JPH0660363B2 - Internal oxidation type alloy and method for producing molded article thereof - Google Patents
Internal oxidation type alloy and method for producing molded article thereofInfo
- Publication number
- JPH0660363B2 JPH0660363B2 JP61143770A JP14377086A JPH0660363B2 JP H0660363 B2 JPH0660363 B2 JP H0660363B2 JP 61143770 A JP61143770 A JP 61143770A JP 14377086 A JP14377086 A JP 14377086A JP H0660363 B2 JPH0660363 B2 JP H0660363B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- internal oxidation
- oxygen
- oxidation type
- type 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.)
- Expired - Lifetime
Links
- 229910045601 alloy Inorganic materials 0.000 title claims description 109
- 239000000956 alloy Substances 0.000 title claims description 109
- 238000007254 oxidation reaction Methods 0.000 title claims description 102
- 230000003647 oxidation Effects 0.000 title claims description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 29
- 230000006698 induction Effects 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims 1
- 238000011282 treatment Methods 0.000 description 38
- 239000000523 sample Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910019819 Cr—Si Inorganic materials 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/80—General aspects of machine operations or constructions and parts thereof
- B29C66/83—General aspects of machine operations or constructions and parts thereof characterised by the movement of the joining or pressing tools
- B29C66/832—Reciprocating joining or pressing tools
- B29C66/8322—Joining or pressing tools reciprocating along one axis
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (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、内部酸化型合金およびその成形物の製造方法
に関するものである。TECHNICAL FIELD The present invention relates to an internal oxidation type alloy and a method for producing a molded product thereof.
従来、内部酸化型合金の製造方法としては、例えば溶製
法により２種以上の金属を混合させて、母相金属中に、
合計が２０重量％以下となる範囲内で母相金属以外の１
種もしくはそれ以上の金属が含有された合金を得たの
ち、内部酸化剤として金属酸化物粉末を当該合金の周囲
に接触させた状態で母相金属の融点近くの高温に加熱す
ることにより合金の内部における母相金属以外の１種も
しくはそれ以上の金属のみを選択的に酸化処理（以下
「選択酸化処理」という）する方法が知られている。Conventionally, as a method for producing an internal oxidation type alloy, for example, by mixing two or more kinds of metals by a melting method,
1 other than the matrix metal within the range where the total is 20% by weight or less
After obtaining an alloy containing one or more metals, the metal oxide powder as an internal oxidizer is heated to a high temperature near the melting point of the parent phase metal in a state of being in contact with the periphery of the alloy to form an alloy. A method is known in which only one or more metals other than the matrix metal inside are selectively oxidized (hereinafter referred to as “selective oxidation”).
このようにして得られる内部酸化型合金は、母相金属の
内部に高強度の微粒子状金属酸化物を含有しており、そ
の微粒子状金属酸化物が転位を阻止する作用を果すた
め、選択酸化処理前のものと比較して引張り強度が上昇
し、しかもこれに加えて母相金属の融点近くの高温にお
いてもなお高強度が維持されるという特性を有するもの
となる。そして内部酸化型合金はこのような優れた特性
を有することから、特に力学的強度と耐熱性との両方が
同時に必要とされるような用途の材料、例えばゴム・プ
ラスチツク用金型材料、タービンブレード、電気接点等
の材料として注目されている。The internal oxidation type alloy thus obtained contains a high-strength fine-grain metal oxide inside the matrix metal, and since the fine-grain metal oxide functions to prevent dislocation, the selective oxidation is performed. The tensile strength is higher than that before the treatment, and in addition to that, the strength is maintained even at a high temperature near the melting point of the matrix metal. And since the internal oxidation type alloy has such excellent properties, it is a material for applications in which both mechanical strength and heat resistance are required at the same time, for example, rubber / plastic mold materials, turbine blades. , Has attracted attention as a material for electrical contacts.
さらに斯かる内部酸化型合金は、上記のような優れた力
学的強度と耐熱性とを有しながらなお母相金属の特性が
そのまま保有されるため、当該母相金属の特性をそのま
ま利用することができ、種々の応用が期待され、具体的
には例えば母相金属が銅である場合に得られる内部酸化
型合金は、銅と同等の高い電気伝導性と熱伝導性を維持
しながら優れた力学的強度と耐熱性とを有するものとな
ることから耐高温導電材料、ヒートシンク材料などとし
ての用途が期待されている。Further, such an internal oxidation type alloy retains the characteristics of the parent phase metal as it is while having the above-mentioned excellent mechanical strength and heat resistance. Therefore, the characteristics of the parent phase metal should be used as they are. , And various applications are expected. Specifically, for example, the internal oxidation type alloy obtained when the matrix metal is copper is excellent while maintaining high electrical conductivity and thermal conductivity equivalent to copper. Since it has mechanical strength and heat resistance, it is expected to be used as a high temperature resistant conductive material, a heat sink material and the like.
しかしながら従来の内部酸化型合金の製造方法において
は以下のような欠点があった。However, the conventional method for producing an internal oxidation type alloy has the following drawbacks.
選択酸化処理工程において、外部から母相金属の融点
近くの高温に加熱することが必要であるため、エネルギ
ー効率が低く、製造コストが高くなり、しかも大量生産
に不利である。In the selective oxidation treatment step, it is necessary to externally heat to a high temperature close to the melting point of the mother phase metal, so that the energy efficiency is low, the manufacturing cost is high, and it is disadvantageous for mass production.
選択酸化処理は、内部酸化剤である金属酸化物粉末の
熱反応による酸素の放出、およびその酸素の合金内部へ
の拡散を利用するため、酸化反応の直接的制御が困難で
あり、しかも酸化反応の速度が非常に低く、また選択酸
化処理は、酸素の合金内部への拡散が酸化反応の律速と
なるため、大きな形状の合金の内部酸化を行うには非常
に長時間を要し、実際上不可能な場合も少なくない。Since the selective oxidation treatment utilizes release of oxygen by thermal reaction of metal oxide powder as an internal oxidant and diffusion of the oxygen into the alloy, it is difficult to directly control the oxidation reaction. The rate of oxidation is very low, and in the selective oxidation treatment, the diffusion of oxygen into the alloy is the rate-determining factor for the oxidation reaction. In many cases it is impossible.
選択酸化処理後において、内部酸化剤の粉末から目的
物である内部酸化型合金を分離するための工程が必要で
ある。そして、選択酸化処理を大きな速度で行うことの
できる点で有利な粒子状の合金を用い、これを選択酸化
処理して得られる粒子状の内部酸化型合金を成形し焼結
して内部酸化型合金成形物を得ることも考えられるが、
この場合には、内部酸化剤も粉末状であることから、選
択酸化処理後の内部酸化型合金と内部酸化剤との分離は
極めて困難である。After the selective oxidation treatment, a step for separating the target internal oxidation type alloy from the powder of the internal oxidizing agent is necessary. Then, a granular alloy, which is advantageous in that the selective oxidation treatment can be carried out at a high speed, is used, and the granular internal oxidation type alloy obtained by subjecting this to selective oxidation treatment is molded and sintered to form an internal oxidation type alloy. It is possible to obtain an alloy molded product,
In this case, since the internal oxidant is also in powder form, it is extremely difficult to separate the internal oxidation type alloy and the internal oxidizer after the selective oxidation treatment.
