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EP0875591B1 - Use of a biocompatible alloy suitable for the skin - Google Patents

Use of a biocompatible alloy suitable for the skin Download PDF

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Publication number
EP0875591B1
EP0875591B1 EP98890116A EP98890116A EP0875591B1 EP 0875591 B1 EP0875591 B1 EP 0875591B1 EP 98890116 A EP98890116 A EP 98890116A EP 98890116 A EP98890116 A EP 98890116A EP 0875591 B1 EP0875591 B1 EP 0875591B1
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EP
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Prior art keywords
alloy
nickel
accordance
carbon
nitrogen
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EP98890116A
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German (de)
French (fr)
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EP0875591A1 (en
Inventor
Markus O. Speidel
Peter J. Uggowitzer
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Voestalpine Boehler Edelstahl GmbH and Co KG
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Boehler Edelstahl GmbH and Co KG
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    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese

Definitions

  • the invention relates to the use of a corrosion-resistant steel alloy Material for objects that are at least partially or temporarily in Contact with the skin or body fluids of living beings, especially of people.
  • Austenitic stainless steels are used very extensively and worldwide.
  • the corrosion-resistant austenitic steels mostly contain essential ones Shares in nickel.
  • nickel can be made from these steels through use extracted and as a corrosion product in the form of nickel ions in the body of Living things get there and trigger allergic reactions.
  • Nickel allergy sufferers cause allergic reactions to nickel that manifest themselves, for example, in flushing, itching, eczema.
  • European countries are already taking legislative measures that Prohibit the use of nickel-containing materials on and in the human body.
  • Gold and titanium alloys are a substitute. But these are expensive and complex to manufacture.
  • the patent DE 195 13 407 C1 (VSG 1996) describes other nickel-free austenitic stainless steels. A very central point is that the ones to be used nickel-free steels must contain at least 0.55% by weight nitrogen to compensate for the lack of austenitizing effects of nickel. The Patent also assumes that carbon is an undesirable Element in such alloys is because until today the generally recognized The doctrine is that carbon is used in austenitic stainless steels Corrosion resistance reduced. DE 195 13 407 therefore limits the Carbon content to a maximum of 0.3 percent by weight.
  • the present invention is based on this completely new finding the task of solving the problem of neck allergy by using a to prevent austenitic stainless steel from targeting the beneficial effect of carbon, especially its contribution to increasing resistance against crevice corrosion.
  • the remaining alloy elements in Austenitic stainless steel according to the invention are according to the one Well-known rules so restricted that the stability of the cubic face-centered crystal lattice is preserved and so the absence of Ferromagnetism as well as toughness and general corrosion resistance preserved and remain as high as possible.
  • the application according to the invention builds up properties: Allergic reactions through nickel and other heavy metal ions (cobalt, chromium) avoided that the alloy to be used is extremely low in nickel and at the same time high is corrosion resistant.
  • the triggering of allergic reactions Contact with the body initially occurs via a corrosion reaction of the Material with body fluids such as sweat or saliva.
  • body fluids such as sweat or saliva.
  • Nickel ions can be extracted from nickel-containing stainless steels.
  • the next Step is the uptake of nickel ions through the skin or tissue and then the resolution of the allergic reaction. So it's not the metallic one Material, but its corrosion product that triggers the allergy reaction. Therefore, the application according to the invention uses a material that both is extremely low in nickel and highly corrosion-resistant.
  • Another advantage of using the highly corrosion resistant Alloy according to the invention lies in the fact that it will in future be very wide Areas of application are the previously widespread nickel-containing austenitic can replace stainless alloys in an economical way because carbon one is a very cheap alloying element.
  • nickel-containing austenitic steels By this replacement of the nickel-containing austenitic steels through nickel-free austenitic steels becomes steady increasing nickel levels of our environment rise less, so that too Static appearance of sensitization to nickel allergy, for example through ingestion food containing nickel, increases less rapidly.
  • the application of the carbon-containing nickel-free according to the invention corrosion-resistant steel act twice: by avoiding the Release of nickel ions and other heavy metal ions (chromium, manganese) in the Contact with the body of living beings, on the other - in the sense of sustainable Technology - by lowering the general environmental nickel level, from to which individual researchers today report that he can raise awareness Allergy to nickel, for example through food. So sensitized Living beings then need nickel-free (lack of nickel) in the steels to whom it comes into contact, and that is why it needs it application of the steel according to the invention.
  • the application of the steel according to the invention in contact with the body of Living beings are made more solid by another property of carbon Solution promoted in steel: carbon increases the strength of the steel Mixed crystal hardening and also increases the strengthening coefficient of the Material, so that high strengths can also be achieved by cold forming can.
  • carbon increases the strength of the steel Mixed crystal hardening and also increases the strengthening coefficient of the Material, so that high strengths can also be achieved by cold forming can.
  • Examples of such applications according to the invention are tooth correction wires, razor wires, surgical cutlery, implants and generally high-strength corrosion-resistant parts of objects, for example Sports equipment that triggers nickel allergic reactions when touched could.
  • the uses of the alloy according to the invention accordingly include Applications on and in the human body of living beings where nickel allergy should not occur.
  • the applications according to the invention relate also medical devices, devices and implants, for example Braces, dental fillings, dental seals, tooth correction devices such as Wires, screws, plates as well as metallic fastenings and fixations in the Bodies, for example, picks, bone nails and temporary as well permanently installed or partially installed plates and screws for healing of broken bones, as well as cannulas, syringes, acupuncture needles, surgical and ophthalmic cutlery and devices to make holes in the body of Bringing in living beings, for example for earrings, so generally all Applications on and in the body, be it permanent or temporary.
  • such components and also belong to the application of the alloy Devices that could cause nickel allergy by being close to the body of Living beings are used or touched by living beings.
  • Rivets and buttons on clothes, belt fittings, jewelry, including Costume jewelry and body piercing jewelry such as earrings and Nose rings, lighters, hospital equipment, beds, railings, handrails, Door handles, cutlery, dishes, kitchen appliances as well as architectural and architectural components Transportation, as well as coins, generally the components that are made with bodies of Living creatures and their body fluids come into contact.
  • the alloy according to the invention can be mixed with known metallurgical ones Process technologies are produced, for example by melting Normal pressure, printer melting, pressure electroslag remelting, by Powder metallurgy, including metal powder injection molding, as well as Surface layer.
  • the alloy according to the invention is preferred in the solution-annealed and then deterred state used. Their strength can be reduced by cold working after solution annealing and quenching as well as through hardening be improved.
  • the simultaneously high carbon and nitrogen content stabilize the face-centered cubic crystal lattice ("austenite") and thus cause that even after cold working the alloy of the invention maintains non-ferromagnetic properties.
  • the effective amount% Cr + 3.3 (% Mo) + 20 (% N) + 20 (% C) a significant part of this corrosion resistance, namely 6.2 out of a total of 40.2 points, can be attributed to the carbon content in solid solution.
  • the alloy has a yield strength of 510 MPa and a notched bar impact energy of 250 J, which means that, in comparison to other austenitic steels, it is extraordinarily strong and tough, and therefore also wear-resistant, in addition to its high corrosion resistance, and is therefore suitable for the above-mentioned applications.
  • the alloy thus obtained was homogeneously austenitic and therefore completely non-magnetic.
  • This alloy has such a high corrosion resistance that crevice corrosion in acidic aqueous 6% FeCl 3 solution only begins at temperatures above 26 ° C.
  • the active formula% Cr + 3.3 (% Mo) + 20 (% N) + 20 (% C) the carbon in solid solution contributes 7.0 points to the overall corrosion resistance of 45.7 points.
  • the 0.35% carbon content causes the same increase in corrosion resistance as an additional 7% chromium content would otherwise.
  • This nickel-free alloy has a yield strength of 530 MPa, so it is extremely strong for austenites and therefore also resistant to wear and, due to its combination of properties, suitable for the applications listed above.
  • the alloy has a yield strength of 560 MPa and is, in comparison to other austenitic steels, extremely hard and strong in addition to its high corrosion resistance and is therefore suitable for the applications listed above.
  • the alloy thus obtained was homogeneously austenitic and therefore completely non-magnetic.
  • This alloy has such a high resistance to corrosion that crevice corrosion in acidic aqueous 6% FeCl 3 solution only begins at temperatures above 60 ° C. This makes the alloy even more corrosion-resistant than the otherwise high-alloyed, very nickel-rich "Superaustenite" and therefore also suitable for the above-mentioned applications.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Powder Metallurgy (AREA)
  • Adornments (AREA)

