CN1697684A - Boron doped blue diamond and its prodn - Google Patents

Boron doped blue diamond and its prodn Download PDF

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Publication number
CN1697684A
CN1697684A CNA028297598A CN02829759A CN1697684A CN 1697684 A CN1697684 A CN 1697684A CN A028297598 A CNA028297598 A CN A028297598A CN 02829759 A CN02829759 A CN 02829759A CN 1697684 A CN1697684 A CN 1697684A
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boron
diamond
doped diamond
powder
core
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孟悦
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Diamond Innovations Inc
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Diamond Innovations Inc
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    • B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
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Abstract

A method for synthesizing boron doped diamond for improving the oxidation resistance of said diamond crystals includes forming a fully dense core (mixture) of graphite, catalyst/solvent metals, optional diamond seed crystals, and a source of boron. This mixture is subjected to diamond-formed high pressure/hgh temperature (HP/HT) conditions for a time adequate for forming diamond. The thus-diamond product is recovered to contain boron substituted into the diamond structure. The fully dense core is substantially devoid of air/nitrogen (N) content. In one embodiment, the boron amorphous B.

Description

Boron doped blue diamond and preparation method thereof
Technical field
The application's relate generally to diamond particles, relating in particular to by boron (B) is replaced to go into diamond crystal increases its compressive failure intensity (compressive fracture strength) and improves its resistance of oxidation (oxidation resistance).
Adamantine hardness and thermal properties only are two features that make that diamond is used in various industrial components.At first, natural diamond is used in the various abrasive application.Owing to had at diamond to be in the ability of utilizing the auxiliary high pressure/high temperature of solvent (HP/HT) technology to come diamond synthesis under the condition of carbon phase thermokinetics stable form, made a lot of additional products on market, obtain approval.Typically, the HP/HT condition that is used for the solvent synthetic method comprises temperature in about 1300 ℃ to 2000 ℃ scope, and pressure arrives in the scope of 10GPa about 5.Usually the polycrystalline diamond composite members (compact) that is supported on columniform or the annular WC upholder has been expanded adamantine product line (product line).But high pressure and pyritous for example require to have become the restriction to product configurations.The typical way of upgrading is adamantine low-pressure growth, is known as to be " chemical vapor deposition " or " CVD ".Make additional product configurations become possibility by this diamond film technology.
No matter whether diamond is natural or synthetical, also no matter man-made diamond is grown in which way, diamond is unsettled at elevated temperatures.As known in the art, under about 600 to 700 ℃ temperature, handle diamond and require inert atmosphere; Otherwise diamond is just oxidized.Therefore, it in the industry cycle is welcome improving adamantine resistance of oxidation.For example, the life-span of diamond tool will prolong because diamond in tool applications resists the ability of oxidation, and, might at elevated temperatures diamond machined be become various instruments and workpiece.
Adamantine another quite valuable character is its compressed rupture strength (compressive fracturestrength).The physical strength of compressive fracture strength measures diamond in the tool applications process in addition, might become diamond machined various tools and workpiece at elevated temperatures.
Another quite valuable character of diamond is its compressed rupture strength.The physical strength of compressive fracture strength measures, and, be to break (or fracture) needed static(al) of this crystal (static force).Compressed rupture strength is the quantifiable mechanical properties of boart boart (grit).Typically, test hundreds of sand, and the mean force that described abrasive material write down of will breaking is used as the compressed rupture strength of this specific sand product.Up to now, the intensity that the etch boart boart improved boart boart in 1 hour in the fused potassium nitrate that is reported in 870 ° of K is arranged, its reason be removed surface irregularity and defective (referring to, the 489-490 page or leaf, the character of man-made diamond " natural and " (The Propertiesof Natural and Synthetic Diamond), J.E.Field writes, 1992).
