CN103964430B - Diamond-nanowire complex and preparation method thereof - Google Patents
Diamond-nanowire complex and preparation method thereof Download PDFInfo
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- CN103964430B CN103964430B CN201310042004.1A CN201310042004A CN103964430B CN 103964430 B CN103964430 B CN 103964430B CN 201310042004 A CN201310042004 A CN 201310042004A CN 103964430 B CN103964430 B CN 103964430B
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- 239000002070 nanowire Substances 0.000 title claims abstract description 175
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000010668 complexation reaction Methods 0.000 title abstract description 5
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 121
- 239000010432 diamond Substances 0.000 claims abstract description 121
- 229910052796 boron Inorganic materials 0.000 claims abstract description 111
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 88
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 21
- 229910052582 BN Inorganic materials 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 238000011065 in-situ storage Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- JXOOCQBAIRXOGG-UHFFFAOYSA-N [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] Chemical compound [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] JXOOCQBAIRXOGG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- -1 norbide Chemical compound 0.000 claims description 3
- 239000011365 complex material Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 39
- 239000011812 mixed powder Substances 0.000 description 29
- 239000010949 copper Substances 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000009413 insulation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 229910000570 Cupronickel Inorganic materials 0.000 description 3
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 3
- 229910001573 adamantine Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 229910001651 emery Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
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Abstract
The present invention relates to diamond-nanowire complex and preparation method thereof.Particularly, the invention provides a kind of diamond-nanowire complex and preparation method, it comprises diamond particles and is incorporated into the nano wire of described diamond particle surfaces, and wherein said nano wire comprises boron nanowire, boride nanowires or its combination.This complex material has excellent performance, applies widely.
Description
Technical field
The invention belongs to diamond composite field.Particularly, the present invention relates to diamond-nanowire complex and preparation method thereof.
Background technology
At present, diamond is the material that occurring in nature thermal conductivity is the highest, the thermal conductivity of high-quality single-crystal diamond can reach 2000W/ (mK), and it also has the features such as specific inductivity is low, thermal expansivity is low, makes diamond composite become the first-selection of packaged material of new generation.But single diamond not easily makes packaged material, and production cost is quite high, seriously hamper adamantine application.But, how both to retain adamantine premium properties, and expanded the production cost of adamantine range of application and reduction diamond simultaneously, remain a large difficult point of this area.
Therefore, in the urgent need to developing, a kind of method for making is easy, the diamond composite of excellent performance in this area.
Summary of the invention
The object of this invention is to provide that a kind of method for making is easy, the diamond composite of excellent performance and method for making thereof.
In a first aspect of the present invention, provide a kind of diamond-nanowire complex, described complex body comprises diamond particles and is incorporated into the nano wire of described diamond particle surfaces, and wherein, described nano wire comprises: boron nanowire, boride nanowires or its combination.
In another preference, described is combined into chemical bonds.
Select in example one, described nano wire is by being formed at diamond particle surfaces growth in situ.
In another preference, described nano wire is that the boron nanowire formed at diamond particle surfaces growth in situ is carried out reacting by heating in reactive atmosphere (as oxygen, nitrogen, ammonia isoreactivity atmosphere), thus obtains the boride nanowires being incorporated into diamond particle surfaces.
In another preference, described nano wire is mixed with metal-powder (as metal-powders such as magnesium powder, carbon dust, aluminium powder, titanium valve, zirconium powder, samarium powder, sulphur powder) and carry out reacting by heating by the boron nanowire formed at diamond particle surfaces growth in situ, thus the boride nanowires being incorporated into diamond particle surfaces obtained.
In another preference, described diamond particles particle diameter is 0.1 ~ 10000 μm.
In another preference, the particle diameter of described diamond particles is 10 ~ 1000 μm; Be more preferably 50 ~ 1000 μm.
In another preference, described nano wire has following characteristics:
I () length is 0.1 ~ 300 μm; And/or
(ii) diameter is 1 ~ 5000nm; And/or
(iii) it is 1 ~ 10000/μm in the density of diamond surface
2.
