JPH01215943A - High corrosion-resistant zirconium alloy - Google Patents
High corrosion-resistant zirconium alloyInfo
- Publication number
- JPH01215943A JPH01215943A JP4121588A JP4121588A JPH01215943A JP H01215943 A JPH01215943 A JP H01215943A JP 4121588 A JP4121588 A JP 4121588A JP 4121588 A JP4121588 A JP 4121588A JP H01215943 A JPH01215943 A JP H01215943A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- corrosion resistance
- corrosion
- zirconium alloy
- kinds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 40
- 230000007797 corrosion Effects 0.000 title claims abstract description 40
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 17
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910052758 niobium Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005253 cladding Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、高耐食性を有するジルコニウム合金、特に
原子炉におけるような高温高圧の水または水蒸気中で使
用するのに好適なジルコニウム合金に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to a zirconium alloy having high corrosion resistance, particularly a zirconium alloy suitable for use in high temperature, high pressure water or steam, such as in a nuclear reactor.
（従来の技術）
ジルコニウム合金は、その適当な機械的性質と小さい熱
中性子吸収断面積および良好な耐食性の故に、沸騰水型
原子炉（ＢＷＲ）および加圧水型原子炉（ＰＷＩＩ）の
燃料被覆管、炉心構造材料等に使用されている。かかる
用途にこれまで使用されてきた代表的な合金としては、
ジルカロイ−２（ＪＩＳ ＺｒＴＮ８０２０）およびジ
ルカロイ−４（ＪＩＳ ＺｒＴＮ８０４Ｄ）がある。BACKGROUND OF THE INVENTION Due to its suitable mechanical properties, small thermal neutron absorption cross section and good corrosion resistance, zirconium alloys are used in boiling water reactors (BWRs) and pressurized water reactors (PWII) fuel cladding, Used as core structural material, etc. Typical alloys that have been used for such purposes include:
There are Zircaloy-2 (JIS ZrTN8020) and Zircaloy-4 (JIS ZrTN804D).
現在の実用炉の運転条件では、上記の既存ジルコニウム
合金は十分にその機能を発揮しており格別の問題はない
。しかし、燃料の燃焼度を高める目的で、燃料被覆管等
の炉内使用期間を更に延長することが計画されており、
そのためにジルコニウム合金の高性能化、特に耐食性の
一層の向上が要望されている。Under the current operating conditions of practical reactors, the existing zirconium alloys described above fully exhibit their functions and there are no particular problems. However, in order to increase the burn-up of the fuel, it is planned to further extend the period of use of fuel cladding tubes, etc.
For this reason, there is a demand for higher performance of zirconium alloys, particularly for further improvement in corrosion resistance.
すなわち、ジルコニウム合金の腐食の問題は、原子炉内
で長期間中性子照射をうけること、および高温高圧の冷
却水に接することに起因する。ジルコニウムの酸化膜は
、腐食初期は黒色で均一な膜厚を有し、次第に均一な腐
食膜の厚みが増加していく。That is, the problem of corrosion of zirconium alloys is caused by being exposed to neutron irradiation for a long period of time in a nuclear reactor and coming into contact with high-temperature, high-pressure cooling water. The zirconium oxide film is black and has a uniform thickness at the initial stage of corrosion, and the thickness of the uniform corrosion film gradually increases.
上記の腐食対策として、製造初期工程においてβ相温度
域に加熱して焼入れするβ処理が行われており、ＢＷＲ
、ＰＷＲについても、上述のように現在、格別の問題は
ないのである。As a countermeasure against the above-mentioned corrosion, β treatment is performed in the initial manufacturing process to heat and harden the BWR to the β phase temperature range.
, PWR, as mentioned above, there are currently no particular problems.
（発明が解決しようとする課題）
しかし、この処理による耐食性向上だけでは、これから
計画・実施されようとする使用期間の延長に対しては不
十分であることが明らかになってきた。(Problems to be Solved by the Invention) However, it has become clear that improving corrosion resistance through this treatment alone is insufficient to extend the period of use that will be planned and implemented in the future.
そこで本発明の目的は、原子炉の運転期間の延長に基づ
く被覆管の長期間の高温高圧水（若しくは水蒸気）によ
る管外表面の均一腐食に対して十分な耐食性を有するジ
ルコニウム合金を提供することにある。Therefore, an object of the present invention is to provide a zirconium alloy that has sufficient corrosion resistance against uniform corrosion of the outer surface of the cladding tube caused by long-term high-temperature, high-pressure water (or steam) due to the extension of the operating period of a nuclear reactor. It is in.
