CN101012129B - Method of modifying diamond film or natural diamond surface - Google Patents
Method of modifying diamond film or natural diamond surface Download PDFInfo
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- CN101012129B CN101012129B CN2006101316064A CN200610131606A CN101012129B CN 101012129 B CN101012129 B CN 101012129B CN 2006101316064 A CN2006101316064 A CN 2006101316064A CN 200610131606 A CN200610131606 A CN 200610131606A CN 101012129 B CN101012129 B CN 101012129B
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Abstract
The invention discloses a surface modifying method of diamond film or natural diamond, which is characterized by the following: arranging collet, connecting proof layer, metal layer, diamond film or natural diamond particle sequently; applying 20Kpa; placing the unit piece in the vacuum heating furnace; aerating hydrogen or methane as reducing protective gas to 500-3000pa; heating the piece to 800-1000 deg.c; insulating 10-50min.
Description
Technical field
The invention belongs to the applications of diamond field, particularly diamond thick-film or natural diamond process for surface modification method.
Background technology
Diamond film (CVD diamond) belongs to ceramic, it is the full matter polycrystalline diamond that adopts the chemical gaseous phase depositing process preparation, its inside is without any metal adhesive, and its physics, chemical property are widely used in fields such as optics, machinery, electronics near natural diamond.Because its surperficial chemical property, this material and most of metal or alloy scolder can not well soak into, therefore, also be not easy to weld together securely, influenced the application of diamond thick-film in fields such as calorifics, electronics, machineries with Wimet or metal base.
The patent of the relevant diamond welding of finding does not at present also relate to the process for modifying surface to large area diamond thick film.
It is generally acknowledged that the general and carbide of scolder can soak into preferably,,, can improve the welding effect of diamond film as Ti, Cr etc. at the direct evaporation one deck of diamond surface strong carbide metal.But because coating is thinner generally speaking, coating is diffused in the scolder and diluted during high-temperature soldering, and diamond surface can not form carbide, therefore this method and be not suitable for the welding of diamond thick-film instrument.
In the calorifics application facet, diamond thick-film has high thermal conductivity, it is preferred material as semiconductor laser thermal sediment, at present, mainly be to realize welding between the heat sink and chip of diamond film at the titanium film (diamond thick-film surface metalation) of diamond film surface vacuum evaporation thin layer, still, it is relatively poor that titanium and diamond film strong closed, thermal resistance is bigger, has seriously influenced radiating effect.
The mechanical workout aspect, the composite bed welding process of titanium valve under the high vacuum or titanium foil+silver-bearing copper weld tabs is mainly adopted in the welding of diamond thick-film at present, operation is: the diamond thick-film polishing is cut evil and is slit into fritter (being generally the cutter head shape)---diamond film and titanium valve or titanium foil under the high vacuum condition+silver-bearing copper weld tabs formation small area composite sheet---, and composite sheet and cutter hub weld under the high frequency, finish the welding process of cutter.
The advantage of this method is: can finish diamond thick-film and Wimet in high vacuum property welding next time, be made into the composite sheet of the diamond thick-film+Wimet of small area; At the interfacial layer place of welding, the diamond film surface forms titanium carbide layer, welding strength height.
But this method also has shortcoming:
When 1, the area of diamond film is big, because diamond and other material coefficient of thermal expansion coefficient differ bigger, interfacial layer produces very big stress and makes welding strength descend, therefore, be not suitable for making large-area composite sheet, can not with the manufacturing technology compatibility of present PCD diamond tool.
2, welding efficiency and productive rate are all very low, are not suitable for the scale production of diamond thick-film welded articles.
Summary of the invention
The technical problem to be solved in the present invention is: the surface modification of diamond membrane with large area, make the diamond film surface have the weldability energy, not only satisfy diamond film and make the welding requirements of cutter, can with existing P CD diamond weldprocedure compatibility, and use the diamond film of modification to make semiconductor laser thermal sediment, the thermal resistance of face of weld is little, can satisfy the heat sink service requirements of high power semiconductor lasers.
