
Filing date: 2012-08-01
Publication date: 2014-05-21
Also published as: WO2013017641A1; GB2503958A; US20180029130A1; US20140165476A1; GB201213706D0

Abstract

A polycrystalline diamond construction comprising a body of polycrystalline diamond material is formed of a mass of diamond grains exhibiting inter-granular bonding and defining a plurality of interstitial regions therebetween, and a non-diamond phase at least partially filling a plurality of the interstitial regions to form non-diamond phase pools, the non-diamond phase pools each having an individual cross-sectional area. The percentage of non- diamond phase in the total area of a cross-section of the body of polycrystalline diamond material and the mean of the individual cross- sectional areas of the non-diamond phase pools in the image analysed using an image analysis technique at a selected magnification is less than 0.7, or less than 0.340 microns squared, or between around 0.005 to 0.340 microns squared depending on the percentage of non-diamond phase in the total area of the cross-section of the polycrystalline diamond construction. There is also disclosed a method of making such a construction.

Description

Polycrystalline diamond stone structure and preparation method thereof

Technical field

The disclosure relate to polycrystalline diamond stone structure, its preparation method being formed by polycrystalline diamond (PCD) material and comprise described polycrystalline diamond stone structure especially but be not exclusively used in to the instrument of holing in soil.

Background technology

Polycrystalline diamond (PCD) material comprises the gap (interstice) between diamond crystals and the diamond crystals mutually combining in a large number.Can be by under the existence being generally such as the sintering aid of the metal of cobalt, nickel, iron or the alloy that contains one or more these metalloids, a large amount of diamond crystalses of assembling are carried out to high pressure and high-temperature process is prepared PCD body of material, and this sintering aid can promote mutually combining of diamond crystals.Described sintering aid also can be described as for adamantine catalyst material and adhesive material.Gap in the PCD material of sintering can be filled with residual catalyst material whole or in part.It is upper that PCD can be formed on base material (substrate), for example cobalt hard tungsten carbide base material, and it can be provided for the source of the Co catalysts material of PCD.

PCD material can be with acting on cutting, machining, mill, grind, hole or degenerate hard or coarse material for example rock, metal, pottery, composite and containing the grinding tool (abrasive compact) in the various instruments of wood materials.For example, in the drill bit that the instrument inserts that, comprises PCD material is widely used in holing in soil in oil and natural gas probing industry.

In many these application, in the time that described PCD material carries out rock or other workpiece or main body operation, its temperature can rise.The mechanical performance of PCD material trends towards deterioratedly as wearability, hardness and intensity in the time that temperature raises, and in PCD body of material, residual catalyst material may promote this deteriorated.

The wearability of wishing PCD body of material in the time being used as the grinding tool of all instruments as mentioned above improves, because this purposes that can allow cutter, drilling machine or wherein settle the machine of described grinding tool to be expanded.Conventionally reach this object by controlling variablees such as average diamond particles/crystallite dimension, total binder content, particle density.

For example, the wearability that improves super-hard compound material by reducing total particle size of ultra-hard particles component is well known in the art.But conventionally because these materials are made more wear-resisting, therefore they become more crisp or are easy to and break.

Therefore, can trend towards having poor impact strength or the resistance to rupture of reduction for improving the grinding tool that polishing machine designs.Balance between this impact resistance and the character of wearability makes, to what optimize, to have inherent self limiting especially for the design of the grinding tool structure of high request purposes.

In addition,, compared with thicker grainiess, because thinner grainiess can contain more solvent/catalyst or metal-to-metal adhesive conventionally, therefore they trend towards demonstrating the heat endurance of reduction.It is this that compared with fine grained structure, the reduction in optimal properties can cause the substantive issue in practical application, but the wearability that optimal performance need to improve in actual applications.

For head it off, the method for prior art has related to conventionally attempts by making in every way thin in the superhard abrasive bed of material and reaching compromise compared with the character combination of extra coarse solid particles.

Another kind of conventional scheme is conventionally from described PCD material, to remove catalyst/solvent or adhesive phase by acidleach.

From PCD plate, particularly from the required thicker PCD plate of existing application, effectively remove most metal catalysts/solvents normally very difficult and consuming time.The leaching degree of depth that reaches certain degree can spend in commercial infeasible time or need less desirable processing, for example, described PCD plate is carried out to acid treatment extremely or physics boring.

Be improved to and be equivalent to compared with coarse grain material for the character that can reach impact resistance and fatigue resistance, still keep the research and development of the grinding tool of the cracking frequency of good wearability and reduction is high expectations simultaneously.

Invention summary

From first aspect, provide a kind of polycrystalline diamond stone structure, the main body that it comprises the polycrystalline diamond abrasive compact being formed by following compositions:

A large amount of diamond crystalses, it demonstrates intergranular in conjunction with also limiting betwixt multiple interstitial areas, and

Non-diamond phase, it fills multiple interstitial areas at least in part to form non-diamond phase pond (pool), and each described non-diamond phase pond has area of section separately,

In the cross section gross area of the main body of wherein said polycrystalline diamond abrasive compact, the percentage of non-diamond phase is about 0 to 5%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, in the analysis image of the cross section through polycrystalline material main body, the mean value of the area of section separately in described non-diamond phase pond is for being less than approximately 0.7 square micron.

From second aspect, provide a kind of polycrystalline diamond stone structure, the main body that it comprises the polycrystalline diamond abrasive compact being formed by following compositions:

Non-diamond phase, it fills multiple interstitial areas at least in part to form non-diamond phase pond, and each described non-diamond phase pond has area of section separately,

In the cross section gross area of the main body of wherein said polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 5 to 10%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, in the analysis image of the cross section through polycrystalline material main body, the mean value of the area of section separately in described non-diamond phase pond is for being less than approximately 0.340 square micron.

From the 3rd aspect, provide a kind of polycrystalline diamond stone structure, the main body that it comprises the polycrystalline diamond abrasive compact being formed by following compositions:

In the cross section gross area of wherein said polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 10 to 15%, and

In the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 3000 times is analyzed, in the analysis image in the cross section through polycrystalline material main body, the mean value of the area of section separately in described non-diamond phase pond is for being less than approximately 0.340 square micron.

From the 4th aspect, provide a kind of polycrystalline diamond stone structure, the main body that it comprises the polycrystalline diamond abrasive compact being formed by following compositions:

In the gross area of the cross section of wherein said polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 15 to 30%, and

In the time using image analysis technology to take advantage of the image area of 960 pixels to analyze with the magnifying power and 1280 of approximately 10000 times, in the analysis image in the cross section through polycrystalline material main body, the mean value of the area of section separately in described non-diamond phase pond is approximately 0.005 to 0.340 square micron.

In some embodiments, the main body of described polycrystalline diamond abrasive compact has about 6mm or larger full-size.

In some embodiments, the main body of described polycrystalline diamond abrasive compact has about 0.3mm or larger thickness.

From the 5th aspect, the method for the preparation of polycrystalline diamond stone structure is provided, described method comprises:

The diamond crystals in a large number with the first average-size is provided;

Described a large amount of diamond crystals is set, makes itself and the body of material that is used to form base material form presintering assembly (pre-sinter assembly); And

About 7GPa or larger hyperpressure and diamond than graphite on thermodynamics under more stable temperature and the existence for adamantine catalyst material, process described presintering assembly, to be sintered together to form complete PCD structure by described diamond crystals with along the base material of interface and its combination; Described diamond crystals demonstrates intergranular in conjunction with also limiting betwixt multiple interstitial areas, and non-diamond is filled multiple interstitial areas mutually at least in part to form non-diamond phase pond, and each described non-diamond phase pond has area of section separately,

In the gross area of the cross section of the main body of wherein said polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 0 to 5%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, be less than approximately 0.7 square micron at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond; Or

In the gross area of the cross section of the main body of described polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 5 to 10%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, be less than approximately 0.340 square micron at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond; Or

In the gross area of the cross section of described polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 10 to 15%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 3000 times is analyzed, at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond for being less than approximately 0.340 square micron; Or

In the gross area of the cross section of described polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 15 to 30%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 10000 times is analyzed, be approximately 0.005 to 0.340 square micron at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond.

