JPH01191756A - Corrosion-resistant zirconium alloy - Google Patents
Corrosion-resistant zirconium alloyInfo
- Publication number
- JPH01191756A JPH01191756A JP1652388A JP1652388A JPH01191756A JP H01191756 A JPH01191756 A JP H01191756A JP 1652388 A JP1652388 A JP 1652388A JP 1652388 A JP1652388 A JP 1652388A JP H01191756 A JPH01191756 A JP H01191756A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- corrosion
- alloy
- zirconium alloy
- zirconium
- 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 72
- 230000007797 corrosion Effects 0.000 title claims abstract description 72
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 37
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 8
- 238000000137 annealing Methods 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052718 tin Inorganic materials 0.000 abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 abstract description 3
- 238000005097 cold rolling Methods 0.000 abstract description 2
- 238000005098 hot rolling Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910001257 Nb alloy Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 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
- 230000008859 change Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Metal Rolling (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高耐食性を有するジルコニウム合金に関し、
特に、原子炉等におけるような高温・高圧の水又は水蒸
気中で使用される部材の素材に適した高耐食性ジルコニ
ウム合金に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a zirconium alloy having high corrosion resistance,
In particular, the present invention relates to a highly corrosion-resistant zirconium alloy suitable as a material for members used in high-temperature, high-pressure water or steam, such as in nuclear reactors.
（従来の技術）
ジルコニウム合金は、強度等適当な機械的性質を有し、
熱中性子吸収断面積も小さく且つ耐食性にも優れている
ことから、例えば沸騰水型原子炉（ＢＷＲ）および加圧
水型原子炉（ＰＷＲ）の燃料被覆管や炉心構造部材等の
素材として使用されている。(Prior art) Zirconium alloy has suitable mechanical properties such as strength,
Because it has a small thermal neutron absorption cross section and excellent corrosion resistance, it is used, for example, as a material for fuel cladding tubes and core structural members of boiling water reactors (BWRs) and pressurized water reactors (PWRs). .
これまでに使用されきた代表的なジルコニウム合金は、
Ｚｒ−３ｎ−Ｆｅ−Ｃｒ−Ｎｉ系のジルカロイ〜２（Ｊ
ＩＳ ＩＩ ４７５１ ＺｒＴＮ ８０２ Ｄ）および
Ｚｒ−５ｎ−Ｆｅ−Ｃｒ系のジルカロイ−４（ＪｒＳ
Ｈ４７５１ＺｒＴＮ ８０４ Ｄ）であり、さらに、上
記以外のものとしては、カナダＣＡＮＤＵ炉の圧力管と
して使用実績が豊富なＺｒ−２，５Ｎｂをはじめとする
Ｚｒ −Ｎｂ系合金がある。Typical zirconium alloys that have been used so far are:
Zr-3n-Fe-Cr-Ni-based Zircaloy~2(J
IS II 4751 ZrTN 802 D) and Zr-5n-Fe-Cr based Zircaloy-4 (JrS
H4751ZrTN 804 D), and in addition to the above, there are Zr-Nb alloys including Zr-2,5Nb, which has been widely used as pressure pipes in Canadian CANDU reactors.
上記のジルコニウム合金は、現在稼働しているＢＷＲお
よびＰＷＲ等の原子炉において、その運転条件下で必要
な機能を発揮しているが、近年、その条件も変わりつつ
ある。その一つに、燃料燃焼度をさらに上昇させる目的
から、前記燃料被覆管や炉心構造部材等の使用期間を現
状よりもさらに延長する計画がある。The above-mentioned zirconium alloys exhibit the necessary functions under the operating conditions in nuclear reactors such as BWRs and PWRs currently in operation, but these conditions have been changing in recent years. One of these is a plan to further extend the usage period of the fuel cladding tubes, core structural members, etc., in order to further increase the fuel burn-up.