Abstract

Carbon steel alloys as materials for structures partly or temporarily in contact with living beings, especially humans or used on, in or near the body of living organisms is claimed. The alloys contain 5-26 wt.% manganese, 11-24 wt.% chromium, > 2.5 to 6 wt.% molybdenum , > 0.2 to 2.0 wt.% nitrogen and > 0.1 to 0.9 wt.% carbon, with > 0.3 wt.% C in alloys containing > 0.55 wt.% N, rest iron (Fe), together with unavoidable impurities from smelting and nickel, silicon, sulphur , bismuth , copper, cobalt, vanadium, niobium, tantalum, titanium, zirconium, hafnium, tungsten, aluminium, boron, cerium and calcium in individual amounts NOTGREATER 2.0 wt.%. The material has austenitic structure after chilling from a solution annealing temperature in the 950-1260 degrees C range and hence is not ferromagnetic.

Description

Die Erfindung betrifft die Verwendung einer korrosionsbeständigen Stahllegierung als Werkstoff für Gegenstände, die zumindest teilweise oder zeitweise in Berührungskontakt mit der Haut oder Körperflüssigkeiten von Lebewesen, insbesondere von Menschen, stehen.The invention relates to the use of a corrosion-resistant steel alloy Material for objects that are at least partially or temporarily in Contact with the skin or body fluids of living beings, especially of people.

Austenitisch rostfreie Stähle finden weltweit sehr große und steigende Anwendung. Die korrosionsbeständigen austenitischen Stähle enthalten zumeist wesentliche Anteile an Nickel. Nickel kann jedoch durch den Gebrauch aus diesen Stählen herausgelöst und als Korrosionsprodukt in Form von Nickelionen in die Körper von Lebewesen gelangen und dort allergische Reaktionen auslösen.Austenitic stainless steels are used very extensively and worldwide. The corrosion-resistant austenitic steels mostly contain essential ones Shares in nickel. However, nickel can be made from these steels through use extracted and as a corrosion product in the form of nickel ions in the body of Living things get there and trigger allergic reactions.

Ein Beispiel ist hier die Anwendung nickelhaltiger austenitisch rostfreier Stähle für Bauteile von Uhren ( Uhrenschalen, Uhrarmbänder). Durch den menschlichen Schweiß zwischen Haut und Uhr können austenitisch rostfreie Stähle so korrodiert werden, daß sie Nickelionen in die Haut gelangen lassen und bei sensibilisierten "Nickelallergiker"-Personen allergische Reaktionen gegen Nickel hervorrufen, die sich zum Beispiel in Errötung, Jucken, Ekzemen, zeigen. Es gibt deshalb in europäischen Ländern schon jetzt gesetzgeberische Maßnahmen, die den Gebrauch nickelhaltiger Werkstoffe am und im menschlichen Körper verbieten. Als Ersatz bieten sich Gold-und Titanlegierungen an. Diese sind aber teuer und aufwendig herzustellen.An example here is the use of nickel-containing austenitic stainless steels for Components of clocks (watch shells, watch bands). Through the human Sweat between the skin and the watch can corrode austenitic stainless steels be that they let nickel ions get into the skin and in sensitized "Nickel allergy sufferers" cause allergic reactions to nickel that manifest themselves, for example, in flushing, itching, eczema. There is therefore in European countries are already taking legislative measures that Prohibit the use of nickel-containing materials on and in the human body. As Gold and titanium alloys are a substitute. But these are expensive and complex to manufacture.

