JPH0127135B2 - - Google Patents
Info
- Publication number
- JPH0127135B2 JPH0127135B2 JP19038984A JP19038984A JPH0127135B2 JP H0127135 B2 JPH0127135 B2 JP H0127135B2 JP 19038984 A JP19038984 A JP 19038984A JP 19038984 A JP19038984 A JP 19038984A JP H0127135 B2 JPH0127135 B2 JP H0127135B2
- Authority
- JP
- Japan
- Prior art keywords
- cao
- alloy
- temperature
- molten metal
- less
- 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
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 229910000601 superalloy Inorganic materials 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000011822 basic refractory Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 description 50
- 239000000292 calcium oxide Substances 0.000 description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 27
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 26
- 229910045601 alloy Inorganic materials 0.000 description 21
- 239000000956 alloy Substances 0.000 description 21
- 238000006477 desulfuration reaction Methods 0.000 description 14
- 230000023556 desulfurization Effects 0.000 description 14
- 239000011819 refractory material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910014459 Ca-Ni Inorganic materials 0.000 description 1
- 229910014473 Ca—Ni Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Description
［産業上の利用分野］
本発明はニツケル（Ni）基超合金の製造方法
に係り、特にニツケル基超合金の戻り材を含む溶
湯の精錬方法に改良を加えることにより、酸素、
窒素ならびに硫黄含有量を極めて少なくするNi
基超合金の製造方法に関するものである。
［従来の技術］
Ni基超合金は、機械的性質、耐熱性ならびに
耐食性等に優れた性質を有し、超耐熱合金として
広範な用途を有する。このNi基超合金において
も、通常の合金と同様に残留酸素、窒素及び硫黄
が多いと加工性が低下するので、残留酸素、窒素
及び硫黄を十分に少なくすることが重要である。
真空またはアルゴンガス雰囲気下での、精錬中
の脱酸、脱硫について、特開昭50−12651号、特
開昭50−126516及び特開昭52−58010号に、それ
ぞれCaO（酸化カルシウム）含有率の高い塩基性
耐火物で裏付けされた溶解炉又は取鍋を用い、真
空又はアルゴンガス雰囲気中で溶湯中にアルミニ
ウム（Al）またはその合金を添加することを特
徴とする脱酸、脱硫方法が提案されている。この
原理は、Alの添加により耐火物中のCaOを還元
し、還元生成物であるカルシウム（Ca）により
溶湯中の硫黄（Ｓ）酸素（Ｏ）を除去するもので
ある。
この方法によれば、Ni基超合金戻り材を含む
Ni基超合金溶湯の、一応の脱酸、脱硫が可能で
あるが、より十分な脱酸、脱硫が可能となる製造
方法が期待されている。
また合金溶湯の脱酸、脱硫法として金属カルシ
ウム（Ca）を添加することも従来行なわれてい
る。（例えば、特開昭50−128633、特公昭56−
39364等）ところが、CaO含有率の少ない耐火物
で裏付けされて溶解槽中でCaを添加した場合に
は、CaOの添加物率が低いと共に酸化物介在量が
多くなつてしまうという問題がある。
即ち、Ni基超合金戻り材を含む合金溶湯を、
CaO含有量が低い耐火物で裏付けされた溶解槽中
にて該溶湯の精錬を行なう場合、
溶湯中の酸化物介在物が生じる、
（特にHfO2系が多い。）
N2含有量が増加する、
（高温溶解すれば除去できるるが、溶解温度を
高くすると耐火物から混入してくる酸化物介在
量が増加する傾向にある。）
Al、Ti、Zr等を含むので、N2トラツプ量が
多い。また耐火物との反応性が大きい、
という傾向があり、酸化物介在量が多くなると共
に、N2含有量も高くなる。
［発明が解決しようとする問題点］
上述の如く、従来の方法では、Ni基超合金戻
り材を含む溶湯中のＯ、Ｎ、Ｓ、とりわけＮを十
分に減少させることができない。また耐火物に帰
因する酸化物系介在量が増加する場合もある。
［問題点を解決するための手段］
本発明は、
CaO40％以上を含有する塩基性耐火物をもつて
裏付けした溶解炉又は取鍋内の、ニツケル基超合
金の戻り材を含む溶湯に、真空又はアルゴン雰囲
気でCa及び／又はCa合金をCaとして0.01〜5wt
％添加した後、その添加時の温度よりも50℃以上
高い温度に保持して脱Ca処理することにより、
Ca：100ppm以下、
Ｏ、Ｎ：その少なくとも一方が30ppm以下で、Ｏ
とＮとの合量が100ppm以下、
Ｓ：50ppm以下、
とすることを特徴とする酸素、硫黄及び窒素含有
量の少ないニツケル基超合金の製造方法、
を要旨とするものである。
以下本発明の構成について詳細に説明する。
Ni基超合金には極めて多くの種類のものがあ
る。一例を第１表に示す。なお第１表以外にも
TRWVIA、TWR−1900、MAR−M412、No.