このような計画に対して、前述したジルカロイをはじめ
とするジルコニウム合金では、その計画期間に十分耐え
うるだけの耐食性を有していないと予想されている。こ
のため、高性能のジルコニウム合金、特に耐食性がより
高いジルコニウム合金の開発が要望されている。It is expected that zirconium alloys, such as the aforementioned Zircaloy, do not have sufficient corrosion resistance to withstand such plans. Therefore, there is a demand for the development of high-performance zirconium alloys, particularly zirconium alloys with higher corrosion resistance.
（発明が解決しようとする課題）
ところで、原子炉におけるジルコニウム合金は、原子炉
内で長期間にわたり中性子照射を受けることおよび高温
高圧の冷却水に接することによって腐食が生じる。そし
て、腐食によって生じた酸化膜は、腐食初期は黒色で均
一な膜厚である０ｇ食の進行によりＢＷＲではノジュラ
ー腐食と呼ばれる白色のこぶ状酸化膜が、前記黒色の均
一腐食膜の上に生成する。一方、ＰＷＲではノジュラー
腐食は発生せずに均一腐食のみが進行して、腐食膜の厚
みが増加していく。(Problems to be Solved by the Invention) By the way, zirconium alloys in nuclear reactors undergo corrosion due to being exposed to neutron irradiation for a long period of time in the nuclear reactor and coming into contact with high-temperature, high-pressure cooling water. The oxide film produced by corrosion is black and has a uniform thickness at the initial stage of corrosion.As 0g corrosion progresses, a white nodular oxide film called nodular corrosion is formed on the black uniform corrosion film in BWR. do. On the other hand, in PWR, no nodular corrosion occurs, only uniform corrosion progresses, and the thickness of the corrosion film increases.
このような腐食に対して、従来の製造工程でとられてい
る対策は、β域の温度に加熱して焼入れ処理することで
ある。即ち、燃料被覆管や炉心構造部材の製造工程にお
いて、その製造初期工程でβ域の温度に加熱して焼入れ
して耐食性を向上させている。この焼入れ処理は特にノ
ジュラー腐食の防止に対する寄与が大きい。その確かな
理由は未だ不明であるが、焼入れ処理することで金属間
化合物の微細分散化が進み、耐食性が向上するものと考
えられている。The countermeasure taken in conventional manufacturing processes against such corrosion is to perform a quenching treatment by heating to a temperature in the β range. That is, in the manufacturing process of fuel cladding tubes and core structural members, corrosion resistance is improved by heating and quenching to a temperature in the β range in the initial manufacturing process. This hardening treatment has a particularly large contribution to preventing nodular corrosion. Although the exact reason for this is still unknown, it is believed that the quenching process promotes fine dispersion of intermetallic compounds and improves corrosion resistance.
しかし、上記の焼入れ処理のみではこれから計画実施さ
れようとしている使用期間延長に対して耐食性、特に耐
均一腐食性が不十分であることが近年判明してきた。However, it has recently become clear that the above-mentioned quenching treatment alone is insufficient in corrosion resistance, particularly uniform corrosion resistance, for the planned extended period of use.
ここに均一腐食とは、まさに腐食が均一に発生すること
をいい、耐均一腐食性が悪いとその均一腐食膜の厚みの
増加が大きくなる。Uniform corrosion here simply means that corrosion occurs uniformly, and if the uniform corrosion resistance is poor, the thickness of the uniform corrosion film will increase significantly.
均一腐食性を改善する方法も従来から提案されている。Methods for improving uniform corrosion have also been proposed.
例えば、Ｚｒ−３ｎ−Ｎｂ合金にＦｅ、 Ｃｒ、 Ｍｏ
等の第３元素を添加した合金を比較的低温で加工する方
法（特開昭６１−１７０５５２号公報）がある、しかし
、この方法でも、使用期間延長の条件を満たすまでの耐
食性を付与するまでに到っていないのが実状である。For example, Zr-3n-Nb alloy contains Fe, Cr, Mo
There is a method (Japanese Unexamined Patent Application Publication No. 170552/1983) in which alloys containing a third element, such as The reality is that this has not yet been achieved.