The method of the surface modification of diamond film of the present invention or natural diamond is to be modified material with the metal level, and said metal level is at two-layer Ag
72Accompanying the Ti powder in the middle of the Cu alloy slice and constitute, be to prevent articulamentum with moly-sulfide or talcum powder or hexagonal boron nitride powder, is collet with molybdenum sheet or graphite flake, carries out modification under the rough vacuum condition; The modified technique process has layoutprocedure, modifying process; Said layoutprocedure is, putting by the order of diamond film or natural diamond, metal level, anti-articulamentum, collet becomes test specimen, and the pressure that adds about 10～30KPa on it is put into vacuum furnace; Said modifying process is, charges into hydrogen or methane to 500～3000Pa in vacuum furnace, and test specimen is heated to 800～1000 ℃, is incubated 10～50 minutes, obtains the diamond film or the natural diamond of surface modification.
In the above-mentioned layoutprocedure, exerting pressure on the test specimen is for the metal level after dissolving is fully contacted with diamond film or natural diamond.The simplest method of on test specimen, exerting pressure, be add thereon one can be anti-pyritous weight more than 1500 ℃, layoutprocedure by bottom-up order is like this: collet, anti-articulamentum, metal level, diamond film (perhaps the natural diamond particle adds collet or metal level again), weight.The test specimen that also can use clip will configure order clips, and reaches required pressure.
Metal layer thickness can be Ag
72The thickness of Cu is 0.1～0.3mm, and the thickness of Ti powder is 5～50 microns.The granularity of Ti powder is 50～1000nm.The thickness of each layer of metal level can be decided according to the thickness of Modified Diamond.
To the surface modification of natural diamond, in layoutprocedure, three diamond particles can be positioned over the position on the Atria summit, and be clipped between two metal levels or be clipped between metal level and the molybdenum sheet.
In modifying process: can be evacuated to vacuum furnace the vacuum tightness of 2Pa, charge into reduction protection gas hydrogen or methane to 500～3000Pa again.Can determine according to modification thickness temperature and soaking time that test specimen is heated.After the insulation, can directly close the test specimen heating power supply, wait for that vacuum furnace was evacuated to about 2Pa when the test specimen temperature naturally cooled to below 400 ℃, test specimen is taken out in venting, can obtain the diamond film or the natural diamond particle of surface modification.
Adopt method of the present invention to carry out surface modification to the diamond thick-film of thickness more than 0.3mm.
Surface modifying method of the present invention in order to prevent the oxidation of diamond film, should carry out under vacuum condition, owing to be modification under rough vacuum, charge into hydrogen or methane as reduction protection gas; Be under certain pressure, diamond surface to be carried out modification between the diamond of test specimen and the metal level by the thermodiffusion principle; Modification temperature is incubated 10～50 minutes at 800 ℃～1000 ℃, makes the diamond film surface that the infiltration of titanium be arranged, and perhaps makes the diamond film surface form titanium carbide layer; Anti-articulamentum effect is that collet is not connected with diamond film; Collet is played a supporting role, and can use high temperature material, for example molybdenum sheet.
Characteristics of the present invention are:
1, the size that is modified of diamond film is big, owing to do not have stress problem, and in principle can be to the diamond thick-film modification of arbitrary dimension.
2, under the rough vacuum condition to diamond thick-film sheet surface modification, technology is simple.
3, the diamond film surface properties after the modification forms the carbide rete of a few to tens of nanometers, has good weldability energy, uses the diamond film tools of modification or heat sink, can with traditional process compatible.
Experiment showed, that the diamond film that adopts this technology to carry out surface modification can satisfy service requirements fully.For example: the finishing tool that adopts this composite sheet to make, in the sharpening process, whet a knife under 1800～3200 rev/mins of boart boart wheel speeds, diameter 100mm, the feed pressure 30 newton's situations, phenomenon can not occur snapping, the finishing tool of making can satisfy service requirements fully.Also can satisfy diamond film as circuit substrate encapsulation, requirement of welding.
Embodiment
Embodiment 1 provides a concrete diamond thick-film surface modification example.
Choose 1 millimeter of thickness, area 4cm
2Diamond thick-film, with the Ag of 200 micron thickness
72Cu alloy slice, mean particle size are made metal level at the thickness of 10 microns of the titanium valves of 500nm, use the hexagonal boron nitride powdered material to make anti-articulamentum.Diamond thick-film and substrate thereof with alcohol wash clean after, the order by collet, anti-articulamentum, metal level, diamond film, high temperature resistant weight sets from bottom to top, puts into vacuum furnace, the quality of institute's cheek weight is 1 kilogram.
