JPH0615706B2 - High corrosion resistant amorphous alloy - Google Patents
High corrosion resistant amorphous alloyInfo
- Publication number
- JPH0615706B2 JPH0615706B2 JP60051036A JP5103685A JPH0615706B2 JP H0615706 B2 JPH0615706 B2 JP H0615706B2 JP 60051036 A JP60051036 A JP 60051036A JP 5103685 A JP5103685 A JP 5103685A JP H0615706 B2 JPH0615706 B2 JP H0615706B2
- Authority
- JP
- Japan
- Prior art keywords
- atomic
- amorphous alloy
- corrosion
- alloy
- present
- 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.)
- Expired - Fee Related
Links
- 238000005260 corrosion Methods 0.000 title claims description 47
- 230000007797 corrosion Effects 0.000 title claims description 47
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 23
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 description 23
- 239000000956 alloy Substances 0.000 description 23
- 238000009835 boiling Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 241001572615 Amorphus Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KUEVMRNKSBZFQV-UHFFFAOYSA-N O(O)O.[Ta] Chemical compound O(O)O.[Ta] KUEVMRNKSBZFQV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000004580 weight loss 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
- C22C45/00—Amorphous alloys
- C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Soft Magnetic Materials (AREA)
- Physical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Powder Metallurgy (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は例えば沸騰濃硝酸あるいは更に酸化剤を含むよ
うな苛酷な酸化性腐食環境下で使用し得る高耐食アモル
ファス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 highly corrosion resistant amorphous alloy that can be used in a severe oxidizing corrosive environment containing, for example, boiling concentrated nitric acid or an oxidizing agent.
［従来の技術］ 従来苛酷な腐食性環境では、例えばＮｂを含む原子力級
高純度のオーステナイトスレンレス鋼などが金属材料と
して用いられている。[Prior Art] Conventionally, in a severely corrosive environment, for example, a nuclear-grade high-purity austenitic stainless steel containing Nb has been used as a metal material.
［発明が解決しようとする問題点］ しかし上述のような沸騰濃硝酸あるいは更に酸化剤を含
む酸化力の激しい高温強酸の環境でステンレス鋼を使用
する場合は、溶解したＣｒ3+イオンが溶液中で酸化され
Ｃｒ6+となり、これが更に金属材料の溶解を加速すると
いう自己触媒的作用によって激しい腐食を受ける。この
腐食形態は粒界腐食であるがこれを平均腐食速度として
換算しても年間１mm以上の厚さにも及ぶことがある。し
たがって、このような環境でステンレス鋼を使用する場
合には腐食による損失を覚悟せざるを得ない。[Problems to be Solved by the Invention] However, when stainless steel is used in the environment of high temperature strong acid with strong oxidizing power containing boiling concentrated nitric acid or an oxidizer as described above, dissolved Cr 3+ ions are in solution. Is oxidized to Cr 6+ , which undergoes severe corrosion due to the autocatalytic action of further accelerating the dissolution of the metal material. This corrosion form is intergranular corrosion, but even if it is converted into an average corrosion rate, it may reach a thickness of 1 mm or more per year. Therefore, when stainless steel is used in such an environment, it is necessary to be prepared for loss due to corrosion.
［問題点を解決するための手段および作用］ 本発明の目的は、酸化剤を含む沸騰濃硝酸のような酸化
性と過酷な腐食性をあわせて備えた環境に耐える高耐食
性を有するアモルファス合金を提供することにある。[Means and Actions for Solving Problems] An object of the present invention is to provide an amorphous alloy having a high corrosion resistance capable of withstanding an environment having both oxidizing property and severe corrosive property such as boiling concentrated nitric acid containing an oxidizing agent. To provide.
本発明は、ＴａとＮｉを必須成分とする特定組成のアモ
ルファス合金によってこの目的を達成するものである。The present invention achieves this object by using an amorphous alloy having a specific composition containing Ta and Ni as essential components.