The sign that boron is incorporated in the diamond lattic structure lattice is adamantine color.Added boron, diamond is blue.Boron doped " blueness " diamond is synthesized out, and they have the optical property and the electrical property of change, and these " blueness " diamonds are disclosed in the prior art (referring to EP 0 892 092 A1; And United States Patent (USP) 2992900; 3141855; 3,148,161; 3268457; 3303053; 3310501; 4,042,673; 4082185; 4,301,134; 4,082,185; 6030595; JP 05200271 and WO8304016).Boron doped blue diamond is considered to have improved resistance of oxidation (referring to " adamantine character and application " (Properties andApplications of Diamond), Wilks, people such as John, ISBN 0-7506-1067-0,1991, the 364th page).WO8304016, United States Patent (USP) 3141855 and United States Patent (USP) 3268475 have instructed via the top layer of DIFFUSION TREATMENT with boron doped diamond crystals.
United States Patent (USP) 4042673,4082185,4301134,6030595 and JP05200271 instruction by the method for the synthetic boron-doped diamond of temperature gradient method.Yet the temperature gradient method that is used to prepare this boron-doped diamond is used for sawing for production and grinds is to be uneconomic for the diamond of purpose, although these diamonds may be the diamonds of jewel ore level.
United States Patent (USP) 2992900,3148161,3303053 and 3310501 disclose the boron-doped diamond that employing layering reaction chamber method (layeredreaction cell method) obtains, and United States Patent (USP) 3310501 has also specified the non-uniform Distribution of needed boron.Stratified chamber is adopted alternately with the discrete catalyst metal of for example dish, bar, cylinder or paper tinsel form and carbon or graphitic composition and is come the homogenizing reaction mass.Diamond nuclei can also can be not included in this reaction mass.It is to finish by the surface that boron compound is imposed on this catalyzer or carbon or graphitic composition that boron mixes.This design is suitable for mass production, still, can not support uniform, the three dimensional growth of diamond crystal from a large amount of chemically different compositions of this layer structure acquisition.The productive rate of high quality crystal is not high.
Verifiedly improved adamantine quality (referring to Chien-Min J Sung by meticulous mixed catalyst, carbon and diamond nuclei, be used for diamond high pressure synthetic and optimize the chamber design, high temperature-high pressure (Optimized celldesign for high-pressure synthesis of diamond, High Temperatures-High Pressures)-2001, vol 33, p489-501).
At present, still there is such demand in the art, that is, be in the mode of economy, the high quality crystal boron-doped diamond that preparation is used in the industrial application of grinding, sawing and other similar applications.The applicant has developed a kind of powder cell method (powder cell method), and boron doped diamond crystal is used for growing.This is the high-quality boron doped diamond crystals that adopts powder chambers device (a powder cell apparatus) preparation for the first time.
Summary of the invention
A kind of preparation is used to grind, the method for the boron-doped diamond of sawing and other processing purposes, comprise, form graphite, catalyst/solvent sintering aid, boron source and the uniform mixture of diamond seeds optionally, basically the core that does not have the complete densification of nitrogen and oxygen (N and O) with preparation, the core of described densification is placed the sufficiently long time under high pressure/high temperature (HP/HT) condition, have the diamond of the boron replacement that runs through diamond crystal structures with formation.
In one embodiment, amorphous boron is used to form boron doped blue diamond of the present invention.
Description of drawings
Fig. 1 is a kind of thermogravimetric analysis result's of not doped diamond sample a graphic representation; And
Fig. 2 is the thermogravimetric analysis result's of boron-doped diamond sample a graphic representation.
These accompanying drawings will be described in detail in an embodiment.
The detailed description of invention
Boron be only two kinds can be in diamond lattic structure one of the element (nitrogen is another kind of) of alternate c atoms. Boron in the diamond lattic structure replaces can be so that this boron doped diamond demonstrates improved mechanical strength and antioxygen The change ability.
