EP0918099A1 - Acier en chrome-manganèse - Google Patents

Acier en chrome-manganèse Download PDF

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Publication number
EP0918099A1
EP0918099A1 EP98120088A EP98120088A EP0918099A1 EP 0918099 A1 EP0918099 A1 EP 0918099A1 EP 98120088 A EP98120088 A EP 98120088A EP 98120088 A EP98120088 A EP 98120088A EP 0918099 A1 EP0918099 A1 EP 0918099A1
Authority
EP
European Patent Office
Prior art keywords
steel alloy
nickel
cobalt
nitrogen
manganese
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.)
Ceased
Application number
EP98120088A
Other languages
German (de)
English (en)
Inventor
Christopher Dr.Sc. Rennhard
Heinz-Juergen Dr. Ing. Osing
Gisbert Kloss-Ulitzka
Klaus-Dieter Dr. Partz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stahlwerk Ergste Westig GmbH
Original Assignee
Stahlwerk Ergste Westig GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stahlwerk Ergste Westig GmbH filed Critical Stahlwerk Ergste Westig GmbH
Priority to EP98120088A priority Critical patent/EP0918099A1/fr
Publication of EP0918099A1 publication Critical patent/EP0918099A1/fr
Ceased legal-status Critical Current

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    • 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
    • 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