Accompanying drawing explanation

Below by the mode with embodiment and describe non-limiting embodiments with reference to the accompanying drawings, wherein:

Fig. 1 is the schematic diagram of the microstructure of PCD body of material;

Fig. 2 is the schematic diagram of the PCD goods that comprise the PCD structure being attached on base material;

Fig. 3 is the diagrammatic side view of the assembly embodiment that comprises the first and second structures;

Fig. 4 be for the preparation of superhard structure the pressure and temperature cycle embodiment the schematic diagram of part;

Fig. 5 to 9 be for the preparation of PCD structure the pressure and temperature cycle embodiment the schematic diagram of part; And

Figure 10 a and 10b are the processing images with the micrograph of the polishing section of the embodiment of the PCD body of material of different diamond density.

Detailed Description Of The Invention

As used herein, " polycrystalline diamond " (PCD) material comprises a large amount of diamond crystalses, wherein directly mutually combine to each other greatly, and wherein adamantine content is described material at least about 80 volume %.In an embodiment of PCD material, the gap between diamond crystals can be filled with the adhesive material comprising for adamantine catalyst at least in part.As used herein, " gap " or " interstitial area " is the region between the diamond crystals of PCD material.In the embodiment of PCD material, gap or interstitial area can substantially or be partially filled the material outside diamond, or described gap or interstitial area can be empty substantially.The embodiment of PCD material can comprise at least one district, removes thus catalyst material from gap, leaves the interstitial void (interstitial void) between diamond crystals.

The main body as used herein, " PCD structure " comprises PCD material.

As used herein, " metal " material is interpreted as the metal that comprises non-alloy or alloy form, and it has the characteristic properties of metal, as high conductivity.

As used herein, also can be called for adamantine solvent/catalyst material for adamantine " catalyst material ", refer to and under the thermodynamically stable pressure and temperature condition of diamond, can promote diamond film or the material of direct diamond-diamond (diamond-to diamond) symbiosis between diamond crystals.

Filler or adhesive material are interpreted as the material that refers to hole, gap or the interstitial area of filling whole or in part in polycrystalline structure.

The multi-modal size distribution (multi-modal size distribution) of great number of grains is interpreted as and refers to that described crystal grain has the size distribution that exceedes a peak, and each peak is corresponding to " mode " separately.Can be by more than one multiple crystal grain source is provided, each source comprises and has the crystal grain of different average-sizes substantially, and the crystal grain in described source or particle are blended together prepares multi-modal polycrystalline main body by coming from.In one embodiment, described PCD structure can comprise the diamond crystals with multi-modal distribution.

As used herein, term " total binder area " is expressed as the percentage of non-diamond phase in the cross section total cross-sectional area of polishing of analyzed PCD body of material.

With reference to Fig. 1, the main body of PCD material 10 comprises the gap 14 between diamond crystals 12 and the diamond crystals 12 directly mutually combining in a large number, and gap 14 can be filled with filler or adhesive material at least partly.

Fig. 2 has shown the embodiment as the PCD composite product 20 of cutter, and it is included in interface 24 and is attached to completely the main body of the PCD material 22 on base material 30.Described base material 30 can be formed by for example hard carbide material, and can be for example hard tungsten carbide, hard ramet, hard titanium carbide, hard molybdenum carbide or its mixture.Can be for example nickel, cobalt, iron or the alloy that contains one or more these metals for the binder metal of this type of carbide.Conventionally, the content of this adhesive is 10 to 20 quality %, but this amount can be low to moderate 6 quality % or less.Some binder metal can be infiltrated in the main body of polycrystalline diamond abrasive compact 22 in the forming process of goods 20.

Referring now to the example of the method for Fig. 3 to 9 description PCD goods 20 for the production of the main body that comprises PCD material 22 as shown in figs. 1 and 2.As shown in Figure 3, PCD structure (the second structure) 200 and hard carbide base material (the first structure) 300 adjacent settings, the relative first type surface that connects PCD structure 200 and base material 300 containing thin layer or the film 400 of Co adhesive material is to form the assembly wrapping in shell 100, for super-pressure and high temperature compacting (not shown).The CTE of the PCD material comprising in PCD structure 200 is approximately 2.5 × 10 ^-6/ ℃ to approximately 4 × 10 ^-6/ ℃, the CTE of the cobalt knot hard tungsten carbide material comprising in base material 300 is approximately 5.4 × 10 ^-6/ ℃ to approximately 6 × 10 ^-6/ ℃ (described CTE value is based on 25 ℃).In this embodiment, base material 300 and PCD structure 200 contain the adhesive material containing Co.Through estimating according to PCD grade, PCD material can have the Young's modulus of approximately 900 giga pascals to approximately 1400 giga pascals, and depend on to a great extent content and the composition of described adhesive material, described base material can have the Young's modulus of approximately 500 giga pascals to approximately 650 giga pascals.

Fig. 4 has shown according to the signal phase diagram of the carbon of pressure p and temperature T axle, has shown the line D-G of thermodynamical equilibrium between diamond and graphite allotrope, more stable on diamond thermodynamics in Gai Tu D district, and more stable on Gai Tu G district graphite thermal mechanics.Line S-L schematically demonstrates described adhesive material and melts or curing temperature under each pressure, and this temperature trends towards improving with the increase of pressure.Should notice that this temperature is probably different from the relevant temperature of the adhesive material of pure form (pure form), due to come from adamantine carbon existence and or the WC expection of some dissolvings can reduce this temperature because the existence expection of carbon in solution reduced the fusing point of cobalt and other metal.Forming under the condition of described PCD material by the diamond crystals aggregation of sintering and base material adjacent setting, the assembly of describing with reference to Fig. 3 can be in approximately 7.5 giga pascals to the temperature of the first pressure P 1 of approximately 8 giga pascals and approximately 1450 ℃ to approximately 1800 ℃.On the one hand under sintering pressure and sintering temperature, the original position of described PCD forms and makes on the other hand described assembly stand can there is no substantial interruption between the first pressure P 1, being more precedence relationship between the reduction of pressure and temperature in the Phase I of related fields and II as this method.Under sintering temperature, Co adhesive material can be melted and expect and promote the direct symbiosis sintering (inter-growth sintering) of described diamond crystals to form described PCD material, under sintering temperature and sintering pressure, be included in diamond in described PCD material substantially more more stable on thermodynamics than graphite.

With further reference to Fig. 4, the pressure and temperature of described assembly can be reduced to ambient level in Phase I, II and III.In specific embodiment, be reduced in approximately 1350 ℃ to approximately 1500 ℃ in temperature, described pressure can be reduced to second pressure P 2 of approximately 5.5 giga pascals to approximately 6 giga pascals from the first pressure P 1 in Phase I, to guarantee the maintenance of pressure-temperature condition, make diamond more stable on thermodynamics than graphite, and described adhesive material keep basic fusing.Then in Phase, described temperature can be reduced to the temperature within the scope of approximately 1100 ℃ to approximately 1200 ℃, keeps on the online D-G of pressure, in the D of diamond stability region, to solidify described adhesive material simultaneously; In Phase I, can pressure and temperature be down to ambient level with the whole bag of tricks.Then can from press device, remove described PCD structure.Should notice that Phase I, II and III, only for key-drawing 4, may significantly not distinguish between these stages in practice.For example, these stages can be smoothly enter into another from one, and do not keep pressure and temperature condition substantial in the time that the stage finishes during.As selection, the some or all of stages can be different, and pressure and temperature condition can keep a period of time in the time that the stage finishes.