The present invention has adopted a kind of powder chambers device to prepare boron-doped diamond.In powder cell method, reactant, for example, graphite/catalyst/nuclei waits mixed and be consolidated into the solid core as powder.This powder cell approach is different from additive method of the prior art, because in the method for layering chamber, reactant is the component that disperses (dish of metal catalyst, the dish of graphite, etc.) in this layering chamber; In the thermal gradient chamber, reactant also is the component that disperses, and, also require to add thermal gradient.
As data will prove, boron doped diamond crystals of the present invention demonstrates the resistance of oxidation of raising.That is, compare with common industrial diamond, this boron doped diamond crystal can tolerate higher temperature.This just means that tool-making can process the instrument of making under higher temperature, and this is useful for tool manufacturer.And this means also that final tool can be used in up to now because the temperature of being estimated and with in the excluded operation of diamond, this temperature is that diamond will suffer from operation field.These advantages should not be limited to any specific instrument.That is to say, the boron diffusion diamond should wortle, resin-bonded instrument (resinbond tools), metal bonded tools (metal bond tools), saw blade, composite members (compacts), and the like in have superiority.
The initial step of this method is from forming the uniform mixture of catalyst metal, boron and graphite.As this area or known, can use diamond seeds.The amount ranges of boron is to account for about 0.1 to about 0.5wt% of whole core composition, preferably about 0.15wt% at present.The boron source comprises, inter alia, and at about 0.1 B in about 0.5wt% scope 4C, preferred 0.25wt%; In that B content is provided is about 0.1 Fe-B alloy in the scope of about 0.5wt%; At about 0.1 metal boron and the amorphous B powder that arrives in the scope of about 0.5wt%, preferably about 0.15wt%.At present preferred B source is amorphous B, and its granularity is about 5 μ m-80 order sizes.In addition, its lower limit is subjected to the domination of operation factors more, especially when commercial scale operations.
For from core, remove be present in wherein by the N that air brought, O or other pollutents, mixture are pressed into the complete densification of nominal.For this purpose, become complete densification and mean the core of being suppressed, notice that air is measured as N content basically without any the gas of carrying secretly.The existence of N has stoped B to mix diamond lattic structure, causes B to exist as impurity inclusion, and therefore causes the diamond crystal of black.This novel boron doped, blue diamond is compared with black diamond, has the less B as impurity inclusion.
In one embodiment, the gasiform pollutent also can adopt other known method to be excluded: adopt and purify " getter " component, find time and replace with other gases that do not influence the diamond crystal growth.Here employed term " scavenging agent (scavenger) " or " purifying getter (scavenging getter) " refer to a kind of material, this material is added in the mixture to remove or the unwanted material of passivation, the N that for example carries secretly, O, or other pollutents.In one embodiment, a kind of purification getter, for example, a kind of scavenger metal plays a part to remove at least a portion that is present in any oxygen in the mixture.The purification of oxygen takes place by oxidising process, wherein, in densified core fused process, oxygen scavenger metal and existing at least some oxygen reactions.This reaction causes the oxygen scavenger metal to be converted into oxide compound.As an example, aluminium (Al) can be used as the oxygen scavenger metal, by with oxygen (O 2) reaction formation aluminum oxide (Al 2O 3).
Then, in high pressure/high temperature (HP/HT) device of routine, with sufficiently high temperature and sufficiently long time, core is carried out conventional HP/HT to be handled, described conventional high pressure/high temperature (HP/HT) device can be belt (belt-type) or pattern (die-type), these devices are at for example United States Patent (USP) 2,941,241; 2,941,248; 2,947,617; 3,609,818; 3,767,371; 4,289,503; 4,409,193; 4,673,414; 4,810,479 and 4,954,139 and French Patent 2,597,087 in description was arranged.In one embodiment, temperature about 1300 ℃ to about 2000 ℃ scope, corresponding pressure about 5 in the scope of about 10GPa.In another embodiment, time range at about 30 seconds to reaching 3 hours.In another embodiment, time range about 5 minutes by 2 hours.