本発明の目的は、２種以上の金属元素より成る合金につ
いて、低温でも速い速度で選択酸化処理を行うことがで
き、しかも選択酸化処理を大きな自由度で制御すること
ができ、従って所要の特性を有する内部酸化型合金を容
易に得ることのできる製造方法を提供することにある。The object of the present invention is to perform an selective oxidation treatment at a high speed even at a low temperature on an alloy composed of two or more kinds of metal elements, and moreover, it is possible to control the selective oxidation treatment with a large degree of freedom, so that the required characteristics can be obtained. Another object of the present invention is to provide a manufacturing method capable of easily obtaining an internal oxidation type alloy having
また本発明の他の目的は、内部酸化型合金より成る成形
物を、その大きさの如何にかかわらず、容易に製造する
ことのできる方法を提供することにある。Another object of the present invention is to provide a method capable of easily producing a molded article made of an internal oxidation type alloy regardless of its size.
〔問題点を解決するための手段〕 本発明においては、内部酸化型合金の製造方法におい
て、２種以上の金属元素より成る合金に、酸素および／
または酸素原子を有する化合物のガス（以下これらを
「酸素含有ガス」という。）の存在下において発生させ
たプラズマ（以下「酸素含有プラズマ」という。）を作
用させながら誘導加熱を行うことにより、前記合金にお
けるいわゆる母相金属以外の少なくとも１種の金属元素
を選択的に酸化させることを特徴とし、これによって内
部酸化型合金が形成される。[Means for Solving Problems] In the present invention, in the method for producing an internal oxidation type alloy, oxygen and / or oxygen is added to an alloy composed of two or more metal elements.
Alternatively, by performing induction heating while operating a plasma (hereinafter, referred to as “oxygen-containing plasma”) generated in the presence of a gas of a compound having an oxygen atom (hereinafter, these are referred to as “oxygen-containing gas”), It is characterized in that at least one metal element other than the so-called matrix metal in the alloy is selectively oxidized, whereby an internal oxidation type alloy is formed.
以下、本発明を具体的に説明する。Hereinafter, the present invention will be specifically described.
本発明においては、内部酸化型合金の原料となる合金に
対し、酸素含有ガスによるプラズマを作用させるが、こ
こに用いる合金は、溶製法、スパッタリング法等の方法
によって作ることができる。合金の製造法は制限される
ものではなく、また粒子状の合金を得る場合において
も、上記のような方法で製造された合金塊を原料とする
機械的粉砕方法、電気分散法、アトマイズ法、真空蒸発
法、ガス還元法、液相還元法、電気分解法等を利用する
ことができる。In the present invention, the plasma used as the oxygen-containing gas is caused to act on the alloy that is the raw material of the internal oxidation type alloy. The alloy used here can be produced by a melting method, a sputtering method, or the like. The method for producing the alloy is not limited, and also in the case of obtaining a particulate alloy, a mechanical pulverizing method using the alloy lump produced by the above method as a raw material, an electrical dispersion method, an atomizing method, A vacuum evaporation method, a gas reduction method, a liquid phase reduction method, an electrolysis method or the like can be used.
内部酸化型合金の原料となる合金を形成する金属元素系
としては下記のような固溶体、共融混合物等を形成する
系を例示することができる。なお下記においては、
〔 〕内が母相金属、〔 〕に続くものの１種またはそ
れ以上が母相金属以外の金属とされる元素である。Examples of the metal element system that forms the alloy that is the raw material for the internal oxidation type alloy include the systems that form the following solid solutions and eutectic mixtures. In the following,
The parenthesized metal is inside [], and one or more elements following [] are elements that are considered to be metals other than the parent metal.
〔Ag〕Al As Be Bi Ca Cd Ce Cu Dy Er Eu Ga Gd Ge Hg Ho In La Li Lu Mg Mn Na Nd Ni Pb Pd Pr Pt Pu Sb Sc Sm Sn Sr Tb Te Th Ti Tl Tm Zn Zr Yb 〔Am〕Pu 〔Al〕Ca Mg 〔As〕Eu Nd 〔At〕Ca Ce Dy Er Ga Gd Ge Hg Ho La Lu Nd Pb Pr Pu Ru Sc Se Sm Tb Th Ｖ Vb 〔Au〕Al 〔Ｂ〕Ca Ce Dy Er Gd Hf Ho La Lu Mn Nd Pm Pr Pt Re Rh Ru Sc Si Sm Ta Tb Th Ti Ｖ Ｗ Ｙ Yb Zr Al 〔Ba〕Be Ca Cu Ga Ge Hg In Ni Pb Pd Se Tl Eu Nd Yb Al 〔Be〕Ca Mg Sr 〔Bi〕Dy Gd Hf In La Lu Mn Na Nd Pb Pr Pu Ｙ Yb 〔Ca〕Ga Hf Sm 〔Cd〕Ce Eu La Nd Np Pr Sm Yb Sr Ca 〔Ce〕Cr Cu Eu Ga In Si Sm Tb Th Ti Zr 〔Co〕Al Dy Er Ga Gd Hf Ho La Lu Mn Nd Pr Sm Ta Tb Te Th Ｙ Yb Zr 〔Cr〕Al Ga Hf Ho Ir Lu Mo Nd Pr Rh Si Sm Ta Tb Ti Tm Ｖ 〔Cs〕In Tl 〔Cu〕Al Ca Er Hf Ir La Rh Sc Se Sr Th Ti Ｖ Yb Si 〔Dy〕Fe Ga Mg Mn Nd Pb Pd Pu Ru Sb Te Th Tl Ｙ Zr Al 〔Er〕Al Fe Ga Hf Hg Mg Mn Nd Ni Pt Pu Re Rh Sc Se Te Th Tl Ｖ Zr 〔Eu〕Al Ca Ga In Mg Ni Pb Pd Te Th Yb Ho 〔Fe〕Al Ga Gd Ho In Lu Mg Mo Nd Pr Sc Si Sm Tb Tc Th Ti Tm Yb 〔Ga〕Al Ca Gd Ho Ｋ La Lu Nd Pm Pr Pt Sc Sm Tm Ｕ Ｙ 〔Gd〕Al Ge Hg Mg Nb Pu Te Re Rh Ru Sb Tb Te Th Tl Yb Zr 〔Ge〕La Li Nd Pd Pr Pt Rb Re Se Sm Sr Ｖ Ｗ Ｙ 〔Hf〕Mn Ni Pu Ru Si Tl Ｖ Al 〔Ni〕Al Ca Sr Tc Th Ｖ Ｗ Yb Zr 〔Si〕Al Ti 〔Ti〕Al 内部酸化型合金の原料となる合金においては、母相金属
以外の金属の合計の割合が重量で２０ppm〜２０％であ
ることが内部酸化型合金として特に優れた機能を発揮さ
せるために肝要である。この母相金属以外の金属の割合
が２０ppm未満の場合には、内部の酸化物による強度や
耐熱性の向上幅が小さく、一方２０％を越える場合に
は、母相金属以外の金属の選択酸化処理が困難であっ
