CN104014280B - A kind of polycrystalline diamond sintering method - Google Patents
A kind of polycrystalline diamond sintering method Download PDFInfo
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- CN104014280B CN104014280B CN201410273051.1A CN201410273051A CN104014280B CN 104014280 B CN104014280 B CN 104014280B CN 201410273051 A CN201410273051 A CN 201410273051A CN 104014280 B CN104014280 B CN 104014280B
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Abstract
The invention provides a kind of polycrystalline diamond sintering method, described method comprises the steps: 1) prepare graphite heating pipe; Step 2) in described graphite heating pipe, place an insulated cavity; Step 3) in described insulated cavity, place an absorbing cavity; Step 4) in described absorbing cavity, place and place successively diamond bisque and metal binding agent layer; Step 5) seal described absorbing cavity, insulated cavity and graphite heating pipe; Step 6) the graphite heating pipe having sealed is placed in peripheral pyrophillite assembled block, carry out pressure sintering.
Description
Technical field
The present invention relates to technical field of superhard material, be specifically related to a kind of sintering method that adopts the synthetic polycrystalline diamond of quiet high-pressure process.
Background technology
Because polycrystalline diamond layer thermal conductivity is good, hardness is high, and wearability is good, makes it in oil drilling, geological drilling and coal mining application, be used widely at high-performance electronic encapsulation function Material Field.
The preparation of polycrystalline diamond mainly contains two kinds of modes, and one is vapour deposition process, and the advantage of the method is that the synneusis sheet thickness of making can accurately be controlled, and can make large diameter sample, and shortcoming is length consuming time, thin thickness, and production capacity is low; The preparation method of another kind of polycrystalline diamond is that diamond dust is added after certain bonding agent, on special diamond hydraulic press, under high pressure high temperature condition, sintering makes, this type of glomerocryst is limited by high-pressure chamber, the sample diameter that does not have at present vapour deposition process to make is large, but it is short that advantage is sintering time, thickness is large, and production capacity is high.
At present, high-pressure sinter class polycrystalline diamond product is mainly divided three classes: the one, and GE company of U.S. growth type polycrystalline diamond, is having greater advantage aspect self-sharpening and toughness, and wear resistance ratio is not high especially; The 2nd, DeBeer company micro mist polycrystalline diamond, taking Si as bonding agent, is having superiority aspect toughness and wear resistance ratio; The 3rd, the polycrystalline diamond of domestic " class concrete " formula structure, distinctive structure makes its each performance indications have larger flexibility, and the different building forms of diversified additive and carbide make it have various performance characteristic.
Find out in conjunction with above analysis from scene application, wear resistance ratio is no longer leading indicator, because three kinds of its wear resistance ratios of system glomerocryst product all can meet the demands, self-sharpening and toughness adapt to bad ground needs and improve bit speed to have decisive action to drill bit, therefore these two indexs rise to main positions. From this angle, G.E. company of U.S. growth type polycrystalline diamond has greater advantages.
G.E. company's growth type polycrystalline diamond is to adopt " sweeping more formula catalysis recrystallization method (SweepThroughCatalyzedRecrystallization, i.e. STCR method) " technique, utilizes the strong catalytic action of metal pair graphite to reach crystal growth. Sweep more formula recrystallization method Co liquid and need sweep more whole polycrystal, thereby the thickness of glomerocryst is restricted, just more helpless for more complicated product.
In addition, adopt quiet high-pressure process synthetically grown type polycrystalline diamond, thermograde is determining the quality stability of polycrystalline diamond. the assembling mode of synthetic piece is determining the Temperature Distribution in cavity, and therefore, assembling is different, and thermograde can be different. in addition, entering after HTHP synthesis phase, because assembling mode cannot change, therefore in building-up process, cannot rely on change assembling mode to adjust the thermograde in synthetic cavity, can say, with regard to current technology, in building-up process, can't accomplish the random regulation and control to thermograde, in the process of polycrystalline diamond, if dimond synneusis layer can bring as inhomogeneous in sintering structure structure under larger thermograde in cavity, occur " bridge formation ", evil mind phenomenon, and composite polycrystal-diamond goods are stablized poor repeatability, local residual stress is larger, the serious performance that affects polycrystalline diamond instrument.