（課題を解決するだめの手段）
本発明者らはジルカロイ−２およびジルカロイ−４合金
に白金族元素を添加すれば、高温高圧水中の全面腐食が
一層改善されることを知見し、本発明を完成した。(Another Means to Solve the Problem) The present inventors have discovered that adding platinum group elements to Zircaloy-2 and Zircaloy-4 alloys further improves general corrosion in high-temperature, high-pressure water, and has developed the present invention. completed.
なお、それらの合金元素が耐食性向上に果たす役割は不
明であるが、Ｒｕ、 Ｒｈ、 Ｐｄ、、Ｐｔ、および八
Ｕについては次のような効果が考えられる。すなわち、
これらの元素はＺｒに比べ非常に酸化されにくい。した
がって均一腐食進行に伴い、酸化膜にとりこまれず母材
界面に濃化される。濃化層が酸素の内部拡散を抑制する
ことで均一腐食進行を遅らせると考えられる。Although it is unclear what role these alloying elements play in improving corrosion resistance, Ru, Rh, Pd, Pt, and 8U are thought to have the following effects. That is,
These elements are much less likely to be oxidized than Zr. Therefore, as the corrosion progresses uniformly, it is not incorporated into the oxide film and is concentrated at the base metal interface. It is thought that the enriched layer slows down the progress of uniform corrosion by suppressing the internal diffusion of oxygen.
ここに、本発明の要旨は、重量％で、Ｓｎ ： ０．５
〜１．７％、Ｆｅ ： ０．０５〜０．５％、Ｃｒ：
０．０５〜０．３％、さらにＲｕ、 Ｒｈ、 Ｐｄ、
Ｐｔ、 ＡｕＯ中から１種または２種以上の合計が０．
００１〜１．０％を含有し、残部がＺｒと不可避の不純
物からなる高耐食性ジルコニウム合金であり、さらに所
望によりこの合金にＮｉ：０．０１〜０．１％および／
またはＮｂ ： ０．００５〜０．５％を加えた合金で
ある。Here, the gist of the present invention is that in weight %, Sn: 0.5
~1.7%, Fe: 0.05~0.5%, Cr:
0.05-0.3%, further Ru, Rh, Pd,
The total amount of one or more of Pt and AuO is 0.
This is a highly corrosion-resistant zirconium alloy containing 0.01 to 1.0% of Ni and the remainder consisting of Zr and unavoidable impurities.If desired, this alloy may also contain 0.01 to 0.1% of Ni and
Or, it is an alloy to which Nb: 0.005 to 0.5% is added.
（作用）
以下、本発明の合金において、含有成分の種類とその含
有量を上記のように選んだ理由を作用効果とともに説明
する。(Function) Hereinafter, in the alloy of the present invention, the reasons for selecting the types of components and their contents as described above will be explained together with the functions and effects.
Ｓｎ： Ｚｒの耐食性は、不純物の窒素により劣化する。Sn: The corrosion resistance of Zr deteriorates due to impurity nitrogen.
Ｓｎはこの窒素の悪影響を除去するため添加されている
。しかし、最近のスポンジＺｒの窒素レベルは数１０ｐ
ｐｍに抑えられており、製造工程での窒素吸収も最小限
になるよう配慮されているので、従来のジルカロイのＳ
ｎ含有量より低い範囲にしてよい。Sn is added to remove the adverse effects of nitrogen. However, the nitrogen level of recent sponge Zr is several tens of points.
PM and nitrogen absorption during the manufacturing process is also minimized, making it possible to reduce the amount of nitrogen absorbed by conventional Zircaloy.
It may be in a range lower than the n content.
多量の添加はむしろ耐食性を劣化させるので、含有量の
上限は１．７％にする。一方、耐食性効果は０．５％以
上で現われるとともにジルコニウム合金の強度を向上さ
せる成分であるから、その効果を狙って下限を０．５％
とする。Since addition of a large amount actually deteriorates corrosion resistance, the upper limit of the content is set at 1.7%. On the other hand, since the corrosion resistance effect appears at 0.5% or more and it is a component that improves the strength of zirconium alloy, the lower limit was set at 0.5% to achieve this effect.
shall be.
