JPH0611890B2 - Method for melting A1-Li alloy - Google Patents
Method for melting A1-Li alloyInfo
- Publication number
- JPH0611890B2 JPH0611890B2 JP1259905A JP25990589A JPH0611890B2 JP H0611890 B2 JPH0611890 B2 JP H0611890B2 JP 1259905 A JP1259905 A JP 1259905A JP 25990589 A JP25990589 A JP 25990589A JP H0611890 B2 JPH0611890 B2 JP H0611890B2
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- Prior art keywords
- alloy
- refractory
- melting
- molten metal
- increased
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、高純度のAl−Li系合金の溶製方法に関するも
のであり、特に、Liは活性度が高く耐火材料と反応しや
すいことから耐火物を特定することによって、溶製され
た合金中の不純物を軽減させるものである。The present invention relates to a method for producing a high-purity Al-Li alloy, and in particular, Li has a high activity and easily reacts with a refractory material. By specifying the refractory from the above, impurities in the melted alloy are reduced.
〔従来の技術〕 Al−Li系合金は、従来のAl合金に比較して軽量かつ高強
度であることから、航空機用材料等の分野で開発が進め
られている。Al−Li系合金の製造法としては、溶解鋳造
方式と粉末冶金方式がある。このうち、溶解鋳造方式で
は、Liの活性が高く、雰囲気ガス及び溶湯と接する耐火
炉材との反応により、合金汚染、Li含有量の減少、
耐火物の侵食、破損などが生じ、高純度の合金が得ら
れず、Li添加の効果が十分発揮されないという問題があ
った。[Prior Art] Al-Li alloys are lighter and have higher strength than conventional Al alloys, and are therefore being developed in fields such as aircraft materials. As a method for manufacturing an Al-Li alloy, there are a melt casting method and a powder metallurgy method. Of these, in the melt casting method, the activity of Li is high, and due to the reaction between the atmosphere gas and the refractory material in contact with the molten metal, alloy contamination, reduction of the Li content,
Corrosion and breakage of refractory materials occur, high-purity alloys cannot be obtained, and the effect of Li addition cannot be fully exerted.
また、カルシャ質耐火物で構成された容器を用いて、非
酸化性雰囲気で溶製する方法（特開昭６２−１５８８３
５号公報）が提案されている。Further, a method of melting in a non-oxidizing atmosphere using a container made of a Karsian refractory (Japanese Patent Laid-Open No. 62-15883).
No. 5) has been proposed.
しかしながら、これらの従来の製造方法のうち、溶解鋳
造方式では、Liが活性金属であることから、空気中の酸
素、窒素、水素、水分などと化合し易く、また、溶湯と
接する耐火炉材による合金汚染やLi2O系酸化物の生成、
Li含有量の減少等の問題が生起する。すなわち、溶製雰
囲気と反応して、 ２Li＋1/2O2 → Li2O ３Li＋1/2N2 → Li3N Li＋1/2H2 → LiH Li＋ H2O → LiOH＋1/2H2 となり、溶湯中のLi含有量を減少させるとともにLi2O
は、溶湯中に残留し、介在物となり、合金汚染の原因と
なる。また、H2は溶湯中に残留し、鋳塊のガス欠陥とな
る。また、耐火物と反応して ４Li＋３SiO2 → Si＋２Li2SiO3 ２Li＋ MgO → Mg＋Li2O ６Li＋Fe2O3 → ２Fe＋３Li2O ６Li＋Cr2O3 → ２Cr＋３Li2O ２Li＋Na2O → ２Na＋Li2O ２Li＋２Ｃ → Li2C2 ３Li＋２Al2O3 → Al＋３LiAlO2 すなわち、耐火物の成分と反応して、耐火物を溶損、破
壊させる。また、Li含有量を減少させるとともに、Li2S
iO3，Li2O，Li2C2などは、溶湯中に残留し、介在物とな
り、合金汚染の原因となる。Si,Ca,Fe,Cr,Naなどは溶湯
中に遊離し、不純物元素を増加させる原因となる。However, among these conventional manufacturing methods, in the melting and casting method, since Li is an active metal, it is easy to combine with oxygen, nitrogen, hydrogen, moisture, etc. in the air, and due to the refractory material in contact with the molten metal. Alloy contamination and formation of Li 2 O-based oxides,
Problems such as reduction of Li content occur. That is, it reacts with the molten atmosphere to become 2Li + 1 / 2O 2 → Li 2 O 3Li + 1 / 2N 2 → Li 3 N Li + 1 / 2H 2 → LiH Li + H 2 O → LiOH + 1 / 2H 2 and the Li content in the molten metal Decrease with Li 2 O
Remains in the molten metal, becomes inclusions, and causes alloy contamination. Further, H 2 remains in the molten metal and causes gas defects in the ingot. Also, by reacting with refractory 4Li + 3SiO 2 → Si + 2Li 2 SiO 3 2Li + MgO → Mg + Li 2 O 6Li + Fe 2 O 3 → 2Fe + 3Li 2 O 6Li + Cr 2 O 3 → 2Cr + 3Li 2 O 2Li + Na 2 O → 2Na + Li 2 O 2Li + 2C → Li 2 C 2 3Li + 2Al 2 O 3 → Al + 3LiAlO 2, that is, it reacts with the components of the refractory material to melt and destroy the refractory material. In addition, the Li content is reduced and Li 2 S
iO 3, Li 2 O, etc. Li 2 C 2 is to remain in the melt, become inclusions, causing the alloy contamination. Si, Ca, Fe, Cr, Na, etc. are liberated in the molten metal and cause the increase of impurity elements.