64BC等が挙げられる。
[Industrial Application Field] The present invention relates to a method for producing a nickel (Ni)-based superalloy, and in particular, by improving the method for refining molten metal containing return material of the nickel-based superalloy, oxygen,
Ni with extremely low nitrogen and sulfur content
The present invention relates to a method for producing a base superalloy. [Prior Art] Ni-based superalloys have excellent properties such as mechanical properties, heat resistance, and corrosion resistance, and have a wide range of uses as superheat-resistant alloys. In this Ni-based superalloy as well, as with normal alloys, if residual oxygen, nitrogen, and sulfur are present in large amounts, workability decreases, so it is important to sufficiently reduce residual oxygen, nitrogen, and sulfur. Regarding deoxidation and desulfurization during refining under vacuum or argon gas atmosphere, CaO (calcium oxide) content is described in JP-A-50-12651, JP-A-50-126516, and JP-A-52-58010, respectively. A deoxidizing and desulfurizing method is proposed, which is characterized by adding aluminum (Al) or its alloy to the molten metal in a vacuum or argon gas atmosphere using a melting furnace or ladle backed with a highly basic refractory. has been done. This principle is that CaO in the refractory is reduced by adding Al, and sulfur (S) and oxygen (O) in the molten metal are removed by the reduction product calcium (Ca). According to this method, containing Ni-based superalloy return material
Although it is possible to deoxidize and desulfurize molten Ni-based superalloy to a certain extent, a manufacturing method that enables more sufficient deoxidation and desulfurization is expected. Furthermore, addition of metallic calcium (Ca) has also been conventionally carried out as a deoxidizing and desulfurizing method for molten alloys. (For example, JP-A-50-128633, JP-A-56-
39364, etc.) However, when Ca is added in the melting tank using a refractory with a low CaO content, there is a problem in that the additive content of CaO is low and the amount of oxides is increased. That is, the molten alloy containing the Ni-based superalloy return material,
When refining the molten metal in a melting tank backed by a refractory with a low CaO content, oxide inclusions occur in the molten metal (particularly HfO 2 -based), and the N 2 content increases. (Although it can be removed by melting at a high temperature, increasing the melting temperature tends to increase the amount of oxides mixed in from the refractory.) Since it contains Al, Ti, Zr, etc., the amount of N2 traps is reduced. many. In addition, there is a tendency for reactivity with refractories to be high, and as the amount of oxides increases, the N 2 content also increases. [Problems to be Solved by the Invention] As described above, the conventional methods cannot sufficiently reduce O, N, and S, especially N, in the molten metal containing the Ni-based superalloy return material. Furthermore, the amount of oxide-based inclusions due to refractories may increase. [Means for Solving the Problems] The present invention provides for applying a vacuum to a molten metal containing a return material of a nickel-based superalloy in a melting furnace or ladle backed with a basic refractory containing 40% or more of CaO. Or 0.01~5wt of Ca and/or Ca alloy as Ca in argon atmosphere
% addition, by holding the temperature at least 50°C higher than the temperature at the time of addition and removing Ca, Ca: 100ppm or less, O, N: at least one of them is 30ppm or less, and O
A method for producing a nickel-based superalloy with low contents of oxygen, sulfur and nitrogen, characterized in that the total amount of N and N is 100 ppm or less, and S: 50 ppm or less. The configuration of the present invention will be explained in detail below. There are many types of Ni-based superalloys. An example is shown in Table 1. In addition to Table 1,
TRWVIA, TWR−1900, MAR−M412, No.
