CN100383035C - Method for preparing nitride using oxide - Google Patents
Method for preparing nitride using oxide Download PDFInfo
- Publication number
- CN100383035C CN100383035C CNB2006100834530A CN200610083453A CN100383035C CN 100383035 C CN100383035 C CN 100383035C CN B2006100834530 A CNB2006100834530 A CN B2006100834530A CN 200610083453 A CN200610083453 A CN 200610083453A CN 100383035 C CN100383035 C CN 100383035C
- Authority
- CN
- China
- Prior art keywords
- nitride
- oxide
- purity
- lithium
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention discloses a method for preparing nitride using oxide, which comprises the following step: alkali metal nitride or alkaline earth metal nitride of enough purity and metal oxides are placed in a reaction vessel after uniformly mixed according to a certain proportion. The reaction vessel is placed in an enclosed environment filled with high-purity nitrogen gas, the temperature of the reaction vessel is increased to 750 to 900 DEG C, and the reaction vessel is naturally cooled down after 2 to 6 hours of heat preservation. Reaction products are taken out, are soaked and cleaned by deionized water, and are dried to obtain corresponding metal nitride. Since the present invention uses reactions of the alkali metal nitride or the alkaline earth metal nitride and the metal oxide to synthesize the nitride, the reactions can be carried out at a temperature of 750 DEG C. The present invention has the advantages of rapid reactions, low cost, simple devices and easy popularization.
Description
Technical field
The present invention relates to a kind of synthetic method of nitride, particularly a kind of method that adopts the oxide compound synthesizing nitride.
Background technology
Nitride is a big class material that has extensive use industrial, and wherein III-V group-III nitride AlN has low thermal coefficient of expansion (4.3 * 10
-6K
-1), high heat conductance (320Wm
-1K
-1), broad-band gap (6.4eV), high resistance (＞10
11Ω m), low-k plurality of advantages such as (8.6), be widely used in fields such as electronic circuit, UV photodetector, pressure detection, thermal radiation detection, field-effect transistor as substrate material and wrapping material, aspect military and civilian, all have to use widely and (consult document 1:Janes.R A, Low.M A, et al, Inorg.Chem.42 (2003) 2714).Some magnesium-yttrium-transition metal nitride are VN, TiN, NbN, ZrN for example, have good crocking resistance, high rigidity, high reflectance, unreactiveness, this class material has obtained at the aspects such as material package of high-temperature structural ceramics, catalyzer, coated material and microelectronics industry using widely at present.
Yet, at present the method for the synthesizing nitride of versatility seldom, industrial acquisition nitride mainly is under greater than 1000 ℃ high temperature, adopt metal simple-substance or anhydrous metal halide directly and nitrogen or ammonia react and prepare nitride.This method needs higher temperature and long reaction times, and the product that obtains also needs further in the atmosphere of nitrogen or ammonia long term annealing to improve the crystallization degree of product.Carbothermic reduction process that development in recent years is got up adopts metal oxide and carbon dust to issue biochemical reaction at nitrogen or ammonia atmosphere to prepare metal nitride, this process still needs higher temperature, for example carbothermic reduction process prepares AlN still need carry out under greater than 1300 ℃ temperature, has restricted popularizing of this method.Another kind of solid phase substitution method (the Solid-state metathesis that grows up by American Kaner, SSM) adopt anhydrous metal halide and basic metal or alkaline-earth nitride effect, the preparation nitride (is consulted document 2:R.B.Kaner, et al, Nature, 349 (1991) 510; ), adopt this method successfully to obtain to comprise most of metal nitride of magnesium-yttrium-transition metal and III family.But because anhydrous halide very easily absorbs water; so all operation must be carried out under protection of inert gas; reaction was simultaneously finished rapidly in the kind at several seconds usually; emit a large amount of heat; some low-melting nitride are decomposed, and the raw material anhydrous halide costs an arm and a leg and has also limited the versatility of this method to a certain extent in addition.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide that a kind of temperature of reaction is lower, the reaction times is short, employing oxide compound with low cost prepares the method for nitride.
For achieving the above object, a kind of method that adopts oxide compound to prepare nitride of the present invention, this method may further comprise the steps: purity is not less than puts into reaction vessel after 99% alkali metal nitride or alkaline-earth nitride and metal oxide mix by a certain percentage, this reaction vessel is placed the closed environment that is filled with high-purity nitrogen, the temperature of reaction vessel is risen to 750-900 ℃, be incubated and make its naturally cooling after 2-6 hour, take out reaction product, with deionized water immersion, cleaning reaction product, promptly obtain the corresponding metal nitride after the oven dry.
