JPH02209443A - Corrosion-resistant zirconium alloy - Google Patents
Corrosion-resistant zirconium alloyInfo
- Publication number
- JPH02209443A JPH02209443A JP3065789A JP3065789A JPH02209443A JP H02209443 A JPH02209443 A JP H02209443A JP 3065789 A JP3065789 A JP 3065789A JP 3065789 A JP3065789 A JP 3065789A JP H02209443 A JPH02209443 A JP H02209443A
- Authority
- JP
- Japan
- Prior art keywords
- corrosion resistance
- alloy
- corrosion
- deterioration
- zirconium alloy
- 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
- 230000007797 corrosion Effects 0.000 title claims abstract description 67
- 238000005260 corrosion Methods 0.000 title claims abstract description 67
- 229910001093 Zr alloy Inorganic materials 0.000 title claims abstract description 34
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 230000006866 deterioration Effects 0.000 abstract description 10
- 239000000446 fuel Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 47
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 230000000694 effects Effects 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 238000010521 absorption reaction Methods 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
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005253 cladding Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、軽水冷却原子炉の燃料被覆管やチャンネルボ
ックスの如く、高温高圧の水中や水蒸気中での使用に適
した高耐食性ジルコニウム合金に関する。なお、本明細
書において耐食性とは、特にことわりのない限り、耐均
一腐食性を指す。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a highly corrosion-resistant zirconium alloy suitable for use in high-temperature, high-pressure water or steam, such as fuel cladding tubes and channel boxes for light water-cooled nuclear reactors. . Note that in this specification, corrosion resistance refers to uniform corrosion resistance unless otherwise specified.
ジルコニウムは、周知の如く、熱中性子吸収断面積が小
さく、その合金は、高温強度等の機械的性質に優れ、且
つ耐食性にも著しく優れている。As is well known, zirconium has a small thermal neutron absorption cross section, and its alloys have excellent mechanical properties such as high-temperature strength and extremely excellent corrosion resistance.
このことから、ジルコニウム合金は、熱中性子を利用す
る原子炉の炉心構造部材に多く使用されており、最も代
表的な使用例としては、軽水冷却原子炉の燃料被覆管や
チャンネルボックスがある。For this reason, zirconium alloys are often used in core structural members of nuclear reactors that utilize thermal neutrons, and the most typical examples of their use are fuel cladding tubes and channel boxes in light water-cooled nuclear reactors.
すなわち、軽水冷却原子炉、特に沸騰水型原子炉の燃料
被覆管には、ジルカロイ−２（ＪＩＳＨ４７５１ＺｒＴ
Ｎ８０２Ｄ）が使用されており、同原子炉のチャンネル
ボックスおよび加圧水型原子炉の燃料舖覆管には、ジル
カロイ−４（ＪＩＳＨ４７５１ＺｒＴＮ８０４Ｄ）が使
用されている。That is, Zircaloy-2 (JISH4751ZrT
Zircaloy-4 (JISH4751ZrTN804D) is used for the channel box of the reactor and the fuel cladding of the pressurized water reactor.
これらのジルコニウム合金は、現在稼働している軽水冷
却原子炉の運転条件下では、優れた耐食性を示し、健全
な状態を保ち続けることが確認されている。このような
状況を背景として、最近では、発電コスト低減のために
、燃料使用期間の延長も計画されている。しかし、燃料
使用期間の延長に対しては、ジルカロイ−２やジルカロ
イ−４といった現行のジルコニウム合金は、十分な耐食
性を示すとは言えないことが判明してきた。It has been confirmed that these zirconium alloys exhibit excellent corrosion resistance and remain in good condition under the operating conditions of light water-cooled nuclear reactors currently in operation. Against this background, recently there are plans to extend the period of fuel use in order to reduce power generation costs. However, it has been found that current zirconium alloys such as Zircaloy-2 and Zircaloy-4 do not exhibit sufficient corrosion resistance for extended fuel usage periods.