64BC etc.
【表】【table】
【表】
本発明においては、合金溶湯中にはNi基超合
金の戻り材（スクラツプ）が含まれる。この戻り
材を含むNi基超合金溶湯は、前述の如く酸化物
介在量を含み易い、N2含有量が増加する、耐火
物との反応性が大きい等の性質を有するのである
が、本発明によれば、後に述べる通り、これらの
問題点が悉く解決される。
本発明においては、CaO40％以上を含む塩基性
耐火物で裏付けされた溶解槽内のNi基超合金溶
湯にCa及び／又はCa合金を添加する。
添加されたCaは、溶湯中のＳ、Ｏと反応し、
脱硫、脱酸が行なわれる。またCaの一部は沸騰
し、撹拌作用を奏し、脱窒、脱硫が行なわれる。
通常、Ni基超合金にはAlやTiが含まれるので、
Ｎが主としてAlN、TiNの形態として存在し、
極めて脱窒し難いのであるが、本発明では、強力
な脱窒作用を働くCa及び／又はCa合金を添加す
ることにより十分な脱窒が行なわれる。
また炉材として高CaO耐火物を用いているが、
この耐火物はCaに対して極めて安定であり、添
加されたCaと実質的に反応しない。そのためCa
の上記脱酸、脱窒、脱硫反応が十分に進行する。
因みに、低CaO耐火物、MgO耐火物等では、炉
材とCaとが反応してCaの歩留りが低くなり、Ca
添加効果が小さくなる。
また一般に、Ni基超合金の溶湯中にはAlが含
まれるのであるが、このAlの一部は、直接に、
溶湯中のＯと結合して脱酸を行なう。またAlの
他の一部は耐火物表面のCaOと反応して、
2Al＋3CaO→Al2O3＋3Ca
となり、CaとAl2O3が生じる。このCaは脱酸、
脱硫反応し、CaO、CaSとなる。
一方、Al2O3は、耐火物壁のCaOと反応して、
Al2O3＋3CaO→3CaO・Al2O3
なる反応によりC3A系を主体とするカルシウムア
ルミネートが耐火物表面に生じる。
このようにして生じたC3Aは、周知の如く、脱
硫性が著しく高い。そのため、溶湯の脱硫が強力
かつ十分に行なわれるようになる。また生じた活
性なCaによつて脱酸と脱硫が行なわれる。
なお一部のNi基超合金においては、Al含有量
が上記脱酸、脱硫反応を行なわしめるには不十分
な量しか含まない場合がある。このような場合に
は、溶湯にAl及び／又はAl合金を添加して上記
脱酸、脱硫反応を行なわせる。
Ca及び／又はCa合金を添加する際の雰囲気は、
真空又はアルゴンとする。
Ca合金を添加する場合には、Ca−Ni合金等が
好適であるが、これに限定されない。Ca及び／
又はCa合金は、粉末状、粒状あるいはワイヤー
状等の形態にて添加されるが、添加直後の表面で
の蒸発が少ないことからワイヤー状とするのが好
ましい。
本発明方法において、使用する裏付け耐火物
は、カルシア耐火物（CaO）、ラルナイト耐火物
（安定化2CaO・SiO2）、メルウイナイト耐火物
（3CaO・MgO・2SiO2）ならびにCaOに富化した
ドロマイト耐火物等があり、いずれもCaOを40％
以上含有する塩基性耐火物である。
本発明方法において、裏付け耐火物のCaO含有
率を40％以上に限定する理由は、40％未満のCaO
を含有する塩基性耐火物にあつては、その中の
CaOは他の酸化物と強固に結合しているため、
CaOの活性が少なく、アルミニウムと反応しにく
く、40％以上CaOを含有する塩基性耐火物中の
CaOは活性が大でアルミニウムによつてよく反応
することができるからである。
また、CaOを40％以上含む耐火物は、Al2O3や
HfO2等の酸化物を反応吸着し易く、従つて、溶
湯中の酸化物を吸収し、酸化物介在量を大幅に減
少させる。またCaOを40％以上含む耐火物はＣ、
Ti、Zr等に対する安定性が高いので、高温溶解
が可能となる。
本発明において、Ca及び／又はCa合金を添加
するときの溶湯温度は溶湯の組成にもよるのであ
るが、通常、1250〜1550℃程度とされる。
本発明においては、Ca及び／又はCa合金を添
加し、脱酸、脱窒、脱硫反応させた後、もしく
は、これらの反応が相当に進んだ段階で、溶湯温
度を50℃以上高くして、例えば1600〜1700℃程度
にまで高める。
このように溶湯温度を高くすると、Ｎ含有量を
更に少なくすることができると共に、余剰のCa
を蒸発させて除去することができる。この場合、
真空にて処理を行なうことにより、脱Ca効率を
高めることができる。なお、一般に、高温にする
と耐火物損耗量が増大し、合金中の酸化物介在量
が増加するのであるが、本発明の如く高CaO耐火
物は極めて安定であり、酸化物介在量は殆ど増加
しない。
本発明方法によれば、最終的には、溶湯中の
Ｏ、Ｎ、Ｓ含有量を、
Ｏ、Ｎ：その少なくとも一方が30ppm以下で、Ｏ
