CN1048762C - Zirconium material prefilming method and its equipment - Google Patents
Zirconium material prefilming method and its equipment Download PDFInfo
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- CN1048762C CN1048762C CN97121973A CN97121973A CN1048762C CN 1048762 C CN1048762 C CN 1048762C CN 97121973 A CN97121973 A CN 97121973A CN 97121973 A CN97121973 A CN 97121973A CN 1048762 C CN1048762 C CN 1048762C
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Abstract
The present invention provides a zirconium material prefilming method which relates to a metal surface filming method used in the manufacturing process of a zirconium material in a nuclear reactor. The zirconium material prefilming method is characterized in that the pressure in the prefilming process is from 0.2 to 0.5MPa, and the constant temperature is from 360 to 500 DEG C. Owing to low filming pressure, the zirconium material prefilming method greatly reduces the difficulty of the filming process and overcomes the defect that the original filming method has high requirement for equipment. Besides, the equipment of the present invention can effectively meet the prefilming requirement of large zirconium parts.
Description
A kind of Zirconium material prefilming method relates to a kind of metallic surface that is used for the nuclear reactor zirconia material course of processing and applies membrane method and equipment thereof.
At present, the application of zirconium and zirconium alloy tube and heterotype tubing mainly is as nuclear reactor fuel can pipe, penstock, isocon structural part, and its sheet material also is the important structure part.These parts need carry out pre-film to parts surface usually and handle before entering reactor.Zirconium and alloy thereof are carried out the surface-treated method, when detecting zirconium alloy sample corrosion resistance nature, existing practical application.Detecting zirconium alloy sample erosion resistance method, is to utilize the zirconium material to react with water under High Temperature High Pressure, generates protective membrane at zirconium material surface oxidation, by the color evaluation zirconium material corrosion resistance on analytical sample oxidation weight gain and surface.The corrosion process of its test is to carry out in the autoclave that stainless steel is made.Use measuring accuracy to be 0.01mm miking sample original size and precision its weight of electrodynamic balance weighing as 0.02mg.Adopt high purity water to make corrosive medium.The etching process parameter is: pH value=6～8 of high purity water, resistivity are 0.5～1.0M Ω .cm, usually 400 ℃, 10.3MPa, 72 hours, or at 360 ℃, 18.6MPa, 336 hours constant temperature, come out of the stove behind the furnace cooling.To Zr-2, the product of Zr-4 alloy corrosion criterion of acceptability is 72 hours, behind 400 ℃, 10.3MPa, high purity water corrosion, and surrosion Δ m＜22mg/dm
2, the surface is shiny black look protective membrane.At present, this method also has been used for the pre-film in surface of the small members of nuclear reactor.It is simple that this method has technology, the characteristics that the pre-membrane process of its product surface is stable.But this method must adopt special autoclave, the equipment requirements height.And, can only be used for the deposited membrane process of small members because existing autoclave volume is little.Do not satisfy the deposited film demand of large-scale component.
At present,, proposed demand, just needed to solve the pre-film problem of large-scale zircon-structure spare inevitably accordingly large-scale zircon-structure spare along with the development of novel nuclear reactor technology.Still there is not report at present both at home and abroad applicable to the autoclave of this large-scale zircon-structure spare.Be used for the existing retort of chemical industry at present and since its to operating temperature require lowly, the pre-film temperature of general zirconium material will be more than 360 ℃, and the temperature that autoclave bears will not satisfy the requirement of the deposited film of zirconium material more than 500 ℃.Make and meet the high temperature and high pressure kettle that the pre-film of large-scale zircon-structure spare uses and also exist the problem of large amount of complex to wait to solve technically.
Purpose of the present invention is exactly in order to overcome in the existing Zirconium material prefilming method, what exist applies the defective that film requires to equipment requirements height, unappeasable large-scale zircon-structure spare, the novel Zirconium material prefilming method that a kind of processing condition are simple, process is easy to realize is provided and is used for a kind of Zirconium material prefilming equipment of the present invention.
The objective of the invention is to be achieved through the following technical solutions.
A kind of Zirconium material prefilming method, comprise: a. carries out surface degreasing, pickling, washing, high temperature washing with zircon-structure spare, b. again zircon-structure spare is placed high purity water heating, constant temperature to carry out the pre-film of oxidation, it is characterized in that: the reaction pressure of its pre-membrane process is 0.2～0.5Mpa, and thermostat temperature is 360～500 ℃.