ジルコニウム合金の耐食性を現行レベルより高めたもの
としては、ジルカロイ−４においてそのＳｎを規格より
減らして０．２〜１．１５％とし、他の合金成分はその
ままで不純物窒素を６０ｐｐｍ以下に制限したジルコニ
ウム合金が、特開昭６３−３５７４９号公報に開示され
ている。また、特開昭６２−２８７０２９号公報ニハ、
Ｆｅを０．１〜１．０％、Ｎｉを０．０１〜１．０％含
有させたジルコニウム合金も開示されている。In order to improve the corrosion resistance of zirconium alloys compared to the current level, we reduced the Sn content of Zircaloy-4 from the standard to 0.2 to 1.15%, and limited the impurity nitrogen to 60 ppm or less while keeping the other alloy components unchanged. A zirconium alloy is disclosed in JP-A-63-35749. Also, Japanese Patent Application Laid-Open No. 62-287029,
A zirconium alloy containing 0.1 to 1.0% of Fe and 0.01 to 1.0% of Ni is also disclosed.
前者のジルコニウム合金では、Ｓｎは耐食性を劣化させ
るとの観点からジルカロイ−４における規格値よりも低
く抑えている。しかし、Ｓｎは元来、耐食性改善を・目
的として添加されてきた元素で、その作用は、耐食性劣
化を引き起こす不純物窒素の働きを相殺する点にあり、
Ｓｎの減量は必ずしも好結果をもたらすとは限らない。In the former zirconium alloy, Sn is kept lower than the standard value for Zircaloy-4 from the viewpoint of deteriorating corrosion resistance. However, Sn is an element originally added for the purpose of improving corrosion resistance, and its action is to offset the action of impurity nitrogen, which causes deterioration of corrosion resistance.
Reducing the amount of Sn does not necessarily lead to favorable results.
すなわち、不純物窒素を含まない理想的な状態では、確
かにＳｎは不必要で、むしろ耐食性を悪化させる原因に
なる。前者のジルコニウム合金では、この観点から、不
純物窒素を厳しく制限した状態でＳｎ量を低下させて耐
食性の改善を図ろうとしているのである。しかるに、Ｚ
ｒは窒素ガスとの反応性が高く、軽水冷却原子炉の燃料
被覆管やヂャンネルボックスでは、加工工程で焼鈍が繰
り返されるために、不純物窒素レベルが増加する可能性
があり、これに依存した前者のジルコニウム合金は、現
実的な対策とは言えない。That is, in an ideal state that does not contain impurity nitrogen, Sn is certainly unnecessary, and rather causes deterioration of corrosion resistance. From this point of view, in the former zirconium alloy, attempts are being made to improve the corrosion resistance by reducing the amount of Sn while strictly limiting the nitrogen impurity. However, Z
r is highly reactive with nitrogen gas, and in the fuel cladding and channel boxes of light water-cooled nuclear reactors, the level of impurity nitrogen may increase due to repeated annealing during the processing process, and The former, zirconium alloy, cannot be said to be a realistic countermeasure.
さらにこの合金に添加されているＦｅ、 Ｃｒは、いず
れも耐食性向上に寄与する合金元素である。しかし両者
の添加量は現行ジルカロイ−４レヘルであり、今後の使
用期間延長により要求される耐食性向上に対して不十分
である。Furthermore, Fe and Cr added to this alloy are alloying elements that contribute to improving corrosion resistance. However, the amount of both added is currently 4 levels of Zircaloy, which is insufficient to improve the corrosion resistance required for the extended period of use in the future.
また、後者のジルコニウム合金では、Ｆｅ、 Ｎｉのみ
で耐食性を改善しようとしている。しかし、上述したと
おり、不純物窒素レベルを抑えることが困難な状態でＳ
ｎを除いてしまうと、不純物窒素による耐食性低下が懸
念され、且つＦｅ、 Ｎｉの多量添加による冷間加工性
の低下や、Ｎｉの多量添加にともなう水素吸収等も問題
になる。したがって、後者のジルコニウム合金も、現実
に則した対策とは言えない。In the latter zirconium alloy, efforts are being made to improve corrosion resistance using only Fe and Ni. However, as mentioned above, S
If n is removed, there is a concern that corrosion resistance will be lowered due to impurity nitrogen, and problems such as lower cold workability due to the addition of large amounts of Fe and Ni and hydrogen absorption due to the addition of large amounts of Ni may also arise. Therefore, the latter zirconium alloy cannot be said to be a realistic countermeasure.