Further, described alkali metal nitride or alkaline-earth nitride obtain by the following method: with purity is that 99% basic metal or alkaline-earth metal are raw material, be under the atmosphere of 99.999% flowing nitrogen in purity, rise to 450 ℃ with 15 ℃/minute speed from room temperature, being incubated after 30 minutes again, the speed with 10 ℃/minute is warming up to 600 ℃, be incubated naturally cooling after 60 minutes, promptly obtain basic metal or alkaline-earth nitride.
Further, described alkali metal nitride or alkaline-earth nitride purity are not less than 99%, with described alkali metal nitride or alkaline-earth nitride and metal oxide agate grind grind and mix in the alms bowl after with the compound compressing tablet.
Further, described alkaline-earth nitride is CaCl2 or magnesium nitride.
Further, described alkali metal nitride is a lithium nitride, and described metal oxide is aluminum oxide (Al
2O
3), the mol ratio of described lithium nitride and aluminum oxide is 2: 1-3: 1.
Further, described alkali metal nitride is a lithium nitride, and described metal oxide is titanium oxide (TiO
2), the mol ratio of lithium nitride and titanium oxide is 1: 1-1.5: 1.
Further, described alkali metal nitride is a lithium nitride, and described metal oxide is zirconium white (ZrO
2), lithium nitride and zirconic mol ratio are 1: 1-1.5: 1, and temperature of reaction is 800 ℃-900 ℃, the reaction times is 3-6 hour.
Further, described alkali metal nitride is a lithium nitride, and described metal oxide is Vanadium Pentoxide in FLAKES (V
2O
5), the mol ratio of lithium nitride and Vanadium Pentoxide in FLAKES is 10: 3-15: 3, and temperature of reaction is 800 ℃-900 ℃, the reaction times is 3-6 hour.
Further, described alkali metal nitride is a lithium nitride, and described metal oxide is Niobium Pentxoxide (Nb
2O
5), the mol ratio of lithium nitride and Niobium Pentxoxide is 10: 3-15: 3, and temperature of reaction is 800 ℃-900 ℃, the reaction times is 4-6 hour.
Further, described reaction vessel is Stainless Steel Crucible, metal platinum crucible, wolfram varbide crucible or aluminium nitride crucible, and described reaction vessel places the sealed silica envelope that is filled with nitrogen, or places the vacuum oven that is filled with nitrogen.
After adopting aforesaid method, because the present invention adopts alkali metal nitride or alkaline-earth nitride and reactive metal oxide to come synthesizing nitride, react and can carry out being low to moderate under 750 ℃ the temperature, and be swift in response, with low cost, equipment simple, be easy to promote; In addition, because basic metal or alkaline-earth nitride obtain by being reacted with flowing nitrogen by highly purified basic metal or alkaline-earth metal among the present invention, guaranteed the purity of basic metal or alkaline-earth nitride, and avoided in basic metal or the alkaline-earth nitride preservation process taking place oxidation and cause the not high situation of purity.
Description of drawings
Fig. 1 is the X ray diffracting spectrum that adopts the aluminium nitride of aluminum oxide preparation among the present invention;
Fig. 2 is the X ray diffracting spectrum that adopts the titanium nitride of titanium oxide preparation among the present invention;
Fig. 3 is the X ray diffracting spectrum that adopts the zirconium nitride of zirconium white preparation among the present invention;
Fig. 4 is the X ray diffracting spectrum that adopts the vanadium nitride of Vanadium Pentoxide in FLAKES preparation among the present invention;
Adopt the X ray diffracting spectrum of the niobium nitride of Niobium Pentxoxide preparation among Fig. 5 the present invention;
Fig. 6 is the stereoscan photograph of the aluminium nitride AlN sample of generation among the embodiment 1;
Fig. 7 is the stereoscan photograph of the titanium nitride TiN sample of generation among the embodiment 4;
Fig. 8 is the stereoscan photograph of the zirconium nitride ZrN sample of generation among the embodiment 7;
Fig. 9 is the stereoscan photograph of the vanadium nitride VN sample of generation among the embodiment 10;
Figure 10 is the stereoscan photograph of the niobium nitride NbN sample of generation among the embodiment 13.