Vacuum furnace is evacuated to 2Pa, charges into hydrogen to 2000Pa, and the test specimen in the vacuum chamber is heated to 900 ℃, heat-insulation pressure keeping 30 minutes.
Close the power supply of test specimen heating, make temperature slowly reduce to about 400 ℃.After vacuumizing, test specimen is taken out in venting, and modification finishes.
Embodiment 2 is about processing condition
On the basis of embodiment 1, use the Akg of 100 microns or 300 micron thickness
72Cu alloy slice, mean particle size are made metal level at the titanium valve of 100nm or 900nm; In modifying process, vacuum furnace charges into methane to 800Pa, and test specimen is heated to 800 ℃ or 1000 ℃, is incubated 50 minutes, and the surface modification of diamond thick-film is not had big influence.
Use talcum powder to make anti-articulamentum, collet is not connected with diamond thick-film.
3 two diamond films of embodiment are the example of single surface modification simultaneously.
The diamond film of 0.4 millimeter of molybdenum sheet collet, metal level, thickness that will scribble anti-articulamentum in order from bottom to top is as a unit test specimen, and the test specimen of another same unit is stacked together, and adds 1 kilogram of weight thereon, puts into vacuum furnace.To the diamond film surface modification, can obtain the diamond film of two single surface modifications according to the technology of example 1.
Method of modifying of the present invention also can carry out the multilayer modification.That is, with the above-mentioned modification unit (not comprising weight) that is configured to, also can fold up a graphite partition between per two modification unit in layoutprocedure, place vacuum furnace, weight is placed in the top.With modifying process and the processing condition of embodiment 1, can once obtain the diamond thick-film sheet of a plurality of modifications equally.
The multilayer modification is exactly simultaneously modification to be carried out on multi-disc diamond film surface.Diamond diaphragm number how much look implementation condition, as the size of the volume of vacuum furnace, diamond film area and decide.General, once modification is carried out on 20 diamond film surfaces and be fine.
The example of the two-sided modification of embodiment 4 diamond thick-films.
Method of modifying of the present invention can carry out two-sided modification to diamond film, and a need increase metal level successively between diamond film and weight and anti-articulamentum gets final product.That is, set, add 1 kilogram of weight thereon, put into vacuum furnace by from bottom to top order order with collet, anti-articulamentum, metal level, two-sided diamond film, metal level, anti-articulamentum.To the diamond film surface modification, can obtain the diamond film of two-sided surface modification according to the technology of example 1.
Embodiment 5 natural diamond surface modification examples
Method of modifying of the present invention can be used for the natural diamond surface modification.Because natural diamond is particulate state, can the modification simultaneously of three diamond particles be used the diamond thick-film of embodiment 1 instead be positioned on the Atria summit three diamond particles and be got final product.Promptly, by from bottom to top order successively with molybdenum sheet collet, anti-articulamentum, metal level, three natural diamonds (such as natural diamond surface modification to 0.4 carat/, put by triangular apex), the order of molybdenum sheet sets, put into vacuum furnace and add ballast.Obtain the diamond particles of three single face modifications according to the technology of example 1.
Also can carry out modification simultaneously, as long as a plurality of natural diamond particle yaws can be placed on the metal level to a plurality of natural diamond particles.
Also can carry out surface modification by method of the present invention to artificial diamond's stone granulate.
Claims (6)
1. the method for the surface modification of a diamond film is characterized in that, is modified material with the metal level, and said metal level is at two-layer Ag
72Accompanying the Ti powder in the middle of the Cu alloy slice and constitute, be to prevent articulamentum with moly-sulfide or talcum powder or hexagonal boron nitride powder, is collet with molybdenum sheet or graphite flake, carries out modification under the rough vacuum condition; The modified technique process has layoutprocedure, modifying process; Said layoutprocedure is that putting by the order of diamond film, metal level, anti-articulamentum, collet becomes test specimen, adds the pressure of 10～30KPa on it, puts into vacuum furnace; Said modifying process is, charges into hydrogen or methane to 500～3000Pa in vacuum furnace, and test specimen is heated to 800～1000 ℃, is incubated 10～50 minutes, obtains the diamond film of surface modification.