Definitions

  • the invention relates to a chrome-manganese steel alloy with 12 to 17% manganese, 0.2 to 1.0% silicon, 1 to 3% copper, 2 to 6% cobalt, 3 to 6% molybdenum, 17 up to 22% chromium and 0.5 to 0.9% nitrogen, balance iron including optional alloying elements and contamination caused by melting.
  • Low-nickel steel alloys of this type are suitable their high biocompatibility as a material for medical technology, for example for implants medical bodies coming into contact with the human body Instruments as well as for on the human body or jewelry to be worn close to the body.
  • Such steel alloys require with regard to adequate corrosion resistance to biological Liquids and secretions as well as to avoid interference in electrical fields, for example in nuclear spin tomography, an austenitic structure.
  • nickel is used as an austenite former out of the question because it is in the milieu of the human body corrosion and penetration of nickel ions into the body tissues and, as a result, too toxic reactions is coming.
  • the nickel content is more biocompatible Steel alloys are therefore legally limited.
  • body-compatible steel alloys sufficient workability and workability own them, for example by cold working without an intermediate annealing to bars, strips, wire, plates and to be able to process bone nails, as well as a mechanical processing, for example by machining, Drilling, embossing and tapping without the risk of Allow surface defects, especially cracks.
  • body tolerance depends on that fulfilling a number of biological, metallurgical, chemical and mechanical requirements from.
  • Known low-nickel steel alloys are sufficient mostly only in the area of individual properties.
  • the invention is based on the problem, the property profile of the aforementioned steel alloy in view to the special requirements of the Medical technology and comparable areas of application noticeably improve.
  • the invention achieves this by narrowing the Content ranges for manganese, molybdenum and chromium imperative presence of copper and cobalt as well as a Coordination of the levels of carbon and nitrogen on the one hand and cobalt and copper on the other.
  • the steel alloy according to the invention contains 0.08 to 0.25% carbon, at most 0.015% sulfur, at most 0.05% phosphorus, 12 to 17% manganese, 0.2 to 1% Silicon, 1 to 3% copper, 2 to 6% cobalt, at most 0.01% titanium, 3 to 6% molybdenum, 17 to 22% chromium, at most 1.0% nickel, 0.01% aluminum, 0.01% Niobium, 0.01% boron and 0.20% vanadium, 0.5 to 0.9% nitrogen, Balance iron preferably at a ratio of Carbon content to total carbon and Nitrogen from 0.08 to 0.3, preferably 0.1 to 0.25 or also 0.12 to 0.16 and with particular advantage if appropriate also a ratio of the cobalt contents and copper from 1 to 6, preferably 1.5 to 3.5 or also 2 to 2.5.
  • the steel alloy has a much better structural stability and allowed within the invention A sufficient or proportionate composition large distance from the two-phase areas (see gray area in the diagram of Fig. 1), i.e. Nickel equivalents over 17, e.g. 18, over 20 or also over 26, behind which there are correspondingly higher ones Chromium, molybdenum, manganese, nitrogen and carbon content as well as the related improvement in for the use of the alloy as a biocompatible Material critical properties, especially one higher corrosion or pitting resistance with high Strength and toughness as well as excellent processability hide.
  • a sufficient or proportionate composition large distance from the two-phase areas (see gray area in the diagram of Fig. 1), i.e. Nickel equivalents over 17, e.g. 18, over 20 or also over 26, behind which there are correspondingly higher ones Chromium, molybdenum, manganese, nitrogen and carbon content as well as the related improvement in for the use of the alloy as a biocompatible Material critical properties, especially one higher corrosion or pitting resistance with high Strength and toughness as well as excellent process
  • the steel alloy allows cold forming up to 90% and remains completely non-magnetic and sufficient tough.
  • the constriction is 70 to 35% with degrees of deformation up to 80%.
  • the steel alloy also has a high fatigue strength, for example over 10 load changes at 700 MPa after a 60% Cold forming.
  • the steel alloy is completely non-magnetic, has high electrical resistance as well a stable and passive surface; their firmness is 1000 to over 2000 MPa or 2500 MPa, each according to the degree of cold deformation, with good toughness and hardness of up to 630 HV 0.5 and a PREN value of 37 or over 45, preferably over 50; their corrosion resistance shows up in the sea water experiment an electrochemical breakdown potential Ep of over 1000 mV or 1150 mV while the breakthrough potential conventional implant steels at around 750 to 800 mV lies.
  • Ep electrochemical breakdown potential
  • the high strength allows smaller cross sections and accordingly a lower weight same contour.
  • the steel alloy according to the invention preferably contains 0.1 to 0.2% carbon, 0.002 to 0.008% sulfur, 0.002 to 0.01% phosphorus, 14 to 16% manganese, 0.5 to 0.8% silicon, 1.5 to 3% copper, 3 to 5% cobalt, at most 0.01% titanium, 3 to 6% molybdenum, 18 to 22% chromium, at most 0.40% nickel, each at most 0.01% aluminum, Niobium and boron, 0.04 to 0.2% vanadium and 0.7 to 0.9% nitrogen.
  • the manganese acts synergistically, although manganese contents of more than 10%, in particular more than 12%, lead to the formation of intermetallic phases and thus to an impairment of the corrosion resistance.
  • Cobalt and copper counteract this; they increase the solubility of Cr 2 N and sigma phase in austenite.