In another preference, described nanowire length is 1 ~ 300 μm.
In another preference, described nanowire diameter is 1 ~ 500nm.
In another preference, described boride comprises: boron oxide, norbide, boron nitride, boronation magnesium, aluminum boride, titanium boride, zirconium boride 99.5004323A8ure, samarium boride, sulfuration boron.
In second aspect present invention, provide the preparation method of a kind of diamond-boron nanowire complex body, it comprises step:
(1) mixture that comprises diamond particles, boron raw material and metal catalyst is provided;
(2) under vacuo or be selected from hydrogen, argon gas, the inert atmosphere of its composition gas or reducing atmosphere, the mixture of step (1) is carried out reacting by heating, thus obtaining diamond-boron nanowire complex body, described complex body comprises diamond particles and is incorporated into the boron nanowire of described diamond particle surfaces.
In another preference, described boron nanowire has following characteristics:
I () length is 0.1 ~ 300 μm; And/or
(ii) diameter is 1 ~ 5000nm; And/or
(iii) it is 1 ~ 10000/μm in the density of diamond surface
2.
In another preference, described diamond particles particle diameter is 0.1 ~ 10000 μm; Be preferably 10 ~ 1000 μm; Be more preferably 50 ~ 1000 μm.
In another preference, described metal catalyst comprises: copper, gold, nickel, platinum or their alloy.
In another preference, calculate by the mixture total weight gauge of step (1), the massfraction of metal catalyst is 10-90wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%.
In another preference, in described step (1), boron raw material is Powdered or liquid; And/or
In described step (1), boron raw material comprises pure boron and boron compound (preferably, described boron compound comprises boric acid); And/or
Calculate by the mixture total weight gauge of step (1), the massfraction of boron raw material is 1-15wt% (being preferably 5-10wt%).
In third aspect present invention, provide the preparation method of a kind of diamond-boride nanowires complex body,
(I) described method comprises step:
A mixture that () provides one to comprise diamond particles, boron raw material and metal catalyst; With
B () is in the reactive atmosphere of oxygen, ammonia or nitrogen, the mixture of step (1) is carried out reacting by heating, thus obtaining diamond-boride nanowires complex body, described complex body comprises diamond particles and is incorporated into the boride nanowires of described diamond particle surfaces;
Or
(II) described method comprises step:
In the reactive atmosphere of oxygen, ammonia or nitrogen, diamond preparation method described in second aspect present invention obtained-boron nanowire complex body carries out reacting by heating, thus obtaining diamond-boride nanowires complex body, described complex body comprises diamond particles and is incorporated into the boride nanowires of described diamond particle surfaces;
Or
(III) described method comprises step:
In a vacuum, reacting by heating is carried out after diamond preparation method described in second aspect present invention obtained-boron nanowire complex body mixes with metal-powder, thus obtaining diamond-boride nanowires complex body, described complex body comprises diamond particles and is incorporated into the boride nanowires of described diamond particle surfaces.
In another preference, described boride nanowires has following characteristics:
I () length is 0.1 ~ 300 μm; And/or
(ii) diameter is 1 ~ 5000nm; And/or
(iii) it is 1 ~ 10000/μm in the density of diamond surface
2.
In another preference, in described method (a), described metal catalyst comprises: copper, gold, nickel, platinum or their alloy.
In another preference, calculate by the mixture total weight gauge of step (a), the massfraction of metal catalyst is 10-90wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%.
In another preference, in described step (a), boron raw material is Powdered or liquid.
In another preference, in described step (a), boron raw material comprises pure boron and boron compound (preferably, described boron compound comprises boric acid).
In another preference, calculate by the mixture total weight gauge of step (a), the massfraction of boron raw material is 1-15wt% (being preferably 5-10wt%).
In another preference, described method (I) or the obtained boride nanowires of method (II) comprise: boron oxide nano wire or boron nitride nanometer line.
In another preference, in described method (III), described metal-powder comprises: magnesium powder, carbon dust, aluminium powder, titanium valve, zirconium powder, samarium powder, sulphur powder.