本発明は、斯かる現状に鑑みなされたもので、不純物窒
素が通常レベルで含有されても、現状のジルコニウム合
金によりも優れた耐食性を有し、しかも冷間加工性の低
下や水素吸収の問題を生じない高耐食性ジルコニウム合
金を提供することを目的とする。The present invention was developed in view of the current situation, and has superior corrosion resistance than current zirconium alloys even if the impurity nitrogen is contained at a normal level, and has problems such as decreased cold workability and hydrogen absorption. The purpose of the present invention is to provide a highly corrosion-resistant zirconium alloy that does not cause corrosion.
〔課題を解決するための手段］
ジルコニウム合金の原料であるジルコニウムスポンジの
不純物窒素レベルを２０〜３０ｐｐｍ以下に抑えること
は難しい。したがって、不純物窒素による耐食性低下の
改善に有効なＳｎは、不可欠な元素と考えられる。しか
し、このＳｎは、不純物窒素による耐食性低下が改善で
きる一方で、それ自体は耐食性の低下原因になるのもま
た事実である。[Means for Solving the Problems] It is difficult to suppress the impurity nitrogen level of zirconium sponge, which is a raw material for zirconium alloy, to 20 to 30 ppm or less. Therefore, Sn is considered to be an essential element since it is effective in improving the corrosion resistance deterioration caused by impurity nitrogen. However, while this Sn can improve the reduction in corrosion resistance caused by impurity nitrogen, it is also true that it itself causes a reduction in corrosion resistance.
本発明者らは、現行のジルコニウム合金より優れた耐食
性を得るには、Ｓｎによる窒素の悪影響防止効果を確保
しつつ、Ｓｎ自体の耐食性に対する悪影響を抑えるのが
、現実的には最も得策であると考え、鋭意実験研究を繰
り返した結果、Ｎｉの微量添加が有効なことを知見した
。The present inventors believe that in order to obtain corrosion resistance superior to that of current zirconium alloys, it is realistically best to suppress the negative effects of Sn itself on corrosion resistance while ensuring the effect of Sn in preventing the negative effects of nitrogen. As a result of intensive experimental research, we discovered that adding a small amount of Ni is effective.
すなわち、Ｓｎに対して微量のＮｉを共存させると、通
常レヘルで不純物窒素が含有された場合にも、不純物窒
素に起因する耐食性低下がＳｎで改善され、なおかつＳ
ｎ自体が原因で生じる耐食性低下を補う以上にＮｉで耐
食性を改善することができるのである。しかも、Ｎｉ添
加がＳｎの耐食性劣化を抑えることにより、要求される
強度保持に必要なだけのＳｎを添加することができ、機
械的性質も満足する。In other words, when a trace amount of Ni coexists with Sn, even when impurity nitrogen is contained in the normal level, Sn improves the corrosion resistance deterioration caused by impurity nitrogen, and
Ni can improve corrosion resistance more than compensating for the decrease in corrosion resistance caused by n itself. Moreover, since the addition of Ni suppresses the deterioration of the corrosion resistance of Sn, it is possible to add just enough Sn to maintain the required strength, and the mechanical properties are also satisfied.
さらにＮｉ添加量はＦｅ、 Ｃｒ量に比べて少なく、Ｎ
ｉによる冷間加工性の低下や水素吸収の問題を発生させ
るおそれもない。Furthermore, the amount of Ni added is smaller than the amount of Fe and Cr;
There is no risk of deterioration in cold workability or problems with hydrogen absorption due to i.
本発明は、斯かる知見に基づきなされたもので、重量％
でＳｎ：０．２〜１．７％、Ｆｅ：０．０３〜０．５０
％、Ｃｒ：０．０３〜０．３０％、Ｎｉ ：０．００８
０〜０゜０３０％を含有し、残部Ｚｒおよび不可避的不
純物からなることを特徴とする高耐食性ジルコニウム合
金を要旨とする。The present invention was made based on this knowledge, and the weight %
Sn: 0.2-1.7%, Fe: 0.03-0.50
%, Cr: 0.03-0.30%, Ni: 0.008
The gist of the invention is a highly corrosion-resistant zirconium alloy characterized by containing 0 to 0.030% Zr and the remainder consisting of Zr and unavoidable impurities.
本発明のジルコニウム合金における各添加元素の含有量
限定理由は次のとおりである。The reason for limiting the content of each additive element in the zirconium alloy of the present invention is as follows.