Werkstoffe, die am und im Körper von Lebewesen verwendet werden, müssen in der Regel eine ganze Reihe von Anforderungen erfüllen. Sie sollen fest, zäh, nicht ferromagnetisch ( "antimagnetisch"), verschleißfest, korrosionsbeständig und erschwinglich sein. Solche Anforderungen werden teilweise erfüllt durch nickelfreie austenitisch rostfreie Stähle. Die Patentschriften CH 684979 B5 ( Böhler Ybbstalwerke 1993) und DE 19513407 C1 (VSG, 1996) beschreiben solche nickelfreie austenitisch rostfreie Stähle und stellen zusammengenommen den Stand der Technik dar. Beide Patentschriften gehen davon aus, daß Kohlenstoff ein unerwünschtes Element in solchen Legierungen sei, weil bis heute die allgemein anerkannte Lehrmeinung ist, daß Kohlenstoff in austenitisch rostfreien Stählen die Korrosionsbeständigkeit vermindert. Die Patentschrift CH 684979 B5 begrenzt deshalb den Kohlenstoffgehalt auf maximal 0,10 Gewichtsprozent bei einem Stickstoffgehalte von 0,55 Gewichtsprozent.Materials that are used on and in the body of living things must be in usually meet a whole range of requirements. They should be firm, tough, not ferromagnetic ("antimagnetic"), wear-resistant, corrosion-resistant and be affordable. Such requirements are partially met by nickel-free austenitic stainless steels. The patent specifications CH 684979 B5 (Böhler Ybbstalwerke 1993) and DE 19513407 C1 (VSG, 1996) describe such austenitic nickel-free stainless steels and put together the stand the technology. Both patents assume that carbon undesirable element in such alloys, because to this day the general The accepted doctrine is that carbon is used in austenitic stainless steels Corrosion resistance reduced. The patent specification CH 684979 B5 limits therefore the carbon content to a maximum of 0.10 percent by weight Nitrogen content of 0.55 percent by weight.

Die Patentschrift DE 195 13 407 C1 (VSG 1996) beschreibt weitere nickelfreie austenitisch rostfreie Stähle. Ein ganz zentraler Punkt ist, daß die zu verwendenden nickelfreien Stähle mindestens 0,55 Gew.-Prozent Stickstoff enthalten müssen, um die fehlende austenitisierende Wirkung des Nickels zu kompensieren. Die Patentschrift geht ebenfalls davon aus, daß Kohlenstoff ein unerwünschtes Element in solchen Legierungen sei, weil bis heute die allgemein anerkannte Lehrmeinung ist, daß Kohlenstoff in austenitisch rostfreien Stählen die Korrosionsbeständigkeit vermindert. DE 195 13 407 begrenzt daher den Kohlestoffgehalt auf höchstens 0,3 Gewichtsprozent.The patent DE 195 13 407 C1 (VSG 1996) describes other nickel-free austenitic stainless steels. A very central point is that the ones to be used nickel-free steels must contain at least 0.55% by weight nitrogen to compensate for the lack of austenitizing effects of nickel. The Patent also assumes that carbon is an undesirable Element in such alloys is because until today the generally recognized The doctrine is that carbon is used in austenitic stainless steels Corrosion resistance reduced. DE 195 13 407 therefore limits the Carbon content to a maximum of 0.3 percent by weight.

In Uggowitzer, P.J. et al., "Nickel Free high nitrogen austenitic steels", ISIJ Int., Bd. 36, Nr. 7, 1996, Seiten 901-908 wird der Kohlenstoffgehalt zwischen 0.008 und 0.020 Gew.% gehalten.In Uggowitzer, P.J. et al., "Nickel Free high nitrogen austenitic steels ", ISIJ Int., Vol. 36, No. 7, 1996, pages 901-908, the Carbon content kept between 0.008 and 0.020% by weight.

Die Erfinder der vorliegenden Patentschrift haben aber nunmehr erkannt, daß Kohlenstoff im Gegensatz zur allgemein anerkannten Fachmeinung die folgende vorteilhafte Wirkung ausübt: Kohlenstoff in fester Lösung erhöht die Beständigkeit gegen Spaltkorrosion austenitisch rostfreier Stähle in sauren Chloridlösungen.However, the inventors of the present patent have now recognized that Carbon contrary to the generally accepted professional opinion the following has an advantageous effect: carbon in solid solution increases resistance against crevice corrosion of austenitic stainless steels in acidic chloride solutions.

Insbesondere läßt sich die korrosionshemmende Wirkung des gelösten Kohlenstoffes im genormten Versuch der Spaltkorrosion in wässriger 6% FeCl3-Lösung quantitativ im Rahmen einer Wirksumme der korrosionshemmenden Legierungselemente wie folgt in erster Näherung beschreiben: Wirksumme: = % Cr +3,3(% Mo) + 20 (%N) + 20 (%C) In particular, the corrosion-inhibiting effect of the dissolved carbon in the standardized test of crevice corrosion in an aqueous 6% FeCl 3 solution can be described quantitatively as part of an effective sum of the corrosion-inhibiting alloy elements as follows: Effective sum: =% Cr +3.3 (% Mo) + 20 (% N) + 20 (% C)

Innerhalb gewisser Grenzen würde also ein Gewichts - Prozent soviel Korrosionsbeständigkeit bewirken wie sonst nur 20 Gewichtsprozent Chrom.Within certain limits, one percent by weight would be so much Corrosion resistance brings about 20% by weight of chromium as usual.