In certain embodiments, for example can prepare and provide in 1 time original position of the first pressure P as following manner for the preparation of the presintering assembly of PCD or PCBN structure.Cover (cup) can be provided, and wherein the aggregation of multiple diamonds or CBN crystal grain and base material can be loaded in this cover, and the interior shape of cover is generally described PCD or the needed shape of PCBN structure (consider in sintering step and may deform).Described aggregation can comprise substantially loose diamond or CBN crystal grain or contain diamond or the front body structure containing CBN, such as granule, dish, wafer or plate.Described aggregation can also comprise for adamantine catalyst material, for the host material of PCBN, or for the precursor material of catalyst or host material, it can mix with diamond or CBN crystal grain, and or deposits on the surface of diamond or CBN crystal grain.Described diamond or CBN crystal grain can have at least about 0.1 micron and or the average-size of approximately 75 microns at the most, and can be essentially single mode or multi-modal.Described aggregation can also be containing being useful on the additive that slows down abnormal diamond or CBN grain growth, or described aggregation can be substantially devoid of catalyst material or additive.Alternatively or additionally, can provide catalyst or host material for example, as another source of cobalt, the adhesive material in hard carbide base material.Enough aggregations can be placed in described cover, then base material can be embedded in cover, near-end pushes described aggregation.The presintering assembly that comprises described aggregation and described base material can wrap in the metallic sheath that comprises cover, heat-treat the organic bond that may comprise with in burning-off aggregation, and encapsulate in the shell (it can be described as container (capsule)) that is suitable for super-pressure compacting.Described shell can be positioned in the equipment of applicable super-pressure compacting, and stands sintering pressure and sintering temperature comprises and base material adjacent to form, and by the PCD connecting containing cobalt binder film of fusing or the assembly of PCBN structure.In the embodiment such as these, described sintering pressure can be considered the first pressure P 1.

In exemplary configuration, can in press device, be prepared and provide for 1 time in the first pressure P as follows for the preparation of the presintering assembly of PCD or PCBN structure.Can provide PCD or PCBN structure by presintering in aforesaid hyperpressure and ultra-high temperature process.Described PCD or PCBN structure can contain adhesive or the host material containing cobalt of the interstitial area that is arranged in diamond that PCD or PCBN material comprise or CBN intergranule.The in the situation that of PCD material, described PCD structure can have the region of at least one basic adhesive-free material.For example, described PCD structure can be through processing in acid, with from least adjacent with the surface of PCD structure gap or substantially run through in the gap of whole volume of PCD structure (or these may in distortion) remove adhesive material, leave the region that at least one can contain hole (pores) or room (voids).In certain embodiments, the available packing material that may comprise or may not comprise adhesive material is filled the room forming like this.Described PCD or PCBN structure can be placed facing to base material, then the prebuild assembly obtaining can be wrapped in the shell that is suitable for super-pressure compacting.Described shell can be positioned in applicable super-pressure press device, be then that at liquid temperature, (being under the condition of region D of Fig. 4) stands the first pressure P 1 at described adhesive material.

Below with reference to Fig. 5 to 9, the embodiment of the method for the preparation of the embodiment of PCD structure is described.In every width figure, partial pressure and temperature cycle are only shown, described part starts from the first pressure P 1 separately, under this pressure, make to be included in the PCD material forming in described structure by sintering, and described part is reduced to and is enough to cure adhesive material and pressure and after the second pressure P 2 declines, finishes in temperature.

In certain embodiments, can provide presintering assembly, comprise and be positioned at the aggregation of tying multiple diamond crystalses of the surperficial adjacent place of the base material of hard carbide containing cobalt.Described diamond crystals can have the average-size of approximately 0.1 to approximately 40 micron.Described presintering assembly can be encapsulated in the container for super-pressure press device, and described container can be loaded into described press device.Described container can at room temperature be pressurized at least about the pressure of 6.5 giga pascals and be heated to the temperature of approximately 1500 ℃ to approximately 1600 ℃, this temperature substantially exceeds the fusing point of the cobalt-based adhesive material (under described pressure) being included in base material, and causes the fusing of cobalt material.At this temperature, described presintering assembly can be placed at the first pressure P 1 time (result raising as temperature at least partly, comparable 7 giga pascals of P1 are slightly higher) within the scope of approximately 7.5 to approximately 10 giga pascals.Described the first pressure P 1 and described temperature can keep substantially at least about 1 minute, in any case or keep the sufficiently long time so that described diamond crystals is sintered together (in these embodiments, described sintering pressure will substantially for P1).Then described pressure can be reduced to the second pressure P 2 within the scope of approximately 5.5 to approximately 8.5 giga pascals from the first pressure P 1.Along with temperature is reduced to the solidification temperature of described adhesive material, described the second pressure also can be reduced to described adhesive material and start curing pressure.

The temperature of described presintering assembly can reduce with pressure simultaneously, and condition is that its maintenance is greater than described cobalt-based adhesive material by completely crued temperature.Along with pressure reduces from P2, temperature also can be reduced to the curing line of described cobalt-based adhesive material, causes solidifying of described adhesive material.In these specific embodiments, reduce from described the first pressure P 1 described pressure basic continous, there is no pause quite of a specified duration through described the second pressure P 2 and the curing pressure of described adhesive material.Described pressure and or temperature reduce speed be variable, or in described pressure and temperature arbitrary or both reduce speed can be substantially invariable, at least until described cobalt-based adhesive material solidify.Also can reduce temperature in basic continous ground, at least until it is enough low to make substantially all cobalt-based adhesive materials solidify.Then temperature and pressure can be down to environmental condition, described container be removed from described super-pressure press device, and remove described structure from described container.Described structure can comprise the PCD structure of the sintering being connected on described base material and form, with same general step by multiple diamond crystalses being sintered together to form described PCD material in described PCD structure is connected on described base material.The thin layer that is rich in cobalt can be present between described PCD structure and described base material, and these structures are linked together.

In concrete illustrative methods illustrated in fig. 5, described the first pressure P 1 is approximately 7.6 giga pascals, and under described the first pressure, described temperature is approximately 1500 ℃ to approximately 1600 ℃, and exemplary the second pressure P 2 is approximately 6.8 giga pascals.

In concrete illustrative methods illustrated in fig. 6, described the first pressure P 1 is approximately 7.7 giga pascals, and under described the first pressure, described temperature is approximately 1500 ℃ to approximately 1600 ℃, and exemplary the second pressure P 2 is approximately 6.9 giga pascals.

In concrete illustrative methods illustrated in fig. 7, described the first pressure P 1 is approximately 7.8 giga pascals, and under described the first pressure, described temperature is approximately 1500 ℃ to approximately 1600 ℃, and exemplary the second pressure P 2 is approximately 6.9 giga pascals.

In concrete illustrative methods illustrated in fig. 8, described the first pressure P 1 is approximately 7.9 giga pascals, and under described the first pressure, described temperature is at approximately 1500 ℃ to approximately 1600 ℃, and exemplary the second pressure P 2 is approximately 5.5 giga pascals.

In the illustrative methods shown in Fig. 9, described the first pressure P 1 is approximately 9.9 giga pascals, and under described the first pressure, described temperature is approximately 2000 ℃, and exemplary the second pressure P 2 can be approximately 8.1 giga pascals.

Should note being shown under the existence of carbon the fusing of cobalt-based adhesive material and the line S-L of solidification temperature based on using valid data calculate and estimate at Fig. 5 to 9 middle finger.In practice, may preferably not exclusively depend on the value of calculating based on S-L, obtain for the fusion temperature of specific adhesive material and solidification temperature and the pressure that uses but carry out trial test and error test.

