JPH0361744B2 - - Google Patents
Info
- Publication number
- JPH0361744B2 JPH0361744B2 JP7090186A JP7090186A JPH0361744B2 JP H0361744 B2 JPH0361744 B2 JP H0361744B2 JP 7090186 A JP7090186 A JP 7090186A JP 7090186 A JP7090186 A JP 7090186A JP H0361744 B2 JPH0361744 B2 JP H0361744B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- weight
- aluminum
- chemical
- aluminum oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910045601 alloy Inorganic materials 0.000 claims description 53
- 239000000956 alloy Substances 0.000 claims description 53
- 239000000126 substance Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910000531 Co alloy Inorganic materials 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- 238000005266 casting Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013060 biological fluid Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
（産業上の利用分野）
本発明は、表面が酸化アルミニウムで被覆され
た耐薬品性合金に関する。
（従来技術及び発明が解決しようととする問題
点）
生体内や最近の化学プラントのような苛酷な腐
食環境下で使用される金属材料の耐食性を向上さ
せるために、金属材料の表面に他の金属層、無機
化合物或いは有機化合物をコーテイングする方法
が研究されている。ところが、このような方法に
より得られた金属材料は、長時間の使用によつて
コーテイングが剥離しやすくなるという欠点があ
つた。
この欠点を改善するために、合金等の金属材料
の表面に金属酸化物の層を形成させるに当り、金
属酸化物の層を単に被覆処理するのではなく、合
金を構成する金属の酸化物層をその表面に析出さ
せるという方法が提案されている。例えば、特開
昭60−262943号公報には、クロムが20〜32重量
％、アルミニウムが0.5〜5.0重量％、モリブデン
が0.5〜4.0重量％、ジルコニウム、ハフニウム及
びイツトリウムからなる群より選ばれた少くとも
１種の金属が0.05〜0.5重量％及び残部が鉄から
なる合金の表面に酸化アルミニウムを主体とした
酸化物皮膜が形成された医療用インプラント合金
が示されている。ここで、合金の表面に酸化アル
ミニウムを主体とした酸化物皮膜を形成させる方
法としては、合金を熱処理する方法が採用されて
いる。ところが、上記の組成の合金の場合、表面
に酸化アルミニウムを主体とする酸化物皮膜の形
成には、長時間が必要となる。酸化物皮膜の形成
を短時間で行なうためには、合金のアルミニウム
の量を増加させることが考えられる。しかしなが
ら、上記のような組成の合金に於いてアルミニウ
ムの量を増加させると、鋳造の際に鋳造割れを起
こしやすくなり、また、鋳造割れを起こさずに鋳
造できたとしても、その合金の表面硬度が極めて
高くなり、通常の機械的な加工が困難になる。
（問題点を解決するための手段）
本発明者らは、耐食性の高い合金について鋭意
研究を重ねてきた結果、ニツケル或いはコバルト
を基とし、これに特定量のクロム及びアルミニウ
ムを含有する合金が、酸化物皮膜の形成が極めて
短時間に行なえるようにアルミニウムの量を増加
させても鋳断割れ等の不都合が生じないことを見
い出し、本発明を完成するに至つた。
即ち、本発明は、
(A) クロムが５〜30重量％、
(B) アルミニウムが0.1〜15重量％、及び
(C) 残部がニツケル及び／又はコバルト
である合金の表面が酸化アルミニウムで被覆され
てなる耐薬品性合金である。
以下に、本発明の合金の各成分について詳細に
説明する。
まず、クロムは、連続したしかも緻密な酸化ア
ルミニウムの被覆層を形成させるために必要な元
素であり、また、ニツケル又はコバルトの機械的
性質及び耐食性を向上させる。クロムの量は５〜
30重量％であることが必要であり、10〜30重量％
の範囲であることが好ましい。クロムが５重量％
未満では、上記した機能が発揮されず、一方、30
重量％を越えると酸化クロムを主体とする被覆層
が生成して耐薬品性が低下するために好ましくな
い。
次に、アルミニウムは、合金表面の酸化アルミ
ニウムの被膜層を形成させるために必要な元素で
ある。その量は、0.1〜15重量％が必要である。
アルミニウムが0.1重量％未満であれば、酸化ア
ルミニウムの良好な被覆層が形成し難く、耐薬品
性に劣り、一方、15重量％を越えると、合金の機
械的性質を低下させるのみならず、加工性も低下
するために好ましくない。
アルミニウムの量は、上記した範囲であればよ
いが、通常の熱処理によつて容易に短時間に酸化
アルミニウムの被覆層を形成させ、しかも、得ら
れた耐薬品性合金の鋳造性や加工性を良好に保つ
ためには、ニツケルを基とする合金の場合には６
〜12重量％、また、コバルトを基とする場合には
８〜15重量％であることが好ましい。
本発明の合金の残部は、ニツケル及び／又はコ
バルトである。ニツケル及びコバルトのいずれも
次のような機能を発揮する。
一般に合金表面に酸化アルミニウムを析出させ
るためにはアルミニウムを多量に添加しなければ
ならないが、アルミニウムの多量添加は硬度を大
きくして加工性を悪くする。ところがニツケルを
主成分にすると少量のアルミニウムで酸化アルミ
ニウムを合金表面へ均一に析出させることができ
るため、加工性を損なうことがない。また、表面
の酸化アルミニウムが何らかの原因で剥離しても
その再生能が大きいため常に良好な耐食性を維持
することができる。
特にこの効果は、ニツケルを基とする合金の場
合に顕著である。
本発明で用いる合金は、上記に述べた組成で十
分実用に供することができるが、さらに次のよう
な金属を含むことが好ましい。
まず、モリブデン、タングステン及び鉄からな
る群から選ばれた金属の少くとも１種が１〜20重
量％、さらに３〜15重量％の範囲で合金に含まれ
ていることが、熱処理により生成する酸化アルミ
ニウムの被覆層を緻密にして耐薬品性が向上する
ために好ましい。
また、周期律表第族（但し、アルミニウムを
除く。）、第族及び第族の金属からなる群から
選ばれた少くとも１種が0.01〜５重量％、さらに
0.01〜２重量％の範囲で含まれていることが、酸
化アルミニウムの被覆層と合金との密着性が高ま
り耐薬品性が向上するために好ましい。ここで、
周期律表第族の金属としてはホウ素、ガリウ
ム、インジウム、イツトリウム、セリウム等が好
ましい。また、同第族の金属しては、シリコー
ン、ゲルマニウム、すず、チタニウム、ジルコニ
ウム、ハフニウム等が好ましい。さらに、同第
族の金属としては、ビスマス、バナジウム、ニオ
ブ及びタンタル等が好適である。
特に、本発明の耐薬品性合金とセラミツクスと
を接合する場合には、これらの金属の中でも、ホ
ウ素、インジウム、イツトリウム、セリウム、シ
リコーン、チタン、ビスマス、ニオブを用いるこ
とが良好な接合強度が得られるために好ましい。
本発明の耐薬品性合金は、以上に述べた合金の
表面に酸化アルミニウムが被覆されてなる。酸化
アルミニウムの被覆層は、合金の実質的全面を覆
つていることが好ましいが、腐食性の液体と合金
との接触面のみ覆つていても良い。また、酸化ア
ルミニウムの被覆層の厚みは、特に制限されない
が、良好な耐薬品性を発揮させるためには、１〜
50μｍの範囲であることが好ましい。上記の酸化
アルミニウムの被覆層は、酸化アルミニウムの純
度が高いほど耐薬品性が良好であるために好まし
いが、一般には、被覆層の90重量％以上が酸化ア
ルミニウムであれば、十分な耐薬品性が得られ
る。
本発明の耐薬品性合金の製造方法は特に限定さ
れるものではないが、前記の組成の合金を酸化雰
囲気中で酸化するか又は、前記合金の組成となる
ように金属粉末を酸化雰囲気中で焼結させる方法
が一般的である。酸化雰囲気としては、酸素、空
気、過熱水蒸気等を用いることが好ましい。ま
た、酸化及び焼結の温度及び時間は、アルミニウ
ムをはじめとする合金の組成、或いは金属粉末の
組成によつて適当な範囲があるため、一概には決
定できないが、一般に1000℃〜1300℃で30分以上
酸化することが好ましい。
（効 果）
本発明の耐薬品性合金は、塩酸や硫酸というよ
うな薬品に対して極めて良好な耐食性を有する。
さらに、生体液に対する耐食性の指標として用い
られている乳酸に対しても本発明の耐薬品性合金
は優れた耐食性を有している。しかも、本発明の
耐薬品性合金は、アルミニウムの含量が比較的多
い場合にも、鋳造性が損われることはなく、ま
た、機械的な加工性にも優れている。さらに、本
発明の耐薬品性合金のうち、ニツケルを基とする
合金は、アルミニウムの含量が比較的低い場合に
於いても容易に短時間で合金表面へ酸化アルミニ
ウムの被覆層の形成が可能である。
以上のように優れた特徴を有する本発明の耐薬
品性合金は、化学プラントの内壁材等の用途のみ
ならず、人工骨或いは人工歯等の生前材料として
も使用し得る。特に、本発明の耐薬品性合金は、
前述したように生体液に耐する耐食性が高いこ
と、鋳造性が優れていること、また、表面が酸化
アルミニウムで被覆されているためにセラミツク
ス等との接着性が良好であること等の理由から、
歯科補綴材、例えば、鋳造歯冠或いは陶材焼付合
金、橋義歯、義歯床等の種々の用途に好適に用い
ることができる。
以下に本発明をさらに具体的に説明するために
実施例を示すが、本発明はこれら実施例に限定さ
れるものではない。
実施例 １
第１表および第２表に示す組成の合金を各500
ｇ真空溶解した後、鍜造、熱間圧延して５mm厚ま
でとし、ついで厚さ２mmまで冷間圧延した。次に
試験片として20mm×20mm×２mmの直方体を切り出
し、これを1200℃の真空中で３時間焼鈍した。こ
れらの試験片を鏡面仕上げした後、合金表面に酸
化被膜を形成させるため1100℃の大気中で所定の
時間加熱処理して実験に供した。
表面酸化物の同定はＸ線回折によつて行ない、
表面硬度（Hv）はビツカース硬度計を用いて測
定した。この結果を第１表および第２表に示し
た。
また、耐食性試験は、試験片を37℃の１％乳酸
溶液、１％塩酸溶液、１％硫酸溶液にそれぞれ７
日間全浸漬した後これを取り出し、溶液中のニツ
ケル又はコバルト溶出量を原子吸光光度法で測定
した。その結果を第１表及び第２表に併せて示し
た。
(Industrial Application Field) The present invention relates to a chemical-resistant alloy whose surface is coated with aluminum oxide. (Prior Art and Problems to be Solved by the Invention) In order to improve the corrosion resistance of metal materials used in severe corrosive environments such as in vivo and in recent chemical plants, other materials are added to the surface of the metal material. Methods of coating metal layers, inorganic compounds, or organic compounds are being investigated. However, the metal material obtained by such a method has the disadvantage that the coating tends to peel off after long-term use. In order to improve this drawback, when forming a metal oxide layer on the surface of metal materials such as alloys, instead of simply coating the metal oxide layer, A method has been proposed in which the compound is deposited on the surface. For example, JP-A No. 60-262943 discloses that chromium is 20 to 32% by weight, aluminum is 0.5 to 5.0% by weight, molybdenum is 0.5 to 4.0% by weight, and a small amount selected from the group consisting of zirconium, hafnium, and yttrium is included. Both patents disclose a medical implant alloy in which an oxide film mainly composed of aluminum oxide is formed on the surface of an alloy consisting of 0.05 to 0.5% by weight of one metal and the balance iron. Here, as a method for forming an oxide film mainly composed of aluminum oxide on the surface of the alloy, a method of heat treating the alloy is adopted. However, in the case of an alloy having the above composition, it takes a long time to form an oxide film mainly composed of aluminum oxide on the surface. In order to form an oxide film in a short time, it is possible to increase the amount of aluminum in the alloy. However, when the amount of aluminum is increased in an alloy with the above composition, casting cracks are more likely to occur during casting, and even if casting is possible without causing casting cracks, the surface hardness of the alloy becomes extremely high, making normal mechanical processing difficult. (Means for Solving the Problems) As a result of intensive research into alloys with high corrosion resistance, the present inventors have found that alloys based on nickel or cobalt and containing specific amounts of chromium and aluminum have been developed. The inventors have discovered that even if the amount of aluminum is increased so that the oxide film can be formed in an extremely short time, problems such as casting cracks do not occur, and the present invention has been completed. That is, the present invention provides an alloy in which the surface of an alloy containing (A) 5 to 30% by weight of chromium, (B) 0.1 to 15% by weight of aluminum, and (C) the balance being nickel and/or cobalt is coated with aluminum oxide. It is a chemical-resistant alloy made of Each component of the alloy of the present invention will be explained in detail below. First, chromium is an element necessary to form a continuous and dense coating layer of aluminum oxide, and also improves the mechanical properties and corrosion resistance of nickel or cobalt. The amount of chromium is 5~
Must be 30% by weight, 10-30% by weight
It is preferable that it is in the range of . 5% chromium by weight
If it is less than 30, the above function will not be achieved.
If it exceeds % by weight, a coating layer mainly composed of chromium oxide will be formed, resulting in a decrease in chemical resistance, which is not preferable. Next, aluminum is an element necessary to form a coating layer of aluminum oxide on the surface of the alloy. Its amount is required to be 0.1 to 15% by weight.
If the aluminum content is less than 0.1% by weight, it will be difficult to form a good coating layer of aluminum oxide and the chemical resistance will be poor. On the other hand, if the content exceeds 15% by weight, it will not only deteriorate the mechanical properties of the alloy but also cause processing problems. This is not preferable because it also reduces performance. The amount of aluminum may be within the above-mentioned range, but it is important that an aluminum oxide coating layer be easily formed in a short time by ordinary heat treatment, and that the castability and workability of the resulting chemical-resistant alloy be improved. 6 for nickel-based alloys to keep them in good condition.
-12% by weight, and preferably 8-15% by weight when based on cobalt. The remainder of the alloy of the invention is nickel and/or cobalt. Both nickel and cobalt exhibit the following functions. Generally, a large amount of aluminum must be added in order to precipitate aluminum oxide on the alloy surface, but adding a large amount of aluminum increases hardness and impairs workability. However, when nickel is used as the main component, aluminum oxide can be uniformly deposited on the alloy surface with a small amount of aluminum, so workability is not impaired. Furthermore, even if the aluminum oxide on the surface peels off for some reason, its regeneration ability is high, so good corrosion resistance can always be maintained. This effect is particularly noticeable in the case of nickel-based alloys. Although the alloy used in the present invention can be put to practical use with the composition described above, it is preferable that the alloy further contains the following metals. First, the alloy contains at least one metal selected from the group consisting of molybdenum, tungsten, and iron in an amount of 1 to 20% by weight, and furthermore 3 to 15% by weight. This is preferable because it makes the aluminum coating layer dense and improves chemical resistance. In addition, at least one metal selected from the group consisting of Group 3 (excluding aluminum), Group 3, and Group metals of the periodic table, in an amount of 0.01 to 5% by weight, and
It is preferable for the content to be in the range of 0.01 to 2% by weight, since this increases the adhesion between the aluminum oxide coating layer and the alloy and improves the chemical resistance. here,
Preferred examples of metals from group 3 of the periodic table include boron, gallium, indium, yttrium, and cerium. Further, as the metal of the same group, silicone, germanium, tin, titanium, zirconium, hafnium, etc. are preferable. Furthermore, as metals of the same group, bismuth, vanadium, niobium, tantalum, etc. are preferable. In particular, when bonding the chemical-resistant alloy of the present invention and ceramics, it is preferable to use boron, indium, yttrium, cerium, silicone, titanium, bismuth, and niobium among these metals to obtain good bonding strength. preferred because it is The chemical-resistant alloy of the present invention is formed by coating the surface of the above-mentioned alloy with aluminum oxide. The aluminum oxide coating layer preferably covers substantially the entire surface of the alloy, but may also cover only the contact surface between the corrosive liquid and the alloy. In addition, the thickness of the aluminum oxide coating layer is not particularly limited, but in order to exhibit good chemical resistance, it is necessary to
Preferably, the range is 50 μm. The above-mentioned aluminum oxide coating layer is preferable because the higher the purity of the aluminum oxide, the better the chemical resistance, but in general, if the coating layer is made up of 90% by weight or more of aluminum oxide, it has sufficient chemical resistance. is obtained. The method for producing the chemical-resistant alloy of the present invention is not particularly limited, but may include oxidizing an alloy having the above-mentioned composition in an oxidizing atmosphere, or oxidizing metal powder in an oxidizing atmosphere so as to have the composition of the above-mentioned alloy. A common method is sintering. As the oxidizing atmosphere, it is preferable to use oxygen, air, superheated steam, or the like. In addition, the temperature and time of oxidation and sintering cannot be determined unconditionally because there are appropriate ranges depending on the composition of the alloy including aluminum or the composition of the metal powder, but it is generally 1000℃ to 1300℃. It is preferable to oxidize for 30 minutes or more. (Effects) The chemical-resistant alloy of the present invention has extremely good corrosion resistance against chemicals such as hydrochloric acid and sulfuric acid.
Furthermore, the chemical-resistant alloy of the present invention has excellent corrosion resistance against lactic acid, which is used as an indicator of corrosion resistance against biological fluids. Moreover, the chemical-resistant alloy of the present invention does not suffer from loss of castability even when the aluminum content is relatively high, and also has excellent mechanical workability. Furthermore, among the chemical-resistant alloys of the present invention, nickel-based alloys allow the formation of an aluminum oxide coating layer on the alloy surface easily and quickly even when the aluminum content is relatively low. be. The chemical-resistant alloy of the present invention, which has the excellent characteristics as described above, can be used not only as an inner wall material for chemical plants, but also as an antemortem material for artificial bones, artificial teeth, and the like. In particular, the chemical resistant alloy of the present invention
As mentioned above, it has high corrosion resistance against biological fluids, excellent castability, and because the surface is coated with aluminum oxide, it has good adhesion to ceramics, etc. ,
It can be suitably used in various applications such as dental prosthetic materials, such as cast crowns, porcelain baked alloys, bridge dentures, and denture bases. Examples are shown below to further specifically explain the present invention, but the present invention is not limited to these Examples. Example 1 500 each of alloys having the compositions shown in Tables 1 and 2
After vacuum melting, it was molded and hot rolled to a thickness of 5 mm, and then cold rolled to a thickness of 2 mm. Next, a 20 mm x 20 mm x 2 mm rectangular parallelepiped was cut out as a test piece, and this was annealed in a vacuum at 1200°C for 3 hours. After mirror-finishing these test pieces, they were heat-treated in the atmosphere at 1100°C for a predetermined period of time in order to form an oxide film on the alloy surface, and then used for experiments. Identification of surface oxides was performed by X-ray diffraction.
Surface hardness (Hv) was measured using a Bitkers hardness meter. The results are shown in Tables 1 and 2. In the corrosion resistance test, test pieces were placed in 1% lactic acid solution, 1% hydrochloric acid solution, and 1% sulfuric acid solution at 37°C for 7 days.
After being completely immersed for a day, it was taken out and the amount of nickel or cobalt eluted into the solution was measured by atomic absorption spectrophotometry. The results are also shown in Tables 1 and 2.
【表】【table】
【表】【table】
【表】【table】
【表】
実施例 ２
実施例１で得られた本発明の耐薬品性合金につ
いて、陶材との接合強度測定を行なつた。まず、
第１表および第２表の組成の合金を各30ｇ真空溶
解し、ロストワツクス法により30mm×６mm×１mm
の板状試験片に鋳造した。次にこれらの試験片を
鏡面仕上げし、第１表および第２表に示した加熱
処理を施した後、４mm×６mm×0.1mmの陶材片の
両面にそれぞれ試験片を焼付け、２枚の試験片を
重ね合わせた。なお、陶材は西独国ビタ
（VITA）社製のオペーク陶材（VMK68）を用い
た。陶材と試験片との焼付けは以下のように行つ
た。まず、水を加えて泥状にした陶材を２枚の試
験片ではさんだ。陶材を乾燥させた後、重ね合わ
せた試験片を800℃の電気炉に入れ、真空中で980
℃まで毎分５℃で昇温して陶材と試験片を焼付け
た。
重ね合わせた２枚の試験片が互いに上下の位置
になるようにみて水平方向に両試験片を互いに反
対側に引張つてこれを破断させ、この時の強度を
接合強度とした。この結果を夫々第３表および第
４表に示した。
また、鋳造の可否も併せて第３表および第４表
に示した。表中○は鋳造可、×は鋳造不可を示す。[Table] Example 2 For the chemical-resistant alloy of the present invention obtained in Example 1, the bonding strength with porcelain was measured. first,
30g each of the alloys with the compositions shown in Tables 1 and 2 were vacuum melted, and 30mm x 6mm x 1mm was melted using the lost wax method.
It was cast into a plate-shaped test piece. Next, these test pieces were mirror-finished and subjected to the heat treatment shown in Tables 1 and 2, and then the test pieces were baked on both sides of each porcelain piece measuring 4 mm x 6 mm x 0.1 mm. The test pieces were superimposed. The porcelain used was opaque porcelain (VMK68) manufactured by VITA in West Germany. The baking of the porcelain and the test piece was carried out as follows. First, a porcelain material made into a slurry by adding water was sandwiched between two test pieces. After drying the porcelain, the stacked test pieces were placed in an electric furnace at 800°C and heated at 980°C in a vacuum.
The porcelain and specimen were baked by increasing the temperature to 5°C per minute. The two stacked test pieces were placed one above the other, and both test pieces were pulled horizontally to opposite sides to break, and the strength at this time was defined as the bonding strength. The results are shown in Tables 3 and 4, respectively. In addition, Tables 3 and 4 also show whether or not it can be cast. In the table, ○ indicates that casting is possible, and × indicates that casting is not possible.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
金の表面が酸化アルミニウムで被覆されてなる
耐薬品性合金。 ２ (A) クロムが５〜30重量％、 (B) アルミニウムが0.1〜15重量％、 (C) モリブデン、タングステン及び鉄からなる群
から選ばれた金属の少くとも１種が１〜20重量
％、 (D) 周期律表第族（但し、アルミニウムを除
く。）、第族及び第族の金属からなる群から
選ばれた少くとも１種が0.01〜５重量％、及び (E) 残部がニツケル及び／又はコバルトである
合金の表面が酸化アルミニウムで被覆されて
なる耐薬品性合金。[Claims] 1. The surface of an alloy containing (A) 5 to 30% by weight of chromium, (B) 0.1 to 15% by weight of aluminum, and (C) the balance being nickel and/or cobalt is coated with aluminum oxide. Chemical resistant alloy. 2 (A) 5 to 30% by weight of chromium, (B) 0.1 to 15% by weight of aluminum, (C) 1 to 20% by weight of at least one metal selected from the group consisting of molybdenum, tungsten, and iron. , (D) 0.01 to 5% by weight of at least one metal selected from the group consisting of metals from Group 3 of the Periodic Table (excluding aluminum), Group 3, and Group 3 metals, and (E) the remainder is nickel. and/or a chemical-resistant alloy made of a cobalt alloy whose surface is coated with aluminum oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7090186A JPS62228444A (en) | 1986-03-31 | 1986-03-31 | Chemical-resistant alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7090186A JPS62228444A (en) | 1986-03-31 | 1986-03-31 | Chemical-resistant alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62228444A JPS62228444A (en) | 1987-10-07 |
| JPH0361744B2 true JPH0361744B2 (en) | 1991-09-20 |
Family
ID=13444895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7090186A Granted JPS62228444A (en) | 1986-03-31 | 1986-03-31 | Chemical-resistant alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62228444A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10227678B2 (en) * | 2011-06-09 | 2019-03-12 | General Electric Company | Cobalt-nickel base alloy and method of making an article therefrom |
| US9034247B2 (en) * | 2011-06-09 | 2015-05-19 | General Electric Company | Alumina-forming cobalt-nickel base alloy and method of making an article therefrom |
-
1986
- 1986-03-31 JP JP7090186A patent/JPS62228444A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62228444A (en) | 1987-10-07 |
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