CN105837223A - Method for synthesizing aluminum nitride power - Google Patents
Method for synthesizing aluminum nitride power Download PDFInfo
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- CN105837223A CN105837223A CN201610289195.5A CN201610289195A CN105837223A CN 105837223 A CN105837223 A CN 105837223A CN 201610289195 A CN201610289195 A CN 201610289195A CN 105837223 A CN105837223 A CN 105837223A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/46—Gases other than oxygen used as reactant, e.g. nitrogen used to make a nitride phase
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Abstract
The invention relates to a method for synthesizing aluminum nitride power .The method comprises the following steps that a bulk porous precursor where aluminum sources and carbon sources are uniformly distributed is prepared, and the bulk porous precursor is provided with a communicating hole structure formed by a surface through hole and an inner through hole at least partly communicated with the surface through hole; the obtained bulk porous precursor is subjected to a carbothermic reduction reaction in a nitrogen atmosphere for carbon removal, and the aluminum nitride power is obtained .The preparation process is simple, there is no strict operation condition, and the synthesized aluminum nitride power has a controllable particle size and morphology, few metal impurities and high sintering activity and can be used for preparing high-thermal-conductivity aluminum nitride ceramic.
Description
Technical field
The invention belongs to a kind of ceramic powder preparation technology, relate to the synthetic method of a kind of aluminium nitride powder.
Background technology
In ceramic material, aluminium nitride (AlN) has that theoretical thermal conductivity is high, thermal coefficient of expansion is little, body resistivity is high, micro-
Ripple dielectric properties are excellent and the chemical stability good characteristic such as well is it is considered to be high density, high-power and high speed integrated electrical base board
With the ideal material of encapsulation, in the fields such as Aero-Space, communication, microelectronics, application prospect is the most wide.
In ceramic material, aluminium nitride (AlN) has that theoretical thermal conductivity is high, thermal coefficient of expansion is little, body resistivity is high, micro-
Ripple dielectric properties are excellent and the chemical stability good characteristic such as well is it is considered to be high density, high-power and high speed integrated electrical base board
With the ideal material of encapsulation, in the fields such as national defence, Aero-Space, communication, microelectronics, application prospect is the most wide.
Since 1877, the synthesis developing history of existing more than 100 year of aluminium nitride powder, but until 70 years 20th century
Just being prepared for middle and late stage densification aluminium nitride ceramics, its thermal conductivity differs greatly with theoretical thermal conductivity, and initial product quality is also
Instability, process repeatability is the most poor, limits its application in terms of substrate and encapsulating material.Cause this phenomenon one
Main cause is that the aluminium nitride powder of synthetic is of low quality, and metal impurities and oxygen impurities content are high, and agglutinating property is poor, is difficult to obtain
Obtain fine and close aluminium nitride ceramics so that the thermal conductivity of end product is far below theoretical value.
Carbothermic method, as one of traditional method preparing aluminium nitride powder, has a many advantages: (1) raw material sources
Extensively, low cost, it is suitable for large-scale production；(2) insensitive to process conditions, good stability；(3) aluminium nitride powder obtained
Purity is higher, narrow diameter distribution, can control product morphology by raw material pattern, and powder is prone to forming and sintering；Etc..So
And, traditional carbo-thermal process using white carbon black as carbon source also exists that raw material mixing is uneven, useful load is low, reaction is incomplete,
The problems such as reaction temperature is high.
In the last few years, domestic and international researcher had done a lot of exploration to improving carbo-thermal process.As CN 101973534 A is public
Opening a kind of method preparing aluminum nitride ceramic powder, using aluminum nitrate or aluminum chloride or aluminum sulfate in the method is aluminum source, and white carbon black is
Carbon source, carbamide, ammonium nitrate, nitric acid are additive, obtain predecessor after reacting by heating, and predecessor is after carbothermic reduction reaction
Carry out carbonization treatment again and obtain aluminium nitride powder.As CN 104402452 A discloses the preparation side of a kind of aluminum nitride ceramic powder
Method, the method utilizes the hydrolysis of rafifinal, it is thus achieved that alumina precursor, and sucrose, as carbon source, uses gel solid method also
In conjunction with carbothermal reduction-nitridation technique, processed by aluminum source and the control of carbon source purity and non-air oxidizing atmosphere decarbonizing technology, it is thus achieved that
The ultra-high purity of high purity 99.99%, high sintering active nitride aluminium powder body.The open a kind of ball of the most such as CN 102686511 A
The manufacture method of shape aluminium nitride powder, it needs first by pelletize, alumina powder or alumina hydrate powder to be formed marumerizer
Thing is re-used as initiation material, then this marumerizer thing is supplied to reduction nitridation operation, and nitrogen is by the gap formed between granule
Penetrate into the inside of granules thus carry out reduction nitridation.But it is incomplete that these methods improved yet suffer from solid-gas reaction
Problem, the most above-mentioned carbothermic reduction reaction is still deposited in reacting furnace with powder as aluminium oxide and the carbon black of raw material, is passed through
The nitrogen of reacting furnace hardly enters inside the powder of accumulation, causes powder body accumulation body upper and lower surface to react inhomogenous phenomenon, thus
Once a large amount of powder can not be reacted.
