CN104707996A - Diamond compound body and diamond surface metallization method - Google Patents
Diamond compound body and diamond surface metallization method Download PDFInfo
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- CN104707996A CN104707996A CN201310682346.XA CN201310682346A CN104707996A CN 104707996 A CN104707996 A CN 104707996A CN 201310682346 A CN201310682346 A CN 201310682346A CN 104707996 A CN104707996 A CN 104707996A
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 143
- 239000010432 diamond Substances 0.000 title claims abstract description 143
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 title abstract 7
- 238000001465 metallisation Methods 0.000 title abstract 2
- 239000002245 particle Substances 0.000 claims abstract description 64
- 229910000521 B alloy Inorganic materials 0.000 claims abstract description 27
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 26
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims description 81
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 48
- 239000002994 raw material Substances 0.000 claims description 39
- 239000011268 mixed slurry Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 24
- 238000007747 plating Methods 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 20
- 230000004044 response Effects 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000005275 alloying Methods 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- FZQBLSFKFKIKJI-UHFFFAOYSA-N boron copper Chemical group [B].[Cu] FZQBLSFKFKIKJI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract 5
- 239000011247 coating layer Substances 0.000 abstract 2
- 239000002103 nanocoating Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 19
- 239000002002 slurry Substances 0.000 description 17
- 238000000635 electron micrograph Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 239000011365 complex material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910001651 emery Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001097 yellow gold Inorganic materials 0.000 description 2
- 239000010930 yellow gold Substances 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BHVBAMIQYZRMLW-UHFFFAOYSA-N boron silver Chemical compound [B].[Ag] BHVBAMIQYZRMLW-UHFFFAOYSA-N 0.000 description 1
- YGBGWFLNLDFCQL-UHFFFAOYSA-N boron zinc Chemical compound [B].[Zn] YGBGWFLNLDFCQL-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a diamond compound body and a diamond surface metallization method. In particular, the invention provides a diamond compound body; the diamond compound body comprises a diamond particle and a compound coating layer bonded on the surface of the diamond particle, wherein the compound coating layer consists of a boron carbide nanometer layer and a boron alloy nanometer layer; the boron carbide nanometer layer is bonded on the surface of the diamond particle; and the boron alloy nanometer layer is combined with the boron carbide nanometer layer. The compound body material has excellent performance and wide application.
Description
Technical field
The invention belongs to diamond composite field.Particularly, the present invention relates to a kind of diamond complex and Ways of Metallizing Cladding onto Diamond Surface.
Background technology
At present, in general diamond tool base material is carbide alloy or stainless steel, and welding diamond chip or diamond particles subject matter are that between diamond and metal, bond strength is low on the substrate.
For improving the life-span of diamond tool, adopting Modified Diamond method to improve diamond surface becomes more rational method with intermetallic wellability and bond strength.Current domestic plating is adopt magnetron sputtering, chemical plating, plating, the method such as PVD, CVD at diamond surface depositing metal layers or carbide lamella to improve diamond and intermetallic adhesion more uniformly.Relative plating, chemical plating, owing to being still in mechanical snap between coated metal and diamond, bond strength is not high therebetween; Then equipment cost is high on the one hand for PVD, CVD and magnetron sputtering, and inefficiency is not suitable for bortz powder surface modification on the other hand, and coating surface uniformity is difficult to control.
In sum, this area is in the urgent need to a kind of low cost, the method significantly improving the diamond particle surfaces modification of diamond and intermetallic binding ability or product.
Summary of the invention
An object of the present invention is to provide that a kind of method for making is easy, the diamond complex material of excellent performance and method for making thereof.
In a first aspect of the present invention, provide a kind of diamond complex, described complex comprises diamond particles and is incorporated into the composite coating of diamond particle surfaces;
Wherein, described composite coating comprises boron carbide nanometer layer and boron alloy nanometer layer, and described boron carbide nanometer layer is incorporated into diamond particle surfaces; Described boron alloy nanometer layer is incorporated into described boron carbide nanometer layer surface.