このようにAl−Li系合金は、通常の耐火物炉材を用いた
溶解では良質な合金は得られず、また、 Liは、溶解時に酸化揮発損失しやすい。As described above, an Al-Li-based alloy cannot be obtained as a high-quality alloy by melting using a normal refractory furnace material, and Li tends to undergo oxidative volatilization loss during melting.
酸化物が溶湯に巻き込まれ、これは極めて除去しがた
い。Oxides are entrained in the melt and are extremely difficult to remove.
ガスを吸収するので材料中に気泡が発生しやすい。Since it absorbs gas, bubbles are easily generated in the material.
等の様々な問題をもっている。Etc. have various problems.
また、カルシャ耐火物炉材を使用し、上記問題点を解消
しようとするものは、酸化物としてのO2は低下するが、
Al−Li合金に有害なCaが溶出して、合金が汚染されると
いう問題がある。また、カルシャ耐火物は吸湿性であ
り、耐火物の保存や築炉から溶製までの管理に注意を要
する。Also, using the Karsya refractory furnace material, trying to solve the above problems, O 2 as an oxide is reduced,
There is a problem that Ca, which is harmful to the Al-Li alloy, is eluted and the alloy is contaminated. In addition, the Karsha refractory is hygroscopic, so care must be taken when storing the refractory and controlling it from furnace construction to melting.
また、AlとLiを均一組成に溶製することは困難で、また
不純物が多いことから、得られるインゴットは塑性加工
に際し極めて割れやすいという欠点がある。Further, it is difficult to melt Al and Li in a uniform composition, and since there are many impurities, the obtained ingot has a drawback that it is extremely fragile during plastic working.
これに対し、粉末冶金方式は、粉末を混合・ホットプレ
ス法等で成形するため、この混合中に雰囲気ガスの巻き
込み等による酸化物の生成があり、しかも得られた粉末
は爆発しやすいことから、保存が困難であるという問題
もある。On the other hand, in the powder metallurgy method, the powder is molded by the mixing / hot pressing method, etc., so that the oxide is generated due to the entrainment of the atmospheric gas during the mixing, and the obtained powder is easy to explode. There is also a problem that it is difficult to store.
本発明は、上記従来の実情に鑑み、Al−Li系合金の工業
的に極めて有利な溶製方法を提供するものであって、Al
−Li系合金を溶製するに際し、溶解炉内面及び溶湯と接
触する部分が窒化けい素(Si3N4)、窒化ホウ素(BN)、窒
化アルミニウム(AlN)、ホウ化ジルコニウム(ZrB2)、ホ
ウ化チタン(TiB2)およびリチュウムアルミネート(LiAlO
2)の１種よりなる耐火物で構成された容器を用いて、Li
に対し不活性なガス雰囲気（Al又はHe）中にて溶製する
ことを特徴とするAl−Li系合金の溶製方法を要旨とする
ものである。In view of the above-mentioned conventional circumstances, the present invention provides an industrially extremely advantageous melting process of Al-Li alloys.
