EP1198604B1 - Nickelarmer austenitischer stahl - Google Patents

Nickelarmer austenitischer stahl Download PDF

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Publication number
EP1198604B1
EP1198604B1 EP00941991A EP00941991A EP1198604B1 EP 1198604 B1 EP1198604 B1 EP 1198604B1 EP 00941991 A EP00941991 A EP 00941991A EP 00941991 A EP00941991 A EP 00941991A EP 1198604 B1 EP1198604 B1 EP 1198604B1
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weight
steel
less
nitrogen
nickel
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German (de)
English (en)
French (fr)
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EP1198604A1 (de
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Markus Speidel
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BASF SE
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BASF SE
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B22F3/1025—Removal of binder or filler not by heating only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • 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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a low-nickel austenitic steel, in particular a nickel, molybdenum, manganese and copper austenitic steel and its use.
  • the invention further relates to processes for the production of articles of such steels.
  • the term "steel” refers to iron-containing alloys and includes carbonaceous iron.
  • Austenite is strictly speaking a high temperature modification of face centered cubic crystal iron (“ ⁇ -iron”) that is thermodynamically stable between 740 ° C and 1538 ° C and 0 to a maximum of 2.1% by weight (at 1153 ° C) of carbon in Contains a solid solution form.
  • ⁇ -iron face centered cubic crystal iron
  • all steels having a cubic face-centered crystal lattice are referred to as austenitic steels or austenites.
  • the cubic face-centered austenite structure is required for many applications of steels or at least advantageous over other modifications (for example, ferritic or martensitic steels);
  • austenite is not ferromagnetic, which makes austenitic steels applicable to electrical or electronic components or other applications where the occurrence of magnetic repulsion or attraction forces is undesirable, such as watches.
  • austenite is thermodynamically unstable at low temperature and at lower temperatures, austenitic steel must be stabilized against conversion to other modifications so that it retains its desired austenitic properties even at normal temperature. This can be done, for example, by adding alloying elements known as stabilizers of the austenite structure.
  • the alloying element most commonly used for this purpose is nickel, typically in an amount of 8 to 10 weight percent.
  • alloying ingredients are used to desirably affect other properties of the steel (eg, corrosion and wear resistance, hardness, toughness, or toughness).
  • other properties of the steel eg, corrosion and wear resistance, hardness, toughness, or toughness.
  • certain alloying constituents also often leads to certain disadvantages, usually quantity-dependent, which can be counteracted to a certain extent by adjusting the alloy composition.
  • carbon and manganese tend to stabilize the austenite structure but reduce it to high Quantities the corrosion resistance.
  • Silicon is a frequently unavoidable impurity, is also partially deliberately added as an oxygen scavenger, but promotes the formation of ⁇ -ferrite. Chromium, molybdenum and tungsten contribute significantly to corrosion resistance, but also favor the formation of ⁇ -ferrite.
  • Nitrogen in turn stabilizes the austenitic structure and increases its corrosion resistance, but excessively high nitrogen contents reduce the toughness of the steel.
  • a difficulty in optimizing steel compositions is that the properties of the steel do not vary linearly with the content of certain alloying constituents, but very large changes in material properties may occur even with small changes in the composition.
  • Another disadvantage of the use of non-ferrous metals as alloying components is usually also their relatively high price.
  • Nickel austenitic steels are sought after materials for a variety of applications.
  • An increasingly important field of use for such steels are articles which, in use, are in contact with the human or animal body, since these steels naturally do not trigger any nickel allergy.
  • Nickel allergies are common causes of contact eczema or other allergic manifestations that occur in contact with nickel-containing steels, for example, when wearing jewelry, watches or implants, or when using medical instruments made from such steels.
  • limits for the nickel content of materials or for their release of nickel in contact with the human or animal body are therefore or are already in force. It is therefore increasingly important to have as many nickel-austenitic steels available for as many applications as possible.
  • EP-A-875 591 teaches the use of a corrosion-resistant largely nickel-free austenitic steel with the essential components 5 - 26 wt .-% Mn, 11 - 24 wt .-% Cr, 2.5 - 6 wt .-% Mo, 0.2 - 2.0 wt % N, 0.1-0.9% by weight C, up to 0.5% by weight Ni, remainder Fe, as a material for producing objects in contact with living beings.