  • the high structural stability of the steel alloy according to the invention 2 illustrates the diagram of FIG solid cooling curve 1 of a conventional one nickel-free austenitic chrome-manganese-nitrogen steel alloy with 0.08% carbon, 11% manganese, 4% Molybdenum and 0.9% nitrogen and the longer cooling times shifted dashed curve 2 of the invention Steel alloy of example 1 (see below). Furthermore, the diagram shows the Fig. 2, the dark gray bounded by curve 1 ' area of development of harmful elimination phases in the known comparative alloy and the light gray delimited by the dashed curve 2 ' created area of the emergence of elimination phases drawn in the steel alloy according to the invention.
  • the diagram shows that the steel alloy according to the invention increasing in the temperature range below 1000 ° C slower cooling and correspondingly larger cross sections allowed without the risk of embrittlement through excretion phases. This is primarily to be attributed to the fact that in the Steel alloy cobalt and copper especially in the area marked by their quantity ratio the solubility of the chromium nitride and the sigma phase improve and at the same time the solubility limit raise to the extent that the risk of emergence is more harmful Elimination phases are significantly lower.
  • the previously required high cooling rates of for example 200 ° C / min decrease on average less than half, and solution annealing can help Temperatures from 1100 ° C to 1150 ° C take place.
  • cobalt is chromium, molybdenum and Spinels containing cobalt favor one Inertization of the surface in the form of a stable Passivation layer and thus an increase in corrosion resistance, but also better adherence for example in the case of a titanium coating as a carrier layer for a coating of hydroxyappatite or Effect calcium phosphate.
  • the improved corrosion resistance of the invention Steel alloy compared to known materials illustrates the diagram of Fig. 3.
  • the Measurements were made using the "anodic current density method" carried out, in which the current rise as Function of the applied potential was measured.
  • electrochemical measurement which is carried out so that a potentiostat Potential of the sample connected as a working electrode to a predetermined value relative to a reference electrode regulates.
  • the current to be measured flows between the working electrode and a counter electrode and is recorded with a writer.
  • the measurements were in a glass container with a saline solution performed at 40 ° C.
  • the good corrosion resistance prevents Nickel ions under the influence of human sweat get into the human body and become allergic Lead reactions.
  • the tensile strength results from the diagram in FIG. 4 the steel alloy according to the invention of the example 1 depending on their degree of deformation during cold forming.
  • the steel alloy according to the invention can be at atmospheric pressure melt in the induction furnace. Doing so preferably produces a high-chrome premelt, into which molybdenum, copper and cobalt were introduced one after the other become. Then manganese nitride is melted with a nitrogen content above 6% in portions of not more than 2% of the operating weight.
  • the tapping temperature is preferably 100 to 120 ° C the liquidus temperature.
  • the steel alloy according to the invention is preferably ascending in a preheated Shed mold. After an equalization anneal at 1150 up to 1250 ° C the casting block can be - if necessary an electric slag remelting (ESR) - by forging and / or hot-rolling into a primary material.
  • ESR electric slag remelting
  • the nitrogen can also be gaseous, for example by embroidering on the print Introduce electroslag remelting.
  • the tensile strength increased after 56% cold working to 2120 MPa with a constriction of 40% and a hardness of 610 HV.
  • the breakthrough potential was in a 1 M sodium chloride solution measured and was Ep> 1230 mV.
  • the steel alloy could be machined very well without that gluing and scaling in the Surface were recognizable.
  • the surface was smooth and glittering. This also resulted in thread cutting a smooth and flawless surface.
  • Another test alloy was used in the same way with 18.5% chromium, 15.4% manganese, 0.18% nickel, 4.8% Molybdenum, 4.6% cobalt, 2.4% copper, 0.65% silicon, 0.14% carbon, 0.01% niobium, 0.86% nitrogen, 0.004% Sulfur, 0.06% vanadium and 0.01% titanium, balance iron including contamination from melting melted with a nickel equivalent of 23.6, cast and a round bar with a diameter of 56 mm forged.
  • the rod became after solution annealing quenched with water at 1130 ° C; he was in quenched state completely non-magnetic and about the entire cross-section free of excretions.
  • a steel alloy was also made in the same way with 20.5% chromium, 13.2% manganese, 0.10% nickel, 4.8% Molybdenum, 2.5% cobalt, 1.4% copper, 0.65% silicon, 0.10% carbon, 0.01% niobium, 0.83% nitrogen, 0.004% Sulfur, 0.05% vanadium and 0.01% titanium, balance iron including contamination from melting melted with a nickel equivalent of 20.1, cast and a round bar with a diameter of 56 mm forged.
  • the staff was also at Annealed at 1130 ° C and quenched with water; he was complete non-magnetic and showed over the entire cross section no elimination phases.
  • the cutting behavior corresponded to that of the steel alloy Example 2 with a slightly better surface gloss.
  • the steel alloy according to the invention fulfills the initially mentioned requirements and is suitable due to their special combination of properties especially as Material for medical technology or for with the human body, especially human sweat objects in contact such as coins, prostheses, Implants, dental wires, bone nails, plates, surgical Instruments, drills and needles, jewelry and Spectacle frames as well as for hospital and laboratory installations, Cutlery, kitchen utensils and utility models, where it depends on the combination of properties described arrives.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
EP98120088A 1997-10-27 1998-10-24 Acier en chrome-manganèse Ceased EP0918099A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98120088A EP0918099A1 (fr) 1997-10-27 1998-10-24 Acier en chrome-manganèse