Upon which smelted -Li alloy, melting furnace inner surface and portions of silicon nitride in contact with the molten metal (Si 3 N 4), boron nitride (BN), aluminum nitride (AlN), zirconium boride (ZrB 2), Titanium boride (TiB 2 ) and lithium aluminate (LiAlO
Using a container made of a refractory made of 1) of 2 ),
On the other hand, the gist is a melting method of an Al-Li alloy, which is characterized in that the melting is performed in an inert gas atmosphere (Al or He).
本発明の構成と作用につき詳細に説明する。なお、本明
細書において「％」は「重量％」を示す。The configuration and operation of the present invention will be described in detail. In addition, in this specification, "%" shows "weight%."
本発明において、Al−Li系合金とは、（1.7〜2.9％）Li
−（0.4〜3.3％）Cu−（0.2〜1.9％）Mg−（0.04〜0.16
％）Zrを含有するAl−Li系合金であって、その他の元素
として、Si,Fe,Mn,Cr,Zn,Ti,Na,Ca,Ｋを一定量以下に制
限する必要がある。このうち、Na,Ca,Kは、靱性の改善
のため、これらの全量で１０ppm以下に制限する必要が
ある。In the present invention, an Al-Li alloy means (1.7 to 2.9%) Li.
− (0.4 to 3.3%) Cu− (0.2 to 1.9%) Mg− (0.04 to 0.16)
%) Zr-containing Al-Li alloy, and as other elements, Si, Fe, Mn, Cr, Zn, Ti, Na, Ca and K must be limited to a certain amount or less. Of these, Na, Ca, and K must be limited to 10 ppm or less in total in order to improve toughness.
本発明においては、このようなAl−Li系合金を、内面が
窒化けい素(Si3N4)、窒化ホウ素(BN)、窒化アルミニウ
ム(AlN)、ホウ化ジルコニウム(ZrB2)、ホウ化チタン(Ti
B2)およびリチュウムアルミネート(LiAlO2)の１種より
なる耐火材料で構成された容器を用い、Liに対して不活
性であるAr,He雰囲気下で、常法例えば高周波あるいは
低周波誘導加熱法等で加熱して溶解させて溶解する。前
記のような耐火材料は、CaO,SiO2含有量が少ないため、
Liとの反応は少なく不純物の生成が軽減されて、溶湯の
汚染は防止される。In the present invention, such Al-Li alloy, the inner surface is silicon nitride (Si 3 N 4), boron nitride (BN), aluminum nitride (AlN), zirconium boride (ZrB 2), titanium boride (Ti
B 2 ) and lithium aluminate (LiAlO 2 ), a container made of a refractory material, and using a conventional method such as high-frequency or low-frequency induction heating in an Ar, He atmosphere that is inert to Li. It is dissolved by heating by a method or the like. Since the refractory material as described above has a low CaO, SiO 2 content,
Since the reaction with Li is small and the generation of impurities is reduced, the contamination of the molten metal is prevented.
これらの物質は、高融点であると共に高温で極めて安定
であり、Liと反応してLi2O酸化物を生成することがなく
溶湯は不純物により汚染することがない。These substances have a high melting point, are extremely stable at high temperatures, do not react with Li to form Li 2 O oxides, and the molten metal is not contaminated by impurities.
このため、内面が前記耐火材料の１つよりなる炉材で構
成された容器を用いることにより、従来溶製困難とされ
た高純度なAl−Li系合金の溶製が可能となった。Therefore, by using a container whose inner surface is made of a furnace material made of one of the refractory materials, it has become possible to melt a high-purity Al-Li alloy, which has been conventionally difficult to melt.
本発明を実施例及び比較例によりさらに具体的に説明す
るが、本発明はその要旨を越えない限り以下の実施例に
限定されるものでとない。The present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist.