Embodiment:
Embodiment one
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic lithium nitride.The aluminium sesquioxide that takes by weighing 0.01mol synthetic lithium nitride and 0.005mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 15MPa, it is 16mm that powder is pressed into the external diameter of packing into after the sheet, internal diameter is 14mm, in the high crucible of making for the stainless steel of 15mm, pack into crucible in the silica tube and the while connects pumped vacuum systems rapidly and is evacuated to 10
-4Behind the Pa, filling with 0.3 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube makes silica tube be warming up to 750 ℃ in 4 hours then, and is incubated 6 hours under this temperature, powered-down, after cooling to room temperature with the furnace silica glass is broken into pieces, sample is taken out, with deionized water immersion, wash products, after the oven dry, can obtain gray target product AlN powder.
Embodiment two
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling obtains lithium nitride; The aluminium sesquioxide that takes by weighing 0.011mol synthetic lithium nitride and 0.005mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 18MPa, it is that 16mm, internal diameter are in 14mm, the high crucible of making for the metal platinum of 15mm that powder is pressed into the external diameter of packing into after the sheet, packs into crucible in the silica tube and the while connects pumped vacuum systems rapidly and is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, make in 4 hours silica tube be warming up to 800 ℃ and under this temperature the insulation 3 hours after powered-down, after cooling to room temperature with the furnace silica glass is broken into pieces, sample is taken out, with deionized water immersion, wash products, after the oven dry, can obtain gray target product AlN powder.
Embodiment three
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic lithium nitride.The aluminium sesquioxide that takes by weighing 0.015mol synthetic lithium nitride and 0.005mol is put into agate and is milled and be milled to the lithium nitride powdering, and both are mixed, use tabletting machine powder to be imposed the pressure of 20MPa, it is 16mm that powder is pressed into the external diameter of packing into after the sheet, internal diameter is 14mm, in the high crucible of making for the stainless steel of 15mm, pack into crucible in the silica tube and the while connects pumped vacuum systems rapidly and is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, and closed quartz tube makes silica tube be warming up to 850 ℃ in 4 hours then.At the powered-down after 2 hours of insulation under this temperature, silica glass is broken into pieces after cooling to room temperature with the furnace, take out sample, with deionized water soak, wash products, after the oven dry, can obtain gray target product AlN powder.
Embodiment four
With purity is that 99% calcium metal is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic CaCl2.The titanium dioxide that takes by weighing 0.005mol synthetic CaCl2 and 0.01mol is put into agate and is milled and be milled to the lithium nitride powdering, both are mixed, use tabletting machine powder to be imposed the pressure of 15MPa, powder is pressed in the crucible that the stainless steel of packing into after the sheet makes, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.3 normal atmosphere purity is 99.999% nitrogen again, and closed quartz tube was warming up to 800 ℃ with silica tube in 4 hours then, at the powered-down after 4 hours of insulation under this temperature, makes silica tube cool to room temperature with the furnace.Silica glass is broken into pieces, taken out sample,, after the oven dry, can obtain the target product TiN powder of black with deionized water immersion, wash products.
Embodiment five
With purity is that 99% MAGNESIUM METAL is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic magnesium nitride.The titanium dioxide that takes by weighing 0.006mol synthetic magnesium nitride and 0.015mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 18MPa, powder is pressed in the wolfram varbide crucible of packing into after the sheet, crucible packed into, and to fill in vacuum oven with 0.3 normal atmosphere purity in the vacuum oven be 99.999% nitrogen again, makes it be warming up to 850 ℃ in 4 hours.Powered-down after being incubated 3 hours under this temperature cools to room temperature with the furnace.Take out sample and, after the oven dry, can obtain the target product TiN powder of black with deionized water immersion, wash products.
Embodiment six
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic lithium nitride.Taking by weighing 0.0075mol synthetic lithium nitride and 0.005mol titanium dioxide puts into agate and mills and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 20MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.3 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, make it be warming up to 900 ℃ and insulation 2 hours under this temperature in 4 hours, powered-down is broken silica glass into pieces after cooling to room temperature with the furnace, take out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product TiN powder of black.
Embodiment seven
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic lithium nitride.The zirconium dioxide that takes by weighing 0.005mol synthetic lithium nitride and 0.005mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 15MPa, it is 16mm that powder is pressed into the external diameter of packing into after the sheet, internal diameter is 14mm, in the high crucible of making for the aluminium nitride of 15mm, pack into crucible in the silica tube and the while connects pumped vacuum systems rapidly and is evacuated to 10
-4Behind the Pa, filling with 0.3 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, make it be warming up to 800 ℃ in 4 hours, powered-down after being incubated 6 hours under this temperature, silica tube after cooling to room temperature with the furnace is broken silica glass into pieces, sample is taken out, with deionized water immersion, wash products, after the oven dry, can obtain the target product ZrN powder of black.