とＮとの合量が100ppm以下、
Ｓ：50ppm以下、
とする。好ましくは、Ｏ、Ｎ、Ｓのいずれをも
30ppm以下とする。また、Ca含有量は100ppm以
下とする。
Ｏ、Ｓは酸化物、硫化物となり、合金の溶接
性、延性、靭性、鍛造性に影響するが、上記範囲
とすることにより、これらの特性が優れたものに
なる。Ｎは窒化物やマイクロポロシテイ等の欠陥
の原因となり、合金の耐熱性、高温強度、靭性、
延性に影響するが、上記範囲とすることにより、
これらの特性が優れたものになる。また、Caが
100ppmを超え、多量に残留すると、得られる合
金の高温における強度や延性が著しく低下する
が、本発明の方法によれば、Ca含有量も100ppm
以下と著しく低減されるため、このような問題も
解決される。
［作用］
叙上の如く、添加されたCa及び／又はCa合金
により、更には炉材表面反応等により、脱酸、脱
窒、脱硫が行なわれる。また、Ni基合金中には
Caが多量に溶け込み易く、Ni基合金はCaを合金
化し易いものであるが、本発明によれば、Ca及
び／又はCa合金添加後に昇温することにより脱
Caが行なわれる。このようなことから、結果的
にＯ、Ｎ、Ｓ、Ca含有量の著しく少ない、高純
度、高特性Ni基合金が得られる。
［実施例］
以下に実施例、比較例及び実験例を挙げて、本
発明をより具体的に説明する。
実施例
第２表に示す組成のCaO耐火物をもつて、裏付
けされた高周波誘導溶解炉中に、１×10-3torrの
真空雰囲気下で、第３表に示す組成のNi基超合
金戻り材を溶解した。[Table] In the present invention, the molten alloy contains return material (scrap) of the Ni-based superalloy. As mentioned above, the Ni-based superalloy molten metal containing this return material has properties such as easy inclusion of oxides, increased N2 content, and high reactivity with refractories. According to this, all of these problems are solved, as will be described later. In the present invention, Ca and/or Ca alloy are added to a Ni-based superalloy molten metal in a melting tank supported by a basic refractory containing 40% or more of CaO. The added Ca reacts with S and O in the molten metal,
Desulfurization and deoxidation are performed. In addition, some of the Ca boils and exerts a stirring action, resulting in denitrification and desulfurization. Usually, Ni-based superalloys contain Al and Ti, so
N mainly exists in the form of AlN and TiN,
Although it is extremely difficult to denitrify, in the present invention, sufficient denitrification can be achieved by adding Ca and/or Ca alloy that has a strong denitrifying effect. In addition, high CaO refractories are used as furnace materials, but
This refractory is extremely stable with respect to Ca and does not substantially react with added Ca. Therefore Ca
The above deoxidation, denitrification, and desulfurization reactions proceed satisfactorily.
