CN101791703B - Method for preparing micro/nano powder of elemental tungsten - Google Patents
Method for preparing micro/nano powder of elemental tungsten Download PDFInfo
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- CN101791703B CN101791703B CN2010101278976A CN201010127897A CN101791703B CN 101791703 B CN101791703 B CN 101791703B CN 2010101278976 A CN2010101278976 A CN 2010101278976A CN 201010127897 A CN201010127897 A CN 201010127897A CN 101791703 B CN101791703 B CN 101791703B
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- wolframic acid
- tungsten
- nano powder
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- inorganic
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Abstract
The invention belongs to the field of nanostructured materials and advanced functional materials and in particular relates to a method for preparing micro/nano powder of elemental tungsten. The method is characterized by using a tungstic acid based inorganic-organic hybrid layer shaped compound as the precursor and pyrolyzing the compound in the non-oxidizing protective atmosphere to obtain the micro/nano powder of tungsten. The method only consumes 2-5h, is simple to operate and has low requirement for the equipment.
Description
(1) technical field
The invention belongs to nano structural material and advanced function material field, particularly a kind of preparation method of micro/nano powder of elemental tungsten.
(2) background technology
Tungsten has excellent physical property, as high-melting-point, high density, high rigidity, tungsten also has excellent elevated temperature strength, high-temp plastic etc. simultaneously, tungsten and alloy thereof are widely used in equipping fields such as process industry, steel and iron industry, electric power electric, information industry, petrochemical industry, Aero-Space and military project, be very important material in modern industry, new and high technology application and the national defence, in Chinese national economy, occupy an important position.Simultaneously, high-melting-point means the high sintering temperature of needs when the block materials of tungsten prepares, though tungsten plasticity when high temperature is very good, but it has the high crisp transition temperature of moulding, so at room temperature tungsten is fragile material, is difficult for processing, in order to overcome above-mentioned difficulties, the researcher has carried out a large amount of tests, discovers that the tungsten nanocrystalline material has low firing temperature and low moulds crisp transition temperature, and ultrafine tungsten powder then is the key of preparation nano material.The preparation method of the nano-tungsten powder of having reported is many, and as mechanical ball milling, laser emission, e-beam induced deposition, high temperature reduction and template etc., but these methods all exist some shortcomings, as length consuming time, and the process complexity, not easy to operate etc.
(3) summary of the invention
The object of the present invention is to provide a kind of preparation method of micro/nano powder of elemental tungsten, to overcome that existing preparation method exists or length consuming time or process complexity, not easy-operating problem.
The technical solution used in the present invention is as follows:
A kind of preparation method of micro/nano powder of elemental tungsten, with the wolframic acid base inorganic-organic lamellar compound that mixes is a presoma, pyrolysis obtains the tungsten micro-nano powder in non-oxidizable protective atmosphere.
Described pyrolytical condition is in 900-1300 ℃ of insulation 2-5h, is cooled to room temperature then.
Further, temperature programming is to 900-1300 ℃, and heating rate is 1-10 ℃/min.
Reaction can be carried out in the programme-control tube furnace.
Described non-oxidizable protective atmosphere specifically can be realized by feeding non-oxidized gas, as Ar, N
2Or H
2, shield gas flow rate is 10-100ml/min.
During concrete operations, presoma can be put into porcelain boat, porcelain boat places the program controlled tube furnace, manages to be alumina tube, vacuumizes earlier, and logical again protective gas is that 1-10 ℃/min is heated to 900-1300 ℃ with the heating rate, behind the reaction 2-5h, naturally cools to room temperature.
The simple substance tungsten that obtains is cube phase, and the I of particle size reaches about 50nm.
Described presoma wolframic acid base is inorganic-organic mix lamellar compound can but be not limited only to following method and obtain: with wolframic acid and carbon number is that the straight chain alkyl amine of 4-18 is a reactant, reacts to obtain in non-polar organic solvent.
The mol ratio of tungsten atom is preferably 2-30 in straight chain alkyl amine and the wolframic acid: 1, and the volume ratio of non-polar organic solvent and alkylamine is preferably 1-10: 1.
Reaction temperature is preferably 10-40 ℃, and the reaction time is 3-20h.
Described wolframic acid is layer structure WO
3XH
2O or H
2W
2O
7XH
2O, the x value is 0.2-4.0; Non-polar solven can select to be under the normal temperature liquid alkane.
