CN109136613A - A kind of preparation method of metallic aluminium cladding cubic boron nitride - Google Patents
A kind of preparation method of metallic aluminium cladding cubic boron nitride Download PDFInfo
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- CN109136613A CN109136613A CN201811158385.9A CN201811158385A CN109136613A CN 109136613 A CN109136613 A CN 109136613A CN 201811158385 A CN201811158385 A CN 201811158385A CN 109136613 A CN109136613 A CN 109136613A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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- C22C1/05—Mixtures of metal powder with non-metallic powder
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Abstract
The present invention provides a kind of preparation methods of metallic aluminium cladding cubic boron nitride, belong to technical field of superhard material.The present invention forms silicon oxygen on cubic boron nitride surface first, again using the cubic boron nitride powder and aluminium powder for being modified with nanometer silica layer in advance by surface as raw material, in chlorate, realize that the melting of aluminium powder cubic boron nitride powder coats by melting-type of cooling processing.Embodiment the result shows that, the present invention is successfully realized metallic aluminium in the cladding of cubic boron nitride powder.
Description
Technical field
The invention belongs to technical field of superhard material, and in particular to a kind of preparation side of metallic aluminium cladding cubic boron nitride
Method.
Background technique
Cubic boron nitride has the high rigidity for being only second to diamond, also has excellent thermal stability and chemical inertness, is
It is used to prepare a kind of important source material of superhard material.But cubic boron nitride powder because itself to be mutually bonded performance poor, no
Easily it is sintered directly into large scale sintering body；Currently, being the polycrystalline cubic boron nitride containing binder used in industry, need to lead to
It crosses binder and cubic boron nitride and is reacted under high-temperature and high-pressure conditions and be just able to be bonded large scale sintering body, common binder
There are metallic titanium powder and metallic aluminium powder etc..
Not only condition is harsh for existing preparation method, also, since the powder granule of same property is easy to assemble agglomerating, causes
Sintered body component is uneven, and powder granule segregation is serious during the sintering process, so that the microstructure of polycrystalline material is uneven, surpasses
Hard material performance is poor；In particular, the two can not be made to connect by conventional means since the liquid aluminium after boron nitride and melting is nonwetting
Together, it is difficult to which the cladding for realizing metallic aluminium cubic boron nitride limits the application of cubic boron nitride.
And high performance material requires ingredient and microcosmic phase institutional framework high uniformity, especially polycrystalline cubic boron nitride superhard
In use, requiring bonding agent and cubic boron nitride uniform in microcosmic undertissue's structure height, two kinds of ingredients have higher material
Contact area it is better.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of metallic aluminium cladding cubic boron nitride, this hair
The preparation method of bright offer can be realized effective cladding of metallic aluminium cubic boron nitride, and improve powder group in sintering process
Poly- problem.
To achieve the goals above, the invention provides the following technical scheme:
The present invention provides a kind of preparation methods of metallic aluminium cladding cubic boron nitride, comprising the following steps:
(1) suspension of cubic boron nitride powder is mixed with organic solvent, organic base and organic silicon source, carries out modification and changes
Property, silica layer is formed on cubic boron nitride surface, obtains modified cubic boron nitride powder；
(2) the modified cubic boron nitride powder is mixed with aluminium powder, chlorate, it is cooling after being melted, obtain metallic aluminium
Coat cubic boron nitride.
Preferably, the temperature melted in the step (2) is 10min in the soaking time of melting temperature at 650 DEG C or more
~4h.
Preferably, the mass ratio of modified cubic boron nitride powder, aluminium powder and chlorate is (10~20) in the step (2):
(10~30): (50~80)；The chlorate include one of sodium chloride, potassium chloride, lithium chloride, barium chloride and calcium chloride or
It is a variety of.
Preferably, the temperature of step (1) modification is 20~90 DEG C, and the time is in 12h or more.
Preferably, the mass ratio of step (1) the suspension cubic boron nitride powder and water is 1:(3~10).
Preferably, the mass ratio of step (1) the suspension cubic boron nitride powder and organic solvent be 5:(48~
240)；The organic solvent includes one of ethyl alcohol, methanol, propyl alcohol and acetone or a variety of.
Preferably, the mass ratio of organic base and suspension cubic boron nitride powder is (3~110) in the step (1):
500；The organic base includes L-lysine and/or L-arginine.