Incidentally, in low CaO refractories, MgO refractories, etc., the furnace material reacts with Ca, resulting in a low Ca yield.
The effect of addition becomes smaller. Generally, Al is contained in the molten metal of Ni-based superalloys, and some of this Al is directly
It combines with O in the molten metal to deoxidize. In addition, another part of Al reacts with CaO on the surface of the refractory, resulting in 2Al + 3CaO → Al 2 O 3 + 3Ca, and Ca and Al 2 O 3 are generated. This Ca deoxidizes,
A desulfurization reaction results in CaO and CaS. On the other hand, Al 2 O 3 reacts with CaO on the refractory wall, and calcium aluminate mainly composed of C 3 A is produced on the refractory surface through the reaction Al 2 O 3 + 3CaO → 3CaO・Al 2 O 3 . . As is well known, the C 3 A produced in this manner has extremely high desulfurization properties. Therefore, the desulfurization of the molten metal becomes strong and sufficient. The generated active Ca also performs deoxidation and desulfurization. Note that some Ni-based superalloys may contain an insufficient amount of Al to carry out the above deoxidation and desulfurization reactions. In such a case, Al and/or Al alloy is added to the molten metal to carry out the deoxidation and desulfurization reactions. The atmosphere when adding Ca and/or Ca alloy is
Use vacuum or argon. When adding a Ca alloy, a Ca-Ni alloy or the like is suitable, but is not limited thereto. Ca and/
Alternatively, the Ca alloy may be added in the form of powder, granules, wire, or the like, but it is preferably in the form of a wire because evaporation on the surface immediately after addition is reduced. In the method of the present invention, the supporting refractories used are calcia refractories (CaO), larnite refractories (stabilized 2CaO・SiO 2 ), melwinite refractories (3CaO・MgO・2SiO 2 ), and CaO-enriched dolomite refractories. All of them contain 40% CaO.
It is a basic refractory containing the above. In the method of the present invention, the reason why the CaO content of the supporting refractory is limited to 40% or more is that the CaO content of less than 40%
For basic refractories containing
Because CaO is tightly bound to other oxides,
The activity of CaO is low, it is difficult to react with aluminum, and it is used in basic refractories containing 40% or more CaO.
This is because CaO has high activity and can react well with aluminum. In addition, refractories containing 40% or more of CaO include Al 2 O 3 and
It easily reacts and adsorbs oxides such as HfO 2 and therefore absorbs oxides in the molten metal, greatly reducing the amount of oxides present. In addition, refractories containing 40% or more of CaO are C,
It has high stability against Ti, Zr, etc., so it can be melted at high temperatures. In the present invention, the temperature of the molten metal when adding Ca and/or Ca alloy depends on the composition of the molten metal, but is usually about 1250 to 1550°C. In the present invention, after adding Ca and/or Ca alloy and causing deoxidation, denitrification, and desulfurization reactions, or at a stage where these reactions have progressed considerably, the molten metal temperature is raised by 50°C or more, For example, raise the temperature to about 1600-1700℃. By raising the molten metal temperature in this way, the N content can be further reduced and excess Ca can be removed.