Ｓｎ：不純物として混入してＺｒの耐食性を劣化させる
窒素の悪影響を抑えるのに有効な元素であり、その含有
量は、通常は不純物窒素の含有量によって変化させるこ
とになる。不純物窒素の含有量は、一般の原料スポンジ
においては２０〜３０ｐｐｍである。また、その後の製
造工程中における吸収量も最小限となるように管理がな
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： １．２０〜１．７％）のよう
に下限を１．２％に制限する必要はなく、不純物窒素に
よる耐食性低下に対して改善効果を発揮し得る０、２％
を下限とする。ただし、Ｓｎは強度確保の点からも重要
元素であるので、０．５％以上が望ましい。一方、Ｓｎ
の窒素悪影響防止効果は１．７％まで認められるので、
これを上限とするが、Ｓｎは単独では耐食性劣化元素で
あるので、１．２％以下とするのが望ましい。Sn: An element effective in suppressing the adverse effects of nitrogen, which is mixed as an impurity and degrades the corrosion resistance of Zr, and its content is usually changed depending on the content of the nitrogen impurity. The content of impurity nitrogen is 20 to 30 ppm in a general raw material sponge. In addition, the amount absorbed during the subsequent manufacturing process is also managed to be kept to a minimum. Therefore, in the zirconium alloy of the present invention, there is no need to limit the lower limit to 1.2% as in Zircaloy (Sn: 1.20 to 1.7%), and it exhibits an improvement effect on corrosion resistance deterioration due to impurity nitrogen. Possible 0.2%
is the lower limit. However, since Sn is an important element from the viewpoint of ensuring strength, it is desirable that it be 0.5% or more. On the other hand, Sn
The effect of preventing negative nitrogen effects is recognized up to 1.7%, so
This is the upper limit, but since Sn alone is an element that deteriorates corrosion resistance, it is desirable to keep it at 1.2% or less.
Ｆｅ：耐食性向上に有効な元素で、有効性は０．０５％
以上で現われる。しかし、Ｆｅの多量の含有は冷間加工
製を損なう。以上のことがらＦｅは０．０３〜０．５０
％の含有量とする。Fe: An element effective in improving corrosion resistance, effectiveness is 0.05%
The above appears. However, a large amount of Fe impairs cold working properties. Based on the above, Fe is 0.03 to 0.50
% content.
Ｃｒ ： Ｃｒも耐食性向上に有効な元素であり、その
効果が発現する０、０３％を下限とする。Ｃｒは又、Ｚ
ｒとの間に金属間化合物を形成し、その析出状況は熱処
理により複雑に変化し、この金属間化合物の析出は基本
的には耐食性を劣化させる。Ｃｒの多量添加は、この析
出物を増加させるために、Ｃｒ量の上限は０．３０％と
する。Cr: Cr is also an effective element for improving corrosion resistance, and the lower limit is set at 0.03%, at which the effect is manifested. Cr is also Z
An intermetallic compound is formed between the metal and the metal, and the state of its precipitation changes in a complicated manner due to heat treatment, and the precipitation of this intermetallic compound basically deteriorates the corrosion resistance. Addition of a large amount of Cr increases this precipitate, so the upper limit of the amount of Cr is set to 0.30%.
Ｎｉ：本発明のジルコニウム合金では、Ｓｎとともに重
要な元素である。このＮｉは微量で耐食性改善効果を示
し、窒素悪影響防止のために添加されたＳｎそれ自体の
耐食性に対する悪影響を抑える。Ｓｎで窒素による耐食
性低下が効果的に抑えられているので、多く含有する必
要はなく、また上述したとおり微量でも優れた耐食性改
善効果を示す。むしろＮｉの多量含有は水素吸収による
脆化促進し、長期使用を考えた場合はこの脆化が大きな
問題になる。このようなことから、Ｎｉ量は０．００８
０〜０゜０３０％とする。Ni: In the zirconium alloy of the present invention, Ni is an important element along with Sn. This Ni exhibits the effect of improving corrosion resistance even in a small amount, and suppresses the negative effects on corrosion resistance of Sn itself, which is added to prevent the negative effects of nitrogen. Since the decrease in corrosion resistance caused by nitrogen is effectively suppressed by Sn, it is not necessary to contain a large amount of Sn, and as mentioned above, even a small amount exhibits an excellent corrosion resistance improving effect. In fact, the large content of Ni promotes embrittlement due to hydrogen absorption, and this embrittlement becomes a major problem when long-term use is considered. From this, the amount of Ni is 0.008
0~0°030%.