In a preference, described composite coating is by being formed in diamond particle surfaces growth in situ one step.
In another preference, described composite coating be by the boron formed at diamond particle surfaces growth in situ and boron carbide and alloying metal blended after obtained through adding thermal response.
In another preference, described composite coating the boron formed at diamond particle surfaces growth in situ and boron carbide is added after chemical plating or plating alloy metal thermal response to obtain.
In another preference, described diamond particles is natural diamond powder, block or film; Or be the diamond powder, block or the film that generate through high temperature, high pressure or chemical vapour deposition (CVD).
In another preference, the gross thickness of described composite coating is 1-1000000nm; Preferably, be 10-500000nm.
In another preference, described composite coating is also containing boron nanometer layer, and described boron nanometer layer is between described boron carbide nanometer layer and boron alloy nanometer layer.
In another preference, the described boron alloy boron alloy that to be boron formed with the alloying metal being selected from lower group: copper, aluminium, nickel, silver or its combine.
In second aspect present invention, provide a kind of preparation method of diamond complex, comprise step:
(1) a kind of mixed slurry comprising diamond particles, boron raw material, copper raw material and organic solvent is provided;
(2) under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, the mixed slurry of step (1) is carried out adding thermal response, thus obtains the diamond complex described in a first aspect present invention; And described boron alloy is boron copper alloy.
In another preference, by the mixed slurry total weight of step (1), the mass fraction of diamond particles is 5-95wt%; Be preferably 20-85wt%; Be more preferably 20-65wt%; And/or
By the mixed slurry total weight of step (1), the mass fraction of boron raw material is 10-90wt%; Be preferably 10-50wt%; Be more preferably 10-40wt%; And/or
By the mixed slurry total weight of step (1), the mass fraction of copper raw material is 10-95wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%; And/or
By the mixed slurry total weight of step (1), the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%.
In third aspect present invention, provide a kind of preparation method of diamond complex, comprise step:
A mixed slurry that () provides one to comprise diamond particles, boron raw material and organic solvent; With
(b) under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, the mixed slurry of step (a) is carried out adding thermal response, thus obtains diamond complex intermediate; With
(c-1) by diamond complex intermediate obtained for step (b) and alloying metal raw material and organic solvent blended, under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, carry out adding thermal response, thus obtain diamond complex; Or
(c-2) the diamond complex intermediate that step (b) is obtained is through chemical plating or electroplating processes, plating one deck alloying metal layer on the surface of this intermediate, then, under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, carry out adding thermal response, thus obtain diamond complex as described in the first aspect of the invention.
In another preference, by the mixed slurry total weight of step (a), the mass fraction of diamond particles is 5-95wt%; Be preferably 20-85wt%; Be more preferably 20-65wt%; And/or
By the mixed slurry total weight of step (a), the mass fraction of boron raw material is 10-90wt%; Be preferably 10-50wt%; Be more preferably 10-40wt%; And/or
By the mixed slurry total weight of step (a), the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%; And/or
In described step (c-1), by blended rear total weight, the mass fraction of alloying metal raw material is 10-95wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%; And/or the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%.
In another preference, described copper raw material, described boron raw material and/or described alloying metal raw material are pulverous; And/or
Described diamond raw material is natural diamond powder, block or film; Or through the diamond powder of high temperature, high pressure or chemical vapor deposition process, block or film.
In another preference, in each step above-mentioned,
The described thermal response that adds is the reaction carried out at 1000-1400 DEG C; And/or
It is described that to add thermal response be in a vacuum or be the reaction carried out in the atmosphere between 1Pa-120kPa at pressure.
In fourth aspect present invention, provide the purposes of the diamond complex described in first aspect present invention, for machinery knives goods, impregnated bit, composite or electronic devices and components.