Summary of the invention
For the problems referred to above, the invention provides a kind of diamond sintering method, it is characterized in that, described method comprises the steps:
Step 1: preparation graphite heating pipe;
Step 2: place an insulated cavity in described graphite heating pipe;
Step 3: place an absorbing cavity in described insulated cavity;
Step 4: place and place successively diamond bisque and metal binding agent layer in described absorbing cavity;
Step 5: seal described absorbing cavity, insulated cavity and graphite heating pipe;
Step 6: the graphite heating pipe having sealed is placed in pyrophillite assembled block, carries out pressure sintering.
In one implementation, in described absorbing cavity, place and place successively diamond bisque and metal binding agent layer refers to: place layer of gold hard rock bisque in the lower floor of described absorbing cavity, then on described diamond bisque, place layer of metal bond layer.
In one implementation, in described absorbing cavity, place and place successively diamond bisque and metal binding agent layer comprises: place layer of gold hard rock bisque in the lower floor of described absorbing cavity, then on described diamond bisque, place layer of metal bond layer, then place layer of gold hard rock bisque on described metal binding agent layer.
In one implementation, in described step 6, described pressure sintering process comprises: first pressurized energy, after reaching sintering pressure, be rapidly heated, 0s-10s reaches sintering temperature, make the rapid melt infiltration of metal binding agent (in the process of heat temperature raising, metal first softens afterwards and melts, when softening, metal can permeate to diamond layer by pressure and capillary force, space in diamond layer can make the pressure decreased of metallic solution, thereby reduced the impulsive force of metallic infiltration, heated up slower, metal sweep that more effect is poorer. After reaching sintering pressure, be rapidly heated, make the viscosity fast reducing of metal binding agent, can make like this metal softening time of heating up shorten, strengthened the more effect of sweeping of metal. And shorten overall sintering time, improve efficiency), after temperature, consider temperature accumulation, in cavity, temperature can raise, and slowly reduces for the given power heating, ensure that in cavity, temperature is substantially constant, complete after high temperature sintering, for the internal stress that prevents that temperature decrease from producing, given power was slowly reduced in 3-30 minute to zero energy given, slow pressure release in 3-30 minute, the end of whole sintering process. Moulding pressure is 5.0-6.0GPa, and sintering temperature is 1200-1500 DEG C, and sintering time is 10-3600 second.
In one implementation, described graphite heating pipe is cylindric, and the two ends up and down of this cylindric graphite heating pipe are sealed by conducting heating plate. In the preferred implementation of one, by heating tube two ends are applied to voltage, heating tube is heated. Preferably, the curve of applied voltage is comprised to first stage, second stage and phase III, in the described first stage, voltage rises to ceiling voltage by sinusoidal manner, after temperature reaches predetermined value (or in the first stage, high-voltage pulse spike is provided, then return to normal voltage), enter described second stage, in described second stage, voltage declines by the first slope, through after the scheduled time, it is constant that voltage keeps, then enter the phase III, in the described phase III, voltage declines with the second slope. This mode is in order to maintain the constant of sintering temperature, reduces stress.
In one implementation, described absorbing cavity is made of porous materials, and described absorbing cavity comprises columned tube wall and top end cap and lower end cap.
In the preferred implementation of one, described absorbing cavity is formed by dusty material compacting. High pressure when this absorbing cavity can bear sintering, and can there is not moderate finite deformation, and also this absorbing cavity can absorb metal binding agent better.
In one implementation, the height of described heating tube is for to be determined by equipment, and heating tube height can be 0.5-10cm at present, and along with equipment enlarging, heating tube height also can increase.
The Thickness Ratio of bortz powder and metal binding agent is 5:1～1:1.
Owing to having adopted technique scheme, the present invention compared with prior art has following beneficial effect:
In the time adopting this sintering method to carry out diamond sintering, after temperature reaches certain limit, metal-to-metal adhesive can reach molten condition, in the time that metallic infiltration is swept more diamond layer, the composition that metal can play the moisture impurity in diamond layer etc. ill effect is swept and is run off diamond layer, plays the effect that purifies diamond layer.