  • DE-A-195 13 407 also teaches the use of a corrosion resistant, largely nickel-free, austenitic steel as a material for making articles in contact with living beings.
  • This steel has the essential components 2 - 26 wt .-% Mn, 11 - 24 wt .-% Cr, 2.5 - 10 wt .-% Mo, 0.55 - 1.2 wt .-% N, below 0 , 3 wt .-% C, to 0.5 wt .-% Ni, balance Fe. JP-A-07/150297 ( Chemical Abstracts: Abstract No.
  • DE-A-196 07 828 teaches a steel of the composition 8-15% by weight Mn, 13-18% by weight Cr, 2.5-6% by weight Mo, 0.55-1.1% by weight N, to 0, 1 wt .-% C, up to 0.5 wt .-% Ni, balance Fe, and its use for various components, in particular generator cap rings.
  • the required high corrosion resistance is paid for with a comparatively high amount of molybdenum, by far the most expensive of the common alloying elements.
  • DE-A-42 42 757 suggests the use of a steel with the essential components 21-35 wt.% Mn, 9-20 wt.% Cr, 0-7 wt.% Mo, 0.3-0.7 wt.% N, to 0.015% by weight of C, up to 0.1% by weight of Ni, up to 0.5% by weight of Si, up to 0.02% by weight of P, up to 0.02% by weight of S and up to 4% by weight.
  • EP-A-422 360 discloses the use of a steel of the composition 17-20 wt% Mn, 16-24 wt% Cr, 0-3 wt% Mo, 0.5-1.3 wt% N, to 0, 20 wt .-% C, balance Fe, for the production of components on rail vehicles.
  • EP-A-432 434 teaches a method of making fasteners from a steel of composition 17.5-20 wt.% Mn, 17.5-20 wt.% Cr, 0-5 wt.% Mo, 0.8-1.2 Wt% N, to 0.12 wt.% C, 0.2-1 wt.% Si, up to 0.05 wt.% P, up to 0.015 wt.% S, up to 3 wt.% Ni, balance Fe.
  • DE-A-25 18 452 teaches a process for producing an austenitic steel having 21-45 wt.% Mn, 10-30 wt.% Cr, 0.85-3 wt.% N, balance Fe, by nitriding a nitrogen-free or -ferior master alloy at least 925 ° C.
  • the steels taught in these publications contain a lower proportion of molybdenum, but a relatively high manganese content, which adversely affects the corrosion properties.
  • DE-A-24 47 318 teaches an austenitic steel having 15 to 45 wt% Mn, 10 to 30 wt% Cr, 0.85 to 3 wt% N, to 1 wt% C, 0 to 2 wt% Si and at least one of the following three alloying constituents: 1-3 wt.% Cu, 1-4 wt.% Ni and 1-5 wt.% Mo, the content of these latter adding up to 5 wt. Remainder iron; wherein the alloy composition must meet certain additional conditions.
  • the alloy may be free of Cu and Ni if a comparatively high manganese content of at least 21% by weight is used. Even in this steel, therefore, only nickel can be dispensed with if a comparatively high molybdenum or manganese content is accepted, and / or at least 1% by weight of copper is contained.
  • EP-A-640 695 discloses a steel of composition 11-25 wt% Mn, 10-20 wt% Cr, up to 1 wt% Mo, 0.05-0.55 wt% N, up to 0.01 wt%. % C, up to 0.5% by weight of Ni, up to 1% by weight of Si, balance Fe, and its use for the production of articles in contact with the skin of living beings.
  • JP-A-07/157847 teaches a steel of composition 9-20 wt.% Mn, 12-20 wt.% Cr, 1-5 wt.% Mo, 0.1-0.5 wt.% N, 0.01-0 , 6 wt .-% C, 0.05 - 2.0 wt .-% Si, 0.05 - 4 wt .-% Cu, balance Fe, and its use for the production of watch scales.
  • JP-A-06/116 683 Chemical Abstracts: Abstract No.
  • 121: 138554 discloses a steel having 5 to 23 wt.% Mn, 13 to 22 wt.% Cr, to 5 wt.% Mo, 0.2 to 0.6 wt.% N, 0.05 to 0, 2 wt .-% C, to 0.1 wt .-% In, to 15 wt .-% Ni, balance Fe.
  • the steels disclosed in these documents contain - at least in some areas of their possible compositions - comparatively little molybdenum and manganese, but their corrosion stability is unsatisfactory.
