JPH0429729B2 - - Google Patents
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- Publication number
- JPH0429729B2 JPH0429729B2 JP9663884A JP9663884A JPH0429729B2 JP H0429729 B2 JPH0429729 B2 JP H0429729B2 JP 9663884 A JP9663884 A JP 9663884A JP 9663884 A JP9663884 A JP 9663884A JP H0429729 B2 JPH0429729 B2 JP H0429729B2
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- JP
- Japan
- Prior art keywords
- weight
- alloy
- fine powder
- sintering
- sintered
- Prior art date
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- 229910045601 alloy Inorganic materials 0.000 claims description 80
- 239000000956 alloy Substances 0.000 claims description 80
- 239000000843 powder Substances 0.000 claims description 71
- 238000005245 sintering Methods 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 14
- 229910052735 hafnium Inorganic materials 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 229910052762 osmium Inorganic materials 0.000 claims description 12
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 9
- 229910000691 Re alloy Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 238000011282 treatment Methods 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 229910020674 Co—B Inorganic materials 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 7
- 238000001513 hot isostatic pressing Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001362 Ta alloys Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- -1 and W. Ti Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Description
（産業上の利用分野）
本発明は巣が少なく、耐摩耗性、抗折力、耐食
性などにすぐれた合金の焼結体、およびその製造
方法に関するものである。
（従来技術および問題点）
従来、一般にRe含有合金は耐摩耗性にすぐれ
ているため、主に万年筆のペン先端材料に使用さ
れている。ペン先端材料をアークによる溶融法で
合金化して小球（直径約１mm）に形成するが、棒
状、円筒状、板状などには形成できない。
Re含有合金は小球以外の種々の形状のものが
得られれば、その特性から万年筆のペン先端材料
以外に、筆記具の先端材料のみならず、耐摩耗
性、抗折力、耐食性を必要とする他の分野のもの
に使用できる。
Re含有合金の種々の形状のものを得るには、
粉末冶金法が最適である。しかし、Re含有合金
を形成する各元素の単体を単に混合して焼結して
も、各元素は高融点のために合金化しないので、
所望形状のものが得られても、高耐摩耗性、高耐
食性がないことは明白である。さらに、高融点合
金は一般に焼結性が悪いために、巣のない高緻密
性の焼結体を得るのは難しく、良好な耐摩耗性、
高抗折力のものは得難い。
高緻密性の焼結体を得るには、耐純度で、微細
粉末の原料粉末を用いると、若干の成果が上が
る。しかし、Re含有合金のように靭性があるも
のでは、微粉末に粉砕し難く所望の微粉末を得難
い。
Re含有合金の良好な焼結体を得るには、(1)不
純物の少ないRe含有合金の微粉末を作製するこ
と、(2)耐摩耗性で、焼結体に適したRe含有合金
組成であること、(3)巣の発生の少ない焼結方法で
あること、である。しかし、現在いずれの点も満
足に解決されていない。
（発明の構成）
本発明者はこれらの点について研究し、所期の
目的を達成した。(1)すぐれた耐摩耗性、耐食性を
得る合金成分はReと、Os、Ir、Ru、Ti、Zr、
Hf、Ｖ、Nb、Ta、Cr、MoおよびＷの少なくと
も１つの組合せであること（（特に、Os、Ir、Ru
は耐食性を一層高める効果がある。）、(2)低温で良
好な焼結体と、緻密な焼結体を得るには、Coお
よびNiの少なくとも１つを使用すること、(3)す
ぐれた耐摩耗性と、良好な焼結体を得るには、Ｂ
を使用すること、が必須であることがわかつた。
前記の成分よりなるRe含有合金を従来の作製
方法で粉末化すると、粒度が粗く、ばらつきが大
きく、緻密性の高い焼結が得られないため、微粉
末化が必要である。
本発明者は前記の成分よりなるRe含有合金の
微粉末化を、サブゼロ処理、水素脆化処理、ター
ボ処理など種々検討した。その中で、水素脆化処
理が合金の性質に何ら悪影響がなく、その後の粉
砕処理により比較的粒径の揃つた微粉末が得られ
ることを見出した。不純物があると、耐摩耗性、
耐食性に悪影響があり好ましくないため、微粉末
後に塩酸溶液に浸漬して不純物を除去すると、純
度が向上することを見出した。このようにして作
製したRe含有合金の微粉末を所望の形状に加圧
成形して高温度で固相焼結すると、緻密で抗折力
の高い焼結体が得られること、さらにRe含有合
金の微粉末にCoおよびNiの少なくとも１つの微
粉末を添加し加圧成形して液相焼結すると、一相
緻密性の高い焼結が得られることを見出した。
本発明は(1)Re：５〜95重量％と、Os、Ir、
Ru、Ti、Zr、Hf、Ｖ、Nb、Ta、Cr、Moおよ
びＷの少なくとも１つ：３〜93重量％と、Coお
