CN102295276B - Method for preparing porous aluminium nitride particle or porous gallium nitride particle by two-step nitridation method - Google Patents
Method for preparing porous aluminium nitride particle or porous gallium nitride particle by two-step nitridation method Download PDFInfo
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Abstract
The invention discloses a method for preparing porous AlN or porous GaN particles by a two-step nitridation method, which comprises the following steps: putting prepared raw materials in a crucible, putting the crucible with the materials into a heating furnace, performing alloy melting, cooling the alloy, performing pulverization, putting the pulverized alloy powder particles into a reaction furnace; vacuumizing the reaction furnace, injecting high-purity nitrogen, heating the alloy powder to 500-750 DEG C for first nitridation, heating to 850-1100 DEG C for second nitridation, soaking the alloy powder particles after nitridation with acids, removing the nitrides of B-component alloy so as to obtain porous A-component nitrides, that is, the porous AlN particles or porous GaN particles. The method of the invention prepares porous AlN particles or GaN particles which have a pore diameter of a hundred nanometers to several tens micrometers, have a particle size within orders of magnitude from several hundreds nanometers to several hundreds micrometers, and have a specific surface area of up to 100 m2/g.
Description
Technical field
The invention belongs to the nonmetal semi-conductor of nano inorganic and photoelectric material scientific and engineering technical field, be specifically related to a kind of method that two step nitridings prepare nitride porous aluminium (AlN) particulate or nitride porous gallium (GaN) particulate.
Background technology
There is the porous Al N of pore structure or GaN particulate and take its porous III family alloy nitride particulate formed for base because of the nonlinear optical properties of the photoelectric response characteristic of high specific surface area, enhancing, enhancing and photocatalysis characteristic etc., there is great application prospect storing up hydrogen, fuel cell, photocatalytic cleavage water, ultraviolet detection and the fields such as sensor and nonlinear optics.Therefore the research of porous Al N or GaN particulate has been become to an important research focus of porous semiconductor research field.Yet up to the present; the major cause that porous Al N or GaN semiconductive particles still can not be used widely in corresponding field is: the nitride porous aluminium particulate that can not effectively synthesize these porous semiconductor particulates or prepare by existing method; the specific surface area in hole is little; it is little that space is occupied in hole, can't be applied in practice.
Summary of the invention
The purpose of this invention is to provide a kind of method that two step nitridings prepare nitride porous aluminium (AlN) particulate or nitride porous gallium (GaN) particulate; it is little to have solved that prior art can't synthesize porous Al N or GaN particulate or the porous Al N prepared effectively or GaN microparticle pores specific surface area is little, space is occupied in hole, the problem that can't be applied in practice.
The technical solution used in the present invention is that two step nitridings prepare the method for nitride porous aluminium particulate or nitride porous gallium particulate, comprise following operation steps:
Step 1, preparation of raw material:
Raw material is comprised of A component and B component; The weight percent that the A component accounts for whole raw material is 10～90%wt;
If prepare nitride porous aluminium particulate: the A component is the industrial pure Al piece; The B component is a kind of in technical pure Mg piece, technical pure Li piece or technical pure Ca grain, or any two or three mixture formed with arbitrary proportion;
If prepare nitride porous gallium particulate: the A component is liquid Ga; The B component is a kind of in technical pure Mg piece, technical pure Li piece or technical pure Ca grain, or any two or three mixture formed with arbitrary proportion;
Step 2, the melting of alloy and preparation:
The raw material prepared is put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, make vacuum tightness in stove be less than or equal to 0.1atm, then be filled with high pure nitrogen in Reaktionsofen, nitrogen pressure in Reaktionsofen reaches 0.7～1.5atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 10 ℃/min～30 ℃/min, when the temperature of powdered alloy reaches 500～750 ℃, insulation 15～40h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 10 ℃/min～30 ℃/min, makes the temperature of powdered alloy reach 850～1100 ℃, then, at this temperature insulation 5～15h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, with acid soak 5～7h, to remove the nitride of B component alloy wherein, stays the nitride of A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 80～200 ℃ of dryings 1～4 hour, can obtain porous Al N particulate or porous GaN particulate in vacuum drying oven.