て、母相金属も酸化されるようになる。(Ag) Al As Be Bi Ca Cd Ce Cu Dy Er Eu Ga Gd Ge Hg Ho In La Li Lu Mg Mn Na Nd Ni Pb Pd Pr Pt Pu Sb Sc Sm Sn Sr Tb Te Th Ti Tl Tm Zn Zr Yb (Am) Pu [Al] Ca Mg [As] Eu Nd [At] Ca Ce Dy Er Ga Gd Ge Hg Ho La Lu Nd Pb Pr Pu Ru Sc Se Sm Tb Th V Vb [Au] Al [B] Ca Ce Dy Er Gd Hf Ho La Lu Mn Nd Pm Pr Pt Re Rh Ru Sc Si Sm Ta Tb Th Ti V W Y Yb Zr Al 〔Ba〕 Be Ca Cu Ga Ge Hg In Ni Pb Pd Se Tl Eu Nd Yb Al 〔Be〕 Ca Mg Sr 〔 Bi] Dy Gd Hf In La Lu Mn Na Nd Pb Pr Pu Y Yb [Ca] Ga Hf Sm [Cd] Ce Eu La Nd Np Pr Sm Yb Sr Ca [Ce] Cr Cu Eu Ga In Si Sm Tb Th Ti Zr Co] Al Dy Er Ga Gd Hf Ho La Lu Mn Nd Pr Sm Ta Tb Te Th Y Yb Zr [Cr] Al Ga Hf Ho Ir Lu Mo Nd Pr Rh Si Sm Ta Tb Ti Tm V [Cs] In Tl [Cu] Al Ca Er Hf Ir La Rh Sc Se Sr Th Ti V Yb Si [Dy] Fe Ga Mg Mn Nd Pb Pd Pu Ru Sb Te Th Tl Y Zr Al [Er] Al Fe Ga Hf Hg Mg Mn Nd Ni Pt Pu Re Rh Sc Se Te Th Tl V Zr [Eu] Al Ca Ga In Mg Ni Pb Pd Te Th Yb Ho [Fe] Al Ga Gd Ho In Lu Mg Mo Nd Pr Sc Si Sm Tb Tc Th Ti Tm Yb [Ga] Al Ca Gd Ho K La Lu Nd Pm Pr Pt Sc Sm Tm U Y [Gd] Al Ge Hg Mg Nb Pu Te Re Rh Ru Sb Tb Te Th Tl Yb Zr [Ge] La Li Nd Pd Pr Pt Rb Re Se Sm Sr V W Y [Hf] Mn Ni Pu Ru Si Tl V Al [Ni] Al Ca Sr Tc Th V W Yb Zr [Si] Al Ti [Ti] Al Internal oxidation type alloy In the alloy as a raw material, it is important that the total proportion of metals other than the matrix metal is 20 ppm to 20% by weight in order to exert a particularly excellent function as an internal oxidation type alloy. When the ratio of the metal other than the mother phase metal is less than 20 ppm, the improvement in strength and heat resistance due to the internal oxide is small, while when it exceeds 20%, the selective oxidation of the metal other than the mother phase metal is performed. The treatment is difficult and the parent phase metal is also oxidized.
次に、酸素含有プラズマによる選択酸化処理は、通常、
以下の条件によって行われる。Next, the selective oxidation treatment with oxygen-containing plasma is usually
It is performed under the following conditions.
使用される酸素含有ガスの種類としては、O2、CO2、N
O2、N2O3、N2O4、N2O5、SO2、SO3、TeO2、TeO3、SeO2Se
O3、P4O10、P4O6、As2O5、As4O6、Sb2O5、Sb4O6、Bi
2O5、Bi4O6、H2O等を挙げることができる。また、He、A
r、Xeなどの希ガスH2、N2、B2などのガスをキャリアガ
スとして酸素含有ガスに加えることもできる。The types of oxygen-containing gas used include O 2 , CO 2 , and N.
O 2, N 2 O 3, N 2 O 4, N 2 O 5, SO 2, SO 3, TeO 2, TeO 3, SeO 2 Se
O 3 , P 4 O 10 , P 4 O 6 , As 2 O 5 , As 4 O 6 , Sb 2 O 5 , Sb 4 O 6 , Bi
2 O 5 , Bi 4 O 6 , H 2 O and the like can be mentioned. Also, He, A
It is also possible to add a rare gas such as r or Xe such as H 2 , N 2 or B 2 as a carrier gas to the oxygen-containing gas.
プラズマ発生空間における真空度は、１×１０-5〜１０
０Torrであることが好ましい。真空度が１×１０-5Torr
未満または１００Torrを越える場合はプラズマを安定に
かつ均一に発生されることは困難になる。The degree of vacuum in the plasma generation space is 1 × 10 −5 to 10
It is preferably 0 Torr. Vacuum degree is 1 × 10 -5 Torr
If it is less than 100 Torr or more than 100 Torr, it becomes difficult to generate plasma stably and uniformly.
そして斯かる条件において、上記酸素含有ガスの分圧が
１×１０-5〜１０Torrであることが好ましく、さらに好
ましくは１×１０-5〜１Torrである。And in such a condition, it is preferable that the partial pressure of the oxygen-containing gas is 1 × 10 -5 to 10 Torr, more preferably from 1 × 10 -5 ~1Torr.
酸素含有ガスの分圧が１×１０-5Torr未満では、選択酸
化処理の速度が極めて遅く、また、１０Torrを越えると
母相金属が酸化されるおそれがある。When the partial pressure of the oxygen-containing gas is less than 1 × 10 −5 Torr, the selective oxidation treatment rate is extremely slow, and when it exceeds 10 Torr, the parent phase metal may be oxidized.
酸素含有プラズマを発生させる手段、態様、装置等につ
いては特に制限はない。例えば反応器としてはベルジヤ
ー型、チューブラーフロー型などを用い、放電のタイプ
は、直流放電、低周波放電、高周波放電、マイクロ波放
電、陰極加熱型放電等の何れでもよく、電極形式は、平
行平板型、高周波放電による場合のコイル型、ホローカ
ソード型のもの等を用いることもできる。更にマイクロ
波放電の場合には、キャビティーを用いるカップリング
若しくははしご形カップリングによるものを用いてもよ
い。There are no particular restrictions on the means, mode, apparatus, etc. for generating the oxygen-containing plasma. For example, a bell jar type or a tubular flow type is used as the reactor, and the discharge type may be any of DC discharge, low frequency discharge, high frequency discharge, microwave discharge, cathode heating type discharge, etc., and the electrode type is parallel. A flat plate type, a coil type in the case of high frequency discharge, a hollow cathode type, etc. can also be used. Further, in the case of microwave discharge, a coupling using a cavity or a ladder coupling may be used.
電極形式のうち、コイル型の具体列としては円筒型、角
型、平型などを挙げることができる。Among the electrode types, specific examples of the coil type include a cylindrical type, a square type, and a flat type.
本発明を実施するに際し、酸素含有プラズマは正イオン
密度が１０5〜１０12個／cm3の範囲であることが望ま
れ、特に１０5〜１０3個/cm3であることが望まれる。こ
の正イオン密度が１０5個／cm3未満の場合にも、従来の
方法と同程度の選択酸化処理速度を得ることはできる
が、本発明の効果の向上幅が小さいものとなる。一方、
正イオン密度が１０12個／cm3を越える場合には、合金
表面のみが酸素含有プラズマにより過度に加熱され、合
金の変形、内部酸化処理の均一性の低下が起る場合があ
る。この正イオン密度の測定は、例えば探針法やマイク
ロ波法を利用して行うことができる（文献「フィジック
ス レビュー（Phys．Rev.）」（１９５０）、８０、５
８、「ジャーナルオブ アプライド フィジックス
（J．Appl．Rhys.）」（１９６２）、３３、５７５「ア
ール シーエイ レビュー（RCA．Rev）（１９５１）、
１２、１９１参照）。正イオン密度が１０5〜１０12個
／cm3の範囲となるように制御することはきわめて容易
に行うことができ、具体的な制御手段としては、誘えば
酸素含有プラズマの放電電流を調節する手段、酸素含有
プラズマの発生空間の真空度を調節する手段、電極形式
が平行平板型の場合には電極間距離を調節する手段、キ
ャリアガスの流量を調節する手段、合金の位置と電極あ
るいはキャビティーの相対位置を調節する手段等、プラ
ズマの状態およびプラズマを作用させる条件に影響を与
える因子を制御する手段から、好ましいものを選んで利
用することができる。In carrying out the present invention, the oxygen-containing plasma preferably has a positive ion density in the range of 10 5 to 10 12 ions / cm 3 , and more preferably 10 5 to 10 3 ions / cm 3 . Even if the positive ion density is less than 10 5 / cm 3 , the selective oxidation treatment rate similar to the conventional method can be obtained, but the improvement of the effect of the present invention is small. on the other hand,
When the positive ion density exceeds 10 12 ions / cm 3 , only the alloy surface is excessively heated by the oxygen-containing plasma, which may cause deformation of the alloy and deterioration of uniformity of internal oxidation treatment. The measurement of the positive ion density can be performed by using, for example, a probe method or a microwave method (reference “Phys. Rev.” (1950), 80 , 5).