During reaction, keep stirring.The product that obtains of reaction is drying under reduced pressure 5-24h at room temperature, the white solid of dry gained is the wolframic acid base inorganic-organic lamellar compound that mixes.
The present invention has following advantage with respect to prior art:
This method with the wolframic acid base inorganic-organic lamellar compound that mixes is that presoma prepares micro/nano powder of elemental tungsten in non-oxidizing atmosphere, its principle is the wolframic acid that utilizes in the C reduction presoma that the presoma pyrolysis produces.The wolframic acid base is inorganic-and organic lamellar compound that mixes has the advantages that inorganic layer, organic layer alternately mix, and can guarantee that tungsten source and carbon source are evenly distributed, and fully contact helps the carrying out that react, so the inventive method weak point consuming time got final product in 2-5 hour; Simple to operate, also not high to the requirement of equipment.
(4) description of drawings
Fig. 1 for the wolframic acid base that obtains among the embodiment 1 inorganic-organic lamellar compound X-ray diffractogram of (amine: wolframic acid=10 add water-wet) that mixes;
Fig. 2 for the wolframic acid base that obtains among the embodiment 1 inorganic-organic SEM figure that mixes lamellar compound (amine: wolframic acid=10 add water-wet);
Fig. 3 for the wolframic acid base that obtains among the embodiment 1 inorganic-organic lamellar compound TG-DTA curve of (amine: wolframic acid=10 add water-wet) that mixes;
Fig. 4 for the wolframic acid base that obtains among the embodiment 1 inorganic-organic lamellar compound Ft-IR curve of (amine: wolframic acid=10 add water-wet) that mixes;
Fig. 5 for the wolframic acid base among the embodiment 1 inorganic-organic mix lamellar compound in argon gas in 975 ℃ of reaction 5h gained sample XRD figures;
Fig. 6 for the wolframic acid base among the embodiment 1 inorganic-organic mix lamellar compound in argon gas in 975 ℃ of reaction 5h gained sample SEM figure;
The wolframic acid base that Fig. 7 obtains for embodiment 2 is inorganic-organic SEM figure that mixes lamellar compound (amine: wolframic acid=15 add water-wet);
Fig. 8 for the wolframic acid base among the embodiment 2 inorganic-organic mix lamellar compound in argon gas in 1000 ℃ of reaction 5h gained sample XRD figures;
Fig. 9 for the wolframic acid base among the embodiment 2 inorganic-organic mix lamellar compound in argon gas in 1000 ℃ of reaction 5h gained sample SEM figure;
The wolframic acid base that Figure 10 obtains for embodiment 3 is inorganic-organic lamellar compound (n-hexylamine: H that mixes
2W
2O
7=10, do not add water-wet) FE-SEM figure;
Figure 11 for the wolframic acid base among the embodiment 3 inorganic-organic mix lamellar compound in argon gas in 1200 ℃ of reaction 2h gained sample XRD figures;
Figure 12 for the wolframic acid base among the embodiment 3 inorganic-organic mix lamellar compound in argon gas in 1200 ℃ of reaction 2h gained sample SEM figure.
(5) specific embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Used instrument is X-ray diffraction analysis (XRD) in following examples: Beijing is general analyse general; Field emission scanning electron microscope (FE-SEM): JEOM-6700F (Japan); SEM (SEM): QUANTA-200 (Holland); Infrared spectrometer: BruckVector22; Microcomputer differential thermal balance: WCT-2C.
Embodiment 1
Take by weighing 10g H
2WO
4, put into the 1000ml conical flask, it is wetting to add 2ml distilled water, take by weighing 52g n-octyl amine (0.4mol, 66ml), 360g normal heptane (530ml) mixes the two, the mixed solution adding of amine and alkane is put in the conical flask of wolframic acid, limit edged vigorous stirring begins to be yellow suspension, along with the prolongation of time, the color of suspension is thin out gradually, present ecru after half an hour, present white after one hour, stir 24h, leave standstill 24h, with white suspension Separation of Solid and Liquid, alcohol wash 5 times (3000r/min, 10min), reduced pressure at room temperature 30h, obtain 18g white wolframic acid base inorganic-organic stratiform compound sample that mixes.