The invention has the beneficial effects as follows, utilize preparation method provided by the invention, in nitrogen pressure, be in 0.7～1.5atm situation, by the nitrogenize for the first time under the lesser temps of a certain temperature in 500～750 ℃ of scopes, (nitridation time is 15～40 hours, the concrete time, the concrete nitriding temperature in stage was relevant therewith) and the comparatively high temps of 850～1100 ℃ of interior a certain temperature of scope under nitrogenize for the second time (nitridation time is 5～15 hours, the concrete time, the nitriding temperature in stage was relevant therewith), from heterogeneity, in the Al alloy or Ga powdered alloy of content and granular size, preparing bore dia is about hundreds of nanometer to tens micron, the grain diameter size is in several microns～hundreds of micron number order magnitude range, specific surface area can reach 100m
2the porous Al N with pore structure that/g is even higher or GaN particulate.Because the present invention's nitrogenize for the first time becomes shell for AlN or GaN particle, nitrogenize for the second time is for the pore-forming of AlN or GaN particle, therefore it is little effectively to prepare aperture, it is large that space is occupied in hole, the porous Al N that the specific surface area in hole is large or GaN particulate, for porous Al N or GaN particulate provide good basis in the application in storage hydrogen, fuel cell, photocatalytic cleavage water, ultraviolet detection and the fields such as sensor and nonlinear optics and the technical progress that promotes these fields thereof.
The accompanying drawing explanation
Fig. 1 is the low resolution SEM figure that utilizes the porous Al N particulate that the inventive method prepares;
Fig. 2 is the low resolution SEM figure that utilizes the porous GaN particulate that the inventive method prepares;
Fig. 3 is the high resolving power SEM figure that utilizes the porous Al N particulate that the inventive method prepares;
Fig. 4 is the high resolving power SEM figure that utilizes the porous GaN particulate that the inventive method prepares.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The invention provides a kind of method that two step nitridings prepare nitride porous aluminium particulate or nitride porous gallium particulate, comprise following operation steps:
Step 1, preparation of raw material:
Raw material is comprised of A component and B component; The weight percent that the A component accounts for whole raw material is 10～90%wt;
If prepare nitride porous aluminium particulate: the A component is the industrial pure Al piece; The B component is a kind of in technical pure Mg piece, technical pure Li piece or technical pure Ca grain, or any two or three mixture formed with arbitrary proportion;
If prepare nitride porous gallium particulate: the A component is liquid Ga; The B component is a kind of in technical pure Mg piece, technical pure Li piece or technical pure Ca grain, or any two or three mixture formed with arbitrary proportion;
Step 2, the melting of alloy and preparation:
The raw material prepared is put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, make vacuum tightness in stove be less than or equal to 0.1atm, and vacuum tightness is more low better, then be filled with high pure nitrogen in Reaktionsofen, nitrogen pressure in Reaktionsofen reaches 0.7～1.5atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 10 ℃/min～30 ℃/min, when the temperature of powdered alloy reaches 500～750 ℃, insulation 15～40h, carry out nitriding treatment for the first time at this holding stage, after nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 10 ℃/min～30 ℃/min, makes the temperature of powdered alloy reach 850～1100 ℃, then, at this temperature insulation 5～15h, at this holding stage, carries out nitriding treatment for the second time, nitrogenize for the first time becomes shell for AlN or GaN particle, and nitrogenize for the second time is for the pore-forming of AlN or GaN particle,
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, with acid soak 5～7h, to remove the wherein nitride of B component alloy, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of the A component of porous; After acid soak, suction filtration obtains powdered sample; Wherein, acid is 0.1M～2M for volumetric molar concentration dilute hydrochloric acid or volumetric molar concentration are 0.1M～2M dilute sulphuric acid;
Step 6, drying:
The powdered sample that suction filtration is obtained in 80～200 ℃ of dryings 1～4 hour, can obtain porous Al N particulate or porous GaN particulate in vacuum drying oven.
Embodiment 1
A kind of two step nitridings prepare the method for porous Al N particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Mg piece that the Al piece that to take 50g purity be 99.5% and 50g purity are 99%, the weight percent that the Al piece accounts for whole raw material is 50%wt;
Step 2, the melting of alloy and preparation:
Al piece and Mg piece are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.1atm, then be filled with the high pure nitrogen that purity is 99.99% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 0.7atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 10 ℃/min, when the temperature of powdered alloy reaches 500 ℃, insulation 40h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 10 ℃/min, makes the temperature of powdered alloy reach 850 ℃, then, at this temperature insulation 15h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the salt acid soak 5h that is 2M by volumetric molar concentration, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 100 ℃ of dryings 3 hours, obtains nitride porous aluminium particulate in vacuum drying oven.
Embodiment 2
A kind of two step nitridings prepare the method for porous GaN particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Mg piece that the Ga liquid that to take 80g purity be 99.95% and 20g purity are 99.95%, the weight percent that Ga liquid accounts for whole raw material is 80%wt;
Step 2, the melting of alloy and preparation:
Ga liquid and Mg piece are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.05atm, then be filled with the high pure nitrogen that purity is 99.999% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 1atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 20 ℃/min, when the temperature of powdered alloy reaches 750 ℃, insulation 15h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 20 ℃/min, makes the temperature of powdered alloy reach 850 ℃, then, at this temperature insulation 15h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the salt acid soak 5h that is 1.2M by volumetric molar concentration, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 150 ℃ of dryings 1 hour, obtains porous GaN particulate in vacuum drying oven.