  • Patent Abstracts of Japan, Vol. 011, No. 069 (C-407) , a summary of the doctrine of JP-A-61/227 154 discloses a heat-resistant cast steel containing 0.2 - 0.7% C, 0.3 - 2% Si, 8 - 25% Mn, at most 5% Ni, 12 - 30% Cr, 0.3 - 2.5% Nb, 0.005 - 0.7% N, remainder contains iron, and is derived from known steels by replacement of nickel by the combination of Nb and N.
  • US-A-4,116,183 discloses an austenitic steel containing, in addition to iron, 18.05-22 wt% Cr, 6.0-10.5 wt% Mn, 0.40-1.10 wt% N, at most 0.08 wt .-% S, at most 0.035 wt .-% P, at most 0.9 wt .-% Si and at most 3 wt .-% Cu.
  • the steel should - also for cost reasons - contain comparatively little other alloying elements, in particular it should be low in molybdenum, manganese and copper, and yet have excellent material properties, in particular to be highly resistant to corrosion.
  • Data in% by weight refer to the composition of the finished steel.
  • the steel according to the invention is low in nickel and preferably nickel-free, austenitic, a good producible and processable and highly corrosion-resistant material, and especially due to the low Molybdfitehalts also inexpensive.
  • the steel of the invention is low in nickel, i. it is nickel, if at all, added only in relatively small amounts, generally at most 2 wt .-%, for example at most 1 wt .-%.
  • the steel of the invention is nickel-free, i. free of intentionally added nickel. (Nickel freedom is therefore a special case of nickel poverty.) Nickel is usually present as an inevitable impurity in small amounts or trace, often due to the general use of steel scrap as a raw material for the production of iron or crude steel.
  • the steel according to the invention in its nickel-free embodiment therefore contains less than 1.0% by weight of nickel and preferably less than 0.5% by weight of nickel. Most preferably, it contains less than 0.3% by weight of nickel.
  • a steel with such low nickel contents gives even in continuous contact with the human or animal body so little nickel that no sensitization or allergy is to be feared.
  • the steel of the invention contains less than 17.0% by weight of manganese, and more preferably at most 16% by weight of manganese. It also contains more than 21.0 and at most 26.0, preferably at most 23 wt .-% chromium, and less than 1.50 wt .-%, preferably at most 1.4 wt .-% molybdenum. Its content of nitrogen is more than 0.70, preferably at least 0.82, and at most 1.70 wt .-%; and its content of carbon is more than 0.11, preferably at least 0.15, for example at least 0.17, and at most 0.70 wt .-%. These alloying elements are essentially in solid solution, ie atomically finely distributed in the austenitic lattice, and not in the form of carbides, nitrides or intermetallic phases.
  • a small addition of other alloying elements, which are often used to improve certain properties for certain applications or as a common supplement in the steel production, does not affect the material properties of the steel according to the invention in general.
  • it may contain copper in an amount of less than 4, for example less than 2.5, preferably less than 2, and most preferably not more than 1, for example 0.5% by weight.
  • It may, for example, also contain tungsten in an amount of less than 2, preferably at most 1 wt .-% and silicon in an amount of less than 2, preferably at most 1 wt .-%.
  • the steel according to the invention is extremely resistant to corrosion.
  • the composition of the steel is within the limits, which are given by its other required material properties (strength, toughness, etc.), optimized for the highest possible sum. In these cases, a lower manganese concentration is preferred. and high carbon and nitrogen content with modest chromium and molybdenum content.
  • a typical field of use for the steel according to the invention is the manufacture of articles in at least occasional contact with the human or animal body, for example spectacles, watches, jewelery, implants, dental implants, metallic parts in clothing such as belt buckles, hooks and eyes, needles , Safety pins, bed frames, handrails, handles, scissors, cutlery, medical instruments such as hypodermic needles, scalpels or other surgical instruments.
  • the surprisingly high corrosion resistance and strength of the steel according to the invention also opens up fields of application in which nickel freedom plays no or only a minor role. It is used, for example, in building construction and civil engineering, for example for the production of reinforcing bars, fastening elements, anchoring elements, hinges, rock anchors, load-bearing structures, façade elements or as prestressing steel. It is also used as a material for the production of technical apparatuses, for example apparatuses or pipelines in oil and gas exploration and production, ocean engineering, shipbuilding or petrochemistry. Furthermore, it is used as a material in traffic engineering, for example for components of equipment and means of transport for water, land and air. Furthermore, it is used in mechanical and plant engineering, for example for energy and power plant technology or for electrical and electronic equipment. The steel according to the invention is also used as a metallic binder phase of hard materials in hard sintered compacts.