よびNiの少なくとも１つ：0.2〜25重量％と、
Ｂ：0.1〜５重量％よりなる、耐摩耗性Re合金の
焼結体、および
(2)Re：５〜95重量％と、Os、Ir、RuTi、Zr、
Hf、Ｖ、Nb、Ta、Cr、MoおよびＷの少なくと
も１つ：３〜93重量％と、CoおよびNiの少なく
とも１つ：0.2〜25重量％と、Ｂ：0.1〜５重量％
よりなる合金微粉末を作製して加圧成形し、その
成形体を固相焼結する、耐摩耗性Re合金の焼結
体の製造方法、および
(3)Re：５〜95重量％と、Os、Ir、Ru、Ti、
Zr、Hf、Ｖ、Nb、Ta、Cr、MoおよびＷの少な
くとも１つ：３〜93重量％と、CoおよびNiの少
なくとも１つ：0.2〜25重量％と、Ｂ：0.1〜５重
量％のよりなる合金微粉末を作製し、Coおよび
Ni少なくとも１つの微粉末：前記合金微粉末の
0.1〜５重量％を前記合金微粉末に添加して前記
合金微粉末を加圧成形し、その成形体を液相焼結
する、耐摩耗性Re合金の焼結体の製造方法であ
る。
Reは単体金属でもかなり良好な耐摩耗性があ
るが、筆記先端材料に要求される高耐摩耗性は
Re単体金属のみでは得られない。耐摩耗性を向
上するには、他の金属を添加して合金化すること
が必要である。巣の少ない緻密性のよいRe含有
合金の焼結体を得るには、Re含有合金の微粉末
が必要であり、耐摩耗性などの性質を低下せずに
微粉末を容易にする合金成分、および焼結性を向
上し緻密性を向上する合金成分を添加することが
必要である。
Reの耐摩耗性、耐食性をさらに向上するため
に有効な元素はOs、Ir、Ru、Ti、Zr、Hf、Ｖ、
Nb、Ta、Cr、Mo、Ｗである。Ti、Zr、Hf、
Ｖ、Nb、Ta、Cr、Mo、ＷはＢと棚化物を形成
し、硬さを増加し、耐摩耗性をさらに向上する効
果がある。Ｂは耐摩耗性を付与し、かつ微粉末化
を容易にする効果がある。
Os、Ir、RuはRe含有合金の耐食性を持に向上
する効果が大きい。
Os、Ir、Ru、Ti、Zr、Hf、Ｖ、Nb、Ta、
Cr、Mo、Ｗの元素を含有した合金は一般に高融
点合金となり、焼結体が悪く、緻密性のよい焼結
体は得難い。
CoおよびNiの少なくとも１つを添加し、さら
にＢを添加すると、CoおよびNiの少なくとも１
つとＢの相互作用によりRe含有合金の特性を向
上する均一な低融点合金となり、高焼結性、緻密
性に効果がある。
Ti、Zr、Hf、Ｖ、Nb、Taは水素脆化処理の
効果が大きく、微粉末化に一層の効果がある。
各元素の含有率は、Re含有合金の耐摩耗性、
耐食性、緻密性、粉砕性などの観点から決める。
Reの含有率は耐摩耗性の観点から、５〜95重
量％、好ましくは10〜90重量％である。この範囲
外では、所望の耐摩耗性は得られない。
Os、Ir、Ru、Ti、Zr、Hf、Ｖ、Nb、Ta、
Cr、Mo、Ｗの含有率は耐摩耗性、粉砕性、耐食
性の観点から、３〜93重量％、好ましくは８〜88
重量％である。この範囲外では、所望の耐摩耗
性、粉砕性、耐食性は得られない。
Co Niの含有率は焼結性の観点から、0.2〜25
重量％、好ましくは３〜20重量％である。この範
囲外では、所望の耐摩耗性は得られない。
Ｂの含有率は耐摩耗性、焼結性、粉砕性、靭性
の観点から、0.1〜５重量％、好ましくは0.2〜４
重量％である。この範囲外では、所望の耐摩耗
性、焼結性、粉砕性、靭性は得られない。
金属の微粉化処理については、数多く提案され
ているが、Re含有合金の微粉末の作製に好適な
ものは見当たらない。本発明者は種々の微粉化処
理を試みたが、高速衝撃紛機での粉が微粉末粒径
が不充分であるが、比較的効果があることを見出
した。
本発明者はある種の金属および合金には水素脆
化効果があるとの知見を得たが、本発明のRe含
有合金は靭性が高く、適用できるか否かは全く不
明であつた。そこで、合金化溶解後のRe含有合
金を水素脆化処理して高速衝撃粉砕機で紛砕した
ところ、合金の脆化による耐摩耗性の劣化、靭性
の低下などの悪影響を起こすことなく、所望の粒
径約20μm以下のものを得ることができた。
この方法で作製したRe含有合金の微粉末は比
較的粒径がよく揃つていて、しかも不純物が少な
い特徴がある。このRe含有合金の微粉末の粒径
との焼結体の緻密性の関係を調べたところ、粒径
はできるだけ小さいほうがよく、所望の緻密性を
得るには少なくとも20μm以下、好ましくは10μm
以下がよいことがわかつた。
Re含有合金の微粉末を、次のようにして作製
する。まず、アーク溶融して得た小球を大気圧の
水素雰囲気で、700〜1300℃、１時間以上保持し
て水素脆化処理する。その後、前記小球をハンマ
ーなどで砕いて直径２mm以下の粒にし、高速衝撃
粉砕機で、例えば溶器内の底部に置き、上方から
突き棒を自然落下して微粉末にする。この微粉末
には、粉砕時にFeなどが混入するので、前記微
粉末を20％HCl水溶液（室温）に浸漬し、かきま
ぜながら１時間以上溶解処理して不純物溶解し、
濾過して分級をし、耐摩耗性、耐食性に悪影響の
ある不純物を除去する。
このRe含有合金の微粉末を有機質バインダー
とよく混ぜて加圧成形し、棒、パイプ、板などの
形状の成形体とする。有機質バインダーはRe合
金の微粉末に適度の活性を与え加圧成形を容易に
し、かつ成形体の形状を維持するのに必要であ
る。
有機質バインダーは例えばポリビニルアルコー
ル、カルボキシメチルセルロース、メチルセルロ
ース、水溶性アクリル樹脂、ポリエチレングリコ
ール、プロピレングリコール、ステアリン酸エマ
ルジヨン（以下親水性）、パラフイン、ワツクス
エマルジヨン、エチレンセルロース、ポリスチレ
ン、アルキツド樹脂、アクリル樹脂である。これ
らの有機質バインダーの２つ以上を使用してもよ
い。
有機質バインダーのRe含有合金の微粉末に対
する混合量は成形体の形状などにより異なるが、
全体で0.5〜10重量％、好ましくは１〜４重量％
である。
加圧成形を押出成形、プレス成形、射出成形、
圧延成形、静水圧プレス成形などで行う。プレス
成形などで比較的太い棒などの成形体成形すると
きは、有機質バインダーは必ずしも必要ではな
い。
Re含有合金の微粉末に、CoおよびNiの少なく
とも１つの微粉末、および有機質バインダーを添
加して加圧成形を行う。この場合は、後工程での
焼結は液相焼結となる。
以上のようにして作成した成形体は巣の少ない
緻密性、耐摩耗性、耐食性などの所望の性能に達
するように焼結する。Re含有合金の微粉末に有
機質バインダーを混ぜて加圧成形して得た成形体
を焼結するときは、固相焼結が進行し、焼結体の
巣を少なくし、緻密性を高めることができる。
成形体より有機質バインダーを熱分解により除
去し、その除去後も成形体が壊れないような強度
を保持するために、無酸化性の雰囲気（例えば、
水素ガス、アルゴンガスなど）で800〜1300℃
（好ましくは1100〜1200℃）、30分〜３時間（好ま