The method for gaging pressure and temperature cycle as shown in Fig. 5 to 9 is to use the general knowledge of the fusion temperature of so-called K type (K-type) thermocouple and copper (Cu) and silver (Ag) to measure.Be published in the geophysical research journal (Journal of Geophysical Research) in the geophysics alliance of the U.S. (American Geophysical Union) on November 10th, 1979 by P.W.Mirwald and G.C.Kennedy in the data that use the Cu of K type thermocouple measurement up to 60 kPas and the fusing point of Ag, 84 volume B12 phases, 6750 to 6756 pages, name is called " gold, silver and the fusion curve of copper under 60-Kbar pressure-study again (The melting curve of gold, silver and copper to60-Kbar pressure – a reinvestigation) " article in.K type thermocouple also can be described as " nichrome-nickel alumin(i)um alloy " thermocouple, and wherein said " nichrome " composition comprises 90% nickel and 10% chromium, and described " nickel alumin(i)um alloy " composition comprises 95% nickel, 2% manganese, 2% aluminium and 1% silicon.Described method comprises to be inserted the abutment of a K type thermocouple in the main body being substantially made up of Cu, and the abutment of the 2nd K type thermocouple is inserted in the main body being substantially made up of Ag, and described two main bodys are positioned over to the proximity of described presintering assembly in described container.Be recorded in the reading that comes from two thermocouples of at least a portion in whole described pressure and temperature cycle, and according to the data processing of described announcement and change described reading to pressure and temperature value.

In certain embodiments, described structure can comprise polycrystal cubic boron nitride (PCBN) structure that is connected to cobalt knot hard carbide base material.In some illustrative methods, can provide the aggregation that comprises cubic boron nitride (CBN) crystal grain.Described CBN crystal grain can have at least about 0.1 micron and the average-size of approximately 30 microns at the most.Described aggregation can comprise tungsten carbide crystal grain and or be used to form precursor (pre-cursor) material of matrix, in described matrix, in the PCBN material that described CBN crystal grain dispersibles at sintering.In certain embodiments, the mixture of the adhesive material that described aggregation can comprise cubic boron nitride powder and contain Ti, Al, W or Co, and use plasticiser material that described mixture is cast to plate (sheets).In certain embodiments, described superhard structure can comprise basic PCBN material described in international application no WO2007049140, and can be prepared by following method, described method comprises provides the powdered composition that is suitable for PCBN production, described powder packets contains CBN particle and the pulverous adhesive material of at least 80 volume %, and described powdered composition is milled.Described composition can comprise the CBN particle that exceedes an average particle size particle size.In various embodiments, the average-size of described CBN particle can be approximately 12 microns or 2 microns at the most at the most.Described adhesive material can comprise the one or more phases that contain aluminium, silicon, cobalt, molybdenum, tantalum, niobium, nickel, titanium, chromium, tungsten, yttrium, carbon and iron.Described adhesive material can comprise in powder and aluminium, silicon, cobalt, nickel, titanium, chromium, tungsten, yttrium, molybdenum, niobium, tantalum, carbon and iron more than one uniform solid solution.

Various super-pressure compactings be can use, belt, many anvils of tetrahedron formula, many anvils of cube formula, fertile gram type (walker-type) or Tuo Luoyi Dare (torroidal) compacting comprised.Likely depend on the required pressure and temperature of superhard material described in the volume of superhard structure to be prepared and sintering for the selection of compacting type.For example, the compacting of tetrahedron and cube can be suitable for going out at sintering at least about 7 giga pascals or under at least about the pressure of 7.7 giga pascals PCD and the PCBN material of a large amount of viable commercial.

Some case methods can comprise by PCD or PCBN structure at least about 500 ℃, at least about 600 ℃ or at least about the temperature of 650 ℃ under heat treatment at least approximately 5 minutes, at least about 15 minutes or at least about 30 minutes.In some embodiments, described temperature can be at the most approximately 850 ℃, approximately 800 ℃ or approximately 750 ℃ at the most at the most.In some embodiments, described PCD structure can be heat-treated to how about 120 minutes or approximately 60 minutes at the most.In one embodiment, described PCD or PCBN structure can be heat-treated under vacuum.For example U.S. Patent number 6,517,902 disclose a kind of for thering is the PCD that is attached to hard tungsten carbide base material with the cobalt binder treated forms in the face of the prefabricated elements of layer (facing table).Described base material comprises interface zone, and wherein the cobalt binder of at least 30 percents by volume is the closely packed crystal structure of hexagonal.

In the situation that not wishing to be entangled in particular theory, because residual stress in described structure is lowered, therefore described method can make the possibility of superhard structure breaking or frequency reduce.

Be described in more detail below non-limiting example.

Embodiment 1

Be prepared as follows the PCD insert for rock-boring drill bit.

Preparation presintering assembly, the aggregation of multiple diamond crystalses that described assembly comprises the near-end that is positioned over common cylindricality hard carbide base material.Described aggregation comprises multiple wafers, and it comprises the diamond crystals being dispersed in organic bond material, and described diamond crystals has at least about 15 microns and the average-size of approximately 30 microns at the most.The WC grain that combines containing Co adhesive material of passing through that described base material comprises approximately 90 % by weight.Described presintering assembly is enclosed in metallic sheath, and the organic bond of heating to comprise in wafer described in burning-off, and the presintering assembly of described band cover is encapsulated in container, for many anvils of high pressure high temperature press device.

Make temperature that described presintering assembly stands the pressure of approximately 7.7 giga pascals and approximately 1550 ℃ so that described diamond crystals direct sintering each other, to form PCD material layer, this PCD material layer is connected to described base material near-end by the fusing from base material containing cobalt binder material membrane.By pressure decreased to approximately 5.5 giga pascals temperature is reduced to approximately 1450 ℃, remain on the diamond comprising in PCD is Thermodynamically stable (with respect to graphite, graphite is the more soft allotrope of carbon) and the condition of adhesive material in liquid phase simultaneously.Then temperature is reduced to approximately 1000 ℃ and comprises with cure adhesive material formation the structure that is attached to the PCD layer of base material by curing adhesive material, then pressure and temperature is down to environmental condition.

Then by described structure be substantially non-oxidizing atmosphere and being, under environmental pressure, to heat-treat approximately 2 hours at 660 ℃ substantially, be then cooled to room temperature.After heat treatment, in PCD layer, there is no obvious crackle.

By grinding and polishing, described structure is processed to be provided for the insert of rock-boring drill bit.

As a comparison, according to the reference structure of preparing as described below.Prepare presintering assembly according to the content of the above-described embodiment about presintering assembly.Make presintering assembly stand the temperature of the pressure of approximately 7.7 giga pascals and approximately 1550 ℃ so that described diamond crystals carrys out mutual direct sintering to form PCD material layer, this PCD material layer is connected to described base material near-end by the fusing from base material containing cobalt binder material membrane.Cool the temperature to approximately 1000 ℃ and comprise to solidify described adhesive material and to form the structure that is attached to the PCD layer of described base material by curing adhesive material, then pressure and temperature is down to environmental condition.Described structure, being non-oxidizing atmosphere substantially and being, under environmental pressure, to heat-treat approximately 2 hours at 660 ℃ substantially, is then cooled to room temperature.After heat treatment, there are seven obvious crackles in the side of PCD layer.

Embodiment 2

Be prepared as follows the PCD insert for rock-boring drill bit.

Preparation presintering assembly, described assembly comprises the PCD structure that has general category disk shape and be disposed at the near-end of common cylindricality hard carbide base material.Prepare PCD structure being included in the front step that under the hyperpressure and high temperature that is less than approximately 7 giga pascals, (diamond is more stable on thermodynamics than graphite at this temperature) is sintered together the aggregation of multiple diamond crystalses.The WC grain that combines containing Co adhesive material of passing through that described base material comprises approximately 90 % by weight.Described presintering assembly is enclosed in metallic sheath, and the organic bond of heating to comprise in wafer described in burning-off, and the presintering assembly of described band cover is encapsulated in container, for many anvils of high pressure high temperature press device.