実施例１ 第１図は本発明の実施に使用する溶解炉の概要を示して
おり、加熱炉１内にArなど不活性雰囲気の流入するよう
にした気密容器２を装入し、該容器に溶湯４を入れた試
験用ルツボ３を収納する。気密容器には酸素濃度計の検
出部５が、試験用ルツボには熱電対６がそれぞれ設置さ
れる。このような溶解炉を用いAl−Li溶湯に対する不純
物量（溶湯汚染）を調査した。使用した耐火物は、第１
表に示す１４種類であり、不純物成分がSi＝１６０pp
m、Fe＝４４０ppm、Ca,Na,Cr,Mgが１０ppm以下であるAl
−2.5％Li合金を、上記１４種類の耐火物ルツボに装入
し（第１図）、これを気密容器に入れ、８５０℃で、Ar
を流通させながら溶解し、溶湯中の不純物の増加量を調
べた。その結果を第１表に示した。Example 1 FIG. 1 shows an outline of a melting furnace used for carrying out the present invention. An airtight container 2 in which an inert atmosphere such as Ar is allowed to flow is placed in the heating furnace 1, and the container is put in the container. The test crucible 3 containing the molten metal 4 is stored. An oxygen concentration detector 5 is installed in the airtight container, and a thermocouple 6 is installed in the test crucible. Using such a melting furnace, the amount of impurities (molten metal contamination) in the Al-Li molten metal was investigated. The refractory used is the first
There are 14 types shown in the table, and the impurity component is Si = 160pp
m, Fe = 440ppm, Ca, Na, Cr, Mg is less than 10ppm Al
-2.5% Li alloy was charged into the above 14 types of refractory crucibles (Fig. 1), and this was placed in an airtight container and heated at 850 ° C for Ar.
Was melted while circulating, and the amount of increase in impurities in the molten metal was examined. The results are shown in Table 1.
No.１〜６は、本発明の耐火物を使用した場合で、Siが
２２０〜２９０ppm、Feが４４０〜４７０ppmに増加した
が、窒化アルミニウムのCa２０ppmを除きCa,Na,Cr,Mgの
増加は認められなかった。 Nos. 1 to 6 were obtained when the refractory material of the present invention was used, Si increased to 220 to 290 ppm and Fe increased to 440 to 470 ppm, but Ca, Na, Cr and Mg were increased except for Ca 20 ppm of aluminum nitride. I was not able to admit.
しかし、比較例のNo.７は、９０％のアルミナ耐火物を
使用した場合で、Siが１０００ppm、Caが２０ppmに増加
し、不純物が多くなり、好ましくない。However, No. 7 of Comparative Example is a case where 90% alumina refractory is used, Si is increased to 1000 ppm, Ca is increased to 20 ppm, and impurities are increased, which is not preferable.
No.８は、通常の８５％のアルミナ耐火物を使用した場
合で、Siが１２５０ppm、Caが２７ppmに増加し、不純物
が多くなり、好ましくない。No. 8 is a case where normal 85% alumina refractory is used, Si is increased to 1250 ppm, Ca is increased to 27 ppm, and impurities are increased, which is not preferable.
No.９は、Al2O3−Cr2O3耐火物を使用した場合で、Siが
１５００ppm、Caが２９００ppm、Crが７％および不溶性
不純物が６％に増加し、不純物が多くなり、好ましくな
い。No. 9 is a case where Al 2 O 3 —Cr 2 O 3 refractory is used, Si is 1500 ppm, Ca is 2900 ppm, Cr is 7% and insoluble impurities are increased to 6%, and impurities are increased, which is preferable. Absent.
No.１０は、MgO耐火物を使用した場合で、Si,Ca,Fe,Mg
が若干増加するほか、不溶性不純物が１％増加し、不純
物が多くなり、好ましくない。ただし、Mgは、本合金の
基本成分として含有する場合があるので、不純物とはな
らないこともある。No. 10 is the case of using MgO refractory, Si, Ca, Fe, Mg
Is slightly increased, insoluble impurities are increased by 1%, and impurities are increased, which is not preferable. However, since Mg may be contained as a basic component of the present alloy, it may not be an impurity.
No.１１は、MgO−CaO耐火物を使用した場合で、Caが１
５００ppmに増加し、好ましくない。No. 11 is the case where MgO-CaO refractory is used and Ca is 1
Increased to 500 ppm, which is not preferable.
No.１２は、Al2O3−MgO耐火物を使用した場合で、Si,Fe
が若干増加した。No. 12 is a case of using Al 2 O 3 -MgO refractory material, Si, Fe
Has increased slightly.
No.１３は、酸化物ボンドで固めたSiC耐火物を使用した
場合で、Si,Ca,Fe,Crおよび不溶性不純物が４％に増加
し、好ましくない。No. 13 is a case where a SiC refractory hardened by an oxide bond is used, and Si, Ca, Fe, Cr and insoluble impurities increase to 4%, which is not preferable.
