CN101906666A - Method for preparing micron/nano tungsten crystal whisker/wire/bar - Google Patents
Method for preparing micron/nano tungsten crystal whisker/wire/bar Download PDFInfo
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- CN101906666A CN101906666A CN2010101259890A CN201010125989A CN101906666A CN 101906666 A CN101906666 A CN 101906666A CN 2010101259890 A CN2010101259890 A CN 2010101259890A CN 201010125989 A CN201010125989 A CN 201010125989A CN 101906666 A CN101906666 A CN 101906666A
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Abstract
The invention discloses a method for preparing a micron/nano tungsten crystal whisker/wire/bar, which comprises the following steps of: taking pure fine tungsten powder, collocating one or two or three of nickel, iron and cobalt metal powder in an amount which is 5 to 15 percent of the total weight of the mixture, ball-milling and mixing the powder uniformly, and spreading the mixed powder in a stainless steel boat; or putting pure fine tungsten powder on the surface of a Mo, Si or SiC flake, and then spreading the flake in the stainless steel boat; pushing the stainless steel boat into a reduction furnace, and ensuring that the stainless steel boat is placed at a high-temperature center position of the reduction furnace; closing a furnace door, and introducing nitrogen and hydrogen into the reduction furnace, wherein the flow rate of N2 to H2 is 8-12: 1 and the nitrogen is first introduced into 80 DEG C deionized water and then guided into the furnace; raising the temperature of the reduction furnace to 500 DEG C from room temperature at a speed of 2 to 5 DEG C per minute; raising the furnace temperature to 800 DEG C from 500 DEG C at a heating speed of 2 DEG C per minute, and then preserving the heat for 4 to 6 hours; and after the reaction is finished and the furnace temperature is reduced to the room temperature, taking a product out, washing the product by ethanol, and filtering and drying the product to obtain the uniformly distributed micron/nano tungsten crystal whisker/wire/bar. The method has the advantages of low reaction temperature, short reaction time, easy control and high yield, and is a good method for producing the tungsten crystal whisker/wire/bar in batch.
Description
Technical field
The invention belongs to the field of powder metallurgy Preparation of Whiskers, especially the preparation method of tungsten whisker/line/rod.
Background technology
Whisker/line/rod is a kind of flawless material that is close to, and has more superior performance than metallic substance, and tungsten whisker/line/rod just shows excellent mechanical property, and its Young's modulus can reach about 400GPa, and tensile strength is up to 32.8GPa.As structured material, come strengthening and toughening high melting point alloy, stupalith etc., the significantly toughness of strongthener and intensity with tungsten whisker/nano wire.As functional materials, tungsten whisker/nano wire has good field emission performance and ionization of gas performance, can be used for fabricating yard emission electrical equipment, flat-panel screens and Gas Ionizer.
Lee Y H etc. are at Appl Phys Lett(2002, and 81 (4): 745) go up report: utilizing the self-catalysis of tungsten film to make diameter is 10～50nm, ganoid high purity tungsten nano wire.Vaddiraju S etc. are at J Am Chem Soc(2003,125 (36): 10792) go up report: under the aerobic conditions, the oxide compound that heating makes the temperature of substrate be higher than tungsten decomposes temperature (about 1450 ℃), and tungsten can impel the formation of pure tungsten nano wire in suprabasil chemical gas phase transmission.Karabacak Tansel etc. are at Appl Phys Lett(2003,83 (15): 3096) go up report: adopt the magnetically controlled DC sputtering device, do substrate with oxidized p-Si (100), purity is that 99.95% W makes negative electrode, substrate is tilted, be 87 ° of angles with target material surface, under the situation of Si substrate rotation, made simple cubic monocrystalline β-W (100) nanometer rod with four (110) crystal faces.Elevations etc. are at investigation of materials journal (2008,22 (6): 577) report: with WO