In the preferred implementation of one, absorbing cavity is made of porous materials. Utilize porous material, make itself and metal function, play the effect that absorbs impurity and hold metal binding agent. Can realize in this way the integral sintered of diamond bisque through experiment showed,, that is, the polycrystalline diamond center forming there will not be not sintering forming section.
And this sintering method is convenient to cavity temperature to control, can in sintering process, change according to chamber substance in vivo, temperature field distributes and heat diffusion changes change heating power, plays the effect of steady temperature field.
And the polycrystalline diamond layer that adopts the sintered components in the present invention to make has the advantages that internal stress is little. Find after testing, by the melting infiltration sintering of alloy, in dimond synneusis layer, residual stress distribution is more even, and residual stress is lower than 300MPa.
Brief description of the drawings
Fig. 1 is the indicative flowchart of sintering method of the present invention;
Fig. 2 is the sectional structure schematic diagram of the constructed sintered components of sintering method of the present invention;
The Electronic Speculum figure of the polycrystalline diamond that the sintering method that Fig. 3 is one embodiment of the invention obtains.
Detailed description of the invention
As shown in Figure 1, in this embodiment, diamond sintering method comprises six steps, will be described one by one below.
Step 1: preparation graphite heating pipe.
First need karbate impervious graphite heating tube, in a kind of implementation of the present embodiment, graphite heating pipe 31 is cylindric, and graphite heating pipe 31 cylindraceous is positioned at the outermost layer of sintered components. The height of graphite heating pipe is preferably chosen at 0.5～10cm. The external diameter of graphite heating pipe and highly depend on the high-pressure space that high-tension apparatus provides, space greatly heating tube can increase accordingly. The wall thickness of graphite heating pipe 31 is chosen between 0.15-2cm. Two ends up and down at graphite heating pipe can cover respectively some conductive heater sheets, and the diameter of this sheet equals the external diameter of heating tube.
Step 2: place an insulated cavity in graphite heating pipe.
Particularly, in this step, need to be close to the inwall of graphite heating pipe and place insulated cavity. Insulated cavity 34 is positioned at the inner side of graphite heating pipe 31, and its height and diameter mate with height and the diameter of the hollow cavity of heating tube 31. Particularly, insulated cavity 34 comprises sidewall and upper and lower end cap, and it is cylindric that sidewall is, and be close to the inwall of heating tube 31. The thickness of the sidewall of insulated cavity 34 is selected between 1-10mm. The thickness of the end cap up and down of insulated cavity 34 can be adjusted as required.
The inside of insulated cavity 34 forms a hollow cavity, in this hollow cavity, absorbing cavity 35 will be set.
Due in the present embodiment, it is the heating by graphite heating pipe is switched on to realize, so, in order to ensure at the inner placement of graphite heating pipe insulated cavity, the space of insulated cavity inside does not have electric current process, like this, itself can not produce heat the absorbing cavity of insulated cavity inside, diamond bisque and metal binding agent layer, but only depends on the heat that absorbs graphite thermal-collecting tube to realize heating. Therefore, more easily realize the homogeneous heating to the material in absorbing cavity.
Step 3: place an absorbing cavity in insulated cavity.
Similarly, in the hollow cavity of insulated cavity, be close to the inwall of insulated cavity, place absorbing cavity 35. In one implementation, absorbing cavity 35 is formed by the compacting of porous class material, comprises sidewall and upper and lower end cap. The thickness of the sidepiece chamber wall of absorbing cavity 35 is: 1-10mm, the thickness of upper and lower end cap is 1-20mm. Here the porous class material mentioned is for the density of metal binding agent, that is, can allow metal binding agent to be adsorbed by it under molten condition. Here the porous mentioned might not mean that it has the hole that naked eyes can be seen, and hole can be relatively fine and close.
Step 4: place and place successively diamond bisque and metal binding agent layer in absorbing cavity.
