CN103521132A - Synthesis technique of high-grade self-sharpening polycrystalline diamond - Google Patents
Synthesis technique of high-grade self-sharpening polycrystalline diamond Download PDFInfo
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Abstract
The invention relates to a synthesis technique of a high-grade self-sharpening polycrystalline diamond, which comprises the following steps: metering and mixing the raw materials for synthesizing the diamond according to percentage by mass, granulating, and pressing into a synthetic stick; putting the synthetic stick into a synthesis block, and drying in a vacuum drying oven at constant temperature for later use, wherein the synthesis block is synthesized at high temperature under superhigh pressure with a cubic press; and taking out the synthetic stick, carrying out after-treatment to obtain a self-sharpening polycrystalline diamond, carrying out in-situ polymerization by a sol-gel process, and applying a zirconia coating on the diamond surface to form the high-grade self-sharpening polycrystalline diamond. The product has the advantages of favorable impact toughness, favorable thermal stability and favorable comprehensive properties, can obviously enhance the holding force of the self-sharpening polycrystalline diamond in a grinding tool, can keep the self-sharpness in the grinding process, and finally, is beneficial to prolonging the service life of th grinding tool and enhancing the machining efficiency of the grinding tool.
Description
Technical field
The invention belongs to the synthesis technical field of superhard material, be specifically related to a kind of synthesis technology with self-sharpening polycrystalline diamond.
Background technology
Diamond is the superhard material that hardness is very high, is mainly used in making various diamond tools, as grinding tool, wire drawing die, cutting tool and boring means etc.The diamond of producing in the world mainly be take monocrystalline as product, obtains a wide range of applications.Artificial in the majority with monocrystalline with natural diamond, crystal itself is exactly a complete large crystal grain.Monocrystalline is the individual particle with perfect crystal profile, and the lattice of granule interior is periodic arrangement, has anisotropy; Polycrystalline is that a particle the inside has a plurality of crystal grain, and the lattice of each crystal grain is periodic arrangement, has isotropism.Polycrystalline is the set of the monocrystalline of numerous orientation crystal grain, and crystal is comprised of various little crystal grain.
The application of single-crystal diamond has certain shortcoming: owing to there being cleavage surface, and easily passivation after a period of time rear edge surface wear in grinding process; Monocrystalline easily whole extracting from matrix loses ground effect, can not give full play to adamantine effectiveness, causes processing cost to raise.In order to overcome the deficiency of single-crystal diamond, people start mainly by electric plating method in diamond surface nickel plating, copper facing or titanizing etc.As Chinese patent CN85100286B, and publication application CN102286742.A, the method for diamond surface metallization is disclosed.Diamond surface, after metallization, can solve the difficulty that diamond can not bond and infiltrate with general low-melting alloy, and this is favourable to preparing the diamond tool of metallic matrix.Chinese patent 200410096957.7 also discloses a kind of composite structure of diamond surface coated with glass, diamond and titanium layers and method thereof, diamond through composite coated and metal-plated processing, volume increases, and the bond strength of diamond and matrix and hold are improved.But these method manufacturing process are complicated, production cost is high, the diamond surface of process surface metalation allows and so lacks active group, still can not form firmly chemical bonds with pottery and resin matrix, to improving life-span and the effect of diamond tool, is limited.
Synthetic self-sharpening polycrystalline diamond is a new technology, polycrystalline diamond abrasive particle is by the coalescent group of forming of a plurality of metastable state diamond crystallites granular solid matter, shape is not as diamond single crystal rule, be various convex-concave rough surfaces, during grinding under effect of stress, when outside micromeritics successively comes off, expose new sharp cutting edge, and grinding force is little, workpiece to be machined surface roughness is low, polycrystalline diamond abrasive particle can be brought into play abundant effectiveness, can solve the problem that single-crystal diamond integral body is extracted, come off too early from matrix.Chinese patent CN101884933B, and publication application CN102698758.A, disclose catalyst of the synthetic use of self-sharpening polycrystalline diamond and preparation method thereof.China publication application CN102941038.A discloses a kind of synthesis technique of high self-sharpening diamond.