Embodiment eight
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic lithium nitride.The zirconium dioxide that takes by weighing 0.006mol synthetic lithium nitride and 0.005mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 18MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, in 4 hours it is warming up to 850 ℃,, silica glass is broken into pieces after cooling to room temperature with the furnace at the powered-down after 4 hours of insulation under this temperature, take out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product ZrN powder of black.
Embodiment nine
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic lithium nitride.The zirconium dioxide that takes by weighing 0.0075mol synthetic lithium nitride and 0.005mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 20MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, make it be warming up to 900 ℃ in 4 hours,, silica glass is broken into pieces after cooling to room temperature with the furnace at the powered-down after 3 hours of insulation under this temperature, take out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product ZrN powder of black.
Embodiment ten
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic lithium nitride.The Vanadium Pentoxide in FLAKES that takes by weighing 0.01mol synthetic lithium nitride and 0.003 is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 5MPa, it is 16mm that powder is pressed into the external diameter of packing into after the sheet, internal diameter is 14mm, in the high crucible of making for the stainless steel of 15mm, pack into crucible in the silica tube and the while connects pumped vacuum systems rapidly and is evacuated to 10
-4Behind the Pa, filling with 0.3 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube was warming up to 800 ℃ with it in 4 hours then, powered-down after being incubated 6 hours under this temperature, cool to room temperature with the furnace, silica glass is broken into pieces, taken out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product VN powder of black.
Embodiment 11
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated powered-down after 60 minutes, furnace cooling, synthetic lithium nitride; The Vanadium Pentoxide in FLAKES that takes by weighing 0.012mol synthetic lithium nitride and 0.003mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 18MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, be warming up to 850 ℃ in 4 hours,, silica glass broken into pieces after cooling to room temperature with the furnace at the powered-down after 4 hours of insulation under this temperature, take out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product VN powder of black.
Embodiment 12
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic lithium nitride; The Vanadium Pentoxide in FLAKES that takes by weighing 0.015mol synthetic lithium nitride and 0.003mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 20MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, and closed quartz tube makes it be warming up to 900 ℃ in 4 hours then.Powered-down after being incubated 3 hours under this temperature cools to room temperature with the furnace, and silica glass is broken into pieces, takes out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product VN powder of black.
Embodiment 13
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic lithium nitride; The Niobium Pentxoxide that takes by weighing 0.01mol gram synthetic lithium nitride and 0.003mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 15MPa, it is 16mm that powder is pressed into the external diameter of packing into after the sheet, internal diameter is 14mm, in the high crucible of making for the stainless steel of 15mm, pack into crucible in the silica tube and the while connects pumped vacuum systems rapidly and is evacuated to 10
-4Behind the Pa, filling with 0.3 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube then, be warming up to 800 ℃ in 4 hours,, silica glass broken into pieces after cooling to room temperature with the furnace at the powered-down after 6 hours of insulation under this temperature, take out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product NbN powder of black.
Embodiment 14
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic lithium nitride; The Niobium Pentxoxide that takes by weighing 0.012mol synthetic lithium nitride and 0.003mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 18MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube is warming up to 850 ℃ in 4 hours then, and under this temperature the insulation 5 hours after powered-down, cool to room temperature with the furnace, silica glass is broken into pieces, taken out sample, with deionized water immersion, wash products, after the oven dry, obtain the target product NbN powder of black.
Embodiment 15
With purity is that 99% metallic lithium is a raw material, is under the atmosphere of 99.999% flowing nitrogen in purity, rises to 450 ℃ with 15 ℃/minute speed from room temperature, is incubated 30 minutes; Be warming up to 600 ℃ with 10 ℃/minute speed again, be incubated 60 minutes; Powered-down, furnace cooling, synthetic lithium nitride; The Niobium Pentxoxide that takes by weighing 0.015 gram synthetic lithium nitride and 0.003mol is put into agate and is milled and be milled to the lithium nitride powdering, both mix, use tabletting machine powder to be imposed the pressure of 20MPa, powder is pressed in the Stainless Steel Crucible of packing into after the sheet, and crucible is packed in the silica tube and connected pumped vacuum systems rapidly simultaneously is evacuated to 10
-4Behind the Pa, filling with 0.4 normal atmosphere purity is 99.999% nitrogen again, closed quartz tube is warming up to 900 ℃ in 4 hours then, and under this temperature the insulation 4 hours after powered-down, cool to room temperature with the furnace, silica glass is broken into pieces, taken out sample, with deionized water immersion, wash products, after the oven dry, can obtain the target product NbN powder of black.