In fifth aspect present invention, provide a kind of goods or composite, comprise the diamond complex described in first aspect present invention.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is the microcosmic stereoscan photograph of the diamond particles without any process; Wherein: A figure is 200 times of displaing micro pictures, B figure is 1500 times of displaing micro pictures.
Fig. 2 is the diamond particles particle surface XRD collection of illustrative plates after powder surface plating nano coating that embodiment 1 obtains.As seen from the figure, there is boron carbide in diamond particle surfaces.
Fig. 3 is the obtained diamond particles particle surface electron micrograph crossed through powder surface plating of embodiment 2 and can spectrogram; Wherein, scheming A and scheming B is electron micrograph; Figure C is energy spectrogram; As seen from the figure: diamond particle surfaces exists boron copper alloy layer.
Fig. 4 is the obtained diamond particles particle surface electron micrograph crossed through powder surface plating of embodiment 3 and can spectrogram; Wherein, scheming A and scheming B is electron micrograph; Figure C is energy spectrogram; As seen from the figure: diamond particle surfaces exists boron aluminium alloy layer.
Fig. 5 is the obtained diamond particles particle surface electron micrograph crossed through powder surface plating of embodiment 4 and can spectrogram; Wherein, scheming A and scheming B is electron micrograph; Figure C is energy spectrogram; As seen from the figure: diamond particle surfaces exists nickel boron alloy layer.
Fig. 6 is the obtained diamond particles particle surface electron micrograph crossed through powder surface plating of embodiment 7 and can spectrogram; Wherein, scheming A is electron micrograph; Figure B is energy spectrogram; As seen from the figure: diamond particle surfaces exists boron Kufil layer gold.
Detailed description of the invention
Inventor is through extensive and deep research, find the diamond complex of a kind of diamond and corrupt split performance excellence, it connects diamond and metal by boron carbide transition zone, significantly improve both Interface adhesive strengths, in many-sides such as diamond cutter, diamond bit, electronics, there is good application prospect.And provide the preparation method of this complex multiple.On this basis, inventor completes the present invention.
Diamond
The present invention's diamond used can be natural diamond powder, block or film, or through the diamond powder of high temperature, high pressure or chemical vapor deposition process, block or film.
Diamond of the present invention can be the particle of arbitrary dimension, and preferably employing particle diameter is the diamond particles of 0.1 μm ~ 10000 μm; Preferably employing particle diameter is the diamond particles of 10 μm ~ 1000 μm; More preferably employing particle diameter is the diamond particles of 20 μm ~ 1000 μm.
Also can be block and the film of any thickness, need according to production application and determine.
Boron raw material
As used herein, described boron raw material is Powdered.
Alloying metal raw material
As used herein, described alloying metal raw material is Powdered or sheet.Described alloying metal can be any metal having certain solubility under high temperature (as 800-1500 DEG C) with boron, such as copper, nickel, aluminium, silver, zinc etc.
Organic solvent
As used herein, described organic moltenly comprise alcohol, polyvinyl alcohol, polyethylene glycol etc., effect makes diamond and boron raw material, alloying metal raw material uniform contact.
The composite coating of diamond particle surfaces
As used herein, described composite coating comprises boron carbide nanometer layer and boron alloy nanometer layer, and described boron carbide nanometer layer is incorporated into diamond particle surfaces; Described boron alloy nanometer layer is incorporated into described boron carbide nanometer layer surface.
Preferably, described composite coating is also containing boron nanometer layer, and described boron nanometer layer is between described boron carbide nanometer layer and boron alloy nanometer layer.
Preferably, described boron alloy nano coating comprises: boron copper alloy nano coating, boron aluminium alloy nano coating, boron zinc alloy nano coating, nickel boron alloy nano coating, boron silver alloy nano coating etc.
Preferably, the gross thickness of described described composite coating is 1 – 1000000nm; Preferably, be 10 – 500000nm.
