CN101603200A - The preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled - Google Patents
The preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled Download PDFInfo
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- CN101603200A CN101603200A CNA2009100438848A CN200910043884A CN101603200A CN 101603200 A CN101603200 A CN 101603200A CN A2009100438848 A CNA2009100438848 A CN A2009100438848A CN 200910043884 A CN200910043884 A CN 200910043884A CN 101603200 A CN101603200 A CN 101603200A
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- crystal whisker
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Abstract
The preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled comprises following processing step: 1. with WO
3Powder and deposition substrate are positioned in the Reaktionsofen that furnace atmosphere is rare gas element or nitrogen successively, are heated to 850～1100 ℃; 2. from described Reaktionsofen, be placed with WO
3One end of powder feeds the mobile carrier gas that carries water vapor, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2Simultaneously, in described Reaktionsofen, feed reducing gas, described reducing gas and described gaseous state WO
2(OH)
2Reduction reaction takes place, and promptly forms the W crystal whisker array on described deposition substrate; 3. after reaching the reaction times of setting, close carrier gas earlier, keep the reaction Deoxidation Atmosphere in Furnace constant, be cooled to room temperature with stove.Technology of the present invention is reasonable, easy to operate, equipment is simple, synthesis temperature is low, productive rate is high, institute's synthetic tungsten diameter of whiskers and length controlled, and synthetic cost is low, energy consumption is low.
Description
Technical field
The present invention relates to a kind of W crystal whisker array preparing technical field, be meant the preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled especially.
Background technology
Refractory metal W has high-density (19.3g/cm
3), high-melting-point (～3420 ℃, the highest in all metals), low-steam pressure (minimum in all metals) and high electron emissivity, excellent mechanical behavior under high temperature, characteristics such as anti-strong acid and alkali corrosion.The W whisker because of its high-density, high-melting-point, high elastic coefficient (～400GPa), (～a series of special performances such as 28GPa), and become the ideal material of making high-performance tungstenalloy armour piercing shot are expected to substitute the depleted uranium bomb with radiativity high strength.Simultaneously, there are some researches show that the W nano whisker is better than carbon nanotube on important performance characteristic such as stability and gain, so be unusual ideal field electron emission source by the array that the W nano whisker is formed.In addition, the W nano whisker is because its excellent electric property is with a wide range of applications in little-nano-electron components and parts.
Before this invention, the synthetic method of relevant W micro-/ nano crystal whisker array has three kinds.
(1) high-temperature physics vapour deposition process: evaporation tungsten source under 1500～1600 ℃ temperature forms the W crystal whisker array by the physical vapor deposition mode; (2) tungsten oxide nanometer whisker reduction method: earlier synthetic tungsten oxide nanometer crystal whisker array makes it be converted to the W crystal whisker array again in reducing atmosphere; (3) autocatalysis method: form the W nanowhisker arrays by the autocatalysis mode of metal W film in annealing process in the substrate.The temperature of reaction that above-mentioned first method requires is very high, and is difficult to the diameter and the length-to-diameter ratio of the W whisker that forms are controlled; Above-mentioned second method can't be synthesized and had the higher monocrystalline W whisker of length-to-diameter ratio, and experiment condition is very harsh; The length of above-mentioned the third synthetic W of method institute nano whisker usually only in 2 microns, can't be synthesized the W whisker of high length-diameter ratio.All deficiencies of aforesaid method have restricted the application of W whisker greatly.
Summary of the invention
The present invention be intended to overcome the deficiency of prior art and provide that a kind of technology is reasonable, easy to operate, equipment is simple, synthesis temperature is low, productive rate is high, the preparation method of the tungsten crystal whisker array of institute's synthetic tungsten diameter of whiskers and length controlled.
The preparation method of the tungsten crystal whisker array of a kind of diameter of the present invention and length controlled comprises following processing step:
The first step: with granularity is that 100～600 orders, purity are 98%～99.99% WO
3Powder and deposition substrate are positioned in the Reaktionsofen that furnace atmosphere is rare gas element or nitrogen successively, and described deposition substrate is apart from WO
3Powder 5～10mm is heated to 850～1100 ℃;
Second the step, from described Reaktionsofen, be placed with WO
3One end of powder feeds the mobile carrier gas that carries water vapor, the direct and described WO of described mobile carrier gas
3The powder contact, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2, described mobile flow rate of carrier gas is 15～100 cubic centimetres/second, pressure is: 10
4～10
6Pa, the dew point of described water vapor are 20～60 ℃; Simultaneously, the reducing gas of feeding and the equidirectional motion of described mobile carrier gas in described Reaktionsofen, described reducing gas and described gaseous state WO
2(OH)
2Reduction reaction takes place, promptly form the W crystal whisker array on described deposition substrate, described reducing gas flow velocity is: 15～100 cubic centimetres/second; Pressure is: 10
4～10
6Pa's;
The 3rd step, reach the reaction times of setting after, close carrier gas earlier, keep the reaction Deoxidation Atmosphere in Furnace constant, be cooled to room temperature with stove.