In another preference, the boride nanowires that described method (III) is obtained comprises: boron carbide nano wires, boronation magnesium nano wire, aluminum boride nano wire, titanium boride nano wire, zirconium boride 99.5004323A8ure nano wire, samarium boride nano wire, sulfuration boron nanowire.
In another preference, in each step above-mentioned, described reacting by heating is the reaction carried out at 800-1250 DEG C; And/or described reacting by heating is in a vacuum or is the reaction carried out in the atmosphere between 1Pa – 120kPa at pressure.
In fourth aspect present invention, provide a kind of purposes of diamond-nanowire complex as described in the first aspect of the invention, for machinework, matrix material or electronic devices and components.
In fifth aspect present invention, provide a kind of goods or matrix material, it comprises the diamond-nanowire 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 diamond particle surfaces boron nanowire growth in situ schematic diagram.First at high temperature, boron atomic diffusion enters in diamond particle surfaces lattice, copper powder melts and defines the small droplets of nanoscale at diamond surface, then boron atom is at copper drop and diamond contact place constantly crystallization, thus at diamond particle surfaces along one-dimensional square to growing boron nanowire.
Fig. 2 is the scanning electron micrographs of diamond-boron nanowire complex body.Wherein, A figure is diamond particle surfaces boron nanowire 10000 times of displaing micro pictures; B figure is diamond particle surfaces boron nanowire 80000 times of displaing micro pictures.
Fig. 3 is the scanning electron micrographs of diamond-boron nitride nanometer line complex body.
Fig. 4 is the transmission electron micrograph of boron nitride nanometer line.The dark particle in top is residual copper nano particles or copper alloy nano particle.
Embodiment
The present inventor is through extensive and deep research, be surprised to find that with diamond to be carrier, under the catalysis of special catalyst (as copper etc.), boron atom can go out boron nanowire or boride nanowires at diamond surface growth in situ, thus form diamond-nanowire complex, this complex body Interface adhesive strength is very strong, has good application prospect in many-sides such as machinery, electronics.On this basis, contriver completes the present invention.
Nano wire
As used herein, nano wire of the present invention comprises: boron nanowire, boride nanowires or its combination.
As used herein, described boron nanowire is the nano wire of pure boron;
As used herein, described boride nanowires is the nano wire of the compound containing boron, and the described compound containing boron preferably includes: boron oxide, norbide, boron nitride, boronation magnesium, aluminum boride, titanium boride, zirconium boride 99.5004323A8ure, samarium boride, sulfuration boron etc.
Preferably, nano wire of the present invention (comprising boron nanowire or boride nanowires) has following characteristics: (i) length is 0.1 ~ 300 μm and (is preferably 1 ~ 300 μm; Be more preferably 10 ~ 100 μm); And/or (ii) diameter be 1 ~ 5000nm (is preferably 1 ~ 500nm; Be more preferably 5 ~ 100nm); And/or (iii) is 1 ~ 10000/μm in the density of diamond surface
2(it is preferably 10-5000/μm
2or 10-2000/μm
2).
The forming process of nano wire of the present invention is now described for boron nanowire, and metal catalyst is for copper, and as shown in Figure 1, copper powder, by adding thermosetting copper nano-liquid droplet, contacts with diamond surface, and becomes the catalyzer of boron nanowire growth.Under certain temperature (as about 1000 DEG C), the boron atomic diffusion of boron amorphous powder enters in diamond lattice, under the katalysis of copper nano-liquid droplet, and the forming core of catalysis boron crystal, growth; Part of boron atom is at the position of copper nano-liquid droplet and diamond contact, separate out from diamond lattice, and form boron crystal at diamond surface, and cause boron atomic percent in this place's diamond lattice to decline, form boron concentration gradient of atoms with neighboring area, thus cause periphery boron atom constantly to spread to this place.Just by this continuous print diffusion-precipitation-crystallisation process, grow boron nanowire at copper nano-liquid droplet and diamond surface contact position.This is an important mechanistic features of the present invention, be one from the brand-new nanowire growth mechanism mentioned without document.