Preferably, the mass ratio of step (1) organic silicon source and suspension cubic boron nitride powder is (2~300):
500。
Preferably, the organic silicon source includes methyl orthosilicate and/or ethyl orthosilicate.
Preferably, after the step (3) is cooling, further includes: after being dissolved using water to obtained cooling salt solution, according to
It is secondary be filtered, solid washing and dry, obtain metallic aluminium cladding cubic boron nitride.
The present invention provides a kind of preparation methods of metallic aluminium cladding cubic boron nitride, first by cubic boron nitride powder
Suspension is mixed with organic solvent, organic base and organic silicon source, carries out modification, forms silicon oxygen on cubic boron nitride surface
Layer obtains modified cubic boron nitride powder；Modified cubic boron nitride powder is mixed with aluminium powder, chlorate again, it is cooling after being melted,
Obtain metallic aluminium cladding cubic boron nitride.
The present invention is in cubic boron nitride surface modification silicon oxygen, then uses the cubic boron nitride powder and aluminium powder for being modified with silica layer
As raw material, in chlorate, realize that the melting of aluminium powder cubic boron nitride powder coats by melting-type of cooling processing,
It is negatively charged due to the presence of oxygen atom in silicon oxygen during melting cladding；And aluminium after thawing since electronics hot activation has centainly
Loss, whole positively charged, the two self assembly under electrostatic attraction, and then during melting cladding, using silica layer as
Intermediary is connected, so that aluminium powder is bonded in cubic boron nitride powder surface by silicon oxygen.Embodiment the result shows that, present invention success is real
Aluminium is showed in the cladding of cubic boron nitride powder.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that aluminium of the present invention coats cubic boron nitride；
Wherein, 1- aluminium clad, 2- surface modification have the cubic boron nitride kernel of silicon oxygen；
Fig. 2 is the SEM figure of cubic boron nitride powder material untreated in embodiment 1；
Fig. 3 is the SEM figure of the cubic boron nitride powder in embodiment 1 after modifying silica layer；
Fig. 4 is the SEM figure that the cubic boron nitride powder after aluminium clad is formed in embodiment 1；
Fig. 5 is the XRD diagram of cubic boron nitride powder material untreated in embodiment 1；
Fig. 6 is the XRD diagram that the cubic boron nitride powder after aluminium clad is formed in embodiment 1；
Fig. 7 is the element spectroscopy detection result of cubic boron nitride powder material untreated in embodiment 1；
Fig. 8 is the element spectroscopy detection result that the cubic boron nitride powder after aluminium clad is formed in embodiment 1；
Fig. 9 is the SEM figure for the mixed powder that 1 tradition machinery mixing method of comparative example obtains；
Figure 10 is the SEM figure for the mixed powder that 1 tradition machinery mixing method of comparative example obtains；
Figure 11~13 are SEM figure of the obtained mixed powder of comparative example 2 under different multiplying.
Specific embodiment
The present invention provides a kind of preparation methods of metallic aluminium cladding cubic boron nitride, comprising the following steps:
(1) suspension of cubic boron nitride powder is mixed with organic solvent, organic base and organic silicon source, carries out modification and changes
Property, silica layer is formed on cubic boron nitride surface, obtains modified cubic boron nitride powder；
(2) the modified cubic boron nitride powder is mixed with aluminium powder, chlorate, it is cooling after being melted, obtain metallic aluminium
Coat cubic boron nitride.
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
The present invention mixes the suspension of cubic boron nitride powder with organic solvent, organic base and organic silicon source, is repaired
Decorations are modified, and are formed silica layer on cubic boron nitride surface, are obtained modified cubic boron nitride powder.In the present invention, described cube of nitrogen
The partial size for changing boron powder is preferably 1~10 μm, and further preferably 2~8 μm.
In the present invention, solvent is preferably water in the suspension of the cubic boron nitride powder, the cubic boron nitride powder
The suspension cubic boron nitride of body and the mass ratio of water are preferably 1:(3~10), further preferably 1:(4~9.5), more excellent
It is selected as 1:(5~7).The present invention does not have particular/special requirement to the preparation method of the suspension of the cubic boron nitride powder, using this
The dispersing mode of material known to the technical staff of field in water.
In the present invention, the organic solvent preferably includes one of ethyl alcohol, methanol, propyl alcohol and acetone or a variety of；Institute
The mass ratio of the suspension cubic boron nitride and organic solvent of stating cubic boron nitride powder is preferably 5:(48~240), into one
Step is preferably 5:(50~200), more preferably 5:130.In the present invention, the organic solvent plays the role of decentralized medium.