Summary of the invention
For the problems referred to above, it is an object of the invention to provide a kind of novel method preparing AlN powder body.This method is grasped
Make simple, with low cost, it is possible to resolve traditional carbo-thermal process raw material useful load is low, solid-vapor contact is insufficient, reaction not
Homogeneous problem, is suitable for industrialized production.
The present invention provides the synthetic method of a kind of aluminium nitride powder at this, comprises the following steps: preparation is evenly distributed with aluminum source
With the block porous presoma of carbon source, described block porous presoma has by surface through hole and at least partly leads to described surface
The intercommunicating pore structure that the interior bone of hole UNICOM is formed；And the block porous presoma of gained is carried out carbon heat also under nitrogen atmosphere
De-carbon after former reaction, i.e. obtains aluminium nitride powder.
Aluminum source and carbon source are first prepared as the block porous presoma with intercommunicating pore structure by the present inventor, more under nitrogen atmosphere
Carry out carbothermal reduction-nitridation.By means of this, on the one hand nitrogen can smoothly enter inside presoma by intercommunicating pore structure, can
Increase the contact area of solid-gas reaction, substantially reduce the response time, significantly improve the uniformity of reaction efficiency and powder body.Separately
On the one hand, forming block porous presoma, polylith presoma can be stacked in reacting furnace and carry out will not occurring the while of reaction simultaneously
The problem that the reaction of powder body accumulation body upper and lower surface is uneven.Additionally, the preparation technology of the present invention is simple, without harsh operating condition,
Aluminium nitride powder particle diameter, the morphology controllable of synthesis, metal impurities are few, sintering activity is high, can be used for preparing high thermal-conductivity aluminum nitride pottery
Porcelain.
It is preferred that pore-size 1～500 μm of described block porous presoma.The void size model of the presoma of the present invention
Enclose wide, the structure of the multi-stage porous formed by aperture, macropore can be formed.
It is preferred that source of aluminium can be the aluminium oxide of crystal habit, gibbsite (such as α-gibbsite), boehmite,
With at least one in hexagonal water aluminum stone.
It is preferred that described carbon source can be at least in white carbon black, activated carbon, sucrose, glucose, starch and citric acid
Kind.
It is preferred that the mass ratio of aluminum source and carbon source can be 1:(0.4～5).
It is preferred that porous presoma heap block described in polylith is overlayed logical nitrogen in reacting furnace carry out carbon thermal reduction simultaneously
Reaction.
It is preferred that the preparation method of described porous presoma comprises the steps:
Aluminum source and carbon source are sufficiently mixed uniformly, obtain raw mixture；
Raw mixture and disperse medium and being used for is formed the additive of gel mix homogeneously and obtain the slurry of stably dispersing, described slurry
Solid content is 20～50wt%, and the content of additive is 0.3～5.0%；And
Carry out mechanical foaming after adding surfactant in the slurry, inject mould and carry out situ-gel solidification, be dried, before obtaining porous
Driving body, described slurry is 1:(0.001～0.10 with the mass ratio of described surfactant).
The present invention prepares porous presoma by gel foam process, and the intercommunicating pore of formation is evenly distributed in presoma surface
And inside, in three-dimensional netted UNICOM, and the presoma obtained has some strength, is suitable for stacking.Additionally, this technique letter
Single, controlled, without severe operating conditions and equipment requirements, it is adaptable to industrialized production.
It is preferred that aluminum source and carbon source can be dry mixed mode by mechanization and mix, such as ball milling mixing.The present invention is direct
By mechanization, aluminum source and carbon source are dry mixed mode mix, so, raw material mixed process can strictly prevent impurity
Introducing so that the aluminium nitride powder particle diameter that finally obtains, morphology controllable, metals content impurity is low, and sintering activity is high.
System, optimization polypropylene acrylamide gel system, polyamine-epoxy resin gel is coagulated it is preferred that described slurry is water base note
System or water solublity maleic base polymer gel rubber system, the wherein the most poly-[(isobutyl of water solublity maleic base polymer
Alkene-alt-maleic acid, ammonium salt)-co-(isobutene .-alt-maleic anhydride)] in any one model or the combination of disposable type.