A kind of Zirconium material prefilming equipment, it is characterized in that pre-film device is made up of following member: a tank body, tank body are cylindrical; At the bottom of one jar, jar end and tank body base Joint; One cover is equipped with tensimeter, safety valve on its cover, cover and tank body upper limb join; One Thermal couple casing pipe, Thermal couple casing pipe are fixed on the cover; One surplus valve pipe, the surplus valve pipe is fixed on the cover; On at the bottom of leak-off pipe, leak-off pipe are fixed in jar.
Zirconium material prefilming method of the present invention because the pressure of its deposited film is low, greatly reduces the difficulty of applying membrane process, has solved original deposited membrane method defective high to equipment requirements, and technological process is easy to realize.Its pre-film device owing to can control the processing parameter of pre-membrane process effectively, is particularly controlled the pressure and the temperature of reaction of reaction process effectively, can satisfy the requirement of Zirconium material prefilming process of the present invention fully.Because its process carries out under lower pressure, the requirement of withstand voltage of equipment is correspondingly reduced, can add the useful volume of large equipment, satisfied the pre-film requirement of large-scale zirconium spare.Be a kind of more satisfactory Zirconium material prefilming equipment.
The invention will be further described below in conjunction with example and accompanying drawing.
Description of drawings.
Fig. 1 is the structural representation that is used for a kind of Zirconium material prefilming equipment of the inventive method.
A kind of Zirconium material prefilming method at first carries out the zirconium structural member surface degreasing, pickling, washing, high temperature washing, B. the zirconium structural member being placed high purity water heating, constant temperature, is 0.2～0.5Mpa at pressure again, and thermostat temperature is 360 Carry out the pre-film of oxidation under～500 ℃ the condition.
A kind of Zirconium material prefilming equipment, it is characterized in that pre-film device is made up of following member: a tank body 1, the tank body is Cylindrical; At the bottom of one tank 2, at the bottom of the tank with tank body base Joint; One tank lid 3, its tank cover be equipped with Pressure gauge 4, Safety valve 5, the tank lid joins with tank body top edge; One Thermal couple casing pipe 6, Thermal couple casing pipe is fixed in tank and covers; One overflows Stream valve pipe 7, overflow valve pipe is fixed in tank and covers; Earial drainage pipe 8 is on the earial drainage pipe is fixed at the bottom of the tank.
The retort of a kind of Zirconium material prefilming equipment of the present invention can adopt vertical installation, before carrying out the reaction of pre-film to tank Body cleans, and its resistivity of the water after the cleaning should be greater than 0.3M Ω .cm. The cleaning of zirconium structural member is pressed before pre-film The method that ASTM G recommends is carried out.
With the deposited membrane process to zirconium-tin alloy is example.
1. cleaning process
(1) oil removing:, clean as non-leaded gasoline with chemical solvents or organic solvent.
(2) pickling: in the formulated pickle solution of hydrofluoric acid and nitric acid and softening water, carry out strict acid cleaning process.
(3) washing: after pickling is finished, structural part is put into the mobile clear water, remove its surperficial acid solution and sour mark.
(4) high temperature washing: in water quality is 0.1～0.5M Ω .cm, and water temperature is that high-purity hot water of 80 ℃ cleans.With stand-by after the cleaned structural part drying, or directly put into retort.
2. pre-membrane process
(1) structural part after will cleaning is put into retort, fills with high purity water, builds cover, fastening, turns on surplus valve, behind the feeding temperature-raising, Yu Shui flows out from surplus valve.
(2) after retort reaches the temperature and pressure that needs, fasten surplus valve, constant temperature had a power failure after preset time, naturally cooling, pre-film spare is cooled under 60 ℃ with jar, turn on the surplus valve valve, open cover, take out pre-film spare and be positioned over ad hoc usefulness such as clean place with handling clean unit clamp.Surplus water or rinse water are emitted from venting valve.Build lid at last, to keep clean in the jar.
With the deposited membrane process to the Zr-4 alloy is example
Embodiment 1
The adopting process condition is the high-purity resistivity of water of pre-film: 0.7M Ω .cm, and pH=7, temperature: 380 ℃, pressure: 0.5MPa, through 60 hours constant temperature, other process was with the deposited membrane process to zirconium-tin alloy.
The result forms one deck compact protective film on the zirconium alloy surface.