しくは１〜２時間）真空焼結する。
次いで、成形体の表面にまで達している無数の
連続孔の巣孔をそれぞれ独立孔とし、巣の数を減
少して緻密性を得るために、10-2〜10-6Torr（好
ましくは10-3〜10-6Torr）の真空で1300〜1750
℃（好ましくは1400〜1750℃）、30分〜３時間
（好ましくは１〜２時間）真空焼結する。
次いで、巣を少なくし緻密性をさらに高めるた
めに、アルゴン雰囲気で1200〜1500℃（好ましく
は1300〜1400℃）、500〜2000気圧（好ましくは
1000〜2000気圧）、30分〜３時間（好ましくは１
〜２時間）熱間静水圧加圧処理する。
有機質バインダーの添加量が比較的多いとき、
または加圧成形の加圧が比較的多いときは、緻密
性の高い焼結体を得るために熱間静水圧加圧処理
が必須である。しかし、有機質バインダーの添加
量が比較的少ないとき、加圧成形の加圧が比較的
高いときは、熱間静水圧加圧処理は必ずしも必須
でない。
本発明では、他の焼結方法として、液相焼結を
すると前記の固相焼結で得られる焼結よりもなお
一層高い緻密性にすぐれたものを得ることができ
る。
Re含有合金の微粉末に液相成分としてCoおよ
びNiの少なくとも１つの微粉末と有機質バイン
ダーを混ぜて加圧成形して得た成形体を焼結す
る。これは液相成分としてCoおよびNiの少なく
とも１つの微粉末が焼結時に溶融し、その融液が
合金の微粉末の粒間を埋めるので、真空焼結時ま
たは熱間静水圧加圧処理時に円滑に焼結が進むた
めに、極めて巣の少ない緻密性に優れた焼結体を
得ることができる。
Re含有合金の微粉末からCoおよびNiを除いた
合金の微粉末に液相成分としてのCoおよびNiを
添加して液相焼結をすると、巣が発生して緻密性
を高める効果がなく、さらに液相焼結時に焼結体
の細棒などの変形が生じやすくなる欠点がある。
本発明では、焼結前のRe含有合金の微粉末中に
合金化されている成分としてのCoおよびNiの少
なくとも１つの含有が固相焼結時のみならず、液
相焼結時に必須の極めて重要な成分である。
液相焼結における液相成分として添加するCo
およびNiの微粉末の割合はRe含有合金の微粉末
に対して0.1〜５重量％、好ましくは0.5〜４重量
％である。この範囲より少ないと巣をなくする効
果がなく、この範囲を越えると巣を多くし逆効果
となる。
液相成分としてのCoおよびNiの少なくとも１
つの微粉末はその粒径ができるだけ小さいものが
よく、約5μm以下がよい。液相焼結における焼結
の方法および条件は固相焼結における時とほぼ同
じであり、まず無酸化性の雰囲気で予備焼結して
有機質バインダーを除去して、成形体の形状保持
性を高める。次に、真空焼結および熱間静水圧加
圧処理で成形体を液相焼結する。予備焼結の処理
条件は固相焼結と同じである。
真空焼結処理条件は固相焼結、液相焼結とも
に、次の通りである。真空度は10-2〜10-6Torr、
好ましくは10-3〜10-5Torrであり、焼結温度は
1300〜1750℃、好ましくは1400〜1650℃であり、
焼結保持時間は30分〜３時間、好ましくは１〜２
時間である。
熱間静水圧加圧処理は次の通りである。加熱温
度は1200〜1500℃、好ましくは1300〜1400℃であ
り、圧力は500〜2000気圧、好ましくは1000〜
1500気圧であり、処理時間は30分〜３時間、好ま
しくは１〜３時間である。
液相焼結では、Re含有合金の微粉末に混合し
た液相成分としてのCoおよびNiの微粉末が焼結
時にRe含有合金中に拡散できずに一部が単体金
属として残るので、最後に10-2〜10-6Torr（好ま
しくは10-4〜10-6Torr）で1500〜1750℃（好ま
しくは1600〜1750℃）、１〜10時間の加熱拡散処
理し、単体として存在しているCoおよびNiをす
べて合金化する。このように処理すると、Re含
有合金の焼結体の耐食性は一層すぐれたものとな
る。
本発明のRe含有合金の焼結体は次の特徴があ
るる。
(1) 耐摩耗性
筆記先端材として最もすぐれた耐摩耗性のイリ
ドスミンよりやや劣るが充分な耐摩耗性があり、
さらに適度の摩耗性があり、紙によくなじむ。
(2) 耐食性
筆記用インキや、硫酸、塩酸などの酸溶液によ
つて腐食されない極めてすぐれた耐食性がある。
腐食しやすい環境下での使用に好適であり、さら
に腐食耗がないので、筆記先端材としても良好な
耐摩耗性がある。
(3) 緻密性、高抗折力
巣が少なく緻密であり、筆記先端材として使用
したとき紙上で滑りがよく紙当たりもすぐれてい
る。緻密性がすぐれているため、抗折力も高く、
細棒、細パイプなどの形状でも比較的折れ難く、
細字用のパイプペン、ドツトワイヤなどに使用で
きる。
（実施例）
本発明の実施例を示す。
実施例 １
50重量％のRe、20重量％のRu、13重量％の
Ｗ、10重量％のTa、６重量％のCo、１重量％の
Ｂのそれぞれの粉末をよく混合してプレス成形
し、直径約10mm、長さ約10mmの円柱状の圧粉体に
した。この圧粉体を約10-1Torrの真空で、アー
ク溶融して直径約10mmの合金球にした。この合金
球を大気圧の水素雰囲気で900℃で３時間水素脆
化処理し、ハンマーで粉砕し直径約２mm以下の合
金粒にした。
高速衝撃粉砕機において、この合金粒を直径32
mmの円筒容器の底部に置き、上方から直径30mmで
重さ６Kgの突き棒を高さ８cmから約60回／分で２
時間自然落して、微粉末にした。
この微粉末を20％HCl水溶液に浸漬し、１時間
かきまぜて濾過して粒度の分級をし、粒径約
10μm以下のRe−Ru−Ｗ−Ta−Co−Ｂ合金の微
粉末にした。
この微粉末に対して、２重量％のCo微粉末
（粒径約μm）、２重量％のプリビニルアルコール、
少量の水を添加し、めのう乳鉢で混練して餅状で
直径約16mmの円柱状にし、孔径0.5mmのダイスの
上に置き、上方から直径16mmのパンチを12トンで
加圧して押出し、直径約0.5mmの棒状の成形体に
し、80℃で３時間乾燥した。
この成形体を順次、大気圧の水素雰囲気で1100
℃で１時間予備焼結し、約10-4Torr真空で1600
℃で１時間真空焼結し、1000気圧のアルゴン雰囲
気で1350℃で１時間熱間水圧加圧処理し、約
10-4Torr真空で1650℃で４時間加熱拡散処理し、
Re−Ru−Ｗ−Ta−Co−合金棒状の焼結体を得
た。
実施例 ２
実施例１と同組成で、同様な方法で作製した
Re−Ru−Ｗ−Ta−Co−Ｂ合金の微粉末に対し
て、４重量％のCo微粉末（粒径約2μm）、４重量
％のポリビニルアルコール、１重量％のステアリ
ン酸エマルジヨン、0.5重量％のグリセリン、少
量の水を添加し、めのう乳鉢で混練して餅状で直
径16mmの円柱状にし、孔径0.6mmのダイスの孔の
中心に設置した直径0.3mmの金属針の上に置き、