Diamond particles
The present invention's diamond particles used is the substrate for nanowire growth of the present invention, is also the carrier of diffused with boron atom simultaneously.And in the present invention, diamond is the requisite solid support material of boron atomic diffusion, does not have it cannot form boron nanowire or boride nanowires.Such as utilize silicon, the materials such as graphite replace diamond, due to the difference of its lattice parameter, all do not have the effect of boron atomic diffusion carrier, cannot form boron nanowire or boride nanowires.
Diamond particles of the present invention can be the particle of arbitrary dimension, and preferably employing particle diameter is the diamond particles of 0.1 ~ 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 50 μm ~ 1000 μm.
Diamond-nanowire complex
Diamond-nanowire complex provided by the invention, wherein, described complex body comprises diamond particles and chemical bonds in the nano wire of the present invention of described diamond particle surfaces, and wherein, described nano wire comprises: boron nanowire, boride nanowires or its combination.
Preferably, described nano wire is by being formed at diamond particle surfaces growth in situ.
In another preference, described nano wire is that the boron nanowire formed at diamond particle surfaces growth in situ is carried out reacting by heating in reactive atmosphere (as oxygen, nitrogen, ammonia isoreactivity atmosphere), thus obtains the boride nanowires being incorporated into diamond particle surfaces.
In another preference, described nano wire is mixed with metal-powder (as metal-powders such as magnesium powder, carbon dust, aluminium powder, titanium valve, zirconium powder, samarium powder, sulphur powder) and carry out reacting by heating by the boron nanowire formed at diamond particle surfaces growth in situ, thus the boride nanowires being incorporated into diamond particle surfaces obtained.
Boron raw material
As used herein, the present invention's boron raw material used can be Powdered or liquid.Certainly described boron raw material can be pure boron or boron-containing compound (preferably, described boron-containing compound comprises boric acid).
Metal catalyst
As used herein, described metal catalyst preferably includes copper, gold, nickel, platinum, silver or their alloy; Be more preferably fine copper (copper as purity or mass content >=99.99%) or copper alloy (such as copper-iron alloy, chromiumcopper, cupronickel etc.).Described metal catalyst can be the metal (alloy) of powder or block.
In reacting by heating, described metal catalyst can form nano-liquid droplet, and becomes the catalyzer of boron nanowire or boride nanowires growth.
Preparation method
In preparation method of the present invention, described reacting by heating is normally carried out under 800-1250 DEG C (preferred 900-1200 DEG C), and the time of reaction is generally 1-60 minute (being preferably 10-40 minute).
One, the invention provides the preparation method of a kind of diamond-boron nanowire complex body, preferably include following steps:
(1) mixture that comprises diamond particles, boron raw material and metal catalyst is provided;
Preferably, calculate by the mixture total weight gauge of step (1), the massfraction of boron raw material is 1-15wt%; Be preferably 5-10wt%.
Preferably, calculate by the mixture total weight gauge of step (1), the massfraction of metal catalyst is 10-90wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%.
(2) under vacuo or in the inert atmosphere or reduced form atmosphere of hydrogen, argon gas or its composition gas in (if pressure is the atmosphere of 1Pa – 120kPa), the mixture of step (1) is carried out reacting by heating (as reacted at 800-1250 DEG C or 900-1200 DEG C), thus obtain diamond-boron nanowire complex body.
The diamond that the method obtains-boron nanowire complex body comprises diamond particles and growth in situ in the pure boron nano wire of described diamond particle surfaces.
Two, the invention provides the preparation method of diamond-boride nanowires complex body.
(I) described method comprises step:
A mixture that () provides one to comprise diamond particles, boron raw material and metal catalyst;
In another preference, calculate by the mixture total weight gauge of step (a), the massfraction of boron raw material is 1-15wt%; Be preferably 5-10wt%.
In another preference, calculate by the mixture total weight gauge of step (a), the massfraction of metal catalyst is 10-90wt%; Be preferably 20-85wt%; Be more preferably 30-75wt%.