Make temperature that described presintering assembly stands the pressure of approximately 7.7 giga pascals and approximately 1550 ℃ to change the microstructure of described PCD structure.By pressure decreased to approximately 5.5 giga pascals temperature is reduced to approximately 1450 ℃, remain on the diamond comprising in PCD is Thermodynamically stable (with respect to graphite, graphite is the more soft allotrope of carbon) and the condition of adhesive material in liquid phase simultaneously.Then temperature is reduced to approximately 1000 ℃ and comprises with cure adhesive material formation the structure that is attached to the PCD layer of base material by curing adhesive material, then pressure and temperature is down to environmental condition.

Then by described structure at basic non-oxidizing atmosphere be under environmental pressure substantially, heat-treat approximately 2 hours then cooling room temperature at 660 ℃.After heat treatment, in PCD layer, there is no obvious crackle.

To briefly explain some term used herein and concept

As used herein, " superhard " refers to the Vickers hardness of at least 25 giga pascals.Synthetic and natural diamond, polycrystalline diamond (PCD), cubic boron nitride (cBN) and polycrystalline cBN(PCBN) material is the example of superhard material.Synthetic (synthetic) diamond, also referred to as artificial (man-made) diamond, is the diamond being produced.

As used herein, PCBN material comprise be scattered in containing metal and or the matrix of ceramic material in cubic boron nitride (cBN) crystal grain.

PCD material comprises in a large number the diamond crystals of (multiple aggregations), and wherein major part is directly together with each other, and wherein adamantine content is described material at least about 80 volume %.Gap between diamond crystals can be filled with the adhesive material comprising for the synthesis of adamantine catalyst material at least partly, or these gaps can be empty substantially.(also can be described as solvent/catalyst material for the synthesis of adamantine catalyst material, reflect following understanding, described material can promote to realize catalysis or solvent function aspect the growth of diamond crystals and the sintering of diamond crystals) can on thermodynamics, under more stable temperature and pressure, promote at synthetic or natural diamond growth and or the direct symbiosis of synthetic or natural diamond crystal grain of diamond synthesis crystal grain than graphite.Example for adamantine catalyst material is Fe, Ni, Co and Mn, and contains some alloy of these compositions.The main body that comprises PCD material can comprise at least one region, from described gap, is removed by this region catalyst material, leaves the interstitial void between diamond crystals.Can prepare the PCD material of various grades.As used herein, PCD grade is the variant of PCD material, it is characterized in that following aspect, i.e. the volume content of the interstitial area between the volume content of diamond crystals and size, diamond crystals and can be present in the composition of the material in described interstitial area.Different PCD grades can have different microstructures and different mechanical properties, such as elasticity (or Young) modulus E, elastic modelling quantity, cross-breaking strength (TRS), toughness (such as so-called K1C toughness), hardness, density and thermal coefficient of expansion (CTE).Different PCD grades also can be different in purposes.For example, the wear rate of different PCD grades may be different with resistance to fracture.

What heat-staple PCD material comprised at least a portion or volume exceedes approximately 400 ℃ being exposed to, or even exceedes the part that does not demonstrate the degeneration of substantial structure deterioration or hardness or wearability after the temperature of approximately 700 ℃.For example, contain be less than approximately 2 % by weight catalytic activity form (for example, with element morphology) for adamantine catalyst metals as Co, Fe, Ni, Mn PCD material can be heat-staple.Substantially the PCD material that does not contain the catalyst material of catalytic activity form is the example of thermally stable P CD.For example, wherein said gap is room or to use at least partly the PCD material of filling such as the ceramic material of SiC or such as the salt material of carbonate compound can be heat-staple substantially.The PCD structure with at least one important area can be described as thermally stable P CD, exhaust from this region for adamantine catalyst material, or wherein catalyst material as the relatively SA form of catalyst.

Other example of superhard material comprises that some contains the composite of diamond or cBN crystal grain, and diamond or cBN particle combine by comprising such as the ceramic material of carborundum (SiC) or for example, such as the matrix of the hard carbide material of the WC material (described in U.S. Patent number 5453105 or 6919040) of Co combination.For example, the diamond of some SiC combination can comprise the diamond crystals in SiC matrix (Si beyond its a small amount of SiC form that can contain) that is scattered at least about 30 volume %.The example of the diamond of SiC combination is described in U.S. Patent number 7008672,6709747,6179886,6447852 and International Publication No. WO2009/013713.

Young's modulus is a type of elastic modelling quantity, is within material list reveals the flexible range of stress, in response to the measurement to uniaxial strain of simple stress.The method of measuring Young's modulus E is by using the horizontal and vertical key element (component) of ultrasonic measurement sound through the speed of material.

As used herein, PCD structure 22,200 or base material 30,300, or the thickness of the some parts of PCD structure or base material is to be substantially perpendicular to the measured thickness in interface 24.In some embodiments, the main body of described PCD structure or PCD material 22,200 can have common thin slice, dish or class disk shape, or is the general type of layer.In some embodiments, described PCD structure 22,200 can have at least about 0.3mm, at least about 0.5mm, at least about 0.7mm, at least about 1mm, at least about 1.3mm or at least about the thickness of 2mm.In one embodiment, described PCD structure 22,200 can have about 2mm to the thickness within the scope of about 3mm.

In some embodiments, described base material 30,300 can have the general shape of thin slice, dish or post, and can be generally cylindrical shape.Described base material 30,300 can have the axial width of the axial width of the main body that is for example at least equal to or greater than PCD material 22,200, and can be for example at least about 1mm, at least about 2.5mm, at least about 3mm, at least about 5mm or even at least about the thickness of 10mm.In one embodiment, described base material 30,300 can have at least thickness of 2cm.

Described PCD structure 22,200 can for example only be attached on base material 30,300 in one side, and the reverse side of described PCD structure is not attached on base material 30,300.

In some embodiments, the full-size of the main body of PCD material 22,200 is about 6mm or larger, and for example, in the embodiment that is column in the main body of PCD material, the diameter of described main body is about 6mm or larger.

In some distortion of described method, before sintering, can be by diamond particles/crystal grain of assembling in a large number conventionally to have at least about 0.6mm, at least about 1mm, at least about 1.5mm or even arrange according to the surface of base material at least about the form of the layer of the thickness of 2mm.In the time of sintering crystal grain under super-pressure, the thickness of these a large amount of diamond crystalses may significantly reduce.

The ultra-hard particles using in the method can be source natural origin or artificial.The mixture of ultra-hard particles can be multi-modal, and it can comprise diamond particles or crystal grain can distinguish the mixture of different multiple parts in its average particle size particle size.Typically, the quantity of part can be:

The particular case of two parts

Three or more parts.

" average grain/crystallite dimension " refers to that each particle/crystal grain has the size range of the average particle/crystallite dimension of representative " on average ".Therefore,, although have the particle/crystal grain of limited quantity higher or lower than the size of this appointment, most particle/crystal grain can be close to described average-size.Therefore, the summit of distribution of particles is in the size of specifying.Be generally self single mode for the distribution of sizes of each superhard particles/crystallite dimension part, but may in specific situation, be multi-modal.In sintered article, term " averaged particles crystallite dimension " will make an explanation in a similar fashion.

The main body of the polycrystalline diamond abrasive compact of being prepared by an embodiment as shown in fig. 1, additionally has adhesive and exists mutually.This adhesive material is preferably the catalyst/solvent for superabrasive particles used.Know in the art for adamantine catalyst/solvent.In adamantine situation, described adhesive is preferably cobalt, nickel, iron or contains one or more the alloy in these metals.Can enter in these a large amount of abrasive grains by infiltration in sintering processes process, or introduce this adhesive as the mixture in these a large amount of abrasive particles with the form of particulate.Infiltration can be by the pad of the binder metal providing or layer, or by occurring in carbide supported thing.Conventionally use the combination of mixing and infiltration processing.