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP97810795 1997-10-27
EP97810795 1997-10-27
EP98120088A EP0918099A1 (fr) 1997-10-27 1998-10-24 Acier en chrome-manganèse

Publications (1)

Publication Number Publication Date
EP0918099A1 true EP0918099A1 (fr) 1999-05-26

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EP98120088A Ceased EP0918099A1 (fr) 1997-10-27 1998-10-24 Acier en chrome-manganèse

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EP (1) EP0918099A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014106306A1 (de) * 2014-05-06 2015-11-12 Hans-Joachim Bergfeld Verfahren zur Herstellung eines Schmuckteiles
EP4014950A1 (fr) 2020-12-18 2022-06-22 Deutsche Edelstahlwerke Specialty Steel GmbH & Co. KG Acier à structure austénitique et utilisation d'un tel acier pour des applications dans la bouche d'un humain ou d'un animal

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2534513A1 (de) * 1974-08-02 1976-02-12 Firth Brown Ltd Rostfreie austenitstaehle
EP0432434A1 (fr) * 1989-12-07 1991-06-19 Vereinigte Schmiedewerke Gmbh Procédé de fabrication d'éléments d'assemblage en acier Cr-Mn ayant une structure complètement austénitique.
EP0640695A1 (fr) * 1992-07-07 1995-03-01 BÖHLER Edelstahl GmbH Alliage résistant à la corrosion, utilisable comme matériau pour articles venant en contact avec des organismes vivants
DE19513407C1 (de) * 1995-04-08 1996-10-10 Vsg En & Schmiedetechnik Gmbh Verwendung einer austenitischen Stahllegierung für hautverträgliche Gegenstände

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2534513A1 (de) * 1974-08-02 1976-02-12 Firth Brown Ltd Rostfreie austenitstaehle
EP0432434A1 (fr) * 1989-12-07 1991-06-19 Vereinigte Schmiedewerke Gmbh Procédé de fabrication d'éléments d'assemblage en acier Cr-Mn ayant une structure complètement austénitique.
EP0640695A1 (fr) * 1992-07-07 1995-03-01 BÖHLER Edelstahl GmbH Alliage résistant à la corrosion, utilisable comme matériau pour articles venant en contact avec des organismes vivants
DE19513407C1 (de) * 1995-04-08 1996-10-10 Vsg En & Schmiedetechnik Gmbh Verwendung einer austenitischen Stahllegierung für hautverträgliche Gegenstände

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CIGADA ET AL: "Corrosion behaviour of high nitrogen stainless steels for biomedical applications", CONFERENCE. COMPATABILITY OF BIOMEDICAL IMPLANTS, vol. 94, no. 19, 23 May 1994 (1994-05-23), pages 185 185, XP002075896 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014106306A1 (de) * 2014-05-06 2015-11-12 Hans-Joachim Bergfeld Verfahren zur Herstellung eines Schmuckteiles
EP4014950A1 (fr) 2020-12-18 2022-06-22 Deutsche Edelstahlwerke Specialty Steel GmbH & Co. KG Acier à structure austénitique et utilisation d'un tel acier pour des applications dans la bouche d'un humain ou d'un animal
WO2022128981A1 (fr) 2020-12-18 2022-06-23 Deutsche Edelstahlwerke Specialty Steel Gmbh & Co. Kg Acier ayant une structure austénitique et utilisation d'un tel acier pour des applications dans la cavité buccale d'un humain ou d'un animal

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