周知のように、通常、合金は固体状態では結晶化してい
るが、合金組成を特定のものとすると共に、溶融状態か
ら超急冷凝固させる、あるいはスパッターデポジション
を行う等の固体形成の過程で長周期秩序を形成させない
処置を行ったり、イオン注入など長周期秩序を破壊する
処置を行うと、固体状態でも結晶構造を持たず、液体に
類似したアモルファス構造となる。このアモルファス合
金は、理想的に均一な固溶体であると共に、所定の特性
を発揮させるのに十分な合金元素を添加できる。そし
て、本発明者らは、高温濃塩酸など非酸化性の酸中で不
動態化する高耐食性を有したアモルファス合金を見出し
た。しかし、これらの材料は酸化性の高温強酸中では、
不動態が破壊されるため十分な耐食性は維持できない。As is well known, alloys are usually crystallized in the solid state, but the alloy composition is made to be a specific one, and it is long-lived during the solid formation process such as super-quench solidification from the molten state or sputter deposition. When a treatment that does not form a periodic order or a treatment that destroys a long-period order such as ion implantation is performed, an amorphous structure similar to a liquid is obtained without a crystal structure even in a solid state. This amorphous alloy is an ideally uniform solid solution, and it is possible to add sufficient alloying elements to exert predetermined characteristics. Then, the present inventors have found an amorphous alloy having high corrosion resistance that is passivated in a non-oxidizing acid such as high temperature concentrated hydrochloric acid. However, these materials, in oxidizing high temperature strong acid,
Sufficient corrosion resistance cannot be maintained because the passivation is destroyed.
本発明者らは、このようなアモリファス合金の優れた特
性に着目して更に研究を行った結果、酸化剤を含む高温
の濃厚な酸中でも不動態皮膜を生じ高耐食性を備えたア
モルファス合金が作り得ることを見出し本発明を達成し
た。As a result of further research focusing on the excellent properties of such an Amorphus alloy, the present inventors have produced an amorphous alloy with a high corrosion resistance by forming a passive film even in a high-temperature concentrated acid containing an oxidizing agent. The present invention has been achieved by finding out what is obtained.
本発明は、特許請求の範囲第１項ないし第４項に示され
る第１ないし第４の発明からなるものであるが次の第１
表に、これら第１なしい第４の発明の構成元素および含
有率を示す。The present invention comprises the first to fourth inventions set forth in claims 1 to 4, and the following first
The table shows the constituent elements and the contents of these first and fourth inventions.
（作用） 上記組成の溶融合金を超急冷凝固させたり、スパッター
デポジションさせるなどアモルファス合金を作製する種
々の方法によって得られるアモルファス合金は前記各元
素が均一に固溶した単相合金である。そのため、本発明
をアモルファス合金を酸化性環境化におくと、その表面
に、極めて均一で高耐食性を有する保護皮膜（不動態皮
膜）が形成される。 (Function) An amorphous alloy obtained by various methods for producing an amorphous alloy, such as super-quenching solidification of a molten alloy having the above composition or sputter deposition, is a single-phase alloy in which the above-mentioned elements are uniformly solid-dissolved. Therefore, when the amorphous alloy of the present invention is placed in an oxidizing environment, an extremely uniform protective film (passive film) having high corrosion resistance is formed on the surface thereof.
ところで、酸化力の高い高温酸溶液中で金属材料は、容
易に酸化され溶解するため、このような環境で金属材料
を使用するためには、安定な保護皮膜を形成する能力を
金属材料に付与する必要がある。これは、有効元素を必
要量含む合金を作ることによって実現される。しかし結
晶質金属の場合、多種多量の合金元素を添加すると、し
ばしば化学的性質の異なる多相構造となり、所定の耐食
性が実現しえないことがある。また、化学的不均一性の
発生はむしろ耐食性に有害である。By the way, since a metal material is easily oxidized and dissolved in a high-temperature acid solution having a high oxidizing power, in order to use the metal material in such an environment, the metal material is given the ability to form a stable protective film. There is a need to. This is achieved by making an alloy containing the required amount of active elements. However, in the case of a crystalline metal, addition of a large amount of various alloying elements often results in a multiphase structure having different chemical properties, and the desired corrosion resistance may not be realized. Also, the occurrence of chemical non-uniformity is rather detrimental to corrosion resistance.
これに対し、本発明のアモルファス合金は、均一固溶体
である。したがって、本発明のアモルファス合金は、安
定な保護皮膜すなわち不動態皮膜を形成させうる所要量
の有効元素を均一に含むものであり、かかるアモルファ
ス合金には、均一な不動態皮膜が生じ、十分に高い耐食
性が発揮される。On the other hand, the amorphous alloy of the present invention is a uniform solid solution. Therefore, the amorphous alloy of the present invention uniformly contains a required amount of effective elements capable of forming a stable protective film, that is, a passivation film. High corrosion resistance is demonstrated.