, self-sharpening polycrystalline diamond product yield is low at present, quality is low, intensity is too low, toughness is low, poor heat stability.Researcher of the present invention finds by research, and the main cause that polycrystalline diamond is not widely applied is that polycrystalline diamond grade is low, and combination property is poor.Develop high grade self-sharpening polycrystalline diamond, need to improve the combination properties such as its toughness, per unit area yield rate, heat endurance.The present invention studies discovery, and self-sharpening polycrystalline diamond has specific multiple grain crystal structure, its specific synthesis condition of growth needs and technology, and especially to the pressurize of once boosting, then the process curve of secondary booster is optimized programming.By controlling efficient selective and the polycrystal Fast Growth mechanism of catalyst, and the condition of self-sharpening polycrystalline diamond crystal growth and pressure and temp coupling adaptability; Catalyst is carried out preferably, and the main chemical compositions of determining catalyst is iron manganese nickel cobalt metal alloy, and additional with trace rare-earth element increase reactivity, catalyst is through vacuum melting, and electronation, reduces catalyst oxygen content, and aerosolization is shaped.Adopt sol-gal process in-situ polymerization at diamond Surfaces of Polycrystalline Diamond, to apply the mullite oxide coating of setting coating layer thickness, further improve adamantine high high-temp stability.Through synthesis technique and the design of raw and auxiliary material system optimization, improve grade and the quality of producing product, particularly can effectively improve toughness and the heat endurance of self-sharpening diamond product, to reach life-span and the working (machining) efficiency that improves self-sharpening polycrystalline diamond grinding tool.
Summary of the invention
The present invention wants technical solution problem to be to provide a kind of synthesis technology that can improve self-sharpening polycrystalline diamond grade, by catalyst preferably, raw and auxiliary material design, synthetic piece package technique improve, control specific high pressure high temperature synthesis condition and process curve, adopts membrane by accelerant process synthetic high grade self-sharpening polycrystalline diamond on cubic pressure machine equipment.
In order to address the above problem by the following technical solutions: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, comprises the steps:
(1) the raw material carbon source graphite of diamond synthesis, catalyst, active lean earth elements, Nano diamond, according to mass percent metering, batch mixing, granulation, be pressed into synthetic rod; The mass percent of described raw material is: carbon source graphite 25～30%, active lean earth elements 0.008～0.02%, Nano diamond 0.5～0.8%, surplus are catalyst;
(2) synthetic rod being pressed in step (1) is put into synthetic piece, and it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature;
(3) synthetic piece step (2) being assembled adopts cubic hinge press to synthesize by high pressure high temperature;
(4) synthetic rod after step (3) is synthetic takes out, and obtains self-sharpening polycrystalline diamond, then by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface, form high grade self-sharpening polycrystalline diamond through post processing.
In described step (1), carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of flakey native graphite is 200 orders; Catalyst is as catalyst, and catalyst adopts aerosolization iron manganese nickel cobalt metal alloy powder powder: Nano diamond, as helping nucleator, is produced by Detonation Process, and size distribution is between 20～100 nanometers.
Described catalyst is additional makes activator with trace rare-earth element, and the mass percent of each component is: Mn 20～25%, Ni 10～15%, Co 1～3%, rare earth element 0.3～0.8%, surplus are Fe.
In described step (2), synthetic piece is assembled by synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe; In horizontal direction, by pyrophillite, insulating tube, conductive carbon pipe, form cylindrical shell successively from outside to inside, in cylindrical shell, comprise successively from top to bottom conducting steel ring, filler, double-deck conducting strip, synthetic rod, double-deck conducting strip, filler, conducting steel ring; Between the two-layer conducting strip of double-deck conducting strip, be provided with insulation sheet.
Described conductive carbon pipe adopts graphite short fiber to strengthen, improve electric conductivity.
