CN102978583A - Method for manufacturing tungsten pipe - Google Patents
Method for manufacturing tungsten pipe Download PDFInfo
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- CN102978583A CN102978583A CN201210489047XA CN201210489047A CN102978583A CN 102978583 A CN102978583 A CN 102978583A CN 201210489047X A CN201210489047X A CN 201210489047XA CN 201210489047 A CN201210489047 A CN 201210489047A CN 102978583 A CN102978583 A CN 102978583A
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Abstract
The invention provides a method for manufacturing a tungsten pipe and relates to a tungsten pipe. The method for manufacturing the tungsten pipe with uniform wall thickness provided by the invention comprises the following steps of: 1) fixing a base material on deposition equipment, directly electrifying and heating the base material, reacting by introducing reactant gas, and increasing current until reaction is finished after reaction begins; 2) introducing protective gas into a system after the reaction is finished, and cooling to room temperature; and 3) removing the base material, so that the tungsten pipe is obtained, wherein the tungsten pipe is a pure tungsten pipe with uniform wall thickness. The phenomenon that the wall thickness of the tungsten pipe is not uniform as raw gas flow can not be accurately controlled, the temperature is not uniform and the concentrate of the reactant gas is changed in a pure tungsten pipe manufacturing process by adopting chemical vapour deposition is avoided, and the wall thickness of the manufactured tungsten pipe is uniform.
Description
Technical field
The present invention relates to a kind of tungsten pipe, especially relate to a kind of manufacture method of tungsten pipe.
Background technology
The fusing point of tungsten is up to 3410 ℃, in all metals, be the highest, other metal of the hardness ratio of tungsten is all large, Young's modulus is high, have excellent conductivity, good thermal conductivity, low thermal expansivity and more stable chemical property, tungsten and goods thereof have been widely used in the industries such as aerospace, nuclear power, weapons, chemical industry, electric light source, electrovacuum, refractory fibre and machinofacture based on its unique performance.The tungsten pipe can be used as military affairs upward or the various ultrahigh-temperature gases on civilian or the pipeline of liquid, can also be as the shower nozzle of rocket, the heatproof sleeve of iraser, the pipeline of special firearms, ultrahigh-temperature, ultrahigh vacuum(HHV) parts, high temperature heating element, atomic pile material, plasma spray device etc. have a wide range of applications.Yet the tungsten pipe is to commonly use at present in tungsten, molybdenum, tantalum, four kinds of refractory metal pipes of niobium the most unmanageable a kind ofly, and because its distortion pulling force is large, it is high to mould crisp transition temperature, causes the difficulty of becoming a useful person, and is difficult for mechanical workout.Generally adopt at present powder metallurgy process to produce the tungsten pipe, but the tungsten pipe purity that this method is produced is low, density is low; Adopt chemical vapour deposition technique can obtain the tungsten pipe of high purity, high-compactness, but be subjected to the reasons such as accurately control of raw material gas flow, non-uniform temperature, reacting gas concentration variation, the tungsten pipe that makes exists inhomogeneity of wall thickness even, the shortcoming that utilization ratio is low.How to develop a kind of high purity high-compactness that both possessed, while wall thickness again uniform tungsten pipe has great practical significance.
Chinese patent CN102242347A discloses a kind of preparation method of the tungsten pipe for heating element, and the red copper matrix is put in the cvd furnace, then the red copper matrix is heated to 500～600 ℃; With WF
6And H
2Mixed gas join in the cvd furnace WF
6And H
2React near the red copper matrix surface reaches, generate W and HF, W is deposited on the red copper matrix surface; After reaction was finished, then stopped heating closed WF
6, continue to pass into H
2Be cooled to room temperature to changing logical protective gas below 300 ℃, then take out the red copper matrix that surface attachment has tungsten, with chemical process the red copper matrix corrosion is fallen namely to obtain the tungsten pipe.
Summary of the invention
The objective of the invention is for adopting chemical vapour deposition to produce in the pure tungsten pipe process, owing to reasons such as being subjected to accurately control of raw material gas flow, non-uniform temperature, reacting gas concentration variation causes the inhomogeneous phenomenon of tungsten thickness of pipe, provide a kind of manufacture method that obtains the uniform tungsten pipe of wall thickness.