Ｆｅ：
Ｆｅも耐食性の改善に有効である。この効果が現れる０
、０５％を下限とし、冷間加工性に悪影響を生しるおそ
れのある多量添加を避けるため、上限を０．５％とする
。Fe: Fe is also effective in improving corrosion resistance. This effect appears 0
The lower limit is set to 0.05%, and the upper limit is set to 0.5% to avoid adding a large amount that may have an adverse effect on cold workability.
Ｃｒ：
Ｃｒの作用効果はＦｅとほぼ同じである。耐食性向上の
効果を得るためには０．０５％の含有量が必要である。Cr: The effects of Cr are almost the same as those of Fe. In order to obtain the effect of improving corrosion resistance, a content of 0.05% is required.
Ｃｒは熱処理の過程で金属間化合物を析出させやすいの
で上限は０．３％とする。Since Cr tends to precipitate intermetallic compounds during heat treatment, the upper limit is set to 0.3%.
Ｎｉ：
Ｎｉは０．０１％から耐食性の向上の効果を発揮するの
で下限を０．０１％とする。一方、Ｎｉは腐食時に発生
する水素を合金中に取り込み、水素脆性を起こす一因と
なる。従って、０．１％以下の範囲で含有させることと
する。Ni: Since Ni exhibits the effect of improving corrosion resistance from 0.01%, the lower limit is set to 0.01%. On the other hand, Ni incorporates hydrogen generated during corrosion into the alloy, contributing to hydrogen embrittlement. Therefore, it is decided to contain it in a range of 0.1% or less.
Ｎｂ：
Ｎｂは耐食性の向上に効果があり、同時にジルコニウム
合金の水素吸収を抑制する効果をもつ。Nb: Nb is effective in improving corrosion resistance, and at the same time has the effect of suppressing hydrogen absorption in the zirconium alloy.
これらの効果が顕著に現れるのは含有量ｏ、ｏｉ％以上
からである。しかし、０．５％を超えると耐均一腐食性
を劣化させるため０．５％を上限とする。These effects become noticeable when the content is o, oi% or higher. However, if it exceeds 0.5%, uniform corrosion resistance deteriorates, so the upper limit is set at 0.5%.
Ｒｕ、、Ｒｈ、 Ｐｄ、 Ｐｔ、およびＡｕ：これら停
元素ＩＵ合計０．００１％以上の含有量でジルコニウム
合金の耐食性を改善する。しかしいずれも高価な元素で
あるとともに多量に添加すると腐食時に発生する水素を
合金中に取込み、水素脆性を引き起す一因となるため上
限を１．０％とする。Ru, Rh, Pd, Pt, and Au: The corrosion resistance of the zirconium alloy is improved by a total IU content of 0.001% or more of these stop elements. However, both are expensive elements and if added in large amounts, hydrogen generated during corrosion will be incorporated into the alloy, causing hydrogen embrittlement, so the upper limit is set at 1.0%.
またこれらの元素は、はぼ均等な作用効果を有するため
２種以上選択して含有させてもよく、その含有量の範囲
も合計量で１種のみ単独添加の場合と同等である。In addition, since these elements have substantially equal effects, two or more of these elements may be selected and contained, and the range of their content is the same as in the case where only one element is added alone in total amount.
以下、本発明を実施例によって更に詳しく説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
（実施例）
添加成分の含有量を変えた多数の合金を溶製し、耐食性
に及ぼず影響を調べた。試験の基本条件は下記のとおり
である。(Example) A large number of alloys with varying contents of additive components were melted and the effects on corrosion resistance were investigated. The basic conditions of the test are as follows.
１、試験材（板厚０．６ ｍｍ ）の製作■ β処理
： １０５０℃×３０分、水冷■ 熱間加ヱ：６５０
℃
■ 最終冷間加工： 加工度８５％
■ 歪取り焼鈍 ＝４６０°ｃｘｌ、５時間（冷却速度
０．１°Ｃ／秒）
ｉｉ、試験片
サイズ： ２０ ｍｍ” Ｘ３０ｍｍ’ Ｘｏ、６
ｍｍＴに加工し＃１０００のペーパーで研磨して、５
Ｖｏｌ、％ＨＦ−４５Ｖｏ１．％ＨＮＯ３５０ＶＯ１，
％Ｈ，Ｏで酸洗。1. Production of test material (plate thickness 0.6 mm) ■ β treatment
: 1050℃ x 30 minutes, water cooling■ Hot heating: 650
°C ■ Final cold working: 85% workability ■ Strain relief annealing = 460°cxl, 5 hours (cooling rate 0.1°C/sec) ii, specimen size: 20 mm" X30 mm' Xo, 6
Processed to mmT and polished with #1000 paper, 5
Vol, %HF-45Vol1. %HNO350VO1,
Pickling with %H,O.