Aufbauend auf dieser völlig neuen Erkenntnis stellt sich die vorliegende Erfindung die Aufgabe, das Problem der Nlckelallergie durch die Verwendung eines austenitisch rostfreien Stahles zu verhindern, der gezielt die vorteilhafte Wirkung des Kohlenstoffes, insbesondere seinen Beitrag zur Erhöhung des Widerstandes gegen Spaltkorrosion nutzt. Die übrigen Legierungselemente im erfindungsgemäßen austenitisch rostfreien Stahl werden nach den einer Fachperson wohlbekannten Regeln so eingeschränkt, daß die Stabilität des kubisch flächenzentrierten Kristellgitters erhalten bleibt und so die Abwesenheit von Ferromagnetismus sowie die Zähigkeit und allgemiene Korrosionsbeständigkeit erhalten und möglichst hoch bleiben.The present invention is based on this completely new finding the task of solving the problem of neck allergy by using a to prevent austenitic stainless steel from targeting the beneficial effect of carbon, especially its contribution to increasing resistance against crevice corrosion. The remaining alloy elements in Austenitic stainless steel according to the invention are according to the one Well-known rules so restricted that the stability of the cubic face-centered crystal lattice is preserved and so the absence of Ferromagnetism as well as toughness and general corrosion resistance preserved and remain as high as possible.

Die gestellte Aufgabe der Verhinderung von Nickelallergie wird erfĂĽllt durch die Verwendung einer Legierung, die die folgende Zusammensetzung ( in Gewichts-Prozent) hat:

Mangan
5 bis 26 %%
Chrom
11 bis 24 %
Molybdän
mehr als 2,5 und bis 6 %
Stickstoff
mehr als 0,2 und bis 2,0%
Kohlenstoff
mehr als 0,1 und bis 0,9,
wobei im Konzentrationsbereich von mehr als 0,55 % Stickstoff der Kohlenstoffgehalt mehr als 0,3 % beträgt, Rest Eisen sowie unvermeidbare erschmelzungsbedingte Verunreinigungen sowie Ni, Si, S, Cu, Co, Nb, Ta, Ti, Zr, Hf, W, Al, B, Ce, Ca einzeln bis höchstens 2,0% mit der Maßgabe, daß der Werkstoff nach dem Abschrecken von einer Lösungsglühtemperatur im Bereich zwischen 950 ° und 1260° eine austenitische Grund-Gefügestruktur aufweist und dadurch nicht ferromagnetisch ist als Werkstoff für Bauteile, die zumindest teilweise oder zeitweise im Berührungskontakt mit Lebewesen, insbesondere Menschen, stehen oder am oder im Körper von Lebewesen angewendet werden.The task of preventing nickel allergy is achieved by using an alloy that has the following composition (in percent by weight):
manganese
5 to 26 %%
chrome
11 to 24%
molybdenum
more than 2.5 and up to 6%
nitrogen
more than 0.2 and up to 2.0%
carbon
more than 0.1 and up to 0.9,
where in the concentration range of more than 0.55% nitrogen the carbon content is more than 0.3%, the rest iron and unavoidable impurities due to melting as well as Ni, Si, S, Cu, Co, Nb, Ta, Ti, Zr, Hf, W, Al, B, Ce, Ca individually up to a maximum of 2.0% with the proviso that after quenching from a solution annealing temperature in the range between 950 ° and 1260 °, the material has an austenitic structure and is therefore not ferromagnetic as a material for components which are at least partially or temporarily in contact with living beings, in particular humans, or are used on or in the body of living beings.

Die durch die Erfindung erreichten Vorteile sind darin zu sehen, daß einerseits durch die geringe Nickelkonzentration keine nickelallergischen Reaktionen bei Kontakt mit dem Körper von Lebewesen ausgelöst werden, andererseits durch die gewählte Zusammensetzung vor allem der Elemente Chrom, Molybdän und Stickstoff, nun aber verstärkt durch die hohen Kohlenstoffgehalte, die Korrosionsbeständigkeit so hoch liegt, daß Körperflüssigkeiten, einschließlich menschlicher Schweiß, keine Korrosion bewirken. Die hohe Korrosionsbeständigkeit, die sich im genormten Spaltkorrosionsversuch nachweisen läßt, bewirkt, daß auch die Herauslösung anderer Schwermetallionen aus der Legierung bei Kontakt mit dem Körper von Lebewesen verhindert wird. Auf diesen Eigenschaften baut die erfindungsgemäße Anwendung auf: Allergische Reaktionen durch Nickel und andere Schwermetallionen (Kobalt, Chrom) werden dadurch vermieden, daß die anzuwendende Legierung äußerst nickelarm und zugleich hoch korrosionsbeständig ist. Die Auslösung allergischer Reaktionen durch Berührungskontakt mit dem Körper läuft zunächst über eine Korrosionsreaktion des Werkstoffes mit den Körperflüssigkeiten wie Schweiß oder Speichel. Hierbei können Nickelionen aus nickelhaltigen rostfreien Stählen herausgelöst werden. Der nächste Schritt ist die Aufnahme von von Nickelionen durch die Haut oder das Gewebe und dann die Auflösung der allergischen Reaktion. Es ist also nicht der metallische Werkstoff, sondern dessen Korrosionsprodukt, das die Allergie-Reaktion auslöst. Deshalb nützt hier die erfindungsgemäße Anwendung einen Werkstoff, der sowohl äußerst nickelarm als auch höchst korrosionsbeständig ist.The advantages achieved by the invention can be seen in the fact that on the one hand due to the low nickel concentration, no nickel allergic reactions Contact with the body can be triggered by living things, on the other hand by the selected composition mainly of the elements chrome, molybdenum and Nitrogen, but now reinforced by the high carbon content Corrosion resistance is so high that body fluids, including human sweat, do not cause corrosion. The height Corrosion resistance, which can be demonstrated in the standardized crevice corrosion test leaves, causes the removal of other heavy metal ions from the Alloy is prevented on contact with the body of living things. On this The application according to the invention builds up properties: Allergic reactions through nickel and other heavy metal ions (cobalt, chromium) avoided that the alloy to be used is extremely low in nickel and at the same time high is corrosion resistant. The triggering of allergic reactions Contact with the body initially occurs via a corrosion reaction of the Material with body fluids such as sweat or saliva. Here you can Nickel ions can be extracted from nickel-containing stainless steels. The next Step is the uptake of nickel ions through the skin or tissue and then the resolution of the allergic reaction. So it's not the metallic one Material, but its corrosion product that triggers the allergy reaction. Therefore, the application according to the invention uses a material that both is extremely low in nickel and highly corrosion-resistant.