The present invention includes following steps:
1) base material is fixed on the depositing device, to the heating of base material direct-electrifying, passes into reactant gases and react, after the reaction beginning, improve electric current, extremely reaction finishes;
2) change logical shielding gas in the system after reaction finishes, be cooled to room temperature;
3) base material is removed, namely got the tungsten pipe, gained tungsten pipe is the uniform pure tungsten pipe of a kind of wall thickness.
In step 1), it is 5～20mm that described base material can adopt diameter, and wall thickness is 0.5～1mm, the stainless steel tube of length＜1500mm or copper pipe; Described base material can adopt ganoid base material; The surface of described base material is preferably cleaned and polished finish in advance, and with being fixed on again on the depositing device behind the alcohol wipe surface; The initial current of described reaction can be 10～40A, and the speed of described raising electric current can be 0.2～1.5A/min, and the reaction times of described reaction can be 2～3h, and the ultimate current value can be 100～300A; The described concrete grammar that passes into reactant gases can be: pass into reactant gases by the constant temperature gas distributing system, described constant temperature gas distributing system comprises stock bottle, insulation can, hot air blower, WF
6Under meter, H
2The devices such as under meter, temperature can be 30～50 ℃; Described reactant gases can adopt WF
6And H
2Mixed gas, described WF
6Purity more preferably greater than 99.9%, described H
2Purity more preferably greater than 99.9%, described WF
6With H
2Volume ratio can be WF
6: H
2=1: (1～4); Described WF
6Flow can be 0.5～2L/min; Described H
2Flow can be 1～8L/min; Described reactant gases reacts at substrate surface, and the W of generation is deposited on substrate surface.
In step 2) in, described shielding gas can adopt hydrogen or nitrogen etc., and the flow of shielding gas can be 1～5L/min; The speed of described cooling can be 2～4 ℃/min, and the time of cooling can be 2～5h.
In step 3), the described concrete grammar that base material is removed can be: base material is cooled to subzero below 40 ℃, utilizes the different of base material and tungsten thermal expansivity, make base material and tungsten pipe natural separation; Or be that 30% nitric acid dissolve is removed base material with concentration.
Compare with existing tungsten pipe manufacturing method, the present invention has overcome the employing chemical vapour deposition and has produced in the pure tungsten pipe process, owing to reasons such as being subjected to accurately control of raw material gas flow, non-uniform temperature, reacting gas concentration variation causes the inhomogeneous phenomenon of tungsten thickness of pipe, prepared tungsten thickness of pipe is even.
The present invention rationally controls electric current and improves speed, reaction times and ultimate current value, and deposition process is utilized depositing base self heating power, and the zone that sedimentation velocity is slow is because relative resistance is large, and temperature is high, corresponding the accelerating of sedimentation velocity meeting; The zone that sedimentation velocity is fast is because relative resistance is little, and temperature is low, and sedimentation velocity can be corresponding slack-off, plays the effect that sedimentation velocity is regulated automatically.Reaction will change nitrogen blowing after finishing in the system, and reduces gradually electric current, and the control temperature slowly is reduced to room temperature.After being cooled to room temperature, utilize the different of base material and tungsten thermal expansivity, remove base material or remove base material with 30% dilute nitric acid dissolution, utilize dilute nitric acid dissolution to remove base material, obtain the uniform tungsten pipe of wall thickness.
Not only purity is high for the tungsten pipe that the present invention makes, density is high, and its maximum advantage is that wall thickness is even, and the purity of tungsten pipe has reached more than 99.9%, and the product that makes does not need secondary processing, can effectively reduce cost.
Description of drawings
Fig. 1 is the constant temperature gas distributing system synoptic diagram that the embodiment of the invention adopts.
Fig. 2 is the depositing device synoptic diagram that the embodiment of the invention adopts.
Fig. 3 is the tungsten thickness of pipe distribution schematic diagram that the embodiment of the invention makes.In Fig. 3, X-coordinate is position/cm along its length, and ordinate zou is wall thickness/mm.