In described step (3), control synthesis pressure process is: initial controlled pressure 84MPa, and pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 130～200s, starts release; Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 100～200s.
In described step (4), sol-gal process in-situ polymerization, concrete grammar at the coated one deck zirconia coating of diamond surface is: take basic zirconium chloride and ammoniacal liquor as raw material, the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:0.5～2.0, at 60～99 ℃, carry out continuously magnetic agitation heating, form gradually transparent colloidal sol; Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 750～850 ℃ of dry 3min, finally obtain self-sharpening polycrystalline diamond.
8. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 7, is characterized in that: baking temperature is 800 ℃.
the present invention according to the efficient selective of catalyst by catalyst being carried out preferably, the main chemical compositions of determining catalyst is iron manganese nickel cobalt metal alloy, and catalyst is through vacuum melting, and aerosolization is shaped, additional active with trace rare-earth element increase chemical reduction reaction, effectively reduce catalyst oxygen content.According to polycrystal Fast Growth mechanism, in synthetic rod, add Nano diamond, effectively improve nucleation and the growth rate of self-sharpening polycrystalline diamond.Condition and the pressure and temp of definite self-sharpening polycrystalline diamond crystal growth mate adaptability, have guaranteed synthetic per unit area yield and the toughness of self-sharpening polycrystalline diamond.Adopt sol-gal process in-situ polymerization at diamond Surfaces of Polycrystalline Diamond, to apply the mullite oxide coating of setting coating layer thickness, further improve adamantine high high-temp stability.Through synthesis technique and the design of raw and auxiliary material system optimization, improve grade and the quality of producing product, synthetic single output reaches 90～136 carats/time.Diamond is polycrystalline core agglomerated particle, crystalline form is irregular, in the majority with pin flake shape, employing standard JB/T10987-2010 test impact flexibility (TI value) is 20～40%, moderate strength, the particularly toughness of self-sharpening diamond product and heat endurance high comprehensive performance, can obviously improve the hold of self-sharpening polycrystalline diamond in grinding tool, during grinding, can keep sharp self-sharpening, finally be conducive to improve life-span and the working (machining) efficiency of grinding tool.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the high grade self-sharpening of the present invention polycrystalline diamond.
Fig. 2 is synthetic piece package assembly schematic diagram in the present invention.
Number in the figure explanation: 1-conducting steel ring, 2-conducting strip, 3-insulation sheet, 4-conducting strip, 5-pyrophillite, 6-insulating tube, 7-synthetic rod, 8-conductive carbon pipe, 9-filler, the gestalt graphite granule impurity in 101-graphite column.
The specific embodiment
Embodiment 1: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, comprises the steps:
(1) the raw material carbon source graphite of diamond synthesis, catalyst, active lean earth elements, Nano diamond, according to mass percent metering, batch mixing, granulation, be pressed into synthetic rod; The mass percent of described raw material is: carbon source graphite 25～30%, active lean earth elements 0.008～0.02%, Nano diamond 0.5～0.8%, surplus are catalyst.
(2) synthetic rod being pressed in step (1) is put into synthetic piece, and it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.
(3) synthetic piece step (2) being assembled adopts cubic hinge press to synthesize by high pressure high temperature.
(4) synthetic rod after step (3) is synthetic takes out, and obtains self-sharpening polycrystalline diamond, then by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface, form high grade self-sharpening polycrystalline diamond through post processing.
Embodiment 2: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, is characterized in that comprising the steps:
(1) the raw material carbon source graphite of diamond synthesis, catalyst, active lean earth elements, Nano diamond, according to mass percent metering, batch mixing, granulation, be pressed into synthetic rod; The mass percent of described raw material is: carbon source graphite 25～30%, active lean earth elements 0.008～0.02%, Nano diamond 0.5～0.8%, surplus are catalyst.
Wherein, carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and % is mass percent, and wherein the granularity of flakey native graphite is 200 orders; Catalyst is as catalyst, and catalyst adopts aerosolization iron manganese nickel cobalt metal alloy powder powder: Nano diamond, as helping nucleator, is produced by Detonation Process, and size distribution is between 20～100 nanometers.