なお、前述したジルカロイ−２およびＺｒ＝Ｎｂ系合金
はノジュラー腐食に対しては優れた耐食性を示すことは
認められているが、均一腐食に対しては十分な耐食性を
有していない。Although it is recognized that the aforementioned Zircaloy-2 and Zr=Nb alloys exhibit excellent corrosion resistance against nodular corrosion, they do not have sufficient corrosion resistance against uniform corrosion.
本発明の目的は、高温・高圧の水又は水蒸気中で耐食性
に優れたジルコニウム合金、特に耐均一腐食性に優れる
新しいジルコニウム合金を提供することにある。An object of the present invention is to provide a zirconium alloy that has excellent corrosion resistance in high-temperature, high-pressure water or steam, particularly a new zirconium alloy that has excellent uniform corrosion resistance.
（課題を解決するための手段）
これまで使用されてきた従来のジルカロイ等のジルコニ
ウム合金では、前述した燃料高燃焼度化および燃料寿命
の延長計画に対しては、その耐食性が不十分である。ジ
ルコニウム合金の耐食性を向上させるは、製造工程を変
更する方法もあるが、製造工程を変更しても充分な耐食
性を得ることは困難である。そこで、本発明者らは製造
工程を変更することなく、より高い耐食性、特に耐均一
腐食性により優れた新しい組成のジルコニウム合金を見
出すべく種々実験を行った結果、Ｚｒ基合金の均一腐食
性は、Ｚｒ −Ｓｎ基合金にＣｕを添加することで改善
されること、従来のジルカロイで添加しているＦｅ、
ＣｒおよびＮｉをさらに添加したＺｒ基合金でもＣｕを
添加することで耐均一腐食性が著しく改善されることを
見出し、本発明を完成した。(Means for Solving the Problems) Conventional zirconium alloys such as Zircaloy that have been used so far have insufficient corrosion resistance to meet the above-mentioned plans for increasing fuel burnup and extending fuel life. One way to improve the corrosion resistance of zirconium alloys is to change the manufacturing process, but it is difficult to obtain sufficient corrosion resistance even by changing the manufacturing process. Therefore, the present inventors conducted various experiments to find a new composition of zirconium alloy with higher corrosion resistance, especially superior uniform corrosion resistance, without changing the manufacturing process. As a result, the uniform corrosion resistance of Zr-based alloy , that it is improved by adding Cu to Zr-Sn-based alloy, that Fe added in conventional Zircaloy,
The present invention was completed based on the discovery that even in a Zr-based alloy to which Cr and Ni are further added, uniform corrosion resistance is significantly improved by adding Cu.
ここに、本発明の要旨とするところは下記の■、■およ
び■にある。Here, the gist of the present invention lies in the following (1), (2), and (2).
０重量％で、Ｓｎ：０．５〜１．７％、Ｃｕ：０．０１
〜１．５％を含有し、残部がＺｒおよび不可避不純物で
ある高耐食性ジルコニウム合金。0% by weight, Sn: 0.5-1.7%, Cu: 0.01
A highly corrosion resistant zirconium alloy containing ~1.5% with the balance being Zr and unavoidable impurities.
０重量％で、Ｓｎ：０．５〜１．７％、Ｃｕ：０．０１
〜１．５％を含有し、さらにＦｅ：０．５％以下とＣｒ
：０．３％以下を含有し、残部がＺｒおよび不可避不純
物である高耐食性ジルコニウム合金。0% by weight, Sn: 0.5-1.7%, Cu: 0.01
~1.5%, further Fe:0.5% or less and Cr
: A highly corrosion-resistant zirconium alloy containing 0.3% or less, with the remainder being Zr and unavoidable impurities.
■重量％で、Ｓｎ：０．５〜１．７％、Ｃｕ：０．０１
〜１．５％を含存し、さらにＦｅ：０．５％以下、Ｃｒ
：０．３％以下およびＮｉ：０．１％以下を含有し、残
部がＺｒおよび不可避不純物である高耐食性ジルコニウ
ム合金。■In weight%, Sn: 0.5-1.7%, Cu: 0.01
~1.5%, further Fe: 0.5% or less, Cr
A highly corrosion-resistant zirconium alloy containing: 0.3% or less and Ni: 0.1% or less, with the balance being Zr and unavoidable impurities.