Then, from described device, collect (recover) boron doped diamond product, promptly reduce temperature, decompression then earlier in the mode of routine.Adopt the trimming of routine to operate (for example, grind, pickling, etc.) collect this product, then, this product is used for various sawings, grinding and other industrial application.
Preferred embodiment is described although the present invention is based on,, those skilled in the art will appreciate that and can make various change, and can carry out equivalent to its key element and replace, and do not depart from scope of the present invention.In addition, can make many improvement,, not get essential scope and do not depart from the present invention so that special situation and material are adapted to instruction of the present invention.Therefore, do not have a mind to limit the invention to those specific embodiments, these embodiments are that conduct realizes preferred forms of the present invention and disclosed, and still, the present invention will comprise whole embodiments of the scope that falls into claims.In this application, unless specialize, all units all are metric systems, and all amounts (amount) and percentage ratio all are based on weight.In addition, all herein quoting all is incorporated herein in the form of references.
Thermo-gravimetric analysis (TGA) is to the continuously measured of example weight in static " air-" atmosphere, under the condition of the temperature that raises.Reducing of example weight is the indication that volatile reaction product is separated out from sample.For diamond, at elevated temperatures, oxygen can react and generate CO, CO 2With its mixture.Referring to, J.E.Field (writing), " adamantine character " (The Properties of Diamond), Academic Press, New York, New York (1979).Compare with the class dimantine that is not doped (being untreated), the verified resistance of oxidation that improved significantly of boron-doped diamond of the present invention, be characterized in that the weight loss of measuring by thermo-gravimetric analysis (TGA) is lower than 1/3rd (1/3) of doped diamond not.
In one embodiment of the invention, the characteristics of boron doped diamond crystals of the present invention are, in air, be lower than 0.25% in 850 ℃ of following per minute rate of weight loss.In another embodiment, be characterized in air, weight loss being arranged since 700 ℃ with higher temperature.
Embodiment
Make on 951 thermogravimetric analyzer of DuPont Instruments during the TGA curve of report in an embodiment, wherein, all samples all place on the platinum sample holder.Speed elevated temperature according to 10 ℃/min.
To be pressed into the state of complete densification by the core that graphite and catalyst/solvent metal (sintering aid) and the amorphous B of 0.15wt% make.Then, described core is placed conventional H P/HT handle.Selecting 140/170 order, its toughness index (TI) is 47 collection part, is that 46 unadulterated reference diamond part is tested together with having identical order footpath and TI.
Toughness index (" TI ") is by 2 carats material is put into container (capsule) with steel ball, acutely shake (agitating) one period regular time, metering needle is to the weight of the fragment of the specific dimensions that specific starting weight produced of specific dimensions.The size of employed steel ball and the time of shaking change according to the size of diamond abrasive grains.In one embodiment, be that the steel ball of 7.94mm is put into a 2ml container (capsule) with diameter by 139 μ m mesh screens and the material that once was retained in the specified quantitative of (corresponding to being of a size of 120/140) on the 107 μ m mesh screens, be placed on the vibration tester, grind (milling) for some time (30.0 ± 0.3 seconds), sieve with 90 μ m mesh screens then.The crystalline amount on the 90 μ m mesh screens of being retained in is to represent based on initial crystalline weight percentage.
Under following test conditions, carry out thermogravimetric analysis:
Still air
Speed with 50 ℃/min is heated to 850 ℃ with sample
Then, sample kept 1 hour at 850 ℃
The weight of monitoring sample, the speed that weight changes in first 8 minutes under this temperature when being recorded in 850 ℃.The existence of air causes the diamond oxidation.
Write down following result:
The weight of reference diamond changes speed: per minute-0.83%
The weight of B doped diamond changes speed: per minute-0.21%
Fig. 1 with curve representation the TGA test-results of comparative sample.The temperature of this sample heating of line 10 expressions, and the amount (wt%) of line 12 representative samples.Fig. 2 with curve representation the TGA test-results of B-doped samples of the present invention.Line 14 shows the Heating temperature of this sample, and line 16 has been represented the amount (wt%) of sample.The resistance of oxidation that these TGA test-results have disclosed by the boron-doped diamond of powder cell method preparation of the present invention has raising.The rate of weight loss of B diffusion samples of the present invention only is about 1/4th of a comparative sample.