(2) synthetic rod being pressed in step (1) is put into synthetic piece, and it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.
Synthetic piece is assembled by synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.In horizontal direction, by pyrophillite, insulating tube, conductive carbon pipe, form cylindrical shell successively from outside to inside, in cylindrical shell, comprise successively from top to bottom conducting steel ring, filler, double-deck conducting strip, synthetic rod, double-deck conducting strip, filler, conducting steel ring.Between the two-layer conducting strip of double-deck conducting strip, be provided with insulation sheet.Filler is pyrophillite and dolomite, and filler is arranged in conducting steel ring.
(3) synthetic piece step (2) being assembled adopts cubic hinge press to synthesize by high pressure high temperature.
Actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, and pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 130～200s, starts release; Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 100～200s.
(4) synthetic rod after step (3) is synthetic takes out, and obtains self-sharpening polycrystalline diamond, then by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface, form high grade self-sharpening polycrystalline diamond through post processing.
Sol-gal process in-situ polymerization, concrete grammar at the coated one deck zirconia coating of diamond surface is: take basic zirconium chloride and ammoniacal liquor as raw material, the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:0.5～2.0, at 60～99 ℃, carry out continuously magnetic agitation heating, form gradually transparent colloidal sol; Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 750～850 ℃ of dry 3min, finally obtain self-sharpening polycrystalline diamond.
Embodiment 3: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, the baking temperature in step (4) is preferably 800 ℃.Other steps are with embodiment 2.
Embodiment 4: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, catalyst in step (1) is additional makes activator with trace rare-earth element, and the mass percent of each component is: Mn 20～25%, Ni 10～15%, Co 1～3%, rare earth element 0.3～0.8%, surplus are Fe.
Other steps are with embodiment 2.
Embodiment 5: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 61.4%; Mn, 25%; Ni, 12%; Co, 1%; Rare earth element, 0.6%.Help nucleator Nano diamond to have Detonation Process to produce, size distribution is in 20～100 nanometers.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 28%, catalyst and active lean earth elements 71.3%, Nano diamond 0.7%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 170s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 180s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 126.6 carats.Again by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface.Take basic zirconium chloride and ammoniacal liquor as raw material, and the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:1, at 75 ℃, carries out continuously magnetic agitation heating, forms gradually transparent colloidal sol.Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 800 ℃ of dry 3min, obtain final self-sharpening polycrystalline diamond product.
Above-mentioned synthesis technique prepares the diamond after coating is coated, and adopting standard JB/T10987-2010 test impact flexibility (TI value) is 40.0%.
Embodiment 6: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 63.5%; Mn, 22%; Ni, 12%; Co, 2%; Rare earth element, 0.5%.Help nucleator Nano diamond to have Detonation Process to produce, size distribution is in 20～100 nanometers.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 30%, catalyst and active lean earth elements 69.4%, Nano diamond 0.6%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 170s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 180s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 118.9 carats.Again by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface.Take basic zirconium chloride and ammoniacal liquor as raw material, and the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:1.2, at 75 ℃, carries out continuously magnetic agitation heating, forms gradually transparent colloidal sol.Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 800 ℃ of dry 3min, obtain final self-sharpening polycrystalline diamond product.
Above-mentioned synthesis technique prepares the diamond after zirconia coating is coated, and adopting standard JB/T10987-2010 test impact flexibility (TI value) is 38.2%.
Embodiment 7: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 63.4%; Mn, 20%; Ni, 15%; Co, 1%; Rare earth element, 0.6%.Help nucleator Nano diamond to have Detonation Process to produce, size distribution is in 20～100 nanometers.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 25%, catalyst and active lean earth elements 74.5%, Nano diamond 0.5%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 170s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 180s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 121.2 carats.Again by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface.Take basic zirconium chloride and ammoniacal liquor as raw material, and the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:1.1, at 75 ℃, carries out continuously magnetic agitation heating, forms gradually transparent colloidal sol.Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 780 ℃ of dry 3min, obtain final self-sharpening polycrystalline diamond product.