B () is in oxygen, ammonia, nitrogen isoreactivity atmosphere (if pressure is the reactive atmosphere of 1Pa – 120kPa), the mixture of step (1) is carried out reacting by heating (as reacted at 800-1250 DEG C or 900-1200 DEG C), thus obtain diamond-boride nanowires complex body.
The diamond that the method obtains-boride nanowires complex body comprises diamond particles and growth in situ in the boride nanowires of the present invention of described diamond particle surfaces, and wherein, described boride preferably includes: boron oxide, boron nitride.
(II) boron nanowire of the present invention at high temperature contacts specific gas molecule and also can be converted into specific boride nanowires, such as in ammonia or nitrogen, heating can generate boron nitride nanometer line, and in oxygen, heating can generate boron oxide nano wire etc.
Therefore diamond of the present invention-boride nanowires complex body also can adopt the preparation method comprised the steps: in oxygen, nitrogen or ammonia isoreactivity atmosphere (if pressure is the atmosphere of 1Pa – 120kPa), diamond of the present invention-boron nanowire complex body is carried out reacting by heating (as reacted at 800-1250 DEG C), thus obtain corresponding diamond-boride nanowires complex body.
The diamond that the method obtains-boride nanowires complex body comprises diamond particles and is incorporated into the boride nanowires of the present invention of described diamond particle surfaces, and wherein, described boride preferably includes: boron oxide, boron nitride etc.
(III) boron nanowire of the present invention at high temperature contacts specific metal-powder and also can be converted into specific boride nanowires, and such as, after mixing with magnesium powder, heating can generate boronation magnesium nano wire.
Therefore diamond of the present invention-boride nanowires complex body can also adopt the preparation method comprised the steps: in a vacuum, diamond of the present invention-boron nanowire complex body and some metal-powder (as magnesium powder, carbon dust, aluminium powder, titanium valve, zirconium powder, samarium powder, sulphur powder) are mixed, then carry out reacting by heating (as reacted at 800-1250 DEG C), thus obtain corresponding diamond-boride nanowires complex body.
The diamond that the method obtains-boride nanowires complex body comprises diamond particles and is incorporated into the boride nanowires of the present invention of described diamond particle surfaces, wherein, described boride preferably includes: norbide, boronation magnesium, aluminum boride, titanium boride, zirconium boride 99.5004323A8ure, samarium boride, sulfuration boron etc.
Application
The material of diamond and boron nanowire or these two kinds of excellent performances of boride nanowires combines by diamond of the present invention-boron nanowire complex body or diamond-boride nanowires complex body, by providing novel diamond complex material at diamond particle surfaces growth in situ boron nanowire or boride nanowires approach.This type material has that interfacial bonding property is strong, thermal conductivity advantages of higher, has good application prospect, such as, for the preparation of machinework, matrix material, electronic devices and components in many-sides such as machinery, material, electronics.
In another preference, described machinework comprises: cutter, grinding tool, file, emery wheel, saw blade, drill bit etc.
In another preference, described matrix material comprises: heat-radiating substrate, radiator element etc.
In another preference, described electronic devices and components comprise: nanometric PN junctions, superconductor etc.
Major advantage of the present invention comprises:
1. the invention provides a kind of novel diamond-nano wire Two-dimensional Composites, diamond and boron nano material link together by this material, interfacial bonding property is strong, and this material has the premium properties of diamond and boron nano material concurrently, at machinery, heat conduction, and electronic devices and components exploitation aspect has a wide range of applications.
2. present invention also offers the preparation method of above-mentioned Two-dimensional Composites.The preparation technology of the one dimension boron nanowire 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 per-cent and number calculate by weight.Unless stated otherwise, the raw materials used or reagent of the present invention all commercially.
Embodiment 1 diamond-boron nanowire complex body
Be that the diamond particles of about 200 μm mixes with high-purity copper powder and a small amount of boron powder and makes mixed powder by median size, by mixed powder total weight, copper powder accounts for 60wt%, and boron powder accounts for 5wt%, mixed powder is put into vacuum carbon tube furnace, is evacuated to vacuum tightness and is about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa – 120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1100 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, cross 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, remove superfluous copper powder and boron powder, obtain diamond-boron nanowire complex body, its electron scanning micrograph as shown in Figure 2, shows the boron nanowire of diamond particle surfaces growth in situ in figure.
