CN103361592B - A kind of method improving high-temperature corrosion resistance of zirconium alloy pipe - Google Patents
A kind of method improving high-temperature corrosion resistance of zirconium alloy pipe Download PDFInfo
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- CN103361592B CN103361592B CN201310316571.1A CN201310316571A CN103361592B CN 103361592 B CN103361592 B CN 103361592B CN 201310316571 A CN201310316571 A CN 201310316571A CN 103361592 B CN103361592 B CN 103361592B
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Abstract
The present invention relates to a kind of method improving high-temperature corrosion resistance of zirconium alloy pipe, it makes the outside surface generation oxidizing reaction of zirconium alloy pipe produce fine and close zirconium white preoxidation rete, and the thickness of zirconium white preoxidation rete is 5 ~ 10 μm.The present invention by forming fine and close zirconium white preoxidation film at zirconium alloy pipe outside surface, the diffusion of oxygen hydrogen when this preoxidation film effectively can stop that zirconium alloy pipe is on active service, thus effectively improve zirconium alloy pipe corrosion resistance under the high temperature conditions.
Description
Technical field
The present invention relates to Zirconium alloy material preparing technical field, particularly relate to a kind of method improving high-temperature corrosion resistance of zirconium alloy pipe.
Background technology
In nuclear power field, zirconium alloy has significant resistance to high temperature corrosion performance and its thermal neutron absorption cross section is low, is therefore widely used in penstock and the fuel sheath of nuclear reactor.Based on the demand to 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 nuclear reactor lifetime of 60 years, this just requires should have more excellent erosion resistance as the can material of fuel element.Extend the improvement that the working life of zirconium alloy is limited to high temperature corrosion resistance to a great extent, this just requires that zirconium alloy has more excellent erosion resistance under 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 through regulating chemical constitution and the content of the alloying element forming zirconium alloy tube, improves zirconium alloy tube corrosion resistance under the high temperature conditions by optimizing material itself.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of method of raising high-temperature corrosion resistance of zirconium alloy pipe newly.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
Improve a method for high-temperature corrosion resistance of zirconium alloy pipe, it makes the outside surface generation oxidizing reaction of zirconium alloy pipe produce fine and close zirconium white preoxidation rete, and the thickness of zirconium white preoxidation rete is 5 ~ 10 μm.
Preferably, described oxidizing reaction is made to carry out in the mixed gas of argon gas and oxygen.More preferably, oxygen accounts for the volume ratio of described mixed gas is 80% ~ 95%.
Preferably, the purity of described argon gas and oxygen is greater than 99.95wt% respectively.
Preferably, oxidizing reaction is carried out in oxidizing reaction special purpose device, this oxidizing reaction special purpose device comprises silica tube, the first end cap be tightly connected respectively with the two ends of silica tube and the second end cap, be arranged on the first end cap, the first inlet pipe on one in second end cap two and the second inlet pipe, be arranged on the first end cap, vapor pipe on another in second end cap two, 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: inserted by zirconium alloy pipe in silica tube, and the both ends of zirconium alloy pipe are connected with the first end cap and the second end cap respectively, HF induction heating apparatus is utilized to heat zirconium alloy pipe, simultaneously, by the first inlet pipe and the second inlet pipe respectively to passing into oxygen and argon gas in silica tube, by vapor pipe, the gas in silica tube is discharged.Take described apparatus and method, technique is relatively simple, controlled.
Preferably, before carrying out oxidizing reaction, the outside surface of such as acetone to zirconium alloy pipe is used to clean.
Further, the total flux of described oxygen and argon gas is 10 ~ 15L/min.
Preferably, described method also makes, when carrying out oxidizing reaction, to pass 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.
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 such as Zr-1.0Nb.
The present invention also provides a kind of through aforesaid method process gained zirconium alloy pipe.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantage:
The present invention by forming fine and close zirconium white preoxidation film at zirconium alloy pipe outside surface, the diffusion of oxygen hydrogen when this preoxidation film effectively can stop that zirconium alloy pipe is on active service, thus effectively improves zirconium alloy pipe corrosion resistance under the high temperature conditions.
Accompanying drawing explanation
Fig. 1 is the structural representation of oxidizing reaction special purpose device 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, further detailed description is done to the present invention.The method of following examples all adopts the oxidizing reaction special purpose device shown in Fig. 1.
Embodiment 1
(1) the Zr-1.0Nb zirconium alloy pipe 3 of diameter 9.8mm, thickness 0.6mm is chosen, with acetone cleaning zirconium alloy pipe 3 outside surface, be fixed on reaction chamber 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 periphery, forms reaction chamber 11 between silica tube 7, second end cap 10, first end cap 1 and sealing-ring 6;
(2) in reaction chamber 11, argon gas and oxygen is carried respectively by the first inlet pipe 2 and the second inlet pipe 5, the total flux of the mixed gas be made up of argon gas and oxygen is 10L/min, the volume ratio of oxygen in mixed gas is 80%, by zirconium alloy pipe endoporus 4, argon gas is sent in zirconium alloy pipe endoporus, argon flow amount 5L/min, play the effect of protection and cooling zirconium alloy pipe 3, the argon gas used and oxygen are the high-purity gas of 99.95%;
(3) induction heating parameter is set: frequency 20000Hz, output rating 4000 watts, oxidization time 15min, during induction oxidation, reactant gases is discharged by vapor pipe 9, by oxidizing reaction, form the zirconium white preoxidation film of one deck densification at the outside surface of zirconium alloy pipe 3, thickness about 5.6 μm.