Above-mentioned synthesis technique prepares the diamond after zirconia coating is coated, and adopting standard JB/T10987-2010 test impact flexibility (TI value) is 35.7%.
Embodiment 8: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 58.5%; Mn, 24%; Ni, 15%; Co, 2%; Rare earth element, 0.5%.Help nucleator Nano diamond to have Detonation Process to produce, size distribution is in 20～100 nanometers.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 30%, catalyst and active lean earth elements 69.2%, Nano diamond 0.8%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 200s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 200s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 131.8 carats.Again by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface.Take basic zirconium chloride and ammoniacal liquor as raw material, and the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:1, at 80 ℃, carries out continuously magnetic agitation heating, forms gradually transparent colloidal sol.Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 800 ℃ of dry 3min, obtain final self-sharpening polycrystalline diamond product.
Above-mentioned synthesis technique prepares the diamond after coating is coated, and adopting standard JB/T10987-2010 test impact flexibility (TI value) is 35.2%.
Embodiment 9: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 63.4%; Mn, 20%; Ni, 15%; Co, 1%; Rare earth element, 0.6%.Help nucleator Nano diamond to have Detonation Process to produce, size distribution is in 20～100 nanometers.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 25%, catalyst and active lean earth elements 74.5%, Nano diamond 0.5%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 170s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 180s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 121.2 carats.
The self-sharpening polycrystalline diamond that above-mentioned synthesis technique prepares, adopting standard JB/T10987-2010 test impact flexibility (TI value) is 22.5%.
Embodiment 10: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 63.4%; Mn, 20%; Ni, 15%; Co, 1%; This comparative example does not add rare earth element.Help nucleator Nano diamond to have Detonation Process to produce, size distribution is in 20～100 nanometers.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 25%, catalyst and active lean earth elements 74.5%, Nano diamond 0.5%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 170s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 180s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 101.7 carats.Again by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface.Take basic zirconium chloride and ammoniacal liquor as raw material, and the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:1.1, at 75 ℃, carries out continuously magnetic agitation heating, forms gradually transparent colloidal sol.Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 780 ℃ of dry 3min, obtain final self-sharpening polycrystalline diamond product.
Above-mentioned synthesis technique prepares the diamond after zirconia coating is coated, and adopting standard JB/T10987-2010 test impact flexibility (TI value) is 31.9%.
Embodiment 11: a kind of synthesis technology of high grade self-sharpening polycrystalline diamond, raw material: carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of native graphite is 200 orders.Catalyst is to adopt aerosolization iron manganese nickel cobalt metal alloy powder powder catalyst, additionally with trace rare-earth element, makes activator.Catalyst adds after activator, and the mass percent that forms each component is controlled and is: Fe, 61.4%; Mn, 25%; Ni, 12%; Co, 1%; Rare earth element, 0.6%.This comparative example does not add and helps nucleator Nano diamond.
Above-mentioned raw and auxiliary material is measured according to following mass percent: carbon source graphite 28%, catalyst and active lean earth elements 72%, through fully batch mixing, granulation, be pressed into synthetic rod.
According to certain order, synthetic rod is put into synthetic piece, it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature.After synthetic piece assembling, comprise: after synthetic piece assembling, comprise: synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe.Conductive carbon pipe adopts graphite short fiber to strengthen.The synthetic piece assembling adopts cubic hinge press to synthesize by high pressure high temperature, and actual synthesis pressure and synthesis temperature adopt intellectualized module programming to control by computer respectively.Controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s boosts to 90MPa in 30s, continues, in 60s, controlled pressure is raised to 95MPa, after pressurize 170s, starts release.Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 180s.
Synthetic rod after synthetic obtains self-sharpening polycrystalline diamond through post processing, and diamond per unit area yield reaches 96.4 carats.Again by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface.Take basic zirconium chloride and ammoniacal liquor as raw material, and the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:1, at 75 ℃, carries out continuously magnetic agitation heating, forms gradually transparent colloidal sol.Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 800 ℃ of dry 3min, obtain final self-sharpening polycrystalline diamond product.