In high pressure-temperature processing procedure, catalyst/solvent material melts and moves through described goods layer, plays catalyst/solvent effect and causes that superhard particles mutually combines together.Once therefore, after preparation, the matrix of the cohesion that described PCD structure has comprised superhard (diamond) particle mutually combining together, forms the superhard polycrystalline composite materials with the many gap or the ponds that accommodate adhesive material as above thus.Therefore in essence, final PCD structure has comprised two-phase composite material, and wherein said super hard abrasive diamond has comprised a phase, and described adhesive (non-diamond phase) is another phase.

In one form, be generally adamantine and describedly superhardly account for mutually 80%-95 volume %, and described solvent/catalyst material is other 5% to 20%.

The relative distribution of described adhesive phase and be filled with the room of this phase or the quantity in pond is limited by the size and dimension of diamond particles to a great extent.

Described adhesive (non-diamond) can help improve the impact resistance of how frangible abrasive material phase mutually, but be far the structure of more weak and less part because adhesive has represented wearability mutually conventionally, therefore the adhesive of a large amount adversely can trend towards affecting wearability mutually.In addition, described adhesive is also active solvent/catalyst material mutually, improve its amount in described structure can balance described in the heat endurance of goods.

Figure 10 a and 10b are the examples of the treated SEM image of PCD material polishing area, with diamond intensity 0(Figure 10 a) and diamond intensity 15(Figure 10 b) demonstrate the border between diamond crystals.These boundary lines provide by image analysis software and for example, for measuring the surface area of the non-diamond phase (adhesive) total in the cross section through the main body of PCD material and being designated as separately the surface area in each non-diamond phase (interstitial) region of black region.For the analysis that will carry out below and the result that will obtain, the described cross section through PCD body of material can be to pass in any direction of described PCD body of material.Be described in more detail below described image analysis technology.

As non-limiting example, can be by a part of cutting described PCD composite product by the mode of line cutting (wire EDM), the cross section showing in Figure 10 a and 10b is exposed to for observing.Can pair cross-section carry out polishing and think by microscope and observe and prepare as SEM (SEM), and obtain a series of micro-images of type shown in Fig. 5 a and 5b.Each image can be analyzed by the mode of image analysis software, to determine between total binder area and diamond crystals adhesive area separately.Determine the value of total binder area and adhesive area separately by carrying out statistical evaluation based on a large amount of collection images with SEM shooting.

The magnifying power of selecting for microstructure analysis has remarkable impact to the accuracy of the data that obtain.Imaging under lower magnifying power is larger particle or the chance of feature in providing and having sampled microstructure typically; but because less particle or feature are not fully distinguished necessarily under this magnifying power, therefore described imaging may be tending towards being not enough to representative less particle or feature.By contrast, given resolution ratio and the detailed measurements to meticulous level feature thus compared with high power, but it can trend towards the larger feature of sampling, thereby described in making, larger feature runs through the border of image, makes thus this feature fully do not measured.Therefore understand, importantly select applicable magnifying power for any quantitative Microbeam Analysis Techniques.Therefore determine suitability by the size of the feature being characterized.Inquire in more detail below for the selected magnifying power of various measurements described herein.

Unless there is other explanation herein, in PCD body of material, the size of total binder region and adhesive area separately refers on the surface of the main body that comprises PCD material or runs through the size of measuring on its cross section, and does not apply three-dimensional correction (stereographic correction).For example, carry out described measurement by the mode of the graphical analysis carried out on polished surface, and do not carry out Saltykov correction in data as herein described.

Measuring by the mode of graphical analysis in the measurement of mean value of quantity or other statistical parameter, use a few width images of the different piece of surface or cross section (hereinafter referred to as sample) to improve reliability and the accuracy of statistics.The quantity that is used for the image of measuring given amount or parameter can be for for example between 10 to 30.If the sample of analyzing is that even so the situation of PCD, depends on magnifying power, can think that 10 to 20 width images can represent this sample well enough uniformly.

The resolution ratio of image needs enough high so that described intergranular and interphase boundary energy are clearly recognized, and for illustrated herein measurement, the image area of 960 pixels is multiplied by use 1280.

In described statistical analysis, the zones of different in the body surfaces that comprises described PCD material is taken 15 width images, and carries out statistical analysis for every width image.

The mode of the scanning electron microscopy picture (SEM) of taking by use backscattered electron signal obtains the image for graphical analysis.Select back scattering pattern, so that the high-contrast based on different atomicities to be provided, and reduce the susceptibility (compared with the second electronic imaging pattern) that effects on surface damages.

Some key factors for picture catching are identified.They are:

SEM voltage, it is for measurement object as herein described, keeps constant and is about 15kV;

Operating distance, also keeps constant and for about 8mm;

Image definition;

Sample quality of finish;

Picture contrast, selects clearly to separate described micro-structural feature to it;

Magnifying power (should change and state as follows bright according to different diamond grain size);

The quantity of photographic images.

In view of above-mentioned condition, the image analysis software using can be separated described diamond phase with adhesive to identification mutually, and is taking backscatter images with respect under approximately 45 ° of sample edge.

The magnifying power using in graphical analysis should be selected by this way, that is: make target signature be differentiated fully and be described by the pixel of effective dose.In PCD graphical analysis, measure the various features of different size and distribution simultaneously, it is unpractiaca therefore using magnifying power separately for each target signature.

In the situation that there is no reference measure result, determine that for each pattern measurement optimum magnifying power is difficult.The magnifying power that different operators uses may be different.Therefore, propose one for selecting the step of magnifying power.

Measure the size of the diamond crystals of statistically significant quantity in microstructure, and average.

As used herein, about crystal grain or particle, unless otherwise indicated or hint, term " size " refers to and use image analysis technology from the side or the length of the crystal grain of observing in cross section.

Determine that the scope of describing the pixel count of this average length and determine pixel value is with fixed power.

In image analysis technology, original image is converted to gray level image.By guaranteeing that diamond peak strength is set picture contrast between appearing at 15 and 20 in grey level histogram.

As mentioned above, a few width images of the different piece in shooting surface or cross section improve reliability and the accuracy of statistics.For example, for the measurement in total non-diamond phase (adhesive) region, amount of images is more, and its result is considered to more accurate.For example, adopt approximately 15000 measurements, every width image 1000 times, totally 15 width images.

The step that image analysis program adopts can be summarized as described below conventionally:

1, original image is converted to gray level image.By guaranteeing that diamond peak strength is set picture contrast between appearing at 10 and 20 in grey level histogram.

2, use automatic threshold feature (auto threshold feature) to carry out image described in binary system and obtain particularly the clearly resolution ratio of diamond phase and adhesive phase.

3, in this analysis, adhesive is main target phase.

4, use and come from Soft Imaging

the trade mark of GmbH(Olympus Soft Imaging Solutions GmbH) the software of trade name analySIS Pro, and from described analysis, get rid of the particle on any contact image border.This need to be to the suitable selection of image magnification ratio:

If a. too low, can reduce fine grain resolution ratio.

If b. too high:

I. reduce the efficiency that coarse grain separates.

Ii. a large amount of coarse grains is cut off by the profile of image (boarder), therefore only analyzed these crystal grain compared with small part.

Iii. therefore must analyze more image to obtain the upper significant knot of statistics

Really.

5, each particle finally represents by the quantity of the contiguous pixels that forms it.

6, AnalySIS software program continues the each particle in detection analysis image.This step can repeat automatically for a few width images.

7, obtain a large amount of available Output rusults.This Output rusults can further carry out post processing, for example use statistical analysis software and/or carry out further signature analysis, the analysis of the mean value of for example mean value in the total binder region for definite all images described below and adhesive area separately.