3Powder is a raw material, is substrate with the monocrystalline silicon piece, and to obtain＜111〉direction length be that 15 μ m, diameter are the tungsten line of 150nm in the reduction tube furnace.Guha Sumit etc. are at Materials and Manufacturing Processes(1994, and 9 (6): 1061) go up report: use Al
2O
3Make growing substrate, pass through WF
6It is 1-2 μ m that the pyrolysated method has made diameter, and length reaches the tungsten whisker of hundreds of micron (100-500).Starliper A.G etc. are at Electro-deposition and Surface Treatment(1974, and 2 (4): 249) go up report: H is used in employing in vacuum oven
2Reduction WCl
6Method, under 2700-3300 ℃ temperature, having obtained mean diameter is 3-4 μ m, length-to-diameter ratio is about 1000, tensile strength is the needle-like tungsten whisker of 2.067-2.756 * 103 MPa.Nataliya F etc. are at J Phys Chem C(2008, and 112 (47): 18455) go up report: 950 ℃, reduce NiWO with CO
4, having obtained the cross section is that sexangle, length are that 10-50 μ m, diameter are the straight tungsten whisker of 0.2-0.3 μ m.Xu Jian etc. are at investigation of materials journal (2006,20 (6): 576) report: earlier 900 ℃ of oxidations of the powdered alloy of tungsten are obtained oxide compound, then restore, having prepared top diameter is 30-70nm, base diameter is 150-200nm, and length is the smooth surface of 2-10 μ m, straight tungsten line.Guise O L etc. are at Nano Letter(2002, and 2 (3): 191) go up report: the tungsten filament that with the diameter is 0.38mm is a raw material, and adopting two-step approach that tungsten filament is carried out chemical etching, finally to have obtained diameter be 5nm even littler tungsten point.Zhang Yousheng etc. are at electron microscopic journal (2004,23 (4): 483) go up report: adopt electrochemical erosion method to obtain the nano level tungsten tip, obtained the about 100nm of diameter, be about the tungsten tip of 2 μ m.LiYadong etc. are at Angew Chem(2002, and 114 (2): 343) report: with sodium wolframate (Na
2WO
4) and cetyl trimethylammonium bromide under hydrothermal condition, react, synthesized layered mesoporous material WO-L, in the tubular type reduction furnace, it is carried out VPC and handle, made diameter and be 20-80nm, length tungsten monocrystal nanowire along the bcc structure of (110) crystal face growth from a few μ m to 30 μ m.Thong etc. are at Appl Phys Lett(2002, and 81 (25): 4823) go up report: with organometallic compound W (CO)
6As precursor, the field transmitter current is controlled at 100nA, having made diameter is 3-4nm, length reaches several microns tungsten nano wire.Mitsuishi K etc. are at App1 Phys Lett(2003, and 83 (10): 2064) report: with W (CO)
6As presoma, prepare nano material with the Subnano-class probe that can launch high-power electron beam, obtained the little tungsten nano wire of diameter to 3.5nm.Recently, Liu Z Q etc. are at Nanotechology(2004, and 15 (5): 414) method with the STEM e-beam induced deposition has made the tungsten nano wire on the C film.
Summary of the invention
The present invention be intended to explore a kind of simple and direct little/receive the novel preparation method of tungsten whisker/line/rod, to accomplish scale production.
Technical scheme of the present invention is: get pure thin tungsten powder, and nickel, iron or the cobalt metal powder that configuration accounts for mixture total weight 5 ~ 15wt% one or both or three kinds wherein, ball milling mixes, and gets powder mix, is tiled in the stainless steel boat; Or pure thin tungsten powder placed Mo, Si or SiC slice surfaces, then be tiled in the stainless steel boat; Stainless steel boat is pushed in the reduction furnace, guarantee that stainless steel boat places reduction furnace high temperature center position; Fasten fire door, feed nitrogen and hydrogen, wherein N
2: H
2Throughput ratio is 8 ~ 12:1, in the deionized water that nitrogen feeding earlier is 80 ℃, and then introduces in the stove; Make reduction furnace rise to 500 ℃ by 2 ~ 5 ℃/min speed from room temperature; By 2 ℃/min heat-up rate, make furnace temperature rise to 800 ℃ from 500 ℃, then be incubated 4 ~ 6 hours; Reaction is finished furnace temperature such as back and is reduced to room temperature, takes out product, cleans, filters, dries through ethanol, can get equally distributed little/receive tungsten whisker/line/rod.