即ち、酸化力の高い高温の強酸に耐える金属材料が具備
すべき条件は、その環境で安定な不動態皮膜が材料に均
一に生ずることである。合金がアモルファス構造を有す
ることは、複雑な組成の合金を単相固溶体として作成す
ることを可能にし、均一な不動態皮膜の形成を保証する
のである。That is, the condition that a metal material having a high oxidizing power and resistance to a strong acid at a high temperature should have is that a stable passivation film is uniformly formed on the material in the environment. The fact that the alloy has an amorphous structure makes it possible to prepare an alloy having a complex composition as a single-phase solid solution and guarantees the formation of a uniform passivation film.
本発明のアモルファス合金の大部分のものは、例えばＣ
ｒ6+イオンのような酸化剤を含む沸騰濃硝酸中において
も全く腐食されない。また本発明合金の中で最低の耐食
性を備えた材料であってもその腐食速度は年間２．５μ
ｍ以下である。Most of the amorphous alloys of the present invention include, for example, C
It is not corroded at all in boiling concentrated nitric acid containing an oxidizing agent such as r 6+ ions. Even if the material of the present invention has the lowest corrosion resistance, its corrosion rate is 2.5 μ / year.
m or less.
次に本発明における各成分組成を限定する理由を述べ
る。Next, the reasons for limiting the composition of each component in the present invention will be described.
Ｎｉは本発明合金の基礎となる元素であって、Ｔａ、Ｔ
ｉ、ＮｂおよびＷなどIVａ、Ｖａ、VIａ族の元素と共存
するとアモルファス構造を形成する元素である。したが
って、本発明の第１および第２の発明においてアモルフ
ァス構造の形成のためにＮｉを２０原子％以上添加する
ことが必要である。Ni is an element that forms the basis of the alloy of the present invention, and Ta, T
It is an element that forms an amorphous structure when coexisting with IVa, Va, and VIa group elements such as i, Nb, and W. Therefore, in the first and second aspects of the present invention, it is necessary to add Ni in an amount of 20 atomic% or more for forming an amorphous structure.
Ｔａは酸化性の激しい高温の強酸中において安定な不動
態皮膜を形成する元素であり、かつ、上述のようにＮｉ
あるいはＮｉの一部をＦｅあるいはＣｏの１種または２
種で置換したものと共存してアモルファス構造を形成す
る元素であって、本発明の第１および第３の発明におい
て、十分な耐食性を保証するために１５原子％以上添加
する必要がある。また、Ｎｉ、Ｆｅ、ＣｏのVIIIａ元素
の総和が２０原子％未満であるとＴａと共存してもアモ
ルファス構造を形成しにくいので、本発明の第１および
第３の発明においてＴａは８０原子％以下にする必要が
ある。Ta is an element that forms a stable passivation film in a strong acid having a strong oxidizing property at a high temperature, and as described above, Ni is used.
Alternatively, a part of Ni may be one or two of Fe or Co.
It is an element that forms an amorphous structure in coexistence with those substituted with seeds, and in the first and third inventions of the present invention, it is necessary to add 15 atom% or more in order to ensure sufficient corrosion resistance. Further, if the total of VIIIa elements of Ni, Fe and Co is less than 20 atomic%, it is difficult to form an amorphous structure even when coexisting with Ta. Therefore, in the first and third inventions of the present invention, Ta is 80 atomic% Must be:
Ｔｉ、Ｎｂ、Ｗは、いずれもＴａに代ってＮｉと共存し
てアモルファス構造を形成する元素であり、かつ酸化性
の激しい高温の強酸中において、不動態皮膜を形成する
能力を有する元素である。しかし、Ｔｉ、ＮｂおよびＷ
の耐食性におよぼす効果は、Ｔａに比べて劣るため、耐
食性を保証するためには、これらの元素でＴａを全量置
換することはできない。但し、Ｔａを１０原子％以上含
む場合、Ｔｉ、ＮｂおよびＷのいずれか１種また２種以
上とＴａの合計が１５原子％以上であれば、耐食性を保
証し得る。これが本発明の第２および第４の発明におい
て、Ｔｉ、ＮｂおよびＷの１種または２種以上と１０原
子％以上のＴａとの合計を１５原子％以上必要とする理
由である。またアモルファス構造を形成を保証するため
には、VIIIａ元素を最低２０原子％含む必要があるの
で、Ｔｉ、ＮｂおよびＷの１種または２種以上と１０原
子％以上のＴａとの合計を本発明の第２および第４の発
明において８０原子％以下にとどめる必要がある。Each of Ti, Nb, and W is an element that coexists with Ni instead of Ta to form an amorphous structure, and has the ability to form a passive film in a strong acid at a high temperature that is highly oxidizing. is there. However, Ti, Nb and W
Since its effect on the corrosion resistance is inferior to that of Ta, it is not possible to completely replace Ta with these elements in order to guarantee the corrosion resistance. However, when Ta is contained in an amount of 10 atomic% or more, corrosion resistance can be guaranteed if the total of Ta, which is one or more of Ti, Nb and W, and Ta is 15 atomic% or more. This is the reason why the second and fourth inventions of the present invention require a total of 15 atomic% or more of one or more kinds of Ti, Nb and W and Ta of 10 atomic% or more. Further, in order to guarantee the formation of an amorphous structure, it is necessary to contain at least 20 atomic% of VIIIa element. In the second and fourth aspects of the present invention, it is necessary to keep it at 80 atomic% or less.