Embodiment 3
A kind of two step nitridings prepare the method for porous Al N particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Li piece that the Al piece that to take 100g purity be 99.5% and 50g purity are 99%, the weight percent that the Al piece accounts for whole raw material is 66.7%wt;
Step 2, the melting of alloy and preparation:
Al piece and Li piece are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.01atm, then be filled with the high pure nitrogen that purity is 99.999% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 1.5atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 30 ℃/min, when the temperature of powdered alloy reaches 500 ℃, insulation 40h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 30 ℃/min, makes the temperature of powdered alloy reach 1100 ℃, then, at this temperature insulation 5h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the sulfuric acid that is 1M by volumetric molar concentration soaks 5h, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, the drying of sample:
The powdered sample that suction filtration is obtained in 80 ℃ of dryings 1.5 hours, obtains nitride porous aluminium particulate in vacuum drying oven.
Embodiment 4
A kind of two step nitridings prepare the method for porous GaN particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Ca grain that the liquid Ga that to take 30g purity be 99.5% and 70g purity are 98.0%, liquid Ga accounts for the weight percent of whole raw material for 30%wt is arranged;
Step 2, the melting of alloy and preparation:
Ga liquid and Ca grain are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.1atm, then be filled with the high pure nitrogen that purity is 99.999% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 0.9atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 20 ℃/min, when the temperature of powdered alloy reaches 750 ℃, insulation 15h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 20 ℃/min, makes the temperature of powdered alloy reach 1100 ℃, then, at this temperature insulation 5h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the salt acid soak 6h that is 1M by volumetric molar concentration, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 200 ℃ of dryings 1 hour, obtains porous GaN particulate in vacuum drying oven.
Embodiment 5
A kind of two step nitridings prepare the method for porous Al N particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Ca grain that the Al piece that to take 40g purity be 99.5%, the Mg piece that 30g purity is 99.5% and 30g purity are 98.0%, to account for the weight percent of whole raw material be 40%wt to the Al piece;
Step 2, the melting of alloy and preparation:
Al piece, Mg piece and Ca grain are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.001atm, then be filled with the high pure nitrogen that purity is 99.999% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 1atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 30 ℃/min, when the temperature of powdered alloy reaches 700 ℃, insulation 20h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 30 ℃/min, makes the temperature of powdered alloy reach 1000 ℃, then, at this temperature insulation 6h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the sulfuric acid that is 0.1M by volumetric molar concentration soaks 7h, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 100 ℃ of dryings 4 hours, obtains nitride porous aluminium particulate in vacuum drying oven.
Embodiment 6
A kind of two step nitridings prepare the method for porous GaN particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Li piece that the liquid Ga that to take 80g purity be 99.95%, the Mg piece that 10g purity is 99.95% and 10g purity are 99%, to account for the weight percent of whole raw material be 80%wt to Ga liquid;
Step 2, the melting of alloy and preparation:
Ga liquid, Mg piece and Li piece are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.05atm, then be filled with the high pure nitrogen that purity is 99.999% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 1atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 20 ℃/min, when the temperature of powdered alloy reaches 600 ℃, insulation 30h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 20 ℃/min, makes the temperature of powdered alloy reach 950 ℃, then, at this temperature insulation 7h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the salt acid soak 5h that is 2M by volumetric molar concentration, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 100 ℃ of dryings 4 hours, obtains porous GaN particulate in vacuum drying oven.
Embodiment 7
A kind of two step nitridings prepare the method for porous Al N particulate, comprise following operation steps:
Step 1, preparation of raw material:
The Ca grain that the Al piece that to take 90g purity be 99.95%, the Mg piece that 4g purity is 99.5%, Li piece that 4g purity is 99.0% and 2g purity are 99.0%, to account for the weight percent of whole raw material be 90%wt to the Al piece;
Step 2, the melting of alloy and preparation:
Al piece, Mg piece, Li piece and Ca grain are put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, making vacuum tightness in stove is 0.001atm, then be filled with the high pure nitrogen that purity is 99.999% in Reaktionsofen, after nitrogen pressure in Reaktionsofen reaches 1atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 30 ℃/min, when the temperature of powdered alloy reaches 700 ℃, insulation 25h, carry out nitriding treatment for the first time at this holding stage; After nitrogenize for the first time finishes, the recycling process furnace, with the rate of heating heating powdered alloy of 30 ℃/min, makes the temperature of powdered alloy reach 900 ℃, then, at this temperature insulation 8h, at this holding stage, carries out nitriding treatment for the second time;
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, the salt acid soak 7h that is 0.1M by volumetric molar concentration, to remove the nitride of B component alloy wherein, stay the nitride of A component, so just in powder particle, in B component nitride position, stay hole, thereby obtained the nitride structure of porous A component; After acid soak, suction filtration obtains powdered sample;
Step 6, drying:
The powdered sample that suction filtration is obtained in 180 ℃ of dryings 2 hours, obtains nitride porous aluminium particulate in vacuum drying oven.