Adopt the tungsten whisker form of the present invention's preparation good, can make length-to-diameter ratio and be tungsten whisker/rod of 5 ~ 200, also can obtain diameter less than 100nm and equally distributed tungsten nano wire.Temperature of reaction of the present invention is low, the reaction times short, is easy to control, and output is higher, and the good and uniform distribution of product form is a kind of method of producing tungsten whisker/line/rod preferably in batches.
Description of drawings
The embodiment of the invention 1 prepared little/receive the SEM figure of tungsten whisker/line/rod.
Embodiment
Embodiment 1:
Take by weighing 200g pure tungsten powder, tungsten powder particle-size is 2 ~ 5 μ m, nickel and the iron metal powder of configuration 7wt%, and ball milling mixes.The effect of sneaking into nickel and iron metal powder is to induce the growth of tungsten whisker.Get powder mix 2.0g, be tiled in the cleaned stainless steel boat, stainless steel boat is pushed in the tubular type reduction furnace that internal diameter is 60mm, guarantee that stainless steel boat places reduction furnace high temperature center position, fasten fire door, feed nitrogen and hydrogen.N wherein
2Flow is 0.3L/min, H
2Flow is 0.03L/min, and the there-necked flask of nitrogen through adding deionized water introduced in the stove, and there-necked flask is placed in the electric mantle.By 3 ℃/min speed heating reduction stove, make stove rise to 500 ℃ from room temperature.Open the electric mantle power supply, 80 ℃ of temperature are set, make deionized water slowly rise to 80 ℃ (these temperature controlled water vapor flow rates).By 2 ℃/min heat-up rate, make furnace temperature rise to 800 ℃ from 500 ℃, then be incubated 6 hours.Reaction is finished furnace temperature such as back and is reduced to room temperature, opens fire door and takes out product, cleans, filters, dries through ethanol, promptly obtain equally distributed little/receive tungsten whisker/line/rod, the product form is good, and whisker/excellent length-to-diameter ratio is 5-200, and wherein visible a small amount of diameter is less than 100nm and equally distributed tungsten nano wire.
Embodiment 2:
Take by weighing the pure tungsten powder 2.0g of granularity 2 ~ 5 μ m, place Mo slice surfaces (inducing the growth of tungsten whisker), then be tiled in the cleaned stainless steel boat, stainless steel boat is pushed in the tubular type reduction furnace that internal diameter is 60mm, guarantee that stainless steel boat places reduction furnace high temperature center position, fasten fire door, feed nitrogen and hydrogen, wherein N
2Flow is 0.3L/min, H
2Flow is 0.03L/min, and the there-necked flask of nitrogen through adding deionized water introduced in the stove, and there-necked flask is placed in the electric mantle.By 4 ℃/min speed heating reduction stove, make stove rise to 500 ℃ from room temperature, open the electric mantle power supply, 80 ℃ of temperature are set, make deionized water slowly rise to 80 ℃ (these temperature controlled water vapor flow rates).By 2 ℃/min heat-up rate, make furnace temperature rise to 800 ℃ from 500 ℃, then be incubated 6 hours, reaction is finished furnace temperature such as back and is reduced to room temperature, opens fire door and takes out product, cleans, filters, dries through ethanol, can get equally distributed little/receive tungsten whisker/line/rod, the product form is good, and whisker/excellent length-to-diameter ratio is 5 ~ 200, and wherein visible a small amount of diameter is less than 100nm and equally distributed tungsten nano wire.
Claims (4)
1. the preparation method of micro-/ nano tungsten whisker/line/rod gets pure thin tungsten powder, nickel, iron and the cobalt metal powder that configuration accounts for mixture total weight 5 ~ 15wt% one or both or three kinds wherein, and ball milling mixes, and gets powder mix, is tiled in the stainless steel boat; Stainless steel boat is pushed in the reduction furnace, guarantee that stainless steel boat places reduction furnace high temperature center position; Fasten fire door, feed nitrogen and hydrogen, wherein N
2: H
2Throughput ratio is 8 ~ 12:1, in the deionized water that nitrogen feeding earlier is 80 ℃, and then introduces in the stove; Make reduction furnace rise to 500 ℃ by 2 ~ 5 ℃/min speed from room temperature; By 2 ℃/min heat-up rate, make furnace temperature rise to 800 ℃ from 500 ℃, then be incubated 4 ~ 6 hours; Reaction is finished furnace temperature such as back and is reduced to room temperature, takes out product, cleans, filters, dries through ethanol, can get equally distributed little/receive tungsten whisker/line/rod.