ＦｅおよびＣｏはＮｉに代ってＴａ、Ｔｉ、Ｎｂ、Ｗな
どと共存することによってアモルファス構造を形成し得
るが、本発明の目的である高耐食性を保証するためＴａ
を１０原子％以上あるいは１５原子％以上添加する場合
は、ＦｅおよびＣｏの１種または２種でＮｉ含量が７原
子％未満になるまで置換すると、アモルファス構造の形
成が困難になる。また７原子％以上のＮｉとＦｅおよび
Ｃｏのいずれか１種または２種との合計が２０原子％未
満の場合は、アモルファス構造の形成が困難になる。し
たがって本発明の第３および第４の発明において、Ｎｉ
を７原子％以上含む必要がある。またＦｅおよびＣｏの
１種または２種と７原子％以上のＮｉとの合計は、２０
原子％以上にする必要がある。Although Fe and Co can form an amorphous structure by coexisting with Ta, Ti, Nb, W, etc. instead of Ni, Ta and Co are required to ensure high corrosion resistance which is the object of the present invention.
In the case of adding 10 atomic% or more or 15 atomic% or more, it is difficult to form an amorphous structure by substituting one or two kinds of Fe and Co until the Ni content becomes less than 7 atomic%. If the total of 7 atomic% or more of Ni and one or two of Fe and Co is less than 20 atomic%, it becomes difficult to form an amorphous structure. Therefore, in the third and fourth aspects of the present invention, Ni
Must be contained at 7 atomic% or more. The total of one or two kinds of Fe and Co and 7 atomic% or more of Ni is 20
It must be at least atomic%.
本発明のアモルファス合金の作製は、既に広く用いられ
ている種々の方法、即ち、液体合金を超急冷凝固させる
方法、気相を経てアモルファス合金を形成させる種々の
方法、イオン注入によって固体の長周期構造を破壊する
方法などアモルファス合金を作製するいずれの方法でも
良い。The amorphous alloy of the present invention can be produced by various methods which are already widely used, that is, a method of rapidly quenching and solidifying a liquid alloy, various methods of forming an amorphous alloy through a gas phase, and a long period of a solid by ion implantation. Any method of producing an amorphous alloy such as a method of destroying the structure may be used.
［実施例］ 実施例１ 第２表に示す組成となるように原料金属を混合し、アル
ゴンアーク溶解法により原料合金を作製した。これらの
合金をアルゴン雰囲気中で再溶融し、単ロール法を用い
て超急冷凝固させることにより、厚さ０．０１〜０．０
５mm、幅１〜３mm、長さ３〜２０ｍのアモルファス合金
薄板を得た。アモルファス構造形成の確認はＸ線回折に
より行った。これらの合金試料のうち主なものの表面を
シリコンカーバイド紙１０００番までシクロヘキサン中
で研磨した。次いで所定の長さの合金試料を切り出し、
１１０℃で沸騰している９ＮのＨＮＯ３溶液に７〜１０
日間浸漬し、浸漬前後の重量をマイクロ天秤を用いて測
定した。浸漬により重量の減少が見られた場合はこれを
年間腐食速度に換算した。Example 1 Example 1 Raw material metals were mixed so as to have the composition shown in Table 2, and a raw material alloy was produced by an argon arc melting method. By remelting these alloys in an argon atmosphere and rapidly quenching and solidifying using a single roll method, a thickness of 0.01 to 0.0
An amorphous alloy thin plate having a width of 5 mm, a width of 1 to 3 mm and a length of 3 to 20 m was obtained. The formation of the amorphous structure was confirmed by X-ray diffraction. The surface of the main one of these alloy samples was polished in cyclohexane up to silicon carbide paper No. 1000. Then cut out a predetermined length of alloy sample,
7-10 in 9N HNO 3 solution boiling at 110 ° C.