上方から直径16mmのパンチを４トンで加圧して押
出し、外径約0.6mm、内径0.3mmの円筒状の成形体
にした。
この成形体を順次、実施例１と同様に乾燥、予
備焼結、真空焼結、熱間静水圧加圧処理、加熱拡
散処理し、Re−Ru−Ｗ−Ta−Co−Ｂ合金の筒
状の焼結体を得た。
実施例 ３
40重量％のRe、40重量％のOS、４重量％の
Ta、15重量％のCo、１重量％のＢのそれぞれの
粉末を実施例１と同様の方法で作製した合金球
を、大気圧の水素雰囲気で1100℃で３時間水素脆
化処理し、ハンマーで粉砕し直約２mm以下の合金
粒にした。
この合金粒を実施例１と同様に、高速衝撃粉砕
機で微粉末にし、酸浸漬処理、粒度の分級をし、
粒径が約10μm以下のRe−Os−Ta−Co−Ｂ合金
の微粉末にした。
この微粉末に対して、0.5重量％のポリビニル
アルコール、１重％のポリエチレグリコール、
0.3重％のグリセリン、少量の水を添加し、めの
う乳鉢で混練して餅状にし、実施例１と同様にし
てダイス（孔径１mm）で押出し、直径約１mmの棒
状の成形体にした。
こ成形体を順次、大気圧の水素雰囲気で1200℃
で２時間予備焼結し、約10-4Torrの真空で1750
℃で２時間真空焼結し、1000気圧のアルゴン雰囲
気で1350℃で１時間熱間静水圧加圧処理し、Re
−Os−Ta−Co−Ｂ合金の棒状の焼結体を得た。
実施例 ４
88重％のRe、４重％Zr、４重量％のTa、３重
量％のCo、１重量％のＢのそれぞれの粉末を実
施例１と同様の方法で作製した合金球を、大気圧
の水素雰囲気で1100℃で１時間水素脆化処理し、
ハンマーで粉砕し直径約２mm以下の合金粒にし
た。
この合金粒を実施例１と同様に、高速衝撃粉砕
機で微粉末にし、酸浸漬処理、粒度の分級をし、
粒径が約10μm以下のRe−Zr−Ta−Co−Ｂ合金
の微粉末にした。
この微粉末に対して、２重量％のCo微粉末
（粒径約2μm）、５重量％のポリスチレン、少量の
トルエンを添加し、めのう乳鉢で混練して餅状に
し、実施例１と同様にして直径約0.5mmの棒状の
成形体にした。
この成形体を順次、大気圧のアルゴンと水素の
混合雰囲気で1200℃で１時間予備焼結し、約
10-4Torrの真空で1600℃で１時間真空焼結し、
1000気圧のアルゴン雰囲気で1350℃で１時間熱間
静水圧加圧処理し、約10-4Torrの真空で1750℃
で２時間加熱拡散処理し、Re−Zr−Ta−Co−Ｂ
合金の棒状の焼結体を得た。
実施例 ５
10重量％のRe、47重量％のCr、28重量％のＷ、
11重量％のNi、４重量％のＢのそれぞれの粉末
を実施例１と同様の方法で作製した合金球を、水
素雰囲気で800℃で３時間水素脆化処理し、ハン
マーで粉砕し直径約２mm以下の合金粒にした。
この合金粒を実施例１と同様に、高速衝撃粉砕
機で微粉末にし、酸浸漬処理、粒度の分級をし、
粒径が約10μm以下のRe−Cr−Ｗ−Ni−Ｂ合金
の微粉末にした。
この微粉末に対して、１重量％のNi微粉末
（粒径約1μm）、１重量％のポリビニルアルコー
ル、0.5重量％のグリセリン、少量の水を添加し、
めのう乳鉢で混練して餅状にし、実施例１と同様
にしてダイス（孔径0.8mm）で押出し、直径約0.8
mmの棒状の成形体にした。
この成形体を順次、大気圧の水素雰囲気で1000
℃で２時間予備焼結し、約10-4Torrの真空で
1350℃で２時間真空焼結し、1000気圧のアルゴン
雰囲気で1350℃で１時間熱間静水圧加圧処理し、
Re−Cr−Ｗ−Ni−Ｂ合金の棒状の焼結体を得
た。
次に、比較例を示す。
比較例
57重量％のRe（粒径約50μm）、20重量％のRu
（粒径約50μm）、13重量％のＷ（粒径約1μm）、10
重量％のTa（粒径約50μm）のそれぞれの粉末を
よく混合して、２重量％のポリビニルアルコー
ル、少量の水を添加し、めのう乳鉢で混練して餅
状にし、実施例１と同様に押出し、外径0.5mmの
棒状の成形体にした。
この成形体を順次、実施例１と同様に乾燥、予
備焼結、真空焼結、熱間静水圧加圧処理し、Re
−Ru−Ｗ−Ta合金の棒状の焼結体を得た。
本発明の実施例１〜実施例５で得られた焼結体
と、比較例で得られた焼結体との巣の程度、物理
的性質、化学的性質についての比較を次表に示
す。
(Industrial Application Field) The present invention relates to a sintered body of an alloy with few cavities and excellent wear resistance, transverse rupture strength, corrosion resistance, etc., and a method for manufacturing the same. (Prior Art and Problems) Re-containing alloys have generally been used as pen tip materials for fountain pens because they generally have excellent wear resistance. The pen tip material is alloyed using an arc melting method and formed into a small ball (about 1 mm in diameter), but it cannot be formed into a rod, cylinder, or plate shape. If Re-containing alloys can be obtained in various shapes other than small spheres, their properties will require not only tip materials for fountain pens and writing instruments, but also abrasion resistance, transverse rupture strength, and corrosion resistance. Can be used in other fields. To obtain various shapes of Re-containing alloys,
Powder metallurgy is the most suitable method. However, even if the individual elements forming the Re-containing alloy are simply mixed and sintered, each element will not form an alloy due to its high melting point.