If use suitable threshold transition method, except rounding relevant little error up to numerical value, described image analysis technology is unlikely further introduced the error of meeting actual influence to the accuracy of these measurements in measurement.In this analysis, use the assembly average of described total binder region and adhesive area separately, because according to central-limit theorem (Central Limitation Theorem), except when the square amount (moments) of estimator of parent distribution is not while existing, no matter therefrom obtain the situation of the distribution of average, along with the increase of sample size, the distribution of average trends towards normal distribution.In statistical engineering, all actual distribution have the square amount of restriction, and therefore Central Limit Theorem is applicable to this situation.Therefore think that it is suitable using assembly average.

Identify non-diamond (for example adhesive or catalyst/solvent) phase region or pond separately by above-mentioned standard picture analysis tool, use electron microscope will its region from described superhard phase or pond, easily identify.Sue for peace to determine total non-diamond phase area (in square micron) in the cross-sectional image of analyzing by the area of the binder pool separately in the area of the whole micro-image to by analysis.

Then the distribution of these data that gather is carried out to statistical evaluation, then determine arithmetic mean of instantaneous value.Calculate thus total binder pool area average in the surface of the microstructure of analyzing.

Based on formation condition, expectation Microstructure Parameter can slightly be done to change to another region from of an abrasive product region.Therefore, carry out microstructure imaging to sample typically the great majority of the super-hard compound material part of described goods.

Other non-limiting example is described now.As three groups of samples of following preparation: prepare multi-modal (three mode) diamond powder mixture of the average diamond grain size with approximately 13 μ m of q.s and the cobalt admixture (admix) of 1 % by weight, to provide each sample about 2g admixture.Then will pour or be placed in addition cup (Niobium inner cup) in niobium into for the admixture of each sample.The hard carbide base material that cobalt content is about to 13 % by weight and has a non-planar interface is positioned on the mixture of powders in each interior cup.Titanium cup is turned over and is placed in this structure, and described assembly is sealed to prepare a cylinder (canister).Described cylinder is carried out to pretreatment by vacuum outgas at approximately 1050 ℃, and be divided into three groups, under different hyperpressures and temperature conditions in three diamond stable regions, in about 5.5GPa(group 1), 6.8GPa(group 2) and 7.7GPa(organize 3) under carry out sintering.Particularly, described cylinder sintering at the temperature that is enough to melt cobalt is there is to the PCD structure of the base material of PCD plate that sintering is good and good bonding with preparation.The technology of above-mentioned relevant Fig. 3 to 9 is applicable in 7.7GPa(group 3) sintering of lower described cylinder.The superhard structure obtaining is not carried out the leaching processing after any synthesizing.

Then use above-mentioned technology, particularly determine and each in these superhard structures carried out to graphical analysis, to determine total binder area average in the cross section of polishing and the averga cross section adhesive area for each sample by above-mentioned applicable magnifying power.

Can repeat experiment to the composition of different diamond grain size, the results are shown in table 1.

table 1

Confirmablely from experiment be above, as using, the image analysis technology of the image area of applying the magnifying power of approximately 1000 times and analyzing 1280 × 960 pixels is determined, for example, for the total non-diamond phase area (adhesive area) in approximately 0 to 5% scope, can obtain and be less than approximately 0.7 μ m ²relevant non-diamond area separately, wherein the full-size of PCD body of material is about 6mm or larger.In these embodiments, the thickness of the main body of PCD material can be for example about 0.3mm or larger.

In addition, determined as using the magnifying power of application between approximately 1000 times and analyzing the image analysis technology of image area of 1280 × 960 pixels, for example, for the total non-diamond phase area (adhesive area) in approximately 5 to 10% scope, can obtain and be less than approximately 0.340 μ m ²the non-diamond phase area separately in relevant cross section, wherein the full-size of PCD body of material is about 6mm or larger.In these embodiments, the thickness of the main body of PCD material can be for example about 0.3mm or larger.

And, determined as using the magnifying power of application between approximately 3000 times and analyzing the image analysis technology of image area of 1280 × 960 pixels, for example, for the total non-diamond phase area (adhesive area) in approximately 10 to 15% scope, can obtain and be less than approximately 0.340 μ m ²the non-diamond phase area separately in relevant cross section, wherein the full-size of PCD body of material is about 6mm or larger.In these embodiments, the thickness of PCD body of material can be, for example about 0.3mm or larger.

And, determined as using the magnifying power of application between approximately 10000 times and analyzing the image analysis technology of image area of 1280 × 960 pixels, for example, for the total non-diamond phase area (adhesive area) in approximately 15 to 30% scope, can obtain approximately 0.005 to approximately 0.340 μ m ²the non-diamond phase area separately in relevant cross section, wherein the full-size of PCD body of material is about 6mm or larger.In these embodiments, the thickness of PCD body of material can be, for example about 0.3mm or larger.

Simultaneously, in the situation that not wishing to be entangled in specific theory, by using condition as herein described, determine the total binder area that can obtain in above-mentioned specified scope, and relevant adhesive area separately in scope above-mentioned.Determined that these contribute to generate the main body of the PCD material that wearability is higher, when as cutter, described main body can obviously strengthen the durability of the cutter of preparing according to embodiments more as herein described.

In addition, various settings and combination can be used for method of the present invention, and the embodiment of described method can further comprise one or more following non exhaustive property and nonrestrictive aspect with various combinations.

The method that can be provided for preparing superhard structure, comprising:

Be connected to the first structure of the second structure, the first structure comprises first material with the first thermal coefficient of expansion (CTE) and the first Young's modulus, and the second structure comprises second material with the 2nd CTE and the second Young's modulus; The one CTE and the 2nd CTE are substantially different each other, and the first Young's modulus is substantially different each other with the second Young's modulus; At least one in the first or second material comprises superhard material; Described method comprises:

Formation comprises the first material, the second material and is configured to the assembly of the adhesive material together with the first and second material bindings, and adhesive material comprises metal; Making assembly stand to make the sufficiently high temperature of adhesive material in liquid state and make superhard material is thermodynamically stable the first pressure; Be thermodynamically stable the second pressure by pressure decreased to superhard material, make temperature keep enough high to keep adhesive material in liquid state; Reduce temperature with cure adhesive material; And make pressure and temperature be down to environmental condition so that superhard structure to be provided.

In some embodiments, at approximately 25 ℃, the CTE of in the first or second material is at least about 2.5 × 10 ^-6/ ℃ and at the most approximately 5.0 × 10 ^-6/ ℃, and another CTE in the first or second material is at least about 3.5 × 10 ^-6/ ℃ and at the most approximately 6.5 × 10 ^-6/ ℃.

In some embodiments, the Young's modulus of one in the first or second material is at least about 500 giga pascals and approximately 1300 giga pascals at the most, and another Young's modulus in the first or second material is at least about 800 giga pascals and approximately 1600 giga pascals at the most.

The Young's modulus of the first and second materials can for example have the difference at least about 10%.

In some embodiments, the CTE of the first and second materials can for example have the difference at least about 10%.

Described method may further include under the existence of sintering catalysis agent material, and the aggregation of multiple crystal grain of superhard material described in sintering under sintering pressure and sintering temperature, to form the second structure.

Described method can comprise that the aggregation that the crystal grain that makes superhard material is set is adjacent to the first structure, and under the existence of adhesive material, forms presintering assembly; Make presintering assembly stand sintering pressure and sintering temperature to melt the crystal grain of adhesive material sintering superhard material, and form the second structure, it comprises the polycrystalline superhard material that is connected to the first structure by the adhesive material of molten state.

In some embodiments, the first pressure is essentially sintering pressure.

Described method may further include provides the first structure, the second structure that comprises polycrystalline superhard material is provided, setting make the first structure be adjacent to the second structure and form structure before (pre-construction) assembly, and assembly before described structure is exerted pressure, be increased to the first pressure from environmental pressure.