  • the steel according to the invention is produced and / or shaped into the desired workpiece by known methods of steelmaking, for example by pressure-free melting, electroslag remelting, pressure-electroslag remelting, casting of the melt, forging, hot and / or cold forming, powder metallurgy, for example pressing and sintering or powder injection molding, both of which are possible with a powder of uniform composition according to the invention or according to the known master-alloy technique, or optionally with subsequent embroidering of a nitrogen-free or low-nitrogen master alloy, if said melting and powder metallurgy processes were not carried out under sufficient nitrogen partial pressure ,
  • the formation of carbides, nitrides and intermetallic phases is avoided or reversed in a likewise known manner by heat treatment.
  • a particularly high strength of workpieces made of the steel according to the invention is achieved by solution annealing and cold working.
  • the workpiece is then tempered. Surprisingly, cold working does not affect crevice corrosion resistance
  • a preferred method of making articles of the steel of the invention is powder metallurgy.
  • a powder of the steel according to the invention or a nitrogen-free or nitrogen-poor master alloy is brought into a mold, for example by pressing, removed from the mold and sintered.
  • the required nitrogen content is set by means of an upsetting process.
  • the constituents of the steel or its precursor may be in the form of a pulverulent mixture of the alloying elements or as a mixture of different alloys and / or pure elements, from which an alloy of the desired gross composition is formed by diffusion during the sintering process according to the master alloy technique.
  • a mixture of pure iron powder and an alloy powder containing the other alloying elements and optionally also iron may be used.
  • thermoplastic injection molding compound is injection molded into a mold with the injection molding technology known from the processing of thermoplastics, the thermoplastic powder injection molding binder is then removed from the injection-molded body ("green body") and the body freed from this binder ("debindering").
  • Braunling sintered to the finished sintered body, and optionally the desired nitrogen content by nitriding (" nitridation ”) adjusted by heat treatment in a nitrogen-containing furnace atmosphere.
  • the nitrogen content is adjusted by nitriding during sintering or immediately before or after it, without intermediate removal of the sintered compact from the sintering furnace or cooling below the sintering or nitriding temperature.
  • debinding which is usually carried out thermally by pyrolysis of the thermoplastic, often causing cracks in the workpiece.
  • a catalytically removable at low temperatures thermoplastic is used.
  • EP-A 413 231 a catalytic debinding method
  • EP-A 465 940 and EP-A 446 708 disclose feedstocks for the production of metallic moldings.
  • the powder injection molding process differs in the performance of conventional powder metallurgical processes such as pressing and sintering by the type of shaping and the additional step required for removing the thermoplastic powder injection molding binder used for shaping.
  • sintering and nitriding are carried out in the same way in all powder metallurgy processes.
  • the steel according to the invention, its precursor or its constituents are used in the form of fine powders.
  • the average particle sizes used are usually in the range below 100 microns, preferably below 50 microns, and most preferably below 20 microns, and generally above 0.1 microns.
  • Such metal powders are commercially available or can be prepared in any known manner, for example by carbonyl decomposition, water or gas atomization.
  • thermoplastic for the production of injection molding compounds are known.
  • thermoplastics for example polyolefins such as polyethylene or polypropylene or polyethers such as polyethylene oxide ("polyethylene glycol").
  • polyethylene glycol polyethylene glycol
  • a polyacetal plastic is used as the basis of the thermoplastic, and in a particularly preferred form polyoxymethylene ("POM", paraformaldehyde, paraldehyde) is used.
  • POM polyoxymethylene
  • the injection molding compound are optionally mixed with auxiliaries to improve their processing properties, for example dispersing aids.
  • Comparable thermoplastic compositions and methods for their preparation and processing by injection molding and catalytic debindering are known and, for example, in EP-A 413 231 .
  • EP-A 444 475 EP-A 800 882 and particularly EP-A 465 940 and their US equivalent US 5,362,791 described, which is hereby incorporated by reference.
  • the polyoxymethylene mono- and copolymers and their preparation are known in the art and described in the literature.