Ｚｒ −Ｓｎ １５合金にＣｕを添加すること、および
ジルカロイで添加しているＦｅ、 Ｃｒ、 Ｎｉをさら
に前記合金に添加したＺｒ基合金にＣｕを添加すること
で耐均一腐食性が向上する確固たる理由は不明であるが
、以下のような機構によるものと考えられる。Solid reason why homogeneous corrosion resistance is improved by adding Cu to Zr-Sn 15 alloy and adding Cu to Zr-based alloy, which is made by adding Fe, Cr, and Ni added in Zircaloy to the alloy. Although it is unclear, it is thought to be due to the following mechanism.
即ち、Ｚｒ −Ｓｎ −Ｃｕ系合金において均一腐食が
進行する場合、Ｃｕはジルコニウムよりも酸化されにく
い元素であり、ジルコニウムのみの酸化が進行する。含
有されているＣｕは金属と酸化膜の境界に濃縮され、こ
のｃｕ＆Ｊｉｔ層により酸素の拡散が抑制されるからと
考えられる。That is, when uniform corrosion progresses in a Zr-Sn-Cu alloy, Cu is an element that is more difficult to oxidize than zirconium, and only zirconium is oxidized. This is thought to be because the contained Cu is concentrated at the boundary between the metal and the oxide film, and this cu&Jit layer suppresses the diffusion of oxygen.
（作用）
以下に成分組成を上記の通りに限定した理由について説
明する。(Function) The reason why the component composition is limited as described above will be explained below.
なお、元素の含有量の％は、特に指定のない限り重量％
である。In addition, the content percentage of elements is weight% unless otherwise specified.
It is.
Ｓｎ：
Ｓｎは、不純物として混入しＺｒの耐食性を劣化する窒
素の悪影響を抑えるのに有効な元素である。Sn: Sn is an element effective in suppressing the adverse effects of nitrogen, which is mixed as an impurity and degrades the corrosion resistance of Zr.
この不可避的に混入する窒素は、スポンジＺｒを溶製す
る場合、現行の溶製技術では数ＩＱｐｐｍ以下にするこ
とができるとともに、その後の製造工程中における吸収
も最小限となるように管理されている。したがって、本
発明のジルコニウム合金では、ジルカロイ （Ｓｎ含有
ｆｆ１１．２０〜１．７０％）のように下限を１．２％
に制限する必要（ｌない。When melting sponge Zr, this unavoidable nitrogen can be reduced to a few IQppm or less using current melting technology, and it is also managed to minimize absorption during the subsequent manufacturing process. There is. Therefore, in the zirconium alloy of the present invention, the lower limit is 1.2% like Zircaloy (Sn content ff11.20-1.70%).
There is no need to limit it to
また、Ｓｎは強度の確保上重要な元素である。したがっ
て、耐食性および強１１６！保のうえから０．５を下限
とする。一方、多量に添加するとジルコニウム合金の耐
均一腐食性を劣化させることになるのでその上限は１．
７％とするのがよい。Further, Sn is an important element for ensuring strength. Therefore, corrosion resistance and strength 116! The lower limit is set at 0.5 from the viewpoint of safety. On the other hand, if added in a large amount, the uniform corrosion resistance of the zirconium alloy will deteriorate, so the upper limit is 1.
A good value is 7%.