Embodiment 2 diamonds-boron nitride nanometer line complex body
Be that the diamond particles of about 200 μm mixes with high-purity copper powder and a small amount of boron powder by median size, make mixed powder, by mixed powder total weight, copper powder accounts for 60wt%, boron powder accounts for 5wt%, and mixed powder is put into vacuum carbon tube furnace, and being evacuated to vacuum tightness is 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa – 120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1150 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous copper powder and boron powder.Then the powder after sieving is put into vacuum carbon tube furnace, being evacuated to vacuum tightness is 10
-2pa, then passes into ammonia or nitrogen, and atmospheric pressure is 1Pa – 120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1100 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous copper powder and boron powder, obtains diamond-boron nitride nanometer line complex body.
Fig. 3 is electron scanning micrograph, shows the boron nitride nanometer line of diamond particle surfaces growth.
Fig. 4 is the transmission electron micrograph of boron nitride nanometer line, shows boron nitride nanometer line crystal formation complete.The dark particle in top is copper nano particles, and this copper particle serves the catalyst action of forming core growth in nanowire growth process.
Embodiment 3 diamonds-boron nitride nanometer line complex body
Be that the diamond particles of about 200 μm mixes with high-purity copper powder and a small amount of boron powder by median size, make mixed powder, by mixed powder total weight, copper powder accounts for 60wt%, boron powder accounts for 5wt%, and mixed powder is put into vacuum carbon tube furnace, and being evacuated to vacuum tightness is 10
-2pa, then passes into ammonia or nitrogen, and atmospheric pressure is 1Pa – 120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1200 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes the inside copper powder and boron powder, obtains diamond-boron nitride nanometer line complex body.
Embodiment 4 diamonds-boron nitride nanometer line complex body
Be that the diamond particles of about 200 μm and high-purity copper powder and a small amount of boric acid are prepared into slurry by median size, by slurry total weight, copper powder accounts for 60wt%, and boron accounts for 5wt%, and slurry is put into vacuum carbon tube furnace, and being evacuated to vacuum tightness is 10
-2pa, then ammonia or nitrogen is passed into, atmospheric pressure is 1Pa – 120kPa, temperature rise rate is that 150 DEG C/min is warming up to 1050 DEG C, and insulation 20min, then cools to room temperature with the furnace, mixed powder pyroprocessing crossed takes out, cross 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, remove superfluous copper powder and boron powder, obtain diamond-boron nitride nanometer line complex body.
Embodiment 5 diamonds-boron nanowire complex body
After the median size diamond particle surfaces that is about 200 μm sputters one deck boron film, then sputter one deck copper film, then the diamond particles after sputtering secondary is put into vacuum carbon tube furnace, being evacuated to vacuum tightness is 10
-2pa, temperature rise rate is that 150 DEG C/min is warming up to 1060 DEG C, and insulation 20min, then cools to room temperature with the furnace, obtains diamond-boron nanowire complex body.
Conventionally measure the length of the boron nanowire prepared of embodiment 1-5 or boride nanowires, diameter or the nano wire density at diamond particle surfaces.Result is as shown in table 1.
Table 1
| Embodiment | Length | Diameter | Density (individual/μm 2) |
| 1 | 40μm | 20nm | 100 |
| 2 | 35μm | 40nm | 354 |
| 3 | 52μm | 64nm | 208 |
| 4 | 28μm | 12nm | 43 |
| 5 | 42μm | 23nm | 1205 |
| 6 | 73μm | 48nm | 128 |
| 7 | 69μm | 36nm | 258 |
| 8 | 35μm | 42nm | 87 |
Embodiment 6 diamonds-boron nanowire complex body
Be that the diamond particles of about 100 μm mixes with chromiumcopper powder and a small amount of boron powder and makes mixed powder by median size, by mixed powder total weight, chromiumcopper powder accounts for 60wt%, and boron powder accounts for 5wt%, mixed powder is put into vacuum carbon tube furnace, is evacuated to vacuum tightness and is about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa-120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1100 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous copper powder and boron powder, obtains diamond-boron nanowire complex body.