Claims (21)

  1. One kind in order to improve resistance of oxidation the method for synthetic boron-doped diamond, comprising:
    (a) mixture at least a and the boron source in compacting non-diamond carbon dust, catalyzer and the type of solvent metal powder forms fine and close core;
    (b) core of described densification is placed form under adamantine high pressure/high temperature (HP/HT) condition, through after a while, described for some time is enough to form and has the diamond that replaces the boron that enters described diamond lattic structure; And
    (c) collect described boron diamond product.
  2. 2. the mixture at least a and boron source in the method for claim 1, wherein described non-diamond carbon dust, catalyzer or the type of solvent metal powder is compacted under fully big pressure, to form the core that does not have gas-entrained densification basically.
  3. 3. the method for claim 1, wherein described mixture also comprises at least a purification getter component, is used for removing basically gas-entrained in described densified core.
  4. 4. the method for claim 1, wherein described mixture also comprises diamond seeds.
  5. 5. the method for claim 1, wherein the amount of the boron in described core accounts for about 0.1 to about 0.5wt% of described whole core.
  6. 6. the method for claim 1, wherein described boron is selected from B4C, FeB alloy, metal boron, and amorphous B powder.
  7. 7. the method for claim 1, wherein described boron is the amorphous boron powder of size in about 5 μ m arrive about 45/50 order scope.
  8. 8. the method for claim 1, wherein described HP/HT condition comprises that about 1300 ℃ are arrived about 2000 ℃ temperature range, and corresponding pressure range is about 5 to about 10Gpa.
  9. In accordance with the method for claim 1 the preparation boron-doped diamond.
  10. 10. the goods that comprise boron-doped diamond as claimed in claim 9.
  11. 11. goods as claimed in claim 10, its form are composite members, wortle, resin-bonded instrument, metal bonded tools or saw blade.
  12. 12. boron doped diamond crystals, wherein, the content of described doping agent boron is evenly distributed in the described diamond crystal, and, wherein, described diamond crystal is so preparation, promptly in the powder chambers device, the described doping agent boron of chien shih is substituted and enters diamond crystal structures under sufficiently high high pressure/high temperature (HP/HT) condition, when sufficiently long.
  13. 13. boron doped diamond crystals as claimed in claim 12, wherein, described doping agent boron exists with about amount of 0.1 to about 0.5wt%.
  14. 14. boron doped diamond crystals as claimed in claim 12, wherein, described doping agent boron is selected from B4C, FeB alloy, metal boron, and amorphous B powder.
  15. 15. boron doped diamond crystals as claimed in claim 12, wherein, described doping agent boron is the amorphous boron powder of size in about 5 μ m arrive about 45/50 order scope.
  16. 16. comprise the goods of boron-doped diamond as claimed in claim 12.
  17. 17. the article of claim 16, its form are composite members, wortle, resin-bonded instrument, metal bonded tools or saw blade.
  18. 18. a boron doped diamond is characterized in that, the weight loss that described diamond had is lower than 1/3rd of the weight loss that do not have the class of described boron dope agent dimantine.
  19. 19. boron doped diamond as claimed in claim 18, its feature also are to have equally distributed boron dope agent in described diamond, and wherein, described boron dope agent is selected from B4C, FeB alloy, metal boron, and amorphous B powder.
  20. 20. a boron doped diamond is characterized in that, the rate of weight loss that had in air, under 850 ℃ are lower than per minute 0.25%.
  21. 21. boron doped diamond as claimed in claim 20, its feature also be, in air, since 700 ℃ or higher temperature weight loss is arranged.
CNA028297598A 2002-10-16 2002-10-16 Boron doped blue diamond and its prodn Pending CN1697684A (en)

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