Even if a desired shape is obtained, it is clear that it does not have high wear resistance or high corrosion resistance. Furthermore, since high-melting point alloys generally have poor sinterability, it is difficult to obtain a highly dense sintered body without cavities, and it is difficult to obtain a sintered body with good wear resistance and
High transverse rupture strength is difficult to obtain. In order to obtain a highly dense sintered body, the use of a raw material powder with high purity and fine powder yields some results. However, tough materials such as Re-containing alloys are difficult to grind into fine powder, making it difficult to obtain the desired fine powder. In order to obtain a good sintered body of a Re-containing alloy, it is necessary to (1) produce a fine powder of a Re-containing alloy with few impurities, and (2) use a Re-containing alloy composition that is wear-resistant and suitable for a sintered body. (3) It is a sintering method that produces fewer cavities. However, none of these points have been satisfactorily resolved at present. (Structure of the Invention) The present inventor studied these points and achieved the intended purpose. (1) The alloy components that provide excellent wear resistance and corrosion resistance are Re, Os, Ir, Ru, Ti, Zr,
At least one combination of Hf, V, Nb, Ta, Cr, Mo and W (especially Os, Ir, Ru
has the effect of further increasing corrosion resistance. ), (2) Use at least one of Co and Ni to obtain a good sintered body and a dense sintered body at low temperatures, (3) Excellent wear resistance and good sintering. To get the body, B
It turns out that it is essential to use . When the Re-containing alloy made of the above components is pulverized by conventional production methods, the grain size is coarse and varies widely, and highly dense sintering cannot be obtained, so pulverization is necessary. The present inventors have studied various methods of pulverizing the Re-containing alloy made of the above-mentioned components, including sub-zero treatment, hydrogen embrittlement treatment, and turbo treatment. Among them, it was discovered that hydrogen embrittlement treatment had no adverse effect on the properties of the alloy, and that subsequent pulverization treatment yielded fine powder with relatively uniform particle size. Impurities can reduce wear resistance,
Since this is undesirable as it has an adverse effect on corrosion resistance, it has been found that purity can be improved by immersing the powder in a hydrochloric acid solution to remove impurities. When the fine powder of the Re-containing alloy produced in this way is press-molded into a desired shape and solid-phase sintered at high temperature, a dense sintered body with a high transverse rupture strength can be obtained. It has been found that when at least one fine powder of Co and Ni is added to the fine powder of , and the mixture is press-molded and liquid-phase sintered, a highly dense one-phase sintered product can be obtained. The present invention includes (1) Re: 5 to 95% by weight, Os, Ir,
At least one of Ru, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W: 3 to 93% by weight, and at least one of Co and Ni: 0.2 to 25% by weight,
B: A sintered body of wear-resistant Re alloy consisting of 0.1 to 5% by weight, and (2) Re: 5 to 95% by weight, Os, Ir, RuTi, Zr,
At least one of Hf, V, Nb, Ta, Cr, Mo and W: 3 to 93% by weight, at least one of Co and Ni: 0.2 to 25% by weight, B: 0.1 to 5% by weight
A method for producing a sintered body of a wear-resistant Re alloy, which comprises preparing and press-molding fine alloy powder, and solid-phase sintering the molded body, and (3) Re: 5 to 95% by weight; Os, Ir, Ru, Ti,
At least one of Zr, Hf, V, Nb, Ta, Cr, Mo and W: 3 to 93% by weight, at least one of Co and Ni: 0.2 to 25% by weight, and B: 0.1 to 5% by weight. A fine alloy powder consisting of Co and
At least one fine powder of Ni: the fine powder of the alloy
This is a method for producing a sintered body of a wear-resistant Re alloy, in which 0.1 to 5% by weight is added to the fine alloy powder, the fine alloy powder is press-molded, and the molded body is liquid-phase sintered. Re has fairly good abrasion resistance even as a single metal, but the high abrasion resistance required for writing tip materials is
Re cannot be obtained from single metals alone. To improve wear resistance, it is necessary to add and alloy other metals. In order to obtain a sintered body of a Re-containing alloy with few cavities and good density, a fine powder of the Re-containing alloy is required, and alloy components that can be easily made into a fine powder without reducing properties such as wear resistance, It is also necessary to add alloy components that improve sinterability and compactness. Effective elements to further improve the wear resistance and corrosion resistance of Re are Os, Ir, Ru, Ti, Zr, Hf, V,
These are Nb, Ta, Cr, Mo, and W. Ti, Zr, Hf,
V, Nb, Ta, Cr, Mo, and W form shelving products with B, which increases hardness and has the effect of further improving wear resistance. B has the effect of imparting wear resistance and facilitating pulverization. Os, Ir, and Ru have a great effect on improving the corrosion resistance of Re-containing alloys. Os, Ir, Ru, Ti, Zr, Hf, V, Nb, Ta,
Alloys containing the elements Cr, Mo, and W are generally high-melting point alloys, which produce poor sintered bodies, making it difficult to obtain sintered bodies with good density. When at least one of Co and Ni is added and B is added, at least one of Co and Ni is added.
The interaction between B and B results in a uniform low melting point alloy that improves the properties of Re-containing alloys, and is effective in high sinterability and compactness. Ti, Zr, Hf, V, Nb, and Ta are highly effective in hydrogen embrittlement treatment, and are even more effective in pulverization. The content of each element is determined by the wear resistance of the Re-containing alloy,
Decide based on corrosion resistance, compactness, crushability, etc. From the viewpoint of wear resistance, the content of Re is 5 to 95% by weight, preferably 10 to 90% by weight. Outside this range, the desired wear resistance cannot be obtained. Os, Ir, Ru, Ti, Zr, Hf, V, Nb, Ta,
The content of Cr, Mo, and W is 3 to 93% by weight, preferably 8 to 88% by weight from the viewpoint of wear resistance, crushability, and corrosion resistance.
Weight%. Outside this range, desired wear resistance, crushability, and corrosion resistance cannot be obtained. The content of Co Ni is 0.2 to 25 from the viewpoint of sinterability.
% by weight, preferably 3-20% by weight. Outside this range, the desired wear resistance cannot be obtained. The content of B is 0.1 to 5% by weight, preferably 0.2 to 4% by weight from the viewpoint of wear resistance, sinterability, crushability, and toughness.
Weight%. Outside this range, desired wear resistance, sinterability, crushability, and toughness cannot be obtained. Although many methods have been proposed for pulverizing metals, none have been found that are suitable for producing fine powders of Re-containing alloys. The present inventor tried various pulverization treatments, and found that the powder produced using a high-speed impact mill was relatively effective, although the fine powder particle size was insufficient. The present inventors have found that certain metals and alloys have a hydrogen embrittlement effect, but the Re-containing alloy of the present invention has high toughness, and it was completely unclear whether or not it could be applied. Therefore, when the Re-containing alloy after alloying and melting was subjected to hydrogen embrittlement treatment and pulverized using a high-speed impact crusher, it was possible to obtain the desired results without causing any adverse effects such as deterioration of wear resistance or decrease in toughness due to embrittlement of the alloy. We were able to obtain particles with a particle size of approximately 20 μm or less. The fine powder of the Re-containing alloy produced by this method has a relatively uniform particle size and is characterized by less impurities. When we investigated the relationship between the particle size of the fine powder of this Re-containing alloy and the density of the sintered body, we found that the particle size should be as small as possible, and in order to obtain the desired density, it is at least 20 μm or less, preferably 10 μm.
I found the following to be good. A fine powder of a Re-containing alloy is produced as follows. First, small spheres obtained by arc melting are subjected to hydrogen embrittlement treatment by holding them at 700 to 1300°C for more than one hour in a hydrogen atmosphere at atmospheric pressure. Thereafter, the small spheres are crushed with a hammer or the like into particles with a diameter of 2 mm or less, placed in a high-speed impact crusher, for example, at the bottom of a melter, and a punch rod is dropped from above to form a fine powder. Since Fe etc. are mixed into this fine powder during crushing, the fine powder is immersed in a 20% HCl aqueous solution (room temperature) and dissolved for over 1 hour while stirring to dissolve impurities.