8, “Journal of Applied Physics (J. Appl. Rhys.)” (1962), 33 , 575 “RCA Rev (RCA. Rev) (1951),
12 , 191). It is extremely easy to control the positive ion density to be in the range of 10 5 to 10 12 ions / cm 3 , and specific control means is to adjust the discharge current of the oxygen-containing plasma. Means, means for adjusting the degree of vacuum in the oxygen-containing plasma generation space, means for adjusting the distance between the electrodes when the electrode type is a parallel plate type, means for adjusting the flow rate of carrier gas, position of the alloy and electrode or cavity A preferable one can be selected and used from the means for controlling the factors that influence the state of the plasma and the conditions under which the plasma acts, such as means for adjusting the relative position of the tee.
酸素含有プラズマを発生させるときの酸素含有ガスの流
量は、例えば内容積１５０のプラズマリアクターを用
いる場合には、０．１〜１００cc（ＳＴＰ）／分の範囲
とするのが好ましい。酸素含有ガスの流量が０．１cc
(ＳＴＰ)／分末端の場合には選択酸化処理速度が小さ
く、１００cc（ＳＴＰ）／分を越える場合には目的とす
る選択酸化処理が困難となって母相金属も酸化されるお
それがある。The flow rate of the oxygen-containing gas when generating the oxygen-containing plasma is preferably in the range of 0.1 to 100 cc (STP) / minute when using a plasma reactor having an inner volume of 150, for example. Oxygen-containing gas flow rate is 0.1cc
In the case of (STP) / minute terminal, the selective oxidation treatment rate is low, and in the case of more than 100 cc (STP) / minute, the target selective oxidation treatment becomes difficult and the parent phase metal may be oxidized.
さらに、本発明における酸素含有プラズマの電子温度
は、通常１０，０００〜１００，０００Ｋである。Further, the electron temperature of the oxygen-containing plasma in the present invention is usually 10,000 to 100,000K.
本発明において合金の選択酸化処理は、既述の酸素含有
ガスを入れた容器内において、酸素含有プラズマを発生
させ、合金に作用させながら誘導加熱を行い、合金を加
熱するこによって行なう。In the present invention, the selective oxidation treatment of the alloy is performed by heating the alloy by generating oxygen-containing plasma in the container containing the oxygen-containing gas described above and performing induction heating while acting on the alloy.
本発明において、誘導加熱とは電気による加熱の一方式
であり、交番磁場中に金属のような良導体を置くと、電
磁誘電作用によりこれにウズ電流が流れ、ウズ電流損で
発熱し、被加熱物体が磁性体の場合にはこれを更にヒス
テリシス損失も加わって良導体が発熱する現象である。In the present invention, induction heating is a method of heating by electricity, and when a good conductor such as a metal is placed in an alternating magnetic field, a nose current flows through it due to an electromagnetic dielectric effect, and heat is generated due to nose current loss, and the object to be heated is heated. When the object is a magnetic material, this is a phenomenon in which a good conductor also generates heat by adding hysteresis loss.
本発明において、この誘導加熱を行う電極、態様、装置
等についても特に制限はなく、例えば電源周波数は、低
周波、高周波、マイクロ波等のいずれでも良いが、一般
的には５０Hz〜３０００ＭＨｚが好ましい。また、試料
となる合金の形状が粒子状の場合にはマイクロ波を用い
ることが好ましい。In the present invention, there are no particular restrictions on the electrodes, modes, devices, etc. that perform this induction heating. For example, the power supply frequency may be any of low frequency, high frequency, microwave, etc., but generally 50 Hz to 3000 MHz is preferable. . Further, it is preferable to use a microwave when the shape of the sample alloy is particulate.
なお、誘導加熱を行うための電極形式としては、例えば
前記に例示されたプラズマを発生させるコイル型と同様
のコイル型のものを用いることができるが、試料となる
合金の形状によって適宜選択する。例えば試料となる合
金の形状が円柱形の場合には円筒型コイルが、合金の形
状が板状の場合には平板コイルが好みしく、試料となる
合金は、通常、コイルの内部に位置させる。As the electrode type for performing the induction heating, for example, a coil type similar to the coil type for generating the plasma described above can be used, but it is appropriately selected depending on the shape of the sample alloy. For example, a cylindrical coil is preferred when the shape of the alloy serving as the sample is a cylindrical shape, and a flat plate coil is preferred when the shape of the alloy is a plate, and the alloy serving as the sample is usually positioned inside the coil.
誘導加熱による合金の温度は、合金の融点以下であれば
特に限定するものではないが、合金の融点を「Tm」とする
と、０．４Tm〜０．９Tmとすることが好ましい。合金の
温度が０．９Tmを越える場合には合金の変形、内部酸化
状態の均一性が悪化する場合があり、また０．４Tm未満
の場合に、選択酸化処理速度がさほど大きくならない。The temperature of the alloy by induction heating is not particularly limited as long as it is equal to or lower than the melting point of the alloy, but when the melting point of the alloy is "Tm", it is preferably 0.4 Tm to 0.9 Tm. If the temperature of the alloy exceeds 0.9 Tm, the deformation of the alloy and the uniformity of the internal oxidation state may deteriorate, and if it is less than 0.4 Tm, the selective oxidation treatment rate does not increase so much.
酸素含有プラズマの発生と誘導加熱は同一容器内で１台
の電極を用いて同時に作用させても２台以上の電極によ
り酸素含有プラズマの発生と誘導加熱を独立あるいは相
補的に作用させてもよい。The generation of oxygen-containing plasma and induction heating may be performed simultaneously by using one electrode in the same container, or the generation of oxygen-containing plasma and induction heating may be performed independently or complementarily by two or more electrodes. .
なお、本発明においては、誘導加熱以外にヒーター、赤
外線等により、外部から補助的に合金を加熱することも
できる。In the present invention, in addition to induction heating, the alloy can be supplementarily heated from the outside by a heater, infrared rays, or the like.