ｉｉｉ 、腐食試験
水蒸気オートクレーブを用いて、４１０℃×１０５ｋｇ
ｆ／ｃｍ２Ｘ ３５００時間の試験をし、単位面積当た
りの腐食増量を調べた。iii. Corrosion test using steam autoclave, 410℃ x 105kg
A test was conducted at f/cm2X for 3,500 hours to examine the corrosion increase per unit area.
第１表に溶製した本発明合金、従来合金および比較合金
の分析結果と腐食試験結果を示す。Table 1 shows the analysis results and corrosion test results of the inventive alloy, conventional alloy, and comparative alloy.
第１表から、本発明合金は優れた耐全面腐食性を有する
ことがわかる。なお原子炉中ではノジュラー腐食（白点
状腐食）が問題になることがあるが、本発明合金はこの
種の腐食にも優れていることが容易に推察される。From Table 1, it can be seen that the alloy of the present invention has excellent general corrosion resistance. Although nodular corrosion (white spot corrosion) may be a problem in a nuclear reactor, it is easily inferred that the alloy of the present invention is also excellent in this type of corrosion.
（発明の効果）
実施例の試験結果にも明らかなとおり、長期の腐食試験
における本発明合金の耐食性は極めて優れている。従っ
て、この合金は、例えば、原子炉の燃料被覆材のごとく
、高温・高圧水もしくは水蒸気にふれる環境で使用され
る部材用として、機器の寿命の延長に寄与するところが
大きい。(Effects of the Invention) As is clear from the test results of Examples, the corrosion resistance of the alloy of the present invention in long-term corrosion tests is extremely excellent. Therefore, this alloy greatly contributes to extending the life of equipment, for example, when used as a fuel cladding material for a nuclear reactor, which is used in an environment where it comes into contact with high-temperature, high-pressure water or steam.
Claims (3)
０５〜０．５％、Ｃｒ：０．０５〜０．３％、さらにＲ
ｕ、Ｒｈ、Ｐｄ、Ｐｔ、Ａｕの中から１種または２種以
上の合計が０．００１〜１．０％を含有し、残部がＺｒ
と不可避の不純物からなる高耐食性ジルコニウム合金。(1) In weight%, Sn: 0.5 to 1.7%, Fe: 0.
05 to 0.5%, Cr: 0.05 to 0.3%, and further R
The total amount of one or more of u, Rh, Pd, Pt, and Au is 0.001 to 1.0%, and the remainder is Zr.
A highly corrosion-resistant zirconium alloy consisting of unavoidable impurities.
〜０．１％を加えた合金。(2) The alloy according to claim (1) further contains Ni: 0.01
Alloy with ~0.1% addition.
ｂ：０．００５〜０．５％を加えた合金。(3) The alloy according to claim (1) or (2) further contains N.
b: Alloy containing 0.005 to 0.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4121588A JPH01215943A (en) | 1988-02-24 | 1988-02-24 | High corrosion-resistant zirconium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4121588A JPH01215943A (en) | 1988-02-24 | 1988-02-24 | High corrosion-resistant zirconium alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01215943A true JPH01215943A (en) | 1989-08-29 |
Family
ID=12602176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4121588A Pending JPH01215943A (en) | 1988-02-24 | 1988-02-24 | High corrosion-resistant zirconium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01215943A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074521A (en) * | 2013-01-16 | 2013-05-01 | 上海大学 | Palladium-containing zirconium alloy for fuel cladding in nuclear power station |
| CN112481522A (en) * | 2020-04-13 | 2021-03-12 | 国核锆铪理化检测有限公司 | Zirconium alloy, preparation method of zirconium alloy and zirconium alloy section |
-
1988
- 1988-02-24 JP JP4121588A patent/JPH01215943A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074521A (en) * | 2013-01-16 | 2013-05-01 | 上海大学 | Palladium-containing zirconium alloy for fuel cladding in nuclear power station |
| CN112481522A (en) * | 2020-04-13 | 2021-03-12 | 国核锆铪理化检测有限公司 | Zirconium alloy, preparation method of zirconium alloy and zirconium alloy section |
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