Filter and classify to remove impurities that adversely affect wear resistance and corrosion resistance. The fine powder of this Re-containing alloy is thoroughly mixed with an organic binder and then pressure-molded to form a compact into a rod, pipe, plate, or other shape. The organic binder is necessary to impart appropriate activity to the Re alloy fine powder, facilitate pressure molding, and maintain the shape of the molded product. Examples of organic binders include polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, water-soluble acrylic resin, polyethylene glycol, propylene glycol, stearic acid emulsion (hereinafter referred to as hydrophilic), paraffin, wax emulsion, ethylene cellulose, polystyrene, alkyd resin, and acrylic resin. be. Two or more of these organic binders may be used. The amount of organic binder mixed with the fine powder of Re-containing alloy varies depending on the shape of the compact, etc.
0.5-10% by weight in total, preferably 1-4% by weight
It is. Pressure molding is extrusion molding, press molding, injection molding,
This is done by rolling molding, isostatic press molding, etc. An organic binder is not necessarily required when molding a relatively thick rod or other molded product by press molding or the like. At least one fine powder of Co and Ni and an organic binder are added to the fine powder of the Re-containing alloy, and pressure molding is performed. In this case, the sintering in the subsequent process will be liquid phase sintering. The molded body produced as described above is sintered to achieve desired performance such as compactness with few cavities, wear resistance, and corrosion resistance. When sintering a compact obtained by mixing fine powder of a Re-containing alloy with an organic binder and press-molding it, solid-phase sintering progresses, reducing the number of cavities in the sintered compact and increasing its compactness. I can do it. The organic binder is removed from the molded body by thermal decomposition, and in order to maintain the strength of the molded body so that it will not break even after removal, a non-oxidizing atmosphere (e.g.
800 to 1300℃ (hydrogen gas, argon gas, etc.)
(preferably 1100 to 1200°C) and vacuum sintering for 30 minutes to 3 hours (preferably 1 to 2 hours). Next, the countless continuous pores reaching the surface of the compact are made into independent pores, and in order to reduce the number of pores and obtain denseness, the temperature is set at 10 -2 to 10 -6 Torr (preferably 10 -3 to 10 -6 Torr) 1300 to 1750 in vacuum
℃ (preferably 1400 to 1750°C) for 30 minutes to 3 hours (preferably 1 to 2 hours). Next, in order to reduce the number of cavities and further improve the compactness, the temperature is heated at 1200 to 1500°C (preferably 1300 to 1400°C) and 500 to 2000 atm (preferably
1000 to 2000 atm), 30 minutes to 3 hours (preferably 1
~2 hours) hot isostatic pressing. When the amount of organic binder added is relatively large,
Alternatively, when the pressure during pressure molding is relatively large, hot isostatic pressing is essential in order to obtain a highly dense sintered body. However, when the amount of organic binder added is relatively small or when the pressure during pressure molding is relatively high, hot isostatic pressing is not necessarily essential. In the present invention, as another sintering method, if liquid phase sintering is used, it is possible to obtain a product with even higher density than that obtained by solid phase sintering. A fine powder of a Re-containing alloy is mixed with at least one fine powder of Co and Ni as a liquid phase component and an organic binder, and a molded body obtained by pressure molding is sintered. This is because at least one fine powder of Co and Ni as a liquid phase component is melted during sintering, and the melt fills the spaces between the fine powders of the alloy, so during vacuum sintering or hot isostatic pressing. Since sintering proceeds smoothly, a sintered body with extremely few voids and excellent density can be obtained. When liquid phase sintering is performed by adding Co and Ni as liquid phase components to a fine powder of an alloy obtained by removing Co and Ni from a fine powder of a Re-containing alloy, cavities are generated and there is no effect of increasing compactness. Furthermore, there is a drawback that deformation of the thin rod of the sintered body is likely to occur during liquid phase sintering.
In the present invention, the inclusion of at least one of Co and Ni as alloyed components in the fine powder of the Re-containing alloy before sintering is extremely important not only during solid phase sintering but also during liquid phase sintering. It is an important ingredient. Co added as a liquid phase component in liquid phase sintering
The proportion of the fine powder of Ni and Ni is 0.1 to 5% by weight, preferably 0.5 to 4% by weight, based on the fine powder of the Re-containing alloy. If it is less than this range, it will not be effective in eliminating nests, and if it exceeds this range, it will increase the number of nests and have the opposite effect. At least one of Co and Ni as liquid phase components
The particle size of the fine powder should be as small as possible, preferably about 5 μm or less. The sintering method and conditions for liquid-phase sintering are almost the same as for solid-phase sintering. First, the organic binder is removed by preliminary sintering in a non-oxidizing atmosphere to improve the shape retention of the compact. enhance Next, the compact is liquid-phase sintered by vacuum sintering and hot isostatic pressing. The processing conditions for preliminary sintering are the same as those for solid phase sintering. The vacuum sintering conditions for both solid phase sintering and liquid phase sintering are as follows. The degree of vacuum is 10 -2 to 10 -6 Torr,
Preferably 10 -3 to 10 -5 Torr, and the sintering temperature is
1300~1750℃, preferably 1400~1650℃,
Sintering holding time is 30 minutes to 3 hours, preferably 1 to 2 hours.
It's time. The hot isostatic pressure treatment is as follows. The heating temperature is 1200~1500℃, preferably 1300~1400℃, and the pressure is 500~2000 atm, preferably 1000~
The pressure is 1500 atm, and the treatment time is 30 minutes to 3 hours, preferably 1 to 3 hours. In liquid phase sintering, the fine powders of Co and Ni as liquid phase components mixed with the fine powder of the Re-containing alloy cannot be diffused into the Re-containing alloy during sintering, and some of them remain as single metals. It is subjected to heat diffusion treatment at 10 -2 to 10 -6 Torr (preferably 10 -4 to 10 -6 Torr) at 1500 to 1750°C (preferably 1600 to 1750°C) for 1 to 10 hours, and exists as a single substance. Alloy Co and Ni. When treated in this way, the corrosion resistance of the sintered body of the Re-containing alloy becomes even better. The sintered body of the Re-containing alloy of the present invention has the following characteristics. (1) Abrasion resistance Although it is slightly inferior to iridosmin, which has the best abrasion resistance as a writing tip material, it has sufficient abrasion resistance.
Furthermore, it has moderate abrasion resistance and blends well with paper. (2) Corrosion resistance It has excellent corrosion resistance and is not corroded by writing ink or acid solutions such as sulfuric acid and hydrochloric acid.
It is suitable for use in corrosive environments, and since it does not wear out due to corrosion, it has good wear resistance as a writing tip material. (3) Denseness, high transverse rupture strength It is dense with few cavities, and when used as a writing tip material, it slides well on paper and has excellent contact with paper. Due to its excellent density, transverse rupture strength is also high.
Even in shapes such as thin rods and pipes, they are relatively hard to break.
Can be used for fine point pipe pens, dot wires, etc. (Example) An example of the present invention will be shown. Example 1 Powders of 50% by weight of Re, 20% by weight of Ru, 13% by weight of W, 10% by weight of Ta, 6% by weight of Co, and 1% by weight of B were mixed well and press-molded. It was made into a cylindrical green compact with a diameter of about 10 mm and a length of about 10 mm. This green compact was arc-fused in a vacuum of about 10 -1 Torr to form an alloy ball with a diameter of about 10 mm. The alloy balls were subjected to hydrogen embrittlement treatment at 900°C for 3 hours in a hydrogen atmosphere at atmospheric pressure, and crushed with a hammer to form alloy particles with a diameter of about 2 mm or less. In a high-speed impact crusher, this alloy granule is crushed into diameter 32 mm.