can be removed by evaporation. in this case,
By performing the treatment in a vacuum, the Ca removal efficiency can be increased. Generally, when the temperature is raised, the amount of refractory wear increases and the amount of oxides included in the alloy increases, but the high CaO refractory of the present invention is extremely stable, and the amount of oxides hardly increases. do not. According to the method of the present invention, the O, N, and S contents in the molten metal are finally adjusted such that at least one of O and N is 30 ppm or less, and O
The total amount of N and S is 100ppm or less, and S: 50ppm or less. Preferably, any of O, N, and S
30ppm or less. In addition, the Ca content shall be 100 ppm or less. O and S become oxides and sulfides and affect the weldability, ductility, toughness, and forgeability of the alloy, but by keeping them within the above range, these properties become excellent. N causes defects such as nitrides and microporosities, and deteriorates the heat resistance, high temperature strength, toughness, and
Although it affects ductility, by keeping it within the above range,
These characteristics make it excellent. Also, Ca
If the Ca content exceeds 100 ppm and remains in large amounts, the strength and ductility of the resulting alloy at high temperatures will decrease significantly, but according to the method of the present invention, the Ca content can also be reduced to 100 ppm.
This problem can also be solved because it is significantly reduced as below. [Function] As mentioned above, deoxidation, denitrification, and desulfurization are performed by the added Ca and/or Ca alloy, and by the surface reaction of the furnace material. In addition, in Ni-based alloys
Although a large amount of Ca easily dissolves and Ni-based alloys are easy to alloy with Ca, according to the present invention, by increasing the temperature after adding Ca and/or Ca alloy, desorption is possible.
Ca is performed. As a result, a high-purity, high-performance Ni-based alloy with extremely low contents of O, N, S, and Ca can be obtained. [Example] The present invention will be explained in more detail by giving Examples, Comparative Examples, and Experimental Examples below. EXAMPLE A Ni-based superalloy with the composition shown in Table 3 was melted in a supported high-frequency induction melting furnace with a CaO refractory having the composition shown in Table 2 under a vacuum atmosphere of 1×10 -3 torr. The material was dissolved.
【表】【table】
【表】
この溶湯の温度を1500℃に維持しながら、アル
ゴン雰囲気下でカルシウムを0.5％相当の割合で
添加し、十分に反応させた後1650℃にて真空処理
を行い金型へ鋳造後、窒素含有量、硫黄含有量、
酸素含有量等を測定した。
その結果を第４表に示す。
比較例 １、２
耐火物を第２表の比較例の欄のもの、比較例１
マグネシア質、比較例２アルミナ質を用いたこと
以外は実施例と同様の手順により実験を行なつ
た。その結果を第４表に示す。
比較例 ３
カルシウム添加後も1500℃のままとし、真空処
理を行なわなかつたこと以外は、実施例と同様の
手順により実験を行なつた。結果を第４表に示
す。[Table] While maintaining the temperature of this molten metal at 1500℃, calcium was added at a rate equivalent to 0.5% under an argon atmosphere, and after sufficient reaction, vacuum treatment was performed at 1650℃, and after casting into a mold, Nitrogen content, sulfur content,
Oxygen content etc. were measured. The results are shown in Table 4. Comparative Examples 1 and 2 Refractories are those in the Comparative Examples column of Table 2, Comparative Example 1
Comparative Example 2 An experiment was carried out in the same manner as in the example except that magnesia was used and alumina was used. The results are shown in Table 4. Comparative Example 3 An experiment was conducted in the same manner as in Example except that the temperature remained at 1500° C. even after calcium addition and no vacuum treatment was performed. The results are shown in Table 4.