In the present invention, the organic base preferably includes L-lysine and/or L-arginine；The organic base and suspension
The mass ratio of cubic boron nitride is preferably (3~110): 500, further preferably (5~100): 500, more preferably (35~
76): 500.In the present invention, the organic base provides hydroxyl for modification process, the catalyst as modification.
In the present invention, the organic silicon source preferably includes methyl orthosilicate and/or ethyl orthosilicate；The organic silicon source
Mass ratio with suspension cubic boron nitride is preferably (2~300): 500, further preferably (5~150): 500, it is more excellent
It is selected as (7~120): 500.
In the present invention, the hybrid mode of the suspension, organic solvent, organic base and organic silicon source preferably will first hang
After turbid is mixed with organic solvent, then organic base is added into mixed liquor, obtains preparation liquid；Being added again into the preparation liquid has
Machine silicon source；The addition of the organic silicon source preferably carries out under agitation, convenient for organic silicon source and cubic boron nitride powder
It comes into full contact with.
After the mixing for completing suspension, organic solvent, organic base and organic silicon source, the present invention carries out gained mixed liquor
Modification forms silica layer on cubic boron nitride surface, obtains modified cubic boron nitride powder.In the present invention, the modification
Modified temperature is preferably 20~90 DEG C, further preferably 40~85 DEG C, more preferably 50~75 DEG C；The modification
Time preferably in 12h or more, further preferably 12~for 24 hours.The present invention is during modification, organic silicon source and organic base
The hydroxyl of offer combines, and forms silicon oxygen, (OH-Necleophilic reaction occurs with silicon atomic core first, generates silanol, suspension is neutral
Square boron nitride powder surface itself has certain hydroxyl, the hydroxyl and suspension cubic boron nitride (cBN) table of generated silanol
Hydrogen bond is formed between the hydroxyl in face, later hydrogen bond bridge on the basis of be further condensed, in the form of B-O key generate silicon and
Chemistry key connection between cBN.Silanol dehydrogenation under alkaline condition simultaneously forms lewis base, continues to other silicon atomic cores
Reaction, and it is dehydrated (or dealcoholysis) polymerization, reticular structure is slowly generated, the SiO for being incorporated in the surface cBN is ultimately generated2Film.) silicon oxygen
Silica layer can be formed on cubic boron nitride surface, obtains modified cubic boron nitride powder in conjunction with cubic boron nitride powder.In this hair
In bright, the thickness of the silica layer is in Nano grade, preferably 10~60nm.
After modification, the present invention mixes the modified cubic boron nitride powder with aluminium powder, chlorate, cold after being melted
But, metallic aluminium cladding cubic boron nitride is obtained.
In the present invention, the partial size of the aluminium powder is preferably 0.1~100 μm, further preferably 0.1~10 μm, more excellent
It is selected as 0.1~5 μm, is further preferably 0.1~3 μm.In the present invention, the chlorate preferably includes sodium chloride, potassium chloride, chlorination
One of lithium, barium chloride and calcium chloride are a variety of.In the present invention, the modified cubic boron nitride powder, aluminium powder and chlorate
Mass ratio be preferably (10~20): (10~30): (50~80), further preferably (15~18): (15~18): (64~
70)。
The present invention does not have particular/special requirement to the hybrid mode of modified cubic boron nitride powder and aluminium powder, chlorate, using ability
Material hybrid mode known to field technique personnel；Salt bath body is obtained after mixing, is used for subsequent melt process.
The present invention is cooling after melting the salt bath body, obtains metallic aluminium cladding cubic boron nitride.In the present invention,
The temperature of the melting is preferably at 650 DEG C or more, and further preferably 650~800 DEG C；The time of the melting be preferably (0,
4h], further preferably 30min~3h.After completing melting, melt is carried out cooling treatment by the present invention, obtains metallic aluminium cladding
Cubic boron nitride；The cooling is preferably with being furnace-cooled to room temperature.The present invention is directly cooling after melting salt bath body, with chloride
In inorganic salts mixture as main component, realize that the melting of aluminium powder cubic boron nitride powder coats by heating-cooling processing；
During melting cladding, aluminium powder is bonded in cubic boron nitride powder surface by silicon oxygen, solves cube nitrogen in the prior art
Change boron and aluminium is difficult to the problem of being bonded (metallurgical release agent of the boron nitride frequently as aluminium in the prior art), obtains with aluminium cladded type
The compound cubic boron nitride powder of structure；It is as follows to coat principle: after villaumite melting, will form conducting liquid environment, while aluminium powder
Also it melts, be dispersed into liquid droplets and spread.Due to Brownian movement, the random motion in the liquid environment of fused salt of cBN particle.
Since liquid melt salt is electrolyte, and metallic aluminium is also conductive.Metallic aluminium powder after melting, wherein sub-fraction is electric
Son will be thermally activated into free electron.Liquid molten salt be it is conductive, therefore one in fuse salt and the liquid metal aluminium of dispersion
A little free electrons can move freely, and become the shared electron cloud of conductive fused salt and aluminium.As a result, due to the slight damage of electronics
It loses, small molten aluminum drop will be positively charged, and the cBN that surface silicon oxygen is modified is negatively charged, and then realizes aluminium in cubic boron nitride powder
The cladding in body surface face.
After the cooling, after being dissolved present invention preferably employs water to cooling salt solution, successively it is filtered, solid is washed
It washs and dries, obtain metallic aluminium cladding cubic boron nitride.Present invention preferably employs water to dissolve cooling molten salt bath, and realization can
The abundant dissolution of molten object；Again by filtering, insoluble solids are isolated；The present invention is washed and is dried to insoluble solids, is obtained
Metallic aluminium coats cubic boron nitride.The present invention is washed to the filtering, solid and dry specific embodiment does not have special want
It asks, using mode well-known to those skilled in the art.
The aluminium cladding cubic boron nitride that the present invention obtains is core-shell structure, including cubic boron nitride nucleome, silicon oxygen adhesive layer
With aluminium clad；The silicon oxygen adhesive layer is incorporated in cubic boron nitride core surface, and the metallic aluminium clad is adhered to silicon oxygen
Tie layer surface.In the present invention, in terms of mass percentage, metallic aluminium cladding cubic boron nitride preferably includes 60~
98.8% cubic boron nitride nucleome, 0.2~20% silicon oxygen adhesive layer and 1~20% aluminium clad；The metallic aluminium cladding cube
The mass percentage of boron nitride cubic boron nitride is more preferably 62.5~98.5%, and more preferably 65~95%；Institute
The mass percentage for stating silicon oxygen adhesive layer in metallic aluminium cladding cubic boron nitride is more preferably 0.5~15%, more preferably
It is 1~13.5%；In the metallic aluminium cladding cubic boron nitride mass percentage of aluminium clad be more preferably 1~
18.5%, more preferably 2.5~15.5%.In the present invention, the metallic aluminium cladding cubic boron nitride is powder, the metal
Aluminium coat cubic boron nitride partial size preferably >=0.1 μm, further preferably 1~10 μm.
The structural schematic diagram of aluminium that the present invention obtains cladding cubic boron nitride is as shown in Figure 1,1 be wherein aluminium clad, 2 are
Surface modification has the cubic boron nitride kernel of silicon oxygen adhesive layer.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to metallic aluminium provided by the invention cladding cube
The preparation method of boron nitride is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
The average grain diameter of cubic boron nitride powder used is 5 μm in following example 1~6, and the partial size of aluminium powder is 2.5 μ
m.The number being previously mentioned in text refers to parts by weight.Its cubic boron nitride powder has been given before carrying out cladding processing
Adequately washing and dehumidifying, are then prepared according to preparation method provided by the invention.
Embodiment 1
(1) the cubic boron nitride powder for weighing 500 mass parts first is added in 1500 mass parts deionized waters, ultrasound
Wave handles to obtain suspension；Then use 4800 mass parts dehydrated alcohols as decentralized medium, 3 parts of L-lysines as catalyst,
Stirring is sufficiently mixed, and 2 mass parts methyl orthosilicates are then added thereto, is stirred to react at a temperature of 40 DEG C 12 hours, is completed
The silicon oxygen modification of cubic boron nitride powder is modified.
(2) will modification silicon oxygen cubic boron nitride powder and aluminium powder and KCl-NaCl salt-mixture (molar ratio of KCl and NaCl is
1:1), it is sufficiently mixed in crucible according to following mass ratioes, obtains salt bath body: the wherein cubic boron nitride powder of surface modification silicon oxygen
The mass fraction that body accounts for entire mixture is 10%, and the mass fraction that aluminium powder accounts for entire mixture is 10%, remaining ingredient is chlorine
Salt dissolving.Then salt bath body being warming up to 660 DEG C, keeps the temperature 2 hours, then furnace cooling first dissolves crucible contents with water, then
Suction filtration, solid washing and dry method therefrom extract product, final to obtain metallic aluminium cladding cubic boron nitride.
Embodiment 2
(1) the cubic boron nitride powder for weighing 500 mass parts first is added in 1500 mass parts deionized waters, ultrasound
Wave is processed into suspension, then uses 7200 mass parts acetone as decentralized medium, and 25 mass parts L-arginines are stirred as catalyst
It mixes and is sufficiently mixed, 70 mass parts methyl orthosilicates are then added thereto, be stirred to react at a temperature of 45 DEG C 18 hours, completion pair
The silicon oxygen modification on the surface of cubic boron nitride powder is modified.
(2) the cubic boron nitride powder for modifying silicon oxygen and aluminium powder and LiCl-NaCl salt-mixture are mixed to (LiCl and NaCl's
Molar ratio is 1:1), it is sufficiently mixed in crucible according to following mass ratioes, obtains salt bath body: wherein modifying cube nitridation of silicon oxygen
The mass fraction that boron powder accounts for entire mixture is 10%, and the mass fraction that aluminium powder accounts for entire mixture is 20%, remaining ingredient
For chlorate, 700 DEG C are then heated to, keeps the temperature 2 hours, then furnace cooling is first dissolved crucible contents with water, then taken out
Filter, solid washing and dry method therefrom extract product, and the final metallic aluminium that obtains coats cubic boron nitride.
Embodiment 3
(1) 500 mass parts cubic boron nitride powders are weighed first, are added in 1500 mass parts deionized waters, ultrasonic wave
It is processed into suspension, then uses 14400 parts of methanol as decentralized medium, 80 mass parts L-lysines as catalyst, fill by stirring
Divide mixing, 165 mass parts ethyl orthosilicates are then added thereto, are stirred to react at a temperature of 55 DEG C 24 hours, completes opposition
The silicon oxygen modification of square boron nitride powder is modified.
(2) by the cubic boron nitride powder of modification silicon oxygen and aluminium powder and CaCl2- KCl salt-mixture (CaCl2The molar ratio of-KCl
For 1:1), be sufficiently mixed in crucible according to following mass ratioes, obtain salt bath body: the cubic boron nitride powder of modification silicon oxygen accounts for whole
The mass fraction of a mixture is 10%, and the mass fraction that aluminium powder accounts for entire mixture is 30%, remaining ingredient is chlorate, so
After be warming up to 800 DEG C, keep the temperature 2 hours, then furnace cooling first dissolves crucible contents with water, then filter, solid washing and
Dry method therefrom extracts product, and the final metallic aluminium that obtains coats cubic boron nitride.
Embodiment 4
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 1, difference is that step (2) is warming up to 800
DEG C, 15min is kept the temperature in the melting temperature.
Embodiment 5
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 2, difference is that step (2) is warming up to 800
DEG C, 30min is kept the temperature in the melting temperature.
Embodiment 6
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 3, difference is that step (2) is warming up to 750
DEG C, 90min is kept the temperature under the melting temperature.
The average grain diameter of cubic boron nitride powder used is 9 μm in following example 7~12, and the partial size of aluminium powder is 2.5 μm；
The number being previously mentioned refers to parts by weight.Its cubic boron nitride powder has been given adequately before carrying out cladding processing
Washing and dehumidifying.
Embodiment 7
(1) 500 parts of cubic boron nitride powders are weighed first, are added in 2500 parts of deionized waters, and ultrasonication is at outstanding
Then turbid uses 8000 parts of methanol as decentralized medium, as catalyst, stirring is sufficiently mixed 30 parts of L-arginines, then to
110 parts of methyl orthosilicates are wherein added, are stirred to react at a temperature of 60 DEG C 12 hours, complete the silicon oxygen of cubic boron nitride powder
Modification modification.
(2) the cubic boron nitride powder and aluminium powder and NaCl-BaCl that will be surface modified2Salt-mixture (NaCl and
BaCl2Molar ratio be 1:1), be sufficiently mixed in crucible according to following mass ratioes, obtain salt bath body: wherein modifying silicon oxygen
The mass fraction that cubic boron nitride powder accounts for entire mixture is 15%, and the mass fraction that aluminium powder accounts for entire mixture is 20%,
Remaining ingredient is chlorate, then heats to 900 DEG C, keeps the temperature 2 hours, then furnace cooling is first used crucible contents water-soluble
Solution, then filter, solid washing and dry method therefrom extract product, final to obtain metallic aluminium cladding cube nitridation
Boron.
Embodiment 8
(1) 500 parts of cubic boron nitride powders are weighed first, are added in 2500 parts of deionized waters, and ultrasonication is at outstanding
Then turbid uses 12000 parts of methanol as decentralized medium, as catalyst, stirring is sufficiently mixed 75 parts of L-lysines, then to
5 parts of ethyl orthosilicates are wherein added, are stirred to react at a temperature of 70 DEG C 18 hours, the silicon oxygen for completing cubic boron nitride powder is repaired
Adorn modifying and decorating.
It (2) will modification silicon oxygen cubic boron nitride powder and aluminium powder and NaCl-KCl-BaCl2Salt-mixture (NaCl, KCl and
BaCl2Molar ratio be 1:1:1), be sufficiently mixed in crucible according to following mass ratioes, obtain salt bath body: wherein modify silicon oxygen
Cubic boron nitride powder to account for the mass fraction of entire mixture be 20%, the mass fraction that aluminium powder accounts for entire mixture is
10%, remaining ingredient is chlorate, and the salt bath body is then warming up to 800 DEG C, keeps the temperature 2 hours, furnace cooling, then to crucible
Content is first dissolved with water, then filter, solid washing and dry method therefrom extract product, finally obtain metallic aluminium
Coat cubic boron nitride.
Embodiment 9
(1) 500 parts of cubic boron nitride powders are weighed first, are added in 2500 parts of deionized waters, and ultrasonication is at outstanding
Then turbid uses 24000 parts of isopropanols as decentralized medium, 14 parts of L-arginines are as catalyst, and stirring is sufficiently mixed, then
140 parts of methyl orthosilicates are added thereto, are stirred to react at a temperature of 75 DEG C 12 hours, complete the silicon of cubic boron nitride powder
The modification of oxygen modification.
(2) by the cubic boron nitride powder of modification silicon oxygen and aluminium powder and BaCl2-CaCl2- NaCl salt-mixture (BaCl2、
CaCl2Molar ratio with NaCl is 1:1:1), it is sufficiently mixed in crucible according to following mass ratioes, obtains salt bath body: wherein repairing
The mass fraction that the cubic boron nitride powder of decorations silicon oxygen accounts for entire mixture is 10%, and aluminium powder accounts for the mass fraction of entire mixture
It is 10%, remaining ingredient is chlorate, and the salt bath body is then warming up to 800 DEG C, keeps the temperature 2 hours, furnace cooling, then to earthenware
Crucible content is first dissolved with water, then filter, solid washing and dry method therefrom extract product, finally obtain metal
Aluminium coats cubic boron nitride.
Embodiment 10
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 7, difference is that step (2) is warming up to 800
DEG C, 4h is kept the temperature in the melting temperature.
Embodiment 11
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 8, difference is that step (2) is warming up to 750
DEG C, 35min is kept the temperature in the melting temperature.
Embodiment 12
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 9, difference is that step (2) is warming up to 700
DEG C, 100min is kept the temperature under the melting temperature.
The average grain diameter of cubic boron nitride powder used is 2 μm in following example 13 and embodiment 14, the grain of aluminium powder
Diameter is 2.5 μm；The number being previously mentioned refers to parts by weight.Its cubic boron nitride powder is before carrying out cladding processing,
Adequately washing and dehumidifying are given, is then prepared according to preparation method provided by the invention.
Embodiment 13
(1) 500 parts of cubic boron nitride powders are weighed first, are added in 5000 parts of deionized waters, and ultrasonication is at outstanding
Then turbid uses 16000 acetone as decentralized medium, as catalyst, stirring is sufficiently mixed 110 parts of L-lysines, then to
110 parts of methyl orthosilicates are wherein added, are stirred to react at a temperature of 85 DEG C 24 hours, complete the silicon oxygen of cubic boron nitride powder
Modification modification.
(2) by the cubic boron nitride powder of modification silicon oxygen and aluminium powder and KCl-LiCl-BaCl2- NaCl salt-mixture (KCl,
LiCl、BaCl2Molar ratio with NaCl is 1:1:1:1), it is sufficiently mixed in crucible according to following mass ratioes, obtains salt bath body:
It is 15% that the cubic boron nitride powder for wherein modifying silicon oxygen, which accounts for the mass fraction of entire mixture, and aluminium powder accounts for the matter of entire mixture
Measuring score is 10%, remaining ingredient is chlorate, and the salt bath body is then warming up to 800 DEG C, keeps the temperature 2 hours, furnace cooling, so
Crucible contents are first dissolved with water afterwards, then filter, solid washing and dry method therefrom extract product, finally obtain
It obtains metallic aluminium and coats cubic boron nitride.
Embodiment 14
(1) 500 parts of cubic boron nitride powders are weighed first, are added in 5000 parts of deionized waters, and ultrasonication is at outstanding
Then turbid uses 24000 parts of acetone as decentralized medium, as catalyst, stirring is sufficiently mixed 15 parts of L-arginines, then to
300 parts of ethyl orthosilicates are wherein added, are stirred to react at a temperature of 90 DEG C 18 hours, complete the silicon oxygen of cubic boron nitride powder
Modification modification.
(2) by the cubic boron nitride powder of modification silicon oxygen and aluminium powder and KCl-NaCl-BaCl2-LiCl-CaCl2Salt-mixture
(KCl、NaCl、BaCl2, LiCl and CaCl2Molar ratio be 1:1:1:1:1), be sufficiently mixed according to following mass ratioes in crucible
In, obtain salt bath body: it is 20% that the cubic boron nitride powder for wherein modifying silicon oxygen, which accounts for the mass fraction of entire mixture, and aluminium powder accounts for
The mass fraction of entire mixture is 10%, remaining ingredient is chlorate；Then the salt bath body is warming up to 800 DEG C, heat preservation 2 is small
When, then furnace cooling first dissolves crucible contents with water, then filter, solid washing and dry method by product therefrom
It extracts, the final metallic aluminium that obtains coats cubic boron nitride.
Electron microscope analysis is scanned to cubic boron nitride raw material untreated in embodiment 1~14, it is as a result similar, implement
The SEM figure of 1 cubic boron nitride powder material of example is as shown in Figure 2.
Electron microscope analysis is scanned to the cubic boron nitride powder after formation silica layer in embodiment 1~14, it is as a result similar,
The testing result of embodiment 1 is as shown in Figure 3.
Metallic aluminium cladding cubic boron nitride equally is finally obtained to embodiment 1~14 and is scanned electron microscope analysis, as a result
Similar, wherein the SEM figure of aluminium cladding cubic boron nitride is as shown in Figure 4 in embodiment 1.Comparison diagram 2 and Fig. 4 are it is found that by this hair
The processing of bright technical solution realizes the aluminium cladding in cubic boron nitride powder surface.
XRD analysis is carried out to cubic boron nitride raw material untreated in embodiment 1~14, it is as a result similar, in embodiment 1
The XRD diagram of cubic boron nitride powder is as shown in Figure 5；Metallic aluminium cladding cubic boron nitride equally is finally obtained to embodiment 1~14
Carry out XRD analysis, it is as a result similar, wherein in embodiment 1 aluminium cladding cubic boron nitride XRD diagram it is as shown in Figure 6.Comparison diagram 5
With Fig. 6 it is found that being finally obtained without aluminium by the processing of the present invention program in the cubic boron nitride powder of uncoated processing
Composite material in contain aluminium.
Energy-spectrum scanning, as a result similar, embodiment 1 are carried out to cubic boron nitride raw material untreated in embodiment 1~14
The energy-spectrum scanning figure of cubic boron nitride powder is as shown in Figure 7；Metallic aluminium cladding cube equally is finally obtained to embodiment 1~14
The carry out energy-spectrum scanning of boron nitride, it is as a result similar, wherein in embodiment 1 aluminium cladding cubic boron nitride energy-spectrum scanning figure such as Fig. 8
It is shown.Comparison diagram 7 and Fig. 8 are it is found that be free of aluminium, by the place of the present invention program in the cubic boron nitride powder of uncoated processing
It manages, contains aluminium in finally obtained composite material.
Comparative example 1
Cubic boron nitride powder and aluminium powder (quality of aluminium powder is the 10% of powder gross mass) are subjected to mechanical mixture, it is difficult to will
Aluminium powder is installed on cubic boron nitride powder, does not form aluminium clad on cubic boron nitride surface.Testing result such as Fig. 9 and figure
Shown in the SEM figure of 10 pairs of mixed powders, it is seen then that apparent aluminium powder or independent bead, there is no on cubic boron nitride surface
Form shell.