Anwendung ist hier definiert als ein Gebrauch der erfindungsgemäßen Legierung, während dessen ein anderer, höher mit Nickel legierter austenitisch rostfreier Stahl Gelegenheit hätte, eine wirksame Menge von Nickelionen an den Körper von Lebewesen abzugeben und so Nickelallergie und allergische Reaktionen auszulösen oder zu fördern.Application is defined here as a use of the alloy according to the invention, another austenitic stainless steel alloyed with nickel Would have an opportunity to apply an effective amount of nickel ions to the body To give off living things and so nickel allergy and allergic reactions trigger or promote.

Ein weiterer Vorteil der Anwendung der hochkorrosionsbeständigen erfindungsgemäßen Legierung liegt darin, daß sie künftig in sehr weiten Anwendungsbereichen die bisher weitverbreiteten nickelhaltigen austenitischen rostfreien Legierungen auf wirtschaftliche Weise ersetzen kann, da Kohlenstoff ein sehr billiges Legierungselement ist. Durch diese Ablösung der nickelhaltigen austenitischen Stähle durch nickelfreie austenitische Stähle wird der stetig steigende Nickelpegel unserer Umwelt weniger ansteigen, so daß auch das statische Auftreten der Sensibilisierung auf Nickel-Allergie, etwa durch Einnahme nickelhaltiger Nahrung, weniger rasch zunimmt. Insofern kann die erfindungsgemäße Anwendung des kohlenstoffhaltigen nickelfreien korrosionsbeständigen Stahles doppelt wirken: Einmal durch das Vermeiden der Freisetzung von Nickelionen und anderer Schwermetallionen (Chrom, Mangan) im Kontakt mit dem Körper von Lebewesen, zum anderen - im Sinne einer nachhaltigen Technik - durch geringere Steigerung des allgemeinen Umwelt-Nickelpegels, von dem heute einzelne Forscher berichten, er könne zur Sensibilisierung auf Nickelallergie, zum Beispiel über die Nahrung, beitragen. Ein so sensibilisiertes Lebewesen braucht dann erst recht Nickelfreiheit (Nickelarmut) in den Stählen, mit denen es in Berührung kommt, und auch deshalb braucht es dann die erfindungsgemäße Anwendung des erfindungsgemäßen Stahles.Another advantage of using the highly corrosion resistant Alloy according to the invention lies in the fact that it will in future be very wide Areas of application are the previously widespread nickel-containing austenitic can replace stainless alloys in an economical way because carbon one is a very cheap alloying element. By this replacement of the nickel-containing austenitic steels through nickel-free austenitic steels becomes steady increasing nickel levels of our environment rise less, so that too Static appearance of sensitization to nickel allergy, for example through ingestion food containing nickel, increases less rapidly. In this respect, the application of the carbon-containing nickel-free according to the invention corrosion-resistant steel act twice: by avoiding the Release of nickel ions and other heavy metal ions (chromium, manganese) in the Contact with the body of living beings, on the other - in the sense of sustainable Technology - by lowering the general environmental nickel level, from to which individual researchers today report that he can raise awareness Allergy to nickel, for example through food. So sensitized Living beings then need nickel-free (lack of nickel) in the steels to whom it comes into contact, and that is why it needs it application of the steel according to the invention.

Die Anwendung des erfindungsgemäßen Stahles im Kontakt mit dem Körper von Lebewesen wird noch durch eine weitere Eigenschaft des Kohlenstoffs in fester Lösung im Stahl gefördert: Kohlenstoff erhöht die Festigkeit des Stahles durch Mischkristallhärtung und steigert zudem den Verfestigungskoeffizient des Werkstoffs, so daß auch durch Kaltverformung hohe Festigkeiten erzielt werden können. Darüber hinaus ist durch die Bildung kleinster Teilchen im Kristallgitter und Segregationszonen, insbesondere nach Kaltverformung, durch Aushärtung eine weitere Festigkeitssteigerung ohne wesentlichen Verlust der Korrosionsbeständigkeit möglich. Dies erschließt Anwendungen im Kontakt mit Körpern, wo vom Werkstoff neben Korrosionsbeständigkeit und Nickelfreiheit auch hohe Festigkeit verlangt wird. Beispiele solcher erfindungsgemäßen Anwendungen sind Zahnkorrekturdrähte, Spickdrähte, chirurgisches Besteck, Implantate und allgemein hochfeste korrosionsbeständige Teile von Gegenständen, zum Beispiel Sportgeräte, die durch Berührungkontakt nickelallergische Reaktionen auslösen könnten.The application of the steel according to the invention in contact with the body of Living beings are made more solid by another property of carbon Solution promoted in steel: carbon increases the strength of the steel Mixed crystal hardening and also increases the strengthening coefficient of the Material, so that high strengths can also be achieved by cold forming can. In addition, due to the formation of tiny particles in the crystal lattice and Segregation zones, especially after cold working, through hardening further strengthening without significant loss of Corrosion resistance possible. This opens up applications in contact with Bodies, where the material in addition to corrosion resistance and freedom from nickel high strength is required. Examples of such applications according to the invention are tooth correction wires, razor wires, surgical cutlery, implants and generally high-strength corrosion-resistant parts of objects, for example Sports equipment that triggers nickel allergic reactions when touched could.