Place it on the bottom of a cylindrical container with a diameter of 30 mm and a weight of 6 kg.
Let it cool down naturally for a while and make it into a fine powder. This fine powder was immersed in a 20% HCl aqueous solution, stirred for 1 hour, filtered, and classified for particle size.
It was made into a fine powder of Re-Ru-W-Ta-Co-B alloy with a size of 10 μm or less. To this fine powder, 2% by weight of Co fine powder (particle size approximately μm), 2% by weight of privinyl alcohol,
Add a small amount of water and knead in an agate mortar to form a rice cake-like cylinder with a diameter of about 16 mm. Place it on a die with a hole diameter of 0.5 mm, and press a 16 mm diameter punch from above with 12 tons to extrude it. It was formed into a rod-shaped molded product of about 0.5 mm and dried at 80°C for 3 hours. This molded body was heated in a hydrogen atmosphere at atmospheric pressure for 1100 min.
Pre-sintered for 1 hour at 1600 °C and approximately 10 -4 Torr vacuum.
℃ for 1 hour, hot water pressure treatment at 1350℃ for 1 hour in an argon atmosphere of 1000 atm.
Heat diffusion treatment was performed at 1650℃ for 4 hours in a 10 -4 Torr vacuum,
A rod-shaped sintered body of Re-Ru-W-Ta-Co alloy was obtained. Example 2 Same composition as Example 1 and produced by the same method
Based on the fine powder of Re-Ru-W-Ta-Co-B alloy, 4% by weight of Co fine powder (particle size approximately 2 μm), 4% by weight of polyvinyl alcohol, 1% by weight of stearic acid emulsion, 0.5% by weight % glycerin and a small amount of water, knead it in an agate mortar to form a rice cake-like cylinder with a diameter of 16 mm, and place it on a metal needle with a diameter of 0.3 mm placed in the center of the hole of a die with a hole diameter of 0.6 mm.
It was extruded from above using a punch with a diameter of 16 mm at a pressure of 4 tons to form a cylindrical molded product with an outer diameter of about 0.6 mm and an inner diameter of 0.3 mm. This molded body was sequentially dried, pre-sintered, vacuum sintered, hot isostatically pressed, and heated and diffused in the same manner as in Example 1 to form a cylindrical shape of Re-Ru-W-Ta-Co-B alloy. A sintered body was obtained. Example 3 40 wt% Re, 40 wt% OS, 4 wt%
Alloy balls prepared using powders of Ta, 15% by weight of Co, and 1% by weight of B in the same manner as in Example 1 were subjected to hydrogen embrittlement treatment at 1100°C for 3 hours in an atmospheric hydrogen atmosphere, and then hammered. It was crushed into alloy grains with diameters of about 2 mm or less. As in Example 1, the alloy particles were pulverized using a high-speed impact pulverizer, immersed in acid, and classified for particle size.
A fine powder of Re-Os-Ta-Co-B alloy with a particle size of about 10 μm or less was prepared. To this fine powder, 0.5% by weight of polyvinyl alcohol, 1% by weight of polyethylene glycol,
0.3% by weight of glycerin and a small amount of water were added, kneaded in an agate mortar to form a rice cake, and extruded in the same manner as in Example 1 using a die (pore diameter: 1 mm) to form a rod-shaped molded product with a diameter of about 1 mm. This molded body was heated at 1200℃ in a hydrogen atmosphere at atmospheric pressure.
Pre-sintered for 2 hours at 1750 in a vacuum of approximately 10 -4 Torr.
℃ for 2 hours, hot isostatic pressing at 1350℃ for 1 hour in an argon atmosphere of 1000 atm.
A rod-shaped sintered body of -Os-Ta-Co-B alloy was obtained. Example 4 An alloy ball was prepared using powders of 88% by weight of Re, 4% by weight of Zr, 4% by weight of Ta, 3% by weight of Co, and 1% by weight of B in the same manner as in Example 1. Hydrogen embrittlement treatment is performed at 1100℃ for 1 hour in a hydrogen atmosphere at atmospheric pressure.
It was crushed with a hammer to produce alloy particles with a diameter of about 2 mm or less. As in Example 1, the alloy particles were pulverized using a high-speed impact pulverizer, immersed in acid, and classified for particle size.
A fine powder of Re-Zr-Ta-Co-B alloy with a particle size of about 10 μm or less was prepared. To this fine powder, 2% by weight of Co fine powder (particle size: about 2 μm), 5% by weight of polystyrene, and a small amount of toluene were added, and the mixture was kneaded in an agate mortar to form a rice cake. A rod-shaped molded product with a diameter of about 0.5 mm was made. This compact was sequentially pre-sintered at 1200℃ for 1 hour in a mixed atmosphere of argon and hydrogen at atmospheric pressure.
Vacuum sintered at 1600℃ for 1 hour in a vacuum of 10 -4 Torr,
Hot isostatic pressure treatment at 1350℃ for 1 hour in an argon atmosphere of 1000 atm, and 1750℃ in a vacuum of about 10 -4 Torr.
After heating and diffusion treatment for 2 hours, Re-Zr-Ta-Co-B
A rod-shaped sintered body of the alloy was obtained. Example 5 10% by weight Re, 47% by weight Cr, 28% by weight W,
Alloy balls made from powders of 11% by weight Ni and 4% by weight B in the same manner as in Example 1 were subjected to hydrogen embrittlement treatment at 800°C for 3 hours in a hydrogen atmosphere, and crushed with a hammer to a diameter of approximately The alloy grains are 2mm or less. As in Example 1, the alloy particles were pulverized using a high-speed impact pulverizer, immersed in acid, and classified for particle size.
A fine powder of Re-Cr-W-Ni-B alloy with a particle size of about 10 μm or less was prepared. To this fine powder, 1% by weight of Ni fine powder (particle size approximately 1 μm), 1% by weight of polyvinyl alcohol, 0.5% by weight of glycerin, and a small amount of water were added.
Knead it in an agate mortar to form a rice cake, extrude it in the same way as in Example 1 using a die (pore diameter 0.8 mm), and make it about 0.8 mm in diameter.
It was made into a rod-shaped molded product of mm. This molded body was heated in a hydrogen atmosphere at atmospheric pressure for 1000 hrs.
Pre-sintered at ℃ for 2 hours and vacuumed at approximately 10 -4 Torr.