By Fig. 1 and Fig. 2, can be found out, the AlN that utilizes preparation method of the present invention to obtain or GaN particle shape are irregular, and its grain diameter size changes between several microns～hundreds of micron, and, at the particle outer wall, the more complete shell coatedparticles of one deck are arranged.
By Fig. 3 and Fig. 4, can be found out, the AlN that utilizes preparation method of the present invention to obtain or GaN particle contain the hole of many apertures between hundreds of nanometer to tens micron.
Claims (1)
1. two step nitridings prepare the method for nitride porous aluminium particulate or nitride porous gallium particulate, it is characterized in that, comprise following operation steps:
Step 1, preparation of raw material:
Raw material is comprised of A component and B component; The weight percent that the A component accounts for whole raw material is 10～90% wt;
If prepare nitride porous aluminium particulate: the A component is the industrial pure Al piece; The B component is a kind of in technical pure Mg piece, technical pure Li piece or technical pure Ca grain, or any two or three mixture formed with arbitrary proportion;
If prepare nitride porous gallium particulate: the A component is liquid Ga; The B component is a kind of in technical pure Mg piece, technical pure Li piece or technical pure Ca grain, or any two or three mixture formed with arbitrary proportion;
Step 2, the melting of alloy and preparation:
The raw material prepared is put into to crucible, then together with crucible, put into process furnace and be smelted into corresponding alloy;
Step 3, the fragmentation of alloy body:
The alloy powder that melting is obtained is broken into the particle that particle diameter is 0.01～1mm;
Step 4, the nitrogenize of powdered alloy:
The alloy powder particle of pulverizing is put into to Reaktionsofen, Reaktionsofen is vacuumized, make vacuum tightness in stove be less than or equal to 0.1atm, then be filled with high pure nitrogen in Reaktionsofen, nitrogen pressure in Reaktionsofen reaches 0.7～1.5atm, carry out nitriding treatment twice in the situation that maintain the alloy powder that remains unchanged of nitrogen pressure in stove: first utilize the rate of heating heating powdered alloy of process furnace with 10 ℃/min～30 ℃/min, when the temperature of powdered alloy reaches 500～750 ℃, insulation 15～40h, carry out nitriding treatment for the first time at this holding stage, after nitrogenize for the first time finishes, the recycling process furnace is with the rate of heating heating powdered alloy of 10 ℃/min～30 ℃/min, make the temperature of powdered alloy reach 850～1100 ℃, then, at this temperature insulation 5～15h, at this holding stage, carry out nitriding treatment for the second time,
Step 5, removal alloying:
The alloy powder particle that nitrogenize is finished is taken out from Reaktionsofen, with acid soak 5～7h, to remove the nitride of B component alloy wherein, stays the nitride of A component; After acid soak, suction filtration obtains powdered sample;
Described acid is the dilute sulphuric acid that the volumetric molar concentration dilute hydrochloric acid that is 0.1M～2M or volumetric molar concentration are 0.1M～2M;
Step 6, drying:
The powdered sample that suction filtration is obtained in 80～200 ℃ of dryings 1～4 hour, can obtain porous Al N particulate or porous GaN particulate in vacuum drying oven.
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| CN103086718B (en) * | 2013-02-03 | 2014-08-06 | 北京工业大学 | Preparation method of in-situ-synthesized composite aluminum nitride powder comprising sintering aid |
| CN105883731A (en) * | 2015-01-22 | 2016-08-24 | 南京杰博宏镓新型材料有限公司 | Preparation method of compound powder material |
| CN111847402A (en) * | 2020-07-29 | 2020-10-30 | 哈尔滨化兴软控科技有限公司 | Preparation method of porous high-purity aluminum nitride raw material |
| CN115403389B (en) * | 2022-08-17 | 2023-06-13 | 中铝山东有限公司 | Spherical-like aluminum nitride powder and preparation method thereof |
| CN115101636B (en) * | 2022-08-24 | 2022-12-02 | 江苏第三代半导体研究院有限公司 | Composite micro-nano semiconductor powder structure, preparation method and application thereof |
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| CN1155508C (en) * | 2000-07-13 | 2004-06-30 | 北京工业大学 | Reaction synthesis process for aluminium nitride powder body |
| US7255844B2 (en) * | 2003-11-24 | 2007-08-14 | Arizona Board Of Regents | Systems and methods for synthesis of gallium nitride powders |
| CN101792133B (en) * | 2010-02-04 | 2011-09-28 | 西安理工大学 | Method for preparing polyporous aluminum nitride particles in aluminum alloy melt |
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