Preparation method
In the preparation method of diamond complex of the present invention, the described thermal response that adds normally is carried out under 800-1400 DEG C (preferred 1150-1350 DEG C), and the time of reaction is generally 1-240 minute (being preferably 60-120 minute).It is described that to add thermal response be in a vacuum or be the reaction carried out in the atmosphere between 1Pa-120kPa at pressure.
In a preference, preparation method of the present invention comprises step:
(1) a kind of mixed slurry comprising diamond particles, boron raw material, copper raw material and organic solvent is provided;
(2) under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, the mixed slurry of step (1) is carried out adding thermal response, thus obtains a diamond complex; And described boron alloy is boron copper alloy.
By the mixed slurry total weight of step (1), the mass fraction of diamond particles is 5-95wt%; Be preferably 20-85wt%; Be more preferably 20-65wt%.
By the mixed slurry total weight of step (1), the mass fraction of boron raw material is 10-90wt%; Be preferably 10-50wt%; Be more preferably 10-40wt%.
By the mixed slurry total weight of step (1), the mass fraction of copper raw material is 10-95wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%.
By the mixed slurry total weight of step (1), the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%.
In another preference, preparation method of the present invention comprises step:
A mixed slurry that () provides one to comprise diamond particles, boron raw material and organic solvent; With
(b) under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, the mixed slurry of step (a) is carried out adding thermal response, thus obtains diamond complex intermediate; With
(c-1) by diamond complex intermediate obtained for step (b) and alloying metal raw material and organic solvent blended, under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, carry out adding thermal response, thus obtain diamond complex; Or
(c-2) the diamond complex intermediate that step (b) is obtained is through chemical plating or electroplating processes, plating one deck alloying metal layer on the surface of this intermediate, then, under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, carry out adding thermal response, thus obtain diamond complex.
By the mixed slurry total weight of step (a), the mass fraction of diamond particles is 5-95wt%; Be preferably 20-85wt%; Be more preferably 20-65wt%; And/or
By the mixed slurry total weight of step (a), the mass fraction of boron raw material is 10-90wt%; Be preferably 10-50wt%; Be more preferably 10-40wt%; And/or
By the mixed slurry total weight of step (a), the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%; And/or
In described step (c-1), by blended rear total weight, the mass fraction of alloying metal raw material is 10-95wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%; And/or the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%.
Now for diamond-boron carbide nanometer layer-boron copper alloy nanometer layer complex, the forming process of diamond complex of the present invention is described.First by diamond particles, boron powder, copper powder and organic solvent, mix formation slurry, then at high temperature, in slurry after organic solvent volatilization, the carbon of the boron and diamond surface that are evenly distributed on diamond particle surfaces reacts and generates boron carbide, copper powder is progressively in thawing or half melting state simultaneously, by melting liquid phase, unreacted boron is transferred to unreacted diamond surface, diamond particle surfaces is made to be uniformly distributed one deck boron carbide layer, then due to boron carbide and the good associativity of boron, make to form one deck boron layer at boron carbide layer outer surface, under this state, in boron layer, boron atom active is larger, a large amount of copper liquid phases of meeting and surrounding form Cu-B alloy layer at diamond particles outermost layer.
Application
Diamond complex of the present invention is firmly combined between diamond and metal by chemical bonds, improves the wetability between diamond and metal, the associativity particularly between diamond powder and metal.This new material, owing to completely solving the problem of associativity between diamond and metal, has good application prospect, such as, for the preparation of machinework, composite, electronic devices and components in many-sides such as machinery, material, electronics.Described machinework can comprise: cutter, grinding tool, file, emery wheel, saw blade, drill bit etc.Described composite can comprise: heat-radiating substrate, fin etc.
Major advantage of the present invention comprises:
1. the invention provides a kind of novel diamond complex material, significantly improve the problem of bond strength between diamond and metal.There is good application prospect, such as, for the preparation of machinework, composite, electronic devices and components in many-sides such as machinery, material, electronics.