It was immersed for a day, and the weight before and after immersion was measured using a microbalance. When a decrease in weight was observed due to immersion, this was converted into an annual corrosion rate.
得られた結果を第３表に示す。The results obtained are shown in Table 3.
第３表における比較材は、高純度金属を原料として自家
製した原子力級高純度の２５Ｃｒ−２０Ｎｉ−０．２５
Ｎｂオーステナイトステンレス鋼であり、沸騰濃硝酸中
で工業的に使用されている鋼である。The comparative material in Table 3 is a high-purity nuclear-grade 25Cr-20Ni-0.25 home-made high-purity metal as a raw material.
Nb austenitic stainless steel, which is industrially used in boiling concentrated nitric acid.
本発明のアモルファス合金の大部分からは腐食による重
量変化が検出されなかった。また、腐食による重量変化
が検出された試料の腐食速度も比較材として用いたオー
ステナイトステンレス鋼の腐食速度の１／２０以下であ
る。また、本発明の合金を浸漬試験の後、Ｘ線光電子分
光法を用いて表面を解析した結果、これら合金の表面に
はＴａＯ２ （ＯＨ）からなるオキシ水酸化タンタル不
動態皮膜が生じており、これが本発明合金の高耐食性の
原因であることが判明した。No weight change due to corrosion was detected in most of the amorphous alloys of the present invention. The corrosion rate of the sample in which the weight change due to corrosion was detected is also 1/20 or less of the corrosion rate of the austenitic stainless steel used as the comparative material. After the immersion test of the alloys of the present invention, the surface was analyzed by X-ray photoelectron spectroscopy. As a result, a tantalum oxyhydroxide passivation film made of TaO 2 (OH) was formed on the surface of these alloys. It was found that this is the cause of the high corrosion resistance of the alloy of the present invention.
実施例２ 実施例１と同様に調整した本発明のアモルファス合金を
試料として用い、１００ｐｐｍのＣｒイオンを含み１１
０℃で沸騰している９NHNO3溶液中で浸漬試験を行っ
た。７〜１０日間の浸漬試験前後の試料の重量変化をマ
イクロ天秤を用いて測定し、浸漬により重量減量が観測
された場合は、これを年間腐食速度に換算した。 Example 2 An amorphous alloy of the present invention prepared in the same manner as in Example 1 was used as a sample and contained 11 ppm of Cr ions.
The immersion test was carried out in a 9 NHNO 3 solution boiling at 0 ° C. The change in weight of the sample before and after the immersion test for 7 to 10 days was measured using a microbalance, and when a weight loss was observed by immersion, this was converted into an annual corrosion rate.
得られた結果を第４表に示す。The results obtained are shown in Table 4.
第４表に示すように、９Ｎの沸騰ＨＮＯ３に酸化剤とし
てわずか１００ｐｐｍのＣｒ6+イオンを添加しただけ
で、比較材として用いたオーステナイトステンレス鋼の
腐食速度は、４０倍以上に増大した。 As shown in Table 4, the corrosion rate of the austenitic stainless steel used as a comparative material increased by 40 times or more by adding only 100 ppm of Cr 6+ ion as an oxidant to 9N boiling HNO 3 .
これに対し、本発明のアモルファス合金の大部分からは
腐食による重量変化が検出されなかった。On the other hand, no change in weight due to corrosion was detected in most of the amorphous alloys of the present invention.
腐食による重量変化が検出された試料の場合でも、これ
らの腐食速度は、比較材として用いたオーステナイトス
テンレス鋼の腐食速度の１／４００以下であって、きわ
めて高い耐食性を備えている。Even in the case of the sample in which the weight change due to corrosion was detected, these corrosion rates were 1/400 or less of the corrosion rate of the austenitic stainless steel used as the comparative material, and the sample had extremely high corrosion resistance.