Particularly, in a kind of implementation kind, can fill metal binding agent layer 32 and diamond layer 33 in the inside of absorbing cavity, metal adhesive layer comprises one or more metals in Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Hf, Ta, W, Re, 0s, Ir, is preferably Ti, V, Mn, the Ni of 1:1:1:2:2, the mixture of Fe. Diamond layer 33 is made up of diamond dust, and bortz powder can adopt micro mist or the varigrained admixed finepowder of same particle sizes.
In the preferred implementation of one, can below metal binding agent layer, diamond layer be set, and Thickness Ratio between metal binding agent layer and diamond layer can be made as 1:4. Present inventor finds, the amount of metal adhesive is unsuitable excessive, the molten carbon content of excessive metal is large, be unfavorable for quick saturated the separating out of carbon, the amount of metal adhesive is also unsuitable too small, the too small space of can not filling completely, causes and can not make whole diamond layer under uniform pressure field, and part diamond layer can not be realized sintering. Being preferably mixed-powder bortz powder and metal binding agent Thickness Ratio is 1:2.
Step 5: seal described absorbing cavity, insulated cavity and graphite heating pipe.
Placed metal binding agent and bortz powder in absorbing cavity after, first, by the upper end cover sealing absorbing cavity of absorbing cavity, then, sealing insulated cavity by insulating materials, last, seal graphite heating pipe by graphite flake.
Step 6: the graphite heating pipe having sealed is placed in peripheral pyrophillite assembled block, carries out pressure sintering. Under normal circumstances, graphite-pipe is tucked in the hole of pyrophillite assembled block, the shape of pyrophillite assembled block can be square.
In this step, conventionally the pyrophillite assembled block assembling is positioned in the middle of cubic hinge press. In the time that needs carry out sintering, in two phase double cones of cubic apparatus, pass to electric current, two addendum cones of energising withstand on respectively on the conducting strip at two ends up and down of pyrophillite. To the pressurization of experiment piece, make graphite heating pipe heating by electric current by cubic apparatus, the heat of graphite heating pipe is successively to internal delivery, and then the heating of realization to diamond bisque and metal binding agent layer. Adopt sintering method of the present invention to carry out diamond sintering, can for sintering provides, temperature be controlled, the sintering environment of pressure field homogeneous, and then realize integral sintered to polycrystalline diamond.
In the time adopting this sintering method to carry out diamond sintering, after temperature reaches certain limit, metal-to-metal adhesive can reach molten condition, in the time that metallic infiltration is swept more diamond layer, owing to additionally having added absorbing cavity between insulating barrier and diamond bisque, absorbing cavity can play and absorbs impurity and hold the effect of metal binding agent, and the composition that promotes like this metal that the moisture impurity in diamond layer etc. is played to ill effect is swept and run off diamond layer.
In the preferred implementation of one, absorbing cavity is made of porous materials. Can realize in this way the integral sintered of diamond bisque through experiment showed.
In the time utilizing sintering method of the present invention to carry out diamond pressure sintering, moulding pressure is preferably 5.0-6.0GPa, and sintering temperature is preferably 1200-1500 DEG C, and the time is preferably 15 seconds-1800 seconds, after sintering cooling release, can make polycrystalline diamond.
In one implementation, metal adhesive layer is positioned at centre or the bottom of diamond bisque.
In another kind of implementation, heating tube, insulated cavity, absorbing cavity all adopt rectangular structure.
The present invention utilizes absorbing cavity and insulated cavity to form a composite cavity, and this composite cavity had both played the effect of insulation, has also played the effect that absorbs and hold metal binding agent. Can realize in this way the integral sintered of diamond bisque through experiment showed.
Sintering method sintering structure of the present invention is evenly fine and close, synthetic reproducible, workable. In sintering process, by the metal filled diamond space of melting, form the pressure field of homogeneous, made sintering environment obtain optimization.