No.１４は、窒化物ボンドで固めたSiC耐火物を使用した
場合で、Si,Ca,Feおよび不溶性不純物が５％に増加し、
好ましくない。No. 14 is the case where SiC refractory hardened by nitride bond is used, Si, Ca, Fe and insoluble impurities increase to 5%,
Not preferable.
実施例２ 実施例１と同様な溶解を行い、８５０℃で１００時間保
持し、耐火物の耐破損性、溶湯浸透性、耐侵食性等を調
査した。その結果を第１表に示す。Example 2 Melting was carried out in the same manner as in Example 1, held at 850 ° C. for 100 hours, and the breakage resistance, molten metal permeability, erosion resistance, etc. of the refractory were investigated. The results are shown in Table 1.
No.１〜６の本発明の耐火物の場合は、溶湯の浸透が若
干見られたが、耐破損性、耐侵食性に優れるものであっ
た。しかし、比較例の耐火物は、溶湯浸透が大きく、破
損や侵食が見られるものがある。In the case of the refractories of the present invention of Nos. 1 to 6, although some penetration of the molten metal was observed, they were excellent in breakage resistance and erosion resistance. However, the refractory materials of Comparative Examples have large penetration of molten metal, and some of them show breakage or erosion.
以上詳述したとおり、本発明のAl−Li系合金の溶製方法
は、 酸化物介在物量が低減され、酸素、窒素、水素等のコ
ンタミの少ないAl−Li系合金を容易に得ることができ
る。As described in detail above, the method for producing an Al-Li alloy according to the present invention can easily obtain an Al-Li alloy having a reduced amount of oxide inclusions and less contamination such as oxygen, nitrogen, and hydrogen. .
従って、得られる合金は極めて強度等の特性に優れた
ものとなる。Therefore, the obtained alloy has extremely excellent properties such as strength.
極めて均質な組成の合金が得られる。An alloy of very homogeneous composition is obtained.
このため、鋳造後のインゴットは、鋳造に際して割れ
ることがなく、Al−Li系合金の溶解、鋳造を安定かつ容
易に行える。Therefore, the ingot after casting does not crack during casting, and the Al—Li alloy can be melted and cast stably and easily.
等の様々な効果が奏され、工業的に極めて有利である。Various effects such as are exhibited, and it is extremely advantageous industrially.
第１図は本発明方法の実施に使用する溶解炉の概要図で
ある。 １…加熱炉 ２…気密容器 ３…試験用ルツボ ４…溶湯 ５…酸素濃度計検出部 ６…熱電対FIG. 1 is a schematic diagram of a melting furnace used for carrying out the method of the present invention. 1 ... Heating furnace 2 ... Airtight container 3 ... Test crucible 4 ... Molten metal 5 ... Oxygen concentration detector 6 ... Thermocouple
Claims (1)
し、溶解炉内面及び溶湯と接触する部分が、窒化けい素
(Si3N4)、窒化ホウ素(BN)、窒化アルミニウム(AlN)、ホ
ウ化ジルコニウム(ZrB2)、ホウ化チタン(TiB2)およびリ
チュウムアルミネート(LiAlO2)の１種で構成された容器
を用いて、不活性ガス雰囲気中にて溶製することを特徴
とするAl−Li系合金の溶製方法。1. When melting an Al- (1.5 to 3.0%) Li-based alloy, the inner surface of the melting furnace and the portion in contact with the molten metal are silicon nitride.
(Si 3 N 4 ), boron nitride (BN), aluminum nitride (AlN), zirconium boride (ZrB 2 ), titanium boride (TiB 2 ), and lithium aluminate (LiAlO 2 ) Is used to melt in an inert gas atmosphere, and a method for melting an Al-Li alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1259905A JPH0611890B2 (en) | 1989-10-06 | 1989-10-06 | Method for melting A1-Li alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1259905A JPH0611890B2 (en) | 1989-10-06 | 1989-10-06 | Method for melting A1-Li alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03122231A JPH03122231A (en) | 1991-05-24 |
| JPH0611890B2 true JPH0611890B2 (en) | 1994-02-16 |
Family
ID=17340561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1259905A Expired - Lifetime JPH0611890B2 (en) | 1989-10-06 | 1989-10-06 | Method for melting A1-Li alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611890B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0645831B2 (en) * | 1986-01-07 | 1994-06-15 | 三井造船株式会社 | Method for melting Al-Li alloy |
-
1989
- 1989-10-06 JP JP1259905A patent/JPH0611890B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03122231A (en) | 1991-05-24 |
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