(4) intercepted length is the zirconium alloy pipe through above-mentioned three step process of 20mm, is placed on 360 DEG C/18.6MPa/3.5ppmLi
++ 1000ppmBO
4 3-autoclave in corrosion 70 days, zirconium alloy pipe oxidation weight gain 33.45mg/dm
2.And undressed zirconium alloy pipe under the same conditions, corrode after 70 days, zirconium alloy pipe oxidation weight gain reaches 36.23mg/dm
2.
Embodiment 2
(1) the Zr-1.0Nb zirconium alloy pipe 3 of diameter 9.8mm, thickness 0.6mm is chosen, with acetone cleaning zirconium alloy pipe 3 outside surface, 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 periphery, and silica tube 7, second end cap 10, first end cap 1 and sealing-ring 6 form reaction chamber 11;
(2) in reaction chamber 11, argon gas and oxygen is carried respectively by the first inlet pipe 2 and the second inlet pipe 5, the total flux of the mixed gas be made up of argon gas and oxygen is 12L/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, the argon gas used and oxygen are the high-purity gas of 99.95%;
(3) induction heating parameter is set, frequency 22000Hz, output rating 3000 watts, oxidization time 40min, during induction oxidation, reactant gases is discharged by vapor pipe 9, passes through oxidizing reaction, the zirconium white preoxidation film of one deck densification is formed, thickness about 6.4 μm at the outside surface of zirconium alloy pipe 3.
(4) intercepted length is the zirconium alloy pipe through above-mentioned three step process of 20mm, is placed on 360 DEG C/18.6MPa/3.5ppmLi
++ 1000ppmBO
4 3-autoclave in corrosion 70 days, zirconium alloy pipe oxidation weight gain 28mg/dm
2.And undressed zirconium alloy pipe under the same conditions, corrode after 70 days, zirconium alloy pipe oxidation weight gain reaches 36.23mg/dm
2.
Embodiment 3
(1) the Zr-1.0Nb zirconium alloy pipe 3 of diameter 9.8mm, thickness 0.6mm is chosen, with acetone cleaning zirconium alloy pipe 3 outside surface, 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 periphery, and silica tube 7, reaction chamber second end cap 10, first end cap 1 and sealing-ring 6 form reaction chamber 11;
(2) in reaction chamber 11, argon gas and oxygen is carried respectively by the first inlet pipe 2 and the second inlet pipe 5, the total flux of argon gas and oxygen is 15L/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, the oxygen used and oxygen are the high-purity gas of 99.95%;
(3) induction heating parameter is set, frequency 23000Hz, output rating 2000 watts, oxidization time 70min, during induction oxidation, reactant gases is discharged by vapor pipe 9, passes through oxidizing reaction, the zirconium white preoxidation film of one deck densification is formed, thickness about 7.3 μm at the outside surface of zirconium alloy pipe 3.
(4) intercepted length is the zirconium alloy pipe through above-mentioned three step process of 20mm, is placed on 360 DEG C/18.6MPa/3.5ppmLi
++ 1000ppmBO
4 3-autoclave in corrosion 70 days, zirconium alloy pipe oxidation weight gain 20mg/dm
2.And undressed zirconium alloy pipe under the same conditions, corrode after 70 days, zirconium alloy pipe oxidation weight gain reaches 36.23mg/dm
2.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. improve a method for high-temperature corrosion resistance of zirconium alloy pipe, it is characterized in that: described method makes 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 μm;
Described oxidizing reaction is carried out in oxidizing reaction special purpose device, described oxidizing reaction special purpose device comprises silica tube, the first end cap be tightly connected respectively with the two ends of described silica tube and the second end cap, be arranged on described first end cap, the first inlet pipe on one in second end cap two and the second inlet pipe, be arranged on described first end cap, vapor pipe on another in second end cap two, 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: inserted by zirconium alloy pipe in silica tube, and the both ends of zirconium alloy pipe are connected with described first end cap and the second end cap respectively, described HF induction heating apparatus is utilized to heat zirconium alloy pipe, simultaneously, by described first inlet pipe and the second inlet pipe respectively to passing into oxygen and argon gas in silica tube, by described vapor pipe, the gas in silica tube is discharged,
Described oxidizing reaction is carried out in the mixed gas of argon gas and oxygen;
The total flux of described oxygen and argon gas is 10 ~ 15L/min;
Described method, also when carrying out oxidizing reaction, passes into shielding gas with the flow of 5 ~ 10L/min in described zirconium alloy pipe, and described shielding gas is argon gas.
2. method according to claim 1, is characterized in that: the volume ratio that oxygen accounts for described mixed gas is 80% ~ 95%.
3. method according to claim 1, is characterized in that: described argon gas and the purity of oxygen are greater than 99.95wt% respectively.
4. method according to claim 1, is characterized in that: the range of frequency of described HF induction heating apparatus is 20000Hz ~ 23000Hz, and output rating is 2000 ~ 4000 watts.
5. the zirconium alloy pipe of the method process gained any one of the Claims 1-4 described in claim.
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| 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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| 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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| 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 |
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