また、同じ浸漬試験を金属タンタルについて行ったとこ
ろ金属光沢が失われた。これに対し、本発明のアモルフ
ァス合金の大部分は腐食速度が検出されないだけでなく
金属光沢を保持しており、金属タンタルより耐食性が高
いことを示していた。Also, when the same immersion test was performed on metal tantalum, the metallic luster was lost. On the other hand, most of the amorphous alloys of the present invention have not only the corrosion rate not detected but also retain the metallic luster, indicating that they have higher corrosion resistance than metallic tantalum.
［効果］ 以上詳述したとおり、本発明のアモルファス合金は、酸
化剤を含む沸騰濃硝酸のような激しい酸化性腐食環境に
おいても安定な不動態皮膜を形成して腐食されない高耐
食合金である。[Effect] As described above in detail, the amorphous alloy of the present invention is a high corrosion resistant alloy that does not corrode by forming a stable passive film even in a severe oxidizing corrosive environment such as boiling concentrated nitric acid containing an oxidizing agent.
また、本発明の合金の作製には、既に広く用いられてい
るアモルファス合金作製の技術のいずれをも適用できる
ため、特殊な装置を改めて必要とせず、本発明合金は実
用性にも優れている。Further, since any of the widely used techniques for producing an amorphous alloy can be applied to the production of the alloy of the present invention, a special apparatus is not required again and the alloy of the present invention is excellent in practicability. .
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭55−89451（ＪＰ，Ａ) 特開 昭55−138049（ＪＰ，Ａ) 特開 昭55−145150（ＪＰ，Ａ) 特開 昭58−91144（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-55-89451 (JP, A) JP-A-55-138049 (JP, A) JP-A-55-145150 (JP, A) JP-A 58- 91144 (JP, A)
Claims (4)
にＮｉよりなる酸化性腐食環境下で耐食性を有する高耐
食アモルファス合金。1. A highly corrosion-resistant amorphous alloy having a corrosion resistance in an oxidative corrosive environment in which 15 to 80 atomic% of Ta is contained and the balance is substantially Ni.
ら選ばれる１種または２種以上の元素とを含み、残部は
実質的にＮｉよりなり、含有率はＴａが１０原子％以
上、前記群から選ばれる１種又は２種以上の元素が、Ｔ
ａとの合量で１５〜８０原子％である酸化性腐食環境下
で耐食性を有する高耐食アモルファス合金。2. Ta, and one or more elements selected from the group consisting of Ti, Nb and W, the balance substantially consisting of Ni, the content of Ta is 10 atomic% or more, One or more elements selected from the above group are T
A highly corrosion-resistant amorphous alloy having a corrosion resistance in an oxidizing corrosive environment in which the total amount with a is 15 to 80 atomic%.
部は実質的にＮｉよりなり、含有率はＴａが１５〜８０
原子％、Ｆｅ及び／又はＣｏが７５原子％以下、Ｎｉが
７原子％以上である酸化性腐食環境下で耐食性を有する
高耐食アモルファス合金3. Ta and Fe and / or Co are contained, and the balance is substantially Ni, and the content is Ta of 15 to 80.
High corrosion resistance amorphous alloy having corrosion resistance in an oxidizing corrosive environment in which atomic%, Fe and / or Co is 75 atomic% or less, and Ni is 7 atomic% or more.