2. according to the method for the surface modification of the described diamond film of claim 1, it is characterized in that said metal level, Ag
72The thickness of Cu is 0.1～0.3mm, and the thickness of Ti powder is 5～50 microns, and granularity is 50～1000nm.
3. according to the method for the surface modification of claim 1 or 2 described diamond films, it is characterized in that said layoutprocedure is configured to a modification unit with diamond film, metal level, anti-articulamentum, collet, carries out 2～20 unitary while modifications.
4. according to the method for the surface modification of claim 1 or 2 described diamond films, it is characterized in that, in layoutprocedure, set by from bottom to top order order collet, anti-articulamentum, metal level, two-sided diamond film, metal level, anti-articulamentum, cheek weight thereon, put into vacuum furnace, realize the two-sided surface modification of diamond film.
5. the method for the surface modification of a natural diamond is characterized in that, is modified material with the metal level, and said metal level is at two-layer Ag
72Accompanying the Ti powder in the middle of the Cu alloy slice and constitute, be to prevent articulamentum with moly-sulfide or talcum powder or hexagonal boron nitride powder, is collet with molybdenum sheet or graphite flake, carries out modification under the rough vacuum condition; The modified technique process has layoutprocedure, modifying process; Said layoutprocedure is, successively the order of molybdenum sheet collet, anti-articulamentum, metal level, natural diamond, molybdenum sheet set by from bottom to top order, puts into vacuum furnace and adds ballast; Said modifying process is, charges into hydrogen or methane to 500～3000Pa in vacuum furnace, and test specimen is heated to 800～1000 ℃, is incubated 10～50 minutes, obtains the natural diamond of surface modification.
6. according to the method for the surface modification of the described natural diamond of claim 5, it is characterized in that said layoutprocedure is configured to a modification unit with natural diamond, metal level, anti-articulamentum, collet, carries out 2～20 unitary while modifications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101316064A CN101012129B (en) | 2006-11-08 | 2006-11-08 | Method of modifying diamond film or natural diamond surface |
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| CN2006101316064A CN101012129B (en) | 2006-11-08 | 2006-11-08 | Method of modifying diamond film or natural diamond surface |
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| CN101012129A CN101012129A (en) | 2007-08-08 |
| CN101012129B true CN101012129B (en) | 2010-04-14 |
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| CN2006101316064A Expired - Fee Related CN101012129B (en) | 2006-11-08 | 2006-11-08 | Method of modifying diamond film or natural diamond surface |
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| CN104591783B (en) * | 2015-01-29 | 2017-01-18 | 吉林大学 | Method for plating boron carbide on diamond surface |
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| US5037704A (en) * | 1985-11-19 | 1991-08-06 | Sumitomo Electric Industries, Ltd. | Hard sintered compact for a tool |
| US5523158A (en) * | 1994-07-29 | 1996-06-04 | Saint Gobain/Norton Industrial Ceramics Corp. | Brazing of diamond film to tungsten carbide |
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| CN1583354A (en) * | 2004-06-03 | 2005-02-23 | 吉林大学 | Method for connecting diamond thick film with hard base firmly |
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2006
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Patent Citations (7)
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| US5037704A (en) * | 1985-11-19 | 1991-08-06 | Sumitomo Electric Industries, Ltd. | Hard sintered compact for a tool |
| CN1006613B (en) * | 1987-11-28 | 1990-01-31 | 国家建筑材料工业局人工晶体研究所 | Welding-type polycrystal composite with synthetic diamond and its manufacturing method |
| US5523158A (en) * | 1994-07-29 | 1996-06-04 | Saint Gobain/Norton Industrial Ceramics Corp. | Brazing of diamond film to tungsten carbide |
| CN1094810C (en) * | 1999-12-27 | 2002-11-27 | 华南理工大学 | Active solder and its preparation |
| CN1583354A (en) * | 2004-06-03 | 2005-02-23 | 吉林大学 | Method for connecting diamond thick film with hard base firmly |
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| 亢世江等.焊接金刚石膜的试验研究及机理分析.焊接学报26 2.2005,26(2),77-80. * |
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Application publication date: 20070808 Assignee: Jilin Rong Rong Technology Co., Ltd. Assignor: Jilin University Contract record no.: 2013220000001 Denomination of invention: Method of modifying diamond film and nature diamond surface Granted publication date: 20100414 License type: Exclusive License Record date: 20130115 |
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