【表】
第４表より、本発明方法によれば、Ｏ、Ｓ、Ｎ
を十分に除去できることができ、しかもCa含量
も低減されることが明らかである。
実験例
実施例で得られたNi基合金及び比較例３で得
られたNi基合金から、各々、引張試験片を切り
出し、室温及び800℃において、引張試験を行な
つた。結果を第５表に示す。[Table] From Table 4, according to the method of the present invention, O, S, N
It is clear that Ca content can be sufficiently removed and the Ca content is also reduced. Experimental Example Tensile test pieces were cut from each of the Ni-based alloy obtained in Example and the Ni-based alloy obtained in Comparative Example 3, and a tensile test was conducted at room temperature and 800°C. The results are shown in Table 5.
【表】
第５表より明らかなように、Ca残留量の多い
比較例３のNi基合金は、強度、延性が高温にお
いて著しく劣化している。
なお、実施例の方法において、昇温温度や真空
度、膜Ca処理時間等を変えることにより、Ca残
留量の異なるNi基合金、即ち、Ca：91ppm、
Ca：120ppm、Ca：141ppm、Ca：230ppmのNi
基合金を製造し、各々800℃における伸び（％）
を調べ、結果を上記結果と共に第１図に示した。
第１図より、Ca含有量が100ppmを超えると、
合金の延性が著しく低下することが明らかであ
る。
［効果］
以上の通り、本発明によれば、戻り材を含む
Ni基超合金の極めて強力な脱酸、脱窒、脱硫、
及び、脱Caを行なうことができ、酸素、窒素、
硫黄、Caが極めて少なく、強度、耐熱性、靭性、
延性、溶接性、鍛造性等の諸特性に著しく優れた
合金を製造することができる。また、酸化物介在
量も極めて少ない。[Table] As is clear from Table 5, the strength and ductility of the Ni-based alloy of Comparative Example 3, which has a large amount of residual Ca, deteriorates significantly at high temperatures. In addition, in the method of the example, by changing the heating temperature, vacuum degree, film Ca treatment time, etc., Ni-based alloys with different Ca residual amounts, that is, Ca: 91 ppm, Ca: 91 ppm,
Ca: 120ppm, Ca: 141ppm, Ca: 230ppm Ni
Elongation (%) at 800℃ of each base alloy produced
The results are shown in Figure 1 together with the above results. From Figure 1, when the Ca content exceeds 100ppm,
It is clear that the ductility of the alloy is significantly reduced. [Effect] As described above, according to the present invention, the
Extremely powerful deoxidation, denitrification, and desulfurization of Ni-based superalloys.
And, it is possible to remove Ca, oxygen, nitrogen,
Extremely low in sulfur and Ca, strength, heat resistance, toughness,
It is possible to produce alloys with extremely excellent properties such as ductility, weldability, and forgeability. Moreover, the amount of oxides present is also extremely small.
第１図は実験例で得られた結果を示すグラフで
ある。
FIG. 1 is a graph showing the results obtained in experimental examples.
Claims (1)
て裏付けした溶解炉又は取鍋内の、ニツケル基超
合金の戻り材を含む溶湯に、真空又はアルゴン雰
囲気でCa及び／又はCa合金をCaとして0.01〜
5wt％添加した後、その添加時の温度よりも50℃
以上高い温度に保持して脱Ca処理することによ
り、 Ca：100ppm以下、 酸素、窒素：その少なくとも一方が30ppm以下
で、酸素と窒素との合量が100ppm以下、 硫黄：50ppm以下、 とすることを特徴とする酸素、硫黄及び窒素含有
量の少ないニツケル基超合金の製造方法。[Claims] 1. Ca and/or molten metal containing a return material of a nickel-based superalloy in a melting furnace or ladle backed with a basic refractory containing 40% or more of CaO in a vacuum or argon atmosphere. Or Ca alloy as Ca 0.01～
After adding 5wt%, the temperature is 50℃ lower than the temperature at the time of addition.