本発明において、内部酸化型合金の成形物を製造する場
合には、粒子状合金を使用し、選択酸化処理を行った
後、成形し焼結することが好ましく、その際粒子状合金
の平均粒径は、５０Å〜１００μｍであることが好まし
い。粒子状合金の平均粒径が５０Å未満の場合には目的
とする母相金属以外の金属の酸化が適正に行われず、例
えば粒子状合金の周辺のみに酸化物領域が偏在するよう
になるほど、粒子状合金中における酸化物の領域が不均
一に分散することとなる。このため、焼結により成形物
としたときに酸化領域の間隔が不均一になり、この結
果、酸化物領域の分散による強化が適正に行われず、良
好な物性を有する成形品を得ることができない。また粒
子状合金の平均粒径が１００μｍを越える場合には、粒
子状合金自体の金属組成比が異種金属間の比重差によっ
て不均一となりやすく、選択酸化処理を行った後、成形
し焼結を行っても酸化物領域の分散がやはり不均一とな
り、また選択酸化処理後の焼結性が悪く、また選択酸化
処理に要する時間も長くなる。In the present invention, in the case of producing a molded product of an internal oxidation type alloy, it is preferable to use a particulate alloy, perform a selective oxidation treatment, and then mold and sinter, in which case the average grain size of the particulate alloy. The diameter is preferably 50Å to 100 μm. If the average particle size of the particulate alloy is less than 50Å, the metal other than the intended mother phase metal is not properly oxidized, and for example, the oxide region becomes unevenly distributed only around the particulate alloy. The oxide regions in the alloy are dispersed unevenly. For this reason, the interval between the oxidized regions becomes nonuniform when formed into a molded product by sintering, and as a result, strengthening due to dispersion of the oxide region is not performed properly, and a molded product having good physical properties cannot be obtained. . Further, when the average particle diameter of the particulate alloy exceeds 100 μm, the metal composition ratio of the particulate alloy itself tends to be non-uniform due to the difference in specific gravity between different metals, and after performing selective oxidation treatment, molding and sintering are performed. Even if it is carried out, the dispersion of the oxide region is still non-uniform, the sinterability after the selective oxidation treatment is poor, and the time required for the selective oxidation treatment becomes long.
なお、内部酸化型合金粒子を成形して焼結する際の温度
は、原料となる合金の融点を「Tm」とすると、通常０．
４Tm〜０．９Tmである。The temperature at which the internal oxidation type alloy particles are molded and sintered is usually 0.degree. C. when the melting point of the raw material alloy is "Tm".
It is 4 Tm to 0.9 Tm.
以下に内部酸化型合金の用途を記す。電子材料として
は、ＩＣ用リードフレーム、サーキットブレーカーやリ
レー等の接点、高温用導線、電磁石用導線、電気コネク
ター、極細導線等の用途があり、主にＣｕ−Ａｌ、Ｃｕ
−Ｓｉ等の銅系内部酸化型合金が好適に用いられる。The uses of the internal oxidation type alloy are described below. Electronic materials include applications such as lead frames for ICs, contacts for circuit breakers and relays, high-temperature conducting wires, electromagnet conducting wires, electrical connectors, and ultra-fine conducting wires. Mainly Cu-Al, Cu
A copper-based internal oxidation type alloy such as -Si is preferably used.
機械用途では、モーター用回転軸やコミューター、熱機
関におけるノズル、ランスチップ、電気用フィードスル
ー、タービンローター、タービンブレード、ピストン、
ピストンリング、シリンダー等、さらに歯車、チェー
ン、ベアリング、ブレーキ用ディスク、溶接用電極、バ
ネ材料等を挙げることができる。これらは銅系のみでな
くＦｅ−Ａｌ、Ｆｅ−Ｓｉ等の鉄系内部酸化型合金やＣ
ｏ−Ｈｆ、Ｃｏ−Ｔｈ等のコバルト系内部酸化型合金、
Ｃｒ−Ｓｉ、Ｃｒ−Ｔｉ等のクロム系内部酸化型合金、
Ｎｉ−Ａｌ、Ｎｉ−Ｖ等のニッケル系内部酸化型合金等
も用いることができる。In mechanical applications, rotary shafts and commuter for motors, nozzles in heat engines, lance tips, electrical feedthroughs, turbine rotors, turbine blades, pistons,
Piston rings, cylinders and the like, as well as gears, chains, bearings, brake discs, welding electrodes, spring materials and the like can be mentioned. These are not only copper-based but also iron-based internal oxidation type alloys such as Fe-Al and Fe-Si and C.
Co-based internal oxidation type alloys such as o-Hf and Co-Th,
Chromium-based internal oxidation type alloys such as Cr-Si and Cr-Ti,
A nickel-based internal oxidation type alloy such as Ni-Al or Ni-V can also be used.
また、銅系内部酸化型合金は、ゴム、樹脂、アルミダイ
カスト等用の高温用金型の材料として用いることができ
る。Further, the copper-based internal oxidation type alloy can be used as a material for a high temperature mold for rubber, resin, aluminum die casting and the like.
Ａｕ−Ａｌ、Ａｇ−Ａｌ、等の貴金属内部酸化型合金
は、導電線材料、接点材料、指輪、ネックレス、時計等
の各種装飾品等に用いることができる。The noble metal internal oxidation type alloys such as Au-Al and Ag-Al can be used for conductive wire materials, contact materials, various ornaments such as rings, necklaces and watches.
実施例１および比較例１ 溶製法によって製造したアルミニウム含有量が１．０重
量％の銅−アルミニウム合金(融点１３５８Ｋ)より成る
長さ５０mm、幅５mm、厚さ２００μｍの板を試料３と
し、マイクロ波導波管を用いる第１図に示す構造のプラ
ズマ発生装置を用い、内容席３の石英製の反応管１内
のキャビティの位置に、上記試料３を誘導加熱が行える
ように保持した。Example 1 and Comparative Example 1 A plate having a length of 50 mm, a width of 5 mm and a thickness of 200 μm made of a copper-aluminum alloy (melting point 1358 K) having an aluminum content of 1.0% by weight, which was manufactured by a melting method, was used as Sample 3, and a micro sample was prepared. Using the plasma generator having the structure shown in FIG. 1 using a wave waveguide, the sample 3 was held at the position of the cavity in the quartz reaction tube 1 in the content seat 3 so that induction heating could be performed.
次いで反応管１内への酸素含有ガスの条件および酸素含
有プラズマ発生条件および誘電加熱温度を第１表に示す
ように設定し、酸素含有プラズマおよび誘導加熱による
選択酸化処理を２時間行い内部酸化型合金を製造した。Next, the conditions of the oxygen-containing gas into the reaction tube 1, the oxygen-containing plasma generation conditions, and the dielectric heating temperature are set as shown in Table 1, and the selective oxidation treatment by the oxygen-containing plasma and induction heating is performed for 2 hours to perform internal oxidation. An alloy was produced.
製造された内部酸化型合金を切断機により切断し、さら
にその断面を研摩し塩化第２鉄腐食液（無水塩化第２鉄
５ｇ＋塩酸２cc＋エタノール９６cc）にて腐食させたの
ち金属顕微鏡にて断面観察を行ったところ内部酸化が行
われている領域は茶色い斑点状に見ることができ、これ
により内部酸化が行われた層の厚みを測定することがで
きた。The produced internal oxidation type alloy is cut with a cutting machine, and the cross section is further polished and corroded with ferric chloride corrosive liquid (anhydrous ferric chloride 5 g + hydrochloric acid 2 cc + ethanol 96 cc) and then observed with a metallurgical microscope. As a result, the region where internal oxidation was carried out could be seen as brown spots, and the thickness of the layer where internal oxidation was carried out could be measured.