ら選ばれる１種または２種以上の元素とＦｅ及び／又は
Ｃｏとを含み、残部は実質的にＮｉよりなり、含有率は
ＴａとＴｉ、ＮｂおよびＷよりなる群から選ばれる１種
または２種以上とが、合量で１５〜８０原子％でありか
つＴａが１０原子％以上であり、Ｆｅ及び／又はＣｏが
７５原子％以下でありＮｉが７原子％以上である酸化性
腐食環境下で耐食性を有する高耐食アモルファス合金。4. Ta, one or more elements selected from the group consisting of Ti, Nb and W, and Fe and / or Co, with the balance being substantially Ni, and the content being Ta. And one or more selected from the group consisting of Ti, Nb and W are 15 to 80 atomic% in total, Ta is 10 atomic% or more, and Fe and / or Co is 75 atomic%. A highly corrosion-resistant amorphous alloy having corrosion resistance in an oxidative corrosion environment in which Ni is 7 atomic% or more.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60051036A JPH0615706B2 (en) | 1985-03-14 | 1985-03-14 | High corrosion resistant amorphous alloy |
| DE19863608656 DE3608656C2 (en) | 1985-03-14 | 1986-03-14 | Use of a glass-like tantalum-nickel alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60051036A JPH0615706B2 (en) | 1985-03-14 | 1985-03-14 | High corrosion resistant amorphous alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61210143A JPS61210143A (en) | 1986-09-18 |
| JPH0615706B2 true JPH0615706B2 (en) | 1994-03-02 |
Family
ID=12875575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60051036A Expired - Fee Related JPH0615706B2 (en) | 1985-03-14 | 1985-03-14 | High corrosion resistant amorphous alloy |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0615706B2 (en) |
| DE (1) | DE3608656C2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6233735A (en) * | 1985-08-06 | 1987-02-13 | Mitsui Eng & Shipbuild Co Ltd | Amorphous alloy having high corrosion resistance |
| US5634989A (en) * | 1987-05-07 | 1997-06-03 | Mitsubishi Materials Corporation | Amorphous nickel alloy having high corrosion resistance |
| WO1988008885A1 (en) * | 1987-05-07 | 1988-11-17 | Mitsubishi Kinzoku Kabushiki Kaisha | Highly corrosion-resistant amorphous alloy |
| CN100453687C (en) * | 2005-12-14 | 2009-01-21 | 中国科学院物理研究所 | A kind of nickel-based bulk metallic glass and its preparation method |
| JP4953371B2 (en) * | 2007-04-27 | 2012-06-13 | 独立行政法人日本原子力研究開発機構 | Ni-based alloy excellent in nitric acid corrosion resistance and method for producing the same |
| JP4953370B2 (en) * | 2007-04-27 | 2012-06-13 | 独立行政法人日本原子力研究開発機構 | Nb-W alloy excellent in nitric acid corrosion resistance and mechanical properties and method for producing the same |
| WO2009054077A1 (en) * | 2007-10-25 | 2009-04-30 | Tohoku University | Metallic glass alloy with resistance to highly oxidative solution and apparatus in which highly oxidative solution is handled |
| JP6406939B2 (en) * | 2014-09-04 | 2018-10-17 | キヤノン株式会社 | Amorphous alloy, mold for molding, and method of manufacturing optical element |
| WO2017058670A1 (en) * | 2015-09-28 | 2017-04-06 | Glassimetal Technology, Inc. | Surface treatment method for nickel-based metallic glasses to reduce nickel release |
| US10458008B2 (en) | 2017-04-27 | 2019-10-29 | Glassimetal Technology, Inc. | Zirconium-cobalt-nickel-aluminum glasses with high glass forming ability and high reflectivity |
| KR102289441B1 (en) * | 2019-04-30 | 2021-08-13 | 한국전력공사 | Ni-based amorphous alloy and preparing method thereof |
| KR102453371B1 (en) * | 2020-10-27 | 2022-10-11 | 한국생산기술연구원 | Ni-based amorphous alloy for prevent corrosion of plant, and preparing method thereof |
| CN114574786B (en) * | 2022-03-11 | 2022-11-18 | 东莞理工学院 | Ternary amorphous alloy film and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1476589A (en) * | 1974-08-07 | 1977-06-16 | Allied Chem | Amorphous metal alloys |
| JPS5589451A (en) * | 1978-12-28 | 1980-07-07 | Takeshi Masumoto | Amorphous alloy containing iron group element and carbon |
| US4365994A (en) * | 1979-03-23 | 1982-12-28 | Allied Corporation | Complex boride particle containing alloys |
| JPS6030734B2 (en) * | 1979-04-11 | 1985-07-18 | 健 増本 | Amorphous alloy containing iron group elements and zirconium with low brittleness and excellent thermal stability |
| JPS5789450A (en) * | 1980-11-21 | 1982-06-03 | Matsushita Electric Ind Co Ltd | Amorphous magnetic alloy |
| CA1205725A (en) * | 1982-09-06 | 1986-06-10 | Emiko Higashinakagawa | Corrosion-resistant and wear-resistant amorphous alloy and a method for preparing the same |
-
1985
- 1985-03-14 JP JP60051036A patent/JPH0615706B2/en not_active Expired - Fee Related
-
1986
- 1986-03-14 DE DE19863608656 patent/DE3608656C2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE3608656A1 (en) | 1986-09-25 |
| JPS61210143A (en) | 1986-09-18 |
| DE3608656C2 (en) | 1994-08-18 |
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