Fig. 1 is the XRD figure of sample, and the strong diffraction maximum that the low angle of diffraction (2 θ＜20 °) zone occurs can belong to the diffraction for (00l) crystal face, shows that this product has typical two-dimensional layered structure.Fig. 2 is product S EM figure, and sample is for being about 1-2 μ m as can be seen, generous about 1 μ m, and thickness is no more than the laminated structure of 100nm.Fig. 3 is a sample TG-DTA curve, from TG figure as can be seen, from room temperature to 150 ℃ because adsorbed water sloughs weightless 1.22%, from 150 ℃ to 250 ℃, mass loss 25.11% mainly is because due to the desorption of n-octyl amine, from 250 ℃ to 600 ℃, mass loss 8.65% may be because removing with the carbon burning of organic matter cracking gained of inorganic layer constitution water is caused.From room temperature to 600 ℃, amount to mass loss 35%, mainly be due to the removing of constitution water and n-octyl amine.Fig. 4 is the infrared spectrum of sample, 3429cm
-1The absworption peak at place can be regarded as the stretching vibration peak of O-H, 685cm
-1Absworption peak corresponding to the vibration of O-W-O, 3211cm
-1Vibration peak corresponding to the flexural vibrations peak of N-H group, methyl (CH
3) and polymethylene ((CH
2)
n-) vibration peak appear at 2854-2956cm
-1, in addition, at 2042cm
-1A faint vibration peak occurred, proved-NH
3+The oxygen at group and W-O structure tip interacts and has formed R-NH
3+...-O-W group.Can know by inference in view of the above between the n-octyl amine embeding layer is by-NH
2Carry out with the interaction of stratiform wolframic acid aspect hydroxyl, n-octyl amine embeds H
2WO
4Interlayer is based on the mechanism of proton adduction, and the interaction between precursor layer and the layer mainly is an electrostatic attraction, mainly is with R-NH after between the n-octyl amine embeding layer
3+Cationic form exists.
Take by weighing the 0.8830g presoma, put into porcelain boat, porcelain boat is put into program controlled high-temperature tubular electric furnace, pipe is for alumina tube, and alumina tube is sealed at both ends, closes air outlet valve and intake valve, open vacuum valve and vacuumize, close vacuum valve, open intake valve, logical argon gas to vacuum meter registration is 0, opens air outlet valve, and argon flow amount is controlled at 10ml/min, begin to heat up, heating rate be during the room temperature to 300 ℃ 2 ℃ add in, 10 ℃/min after 300 ℃, rise to 975 ℃, insulation 5h cools off with stove.Obtain the 0.3609g sample, X-ray diffraction analysis figure as shown in Figure 5, as can be seen from the figure, the main thing of gained sample is a cube phase W (JCPDS card No.04-0806) mutually, Fig. 6 is the SEM figure of sample, the W particle size is greatly about 0.2-2 μ m.
Embodiment 2
Take by weighing 5g H
2WO
4, put into the 1000ml conical flask, it is wetting to add 1ml distilled water, take by weighing 39g n-octyl amine (0.3mol, 50ml), 270g normal heptane (400ml) mixes the two, the mixed solution adding of amine and alkane is put in the conical flask of wolframic acid, limit edged vigorous stirring begins to be yellow suspension, along with the prolongation of time, the color of suspension is thin out gradually, present ecru after half an hour, present white after one hour, stir 24h, leave standstill 24h, with white suspension Separation of Solid and Liquid, alcohol wash 5 times (3000r/min, 10min), reduced pressure at room temperature 30h, obtain 10g wolframic acid base inorganic-organic lamellar compound white sample that mixes.Fig. 7 is product S EM figure, and sample presents the pattern that is similar to the one dimension band shape as can be seen, and size is more even, and length is 5～20 μ m, and width is 200～700nm, and thickness is no more than 100hm.
Take by weighing the 0.9920g presoma, put into porcelain boat, porcelain boat is put into program controlled high-temperature tubular electric furnace, pipe is for alumina tube, and alumina tube is sealed at both ends, closes air outlet valve and intake valve, open vacuum valve and vacuumize, close vacuum valve, open intake valve, logical argon gas to vacuum meter registration is 0, opens air outlet valve, and argon flow amount is controlled at 10ml/min, begin to heat up, heating rate is 100 ℃/h during the room temperature to 300 ℃, 10 ℃/min after 300 ℃, rise to 1000 ℃, insulation 5h cools off with stove.Obtain the 0.3802g sample.X-ray diffraction analysis figure as shown in Figure 8, as can be seen from the figure, the main thing of gained sample is a cube phase W (JCPDS card No.04-0806) mutually, Fig. 9 is the SEM figure of sample, the W particle size is greatly about about 500nm.