The Electronic Speculum figure of the polycrystalline diamond that the sintering method that Fig. 3 is one embodiment of the invention obtains. As shown in Figure 3, pass through ESEM, we further find that dimond synneusis cross section is smooth, the metal of initial residual is removed by acid treatment, form the direct combination between large-area diamond crystals, illustrate in this region that diamond crystals, by regrowth and take knot, has formed high densification and high-intensity growth type glomerocryst layer. In the diamond layer of entirety, particle is all bonded to each other, and has realized integral sintered.
It should be noted that; the shape of all parts in accompanying drawing of the present invention is all schematic; there is some difference not get rid of itself and its true shape, and accompanying drawing is only for principle of the present invention is described, and the detail of parts shown in figure is the restriction to invention protection domain not. Those skilled in the art also should be appreciated that, above-described embodiment is only also the explanation to schematic implementation of the present invention, not limiting the scope of the invention.
Claims (6)
1. a polycrystalline diamond sintering method, is characterized in that, described method comprises the steps:
Step 1: preparation graphite heating pipe;
Step 2: place an insulated cavity in described graphite heating pipe;
Step 3: place an absorbing cavity in described insulated cavity;
Step 4: place successively diamond bisque and metal binding agent layer in described absorbing cavity;
Step 5: seal described absorbing cavity, insulated cavity and graphite heating pipe;
Step 6: the described graphite heating pipe having sealed is placed in pyrophillite assembled block, pressurizesSintering, wherein, described absorbing cavity is made of porous materials, and described absorbing cavity comprises columned tube wallAnd top end cap and lower end cap.
2. polycrystalline diamond sintering method according to claim 1, is characterized in that,
In described absorbing cavity, place successively diamond bisque and metal binding agent layer comprises: in described suctionLayer of gold hard rock bisque is placed by the lower floor of receiving chamber, then on described diamond bisque, places layer of metalBond layer.
3. polycrystalline diamond sintering method according to claim 1, is characterized in that,
In described absorbing cavity, place successively diamond bisque and metal binding agent layer comprises: in described suctionLayer of gold hard rock bisque is placed by the lower floor of receiving chamber, then on described diamond bisque, places layer of metalBond layer, then on described metal binding agent layer, place layer of gold hard rock bisque.
4. polycrystalline diamond sintering method according to claim 1, is characterized in that, describedIn step 6, moulding pressure is 5.0-6.0GPa, and sintering temperature is 1200-1500 DEG C, and sintering time is10-3600 second.
5. polycrystalline diamond sintering method according to claim 1, is characterized in that, described stoneChina ink heating tube is cylindric, and the two ends up and down of this cylindric graphite heating pipe are sealed by conducting heating plate.
6. polycrystalline diamond sintering method according to claim 1, is characterized in that, described stoneThe height of China ink heating tube is 0.5-7cm.
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| CN106582448B (en) * | 2016-12-28 | 2019-02-19 | 安徽工业大学 | A kind of method that hydrothermal synthesis carbon ball prepares polycrystalline diamond micron ball |
| CN107376787B (en) * | 2017-08-24 | 2020-01-03 | 河南理工大学 | Method for rapidly synthesizing large-volume high-conductivity porous diamond electrode |
| CN107376786B (en) * | 2017-08-24 | 2020-12-18 | 河南理工大学 | High-hardness polycrystalline diamond sintering equipment and corresponding sintering method |
| CN112047740B (en) * | 2020-08-18 | 2021-08-03 | 北京科技大学 | Preparation method of aluminum nitride/diamond polycrystalline material |
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| CN1092481A (en) * | 1993-03-16 | 1994-09-21 | 黄河金刚石有限公司 | The production technique of man-made diamond |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63278545A (en) * | 1987-05-11 | 1988-11-16 | Sumitomo Electric Ind Ltd | Method for synthesizing diamond |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092481A (en) * | 1993-03-16 | 1994-09-21 | 黄河金刚石有限公司 | The production technique of man-made diamond |
Non-Patent Citations (2)
| Title |
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| "热稳定金刚石聚晶的制备及表征";黄海亮等;《超硬材料工程》;20110630;第1-5页 * |
| "铁基合金助剂制备金刚石复合片结构及物性研究";贾洪声等;《功能材料》;20131231;第2473-2475页 * |
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