2. present invention also offers the preparation method of above-mentioned composite.The preparation technology of the diamond surface coating that the method is different from the past, has treatment facility simple, cheap, preparation technology simply, advantage fast.
Below in conjunction with concrete enforcement, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise percentage and number calculate by weight.Unless stated otherwise, the raw materials used or reagent of the present invention all commercially.
Embodiment 1 diamond-boron carbide-boron nano coating complex (as diamond complex intermediate of the present invention)
Be that the diamond particles of about 100 μm mixes make mixture with high purity boron powder and a small amount of polyethylene glycol (molecular weight is 2000) by average grain diameter, calculate by mixture total weight gauge, boron powder accounts for 10wt%, and polyethylene glycol accounts for 5wt%.Mixture is placed in mixer to be uniformly mixed and is prepared into slurry.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1250 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 orders, 300 mesh sieves, then ultrasonic ion respectively, removes superfluous boron powder, obtains diamond-boron carbide-boron nano coating complex.The XRD diffraction picture of this complex as shown in Figure 2, shows diamond particle surfaces and generates boron carbide in figure.
Embodiment 2 diamonds-boron carbide-boron copper alloy nano coating complex
Diamond-boron carbide-boron nano coating the complex obtained by embodiment 1 and copper powder, alcohol are for form slurry, and then press slurry total weight, copper powder accounts for 10wt%, and alcohol accounts for 5wt%.Slurry is placed in mixer and is uniformly mixed.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1000 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 orders, 300 mesh sieves, then ultrasonic ion respectively, removes superfluous copper powder, obtains diamond-boron carbide-boron copper alloy nano coating complex.Its electron micrograph and energy spectrogram are as shown in Figure 3.
The electron scanning micrograph of this complex is as shown in the A figure and B figure of Fig. 3, and showing diamond particle surfaces growth in figure has a coating.
The EDS photo of this complex is as shown in the C figure of Fig. 3.The energy spectrum analysis of this coating can determine the distribution situation of diamond particle surfaces element: there is copper, boron, carbon in this coating.
Embodiment 3 diamonds-boron carbide-boron aluminium alloy nano coating complex
Diamond-boron carbide-boron nano coating the complex obtained by embodiment 2 and aluminium powder, alcohol are for form slurry, and then press slurry total weight, aluminium powder accounts for 10wt%, and alcohol accounts for 5wt%.Slurry is placed in mixer and is uniformly mixed.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1000 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 orders, 300 mesh sieves respectively, removes superfluous aluminium powder, obtains diamond-boron carbide-boron aluminium alloy nano coating complex.Its electron micrograph and energy spectrogram are as shown in Figure 4.
Embodiment 4 diamonds-boron carbide-nickel boron alloy nano coating complex
Diamond-boron carbide-boron nano coating the complex obtained by embodiment 2 and nickel powder, alcohol are for form slurry, and then press slurry total weight, nickel powder accounts for 20wt%, and alcoholic solution accounts for 5wt%.Slurry is placed in mixer and is uniformly mixed.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1000 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 orders, 300 mesh sieves, then ultrasonic ion respectively, removes superfluous nickel powder, obtains diamond-boron carbide-nickel boron alloy nano coating complex.Its electron micrograph and energy spectrogram are as shown in Figure 5.
Embodiment 5 diamonds-boron carbide-boron copper alloy coating complex
Diamond-boron carbide-boron nano coating complex that embodiment 2 is obtained is put into chemical copper plating solution or copper electroplating solution in above-mentioned powder surface plating one deck layers of copper, then the powder of this plated copper is put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1000 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 orders, 300 mesh sieves, then ultrasonic ion respectively, obtains diamond-boron carbide-boron copper alloy nano coating complex.
Embodiment 6 diamonds-boron carbide-nickel boron alloy coating complex
Diamond-boron carbide-boron nano coating complex that embodiment 2 is obtained is put into chemical nickel-plating solution or nickel plating solution at above-mentioned powder surface plating one deck nickel dam, then the powder of this plated nickel is put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1000 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 orders, 300 mesh sieves, then ultrasonic ion respectively, obtains diamond-boron carbide-nickel boron alloy nano coating complex.