Embodiment
Referring to Fig. 1～3, a ganoid base material at first is provided, can select stainless steel tube or copper pipe, diameter 5～20mm, wall thickness 0.5～1mm, length＜1500mm selects diameter 14mm in following examples, wall thickness 1mm, the copper pipe base material of length 1000mm.With the substrate surface of choosing clean with polished finish after be fixed on the depositing device, this depositing device is provided with reacting furnace-e/or 12, copper base material 11, insulation covering 13, inlet mouth 14, air outlet 15(referring to Fig. 2).Under gas shield, begin base material energising heating is also improved electric current to 10～40A gradually, this shielding gas can be nitrogen or hydrogen; flow control is at 1～5L/min; the present invention selects hydrogen as shielding gas, and flow is 3L/min, and the base material electric current is brought up to 30A.
Then utilize the constant temperature gas distributing system to pass into reactant gases H
2, this constant temperature gas distributing system (referring to Fig. 1) is provided with stock bottle 6, insulation can 4, hot air blower 1, WF
6Under meter 7, H
2Under meter 5, temperature control are at 30～50 ℃, and the present invention is controlled at 40 ℃ with temperature.Reactant gases is purity greater than 99.9% WF
6With purity greater than 99.9% H
2, WF
6Flow control is at 0.5～2L/min, the volume ratio scope WF of gas
6: H
2=1: (1～4), what the present invention selected is that purity is 99.9% WF
6And H
2, WF
6Flow is 1L/min, and the volume ratio of gas adopts WF
6: H
2=1: 3, H
2Flow is 3L/min.
Improve the base material electric current by given pace after the reaction beginning, electric current improves speed and can be controlled in 0.2～1.5A/5min, and the reaction times can be 2～3h, until reaction finishes, the present invention improves rate-controlling at 1A/min with electric current, and the reaction times is controlled at 3h.The ultimate current value can be 100～300A, and ultimate current of the present invention is 210A.Deposition process is utilized depositing base self heating power, and the zone that sedimentation velocity is slow is because relative resistance is large, and temperature is high, corresponding the accelerating of sedimentation velocity meeting; The zone that sedimentation velocity is fast is because relative resistance is little, and temperature is low, and sedimentation velocity can be corresponding slack-off, plays the effect that sedimentation velocity is regulated automatically.Reaction will change nitrogen blowing after finishing in the system, and reduces gradually electric current, and the control temperature slowly is reduced to room temperature, and rate of temperature fall can be 2～4 ℃/min, and temperature fall time can be 2～5h, and cooling rate is controlled to be 3 ℃/min among the present invention, temperature fall time 3h.
After being cooled to room temperature, can utilize the different of base material and tungsten thermal expansivity, remove base material or remove base material with 30% dilute nitric acid dissolution, base material is copper pipe among the present invention, utilizes 30% dilute nitric acid dissolution to remove base material, obtains the uniform tungsten pipe of wall thickness.Not only purity is high for the tungsten pipe that the present invention makes, density is high, and its maximum advantage is that wall thickness is even, and the product that makes does not need secondary processing, can effectively reduce cost.
The Thickness Distribution situation that the tungsten pipe is gone up along its length can find out that wall thickness is even along its length as shown in Figure 3.
The tungsten pipe is analyzed with plane-grating spectrograph after processing, checked for impurities content, the result is as shown in table 1.
Table 1 tungsten pipe foreign matter content analytical results unit: ppmw
| Cu | Cd | V | Ca | Mo | Ti | Bi | Co | Cr | Ni | Fe |
| 5.6 | 2 | 0.8 | 6.4 | 56 | 3.6 | 0.4 | 5.6 | 4.4 | 5.6 | 10 |
| Mn | Sn | Mg | Pb | Sb | Al | Si | As | K | Na | Add up to |
| 2.4 | 0.8 | 3.2 | 0.8 | 9.6 | 5.2 | 16.8 | 17.6 | 8.1 | 17.7 | 182.6 |
As seen from Table 1, the purity of tungsten pipe has reached more than 99.9%.
Claims (10)
1. the manufacture method of a tungsten pipe is characterized in that may further comprise the steps:
1) base material is fixed on the depositing device, to the heating of base material direct-electrifying, passes into reactant gases and react, after the reaction beginning, improve electric current, extremely reaction finishes;
2) change logical shielding gas in the system after reaction finishes, be cooled to room temperature;
3) base material is removed, namely got the tungsten pipe, gained tungsten pipe is the uniform pure tungsten pipe of a kind of wall thickness.
2. the manufacture method of a kind of tungsten pipe as claimed in claim 1 is characterized in that in step 1), and it is 5～20mm that described base material adopts diameter, and wall thickness is 0.5～1mm, the stainless steel tube of length＜1500mm or copper pipe.
3. the manufacture method of a kind of tungsten pipe as claimed in claim 1 is characterized in that in step 1), and described base material adopts ganoid base material; The surface of described base material is cleaned and polished finish in advance, and with being fixed on the depositing device again behind the alcohol wipe surface.
4. the manufacture method of a kind of tungsten pipe as claimed in claim 1, it is characterized in that in step 1) the initial current of described reaction is 10～40A, the speed of described raising electric current is 0.2～1.5A/min, the reaction times of described reaction is 2～3h, and the ultimate current value is 100～300A.
5. the manufacture method of a kind of tungsten pipe as claimed in claim 1, it is characterized in that in step 1), the described concrete grammar that passes into reactant gases is: pass into reactant gases by the constant temperature gas distributing system, described constant temperature gas distributing system comprises stock bottle, insulation can, hot air blower, WF
6Under meter, H
2Under meter, temperature are 30～50 ℃.
6. the manufacture method of a kind of tungsten pipe as claimed in claim 1 is characterized in that in step 1), and described reactant gases adopts WF
6And H
2Mixed gas.
7. the manufacture method of a kind of tungsten pipe as claimed in claim 1 is characterized in that in step 1), described WF
6Purity greater than 99.9%, described H
2Purity greater than 99.9%, described WF
6With H
2Volume ratio be WF
6: H
2=1: (1～4); Described WF
6Flow be 0.5～2L/min.
8. the manufacture method of a kind of tungsten pipe as claimed in claim 1 is characterized in that in step 1), described H
2Flow be 1～8L/min.
9. the manufacture method of a kind of tungsten pipe as claimed in claim 1 is characterized in that in step 2) in, described shielding gas adopts hydrogen or nitrogen, and the flow of shielding gas can be 1～5L/min; The speed of described cooling can be 2～4 ℃/min, and the time of cooling can be 2～5h.
10. the manufacture method of a kind of tungsten pipe as claimed in claim 1, it is characterized in that in step 3), the described concrete grammar that base material is removed is: base material is cooled to subzero below 40 ℃, utilizes the different of base material and tungsten thermal expansivity, make base material and tungsten pipe natural separation; Or be that 30% nitric acid dissolve is removed base material with concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489047.XA CN102978583B (en) | 2012-11-26 | 2012-11-26 | Method for manufacturing tungsten pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489047.XA CN102978583B (en) | 2012-11-26 | 2012-11-26 | Method for manufacturing tungsten pipe |
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| Publication Number | Publication Date |
|---|---|
| CN102978583A true CN102978583A (en) | 2013-03-20 |
| CN102978583B CN102978583B (en) | 2015-01-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210489047.XA Active CN102978583B (en) | 2012-11-26 | 2012-11-26 | Method for manufacturing tungsten pipe |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107009093A (en) * | 2017-01-12 | 2017-08-04 | 厦门虹鹭钨钼工业有限公司 | A kind of preparation method of rear-earth-doped tungsten pipe |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242347A (en) * | 2011-06-29 | 2011-11-16 | 北京理工大学 | Method for preparing tungsten tube for heating body |
-
2012
- 2012-11-26 CN CN201210489047.XA patent/CN102978583B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102242347A (en) * | 2011-06-29 | 2011-11-16 | 北京理工大学 | Method for preparing tungsten tube for heating body |
Non-Patent Citations (1)
| Title |
|---|
| 李汉广等: "氟化物CVD法直接制取特纯高致密异型钨制品", 《稀有金属材料与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107009093A (en) * | 2017-01-12 | 2017-08-04 | 厦门虹鹭钨钼工业有限公司 | A kind of preparation method of rear-earth-doped tungsten pipe |
| CN107009093B (en) * | 2017-01-12 | 2019-01-29 | 厦门虹鹭钨钼工业有限公司 | A kind of production method of rear-earth-doped tungsten pipe |
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| Publication number | Publication date |
|---|---|
| CN102978583B (en) | 2015-01-14 |
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