Vacuum sintering at 1350℃ for 2 hours, hot isostatic pressing at 1350℃ for 1 hour in an argon atmosphere of 1000 atm,
A rod-shaped sintered body of Re-Cr-W-Ni-B alloy was obtained. Next, a comparative example will be shown. Comparative example: 57 wt% Re (particle size approximately 50 μm), 20 wt% Ru
(particle size approx. 50 μm), 13 wt% W (particle size approx. 1 μm), 10
Mix well each powder of Ta (particle size: about 50 μm) at % by weight, add 2% by weight of polyvinyl alcohol and a small amount of water, knead in an agate mortar to form a rice cake, and prepare in the same manner as in Example 1. It was extruded into a rod-shaped molded product with an outer diameter of 0.5 mm. This molded body was sequentially dried, pre-sintered, vacuum sintered, and hot isostatically pressed in the same manner as in Example 1.
- A rod-shaped sintered body of Ru-W-Ta alloy was obtained. The following table shows a comparison of the degree of cavities, physical properties, and chemical properties between the sintered bodies obtained in Examples 1 to 5 of the present invention and the sintered bodies obtained in comparative examples.
【表】
巣の等級記号：超硬工具協会「超硬合金の有孔度
分類標準」CIS−006により評価した。
摩耗量：焼結体の角柱（0.35mmXO.35mm）に形成
した先端を角度45゜、荷重50ｇで紙面に接
触し、その接触箇所に万年筆インク（出願
人製のブルーブラツクインク）を常時流出
して摩耗距離3000mにおける摩耗体積であ
る。
腐食電流：ポテンシオスタツトにおける500mV
（飽和甘汞電極基準）、５％H2SO4溶液、
20℃における発生電流値である。
この表より明らかのように、本発明の焼結体は
総合的にすぐれており、パイプペン、ドツトピン
の先端、IC製造に使用するボンデイングキヤピ
ラリ、その他の耐摩耗性の工業ノズルなどに使用
できる。[Table] Pore grade symbol: Evaluated according to the Cemented Carbide Tool Association's "Porosity Classification Standard for Cemented Carbide" CIS-006. Amount of wear: The tip of a sintered body (0.35mm x O.35mm) was brought into contact with the paper surface at an angle of 45° and under a load of 50g, and fountain pen ink (Blue Black ink manufactured by the applicant) constantly flowed out at the contact point. This is the wear volume at a wear distance of 3000 m. Corrosion current: 500mV at potentiostat
(Saturated Gantan electrode standard), 5% H 2 SO 4 solution,
This is the generated current value at 20℃. As is clear from this table, the sintered body of the present invention is excellent overall and can be used for pipe pens, dot pin tips, bonding capillaries used in IC manufacturing, and other wear-resistant industrial nozzles.
Claims (1)
Zr、Hf、Ｖ、Nb、Ta、Cr、MoおよびＷの少な
くとも１つ：３〜93重量％と、CoおよびNiの少
なくとも１つ：0.2〜25重量％と、Ｂ：0.1〜５重
量％よりなる、耐摩耗性Re合金の焼結体。 ２ Re：５〜95重量％と、Os、Ir、Ru、Ti、
Zr、Hf、Ｖ、Nb、Ta、Cr、MoおよびＷの少な
くとも１つ：３〜93重量％と、CoおよびNiの少
なくとも１つ：0.2〜25重量％と、Ｂ：0.1〜５重
量％よりなる合金微粉末を作製して加圧成形し、
その成形体を固相焼結する、耐摩耗性Re合金の
焼結体の製造方法。 ３ Re：５〜95重量％と、Os、Ir、Ru、Ti、
Zr、Hf、Ｖ、Nb、Ta、Cr、MoおよびＷの少な
くとも１つ：３〜93重量％と、CoおよびNiの少
なくとも１つ0.2〜25重量％と、Ｂ：0.1〜５重量
％よるなる合金微粉末を作製し、CoおよびNiの
少なくとも１つの微粉末：前記合金微粉末の0.1
〜５重量％を前記合金微粉末に添加して前記合金
微粉末を加圧成形し、その成形体を液相焼結す
る、耐摩耗性Re合金の焼結体の製造方法。[Claims] 1 Re: 5 to 95% by weight, Os, Ir, Ru, Ti,
At least one of Zr, Hf, V, Nb, Ta, Cr, Mo and W: 3 to 93% by weight, at least one of Co and Ni: 0.2 to 25% by weight, and B: 0.1 to 5% by weight A sintered body of wear-resistant Re alloy. 2 Re: 5 to 95% by weight, Os, Ir, Ru, Ti,
At least one of Zr, Hf, V, Nb, Ta, Cr, Mo and W: 3 to 93% by weight, at least one of Co and Ni: 0.2 to 25% by weight, and B: 0.1 to 5% by weight A fine alloy powder is prepared and pressure-molded,
A method for manufacturing a wear-resistant Re alloy sintered body by solid-phase sintering the molded body. 3 Re: 5 to 95% by weight, Os, Ir, Ru, Ti,
At least one of Zr, Hf, V, Nb, Ta, Cr, Mo and W: 3-93% by weight; at least one of Co and Ni: 0.2-25% by weight; B: 0.1-5% by weight A fine alloy powder is prepared, and at least one fine powder of Co and Ni: 0.1 of the fine alloy powder.
A method for producing a sintered body of a wear-resistant Re alloy, which comprises adding ~5% by weight to the fine alloy powder, press-molding the fine alloy powder, and liquid-phase sintering the molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9663884A JPS60243242A (en) | 1984-05-16 | 1984-05-16 | Sintered body of wear resistant re alloy and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9663884A JPS60243242A (en) | 1984-05-16 | 1984-05-16 | Sintered body of wear resistant re alloy and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60243242A JPS60243242A (en) | 1985-12-03 |
| JPH0429729B2 true JPH0429729B2 (en) | 1992-05-19 |
Family
ID=14170368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9663884A Granted JPS60243242A (en) | 1984-05-16 | 1984-05-16 | Sintered body of wear resistant re alloy and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60243242A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3910588B2 (en) * | 2001-10-31 | 2007-04-25 | 独立行政法人科学技術振興機構 | ReCr alloy coating for diffusion barrier |
| JP3857689B2 (en) * | 2001-10-31 | 2006-12-13 | 独立行政法人科学技術振興機構 | ReCrNi alloy coating for diffusion barrier |
| US7270782B2 (en) * | 2002-09-13 | 2007-09-18 | Honeywell International, Inc. | Reduced temperature and pressure powder metallurgy process for consolidating rhenium alloys |
| US6902809B1 (en) | 2004-06-29 | 2005-06-07 | Honeywell International, Inc. | Rhenium tantalum metal alloy |
| JP5936487B2 (en) * | 2012-08-23 | 2016-06-22 | キヤノン株式会社 | Amorphous alloy, molding die, and optical element manufacturing method |
| CN109182797A (en) * | 2018-10-14 | 2019-01-11 | 昆山建金工业设计有限公司 | A kind of composite device of wolfram element and nickel element |
-
1984
- 1984-05-16 JP JP9663884A patent/JPS60243242A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60243242A (en) | 1985-12-03 |
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