2. the preparation method of micro-/ nano tungsten whisker/line/rod gets pure thin tungsten powder, places Mo thin slice or Si thin slice or SiC slice surfaces, then is tiled in the stainless steel boat; Stainless steel boat is pushed in the reduction furnace, guarantee that stainless steel boat places reduction furnace high temperature center position; Fasten fire door, feed nitrogen and hydrogen, wherein N
2: H
2Throughput ratio is 8 ~ 12:1, in the deionized water that nitrogen feeding earlier is 80 ℃, and then introduces in the stove; Make reduction furnace rise to 500 ℃ by 2 ~ 5 ℃/min speed from room temperature; By 2 ℃/min heat-up rate, make furnace temperature rise to 800 ℃ from 500 ℃, then be incubated 4 ~ 6 hours; Reaction is finished furnace temperature such as back and is reduced to room temperature, takes out product, cleans, filters, dries through ethanol, can get equally distributed little/receive tungsten whisker/line/rod.
3. the method for claim 1 is characterized in that: dispose nickel and the iron metal powder that accounts for mixture total weight 7wt% in the pure thin tungsten powder.
4. as the described method of one of claim 1 ~ 3, it is characterized in that: described N
2: H
2Throughput ratio is 10:1.
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| CN2010101259890A CN101906666A (en) | 2010-03-17 | 2010-03-17 | Method for preparing micron/nano tungsten crystal whisker/wire/bar |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110295342A (en) * | 2019-07-18 | 2019-10-01 | 大连民族大学 | A kind of method that plasma pretreatment prepares tungsten oxide nanometer stick |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344674A (en) * | 2000-09-26 | 2002-04-17 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| CN1718535A (en) * | 2005-07-27 | 2006-01-11 | 中山大学 | Method of directly growing tridimensional nano net structure |
| CN101260564A (en) * | 2007-03-08 | 2008-09-10 | 中南大学 | Method for preparing micron/nano tungsten oxide crystal whisker/wire/bar |
| CN101555622A (en) * | 2009-05-08 | 2009-10-14 | 中南大学 | Low temperature catalysis and synthesis method of tungsten monocrystalline whisker |
-
2010
- 2010-03-17 CN CN2010101259890A patent/CN101906666A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344674A (en) * | 2000-09-26 | 2002-04-17 | 天津南开戈德集团有限公司 | Prepn of nano-carbon tube |
| CN1718535A (en) * | 2005-07-27 | 2006-01-11 | 中山大学 | Method of directly growing tridimensional nano net structure |
| CN101260564A (en) * | 2007-03-08 | 2008-09-10 | 中南大学 | Method for preparing micron/nano tungsten oxide crystal whisker/wire/bar |
| CN101555622A (en) * | 2009-05-08 | 2009-10-14 | 中南大学 | Low temperature catalysis and synthesis method of tungsten monocrystalline whisker |
Non-Patent Citations (4)
| Title |
|---|
| 《Journal of Alloys and Compounds》 20090311 ShiliangWang等 Growth of single-crystalWwhiskers during humid H2/N2 reduction of Ni, Fe-Ni,and Co-Ni doped tungsten oxide 第61-66页 第482卷, 2 * |
| 《中国钨金》 20060430 徐剑 等 Ni、Fe含量对制备钨纳米晶须的影响 第25-32页 第21卷, 第2期 2 * |
| 《材料导报：综述篇》 20100228 马运柱 等 钨晶须/纳米线的制备工艺原理及最新研究进展 第65-71页 第24卷, 第2期 2 * |
| 《材料研究学报》 20061231 徐剑 等 一种制备金属钨纳米针的新方法 第576-580页 第20卷, 第6期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110295342A (en) * | 2019-07-18 | 2019-10-01 | 大连民族大学 | A kind of method that plasma pretreatment prepares tungsten oxide nanometer stick |
| CN110295342B (en) * | 2019-07-18 | 2021-03-16 | 大连民族大学 | Method for preparing tungsten oxide nano rod by plasma pretreatment |
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Application publication date: 20101208 |