Ｃｕ：
Ｃｕは、耐食性を向上させる効果がある。Ｚｒ−５ｎ系
合金にＣｕを添加すると耐均一腐食性は著しく向上する
。また、この合金にさらにＦｅ５Ｃｒ、 Ｎｉを添加し
たＺｒ基合金でも同様に耐均一腐食性が向上する。その
含有量が０．０１％より少ないと耐食性の向上が小さく
、一方、１．５％を超えて含有されるとＺｒｌＣｕ、
ＺｒＣｕ等の金属間化合物の析出量が増して耐食性およ
び冷間加工性を劣化させる。Cu: Cu has the effect of improving corrosion resistance. When Cu is added to Zr-5n alloy, uniform corrosion resistance is significantly improved. Further, a Zr-based alloy in which Fe5Cr and Ni are further added to this alloy also has improved homogeneous corrosion resistance. If the content is less than 0.01%, the improvement in corrosion resistance will be small, while if the content exceeds 1.5%, ZrlCu,
The amount of precipitated intermetallic compounds such as ZrCu increases, deteriorating corrosion resistance and cold workability.
以上の成分の外、残部がＺｒおよび不可避不純物からな
るものが第１の発明のジルコニウム合金である。第２の
発明のジルコニウム合金は、これらの元素に加えて更に
Ｆｅ：０．５％以下とＣｒ：０．３％以下を含有するも
のおよび第３の発明のジルコニウム合金は、これらの元
素に更にＮｉ：０．１％以下を含有するものである。In addition to the above components, the zirconium alloy of the first invention consists of Zr and unavoidable impurities. The zirconium alloy of the second invention further contains Fe: 0.5% or less and Cr: 0.3% or less in addition to these elements, and the zirconium alloy of the third invention further contains these elements. Ni: Contains 0.1% or less.
これらＦｅ、 ＣｒおよびＮｉの作用効果は次の通りで
ある。The effects of these Fe, Cr and Ni are as follows.
Ｆｅ：
・Ｆｅも耐食性を向上させる作用効果がある。しかし、
多量に含有させると冷間加工性を損なうので、その含有
量を０．５％以下とする。好ましい範囲は、０．０５％
〜０．Ｓ％である。Fe: -Fe also has the effect of improving corrosion resistance. but,
Since a large amount of Ni impairs cold workability, the content is limited to 0.5% or less. The preferred range is 0.05%
~0. It is S%.
Ｃｒ：
ＣｒもＦｅと同様の作用効果がある。しかし、Ｃｒは熱
処理に敏感な元素であって、ＺｒＣｒｔの金属間化合物
となって析出しやすく、多量に添加すると金属間化合物
の析出量が増して逆に耐食性を劣化させることになるの
で、その含有量を０．３％以下とする。好ましい範囲は
、０．０５％〜０．３％である。Cr: Cr also has the same effect as Fe. However, Cr is an element that is sensitive to heat treatment and easily precipitates as an intermetallic compound of ZrCrt.Adding a large amount increases the amount of intermetallic compound precipitated and conversely deteriorates corrosion resistance. The content shall be 0.3% or less. The preferred range is 0.05% to 0.3%.
Ｎｉ ：
Ｎｉは耐食性向上に少量から非常に有効な元素であるが
、含有量の増加につれ腐食時に発生する水素を母材中に
取り込む量も多くなり、水素脆化を起こす一因となる。Ni: Ni is an element that is very effective in improving corrosion resistance even in small amounts, but as its content increases, the amount of hydrogen generated during corrosion is taken into the base metal, which becomes a cause of hydrogen embrittlement.
即ち、その含有量が０，１％を超えると水素脆化が生じ
やすくなる。好ましい範囲は、０．０１％〜０．１％で
ある。That is, if the content exceeds 0.1%, hydrogen embrittlement is likely to occur. The preferred range is 0.01% to 0.1%.
以下、実施例によって本発明を更に具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
（実施例）
アルゴンアークボタン溶解炉を用いて、第１表に示す合
金成分の小型インゴット（約０．５ｋｇ）を溶製し、次
いで、Ｉ Ｘ １０−’Ｔｏｒｒの真空雰囲気中で１０
００°Ｃ×２時間加熱して溶体化処理を施した後、下記
の製造条件で熱間圧延、中間焼鈍、冷間圧延および最終
焼鈍して板厚２ＩＩＩ１１の板状試料を製作した。(Example) A small ingot (approximately 0.5 kg) having the alloy components shown in Table 1 was melted using an argon arc button melting furnace, and then melted in a vacuum atmosphere of I
After performing solution treatment by heating at 00°C for 2 hours, hot rolling, intermediate annealing, cold rolling and final annealing were performed under the following manufacturing conditions to produce a plate-shaped sample with a plate thickness of 2III11.