以下に本発明をその実施例について具体的に説明する。 The present invention will be specifically described below with reference to examples thereof.
非消耗型アルゴンアーク溶解法により第１表に示ス組成
のジルコニウム合金からなる小型インゴット（約５００
ｇ）を溶製した。次に、各小型インゴットをｌＸｌ０
−’Ｔｏｒｒ以下の真空中で１０５０°ＣＸ２時間加熱
し、水焼入れの後、溶体化処理を行った。しかる後、各
小型インゴットを下記条件で加工処理して厚み約２ｍｍ
の板材となし、各板材より長さ５０ｍ×幅３０ｍｍＸ厚
み２ｍｍの腐食試験片を採取した。腐食試験片中の不純
物窒素量は第１表に示すように約８０ｐｐｍである。A small ingot (approximately 500
g) was dissolved. Next, each small ingot is
It was heated at 1050° C. for 2 hours in a vacuum of -' Torr or less, and after water quenching, solution treatment was performed. After that, each small ingot was processed under the following conditions to a thickness of approximately 2 mm.
Corrosion test pieces with a length of 50 m x width of 30 mm x thickness of 2 mm were taken from each plate. The amount of impurity nitrogen in the corrosion test piece is about 80 ppm as shown in Table 1.
（ｉ）熱間圧延 ７００°ＣＸ２ｈｒ加熱（Ａｒ中）圧
下率６０％
（１１）中間焼鈍 ６５０°ＣＸ２ｈｒ（真空中）（ｊ
ｉ）冷間圧延 圧下率７２％
（ｉｖ）最終焼鈍 ４５０°ｃｘ２ｈｒ（真空中）そし
て、各試験片を（＃６００ＳｉＣ）により湿式で表面研
磨した後、硝沸酸（５％ＨＦ／４５％ＨＮＯ３１５０％
Ｈ，０）にて酸洗し、更に水で洗浄して腐食試験に供し
た。腐食試験は、水蒸気中での３８０°ＣＸ １０５ｋ
ｇｆ ７ｃｍ２Ｘ３０００時間のオートクレーブ処理と
し、耐食性は試験前後での重量変化から求めた腐食増量
（ｍｇ／ｄｍ２）にて評価した。結果を第１表に示す。(i) Hot rolling 700°CX2hr heating (in Ar) reduction rate 60% (11) Intermediate annealing 650°CX2hr (in vacuum) (j
i) Cold rolling rolling reduction 72% (iv) Final annealing 450°cx2hr (in vacuum) Then, after wet surface polishing of each test piece with (#600SiC), nitric acid (5%HF/45%HNO3150) %
The sample was pickled with H.O.), further washed with water, and subjected to a corrosion test. Corrosion test: 380°C x 105k in steam
Autoclave treatment was performed for gf 7cm2 x 3000 hours, and corrosion resistance was evaluated by corrosion weight increase (mg/dm2) determined from the weight change before and after the test. The results are shown in Table 1.
第
■
表
本発明範囲外
第１表から明らかなように、本発明のジルコニウム合金
Ｎｏ、 １〜８では、いずれも腐食増量が１００ｍｇ／
ｄｍ”未満に抑制されている。Table 1: Outside the scope of the present invention As is clear from Table 1, in zirconium alloys Nos. 1 to 8 of the present invention, the corrosion weight increase was 100 mg/
dm".
これに対し、比較合金Ｎｏ、 ９はジルカロイ−４相当
のジルコニウム合金で、Ｓｎを比較的多く含むもののＮ
ｉが事実上台まれていないために、上記腐食試験は腐食
増量は１２６ｍｇ／ｄｍ２に達し腐食が著しい。Ｎ０１
０〜１６ではＮｉを含むものの、他の成分が本発明条件
を満足していないため、腐食増量が１００ｍｇ／ｄｍ”
まで低下していない。このうち、Ｎｏ、 １５はＳｎと
して現状レベル（ジルカロイレベル）よりも低下させた
合金であるが、不純物窒素が約ｓｏｐｐｍ含まれる状態
では、Ｎｉ添加が行われていないために、十分な耐食性
改善効果を現わしていない。また、Ｎｏ、 １６はＦｅ
、 Ｎｉの大量添加で耐食性改善を図った合金であるが
、Ｓｎ添加が行われていないため腐食増量は１４５ｍｇ
／ｄｍ”と高い価を示している。On the other hand, comparative alloy No. 9 is a zirconium alloy equivalent to Zircaloy-4, and although it contains a relatively large amount of Sn, it
Since i was not actually crushed, the corrosion increase in the above corrosion test reached 126 mg/dm2, resulting in significant corrosion. N01
0 to 16 contain Ni, but the other components do not satisfy the conditions of the present invention, so the corrosion weight increase is 100 mg/dm.