また、内部酸化が行われた層についてマイクロビッカー
ス硬度計（明石製作所製「ＭＶＫ−１型」）によりビッ
カース硬度を測定し、さらにオートグラフ（島津製作所
製「ＤＳＳ−５００型」）により引張り降伏強度を測定
した。なおオートグラフは赤外線イメージ炉により高温
加熱可能にしたものであり、試料をチャックに固定した
のち温度を６７３Ｋに昇温することによって測定した。In addition, the Vickers hardness of the layer subjected to internal oxidation was measured with a micro Vickers hardness meter (“MVK-1 type” manufactured by Akashi Seisakusho), and the tensile yield strength was measured with an autograph (“DSS-500 type” manufactured by Shimadzu Corporation). Was measured. The autograph was made capable of being heated to a high temperature by an infrared image furnace, and was measured by fixing the sample to a chuck and then raising the temperature to 673K.
これらの結果を第１表に記す。第１表中の実験No.１８
は比較例１であり、内部酸化処理を行わなかった場合の
銅−アルミニウム合金のビッカース硬度および引張り降
伏強度である。The results are shown in Table 1. Experiment No. 18 in Table 1
Is Comparative Example 1, which is the Vickers hardness and the tensile yield strength of the copper-aluminum alloy when the internal oxidation treatment was not performed.
実施例２ 第２図に示す構造のチューブラーフロータイプの誘導カ
ップリングプラズマ発生装置を用い、内容積５の石英
製の反応管１０に配置した高周波コイル１１の位置に実
施例１で用いた試料１２を置き、酸素含有ガスの条件を
第２表に示すように設定し高周波コイル１１により酸素
含有プラズマを発生させながら誘導加熱を行い、合金選
択酸化処理を２時間行い内部酸化型合金を製造した。製
造された内部酸化型合金について、実施例１と同様の評
価を行った。これらの結果を第２表に記す。 Example 2 The sample used in Example 1 at the position of the high frequency coil 11 arranged in the quartz reaction tube 10 having an inner volume of 5 using the tubular flow type induction coupling plasma generator having the structure shown in FIG. 12, the conditions of oxygen-containing gas were set as shown in Table 2, induction heating was performed while oxygen-containing plasma was generated by the high frequency coil 11, and alloy selective oxidation treatment was performed for 2 hours to produce an internal oxidation type alloy. . The same evaluation as in Example 1 was performed on the manufactured internal oxidation type alloy. These results are shown in Table 2.
比較例２ 実施例１で用いた試料の周囲に、酸化銅(Cu2O)と銅の混
合粉末(平均粒径１００μｍ)を内部酸化剤として接触さ
せた状態で電気炉による加熱を行い温度を９７３Ｋとし
て、選択酸化処理を２時間行うことにより内部酸化型合
金を製造した。製造された内部酸化型合金を実施例１と
同様の評価を行った。その結果を第２表に併せて記す。Comparative Example 2 Around the sample used in Example 1, a mixed powder of copper oxide (Cu 2 O) and copper (average particle size 100 μm) was contacted as an internal oxidant and heated by an electric furnace to raise the temperature. The internal oxidation type alloy was manufactured by performing selective oxidation treatment at 973 K for 2 hours. The produced internal oxidation type alloy was evaluated in the same manner as in Example 1. The results are also shown in Table 2.
実施例３ マイクロ波導波管を用いるマイクロ波プラズマ発生装置
と高周波コイルによる誘導加熱装置を有する第３図に示
す構造のプラズマ発生装置を用い、内容積３の石英製
の反応管２０内の高周波コイル２１の位置に実施例１で
用いた試料２２を置き、高周波コイル２１による誘導加
熱により試料を９７３Ｋに保ちつつマイクロ波導波管２
３により酸素含有プラズマを発生させ、試料に酸素含有
プラズマを作用させ選択酸化処理を２時間行い内部酸化
型合金を製造した。 Example 3 A high frequency coil in a reaction tube 20 made of quartz and having an inner volume of 3 was used, using a plasma generator having a structure shown in FIG. 3 having a microwave plasma generator using a microwave waveguide and an induction heating device using a high frequency coil. The sample 22 used in Example 1 is placed at the position 21 and the microwave waveguide 2 is maintained while the sample is kept at 973 K by induction heating by the high frequency coil 21.
3, oxygen-containing plasma was generated, and oxygen-containing plasma was made to act on the sample to perform selective oxidation treatment for 2 hours to produce an internal oxidation type alloy.
製造された内部酸化型合金について、実施例１と同様の
評価を行った。それらの結果を第３表に記す。The same evaluation as in Example 1 was performed on the manufactured internal oxidation type alloy. The results are shown in Table 3.
比較例３ 実施例３において、高周波コイルによる誘導加熱を行わ
ず代りに赤外線イメージ炉を用いて試料を９７３Ｋに加
熱した以外は、実施例３と同様の条件で選択酸化処理を
行い内部酸化型合金を製造した。製造された内部酸化型
合金について実施例１と同様の評価を行った。それらの
結果を第３表に併せて示す。Comparative Example 3 An internal oxidation alloy was prepared by performing selective oxidation treatment under the same conditions as in Example 3, except that the sample was heated to 973 K using an infrared image furnace instead of performing induction heating with a high frequency coil. Was manufactured. The same evaluation as in Example 1 was performed on the manufactured internal oxidation type alloy. The results are also shown in Table 3.
実施例４ 溶製法により作製した０．３重量％のケイ素を含有する
鉄−ケイ素合金（融点：１８０８Ｋ）より成る厚み１m
m、長さ５０mm、幅５mmの板を試料とし、第１図に示す
構成を有する装置を用い、試料の融点１８０８Ｋに対し
て、誘導加熱による温度が０．５Tm（９０４Ｋ）、０．
６Ｔｍ(１０８５Ｋ)、０．７Ｔｍ（１２６６Ｋ）の各温
度になるようマイクロ波放電電力を調節し、酸素ガス流
量２cc／min、圧力２０ｍTorrに設定し、正イオン密度
が５×１０10個／cm3となる条件下において、酸素含有
プラズマによる選定酸化処理を１０時間行い、内部酸化
型合金を製造した。 Example 4 An iron-silicon alloy (melting point: 1808K) containing 0.3% by weight of silicon, prepared by the melting method, and having a thickness of 1 m.
A plate having a size of 50 m, a length of 50 mm, and a width of 5 mm was used as a sample, and the melting point of the sample was 1808 K, and the temperature by induction heating was 0.5 Tm (904 K).
The microwave discharge power was adjusted to each temperature of 6 Tm (1085 K) and 0.7 Tm (1266 K), the oxygen gas flow rate was set to 2 cc / min and the pressure was set to 20 mTorr, and the positive ion density was 5 × 10 10 pieces / cm 3. Under these conditions, selective oxidation treatment with oxygen-containing plasma was performed for 10 hours to produce an internal oxidation type alloy.
斯くして製造された内部酸化型合金の試料をダイアモン
ドカッターにより切断し、更にその断面を研摩したのち
金属顕微鏡にて倍率１０００倍で断面観察を行ったとこ
ろ、内部酸化が行われている領域は黒い斑点状に見るこ
とができ、これにより内部酸化が行われた層の厚みを測
定することができた。その結果を第４表に記す。The sample of the internal oxidation type alloy thus manufactured was cut with a diamond cutter, and the cross section was further polished, and the cross section was observed with a metallurgical microscope at a magnification of 1000. It can be seen as black spots, which allows the thickness of the layer undergoing internal oxidation to be measured. The results are shown in Table 4.