The adopting process condition is the high-purity resistivity of water of pre-film: 0.7M Ω .cm, and pH=7, temperature: 420 ℃, pressure: 0.3MPa, through 16 hours constant temperature, other process was with the deposited membrane process to zirconium-tin alloy.
The result forms one deck compact protective film on the zirconium alloy surface.
The adopting process condition is the high-purity resistivity of water of pre-film: 0.7M Ω .cm, and pH=7, temperature: 480 ℃, pressure: 0.2MPa, through 4 hours constant temperature, other process was with the deposited membrane process to zirconium-tin alloy.
The result forms one deck compact protective film on the zirconium alloy surface.
Adopt the Zr-4 sheet alloy, the method that provides by ASTM G cleans up sample, places in the retort, high-purity resistivity of water in jar: 0.7M Ω .cm, pH=7 is warming up to 140 ℃, and steam discharge is got rid of a jar interior air fast, the follow-up temperature of continuing rising of steam bleeding, etc. 440 ℃ of retort Nei Wenduda, pressure: 0.2～0.5MPa, constant temperature 7 hours, cool to 60 ℃ with the furnace, take out pre-film sample.Through observation analysis, specimen surface forms the black protective film of one deck densification, its 13mg/dm that increases weight
2～18mg/dm
2, consistent with the result that the pre-embrane method of traditional autoclave obtains.
Claims (2)
1. Zirconium material prefilming method, comprise: a. carries out surface degreasing, pickling, washing, high temperature washing with zircon-structure spare, b. again zircon-structure spare is placed high purity water heating, constant temperature to carry out the pre-film of oxidation, it is characterized in that: the reaction pressure of its pre-membrane process is 0.2～0.5MPa, and thermostat temperature is 360～500 ℃.
2. Zirconium material prefilming equipment is characterized in that pre-film device is made up of following member:
One tank body, tank body are cylindrical;
At the bottom of one jar, jar end and tank body base Joint;
One cover is equipped with tensimeter, safety valve on its cover, cover and tank body upper limb join;
One Thermal couple casing pipe, Thermal couple casing pipe are fixed on the cover;
One surplus valve pipe, the surplus valve pipe is fixed on the cover;
On at the bottom of one leak-off pipe, leak-off pipe are fixed in jar.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121973A CN1048762C (en) | 1997-12-03 | 1997-12-03 | Zirconium material prefilming method and its equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121973A CN1048762C (en) | 1997-12-03 | 1997-12-03 | Zirconium material prefilming method and its equipment |
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| Publication Number | Publication Date |
|---|---|
| CN1188157A CN1188157A (en) | 1998-07-22 |
| CN1048762C true CN1048762C (en) | 2000-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN97121973A Expired - Lifetime CN1048762C (en) | 1997-12-03 | 1997-12-03 | Zirconium material prefilming method and its equipment |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076763C (en) * | 1998-09-09 | 2001-12-26 | 北京航空航天大学 | In-situ preparing of insulating film on surface of marmem |
| CN111101089A (en) * | 2020-02-18 | 2020-05-05 | 苏州微创关节医疗科技有限公司 | Method for forming oxide layer on surface of zirconium or zirconium alloy and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS625485A (en) * | 1985-06-29 | 1987-01-12 | Toshiba Corp | Optical character recognizing device |
| CN1030261A (en) * | 1987-06-23 | 1989-01-11 | 弗拉马托姆联合股份公司 | Be used for the manufacture method and the application thereof of the Zirconium-based alloy tube of nuclear reactor |
| JPH06230161A (en) * | 1993-01-29 | 1994-08-19 | Nippon Nuclear Fuel Dev Co Ltd | Zirconium based alloy |
-
1997
- 1997-12-03 CN CN97121973A patent/CN1048762C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS625485A (en) * | 1985-06-29 | 1987-01-12 | Toshiba Corp | Optical character recognizing device |
| CN1030261A (en) * | 1987-06-23 | 1989-01-11 | 弗拉马托姆联合股份公司 | Be used for the manufacture method and the application thereof of the Zirconium-based alloy tube of nuclear reactor |
| JPH06230161A (en) * | 1993-01-29 | 1994-08-19 | Nippon Nuclear Fuel Dev Co Ltd | Zirconium based alloy |
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| Publication number | Publication date |
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| CN1188157A (en) | 1998-07-22 |
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