Embodiment 7 diamonds-boron carbide-boron yellow gold coating complex
Be that the diamond particles of about 10 μm mixes with high purity boron powder and a small amount of polyethylene glycol and makes mixture by average grain diameter, calculate by mixture total weight gauge, boron powder accounts for 10wt%, and polyethylene glycol accounts for 5wt%.Mixture is placed in mixer to be uniformly mixed and is prepared into slurry.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1250 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, removal of impurities, removes superfluous boron powder, obtains diamond-boron carbide-boron nano coating complex.
By diamond-boron carbide-boron nano coating complex obtained for above-mentioned steps and silver powder, copper powder, alcohol for form slurry, then slurry total weight is pressed, silver-bearing copper powder (copper: silver=40:60 (w/w)) accounts for 10wt%, and alcohol accounts for 5wt%.Slurry is placed in mixer and is uniformly mixed.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa – 120kPa, and heating rate is that 10 DEG C/min is warming up to 1000 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, removal of impurities, removes superfluous copper silver powder, obtains diamond-boron carbide-boron yellow gold coating complex.Its electron micrograph and energy spectrogram are as shown in Figure 6.
Embodiment 8 diamonds-boron carbide-boron copper alloy nano coating complex
Be diamond particles and high-purity (purity >=99.99%) boron powder of about 100 μm by average grain diameter, copper powder and a small amount of alcohol mixes and make mixture, calculate by mixture total weight gauge, copper powder accounts for 30wt%, and boron powder accounts for 10wt%, and alcohol accounts for 5wt%.Mixture is placed in mixer to be uniformly mixed and is prepared into slurry.Put into vacuum carbon tube furnace, be evacuated to vacuum and be about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and heating rate is that 10 DEG C/min is warming up to 1250 DEG C, and insulation 60min, then cools to room temperature with the furnace.
Mixture high-temperature process crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous boron powder, obtains diamond-boron carbide-boron copper alloy nano coating complex.
Embodiment 9
Diamond-boron carbide after above-mentioned process-boron copper alloy nano coating complex is prepared into metal wheel, and intersect common domestic emery wheel, cutting speed improves more than 4 times, and the working durability improves more than 5 times, and machining accuracy increases substantially.
The above is preferred embodiment of the present invention, but the present invention should not be confined to diamond-boron carbide-boron-boron copper alloy coating complex, diamond-boron carbide-boron-nickel boron alloy coating complex, the preparation of diamond-boron carbide-boron-boron silver alloy coating complex.The complex material of the class dimantine-boron carbide-boron-boron metal composite coating formed at the element adopting all energy such as this preparation side other diamond-boron of acquisition and compound-boron metal coating complex thereof and diamond particle surfaces to grow carbide all should in scope.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (13)
1. a diamond complex, is characterized in that, described complex comprises diamond particles and is incorporated into the composite coating of diamond particle surfaces;
Wherein, described composite coating comprises boron carbide nanometer layer and boron alloy nanometer layer, and described boron carbide nanometer layer is incorporated into diamond particle surfaces; Described boron alloy nanometer layer is incorporated into described boron carbide nanometer layer surface.
2. diamond complex as claimed in claim 1, it is characterized in that, described diamond particles is natural diamond powder, block or film; Or be the diamond powder, block or the film that generate through high temperature, high pressure or chemical vapour deposition (CVD).
3. diamond complex as claimed in claim 1, it is characterized in that, the gross thickness of described composite coating is 1-1000000nm.
4. diamond complex as claimed in claim 1, is characterized in that, described composite coating is also containing boron nanometer layer, and described boron nanometer layer is between described boron carbide nanometer layer and boron alloy nanometer layer.