Die erfindungsgemäßen Verwendungen der Legierung umfassen demnach Anwendungen am und im menschlichen Körper von Lebewesen, wo Nickelallergie nicht auftreten soll. Dies betrifft sowohl Schmuck (Ohrringe, Ringe, Ketten) als auch Modeartikel (Gürtelschnallen, Knöpfe, Reißverschlüsse), Brillen, Uhren, Armbänder und alle Metallgegenstände, die auf dem Körper oder im Körper - sei es auch nur kurze Zeit - getragen werden, Die erfindungsgemäßen Anwendungen betreffen ferner medizinische Geräte, Vorrichtungen und Implantate, beispielsweise Zahnspangen, Zahnfüllungen, Zahnplomben, Zahnkorrektur-Vorrichtungen wie Drähte, Schrauben, Platten sowie metallische Befestigungen und Fixationen im Körper, zum Beispiel Spickdrähte, Knochennägel und vorübergehend sowie dauernd eingebaute oder teilweise eingebaute Platten und Schrauben zur Heilung von Knochenbrüchen, sowie Kanülen, Spritzen, Akupunkturnadeln, chirurgisches und ophtalmologisches Besteck und Geräte, um Löcher in den Körper von Lebewesen einzubringen, beispielsweise für Ohrringe, also ganz generell alle Anwendungen am und im Körper, sei es dauernd oder zeitweise.The uses of the alloy according to the invention accordingly include Applications on and in the human body of living beings where nickel allergy should not occur. This applies to jewelry (earrings, rings, chains) as well Fashion items (belt buckles, buttons, zippers), glasses, watches, bracelets and all metal objects on the body or in the body - if only short time - to be worn, The applications according to the invention relate also medical devices, devices and implants, for example Braces, dental fillings, dental seals, tooth correction devices such as Wires, screws, plates as well as metallic fastenings and fixations in the Bodies, for example, picks, bone nails and temporary as well permanently installed or partially installed plates and screws for healing of broken bones, as well as cannulas, syringes, acupuncture needles, surgical and ophthalmic cutlery and devices to make holes in the body of Bringing in living beings, for example for earrings, so generally all Applications on and in the body, be it permanent or temporary.

Erfindungsgemäß gehören zur Anwendung der Legierung auch solche Bauteile und Geräte, die dadurch Nickelallergie auslösen könnten, daß sie nahe dem Körper von Lebewesen verwendet oder von Lebewesen berührt werden. Dies betrifft auch Nieten und Knöpfe an Kleidern, Gürtelbeschläge, Schmuck, einschließlich Modeschmuck und den Körper durchdringenden Schmuck wie Ohrringe und Nasenringen, Feuerzeuge, Spitaleinrichtungen, Betten, Geländer, Haltestangen, Türgriffe, Besteck, Geschirr, Küchengeräte sowie Bauteile von Architektur und Verkehrsmitteln, sowie Münzen, ganz generell die Bauteile, die mit Körpern von Lebewesen und deren Körperflüssigkeiten in Berührung kommen.According to the invention, such components and also belong to the application of the alloy Devices that could cause nickel allergy by being close to the body of Living beings are used or touched by living beings. This also applies Rivets and buttons on clothes, belt fittings, jewelry, including Costume jewelry and body piercing jewelry such as earrings and Nose rings, lighters, hospital equipment, beds, railings, handrails, Door handles, cutlery, dishes, kitchen appliances as well as architectural and architectural components Transportation, as well as coins, generally the components that are made with bodies of Living creatures and their body fluids come into contact.

Die erfindungsgemäße Legierung kann mit bekannten metallurgischen Verfahrenstechniken hergestellt werden, so zum Beispiel durch Erschmelzen bei Normaldruck, Druckerschmelzen, Druck-Elektroschlacke-Umschmelzen, durch Pulvermetallurgie, einschließlich Metallpulverspritzgießen, sowie als Oberflächenschicht.The alloy according to the invention can be mixed with known metallurgical ones Process technologies are produced, for example by melting Normal pressure, printer melting, pressure electroslag remelting, by Powder metallurgy, including metal powder injection molding, as well as Surface layer.

Die erfindungsgemäße Legierung wird bevorzugt im lösungsgeglühten und danach abgeschreckten Zustand eingesetzt. Ihre Festigkeit kann durch Kaltverformung nach dem Lösungsglühen und Abschrecken sowie durch Aushärtung deutlich verbessert werden. Der gleichzeitig hohe Kohlenstoffgehalt und Stickstoffgehalt stabilisieren das kubisch-flächenzentrierte Kristallgitter ("Austenit") und bewirken so, daß auch nach Kaltverformen die erfindungsgemäße Legierung ihre nichtferromagnetischen Eigenschaften beibehält.The alloy according to the invention is preferred in the solution-annealed and then deterred state used. Their strength can be reduced by cold working after solution annealing and quenching as well as through hardening be improved. The simultaneously high carbon and nitrogen content stabilize the face-centered cubic crystal lattice ("austenite") and thus cause that even after cold working the alloy of the invention maintains non-ferromagnetic properties.

Anhand der folgende Beispiele wird die Erfindung näher erläutert:The invention is explained in more detail using the following examples:

Beispiel 1example 1

Eine Legierung mit der chemischen Zusammensetzung 17% Cr, 3% Mo, 10% Mn, 0,31% C, 0,35% N, Rest Eisen, wurde im Vakuum-Induktionsofen erschmolzen, bei 1250 °C homogenisiert und anschließend bei 1150 °C geschmiedet. Nach einer Lösungsglühung bei 1120 °C und nachfolgender Wasserabschreckung ist die Legierung homogen austenitisch, frei von Ausscheidungen und frei von Deltaferrit, somit vollkommen unmagnetisch. Diese nickelfreie Legierung hat eine so hohe Beständigkeit gegen Spaltkorrosions in saurer wäßriger 6% FeCl3-Lösung, daß Spaltkorrosion erst bei Temperaturen über 23 °C einsetzt. Damit überschreitet sie bei weitem die Korrosionsbeständigkeit der besten heute für Uhren benützten rostfreien Stähle. Gemäß der Wirksumme % Cr + 3,3 (% Mo) + 20 (% N) + 20 (% C) ist ein wesentlicher Teil dieser Korrosionsbeständigkeit, nämlich 6,2 von insgesamt 40,2 Punkten auf den Kohlenstoffgehalt in fester Lösung zurückzuführen. Die Legierung hat eine Streckgrenze von 510 MPa und eine Kerbschlagarbeit von 250 J, ist also im Vergleich zu anderen austenitischen Stählen zusätzlich zu ihrer hohen Korrosionsbeständigkeit außerordentlich fest und zäh und damit auch verschleißbeständig und somit für die oben angeführten Anwendungen geeignet.An alloy with the chemical composition 17% Cr, 3% Mo, 10% Mn, 0.31% C, 0.35% N, the rest iron, was melted in a vacuum induction furnace, homogenized at 1250 ° C and then at 1150 ° C forged. After solution annealing at 1120 ° C and subsequent water quenching, the alloy is homogeneously austenitic, free of precipitates and free of delta ferrite, and thus completely non-magnetic. This nickel-free alloy has such a high resistance to crevice corrosion in acidic aqueous 6% FeCl 3 solution that crevice corrosion only sets in at temperatures above 23 ° C. It far exceeds the corrosion resistance of the best stainless steels used today for watches. According to the effective amount% Cr + 3.3 (% Mo) + 20 (% N) + 20 (% C), a significant part of this corrosion resistance, namely 6.2 out of a total of 40.2 points, can be attributed to the carbon content in solid solution. The alloy has a yield strength of 510 MPa and a notched bar impact energy of 250 J, which means that, in comparison to other austenitic steels, it is extraordinarily strong and tough, and therefore also wear-resistant, in addition to its high corrosion resistance, and is therefore suitable for the above-mentioned applications.

Beispiel 2Example 2

Eine Uhrenschalen-Vorform mit der chemischen Zusammensetzung 17,2% Cr, 3,25% Mo, 13% Mn, 0,35% C und 0,54% N, Rest Eisen, wurde aus Metallpulver durch Sintern in Argon/Stickstoffatmosphäre hergestellt und von 1200 °C im bewegten Gasstrom rasch abgekühlt. Die so erhaltene Legierung war homogen austenitisch und somit völlig unmagnetisch. Diese Legierung hat eine so hohe Korrosionsbeständigkeit, daß Spaltkorrosion in saurer wäßriger 6 % FeCl3-Lösung erst bei Temperaturen über 26 °C einsetzt. Gemäß der Wirksummenformel % Cr + 3,3 (% Mo) + 20 (% N) + 20 (% C) trägt der Kohlenstoff in fester Lösung 7,0 Punkte zur gesamten Korrosionsbeständigkeit von 45,7 Punkten bei. In anderen Worten, der Kohlenstoffgehalt von 0,35% bewirkt die gleiche Zunahme der Korrosionsbeständigkeit wie dies sonst nur ein zusätzlicher Gehalt von 7% Chrom tun würde. Diese nickelfreie Legierung hat eine Streckgrenze von 530 MPa, ist also für Austenite außerordentlich fest und damit auch verschleißbeständig und aufgrund ihrer Eigenschaftskombination für die oben aufgeführten Anwendungen geeignet.A watch shell preform with the chemical composition 17.2% Cr, 3.25% Mo, 13% Mn, 0.35% C and 0.54% N, balance iron, was made from metal powder by sintering in an argon / nitrogen atmosphere and cooled rapidly from 1200 ° C in the moving gas stream. The alloy thus obtained was homogeneously austenitic and therefore completely non-magnetic. This alloy has such a high corrosion resistance that crevice corrosion in acidic aqueous 6% FeCl 3 solution only begins at temperatures above 26 ° C. According to the active formula% Cr + 3.3 (% Mo) + 20 (% N) + 20 (% C), the carbon in solid solution contributes 7.0 points to the overall corrosion resistance of 45.7 points. In other words, the 0.35% carbon content causes the same increase in corrosion resistance as an additional 7% chromium content would otherwise. This nickel-free alloy has a yield strength of 530 MPa, so it is extremely strong for austenites and therefore also resistant to wear and, due to its combination of properties, suitable for the applications listed above.

Beispiel 3Example 3

Eine Legierung mit der chemischen Zusammensetzung 17,2% Cr, 3,25% Mo, 11% Mn, 0,35% C und 0,60% N, Rest Eisen, wurde im Druck-Elektroschlacke-Umschmelzverfahren hergestellt, bei 1250 °C homogenisiert und anschließend bei 1150 °C geschmiedet. Nach einer Lösungsglühung bei 1150 °C und nachfolgender Wasserabschreckung ist die Legierung homogen austenitisch, frei von Ausscheidungen und frei von Deltaferrit, somit vollkommen unmagnetisch. Diese nickelfreie Legierung hat eine so hohe Beständigkeit gegen Spaltkorrosion in saurer wäßriger 6% FeCl3-Lösung, daß Spaltkorrosion erst über 35 °C einsetzt. Gemäß der Wirksumme von % Cr + 3,3 (% Mo) + 20 (% N) + 20 (% C) ist ein wesentlicher Teil dieser Korrosionsbeständigkeit, nämlich 7,0 Punkte von insgesamt 47 Punkten auf den Kohlenstoffgehalt in fester Lösung zurückzuführen. Die Legierung hat eine Streckgrenze von 560 MPa und ist damit im Vergleich zu anderen austentischen Stählen zusätzlich zu ihrer hohen Korrosionsbeständigkeit außerordentlich hart und fest und somit für die oben aufgeführten Anwendungen geeignet.An alloy with the chemical composition 17.2% Cr, 3.25% Mo, 11% Mn, 0.35% C and 0.60% N, the rest iron, was produced in the pressure-electroslag remelting process, at 1250 ° C. homogenized and then forged at 1150 ° C. After solution annealing at 1150 ° C and subsequent water quenching, the alloy is homogeneously austenitic, free of precipitates and free of delta ferrite, and thus completely non-magnetic. This nickel-free alloy has such a high resistance to crevice corrosion in acidic aqueous 6% FeCl 3 solution that crevice corrosion only sets in above 35 ° C. According to the effective sum of% Cr + 3.3 (% Mo) + 20 (% N) + 20 (% C), a significant part of this corrosion resistance, namely 7.0 points out of a total of 47 points, can be attributed to the carbon content in solid solution. The alloy has a yield strength of 560 MPa and is, in comparison to other austenitic steels, extremely hard and strong in addition to its high corrosion resistance and is therefore suitable for the applications listed above.