Embodiment 7 diamonds-boron nanowire complex body
Be that the diamond particles of about 100 μm mixes with cupronickel powder and a small amount of boron powder and makes mixed powder by median size, by mixed powder total weight, cupronickel powder accounts for 60wt%, and boron powder accounts for 5wt%, mixed powder is put into vacuum carbon tube furnace, is evacuated to vacuum tightness and is about 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa – 120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1100 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous copper powder and boron powder, obtains diamond-boron nanowire complex body.
Embodiment 8 diamonds-boronation magnesium nanowire complex
Be that the diamond particles of about 100 μm mixes with high-purity copper powder and a small amount of boron powder by median size, make mixed powder, by mixed powder total weight, copper powder accounts for 60wt%, boron powder accounts for 5wt%, and mixed powder is put into vacuum carbon tube furnace, and being evacuated to vacuum tightness is 10
-2pa, then passes into hydrogen, and atmospheric pressure is 1Pa – 120kPa, and temperature rise rate is that 150 DEG C/min is warming up to 1150 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous copper powder and boron powder.Then the powder after sieving is put into vacuum carbon tube furnace, being evacuated to vacuum tightness is 10
-2pa, then imbeds in magnesium powder, and temperature rise rate is that 150 DEG C/min is warming up to 660 DEG C, and insulation 20min, then cools to room temperature with the furnace.
Mixed powder pyroprocessing crossed takes out, and crosses 30 orders, 60 orders, 80 orders, 100 orders, 150 mesh sieves respectively, removes superfluous copper powder and boron powder, obtains diamond-boronation magnesium nanowire complex.
The application of embodiment 9 diamonds-boron nanowire complex body
Diamond-the nanowire complex of arbitrary for embodiment 1-8 preparation is mixed jointly with high-purity copper powder, by mixed powder total weight, copper powder massfraction is 70%, mixed powder is heated to 950 DEG C with temperature rise rate 150 DEG C/min in discharge plasma sintering oven mould sinter, sintering pressure is 30MPa, obtain the matrix material of diamond and copper, conventionally measure the density of described matrix material, thermal conductivity, thermal expansivity.Its density is at 6-9g/cm
3between, thermal conductivity is between 600-800W/mK, and thermal expansivity is between 5-8 μm/mK.
Visible, the matrix material that diamond-nanowire complex of the present invention obtains has excellent performance.
Diamond-nanowire complex of the present invention can also for the preparation of the machinework of various excellent performance, as cutter, grinding tool, file, emery wheel, saw blade, drill bit etc.Visible diamond-nanowire complex of the present invention has good application prospect.
The above is preferred embodiment of the present invention, but the present invention should not be confined to diamond-boron nanowire, diamond-boron nitride nanometer line, diamond-boron oxide nano wire, the preparation of diamond-boronation magnesium material-nanowire composites.Adopting the nano wires such as this preparation side other boride nanowires of acquisition such as norbide, aluminum boride, titanium boride, zirconium boride 99.5004323A8ure, samarium boride, sulfuration boron etc. 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 after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. diamond-nanowire complex, is characterized in that, described complex body comprises diamond particles and is incorporated into the nano wire of described diamond particle surfaces, and wherein, described nano wire comprises: boron nanowire, boride nanowires or its combination;
Further, described nano wire is by being formed at diamond particle surfaces growth in situ.
2. diamond-nanowire complex as claimed in claim 1, it is characterized in that, described diamond particles particle diameter is 0.1 ~ 10000 μm.
3. diamond-nanowire complex as claimed in claim 1, it is characterized in that, described nano wire has following characteristics:
I () length is 0.1 ~ 300 μm; And/or
(ii) diameter is 1 ~ 5000nm; And/or
(iii) it is 1 ~ 10000/μm in the density of diamond surface
2.
