CN109020557A - 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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- CN109020557A CN109020557A CN201811158386.3A CN201811158386A CN109020557A CN 109020557 A CN109020557 A CN 109020557A CN 201811158386 A CN201811158386 A CN 201811158386A CN 109020557 A CN109020557 A CN 109020557A
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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.It is modified that present invention cubic boron nitride first carries out surface hydroxylation, the cubic boron nitride surface grafting hydroxyl is convenient for forming silicon oxygen on cubic boron nitride surface, 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) cubic boron nitride powder and modifying agent are mixed, carries out surface hydroxylation, obtains hydroxylating boron nitride；It is described
Modifying agent is mixture, concentrated nitric acid or the chloroazotic acid of the concentrated sulfuric acid and hydrogen peroxide；
(2) suspension of the hydroxylating boron nitride is mixed with organic solvent, organic base and organic silicon source, is modified
It is modified, silica layer is formed on cubic boron nitride surface, obtains modified cubic boron nitride powder；
(3) 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 (3) 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 (3):
(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 (2) modification is 20~90 DEG C, and the time is in 12h or more.
Preferably, the mass ratio of hydroxyl boron nitride and water is 1:(3 in the suspension of step (2) the hydroxylating boron nitride
~10).
Preferably, in the step (2) in the suspension of hydroxylating boron nitride hydroxylating boron nitride and organic solvent matter
Amount is than being 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 hydroxylating boron nitride is (3~110) in organic base and suspension in the step (2):
500；The organic base includes L-lysine and/or L-arginine.
Preferably, organic silicon source and the mass ratio of hydroxylating boron nitride in suspension are (2~300) in the step (2):
500；The organic silicon source includes methyl orthosilicate and/or ethyl orthosilicate.
Preferably, in the step (1) time of surface hydroxylation in 10min or more.
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 and
Modifying agent mixing, carries out surface hydroxylation, obtains hydroxylating boron nitride, wherein modifying agent is the mixing of the concentrated sulfuric acid and hydrogen peroxide
Object, concentrated nitric acid or chloroazotic acid；Then, the suspension of hydroxylating boron nitride is mixed with organic solvent, organic base and organic silicon source, into
Row modification forms silica layer on cubic boron nitride surface, obtains modified cubic boron nitride powder；It again will modified cubic boron nitride
Powder is mixed with aluminium powder, chlorate, cooling after being melted, and obtains metallic aluminium cladding cubic boron nitride.
Present invention cubic boron nitride first carries out surface hydroxylation and is modified, which is convenient for
In cubic boron nitride surface bond silicon oxygen, then using the cubic boron nitride powder and aluminium powder for being modified with silica layer as raw material, in chlorine
In salt dissolving, realize that the melting of aluminium powder cubic boron nitride powder coats by melting-type of cooling processing, due to oxygen atom in silicon oxygen
Presence, it is negatively charged；And aluminium after thawing since electronics hot activation has certain loss, whole positively charged, the two is inhaled in electrostatic
Self assembly under gravitation, and then during melting cladding, using silica layer as connection intermediary, so that aluminium powder is bonded in by silicon oxygen
Cubic boron nitride powder surface.Embodiment the result shows that, the present invention is successfully realized aluminium 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 transmission electron microscopy figure of powder after 1 step of embodiment (2) processing；
Figure 10 is the transmission electron microscopy figure of powder after 1 step of embodiment (2) processing；
Figure 11 is the SEM figure for the mixed powder that 1 tradition machinery mixing method of comparative example obtains；
Figure 12 is the SEM figure for the mixed powder that 1 tradition machinery mixing method of comparative example obtains；
Figure 13~15 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) cubic boron nitride powder and modifying agent are mixed, carries out surface hydroxylation, obtains hydroxylating boron nitride；It is described
Modifying agent is mixture, concentrated nitric acid or the chloroazotic acid of the concentrated sulfuric acid and hydrogen peroxide；
(2) suspension of the hydroxylating boron nitride is mixed with organic solvent, organic base and organic silicon source, is modified
It is modified, silica layer is formed on cubic boron nitride surface, obtains modified cubic boron nitride powder；
(3) 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 cubic boron nitride powder and modifying agent, carries out surface hydroxylation, obtains hydroxylating boron nitride.?
In the present invention, the partial size of the cubic boron nitride powder is preferably 1~10 μm, and further preferably 2~8 μm；The modifying agent
For the mixture of the concentrated sulfuric acid and hydrogen peroxide, concentrated nitric acid or chloroazotic acid.In the present invention, in the mixture of the concentrated sulfuric acid and hydrogen peroxide
The volume ratio of the concentrated sulfuric acid and hydrogen peroxide is preferably (70~75): (25~30), further preferably (72~75): (25~28)；
The mass concentration of the concentrated sulfuric acid is preferably 96~98%, and the mass concentration of hydrogen peroxide is preferably 25~30%.In the present invention,
The mass concentration of the concentrated nitric acid is preferably 35~69%, and further preferably 40~65%, more preferably 50~60%.At this
In the embodiment of invention, the mixture of the concentrated sulfuric acid and hydrogen peroxide is provided with the commercial goods of Piranha washing lotion.The present invention couple
The hybrid mode of the cubic boron nitride powder and modifying agent does not have particular/special requirement, to be able to achieve modifying agent in cubic boron nitride powder
The stop in body surface face.In the present invention, the time of the surface hydroxylation is preferably in 10min or more, further preferably
15~30min.Present invention preferably employs modifying agent cubic boron nitride powders to be cleaned, and carries out surface hydroxylation, obtains hydroxyl
Base boron nitride.The present invention does not have particular/special requirement to the dosage of the cubic boron nitride powder and modifying agent, using arbitrary proportion
?；In an embodiment of the present invention, the quality of the cubic boron nitride powder is about the 10% of modifying agent quality.The present invention will
The surface hydroxylation of modifying agent cubic boron nitride powder, cube nitrogen are realized in cubic boron nitride powder and modifying agent mixed process
The hydroxyl for changing boron powder surface is easier in conjunction with silicon oxygen, the combination convenient for subsequent silicon oxygen in cubic boron nitride powder surface, shape
At silica layer.
After surface hydroxylation, the present invention is by the suspension of the hydroxylating boron nitride and organic solvent, organic base and organic
Silicon source mixing, carries out modification, forms silica layer on cubic boron nitride surface, obtains modified cubic boron nitride powder.
In the present invention, solvent is preferably water in the suspension of the hydroxylating boron nitride, the hydroxylating boron nitride
The mass ratio of hydroxyl boron nitride and water is preferably 1:(3~10 in suspension), further preferably 1:(4~9.5), more preferably
1:(5~7).The present invention does not have particular/special requirement to the preparation method of the suspension of the hydroxylating boron nitride, using this field skill
The dispersing mode of material known to art personnel 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
Stating the mass ratio of hydroxylating boron nitride and organic solvent in the suspension of hydroxylating boron nitride 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 middle hydroxylating 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；Described and suspension
The mass ratio of middle hydroxylating boron nitride is preferably (2~300): 500, further preferably (5~150): 500, more preferably (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 filling for organic silicon source and hydroxylating boron nitride
Tap touching.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, the hydroxyl of silanol
Hydrogen bond is formed between the hydroxyl on the surface cubic boron nitride (cBN), is further condensed on the basis of hydrogen bond bridges later, with
The form of B-O key generates the chemistry key connection between silicon and cBN.Silanol dehydrogenation under alkaline condition simultaneously forms Louis
Alkali continues to react other silicon atomic cores, and is dehydrated (or dealcoholysis) polymerization, slowly generates reticular structure, ultimately generates and be incorporated in
The SiO on the surface cBN2Film.) silicon oxygen can be particularly susceptible in conjunction with cubic boron nitride powder through cubic boron nitride powder surface
Hydroxy combining forms silica layer in cubic boron nitride powder surface, on cubic boron nitride surface, obtains modified cubic boron nitride powder.
In the present invention, the thickness of the silica layer is in Nano grade, preferably 1~60nm.
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 650~900 DEG C；The soaking time of the melting is preferably
(0,4h], further preferably 30min~3h.After completing melting, melt is carried out cooling treatment by the present invention, obtains metallic aluminium packet
Cover 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 chlorination
In object inorganic salts mixture as main component, the melting packet of aluminium powder cubic boron nitride powder is realized by heating-cooling processing
It covers；During melting cladding, aluminium powder is bonded in cubic boron nitride powder surface by silicon oxygen, solves in the prior art cube
Boron nitride and aluminium are difficult to the problem of being bonded (metallurgical release agent of the boron nitride frequently as aluminium in the prior art) and obtain with aluminium cladding
The compound cubic boron nitride powder of type structure；It is as follows to coat principle: after villaumite melting, will form conducting liquid environment, while aluminium
Powder also melts, and is dispersed into liquid droplets and spreads.Due to Brownian movement, cBN particle is transported at random in the liquid environment of fused salt
It is dynamic.Since liquid melt salt is electrolyte, and metallic aluminium is also conductive.Metallic aluminium powder after melting, wherein a small portion
Divide electronics that will be thermally activated into free electron.Liquid molten salt is conductive, therefore in fuse salt and the liquid metal aluminium of dispersion
Some free electrons can move freely, and become the shared electron cloud of conductive fused salt and aluminium.As a result, slight due to electronics
Loss, 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
The cladding of powder surface.
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；For the silicon oxygen adhesive layer by hydroxy combining in cubic boron nitride core surface, the metallic aluminium clad is viscous
Invest silicon oxygen tie layer surface.In the present invention, in terms of mass percentage, the metallic aluminium cladding cubic boron nitride is preferably wrapped
Include 60~98.8% cubic boron nitride nucleomes, 0.2~20% silicon oxygen adhesive layer and 1~20% aluminium clad；The metallic aluminium packet
The mass percentage for covering cubic boron nitride cubic boron nitride is more preferably 62.5~98.5%, more preferably 65~
95%；The mass percentage of silicon oxygen adhesive layer is more preferably 0.5~15% in the metallic aluminium cladding cubic boron nitride,
More preferably 1~13.5%；The mass percentage of aluminium clad is further preferred in the metallic aluminium cladding cubic boron nitride
It is 1~18.5%, more preferably 2.5~15.5%.In the present invention, the metallic aluminium cladding cubic boron nitride is powder, institute
State metallic aluminium cladding 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) it uses mass concentration to carry out hydroxylating processing for 66% concentrated nitric acid cubic boron nitride powder first: will stand
Square boron nitride powder and concentrated nitric acid mixing 10min；Then cubic boron nitride powder is taken out from nitric acid and it is washed
And drying.
(2) first weigh 500 mass parts it is above-mentioned by hydroxylating handle boron nitride powder, be added to 1500 mass parts go from
In sub- water, ultrasonication obtains 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, complete the silicon oxygen modification modification of cubic boron nitride powder.
(3) 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, finally obtain metallic aluminium cladding cubic boron nitride.
Embodiment 2
(1) it uses mass concentration to carry out hydroxylating processing for 69% concentrated nitric acid cubic boron nitride powder first: will stand
After square boron nitride powder and concentrated nitric acid mixing 10min, cubic boron nitride powder is taken out from nitric acid and it is carried out washing and
It is dry.
(2) first weigh 500 mass parts it is above-mentioned by hydroxylating handle boron nitride powder, be added to 1500 mass parts go from
In sub- water, then ultrasonication uses 7200 mass parts acetone as decentralized medium at suspension, 25 mass parts L-arginines are made
For catalyst, stirring is sufficiently mixed, and 70 mass parts methyl orthosilicates are then added thereto, is stirred to react 18 at a temperature of 45 DEG C
Hour, complete the silicon oxygen modification modification on the surface of cubic boron nitride powder.
(3) 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, finally obtain metallic aluminium cladding cubic boron nitride.
Embodiment 3
(1) mixed modifier for the hydrogen peroxide that mass concentration is 30% for 98% concentrated sulfuric acid and mass concentration is used first
(volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 75:25) cubic boron nitride powder carries out hydroxylating processing: by cubic boron nitride powder
Body and mixed modifier mixing 15min, then cubic boron nitride powder is taken out and wash from mixed modifier to it afterwards
It washs and dries.
(2) first weigh 500 mass parts it is above-mentioned by hydroxylating handle boron nitride powder, be added to 1500 mass parts go from
In sub- water, then ultrasonication uses 14400 parts of methanol as decentralized medium, 80 mass parts L-lysine conducts at suspension
Catalyst, stirring are sufficiently mixed, and 165 mass parts ethyl orthosilicates are then added thereto, are stirred to react 24 at a temperature of 55 DEG C
Hour, complete the silicon oxygen modification modification of cubic boron nitride powder.