Among the present invention, described Reaktionsofen is a horizontal pipe furnace.
Among the present invention, described mobile carrier gas is a kind of in rare gas element or the nitrogen.
Among the present invention, described reducing gas is a kind of in hydrogen or the CO (carbon monoxide converter) gas.
Among the present invention, described deposition substrate is a silicon, a kind of in quartz or the aluminum oxide.
The present invention compared with prior art, has the following advantages owing to adopt above-mentioned technology:
1.W the synthesis temperature of whisker is low, the present invention can synthesize the W crystal whisker array at 850～1100 ℃, and far below 1500～1600 ℃ of the physical gas-phase deposite method requirement, therefore, synthetic cost is low, energy consumption is low;
2.W do not add catalyzer or template in the building-up process of whisker, therefore, institute's synthetic W whisker has intact single crystal structure, does not have surface and subsurface defect, the purity height, and synthesis device is simple, the productive rate height;
3. can be by regulating synthesis temperature, the diameter of control institute synthetic tungsten whisker;
4. can be by regulating the vapour deposition time, the length of the control synthetic W of institute whisker.
In sum, technology of the present invention is reasonable, easy to operate, equipment is simple, synthesis temperature is low, productive rate is high, institute's synthetic tungsten diameter of whiskers and length controlled, and synthetic cost is low, energy consumption is low.
Description of drawings
The stereoscan photograph of the W crystal whisker array that accompanying drawing 1 is obtained for the invention process 1.
The X ray diffracting spectrum of the W whisker that accompanying drawing 2 is obtained for the invention process 1.
The low power transmission electron microscope photo of the W whisker that accompanying drawing 3 is obtained for the invention process 1.
The high-resolution-ration transmission electric-lens photo of the W whisker that accompanying drawing 4 is obtained for the invention process 1 and corresponding selected area electron diffraction collection of illustrative plates.
The stereoscan photograph of the W crystal whisker array that accompanying drawing 5 is obtained for the invention process 2.
The stereoscan photograph of the W crystal whisker array that accompanying drawing 6 is obtained for the invention process 3.
The stereoscan photograph of the W crystal whisker array that accompanying drawing 7 is obtained for the invention process 4.
The low power transmission electron microscope photo of the W whisker that accompanying drawing 8 is obtained for the invention process 4 and corresponding selected area electron diffraction collection of illustrative plates.
Wherein:
Accompanying drawing 2 shows that the W whisker of formation has body-centered cubic structure, and does not have other impurity such as Tungsten oxide 99.999 in the product, and Si diffraction peak wherein comes from the Si substrate.
Accompanying drawing 3 shows that the W whisker of formation has the very diameter of homogeneous in the axial direction, surface step do not occur; Therefore can not introduce surface imperfection because of surface step.
Accompanying drawing 4 shows that the W whisker has body-centered cubic structure, and along＜111〉direction growths, whisker has intact single crystal structure, without any subsurface defect.
Accompanying drawing 8 shows that the W whisker has intact single crystal structure, has the very diameter of homogeneous in the axial direction, surface step do not occur.
Concrete enforcement
Embodiment 1
1, be that 100 orders, purity are 98%～99.99%WO with 10 gram particle degree
3It is an end of the clean silica tube of 20mm that powder places diameter, then, and in the burner hearth with silica tube load level tube furnace; Get single crystalline Si (111) sheet that is of a size of 10mm * 5mm * 1mm, prior to cleaning in the hydrofluoric acid, ultrasonic cleaning 5 minutes in dehydrated alcohol after the drying, is placed in the tube furnace then, is placed with WO apart from silica tube
3The port 5mm place of powder; In horizontal pipe furnace, feed argon gas; Simultaneously, tube furnace is heated to 900 ℃.