4. diamond-nanowire complex as claimed in claim 1, it is characterized in that, described boride comprises: boron oxide, norbide, boron nitride, boronation magnesium, aluminum boride, titanium boride, zirconium boride 99.5004323A8ure, samarium boride, sulfuration boron.
5. a preparation method for diamond-boron nanowire complex body, is characterized in that, comprise step:
(1) mixture that comprises diamond particles, boron raw material and metal catalyst is provided;
(2) under vacuo or be selected from hydrogen, argon gas, the inert atmosphere of its composition gas or reducing atmosphere, the mixture of step (1) is carried out reacting by heating, thus obtaining diamond-boron nanowire complex body, described complex body comprises diamond particles and is incorporated into the boron nanowire of described diamond particle surfaces.
6. preparation method as claimed in claim 5, is characterized in that,
In described step (1), boron raw material is Powdered or liquid; And/or
In described step (1), boron raw material comprises pure boron and boron compound; And/or
Calculate by the mixture total weight gauge of step (1), the massfraction of boron raw material is 1-15wt%.
7. a preparation method for diamond-boride nanowires complex body, is characterized in that,
(I) described method comprises step:
A mixture that () provides one to comprise diamond particles, boron raw material and metal catalyst; With
B () is in the reactive atmosphere of oxygen, ammonia or nitrogen, the mixture of step (1) is carried out reacting by heating, thus obtaining diamond-boride nanowires complex body, described complex body comprises diamond particles and is incorporated into the boride nanowires of described diamond particle surfaces;
Or
(II) described method comprises step:
In the reactive atmosphere of oxygen, ammonia or nitrogen, diamond preparation method according to claim 5 obtained-boron nanowire complex body carries out reacting by heating, thus obtaining diamond-boride nanowires complex body, described complex body comprises diamond particles and is incorporated into the boride nanowires of described diamond particle surfaces;
Or
(III) described method comprises step:
In a vacuum, reacting by heating is carried out after diamond preparation method according to claim 5 obtained-boron nanowire complex body mixes with metal-powder, thus obtaining diamond-boride nanowires complex body, described complex body comprises diamond particles and is incorporated into the boride nanowires of described diamond particle surfaces.
8. the preparation method as described in claim 5 or 7, is characterized in that, in each step above-mentioned,
Described reacting by heating is the reaction carried out at 800-1250 DEG C; And/or
Described reacting by heating is in a vacuum or is the reaction carried out in the atmosphere between 1Pa – 120kPa at pressure.
9. the purposes of diamond-nanowire complex as claimed in claim 1, is characterized in that, for machinework, matrix material or electronic devices and components.
10. goods or a matrix material, is characterized in that, comprises diamond-nanowire complex according to claim 1.
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| CN101807606A (en) * | 2010-03-04 | 2010-08-18 | 吉林大学 | n-type zinc oxide/p-type diamond heterojunction tunnel diode and manufacturing method thereof |
| CN102383014A (en) * | 2011-11-11 | 2012-03-21 | 华中科技大学 | Method for preparing diamond-copper composite material by virtue of metallization of high-temperature blending surface |
| WO2012134133A2 (en) * | 2011-03-31 | 2012-10-04 | 고려대학교 산학협력단 | Nanowire having diamond deposited thereon, manufacturing method thereof, and biosensor including same |
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| CN101000865A (en) * | 2006-01-12 | 2007-07-18 | 国际商业机器公司 | Method for fabricating an inorganic nanocomposite and method for fabricating solar battery |
| CN101531374A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院物理研究所 | Method for producing boron nanowire |
| CN101807606A (en) * | 2010-03-04 | 2010-08-18 | 吉林大学 | n-type zinc oxide/p-type diamond heterojunction tunnel diode and manufacturing method thereof |
| WO2012134133A2 (en) * | 2011-03-31 | 2012-10-04 | 고려대학교 산학협력단 | Nanowire having diamond deposited thereon, manufacturing method thereof, and biosensor including same |
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