熱１旧り延２：
アルゴンガス雰囲気中で７００℃×２時間加熱後、６０
％の加工度で圧延。Heat 1 Old Roll 2: After heating at 700°C for 2 hours in an argon gas atmosphere,
% rolling.
主町炸鍾：
Ｉ Ｘ １０” ’Ｔｏｒｒの真空雰囲気中で６００°
ＣＸ２時間加熱後、炉冷。Main Town: I x 10” 600° in a vacuum atmosphere of Torr
After heating CX for 2 hours, cool in the furnace.
痘皿圧延； ７５％の加工度で圧延。Pox plate rolling; Rolled with 75% workability.
最終焼鈍：
Ｉ Ｘ １０− ’Ｔｏｒｒの真空雰囲気中で４５０℃
×２時間加熱後、炉冷。Final annealing: 450°C in a vacuum atmosphere of I x 10-' Torr
After heating for 2 hours, cool in the furnace.
このようにして得られた板状試料から２０穏■幅×２０
＋ｎｌ１１長さの腐食試験片を作成し、下記の（ａ）〜
（ｅ）に示す前処理を施した後、腐食試験を行った。From the plate-shaped sample obtained in this way,
Create a corrosion test piece with a length of +nl11, and perform the following (a) ~
After performing the pretreatment shown in (e), a corrosion test was conducted.
（ａ） １６００のＳｉＣペーパで表面を研磨。(a) Surface polished with 1600 SiC paper.
（ｂ）研磨後、硝弗酸（５ｖｏｊ！％ＨＦ ４５ｖｏ
ｊ！％ＨＮＯｓ−５Ｑｖｏ １％ＨｔＯ）にて２分間
酸洗。(b) After polishing, nitrofluoric acid (5voj!%HF 45vo
j! %HNOs-5Qvo 1%HtO) for 2 minutes.
（Ｃ）酸洗後、流水中で１０分間洗浄。(C) After pickling, wash in running water for 10 minutes.
（ｄ）イオン交換水中で３０分間煮沸。(d) Boiling in ion-exchanged water for 30 minutes.
（ｅ）エタノールで洗浄後、乾燥基中で１時間乾燥。(e) After washing with ethanol, dry for 1 hour in a desiccator.
腐食試験には、例えばジルカロイの耐食性判定に適用さ
れている、ｓｏｏ ’ｃ近傍で行うフジエラー腐食性判
定法と、４００°Ｃの温度で７２時間加熱して行うＡＳ
ＴＭ Ｇ２による判定法がある。しかし、これら判定法
では長期にわたる耐均一腐食性の判定には不十分なため
、この実施例では前記前処理後の腐食試験片を３９０°
Ｃの水蒸気中で１０５ ｋｇ／ｃＪの圧力を付加して３
２００時間保持する水蒸気オートクレーブ処理により行
い、試験末期の腐食速度の大きさで耐食性の判定を行っ
た。その結果を同じく第１表に示す。Corrosion tests include, for example, the Fuji error corrosion test method, which is performed near soo'c, which is applied to determine the corrosion resistance of Zircaloy, and the AS test, which is performed by heating at a temperature of 400°C for 72 hours.
There is a determination method based on TM G2. However, these evaluation methods are insufficient for determining long-term uniform corrosion resistance, so in this example, the corrosion test piece after the pretreatment was
3 by applying a pressure of 105 kg/cJ in water vapor of C.
A steam autoclave treatment was performed for 200 hours, and the corrosion resistance was determined based on the corrosion rate at the end of the test. The results are also shown in Table 1.