2, to feed flow velocity be 15 cubic centimetres/second to an end that is placed with silica tube from tube furnace; Pressure is: 10
4Pa; The Ar gas that carries water vapor to the silica tube directly with described WO
3The powder contact, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2, the dew point of described water vapor is 20 ℃; Simultaneously, the hydrogen of feeding and the equidirectional motion of described Ar gas in tube furnace, described hydrogen and described gaseous state WO
2(OH)
2Reduction reaction takes place, and promptly forms the W crystal whisker array in described single crystalline Si (111) sheet substrate; The flow velocity of described hydrogen is 15 cubic centimetres/second; Pressure is: 10
4Pa;
3, under this temperature, be incubated 4 hours, close argon gas, keep hydrogen flow rate constant, the tube furnace temperature is dropped to room temperature, the mean diameter of the W whisker that is obtained: 180 nanometers, mean length: 19 microns.
Embodiment 2
1, be that 100 orders, purity are 98%～99.99%WO with 10 gram particle degree
3It is an end of the clean silica tube of 20mm that powder places diameter, then, and in the burner hearth with silica tube load level tube furnace; Get single crystalline Si (111) sheet that is of a size of 10mm * 5mm * 1mm, prior to cleaning in the hydrofluoric acid, ultrasonic cleaning 5 minutes in dehydrated alcohol after the drying, is placed in the tube furnace then, is placed with WO apart from silica tube
3The port 5mm place of powder; In horizontal pipe furnace, feed argon gas; Simultaneously, tube furnace is heated to 1050 ℃.
2, to feed flow velocity be 60 cubic centimetres/second to an end that is placed with silica tube from tube furnace; Pressure is: 10
4Pa; The Ar gas that carries water vapor to the silica tube directly with described WO
3The powder contact, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2, the dew point of described water vapor is 20 ℃; Simultaneously, the hydrogen of feeding and the equidirectional motion of described Ar gas in tube furnace, described hydrogen and described gaseous state WO
2(OH)
2Reduction reaction takes place, and promptly forms the W crystal whisker array in described single crystalline Si (111) sheet substrate; The flow velocity of described hydrogen is 100 cubic centimetres/second; Pressure is: 10
4Pa;
3, under this temperature, be incubated 4 hours, close argon gas, keep hydrogen flow rate constant, the tube furnace temperature is dropped to room temperature, the mean diameter of the W whisker that is obtained: 2.25 microns, whisker mean length: 20.5 microns.
Embodiment 3
1, be that 100 orders, purity are 98%～99.99%WO with 10 gram particle degree
3It is an end of the clean silica tube of 20mm that powder places diameter, then, and in the burner hearth with silica tube load level tube furnace; Get single crystalline Si (111) sheet that is of a size of 10mm * 5mm * 1mm, prior to cleaning in the hydrofluoric acid, ultrasonic cleaning 5 minutes in dehydrated alcohol after the drying, is placed in the tube furnace then, is placed with WO apart from silica tube
3The port one 0mm place of powder; In horizontal pipe furnace, feed argon gas; Simultaneously, tube furnace is heated to 900 ℃;
2, to feed flow velocity be 45 cubic centimetres/second to an end that is placed with silica tube from tube furnace; Pressure is: 10
5Pa; The Ar gas that carries water vapor to the silica tube directly with described WO
3The powder contact, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2, the dew point of described water vapor is 40 ℃; Simultaneously, the hydrogen of feeding and the equidirectional motion of described Ar gas in tube furnace, described hydrogen and described gaseous state WO
2(OH)
2Reduction reaction takes place, and promptly forms the W crystal whisker array in described single crystalline Si (111) sheet substrate; The flow velocity of described hydrogen is 45 cubic centimetres/second; Pressure is: 10
5Pa;
3, under this temperature, be incubated 18 hours, close argon gas, keep hydrogen flow rate constant, the tube furnace temperature is dropped to room temperature, the mean diameter of the W whisker that is obtained: 200 nanometers, whisker mean length: 40 microns.
Embodiment 4
1, be that 100 orders, purity are 98%～99.99%WO with 10 gram particle degree
3It is an end of the clean silica tube of 20mm that powder places diameter, then, and in the burner hearth with silica tube load level tube furnace; Get the alumina wafer that is of a size of 10mm * 5mm * 1mm, prior to cleaning in the hydrofluoric acid, ultrasonic cleaning 5 minutes in dehydrated alcohol after the drying, is placed in the tube furnace then, is placed with WO apart from silica tube
3The port 8mm place of powder; In horizontal pipe furnace, feed argon gas; Simultaneously, tube furnace is heated to 850 ℃;
2, to feed flow velocity be 100 cubic centimetres/second to an end that is placed with silica tube from tube furnace; Pressure is: 10
6Pa; The Ar gas that carries water vapor to the silica tube directly with described WO
3The powder contact, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2, the dew point of described water vapor is 60 ℃; Simultaneously, the hydrogen of feeding and the equidirectional motion of described Ar gas in tube furnace, described hydrogen and described gaseous state WO
2(OH)
2Reduction reaction takes place, and promptly forms the W crystal whisker array in described alumina wafer substrate; The flow velocity of described hydrogen is 100 cubic centimetres/second; Pressure is: 10
6Pa;
3, under this temperature, be incubated 4 hours, close argon gas, keep hydrogen flow rate constant, the tube furnace temperature is dropped to room temperature, the mean diameter of the W whisker that is obtained: 170 nanometers, mean length: 20 microns.
Claims (5)
1, the preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled comprises following processing step:
The first step: with granularity is that 100～600 orders, purity are 98%～99.99% WO
3Powder and deposition substrate are positioned in the Reaktionsofen that furnace atmosphere is rare gas element or nitrogen successively, and described deposition substrate is apart from WO
3Powder 5～10mm is heated to 850～1100 ℃;
Second the step, from described Reaktionsofen, be placed with WO
3One end of powder feeds the mobile carrier gas that carries water vapor, the direct and described WO of described mobile carrier gas
3The powder contact, the direct and described WO of water vapor wherein
3Powdered reaction generates gaseous state WO
2(OH)
2, described mobile flow rate of carrier gas is 15～100 cubic centimetres/second, pressure is: 10
4～10
6Pa, the dew point of described water vapor are 20～60 ℃; Simultaneously, the reducing gas of feeding and the equidirectional motion of described mobile carrier gas in described Reaktionsofen, described reducing gas and described gaseous state WO
2(OH)
2Reduction reaction takes place, promptly form the W crystal whisker array on described deposition substrate, described reducing gas flow velocity is: 15～100 cubic centimetres/second; Pressure is: 10
4～10
6Pa's;
The 3rd step, reach the reaction times of setting after, close carrier gas earlier, keep the reaction Deoxidation Atmosphere in Furnace constant, be cooled to room temperature with stove.
2, the preparation method of the tungsten crystal whisker array of a kind of diameter according to claim 1 and length controlled is characterized in that: described Reaktionsofen is a horizontal pipe furnace.
3, the preparation method of the tungsten crystal whisker array of a kind of diameter according to claim 1 and length controlled is characterized in that: described mobile carrier gas is a kind of in rare gas element or the nitrogen.
4, the preparation method of the tungsten crystal whisker array of a kind of diameter according to claim 1 and length controlled is characterized in that: described reducing gas is a kind of in hydrogen or the CO (carbon monoxide converter) gas.
5, the preparation method of the tungsten crystal whisker array of a kind of diameter according to claim 1 and length controlled is characterized in that: described deposition substrate is a silicon, a kind of in quartz or the aluminum oxide.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100438848A CN101603200A (en) | 2009-07-10 | 2009-07-10 | The preparation method of the tungsten crystal whisker array of a kind of diameter and length controlled |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498190A (en) * | 2013-09-16 | 2014-01-08 | 中国地质大学（北京） | Preparation method of high-purity dendrite FeWO4/FeS core-shell nano structure |
| CN103498191A (en) * | 2013-09-16 | 2014-01-08 | 中国地质大学（北京） | Preparation method of high-purity short-rod-like crystalline FeWO4/FeS core-shell nano structure |
-
2009
- 2009-07-10 CN CNA2009100438848A patent/CN101603200A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103498190A (en) * | 2013-09-16 | 2014-01-08 | 中国地质大学（北京） | Preparation method of high-purity dendrite FeWO4/FeS core-shell nano structure |
| CN103498191A (en) * | 2013-09-16 | 2014-01-08 | 中国地质大学（北京） | Preparation method of high-purity short-rod-like crystalline FeWO4/FeS core-shell nano structure |
| CN103498191B (en) * | 2013-09-16 | 2015-11-11 | 中国地质大学（北京） | High purity corynebacterium crystallization FeWO 4the preparation method of/FeS nanometer nuclear shell nano-structure |
| CN103498190B (en) * | 2013-09-16 | 2015-11-25 | 中国地质大学（北京） | The preparation method of high purity dendrite FeWO4/FeS nanometer nuclear shell nano-structure |
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Open date: 20091216 |