(3) 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, finally obtains metallic aluminium cladding cubic boron nitride.
Embodiment 4
Metallic aluminium cladding cubic boron nitride is prepared in the way of embodiment 1, difference is that step (3) is warming up to 800
DEG C, 10min 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 (3) 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 (3) is warming up to 700
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) mass concentration is used to carry out hydroxylating processing for 35% concentrated nitric acid cubic boron nitride powder first: general cube
Boron nitride powder and concentrated nitric acid mixing 10min；Then cubic boron nitride powder is taken out from nitric acid and it is carried out washing and
It is dry.
(2) 500 parts of above-mentioned boron nitride powders handled by hydroxylating are first weighed, are added in 2500 parts of deionized waters,
Then ultrasonication uses 8000 parts of methanol as decentralized medium at suspension, 30 parts of L-arginines as catalyst, fill by stirring
Divide mixing, 110 parts of methyl orthosilicates are then added thereto, are stirred to react at a temperature of 60 DEG C 12 hours, completes to a cube nitrogen
Change the silicon oxygen modification modification of boron powder.
(3) 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, finally obtain metallic aluminium cladding cube nitridation
Boron.
Embodiment 8
(1) hydroxylating processing is carried out using chloroazotic acid cubic boron nitride powder first: by cubic boron nitride powder and chloroazotic acid
Mix 20min；Then cubic boron nitride powder is taken out from chloroazotic acid and it is washed and is dried.
(2) 500 parts of above-mentioned boron nitride powders handled by hydroxylating are first weighed, are added in 2500 parts of deionized waters,
Then ultrasonication uses 12000 parts of methanol as decentralized medium, 75 parts of L-lysines are as catalyst, stirring at suspension
It is sufficiently mixed, 5 parts of ethyl orthosilicates is then added thereto, are stirred to react at a temperature of 70 DEG C 18 hours, complete to a cube nitrogen
Change the silicon oxygen modification modification of boron powder.
It (3) 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) mixed modifier for the hydrogen peroxide that mass concentration is 30% for 98% concentrated sulfuric acid and mass concentration is used first
(volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 70:30) cubic boron nitride powder carries out hydroxylating processing: by the cubic boron nitride
Powder and mixed modifier mixing；Then cubic boron nitride powder is taken out from mixed modifier and it is washed and is done
It is dry.
(2) 500 parts of above-mentioned boron nitride powders handled by hydroxylating are first weighed, are added in 2500 parts of deionized waters,
Then ultrasonication uses 24000 parts of isopropanols as decentralized medium at suspension, 14 parts of L-arginines are stirred as catalyst
It mixes and is sufficiently mixed, 140 parts of methyl orthosilicates are then added thereto, are stirred to react at a temperature of 75 DEG C 12 hours, complete opposition
The silicon oxygen modification of square boron nitride powder is modified.
(3) 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 (3) is warming up to 800
DEG C, 35min 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 (3) is warming up to 850
DEG C, 25min 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 (3) is warming up to 700
DEG C, 90min 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) mass concentration is used to carry out hydroxylating processing for 69% concentrated nitric acid cubic boron nitride powder first: by this
Cubic boron nitride powder and concentrated nitric acid mixing 10min, then cubic boron nitride powder is taken out and wash from nitric acid to it
It washs and dries.
(2) 500 parts of above-mentioned boron nitride powders handled by hydroxylating are first weighed, are added in 5000 parts of deionized waters,
Then ultrasonication uses 16000 parts of acetone as decentralized medium, 110 parts of L-lysines are as catalyst, stirring at suspension
Be sufficiently mixed, then thereto be added 110 parts of methyl orthosilicates, be stirred to react at a temperature of 85 DEG C 24 hours, complete to cube
The silicon oxygen modification of boron nitride powder is modified.
(3) 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, final
Cubic boron nitride is coated to metallic aluminium.
Embodiment 14
(1) mixed modifier for the hydrogen peroxide that mass concentration is 30% for 98% concentrated sulfuric acid and mass concentration is used first
(volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 72:30~28) cubic boron nitride powder carries out hydroxylating processing: will cube nitridation
Boron powder and mixed modifier mixing 20min；Then, cubic boron nitride powder is taken out from mixed modifier and it is carried out
Washing and drying.
(2) 500 parts of above-mentioned boron nitride powders handled by hydroxylating are first weighed, are added in 5000 parts of deionized waters,
Then ultrasonication uses 24000 parts of acetone as decentralized medium, 15 parts of L-arginines are as catalyst, stirring at suspension
Be sufficiently mixed, then thereto be added 300 parts of ethyl orthosilicates, be stirred to react at a temperature of 90 DEG C 18 hours, complete to cube
The silicon oxygen modification of boron nitride powder is modified.
(3) 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, finally obtains metallic aluminium cladding 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 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, it is seen then that cubic boron nitride powder surface to form one layer of clad.
Metallic aluminium cladding cubic boron nitride equally is finally obtained to embodiment 1~14 and is scanned electron microscope analysis, as a result class
Seemingly, 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 the present invention
The processing of technical solution realizes the aluminium cladding in cubic boron nitride powder surface.
Meanwhile the micro- detection of electronic transmission is carried out to the powder that 1~14 step of embodiment (2) obtains, with the inspection of embodiment 1
It surveys result and is illustrated as example, as shown in Figure 9 and Figure 10, Fig. 9 is global transmission electron microscope TEM picture, it is seen that boron nitride outsourcing
Cover the translucent silicon oxygen shell of this circle；Figure 10 is partial enlargement transmission electron microscope TEM picture, and boron nitride outermost has obviously
Clad, it is seen that have the presence of apparent silica layer between two arrows.
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 Figure 11 and
Shown in SEM figure of the Figure 12 to mixed powder, it is seen then that apparent aluminium powder or bead, there is no form on cubic boron nitride surface
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 is scanned to the powder body material that the comparative example obtains, such as figure of the SEM figure under difference observation multiplying power is such as
Shown in Figure 13~15.
By Figure 13~15 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, it, still can not be in cubic boron nitride surface alclad, aluminium picture even across same smelting process
The oil of non-stick pan 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) cubic boron nitride powder and modifying agent are mixed, carries out surface hydroxylation, obtains hydroxylating boron nitride；The modification
Agent is mixture, concentrated nitric acid or the chloroazotic acid of the concentrated sulfuric acid and hydrogen peroxide；
(2) suspension of the hydroxylating boron nitride 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；
(3) 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 (3) 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 (3)
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 (2) 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 the suspension of step (2) the hydroxylating boron nitride
The mass ratio of middle hydroxyl boron nitride and water is 1:(3~10).
6. preparation method according to claim 1, which is characterized in that hydroxylating boron nitride is suspended in the step (2)
The mass ratio of hydroxylating boron nitride and organic solvent is 5:(48~240 in liquid)；The organic solvent includes ethyl alcohol, methanol, third
One of pure and mild acetone is a variety of.
7. preparation method according to claim 1, which is characterized in that hydroxyl in organic base and suspension in the step (2)
The mass ratio of base 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 (2) in organic silicon source and suspension
The mass ratio of hydroxylating boron nitride is (2~300): 500；The organic silicon source includes methyl orthosilicate and/or ethyl orthosilicate.
9. preparation method according to claim 1, which is characterized in that the time of surface hydroxylation exists in the step (1)
10min or more.
10. preparation method according to claim 1, which is characterized in that after the step (3) 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484626A (en) * | 2020-04-24 | 2020-08-04 | 叶笃梁 | Modified boron nitride grafted waterborne acrylic resin insulating material and preparation method thereof |
| CN117534449A (en) * | 2024-01-10 | 2024-02-09 | 洛阳铂信耐火材料有限公司 | Corundum castable for copper chute and preparation method thereof |
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2018
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484626A (en) * | 2020-04-24 | 2020-08-04 | 叶笃梁 | Modified boron nitride grafted waterborne acrylic resin insulating material and preparation method thereof |
| CN117534449A (en) * | 2024-01-10 | 2024-02-09 | 洛阳铂信耐火材料有限公司 | Corundum castable for copper chute and preparation method thereof |
| CN117534449B (en) * | 2024-01-10 | 2024-03-26 | 洛阳铂信耐火材料有限公司 | Corundum castable for copper chute and preparation method thereof |
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