By holding the temperature at a higher temperature and removing Ca, Ca: 100ppm or less, Oxygen and Nitrogen: At least one of them is 30ppm or less, the total amount of oxygen and nitrogen is 100ppm or less, and Sulfur: 50ppm or less. A method for producing a nickel-based superalloy with low oxygen, sulfur and nitrogen contents, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19038984A JPS6167729A (en) | 1984-09-11 | 1984-09-11 | Manufacture of super alloy of nickel group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19038984A JPS6167729A (en) | 1984-09-11 | 1984-09-11 | Manufacture of super alloy of nickel group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6167729A JPS6167729A (en) | 1986-04-07 |
| JPH0127135B2 true JPH0127135B2 (en) | 1989-05-26 |
Family
ID=16257349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19038984A Granted JPS6167729A (en) | 1984-09-11 | 1984-09-11 | Manufacture of super alloy of nickel group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6167729A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312113B (en) * | 2011-09-28 | 2013-10-23 | 沈阳黎明航空发动机(集团)有限责任公司 | Melting method of high chromium K4648 nickel-based casting alloy revert |
| JP6048805B2 (en) * | 2012-09-28 | 2016-12-21 | 国立研究開発法人物質・材料研究機構 | Direct recycling method for Ni-based single crystal superalloy parts |
| JPWO2017029856A1 (en) * | 2015-08-18 | 2018-08-09 | 国立研究開発法人物質・材料研究機構 | Recycling method for Ni-base superalloy parts |
-
1984
- 1984-09-11 JP JP19038984A patent/JPS6167729A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6167729A (en) | 1986-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6237687B2 (en) | ||
| US4729787A (en) | Method of producing an iron; cobalt and nickel base alloy having low contents of sulphur, oxygen and nitrogen | |
| US5268141A (en) | Iron based alloy having low contents of aluminum silicon, magnesium, calcium, oxygen, sulphur, and nitrogen | |
| JP5458607B2 (en) | Manufacturing method of clean steel with excellent resistance to sulfide corrosion cracking | |
| JPH0127135B2 (en) | ||
| JPH03223414A (en) | Production of iron-nickel-cobalt-base alloy minimal in respective contents of sulfur, oxygen, and nitrogen | |
| JPH03236434A (en) | Nickel-base alloy in which each content of sulfur, oxygen and nitrogen extremely low | |
| JPS6252021B2 (en) | ||
| JPH07207316A (en) | Wire for desulfurization of molten iron having high desulfurization efficiency | |
| US5225156A (en) | Clean steel composition | |
| JP2616928B2 (en) | Iron-rare earth metal master alloy and method for producing the same | |
| JPH0873923A (en) | Method for producing clean steel with excellent resistance to hydrogen-induced cracking | |
| JPS6286111A (en) | Calcia refractory composition for refining and desulfurization method using said composition | |
| EP2045338A1 (en) | Flux for obtaining steel reduced in nitrogen, oxygen, and sulfur contents through smelting | |
| RU2375463C2 (en) | Wire for out-of-furnace treatment of metallurgical melts | |
| RU2779272C1 (en) | Modifier for iron-carbon melts and method for its production | |
| JPS6025486B2 (en) | Method for manufacturing clean steel with low oxygen, sulfur, and nitrogen content | |
| JPH0366374B2 (en) | ||
| JP3697987B2 (en) | Desulfurization agent for molten steel desulfurization | |
| JP2004344891A (en) | Ca ADDING METHOD IN CONTINUOUS CASTING OF BILLET | |
| JPS62132761A (en) | Refractories for refinement and method therefor | |
| JPS61149414A (en) | Method for removing copper and tin from molten iron | |
| JPH02179812A (en) | Method for refining stainless steel | |
| SU1560602A1 (en) | Alloying composition for steel and alloys | |
| JPS62128960A (en) | Refractories for refinement and refining process |