Described method can for example comprise that the aggregation of the multiple crystal grain that make superhard material stands described superhard material and can be sintered to form sintering pressure and the sintering temperature of the second material, and makes pressure and temperature be down to environmental condition so that the second structure to be provided; The first pressure is greater than sintering pressure substantially.

The second structure can comprise diamond, and adhesive material comprises for adamantine catalyst material.

The first and second structures can each self-contained diamond, and adhesive material comprises for adamantine catalyst material.

In some embodiments, the difference between the second pressure and the first pressure is at least about 0.5 giga pascals.

Described method may further include and makes described superhard structure is to stand further heat treatment under the metastable treatment temperature of thermodynamics and processing pressure at superhard material.

Described superhard material can comprise diamond, and described treatment temperature is at least about 500 ℃, and described processing pressure is for being less than approximately 1 giga pascals.

Described method can comprise from described the first pressure pressure decreased to intermediate pressure is kept to a period of time, then further from described intermediate pressure by pressure decreased the step to described the second pressure.

Described the first pressure can for example be at least about 7 giga pascals, described intermediate pressure can be for for example at least about 5.5 giga pascals and be less than approximately 10 giga pascals, the described retention time can for example be at least about 1 minute, and described the second pressure can for example be at least about 5.5 giga pascals and approximately 7 giga pascals at the most.

In some embodiments, in response to temperature reduce described adhesive material start to solidify pressure can for example be substantially equal to described the second pressure.

In other embodiments, the described adhesive material reducing corresponding to temperature starts curing pressure and can for example substantially be less than described the second pressure.

In some embodiments, described the first structure comprises cobalt knot hard tungsten carbide material and described the second material comprises PCD material, and the CTE of described hard carbide material is approximately 4.5 × 10 ^-6/ ℃ to approximately 6.5 × 10 ^-6/ ℃, the CTE of described PCD material is approximately 3.0 × 10 ^-6/ ℃ to approximately 5.0 × 10 ^-6/ ℃; The Young's modulus of described hard carbide material is approximately 500 to approximately 1000 giga pascals, and the Young's modulus of described PCD material is approximately 800 to approximately 1600 giga pascals; Described the first pressure is approximately 6 to approximately 10 giga pascals, and described the second pressure is approximately 5.5 to approximately 8 giga pascals.

In some embodiments, the cobalt-based adhesive material comprising in described hard carbide material starts curing pressure and equals described the second pressure.

Described the second pressure can be for example approximately 6.5 to approximately 7.5 giga pascals.

In some embodiments, described the second structure comprises PCD material, and described method comprises makes described superhard structure stand further heat treatment, and the processing time of approximately 30 minutes to approximately 90 minutes is experienced in described heat treatment under the treatment temperature of approximately 550 ℃ to approximately 650 ℃.

Described method can comprise that the superhard structure of processing is to provide tool elements.Described superhard structure goes for the insert of rock-boring drill bit, for example, for the percussion tool on fractured rock or road surface or for lathe.

Disclosed method, while standing the temperature of heating or raising, has the advantage that reduces the possibility of breaking of superhard structure or the aspect of frequency while particularly use in follow-up preparation process.

Claims

1. polycrystalline diamond stone structure, comprises the main body by the following polycrystalline diamond abrasive compact forming:

In the cross section gross area of the main body of wherein said polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 0 to 5%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, at the mean value of the area of section separately through non-diamond phase pond described in the cross-section analysis image of polycrystalline material main body for being less than approximately 0.7 square micron.

2. polycrystalline diamond stone structure, comprises the main body by the following polycrystalline diamond abrasive compact forming:

In the cross section gross area of the main body of wherein said polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 5 to 10%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, at the mean value of the area of section separately in non-diamond phase pond described in the analysis image in the cross section through polycrystalline material main body for being less than approximately 0.340 square micron.

3. polycrystalline diamond stone structure, comprises the main body by the following polycrystalline diamond abrasive compact forming:

In the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 3000 times is analyzed, at the mean value of the area of section separately in the pond of non-diamond phase described in the analysis image in the cross section by polycrystalline material main body for being less than approximately 0.340 square micron.

4. polycrystalline diamond stone structure, comprises the main body by the following polycrystalline diamond abrasive compact forming:

In the cross section gross area of wherein said polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 15 to 30%, and

In the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 10000 times is analyzed, be approximately 0.005 to 0.340 square micron at the mean value of the area of section separately in non-diamond phase pond described in the analysis image in the cross section through polycrystalline material main body.

5. according to the polycrystalline diamond stone structure described in any one in aforementioned claim, the main body of wherein said polycrystalline diamond abrasive compact has about 6mm or larger full-size.

6. according to the polycrystalline diamond stone structure described in any one in aforementioned claim, the main body of wherein said polycrystalline diamond abrasive compact has about 0.3mm or larger thickness.

7. according to the polycrystalline diamond stone structure described in any one in aforementioned claim, further comprise the base material that is attached to the main body of described polycrystalline diamond abrasive compact along interface.

8. polycrystalline diamond stone structure according to claim 7, the interface between wherein said base material and the main body of described polycrystalline diamond abrasive compact is substantially nonplanar.

9. according to the polycrystalline diamond stone structure described in any one in claim 7 or 8, wherein said base material comprises hard carbide.

10. according to the polycrystalline diamond stone structure described in any one in claim 7 to 9, the thickness of wherein said base material is at least equal to or greater than the thickness of the main body of described polycrystalline diamond abrasive compact.

11. for drilling the cutter in soil, comprises the polycrystalline diamond stone structure described in any one in aforementioned claim.

12. for drilling the PCD element of rotational shear head in soil, for digging up mine or drill hammer or the hoe of pitch fragmentation, comprises the polycrystalline diamond stone structure described in any one in claim 1 to 10.

13. for drilling the drill bit in soil or the parts of drill bit, comprises the polycrystalline ultrahard diamond structure described in any one in claim 1 to 10.

14. methods for the preparation of polycrystalline diamond stone structure, described method comprises:

The diamond crystals in a large number with the first average-size is provided;

Described a large amount of diamond crystals is set makes itself and the body of material that is used to form base material form presintering assembly; And

About 7GPa or larger hyperpressure and diamond than graphite on thermodynamics at more stable temperature, and under the existence for adamantine catalyst material, process described presintering assembly so that described diamond crystals and be sintered together to form complete PCD structure in conjunction with the base material on it along interface; Described diamond crystals demonstrates intergranular in conjunction with also limiting betwixt multiple interstitial areas, and non-diamond is filled multiple interstitial areas mutually at least in part to form non-diamond phase pond, and each described non-diamond phase pond has area of section separately,

In the cross section gross area of the main body of wherein said polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 0 to 5%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond for being less than approximately 0.7 square micron; Or

In the cross section gross area of the main body of described polycrystalline diamond abrasive compact, the percentage of non-diamond phase is approximately 5 to 10%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 1000 times is analyzed, at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond for being less than approximately 0.340 square micron; Or

In the cross section gross area of described polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 10 to 15%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 3000 times is analyzed, at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond for being less than approximately 0.340 square micron; Or

In the cross section gross area of described polycrystalline diamond stone structure, the percentage of non-diamond phase is approximately 15 to 30%, in the time that the image area that uses image analysis technology to be multiplied by 960 pixels with the magnifying power and 1280 of approximately 10000 times is analyzed, be approximately 0.005 to 0.340 square micron at the mean value of the area of section separately in the phase of non-diamond described in analysis image pond.

The method of the polycrystalline diamond stone structure described in 15. any one that form in claim 1 to 10.

16. with reference to the arbitrary embodiment polycrystalline diamond stone structure described above substantially as the embodiment illustrating in Fig. 3 to 10b of accompanying drawing.

17. with reference to the arbitrary embodiment method of formation polycrystalline diamond stone structure described above substantially as the embodiment illustrating in Fig. 3 to 10b of accompanying drawing.