5. diamond complex as claimed in claim 1, is characterized in that, described boron alloy is the boron alloy that boron is formed with the alloying metal being selected from lower group: copper, aluminium, nickel, silver or its combine.
6. a preparation method for diamond complex, is characterized in that, comprises step:
(1) a kind of mixed slurry comprising diamond particles, boron raw material, copper raw material and organic solvent is provided;
(2) under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, the mixed slurry of step (1) is carried out adding thermal response, thus obtains a diamond complex as claimed in claim 1; And described boron alloy is boron copper alloy.
7. preparation method as claimed in claim 6, is characterized in that,
By the mixed slurry total weight of step (1), the mass fraction of diamond particles is 5-95wt%; Be preferably 20-85wt%; Be more preferably 20-65wt%; And/or
By the mixed slurry total weight of step (1), the mass fraction of boron raw material is 10-90wt%; Be preferably 10-50wt%; Be more preferably 10-40wt%; And/or
By the mixed slurry total weight of step (1), the mass fraction of copper raw material is 10-95wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%; And/or
By the mixed slurry total weight of step (1), the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%.
8. a preparation method for diamond complex, is characterized in that, comprises step:
A mixed slurry that () provides one to comprise diamond particles, boron raw material and organic solvent; With
(b) under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, the mixed slurry of step (a) is carried out adding thermal response, thus obtains diamond complex intermediate; With
(c-1) by diamond complex intermediate obtained for step (b) and alloying metal raw material and organic solvent blended, under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, carry out adding thermal response, thus obtain diamond complex; Or
(c-2) the diamond complex intermediate that step (b) is obtained is through chemical plating or electroplating processes, plating one deck alloying metal layer on the surface of this intermediate, then, under vacuo or hydrogen, argon gas or its combination inert atmosphere or reducing atmosphere in, carry out adding thermal response, thus obtain diamond complex according to claim 1.
9. preparation method as claimed in claim 8, is characterized in that,
By the mixed slurry total weight of step (a), the mass fraction of diamond particles is 5-95wt%; Be preferably 20-85wt%; Be more preferably 20-65wt%; And/or
By the mixed slurry total weight of step (a), the mass fraction of boron raw material is 10-90wt%; Be preferably 10-50wt%; Be more preferably 10-40wt%; And/or
By the mixed slurry total weight of step (a), the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%; And/or
In described step (c-1), by blended rear total weight, the mass fraction of alloying metal raw material is 10-95wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%; And/or the mass fraction of organic solvent is 0-90wt%; Be preferably 1-35wt%; Be more preferably 1-5wt%.
10. the preparation method as described in claim 6 or 8, is characterized in that,
Described copper raw material, described boron raw material and/or described alloying metal raw material are pulverous; And/or
Described diamond raw material is natural diamond powder, block or film; Or through the diamond powder of high temperature, high pressure or chemical vapor deposition process, block or film.
11. preparation methods as described in claim 6 or 8, is characterized in that, in each step above-mentioned,
The described thermal response that adds is the reaction carried out at 1000-1400 DEG C; And/or
It is described that to add thermal response be in a vacuum or be the reaction carried out in the atmosphere between 1Pa – 120kPa at pressure.
The purposes of 12. diamond complexes as claimed in claim 1, is characterized in that, for machinery knives goods, impregnated bit, composite or electronic devices and components.
13. 1 kinds of goods or composite, is characterized in that, comprises diamond complex according to claim 1.
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| CN108326289A (en) * | 2018-04-20 | 2018-07-27 | 佛山市金纳新材料科技有限公司 | A kind of method of modifying and Nano metal powder modification diamond of diamond |
| CN108941540A (en) * | 2018-07-25 | 2018-12-07 | 芜湖昌菱金刚石工具有限公司 | A kind of preparation method of diamond surface cladding boron alloy cladding |
| CN108941541A (en) * | 2018-07-25 | 2018-12-07 | 芜湖昌菱金刚石工具有限公司 | A kind of method that diamond surface forms high-temperature stable coating |
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