比較例４ 実施例４で用いた試料を、酸化鉄（Ｆｅ2Ｏ3）粉末（平
均粒径１００μｍ）を内部酸化剤として用いた従来法に
より、温度を実施例４と同じく０．５Tm、０．６Tm、
０．７Tmとして選択酸化処理を１０時間行うことにより
内部酸化型合金を製造した。そして実施例４の同様に内
部酸化が行われた層の厚みを測定し、その結果を第４表
に併せて示す。Comparative Example 4 The sample used in Example 4 was subjected to a conventional method using iron oxide (Fe 2 O 3 ) powder (average particle size 100 μm) as an internal oxidant, and the temperature was 0.5 Tm, 0 as in Example 4. .6 Tm,
An internal oxidation type alloy was manufactured by performing selective oxidation treatment at 0.7 Tm for 10 hours. Then, the thickness of the layer subjected to internal oxidation was measured in the same manner as in Example 4, and the results are also shown in Table 4.
比較例５ 実施例４において誘導加熱を用いずに赤外線加熱により
Ｔｍを調節した以外は、実施例４と同様にして内部酸化
型合金を製造した。結果を第４表に併せて示す。Comparative Example 5 An internal oxidation type alloy was produced in the same manner as in Example 4 except that Tm was adjusted by infrared heating without using induction heating. The results are also shown in Table 4.
第４表から、本発明の方法によれば低い温度、速い速度
で選択酸化処理を行うことができることが明らかであ
る。 From Table 4, it is clear that the method of the present invention enables selective oxidation treatment at low temperature and high speed.
実施例５ ０．０３重量％のアルミニウムを含有する銅−アルミニ
ウム合金（融点：１３５８Ｋ）より成る平均粒径３０μ
ｍの粉末を、溶製法によって製造した合金塊を過流ミル
によって機械的に粉砕することによって得た。Example 5 Average particle size 30 μm of copper-aluminum alloy (melting point: 1358K) containing 0.03% by weight of aluminum
The powder of m was obtained by mechanically grinding the alloy ingot produced by the ingot method by means of a countercurrent mill.
第４図に示す構造のプラズマ発生装置を用い、内容積５
の石英製の反応管３０内の高周波コイル３１の位置に
前記粉末状の合金３２を置き、モーター３３により反応
管３０を水平な軸の周りに回転させて合金を撹拌しなが
ら、酸素含有ガスを図の右方より導入すると共に左方よ
り排出するようにした状態において、第５表に示す条件
に従って高周波コイル３１により酸素含有プラズマを発
生させながら誘導加熱を行い、合金を９７３Ｋに保ちつ
つ、プラズマを作用させ選択後酸化処理を行った。Using the plasma generator having the structure shown in FIG.
The powdery alloy 32 is placed at the position of the high-frequency coil 31 in the quartz reaction tube 30 and the reaction tube 30 is rotated by a motor 33 around a horizontal axis to stir the alloy while the oxygen-containing gas is supplied. In the state of being introduced from the right side of the figure and discharged from the left side, induction heating was performed while generating oxygen-containing plasma by the high frequency coil 31 according to the conditions shown in Table 5, and the plasma was maintained while keeping the alloy at 973K. After the selection, an oxidation treatment was carried out.
このようにして得られた内部酸化型合金の粉末を、ホッ
トプレス法により、温度９２３Ｋ、圧力１２０kg／c
m2、時間１０分間の条件で焼結し、長さ１５０mm、直径
２mmの円柱状成形物を作製した。The internal oxidation type alloy powder thus obtained was subjected to a hot pressing method at a temperature of 923 K and a pressure of 120 kg / c.
Sintering was carried out under conditions of m 2 and time of 10 minutes to produce a cylindrical molded product having a length of 150 mm and a diameter of 2 mm.
この成形物を試料として、第５図に示すように試料４０
の一端部がＰから５０mm突出するように万力４１で固定
し、試料４０左右にそれぞれ９０度繰り返し折り曲げる
操作をゆっくりと行い、万力４１による固定端付近に亀
裂が発生するまでの往復折り曲げ回数を測定した。結果
を第５表に記す。Using this molded product as a sample, as shown in FIG.
Fix it with a vise 41 so that one end of it protrudes from P by 50 mm, and slowly bend the sample 40 left and right repeatedly 90 degrees, and repeat the number of reciprocating bends until a crack is generated near the fixed end by the vise 41. Was measured. The results are shown in Table 5.
比較例６ 実施例５において、合金の粉末に対して酸素含有プラズ
マによる選択酸化処理を行わずにそのまま焼結した。そ
して実施例５と同様にして往復折り曲げ回数を測定し
た。結果を第５表に記す。Comparative Example 6 In Example 5, the alloy powder was directly sintered without being subjected to the selective oxidation treatment with the oxygen-containing plasma. Then, in the same manner as in Example 5, the number of reciprocal bendings was measured. The results are shown in Table 5.
〔発明の効果〕 本発明によれば、次のような効果が奏される。 [Effects of the Invention] According to the present invention, the following effects are achieved.
(1) ０．９Tm以下の低い温度で内部酸化型合金を高速で
製造することができる。これは、生産性、大量生産とい
う観点においてきわめて大きな利点である。(1) The internal oxidation type alloy can be produced at a high speed at a low temperature of 0.9 Tm or less. This is a great advantage in terms of productivity and mass production.
(2) 加熱法として誘導加熱を用いることにより、他の加
熱法により高い内部酸化速度を実現でき、製造コストの
低減をはかれる。(2) By using induction heating as the heating method, a higher internal oxidation rate can be realized by other heating methods, and the manufacturing cost can be reduced.
(3) 金属酸化粉末等からなる固体状の内部酸化剤を用い
ずに目的とする選択酸化処理を行うことができるため、
合金が汚染されず、母相金属の特性を損なうことなくそ
のまま保有させることができる。しかも内部酸化処理
後、内部酸化剤の粉末と目的物である内部酸化型合金と
を分離する工程が不要となり、これは合金が粉末である
場合に極めて大きい工業的意義を有する。(3) Since the desired selective oxidation treatment can be performed without using a solid internal oxidizing agent made of metal oxide powder or the like,
The alloy is not contaminated and can be retained as it is without impairing the properties of the matrix metal. Moreover, after the internal oxidation treatment, the step of separating the powder of the internal oxidizer and the target internal oxidation type alloy becomes unnecessary, which has an extremely great industrial significance when the alloy is a powder.
(4) 選択酸化処理時間が短い点で有利な粒子状合金を用
いたときにも、選択酸化処理後の合金粉末中に内部酸化
剤が残留することがないので、これを成形焼結すること
により、優れた初期の特性を有する成形物を確実に得る
ことができる。(4) Even when using a particulate alloy, which is advantageous in that the selective oxidation treatment time is short, the internal oxidizing agent does not remain in the alloy powder after the selective oxidation treatment. As a result, it is possible to reliably obtain a molded product having excellent initial properties.
(5) 酸素含有プラズマの発生条件およびその合金に対す
る作用条件、例えば正イオン密度、真空度等を広い範囲
において選択することができ、しかもその制御が容易で
あるので、目的とする選択酸化処理を再現性よく行うこ
とができる。(5) Oxygen-containing plasma generation conditions and its alloy working conditions, such as positive ion density and vacuum degree, can be selected in a wide range, and its control is easy. It can be performed with good reproducibility.