Comparative example 2
The cubic boron nitride powder material for weighing 500 mass parts first is handled, directly and aluminium powder without silica layer formation
And KCl-NaCl salt-mixture (molar ratio of KCl and NaCl are 1:1), it is sufficiently mixed in crucible, obtains according to following mass ratioes
To salt bath body: it is 10% that wherein the cubic boron nitride powder of surface modification silicon oxygen, which accounts for the mass fraction of entire mixture, and aluminium powder accounts for
The mass fraction of entire mixture is 10%, remaining ingredient is chlorate.Then salt bath body is warming up to 660 DEG C, heat preservation 2 is small
When, then furnace cooling first dissolves crucible contents with water, then filter, solid washing and dry method by product therefrom
It extracts, obtains powder body material.
Electron microscope analysis, SEM figure such as Figure 11 under difference observation multiplying power are scanned to the powder body material that the comparative example obtains
Shown in~13.
By Figure 11~13 as it can be seen that cBN (cubic boron nitride) surface does not form any clad, comparison diagram 4, it is known that if not
It is modified by nano surface silicon oxygen, still can not be in cubic boron nitride surface alclad even across same smelting process, aluminium picture is not
The oil of viscous pot is the same, and never absorption is got on.
As seen from the above embodiment, the present invention is successfully realized metallic aluminium cladding cubic boron nitride, solves in the prior art
Aluminium and cubic boron nitride are difficult to the drawbacks of mutually bonding.And coat it is at low cost, be convenient for commercial introduction.And realize metallic aluminium packet
After covering cubic boron nitride, when preparing the sintered body of cubic boron nitride with this, will not occur the powder granule of same property again
Occur aggregation it is agglomerating, it is difficult to play the cementation of binder cubic boron nitride, it is ensured that sintered body component is uniform, bonding agent and
Cubic boron nitride improves superhard material so that the microstructure of polycrystalline material is uniform in the high uniformity of microcosmic undertissue's structure
Performance.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of preparation method of metallic aluminium cladding cubic boron nitride, comprising the following steps:
(1) suspension of cubic boron nitride powder is mixed with organic solvent, organic base and organic silicon source, carries out modification,
Silica layer is formed on cubic boron nitride surface, obtains modified cubic boron nitride powder；
(2) the modified cubic boron nitride powder is mixed with aluminium powder, chlorate, it is cooling after being melted, obtain metallic aluminium cladding
Cubic boron nitride.
2. preparation method according to claim 1, which is characterized in that the temperature melted in the step (2) 650 DEG C with
On, it is 10min~4h in the soaking time of melting temperature.
3. preparation method according to claim 1 or 2, which is characterized in that modified cubic boron nitride in the step (2)
The mass ratio of powder, aluminium powder and chlorate is (10~20): (10~30): (50~80)；The chlorate includes sodium chloride, chlorination
One of potassium, lithium chloride, barium chloride and calcium chloride are a variety of.
4. preparation method according to claim 1, which is characterized in that the temperature of step (1) modification be 20~
90 DEG C, the time is in 12h or more.
5. preparation method according to claim 1, which is characterized in that step (1) the suspension cubic boron nitride and
The mass ratio of water is 1:(3~10).
6. preparation method according to claim 1, which is characterized in that step (1) the suspension cubic boron nitride with
The mass ratio of organic solvent is 5:(48~240)；The organic solvent include one of ethyl alcohol, methanol, propyl alcohol and acetone or
It is a variety of.
7. preparation method according to claim 1, which is characterized in that organic base and suspension are neutral in the step (1)
The mass ratio of square boron nitride is (3~110): 500；The organic base includes L-lysine and/or L-arginine.
8. preparation method according to claim 1, which is characterized in that in the step (1) in organic silicon source and suspension
The mass ratio of cubic boron nitride is (2~300): 500.
9. preparation method according to claim 1 or 8, which is characterized in that the organic silicon source include methyl orthosilicate and/
Or ethyl orthosilicate.
10. preparation method according to claim 1, which is characterized in that after the step (2) is cooling, further includes: use water
It after being dissolved to obtained cooling salt solution, is successively filtered, solid washing and dry, obtains metallic aluminium cladding cube nitrogen
Change boron.
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