By selecting these water base notes to coagulate system, can form gel without adding other additive, reduce drawing of impurity further
Enter.
It is preferred that the mass ratio of described slurry and described surfactant is 1:(0.001～0.10).Surfactant is permissible
The structure in the hole that stable stirring foaming is formed.
It is preferred that nitrogen flow rate can be 1～20L/ minute during carbothermic reduction reaction.
It is preferred that the reaction temperature of carbothermic reduction reaction can be 1400 DEG C～1700 DEG C, the response time can be 1～5 hour.
It is preferred that de-carbon temperature can be 500 DEG C～750 DEG C, the de-carbon time can be 1～5 hour.
The present invention also provides for the purity of aluminium nitride powder described in a kind of aluminium nitride powder synthesized according to above-mentioned synthetic method
More than 97%.
The aluminium nitride powder impurity content that the present invention provides is low, and sintering activity is good, is expected to be prepared as compact aluminum oxide ceramic.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope microscopic analysis figure of the presoma that embodiment 1 prepares；
Fig. 2 is the aluminium nitride powder scanning electron microscope microscopic analysis figure of embodiment 1 synthetic product sampling；
Fig. 3 is the aluminium nitride powder X-ray diffractogram of embodiment 1 synthetic product sampling；
Fig. 4 is the scanning electron microscope microscopic analysis figure of the presoma that embodiment 2 prepares；
Fig. 5 is the aluminium nitride powder scanning electron microscope microscopic analysis figure of embodiment 2-in-1 one-tenth product sampling；
Fig. 6 is the aluminium nitride powder X-ray diffractogram of embodiment 2-in-1 one-tenth product sampling；
Fig. 7 is the scanning electron microscope microscopic analysis figure of the presoma that embodiment 3 prepares；
Fig. 8 is the aluminium nitride powder scanning electron microscope microscopic analysis figure of embodiment 3 synthetic product sampling；
Fig. 9 is the aluminium nitride powder X-ray diffractogram of embodiment 3 synthetic product sampling；
Figure 10 is the scanning electron microscope microscopic analysis figure of the presoma that embodiment 4 prepares；
Figure 11 is the aluminium nitride powder scanning electron microscope microscopic analysis figure of embodiment 4 synthetic product sampling；
Figure 12 is the aluminium nitride powder X-ray diffractogram of embodiment 4 synthetic product sampling；
Figure 13 is the powder body product sampling X-ray diffractogram that comparative example 1 obtains；
Figure 14 is the presoma pictorial diagram that the method by the present invention prepares；
Figure 15 is that polylith presoma stacks pictorial diagram.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that accompanying drawing and following embodiment are only below in conjunction with accompanying drawing and following embodiment
For the present invention is described, and the unrestricted present invention.
After aluminum source and carbon source are first made the block porous presoma of through-hole structure by the present invention, then it is placed under blanket of nitrogen and carries out carbon
Thermal reduction reaction；The powder obtained after reaction is carried out de-carbon, i.e. obtains high-quality aluminium nitride powder.
As aluminum source, can be aluminium oxide and/or hydrated alumina, specifically, include but not limited to various crystalline
The aluminium oxide (including α, γ, θ, η, δ, К, Х) of state, gibbsite (such as α-gibbsite), Bo Mu
Stone, hexagonal water aluminum stone or the mixture being arbitrarily made up of these materials.
As carbon source, it is possible to use carbon simple substance and at high temperature can crack and become the organic carbon precursor of carbon simple substance, specifically
For, such as simple substance carbon includes but not limited to white carbon black, activated carbon, and can crack under high temperature becomes the organic carbon precursor of carbon simple substance and include
But it is not limited to sucrose, glucose, starch, citric acid.
In block porous presoma, aluminum source can be 1:(0.4～5 with the mass ratio of carbon source), preferably 1:(0.4～3).
Aluminum source is more than 1:0.4 with the mass ratio of carbon source, can make the reaction of aluminum source the most completely；Aluminum source is 1:5 with the mass ratio of carbon source
Time following, too much carbon source residue will not be produced and cause waste and the problem increasing de-carbon cost.
Described block porous presoma is interpreted as having some strength thus convenient carrying transfer, stacking process etc..Block
Being not limited to square block, its outer surface does not the most require that absolute becomes plane.
The pore structure of block porous presoma is preferably intercommunicating pore, i.e. at least has the surface through hole with external communication and (opens
Hole), and with the interior bone of surface through hole UNICOM, so can make solid-vapor contact more fully and uniformly.Porous presoma
Porosity can be 50～85%, preferably 60～80%.If porosity is less than 50%, solid-vapor contact may be made insufficient；
If porosity more than 85%, then can cause, reacting furnace cavity space utilization rate is low, production efficiency is low.It addition, the hole of porous presoma
Gap size can be 1～800 μm, preferably 200～500 μm.The void size scope of the presoma of the present invention is wide, can be with shape
Become the structure of the multi-stage porous formed by aperture, macropore.
Block porous presoma used by the present invention may utilize gel foam process to be prepared.Such as, make dispersed have aluminum source
With carbon source and for formed gel additive slurry (gel rubber system) foaming after gel solidification and obtain porous presoma.
Hereinafter, as example, this gel foam process is described.
First, raw material mixing pretreatment is carried out: be sufficiently mixed uniformly in aluminum source and carbon source, obtain raw mixture.Aluminum source
Can be aluminium oxide and/or hydrated alumina as mentioned above, so can strictly prevent the introducing of impurity.Aluminum source can be purchased from
Commercialization or self-control, for example, it is possible to by alkoxide process, Bayer process, ammonia-alum thermal decomposition method, ammonia dawsonite (ammonium
Dawsonite) thermal decomposition method obtains.Median as the aluminum source of raw material can be 10～3500nm, BET specific surface area
Can be 1～1000m2/g.Median as the carbon source of raw material can be 5～50nm, BET specific surface area can be 50～
1000m2/g.The proportioning of aluminum source and carbon source can be by weight aluminum source: carbon source=1:(0.4～5).Aluminum source and the mixing side of carbon source
Formula preferably mechanization is dry mixed, and so can strictly prevent the introducing of impurity.It can be three-dimensional motion mixer, rolling that mechanization is dry mixed
Any one in dynamic ball mill, planetary ball mill.Mixed process selects wear-resistant liner and ball-milling medium.Inner lining material includes
But it is not limited to any one in nylon, polyurethane, aluminium oxide ceramics, aluminium nitride ceramics.Ball-milling medium includes but not limited to oxygen
Change aluminum ball, aluminium nitride ball, nylon ball, nylon cladding steel ball in any one.Material: ball weight ratio=1:(1.5～3), ball
Consuming time 0.5～5 hour so that it is be sufficiently mixed uniformly, mixing raw material sieves through 40 eye mesh screens after taking out.
Then, preparation slurry: raw mixture and disperse medium and being used for is formed the additive of gel and mixs homogeneously and obtain
The slurry of stably dispersing.Disperse medium includes but not limited to water, ethanol, acetone etc., and preferably deionized water (is i.e. formed water base
The solidifying system of note).Quinary system (polyacrylamide gel system), triplet is included but not limited to for forming the additive of gel
System's (polyamine-epoxy resin gel rubber system) and unitary system (water solublity maleic base polymer gel rubber system) etc..And water
Dissolubility maleic base polymer is appointing in poly-[(isobutene .-alt-maleic acid, ammonium salt)-co-(isobutene .-alt-maleic anhydride)]
The combination of a kind of model or the disposable type of anticipating.Raw mixture, disperse medium, the mass ratio of additive can be 1:(0.5～5):
(0.003～0.05).The hybrid mode of this three can be wet ball grinding.Can be selected for wear-resistant liner and ball-milling medium.Inner lining material
Include but not limited in nylon, polyurethane, aluminium oxide ceramics, aluminium nitride ceramics any one.Ball-milling medium includes but does not limits
In alumina balls, aluminium nitride ball, nylon ball, nylon cladding steel ball in any one.Material: ball weight ratio=1:(1.5～
3), Ball-milling Time 1～3 hours, obtain the slurry of stably dispersing, the slurry solid content of formation is 20～50wt%, additive
Content be 0.3～5.0wt%.
In the slurry prepared add surfactant, weight ratio can be slurry: surfactant=1:(0.001～
0.10), preferably 1:(0.01～0.05).As surfactant, include but not limited to that anion surfactant is (as firmly
Fat acid, dodecylbenzene sodium sulfonate), cationic surfactant (such as quaternary ammonium compound), zwitterionic surfactant is (such as ovum
Phospholipid, amino acid pattern, glycine betaine) and nonionic surfactant (such as fatty glyceride, fatty acid Pyrusussuriensis Pyrusussuriensis smooth, poly-
Ester).Slurry carries out mechanical foaming (such as stirring foaming), and mixing time can be 0.5～5 minute.Then slurry is injected
Mould carries out situ-gel solidification (such as standing 2～5 hours at 15～60 DEG C), and is dried (such as at 20 DEG C～60 DEG C
Under be dried 2～7 days), obtain block porous presoma.Wherein, mould includes but not limited to mould of plastics, glass molds
Tool, rubber mold, metal or wooden assembled mould.
Seeing Fig. 1 and Figure 14, it illustrates that the photo in kind of block porous presoma that said method prepares and cross section are shone
Sheet, the most visible, block porous presoma has surface holes and internal intercommunicating pore, in three-dimensional netted distribution pore passage structure.Join again
Seeing Figure 15, the stackable placement of polylith presoma, the block porous presoma that the surface present invention prepares has some strength.
The above-mentioned preparation method illustrating porous presoma as a example by gel foam process, it should be appreciated that the present invention relates to
Porous presoma can be obtained by other porous ceramicss preparation technology.These techniques are the most as described below.
(1) pore creating material method is added
Flammable or volatility pore creating material is added in slurry preparation process (preparing referring for example to the slurry in above-mentioned gel foam process)
(such as paraffin, starch, sucrose etc.), after slurry curing, pore creating material can be burnt by low temperature and lose or directly vapor away, thus
Presoma surface and inside leave a large amount of hole.Porous can be regulated and controled by controlling the shape of pore creating material granule, size and addition
The shapes and sizes of the hole of presoma.
(2) Polymeric sponge method
Organic Foam Material is impregnated in the slurry (preparing referring for example to the slurry in above-mentioned gel foam process) of stably dispersing, repeatedly
Extruding, so that ceramic powders adheres on hole wall or the hole muscle of organic foam, thus replicates foaming structure, and dried burn off is organic
Foam, i.e. obtains porous presoma.Porous presoma can be regulated and controled by the pore structure and pore size controlling Organic Foam Material
The structure of hole and size.
(3) sol-gel process
First by metallic aluminium or the hydrolysis of alkoxide of aluminum, obtain colloidal sol, be subsequently adding organic carbon source (such as sucrose, glucose, starch, lemon
Lemon acid etc.), regulate pH value, by cohesion condensation reaction, form the gel of unformed network structure, finally by gel drying
And doing heat treatment, Organic substance decomposes, and i.e. obtains porous presoma.
(4) freeze-drying
Utilize the frost action of water-based slurry (preparing referring for example to the slurry in above-mentioned gel foam process), control ice growth side simultaneously
To, and make ice distil by drying under reduced pressure, i.e. obtain the porous presoma with Complicated Pore Structures.
Bulk porous presoma stacking is carried out carbothermic reduction reaction, under nitrogen atmosphere to generate aluminium nitride.Reaction temperature can
Being 1400 DEG C～1700 DEG C, the response time can be 1～5 hour, preferably 1～4 hour.The flow velocity of nitrogen can be 1～
20L/min.Carry out de-carbon, i.e. can get aluminium nitride powder.De-carbon temperature can be 500 DEG C～750 DEG C, and the de-carbon time can be
1～5 hour.The particle diameter of the aluminium nitride powder obtained is 0.1～2 μm, pattern be spherical, elliposoidal, hexagon or other
Irregular polyhedrons shape, purity is more than 97%.
The present invention mainly has the following advantages:
(1) presoma prepared has the pore passage structure of three-dimensional netted distribution, can increase the contact area of solid-gas reaction, be greatly shortened
In the response time, significantly improve the uniformity of reaction efficiency and powder body；
(2) present invention forms block presoma, and polylith presoma can be stacked in reacting furnace and react simultaneously, and useful load is high,
It is suitable for large-scale production；
(3) raw material sources extensive, cheap, transport convenient storage, preparation technology is simple, controlled, without severe operating conditions with
Equipment requirements, it is adaptable to industrialized production；
(4) present invention can strictly prevent the introducing of impurity in material choice during mixing, by select raw material particle diameter,
The particle diameter of the aluminium nitride powder that morphology controllable system finally obtains, pattern, metals content impurity is low, and sintering activity is high, can be used for making
The aluminium nitride ceramics of standby high heat conductance.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Bright it is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to the present invention's
Some nonessential improvement and adjustment that foregoing is made belong to protection scope of the present invention.The technique ginseng that following example is concrete
Number etc. is the most only an example in OK range, in the range of i.e. those skilled in the art can be done suitably by explanation herein
Select, and do not really want to be defined in the concrete numerical value of hereafter example.
Structure and the method for testing of performance
(particle diameter)
Aluminum source, carbon source, the method for testing of particle diameter of aluminium nitride powder are laser method.
(specific surface area)
Calculate by Brunauer Emmett Teller (BET) method.
(porosity)
The porosity computational methods of porous presoma are as follows: sample is processed into regular shape, measure length, calculate volume
V, then weighs and obtains quality m, and its apparent density is:
ρ '=m/V
Then presoma overall porosity is:
P=1-ρ '/Dth
Wherein, DthIt it is the solid density of material.
(pore-size)
The pore-size method of testing of porous presoma is as follows: the pore-size of porous presoma can be come really by section direct observational method
Fixed, the pore-size of presoma is i.e. directly observed by scanning electron microscope.
(purity of aluminium nitride powder)
The purity of aluminium nitride powder is measured by ICP-AES (ICP).
Embodiment 1:
(1) γ-Al is selected2O3(median 20nm, BET 126m2/ g) it is aluminum source, white carbon black (median 10nm, BET
320m2/ g) it is carbon source, by weight aluminium oxide: white carbon black=7:3 carries out machinery and is dry mixed, select nylon inner lining, with alumina balls
For ball-milling medium, material: ball weight ratio=1:1.5, Ball-milling Time 0.5 hour so that it is be sufficiently mixed uniformly, mixing raw material takes out
Sieve by 40 eye mesh screens；
(2) use unitary gel rubber system, by weight raw material: deionized water: water solublity maleic base polymer=1:4:0.01, claim
Take raw material, deionized water and polymer and mix through wet ball grinding, selecting nylon inner lining, with alumina balls as ball-milling medium,
Material: ball weight ratio=1:1.5, Ball-milling Time 1 hour, obtains the slurry of dispersibility, good stability；
(3) by weight slurry: surfactant=1:0.005 adds surfactant sodium dodecyl base sulphuric acid three ethanol in the slurry
Amine, mechanical foaming injects after 2 minutes in metal die, and situ-gel solidifies, and is dried 3 days at 20 DEG C, before obtaining
Driving body porosity is 80%, and pore-size is not of uniform size, from tens to hundreds of micron, and the picture of presoma such as Fig. 1 institute
Show, it can be seen that presoma pore structure is based on through hole, and aperture difference is relatively big, and presoma is isotropism；
(4) presoma is carried out under nitrogen atmosphere carbothermic reduction reaction, reaction temperature 1600 DEG C, nitrogen flow rate 10L/min, reaction
4 hours time；The powder obtained after reaction is carried out de-carbon, de-carbon temperature 650 DEG C, 3 hours de-carbon time, i.e. obtains nitrogen
Changing aluminium powder body, its scanning electron microscope microscopic analysis figure is as shown in Figure 2, it can be seen that powder body homogeneity is preferable, its X-ray diffraction
Figure is as shown in Figure 3, it can be seen that under the conditions of Gai, aluminium oxide be completely converted into aluminium nitride, reacts completely, wherein position grain
Footpath D50For 530nm, purity is 97%.
Embodiment 2:
(1) α-Al is selected2O3(median 450nm, BET 6.4m2/ g) it is aluminum source, white carbon black (median 10nm, BET
320m2/ g) it is carbon source, by weight aluminium oxide: white carbon black=3:2 carries out machinery and is dry mixed, select nylon inner lining, with alumina balls
For ball-milling medium, material: ball weight ratio=1:2, Ball-milling Time 1 hour so that it is be sufficiently mixed uniformly, warp after mixing raw material taking-up
40 eye mesh screens sieve；
(2) unitary gel rubber system is used.By weight raw material: deionized water: water solublity maleic base polymer=1:5:0.04, claim
Take raw material, deionized water and polymer and mix through wet ball grinding, with alumina balls as ball-milling medium, material: ball weight ratio
=1:2, Ball-milling Time 2 hours, obtain the slurry of dispersibility, good stability；
(3) by weight slurry: surfactant=1:0.01 adds surfactant sodium dodecyl base sulphuric acid triethanolamine in the slurry,
Mechanical foaming injects after 3 minutes in metal die, and situ-gel solidifies, and is dried 3 days at 20 DEG C, and obtaining porosity is
The presoma of 75%, such as Fig. 4, presoma pore-size is not of uniform size, from tens to hundreds of micron, presoma be each to
The same sex；
(4) presoma carrying out carbothermic reduction reaction under nitrogen atmosphere, reaction temperature 1650 DEG C, nitrogen flow rate 8L/min, during reaction
Between 4 hours；The powder obtained after reaction is carried out de-carbon, de-carbon temperature 650 DEG C, 3 hours de-carbon time, is i.e. nitrogenized
Aluminium powder body, its scanning electron microscope microscopic analysis figure is as shown in Figure 5, it can be seen that powder body homogeneity is preferable, its X-ray diffractogram
As shown in Figure 6, it can be seen that under the conditions of Gai, aluminium oxide be completely converted into aluminium nitride, react completely, its median
D50For 695nm, purity is 97%.
Embodiment 3:
(1) boehmite (median 540nm, BET 5.3m is selected2/ g) it is aluminum source, sucrose is carbon source, by weight oxidation
Aluminum: white carbon black=1:5 carries out machinery and is dry mixed, selects nylon inner lining, with alumina balls as ball-milling medium, and material: ball weight ratio=1:2,
Ball-milling Time 1 hour so that it is be sufficiently mixed uniformly, mixing raw material sieves through 40 eye mesh screens after taking out；
(2) ternary gel rubber system is used.By weight raw material: deionized water: polyamine-epoxy resin=1:2:0.02, weigh raw material,
Deionized water and polymer also mix through wet ball grinding, and with alumina balls as ball-milling medium, material: ball weight ratio=1:2, during ball milling
Between 2 hours, obtain the slurry of dispersibility, good stability；
(3) by weight slurry: surfactant=1:0.001 adds surfactant sodium dodecyl base sulphuric acid three ethanol in the slurry
Amine, mechanical foaming injects after 1 minute in metal die, and situ-gel solidifies, and is dried 3 days at 20 DEG C, obtains hole
Rate is the presoma of 50%, and such as Fig. 7, presoma pore-size is not of uniform size, from tens to hundreds of micron, presoma in
Isotropism；
(4) presoma carrying out carbothermic reduction reaction under nitrogen atmosphere, reaction temperature 1400 DEG C, nitrogen flow rate 1L/min, during reaction
Between 2 hours；The powder obtained after reaction is carried out de-carbon, de-carbon temperature 650 DEG C, 3 hours de-carbon time, is i.e. nitrogenized
Aluminium powder body, its scanning electron microscope microscopic analysis figure is as shown in Figure 8, it can be seen that powder body homogeneity is preferable, its X-ray diffractogram
As shown in Figure 9, it can be seen that under the conditions of Gai, aluminium oxide be completely converted into aluminium nitride, react the most complete.Its median
D50For 763nm, purity is 97%.
Embodiment 4
(1) gibbsite (median 521nm, BET 6.1m is selected2/ g) it is aluminum source, activated carbon (median 10nm,
BET 332m2/ g) it is carbon source, by weight aluminium oxide: white carbon black=1:5 carries out machinery and is dry mixed, select nylon inner lining, with oxidation
Aluminum ball is ball-milling medium, material: ball weight ratio=1:3, Ball-milling Time 2 hours so that it is be sufficiently mixed uniformly, and mixing raw material takes out
Sieve by 40 eye mesh screens；
(2) five yuan of gel rubber systems are used.By weight raw material: deionized water: polyacrylamide=1:5:0.03, weigh raw material, go
Ionized water and polymer also mix through wet ball grinding, and with alumina balls as ball-milling medium, material: ball weight ratio=1:1.5, during ball milling
Between 3 hours, obtain the slurry of dispersibility, good stability；
(3) by weight slurry: surfactant=1:0.1 adds surfactant fatty acid glyceride, mechanical foaming 5 in the slurry
Injecting after minute in metal die, situ-gel solidifies, and is dried 3 days at 20 DEG C, obtains the forerunner that porosity is 85%
Body, such as Figure 10, differs sized by presoma pore-size, and from tens to hundreds of micron, presoma is anisotropy；
(4) presoma is carried out under nitrogen atmosphere carbothermic reduction reaction, reaction temperature 1700 DEG C, nitrogen flow rate 20L/min, reaction
Time 2 h；The powder obtained after reaction is carried out de-carbon, de-carbon temperature 500 DEG C, 5 hours de-carbon time, i.e. obtains nitrogen
Changing aluminium powder body, its scanning electron microscope microscopic analysis figure is as shown in figure 11, it can be seen that powder body homogeneity is preferable, its X-ray diffraction
Figure is as shown in figure 12, it can be seen that under the conditions of Gai, aluminium oxide be completely converted into aluminium nitride, reacts the most complete.Wherein position
Particle diameter D50For 754nm, purity is 97%.
Comparative example 1
(1) with embodiment 1；
(2) with embodiment 1；
(3) injecting in metal die by slurry, situ-gel solidifies, and is dried 3 days at 20 DEG C, obtains presoma；
(4) by presoma ball mill pulverizing, it is thus achieved that precursor powder, presoma powder body is carried out under nitrogen atmosphere carbothermic reduction reaction, instead
Answer temperature 1600 DEG C, nitrogen flow rate 10L/min, 4 hours response time；The powder obtained after reaction is carried out de-carbon, de-carbon
Temperature 650 DEG C, 3 hours de-carbon time, i.e. obtains aluminium nitride powder, such as Figure 13, this aluminium nitride powder is carried out XRD and divides
Analysis finds, there is aluminium oxide diffraction maximum in products therefrom, raw material not yet reacts complete the most under these conditions, and utilizes embodiment
The method of 1, XRD can't detect impurity peaks, shows that raw material reaction is complete, and this explanation present invention is for improving carbothermic method
It is practicable for preparing aluminium nitride powder.
Claims (10)
1. the synthetic method of an aluminium nitride powder, it is characterised in that comprise the following steps:
Preparation is evenly distributed with the block porous presoma of aluminum source and carbon source, and described block porous presoma has the intercommunicating pore structure formed by surface through hole and at least part of interior bone with described surface through hole UNICOM；And
The block porous presoma of gained is carried out under nitrogen atmosphere de-carbon after carbothermic reduction reaction, i.e. obtains aluminium nitride powder.
Synthetic method the most according to claim 1, it is characterised in that the porosity of described block porous presoma is 50～85%, and pore-size is 1～800 m.
Synthetic method the most according to claim 1 and 2, it is characterised in that source of aluminium is at least one in the aluminium oxide of crystal habit, gibbsite, boehmite and hexagonal water aluminum stone；Described carbon source is at least one in white carbon black, activated carbon, sucrose, glucose, starch and citric acid；Aluminum source is 1:(0.4～5 with the mass ratio of carbon source).
Synthetic method the most according to any one of claim 1 to 3, it is characterised in that porous presoma heap block described in polylith is overlayed logical nitrogen in reacting furnace and carries out carbothermic reduction reaction simultaneously.
Synthetic method the most according to any one of claim 1 to 4, it is characterised in that the preparation method of described block porous presoma comprises the steps:
Aluminum source and carbon source are sufficiently mixed uniformly, obtain raw mixture；
Raw mixture and disperse medium and being used for being formed the additive of gel mix homogeneously and obtain the slurry of stably dispersing, described slurry solid content is 20～50wt%, and the content of additive is 0.3～5.0%；And
Carrying out mechanical foaming after adding surfactant in the slurry, inject mould and carry out situ-gel solidification, be dried, obtain porous presoma, described slurry is 1:(0.001～0.10 with the mass ratio of described surfactant).
Synthetic method the most according to claim 5, it is characterized in that, described slurry is that water base note coagulates system, optimization polypropylene acrylamide gel system, polyamine-epoxy resin gel rubber system or water solublity maleic base polymer gel rubber system, wherein any one model in water solublity maleic base polymer the most poly-[(isobutene .-alt-maleic acid, ammonium salt)-co-(isobutene .-alt-maleic anhydride)] or the combination of disposable type.
7. according to the synthetic method described in claim 5 or 6, it is characterised in that obtain described slurry, wherein, material: ball weight ratio=1:1.5～3, Ball-milling Time is 1～3 hour by wet ball grinding hybrid mode.
Synthetic method the most according to any one of claim 1 to 7, it is characterised in that during carbothermic reduction reaction, nitrogen flow rate is 1～20L/ minute.
Synthetic method the most according to any one of claim 1 to 8, it is characterised in that the reaction temperature of carbothermic reduction reaction is 1400 DEG C～1700 DEG C, and the response time is 1～5 hour；De-carbon temperature is 500 DEG C～750 DEG C, and the de-carbon time is 1～5 hour.
10. the aluminium nitride powder of the synthetic method synthesis according to any one of a claim 1 to 9, it is characterised in that the purity of described aluminium nitride powder is more than 97%.
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| WO2018009769A1 (en) * | 2016-07-08 | 2018-01-11 | Alcoa Usa Corp. | Systems and methods for making ceramic powders |
| CN107759226A (en) * | 2017-10-29 | 2018-03-06 | 贵州喜文化艺术有限责任公司 | A kind of ceramic powder preparation method |
| CN108863394A (en) * | 2017-05-10 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of method that gel pouring combination freeze-drying prepares porous ceramics |
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| CN112390653A (en) * | 2020-11-16 | 2021-02-23 | 中国工程物理研究院材料研究所 | Method for preparing ceramic powder based on freezing casting molding |
| CN112390651A (en) * | 2020-11-16 | 2021-02-23 | 中国工程物理研究院材料研究所 | AlN ceramic powder preparation method based on 3D printing molding |
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| CN116062714A (en) * | 2023-01-18 | 2023-05-05 | 大连海事大学 | Pure-phase nanometer AlN powder and preparation method and application thereof |
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