(6) 上記（５）とも関連して、種々の処理条件も大きな
自由度をもって選択することができるため、得られる内
部酸化型合金についてその組織構造を広い範囲で制御す
ることが可能となり、求められる組織構造を有する内部
酸化型合金を容易に製造することができる。すなわち、
通常、この組織構造は、合金内部の酸化された領域の平
均直径Ｄとそれらの間隔λとによって特徴づけられる
が、従来法におけるこの組織構造に影響を与えるパラメ
ーターが温度だけであるためＤとλを独立に変化させる
ことは不可能であったが、本発明方法によれば、温度と
プラズマの状態（特に正イオン密度）を独立に変化させ
得るため、Ｄとλを互いに独立にかつ広い範囲で制御可
能であり、この結果、従来法では内部酸化型合金を得る
ことのできない、例えば０．５Tm程度の低温において
も、Ｄおよびλの値が極めて小さな内部酸化型合金を得
ることができる。(6) In connection with the above (5), various processing conditions can be selected with a large degree of freedom, so that it becomes possible to control the structural structure of the obtained internal oxidation type alloy in a wide range. It is possible to easily manufacture an internal oxidation type alloy having a structured structure. That is,
Usually, this microstructure is characterized by the average diameter D of the oxidized regions inside the alloy and their spacing λ, but D and λ are the only parameters affecting this microstructure in the conventional method. However, according to the method of the present invention, the temperature and the plasma state (particularly, the positive ion density) can be changed independently. Therefore, D and λ can be changed independently of each other and in a wide range. As a result, it is possible to obtain an internal oxidation type alloy having extremely small values of D and λ even at a low temperature of, for example, about 0.5 Tm, which cannot be obtained by the conventional method.
(7) 上記（６）とも関連して、Ｄおよびλの値が極めて
小さな内部酸化型合金を得ることができるため、従来に
ない高硬度の内部酸化型合金を得ることができる。(7) In connection with (6) above, an internal oxidation type alloy having extremely small values of D and λ can be obtained, so that an internal oxidation type alloy having a high hardness that has never been obtained can be obtained.
第１〜４図は本発明方法の実施に用いられる装置の説明
図、第５図は往復折り曲げ回数の測定についての説明図
である。 １、１０、２０、３０……反応管、２、２３……マイク
ロ波導波管、３、１２、２２、３２……試料。1 to 4 are explanatory views of an apparatus used for carrying out the method of the present invention, and FIG. 5 is an explanatory view of measurement of the number of reciprocal bending. 1, 10, 20, 30 ... Reaction tube, 2, 23 ... Microwave waveguide, 3, 12, 22, 32 ... Sample.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ２３Ｃ 8/36 7516−4Ｋ (72)発明者 近藤 文治 京都府京都市左京区田中大堰町49番地 財 団法人應用科学研究所内 (72)発明者 高田 潤 京都府京都市北区紫竹下竹殿町42 審査官 岡田 萬里─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Office reference number FI technical display location // C23C 8/36 7516-4K (72) Inventor Bunji Kondo Tanaka Oiyan-cho, Sakyo-ku, Kyoto City, Kyoto Prefecture Address 49 Inside Institute for Applied Sciences (72) Inventor Jun Takada 42 Shishitakeshitatakedencho, Kita-ku, Kyoto-shi, Kyoto Prefecture Examiner Manri Okada
Claims (2)
および／または酸素原子を有する化合物のガスの存在下
において発生させたプラズマを作用させながら誘導加熱
を行い、前記合金の母相金属以外の少なくとも１種の金
属元素を選択的に酸化させることを特徴とする内部酸化
型合金の製造方法。1. A matrix metal of an alloy comprising two or more kinds of metal elements, which is subjected to induction heating while causing plasma generated in the presence of a gas of a compound having oxygen and / or oxygen atoms to act on the alloy. A method for producing an internal oxidation type alloy, which comprises selectively oxidizing at least one metal element other than the above.
に、酸素および／または酸素原子を有する化合物のガス
存在下において発生させたプラズマを作用させながら誘
導加熱を行い、前記合金の母相金属以外の少なくとも１
種の金属元素を選択的に酸化させて内部酸化型合金粒子
を得、これを成形して焼結することを特徴とする内部酸
化型合金成形物の製造方法。2. A matrix alloy of two or more kinds of metal elements is subjected to induction heating while applying plasma generated in the presence of a gas of oxygen and / or a compound having an oxygen atom, to induce induction heating. At least 1 other than metal
A method for producing a molded article of an internal oxidation type alloy, which comprises selectively oxidizing a certain kind of metal element to obtain an internal oxidation type alloy particle, and shaping and sintering the particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61143770A JPH0660363B2 (en) | 1986-06-19 | 1986-06-19 | Internal oxidation type alloy and method for producing molded article thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61143770A JPH0660363B2 (en) | 1986-06-19 | 1986-06-19 | Internal oxidation type alloy and method for producing molded article thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63427A JPS63427A (en) | 1988-01-05 |
| JPH0660363B2 true JPH0660363B2 (en) | 1994-08-10 |
Family
ID=15346617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61143770A Expired - Lifetime JPH0660363B2 (en) | 1986-06-19 | 1986-06-19 | Internal oxidation type alloy and method for producing molded article thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660363B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7410610B2 (en) * | 2002-06-14 | 2008-08-12 | General Electric Company | Method for producing a titanium metallic composition having titanium boride particles dispersed therein |
| US7416697B2 (en) | 2002-06-14 | 2008-08-26 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
-
1986
- 1986-06-19 JP JP61143770A patent/JPH0660363B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63427A (en) | 1988-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4701301A (en) | Process for producing an internal-oxidized alloy or a shaped article thereof | |
| CN113061763B (en) | A kind of high entropy alloy and preparation method thereof | |
| JP5575622B2 (en) | Method for producing high-purity metal nanopowder and nanopowder produced by this method | |
| US5004498A (en) | Dispersion strengthened copper alloy and a method of manufacturing the same | |
| JP3949848B2 (en) | Method for producing scutteldite thermoelectric material | |
| JPH0925526A (en) | Method for producing oxide-particle-dispersed metal-based composite material | |
| CN100477309C (en) | Filled skutterudite-based alloy, method for forming same, and thermoelectric conversion device using same | |
| JP2012190984A (en) | Magnesium silicide powder, sintered compact and thermoelectric conversion element using the same, and method for producing the same | |
| JP2014520207A (en) | Nickel alloys for hydrogen storage and energy generation therefrom | |
| CN1058619A (en) | Silver-or silver-copper alloy-metal oxide composite and production method thereof | |
| CN103233136B (en) | Technology for preparing silver rare earth oxide electric contact material for low voltage electric apparatus with liquid phase method | |
| JPH0612926A (en) | Superconducting wire and composite superconducting conductor | |
| CN110106386A (en) | The preparation method and platinum rhodium base composite wire material of oxide reinforcing platinum rhodium base composite wire material | |
| US20120282130A1 (en) | Method for producing permanent magnet materials and resulting materials | |
| JPH0660363B2 (en) | Internal oxidation type alloy and method for producing molded article thereof | |
| CN102864325A (en) | Multielement rare earth silver electric contact as well as preparation method and application thereof | |
| Kim S.-H. et al. | Technical note Fabrication of alumina dispersion strengthened copper strips by internal oxidation and hot roll bonding | |
| US7381368B2 (en) | Palladium-boron alloys and methods for making and using such alloys | |
| JP4014149B2 (en) | Method for producing MgB2-based superconducting wire | |
| Aslanoglu et al. | Effects of nickel addition on properties of Ag–W electrical contact materials | |
| JP3300460B2 (en) | Method for producing ultrafine monodispersed gold particles | |
| JPS6148573B2 (en) | ||
| JP2006086512A (en) | Thermoelectric conversion system using filled skutterudite alloy. | |
| JP2665014B2 (en) | Manufacturing method of thermoelectric conversion element material | |
| JPH01164731A (en) | Superconducting material and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |