CN103361592A - Method for improving high-temperature corrosion resistance of zirconium alloy pipe - Google Patents
Method for improving high-temperature corrosion resistance of zirconium alloy pipe Download PDFInfo
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- CN103361592A CN103361592A CN2013103165711A CN201310316571A CN103361592A CN 103361592 A CN103361592 A CN 103361592A CN 2013103165711 A CN2013103165711 A CN 2013103165711A CN 201310316571 A CN201310316571 A CN 201310316571A CN 103361592 A CN103361592 A CN 103361592A
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Abstract
The method relates to a method for improving high-temperature corrosion resistance of a zirconium alloy pipe. According to the method, the outer surface of the zirconium alloy pipe is made to be oxidized to generate a compact zirconia pre-oxide film, and the thickness of the compact zirconia pre-oxide film is 5-10 mu m. By genBy forming the compact zirconia pre-oxide film on the outer surface of the zirconium alloy pipe, the pre-oxide film can help to effectively block dispersion of oxygen and hydrogen when the zirconium alloy pipe is on active service, and thereby the corrosion resistance of the zirconium alloy pipe in high temperature is effectively improved.
Description
Technical field
The present invention relates to the Zirconium alloy material preparing technical field, relate in particular to a kind of method that improves the zirconium alloy pipe elevated temperature corrosion resistant.
Background technology
In the nuclear power field, zirconium alloy have significant resistance to high temperature corrosion performance and its thermal neutron absorption cross section low, therefore be widely used in penstock and the fuel sheath of nuclear reactor.Based on the demand to the nuclear power energy technology, Nuclear Power Technology is to the development of high burnup, long fuel cycle period, in order to improve the burnup of fuel element, in order to reach the lifetime in 60 years of nuclear reactor, the can material of this element that just requires to act as a fuel should have more excellent erosion resistance.The working life that prolongs zirconium alloy is subject to the improvement of high temperature corrosion resistance to a great extent, and this just requires zirconium alloy to have more excellent erosion resistance under the envrionment conditions under arms.In addition, along with the development of China's Nuclear Electricity, the production domesticization of reactor structural material and fuel and respective handling technology thereof is inexorable trend.
Prior art mainly by regulating chemical constitution and the content of the alloying element that consists of zirconium alloy tube, improves the corrosion resistance of zirconium alloy tube under hot conditions by optimizing material itself.
Summary of the invention
Technical problem to be solved by this invention is, a kind of method of new raising zirconium alloy pipe elevated temperature corrosion resistant is provided.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of method that improves the zirconium alloy pipe elevated temperature corrosion resistant, it is to make the outside surface generation oxidizing reaction of zirconium alloy pipe produce fine and close zirconium white preoxidation rete, the thickness of zirconium white preoxidation rete is 5 ~ 10 μ m.
Preferably, described oxidizing reaction is carried out in the mixed gas of argon gas and oxygen.More preferably, to account for the volume ratio of described mixed gas be 80% ~ 95% to oxygen.
Preferably, the purity of described argon gas and oxygen is respectively greater than 99.95wt%.
Preferably, oxidizing reaction is carried out in the oxidizing reaction isolated plant, this oxidizing reaction isolated plant comprises silica tube, the first end cap and the second end cap that are tightly connected respectively with the two ends of silica tube, be arranged on the first end cap, the first inlet pipe and the second inlet pipe on one in two of the second end caps, be arranged on the first end cap, vapor pipe in two of the second end caps another, and HF induction heating apparatus, the ruhmkorff coil of HF induction heating apparatus is arranged on the periphery of silica tube, described method is implemented as follows: zirconium alloy pipe is inserted in the silica tube, and the both ends of zirconium alloy pipe respectively with the first end cap be connected end cap and be connected, utilize HF induction heating apparatus that zirconium alloy pipe is heated, simultaneously, in silica tube, pass into oxygen and argon gas respectively by the first inlet pipe and the second inlet pipe, by vapor pipe the gas in the silica tube is discharged.Take described apparatus and method, technique is relatively simple, controlled.
Preferably, before carrying out oxidizing reaction, use acetone for example that the outside surface of zirconium alloy pipe is cleaned.
Further, the total flux of described oxygen and argon gas is 10 ~ 15 L/min.
Preferably, described method also makes when carrying out oxidizing reaction, passes into shielding gas with the flow of 5 ~ 10L/min in zirconium alloy pipe.Shielding gas is preferably argon gas.Shielding gas can effectively be protected zirconium alloy pipe and cool off.
Preferably, the range of frequency of described HF induction heating apparatus is 20000Hz ~ 23000Hz, and output rating is 2000 ~ 4000 watts.
The time of described oxidizing reaction is 15 ~ 70min.
Described zirconium alloy pipe can be known various zirconium alloy tubes Zr-1.0Nb for example.
The present invention also provides a kind of and processes the gained zirconium alloy pipe through aforesaid method.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
The present invention is by forming fine and close zirconium white preoxidation film at the zirconium alloy pipe outside surface, this preoxidation film can effectively stop the diffusion of oxygen hydrogen when zirconium alloy pipe is on active service, thus Effective Raise the corrosion resistance of zirconium alloy pipe under hot conditions.
Description of drawings
Fig. 1 is the structural representation of oxidizing reaction isolated plant of the present invention;
Wherein: 1, the first end cap; 2, the first inlet pipe; 3, zirconium alloy pipe; 4, zirconium alloy pipe endoporus; 5, the second inlet pipe; 6, sealing-ring; 7, silica tube; 8, ruhmkorff coil; 9, vapor pipe; 10, the second end cap.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done further detailed description.The method of following examples all adopts oxidizing reaction isolated plant shown in Figure 1.
Embodiment 1
(1) chooses the Zr-1.0Nb zirconium alloy pipe 3 of diameter 9.8 mm, thickness 0.6 mm, clean zirconium alloy pipe 3 outside surfaces with acetone, be fixed on reaction chamber the second end cap 10 and the first end cap 1, the ruhmkorff coil 8 of HF induction heating apparatus is placed on the middle part of silica tube 7 peripheries, consists of reaction chamber 11 between silica tube 7, the second end cap 10, the first end cap 1 and the sealing-ring 6;
(2) pass through respectively the first inlet pipe 2 and the second inlet pipe 5 to reaction chamber 11 interior conveying argon gas and oxygen, the total flux of the mixed gas that is made of argon gas and oxygen is 10 L/min, the volume ratio of oxygen in mixed gas is 80%, by zirconium alloy pipe endoporus 4 argon gas is sent in the zirconium alloy pipe endoporus, argon flow amount 5L/min, play the effect of protection and cooling zirconium alloy pipe 3, employed argon gas and oxygen are 99.95% high-purity gas;
(3) induction heating parameter: frequency 20000Hz is set, 4000 watts of output ratings, oxidization time 15min, reactant gases is discharged by vapor pipe 9 during the induction oxidation, by oxidizing reaction, form the zirconium white preoxidation film of one deck densification, the about 5.6 μ m of thickness at the outside surface of zirconium alloy pipe 3.
(4) intercepted length is the zirconium alloy pipe of above-mentioned three step process of process of 20mm, is placed on 360 ℃/18.6MPa/3.5ppmLi
++ 1000ppm BO
4 3-Autoclave in the corrosion 70 days, zirconium alloy pipe oxidation weight gain 33.45mg/dm
2And undressed zirconium alloy pipe under the same conditions, corrodes after 70 days, and the zirconium alloy pipe oxidation weight gain reaches 36.23mg/dm
2
Embodiment 2
(1) chooses the Zr-1.0Nb zirconium alloy pipe 3 of diameter 9.8 mm, thickness 0.6 mm, clean zirconium alloy pipe 3 outside surfaces with acetone, be fixed on the second end cap 10 and the first end cap 1, the ruhmkorff coil 8 of HF induction heating apparatus is placed on the middle part of silica tube 7 peripheries, and silica tube 7, the second end cap 10, the first end cap 1 and sealing-ring 6 consist of reaction chamber 11;
(2) pass through respectively the first inlet pipe 2 and the second inlet pipe 5 to reaction chamber 11 interior conveying argon gas and oxygen, the total flux of the mixed gas that is made of argon gas and oxygen is 12 L/min, the volume ratio of oxygen in mixed gas is 86%, by zirconium alloy pipe endoporus 4 argon gas is sent into zirconium alloy pipe endoporus 4, argon flow amount 8L/min, play the effect of protection and cooling zirconium alloy pipe 3, employed argon gas and oxygen are 99.95% high-purity gas;
(3) the induction heating parameter is set, frequency 22000Hz, 3000 watts of output ratings, oxidization time 40min, reactant gases is discharged by vapor pipe 9 during the induction oxidation, passes through oxidizing reaction, form the zirconium white preoxidation film of one deck densification, the about 6.4 μ m of thickness at the outside surface of zirconium alloy pipe 3.
(4) intercepted length is the zirconium alloy pipe of above-mentioned three step process of process of 20mm, is placed on 360 ℃/18.6MPa/3.5ppmLi
++ 1000ppm BO
4 3-Autoclave in the corrosion 70 days, zirconium alloy pipe oxidation weight gain 28mg/dm
2And undressed zirconium alloy pipe under the same conditions, corrodes after 70 days, and the zirconium alloy pipe oxidation weight gain reaches 36.23mg/dm
2
Embodiment 3
(1) chooses the Zr-1.0Nb zirconium alloy pipe 3 of diameter 9.8 mm, thickness 0.6 mm, clean zirconium alloy pipe 3 outside surfaces with acetone, be fixed on the second end cap 10 and the first end cap 1, the ruhmkorff coil 8 of HF induction heating apparatus is placed on the middle part of silica tube 7 peripheries, and silica tube 7, reaction chamber the second end cap 10, the first end cap 1 and sealing-ring 6 consist of reaction chamber 11;
(2) pass through respectively the first inlet pipe 2 and the second inlet pipe 5 to reaction chamber 11 interior conveying argon gas and oxygen, the total flux of argon gas and oxygen is 15 L/min, the volume ratio of oxygen in mixed gas is 95%, by zirconium alloy pipe endoporus 4 argon gas is sent into zirconium alloy pipe endoporus 4, argon flow amount 15L/min, play the effect of protection and cooling zirconium alloy pipe 3, employed oxygen and oxygen are 99.95% high-purity gas;
(3) the induction heating parameter is set, frequency 23000Hz, 2000 watts of output ratings, oxidization time 70min, reactant gases is discharged by vapor pipe 9 during the induction oxidation, passes through oxidizing reaction, form the zirconium white preoxidation film of one deck densification, the about 7.3 μ m of thickness at the outside surface of zirconium alloy pipe 3.
(4) intercepted length is the zirconium alloy pipe of above-mentioned three step process of process of 20mm, is placed on 360 ℃/18.6MPa/3.5ppmLi
++ 1000ppm BO
4 3-Autoclave in the corrosion 70 days, zirconium alloy pipe oxidation weight gain 20mg/dm
2And undressed zirconium alloy pipe under the same conditions, corrodes after 70 days, and the zirconium alloy pipe oxidation weight gain reaches 36.23mg/dm
2
Above-described embodiment only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. method that improves the zirconium alloy pipe elevated temperature corrosion resistant is characterized in that: described method is to make the outside surface generation oxidizing reaction of zirconium alloy pipe produce fine and close zirconium white preoxidation rete, and the thickness of described zirconium white preoxidation rete is 5 ~ 10 μ m.
2. method according to claim 1 is characterized in that: described oxidizing reaction is carried out in the mixed gas of argon gas and oxygen.
3. method according to claim 2, it is characterized in that: the volume ratio that oxygen accounts for described mixed gas is 80% ~ 95%.
4. method according to claim 2, it is characterized in that: the purity of described argon gas and oxygen is respectively greater than 99.95wt%.
5. the described method of each claim in 4 according to claim 1, it is characterized in that: described oxidizing reaction is carried out in the oxidizing reaction isolated plant, described oxidizing reaction isolated plant comprises silica tube, the first end cap and the second end cap that are tightly connected respectively with the two ends of described silica tube, be arranged on described the first end cap, the first inlet pipe and the second inlet pipe on one in two of the second end caps, be arranged on described the first end cap, vapor pipe in two of the second end caps another, and HF induction heating apparatus, the ruhmkorff coil of described HF induction heating apparatus is arranged on the periphery of described silica tube, described method is implemented as follows: zirconium alloy pipe is inserted in the silica tube, and the both ends of zirconium alloy pipe respectively with described the first end cap be connected end cap and be connected, utilize described HF induction heating apparatus that zirconium alloy pipe is heated, simultaneously, in silica tube, pass into oxygen and argon gas respectively by described the first inlet pipe and the second inlet pipe, by described vapor pipe the gas in the silica tube is discharged.
6. method according to claim 5, it is characterized in that: the total flux of described oxygen and argon gas is 10 ~ 15 L/min.
7. method according to claim 5 is characterized in that: described method passes into shielding gas with the flow of 5 ~ 10L/min also when carrying out oxidizing reaction in described zirconium alloy pipe.
8. method according to claim 7, it is characterized in that: described shielding gas is argon gas.
9. method according to claim 5, it is characterized in that: the range of frequency of described HF induction heating apparatus is 20000Hz ~ 23000Hz, output rating is 2000 ~ 4000 watts.
One kind in claim 1 to 9 the described method of each claim process the zirconium alloy pipe of gained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559942A (en) * | 2018-05-14 | 2018-09-21 | 中鼎特金秦皇岛科技股份有限公司 | A method of preparing black ceramic layer on zirconium-base alloy surface |
| CN113699480A (en) * | 2021-08-23 | 2021-11-26 | 华能国际电力股份有限公司 | Method and device for simultaneously improving corrosion resistance of inner wall and outer wall of power station boiler tube |
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| US20090108329A1 (en) * | 2007-10-31 | 2009-04-30 | Hynix Semiconductor Inc. | Non-volatile semiconductor device and method of fabricating the same |
| CN103172382A (en) * | 2013-04-22 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of ultra-temperature oxidative damage resistant zirconium diboride-silicon carbide ceramic base composite material |
| CN103194718A (en) * | 2013-04-21 | 2013-07-10 | 北京工业大学 | High-temperature corrosion resisting zirconium alloy tube and laser surface pre-oxidation method of zirconium alloy tube |
-
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- 2013-07-25 CN CN201310316571.1A patent/CN103361592B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090108329A1 (en) * | 2007-10-31 | 2009-04-30 | Hynix Semiconductor Inc. | Non-volatile semiconductor device and method of fabricating the same |
| CN103194718A (en) * | 2013-04-21 | 2013-07-10 | 北京工业大学 | High-temperature corrosion resisting zirconium alloy tube and laser surface pre-oxidation method of zirconium alloy tube |
| CN103172382A (en) * | 2013-04-22 | 2013-06-26 | 哈尔滨工业大学 | Preparation method of ultra-temperature oxidative damage resistant zirconium diboride-silicon carbide ceramic base composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559942A (en) * | 2018-05-14 | 2018-09-21 | 中鼎特金秦皇岛科技股份有限公司 | A method of preparing black ceramic layer on zirconium-base alloy surface |
| CN113699480A (en) * | 2021-08-23 | 2021-11-26 | 华能国际电力股份有限公司 | Method and device for simultaneously improving corrosion resistance of inner wall and outer wall of power station boiler tube |
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