Embodiment 3
Take by weighing 10g H
2W
2O
7, put into the 1000ml conical flask, take by weighing 40g n-hexylamine (0.4mol, 50ml), 330g n-hexane (500ml) mixes the two, the mixed solution adding of amine and alkane is put in the conical flask of wolframic acid, and limit edged vigorous stirring stirs 24h, leave standstill 48h, with white suspension Separation of Solid and Liquid, alcohol wash 5 times (3000r/min, 10min), reduced pressure at room temperature 30h, obtain 19.5g white wolframic acid base inorganic-organic stratiform compound sample that mixes.Figure 10 is product FE-SEM figure, and sample presents the pattern that is similar to the one dimension band shape as can be seen, and size is more even, and being about is 20 μ m, the about 1 μ m of width.
Take by weighing the 0.9874g presoma, put into porcelain boat, porcelain boat is put into program controlled high-temperature tubular electric furnace, pipe is for alumina tube, and alumina tube is sealed at both ends, closes air outlet valve and intake valve, opening vacuum valve vacuumizes, close vacuum valve, open intake valve, logical argon gas to vacuum meter registration is 0, open air outlet valve, argon flow amount is controlled at about 10ml/min, begins to heat up, and heating rate is 2 ℃/min during the room temperature to 300 ℃, 10 ℃/min after 300 ℃, rise to 1200 ℃, insulation 2h cools off with stove.Obtain the 0.3769g sample.X-ray diffraction analysis figure as shown in figure 11, as can be seen from the figure, the main thing of gained sample is a cube phase W (JCPDS card No.04-0806) mutually, Figure 12 is the SEM figure of sample, the W particle size is greatly about about 2 μ m.
Claims (3)
1. the preparation method of a micro/nano powder of elemental tungsten is characterized in that, with the wolframic acid base inorganic-organic lamellar compound that mixes is a presoma, pyrolysis obtains the tungsten micro-nano powder in non-oxidizable protective atmosphere;
Wherein said wolframic acid base is inorganic-and organic lamellar compound that mixes is to be that the straight chain alkyl amine of 4-18 is a reactant with wolframic acid and carbon number, reaction obtains in non-polar organic solvent, the mol ratio of tungsten atom is 2-30 in straight chain alkyl amine and the wolframic acid: 1, the volume ratio of non-polar organic solvent and alkylamine is 1-10: 1, and described wolframic acid is layer structure WO
3XH
2O or H
2W
2O
7XH
2O, the x value is 0.2-4.0; Non-polar solven selects normal temperature to be liquid alkane down; Reaction temperature is 10-40 ℃, and the reaction time is 3-20h;
Described pyrolytical condition is: be warming up to 900-1300 ℃ of insulation 2-5h, heating rate is 1-10 ℃/min, is cooled to room temperature then.
2. the preparation method of micro/nano powder of elemental tungsten as claimed in claim 1 is characterized in that, is reflected in the programme-control tube furnace to carry out.
3. the preparation method of micro/nano powder of elemental tungsten as claimed in claim 1 is characterized in that, described non-oxidizable protective atmosphere realizes that by feeding non-oxidized gas gas flow is 10-100ml/min.
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| CN103302300B (en) * | 2013-06-24 | 2015-08-19 | 朱兰英 | A kind of preparation method of tungsten nanometer powder |
| CN106216706A (en) * | 2016-09-08 | 2016-12-14 | 苏州大学 | A kind of preparation method of metal fine powder |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1017123B (en) * | 1990-08-20 | 1992-06-24 | 中国科学院化工冶金研究所 | Prepn. of ultrafine trngsten powder |
| CN1234489C (en) * | 2003-09-10 | 2006-01-04 | 厦门金鹭特种合金有限公司 | Preparation method of high performance nanometer sized and superfine tungsten powder |
| CN101318702A (en) * | 2007-06-08 | 2008-12-10 | 郑州大学 | Tungstic trioxide nano-slice and preparation method thereof |
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2010
- 2010-03-19 CN CN2010101278976A patent/CN101791703B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1017123B (en) * | 1990-08-20 | 1992-06-24 | 中国科学院化工冶金研究所 | Prepn. of ultrafine trngsten powder |
| CN1234489C (en) * | 2003-09-10 | 2006-01-04 | 厦门金鹭特种合金有限公司 | Preparation method of high performance nanometer sized and superfine tungsten powder |
| CN101318702A (en) * | 2007-06-08 | 2008-12-10 | 郑州大学 | Tungstic trioxide nano-slice and preparation method thereof |
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