第 １ 表
第 １ 表 （続き１）
第 １ 表（続き２）
＊；本発明の範囲外
なお、第１表の比較合金のうち試料Ｎｏ、１の合金は、
ＪＩＳ Ｈ４７５１ＺｒＴＮ ８０２ Ｄに相当するも
のおよび試料Ｎｏ、２の合金はＪＩＳ Ｈ４７５１Ｚｒ
ＴＮ ８０４ Ｄに相当するものである。Table 1 Table 1 (Continued 1) Table 1 (Continued 2) *; Outside the scope of the present invention Among the comparative alloys in Table 1, the alloy of sample No. 1 was
The alloy corresponding to JIS H4751ZrTN 802 D and sample No. 2 are JIS H4751Zr
It corresponds to TN 804D.
第１表より明らかなように、本発明のジルコニウム合金
は従来合金および比較合金に比べ、腐食速度は遅く耐均
一腐食性に優れている。As is clear from Table 1, the zirconium alloy of the present invention has a lower corrosion rate and excellent uniform corrosion resistance than conventional alloys and comparative alloys.
（発明の効果）
以上説明した如く、本発明のジルコニウム合金は耐均一
腐食性に優れるから、燃料被覆管や炉心構造部材等の使
用期間が延長されても、その延長に十分耐えることがで
きる。(Effects of the Invention) As explained above, since the zirconium alloy of the present invention has excellent uniform corrosion resistance, even if the period of use of fuel cladding tubes, core structural members, etc. is extended, it can sufficiently withstand the extension.
Claims (3)
含有し、残部がＺｒおよび不可避不純物であることを特
徴とする高耐食性ジルコニウム合金。(1) A highly corrosion-resistant zirconium alloy containing, in weight percent, Sn: 0.5-1.7%, Cu: 0.01-1.5%, with the balance being Zr and inevitable impurities.
含有し、さらにＦｅ：０．５％以下とＣｒ：０．３％を
含有し、残部がＺｒおよび不可避不純物であることを特
徴とする高耐食性ジルコニウム合金。(2) Contains Sn: 0.5 to 1.7%, Cu: 0.01 to 1.5%, and further contains Fe: 0.5% or less and Cr: 0.3% in weight%. , the balance being Zr and unavoidable impurities.
含有し、さらにＦｅ：０．５％以下、Ｃｒ：０．３％以
下およびＮｉ：０．１％以下を含有し、残部がＺｒおよ
び不可避不純物であることを特徴とする高耐食性ジルコ
ニウム合金。(3) Contains Sn: 0.5 to 1.7%, Cu: 0.01 to 1.5%, and further contains Fe: 0.5% or less, Cr: 0.3% or less, and Ni : A highly corrosion-resistant zirconium alloy characterized by containing 0.1% or less, with the remainder being Zr and unavoidable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1652388A JPH01191756A (en) | 1988-01-27 | 1988-01-27 | Corrosion-resistant zirconium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1652388A JPH01191756A (en) | 1988-01-27 | 1988-01-27 | Corrosion-resistant zirconium alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01191756A true JPH01191756A (en) | 1989-08-01 |
Family
ID=11918633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1652388A Pending JPH01191756A (en) | 1988-01-27 | 1988-01-27 | Corrosion-resistant zirconium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01191756A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073336A (en) * | 1989-05-25 | 1991-12-17 | General Electric Company | Corrosion resistant zirconium alloys containing copper, nickel and iron |
| CN112458337A (en) * | 2020-04-13 | 2021-03-09 | 国核锆铪理化检测有限公司 | Zirconium alloy, preparation method of zirconium alloy and zirconium alloy section |
-
1988
- 1988-01-27 JP JP1652388A patent/JPH01191756A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073336A (en) * | 1989-05-25 | 1991-12-17 | General Electric Company | Corrosion resistant zirconium alloys containing copper, nickel and iron |
| CN112458337A (en) * | 2020-04-13 | 2021-03-09 | 国核锆铪理化检测有限公司 | Zirconium alloy, preparation method of zirconium alloy and zirconium alloy section |
| CN112458337B (en) * | 2020-04-13 | 2022-02-18 | 国核宝钛锆业股份公司 | Zirconium alloy and preparation method of zirconium alloy profile |
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