In addition, in process of the present invention, described lithium nitride can adopt the enough finished product lithium nitrides of purity.
Shown in Fig. 1-5, be respectively the X ray diffracting spectrum of the aluminium nitride that adopts the inventive method to obtain, titanium nitride, zirconium nitride, vanadium nitride, niobium nitride, therefrom as can be seen, the product that obtains is single-phase, free from foreign meter; Fig. 6-10 is respectively the stereoscan photograph of aluminium nitride AlN sample, titanium nitride TiN sample, zirconium nitride ZrN sample, vanadium nitride VN sample, niobium nitride NbN sample, and as can be seen from the figure the particle diameter ratio of product is more even.
Claims (10)
1. method that adopts oxide compound to prepare nitride, it is characterized in that, this method may further comprise the steps: purity is not less than puts into reaction vessel after 99% alkali metal nitride or alkaline-earth nitride and metal oxide mix by a certain percentage, this reaction vessel is placed the closed environment that is filled with high-purity nitrogen, the temperature of reaction vessel is risen to 750-900 ℃, be incubated and make its naturally cooling after 2-6 hour, take out reaction product, with deionized water immersion, cleaning reaction product, promptly obtain the corresponding metal nitride after the oven dry.
2. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkali metal nitride or alkaline-earth nitride obtain by the following method: with purity is that 99% basic metal or alkaline-earth metal are raw material, be under the atmosphere of 99.999% flowing nitrogen in purity, rise to 450 ℃ with 15 ℃/minute speed from room temperature, being incubated after 30 minutes again, the speed with 10 ℃/minute is warming up to 600 ℃, be incubated naturally cooling after 60 minutes, promptly obtain basic metal or alkaline-earth nitride.
3. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, with described alkali metal nitride or alkaline-earth nitride and metal oxide agate grind grind and mix in the alms bowl after with the compound compressing tablet.
4. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkaline-earth nitride is CaCl2 or magnesium nitride.
5. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkali metal nitride is a lithium nitride, and described metal oxide is an aluminum oxide, and the mol ratio of described lithium nitride and aluminum oxide is 2: 1-3: 1.
6. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkali metal nitride is a lithium nitride, and described metal oxide is a titanium oxide, and the mol ratio of lithium nitride and titanium oxide is 1: 1-1.5: 1.
7. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkali metal nitride is a lithium nitride, described metal oxide is a zirconium white, lithium nitride and zirconic mol ratio are 1: 1-1.5: 1, temperature of reaction is 800 ℃-900 ℃, and the reaction times is 3-6 hour.
8. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkali metal nitride is a lithium nitride, described metal oxide is a Vanadium Pentoxide in FLAKES, the mol ratio of lithium nitride and Vanadium Pentoxide in FLAKES is 10: 3-15: 3, temperature of reaction is 800 ℃-900 ℃, and the reaction times is 3-6 hour.
9. employing oxide compound as claimed in claim 1 prepares the method for nitride, it is characterized in that, described alkali metal nitride is a lithium nitride, described metal oxide is a Niobium Pentxoxide, the mol ratio of lithium nitride and Niobium Pentxoxide is 10: 3-15: 3, temperature of reaction is 800 ℃-900 ℃, and the reaction times is 4-6 hour.