It has not decreased to Among these, No. 15 is an alloy in which the Sn content is lower than the current level (Zircaloy level), but in a state where about soppm of impurity nitrogen is included, since Ni is not added, it does not have a sufficient corrosion resistance improvement effect. does not appear. Also, No. 16 is Fe
This alloy has improved corrosion resistance by adding a large amount of Ni, but since no Sn is added, the corrosion increase is only 145 mg.
/dm”, indicating a high value.
このように本発明のジルカロイ合金では、上記腐食試験
で腐食増量が１００ ｍ ｇ ／ｄｍ２未満に抑制され
る。上記腐食試験で現行のジルカロイ−４（Ｎｏ、９）
が腐食増量１２６ ｍ ｇ ／ｄｍ”であることを考慮
すると、本発明のジルカロイ合金は、軽水冷却原子炉で
今後予測される燃料使用期間延長に対しても十分な対応
が期待できる。As described above, in the Zircaloy alloy of the present invention, the corrosion weight increase is suppressed to less than 100 mg/dm2 in the above corrosion test. Current Zircaloy-4 (No. 9) in the above corrosion test
Considering that the corrosion weight increase is 126 mg/dm, the Zircaloy alloy of the present invention can be expected to sufficiently cope with the expected future extension of the fuel usage period in light water-cooled nuclear reactors.
〔発明の効果〕
以上の説明から明らかなように、本発明のジルカロイ合
金は、不純物窒素を特に低減させなくても現行の合金よ
りも優れた耐食性を示す。したがって、耐久性に優れ、
なおかつ、その製造ならびに加工処理が容易である。ま
た、Ｎｉ、 Ｆｅの多量添加に依存することなく、耐食
性改善を図っているので、冷間加工性の低下がなく、更
に水素吸収による脆化促進の懸念もなく、この点からも
十分な耐久性が保証される。[Effects of the Invention] As is clear from the above description, the Zircaloy alloy of the present invention exhibits better corrosion resistance than current alloys even without particularly reducing impurity nitrogen. Therefore, it is highly durable and
Moreover, its manufacture and processing are easy. In addition, since corrosion resistance is improved without relying on the addition of large amounts of Ni and Fe, there is no reduction in cold workability, and there is no concern about accelerated embrittlement due to hydrogen absorption, and from this point of view, it has sufficient durability. gender is guaranteed.
Claims (1)
〜０．５０％、Ｃｒ：０．０３〜０．３０％、Ｎｉ：０
．００８０〜０．０３０％を含有し、残部Ｚｒおよび不
可避的不純物からなることを特徴とする高耐食性ジルコ
ニウム合金。1. Sn: 0.2-1.7%, Fe: 0.03 in weight%
~0.50%, Cr:0.03~0.30%, Ni:0
．． A highly corrosion-resistant zirconium alloy characterized by containing 0.080 to 0.030%, with the remainder consisting of Zr and inevitable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3065789A JPH02209443A (en) | 1989-02-08 | 1989-02-08 | Corrosion-resistant zirconium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3065789A JPH02209443A (en) | 1989-02-08 | 1989-02-08 | Corrosion-resistant zirconium alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02209443A true JPH02209443A (en) | 1990-08-20 |
Family
ID=12309839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3065789A Pending JPH02209443A (en) | 1989-02-08 | 1989-02-08 | Corrosion-resistant zirconium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02209443A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0712938A1 (en) * | 1994-11-21 | 1996-05-22 | General Electric Company | Zirconium alloy |
-
1989
- 1989-02-08 JP JP3065789A patent/JPH02209443A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0712938A1 (en) * | 1994-11-21 | 1996-05-22 | General Electric Company | Zirconium alloy |
| US5699396A (en) * | 1994-11-21 | 1997-12-16 | General Electric Company | Corrosion resistant zirconium alloy for extended-life fuel cladding |
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