Above-mentioned synthesis technique prepares the diamond after coating is coated, and adopting standard JB/T10987-2010 test impact flexibility (TI value) is 36.6%.
Claims (8)
1. a synthesis technology for high grade self-sharpening polycrystalline diamond, is characterized in that comprising the steps:
(1) the raw material carbon source graphite of diamond synthesis, catalyst, active lean earth elements, Nano diamond, according to mass percent metering, batch mixing, granulation, be pressed into synthetic rod; The mass percent of described raw material is: carbon source graphite 25～30%, active lean earth elements 0.008～0.02%, Nano diamond 0.5～0.8%, surplus are catalyst;
(2) synthetic rod being pressed in step (1) is put into synthetic piece, and it is standby that the synthetic piece assembling is placed in vacuum drying chamber freeze-day with constant temperature;
(3) synthetic piece step (2) being assembled adopts cubic hinge press to synthesize by high pressure high temperature;
(4) synthetic rod after step (3) is synthetic takes out, and obtains self-sharpening polycrystalline diamond, then by sol-gal process in-situ polymerization, at the coated one deck zirconia coating of diamond surface, form high grade self-sharpening polycrystalline diamond through post processing.
2. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 1, it is characterized in that: in described step (1), carbon source graphite is the mixture of 99% flakey native graphite and 1% CNT, and wherein the granularity of flakey native graphite is 200 orders; Catalyst is as catalyst, and catalyst adopts aerosolization iron manganese nickel cobalt metal alloy powder powder: Nano diamond, as helping nucleator, is produced by Detonation Process, and size distribution is between 20～100 nanometers.
3. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 2, it is characterized in that: described catalyst is additional makes activator with trace rare-earth element, and the mass percent of each component is: Mn 20～25%, Ni 10～15%, Co 1～3%, rare earth element 0.3～0.8%, surplus are Fe.
4. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 1, it is characterized in that: in described step (2), synthetic piece is assembled by synthetic rod, pyrophillite, conducting steel ring, conducting strip, insulation sheet, insulating tube and conductive carbon pipe; In horizontal direction, by pyrophillite, insulating tube, conductive carbon pipe, form cylindrical shell successively from outside to inside, in cylindrical shell, comprise successively from top to bottom conducting steel ring, filler, double-deck conducting strip, synthetic rod, double-deck conducting strip, filler, conducting steel ring; Between the two-layer conducting strip of double-deck conducting strip, be provided with insulation sheet.
5. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 4, is characterized in that: described conductive carbon pipe adopts graphite short fiber to strengthen, improve electric conductivity.
6. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 1, it is characterized in that: in described step (3), controlling synthesis pressure process is: initial controlled pressure 84MPa, pressurize 100s, in 30s, boost to 90MPa, continuation is raised to 95MPa by controlled pressure in 60s, after pressurize 130～200s, starts release; Synthesis temperature is realized by controlling heating power, and starting heating power is 11kW, keeps, after 200s, heating power is down to 88kW, continues to stop after insulation 100～200s.
7. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 1, it is characterized in that: in described step (4), sol-gal process in-situ polymerization, concrete grammar at the coated one deck zirconia coating of diamond surface is: take basic zirconium chloride and ammoniacal liquor as raw material, the initial molar ratio of controlling basic zirconium chloride and ammoniacal liquor is 1:0.5～2.0, at 60～99 ℃, carry out continuously magnetic agitation heating, form gradually transparent colloidal sol; Add subsequently self-sharpening polycrystalline diamond, be fully uniformly mixed, then be washed with water to silver nitrate reagent test without chlorion, at 750～850 ℃ of dry 3min, finally obtain self-sharpening polycrystalline diamond.
8. the synthesis technology of high grade self-sharpening polycrystalline diamond according to claim 7, is characterized in that: baking temperature is 800 ℃.
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