Beispiel 4Example 4

Eine Uhrenschalen-Vorform mit der chemischen Zusammensetzung 17% Cr, 3,0 % Mo, 11% Mn, 0,35% C und 1,6% N, Rest Eisen, wurde aus Metallpulver durch Sintern in Formiergas hergestellt und danach von 1200 °C in Wasser abgeschreckt. Die so erhaltene Legierung war homogen austenitisch und somit völlig unmagnetisch. Diese Legierung hat eine so hohe Korrosionsbeständigkeit, daß Spaltkorrosion in saurer wäßriger 6% FeCl3-Lösung erst bei Temperaturen über 60 °C einsetzt. Dies macht die Legierung noch korrosionsbeständiger als die sonst hochlegierten sehr nickelreichen "Superaustenite" und damit auch geeignet für die oben genannten Anwendungen.A watch-shell preform with the chemical composition 17% Cr, 3.0% Mo, 11% Mn, 0.35% C and 1.6% N, balance iron, was made from metal powder by sintering in forming gas and then from 1200 ° C quenched in water. The alloy thus obtained was homogeneously austenitic and therefore completely non-magnetic. This alloy has such a high resistance to corrosion that crevice corrosion in acidic aqueous 6% FeCl 3 solution only begins at temperatures above 60 ° C. This makes the alloy even more corrosion-resistant than the otherwise high-alloyed, very nickel-rich "Superaustenite" and therefore also suitable for the above-mentioned applications.

Claims (9)

  1. Use of a carbon-containing steel alloy with (in per cent by weight):
    Manganese
    5 to 26%
    Chromium
    11 to 24%
    Molybdenum
    more than 2.5 and up to 6%
    Nitrogen
    more than 0.2 and up to 2.0%
    Carbon
    more than 0.1 and up to 0.9%, in which within the concentration range of more than 0.55% nitrogen, the carbon content amounts to more than 0.3%
    Residue iron and unavoidable smelting-determined impurities as well as Ni, Si, S, Bi, Cu, Co, V, Nb, Ta, Ti, Zr, Hf, W, Al, B, Ce, Ca individually up to a maximum of 2.0%, provided that, after quenching from a solution-treatment temperature within the range between 950° and 1260°C, the material has an austenitic primary structure and is thus not ferromagnetic, as material for structural members which are at least partially or occasionally in contact with live organisms, in particular humans, or are used on or in the bodies of live organisms.
  2. Use of an alloy in accordance with Claim 1, characterised in that it has, in per cent by weight,
    Manganese
    5 to 16%
    Chromium
    15 to 22%
    Molybdenum
    more than 2.5 and up to 4.5%
    Nitrogen
    more than 0.2 and up to 2.0%
    Carbon
    more than 0.15 and up to 0.80%, in which within the concentration range of more than 0.55% nitrogen, the carbon content amounts to more than 0.3% and up to 0.60%.
  3. Use of an alloy in accordance with Claim 1 or 2, characterised in that its nickel content is below 0.5% by weight.
  4. Use of an alloy in accordance with Claim 1 or 2, characterised in that its nickel weight is below 0.25% by weight.
  5. Use of an alloy in accordance with Claim 1, 2, 3 or 4 in the solution heat-treated state for the purpose according to Claim 1, characterised in that it was solution heat-treated between the temperatures 950°C and 1260°.
  6. Use of an alloy in accordance with Claim 1, 2, 3, 4 or 5 in the solution heat-treated and subsequently quenched state for the purpose according to Claim 1, characterised in that it was cold-worked.
  7. Use of an alloy in accordance with Claim 1, 2, 3 or 4 in the solution heat-treated and subsequently quenched and then cold-worked state for the purpose according to Claim 1, characterised in that after cold-working the alloy was re-tempered.
  8. Use of an alloy in accordance with Claim 1, 2, 3, 4, 5, 6 or 7 for the purpose according to Claim 1, characterised in that the alloy is formed only as a surface layer.
  9. Use of an alloy in accordance with Claim 1, 2, 3, 4, 5, 6, 7 or 8, characterised in that during manufacture and use it gives off no active quantities of nickel compounds or nickel ions which are taken up into the body of live organisms via the nutrition thus contributing to nickel allergy or allergic reactions.
EP98890116A 1997-04-29 1998-04-22 Use of a biocompatible alloy suitable for the skin Expired - Lifetime EP0875591B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3147378A1 (en) 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickel-free austenitic stainless steel

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Publication number Priority date Publication date Assignee Title
CH694401A5 (en) 1999-05-26 2004-12-31 Basf Ag Low-nickel, low-molybdenum, biocompatible, non-allergenic, corrosion-resistant austenitic steel.
CN1495281A (en) 1999-06-24 2004-05-12 Basf Application of low-nickel austenite steel
GB9922757D0 (en) * 1999-09-27 1999-11-24 Heymark Metals Ltd Improved steel composition
EP2617839A1 (en) * 2012-01-18 2013-07-24 MeKo Laserstrahl-Materialbearbeitungen e.K. Nickel-free iron alloy for stents
EP2676685A1 (en) * 2012-06-18 2013-12-25 Biotronik AG Stent composed of an iron alloy

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AT397968B (en) * 1992-07-07 1994-08-25 Boehler Ybbstalwerke CORROSION-RESISTANT ALLOY FOR USE AS A MATERIAL FOR PARTS IN CONTACT WITH LIFE
EP0641868B1 (en) * 1993-09-03 1998-05-27 Sumitomo Metal Industries, Ltd. A nonmagnetic ferrous alloy with excellent corrosion resistance and workability

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3147378A1 (en) 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickel-free austenitic stainless steel
EP3147380A1 (en) 2015-09-25 2017-03-29 The Swatch Group Research and Development Ltd. Nickel-free austenitic stainless steel

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