10. the method for preparing nitride as the arbitrary described employing oxide compound of claim 1-9, it is characterized in that, described reaction vessel is Stainless Steel Crucible, metal platinum crucible, wolfram varbide crucible or aluminium nitride crucible, described reaction vessel places the sealed silica envelope that is filled with nitrogen, or places the vacuum oven that is filled with nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100834530A CN100383035C (en) | 2006-05-31 | 2006-05-31 | Method for preparing nitride using oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100834530A CN100383035C (en) | 2006-05-31 | 2006-05-31 | Method for preparing nitride using oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1850588A CN1850588A (en) | 2006-10-25 |
| CN100383035C true CN100383035C (en) | 2008-04-23 |
Family
ID=37132089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100834530A Expired - Fee Related CN100383035C (en) | 2006-05-31 | 2006-05-31 | Method for preparing nitride using oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100383035C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111490260A (en) * | 2019-01-25 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Oxygen reduction electrocatalyst material and preparation method thereof |
| CN114466817A (en) * | 2019-10-02 | 2022-05-10 | 古河机械金属株式会社 | Method for producing lithium nitride |
| CN115397770A (en) * | 2020-04-16 | 2022-11-25 | 古河机械金属株式会社 | Lithium nitride manufacturing apparatus and lithium nitride manufacturing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851203A (en) * | 1986-04-03 | 1989-07-25 | Atochem | Metal carbide and nitride powders |
| CN1396111A (en) * | 2002-07-26 | 2003-02-12 | 中国科学院上海硅酸盐研究所 | Process for preparing nano cubic niobium nitride powder |
| CN1410348A (en) * | 2002-10-25 | 2003-04-16 | 中国科学院上海硅酸盐研究所 | Preparation method of nano indium nitride powder |
| CN1422800A (en) * | 2001-12-04 | 2003-06-11 | 攀枝花钢铁(集团)公司 | Method for producing vanadium nitride |
| JP2005154193A (en) * | 2003-11-25 | 2005-06-16 | Kitagawa Ind Co Ltd | Method of manufacturing group iii nitride |
-
2006
- 2006-05-31 CN CNB2006100834530A patent/CN100383035C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4851203A (en) * | 1986-04-03 | 1989-07-25 | Atochem | Metal carbide and nitride powders |
| CN1422800A (en) * | 2001-12-04 | 2003-06-11 | 攀枝花钢铁(集团)公司 | Method for producing vanadium nitride |
| CN1396111A (en) * | 2002-07-26 | 2003-02-12 | 中国科学院上海硅酸盐研究所 | Process for preparing nano cubic niobium nitride powder |
| CN1410348A (en) * | 2002-10-25 | 2003-04-16 | 中国科学院上海硅酸盐研究所 | Preparation method of nano indium nitride powder |
| JP2005154193A (en) * | 2003-11-25 | 2005-06-16 | Kitagawa Ind Co Ltd | Method of manufacturing group iii nitride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1850588A (en) | 2006-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Effects of B2O3 content variation on the Bi ions in Bi2O3–B2O3–SiO2 glass structure | |
| EP3150897B1 (en) | Vacuum heat-insulating material | |
| CN101707089B (en) | Method for improving upper critical field and critical current density of iron-based superconductor | |
| CN100383035C (en) | Method for preparing nitride using oxide | |
| CN105200520B (en) | One kind prepares Bi2(SexTe1‑x)3The method of single crystal nanoplate | |
| CN109796209A (en) | One kind (Ti, Zr, Hf, Ta, Nb) B2High entropy ceramic powder and preparation method thereof | |
| CN101531520A (en) | Method for preparing gamma-AlON ceramic powder based on carbon thermal reduction nitridation | |
| CN104945024A (en) | Novel aluminum nitride microsphere powder preparation method | |
| CN110204341A (en) | One kind (Hf, Ta, Nb, Ti) B2High entropy ceramic powder and preparation method thereof | |
| CN101195481A (en) | Method for preparing high purity lithium hexafluorophosphate | |
| CN101302004B (en) | Single-phase Mn6N2.58 power preparation | |
| CN1876859A (en) | Process for preparing anti-perovskite type manganese-based nitride | |
| CN106565246A (en) | Aluminum nitride/yttrium nitride composite powder preparation method | |
| CN105503236A (en) | Preparation method for porous aluminum nitride ceramic material | |
| JPS6255896B2 (en) | ||
| CN101323451A (en) | Preparation of Si3W5 powder | |
| CN106379933A (en) | Preparation method of lithium titanate powder | |
| CN101928150A (en) | Method for preparing gamma-aluminum oxynitride transparent ceramic powder with low cost | |
| JP2009023899A (en) | Electroconductive ceramic material and method for manufacturing the same | |
| Jepsen et al. | Synthesis and decomposition of Li 3 Na (NH 2) 4 and investigations of Li–Na–N–H based systems for hydrogen storage | |
| CN103274375B (en) | Method for preparing aluminum nitride powder | |
| CN100366538C (en) | Method for preparing lanthanide nitride using metal oxide | |
| CN100427399C (en) | Method for preparing neodymium hexaboride | |
| CN108155284A (en) | A kind of preparation method of the electrode of high temperature heat-resistant electrical part | |
| CN100376702C (en) | Method for preparing single-phase oxide by alloy direct oxidation under low temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080423 Termination date: 20150531 |
|
| EXPY | Termination of patent right or utility model |