  • the homopolymers are usually prepared by polymerization (usually catalyzed polymerization) of formaldehyde or trioxane.
  • a cyclic ether or cyclic ethers as comonomer is or are conveniently used together with formaldehyde and / or trioxane in the polymerization so that the polyoxymethylene chain is interrupted by units of (-OCH 2 ) units of units where more than one carbon atom is located between two oxygen atoms.
  • cyclic ethers suitable as comonomers are ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-dioxane, 1,3-dioxolane, dioxepane, linear oligo- and polyformals, such as polydioxolane or polydioxepane, and oxymethylene terpolymers.
  • component b2) are in principle polymers which are immiscible with the polyoxymethylene homo- or -compolymerisat b1). Such polymers and their preparation are known in the art and described in the literature.
  • Preferred polymers of this type are polyolefins, vinylaromatic polymers, polymers of vinyl esters of aliphatic C 1 -C 8 -carboxylic acids, polymers of vinylalkyl ethers having 1 to 8 C atoms in the alkyl group or polymers of methacrylic acid esters having at least 70% by weight of units which are derived from methacrylic acid esters or mixtures thereof.
  • Suitable polyolefins are, for example, polymers of olefins having 2 to 8 C atoms, in particular 2, 3 or 4 C atoms, and also copolymers thereof. Particularly preferred are polyethylene and polypropylene and their copolymers. Such polymers are mass-produced, widely used commodities and therefore known to those skilled in the art.
  • Suitable vinylaromatic polymers are, for example, polystyrene and poly- ⁇ -methylstyrene and copolymers thereof with up to 30% by weight of comonomers from the group of acrylic esters and also acrylonitrile or methacrylonitrile. Such polymers are common commercial goods.
  • Suitable polymers of vinyl esters of aliphatic C 1 -C 8 -carboxylic acids are, for example, polyvinyl acetate or polyvinyl propionate
  • suitable polymers of C 1 -C 8 -vinyl alkyl ethers are, for example, polyvinyl methyl ether or polyvinyl ethyl ether.
  • polymers of methacrylic acid esters with at least 70 wt .-% of units derived from methacrylic acid esters for example, copolymers having at least 70 wt .-% methacrylic acid esters of C 1 -C 14 alcohols, in particular methyl methacrylate and / or ethyl methacrylate, used as monomer units.
  • comonomers for example 0 to 30 wt .-%, preferably 0 to 20 wt .-% of acrylic acid esters, preferably methyl acrylate and / or ethyl acrylate can be used.
  • Component c) is a dispersing aid.
  • Dispersing aids are widely used and known to those skilled in the art. In general, any dispersing aid may be used which results in improving the homogeneity of the injection molding compound.
  • Preferred dispersing aids are oligomeric polyethylene oxide having an average molecular weight of 200 to 400, stearic acid, hydroxystearic acid, fatty alcohols, fatty alcohol sulfonates and block copolymers of ethylene oxide and propylene oxide.
  • As a dispersing agent a mixture of various substances having dispersing properties can also be used.
  • the metal powder is - in the powder injection molding process after prior mixing with the thermoplastic binder and optionally with the excipients - brought with a forming tool, such as a press, in a form as possible to avoid any costly reworking of the finished sintered part of its desired geometric final shape comes close.
  • a forming tool such as a press
  • the deformation of the powder injection feedstocks is carried out in a conventional manner with conventional injection molding machines.
  • the moldings are freed from the thermoplastic powder injection molding binder in the usual way, for example by pyrolysis ("debindering").
  • the binder is preferably removed catalytically by heat treating the green bodies in a known manner with an atmosphere containing a gaseous acid.
  • This atmosphere is prepared by evaporating an acid of sufficient vapor pressure, conveniently by passing a carrier gas, especially nitrogen, through a storage vessel with an acid, advantageously nitric acid, and then introducing the acidic gas into the debinding furnace.
  • the optimum acid concentration in the debinding furnace depends on the desired steel composition and on the dimensions of the workpiece and is determined on a case-by-case basis by routine tests. In general, for debinding treatment in such an atmosphere will be sufficient at temperatures in the temperature range of 20 ° C to 180 ° C over a period of 10 minutes to 24 hours. After debinding any remaining of the thermoplastic binder and / or the excipients are pyrolyzed during heating to sintering temperature and thereby completely removed.
  • the molding After shaping, and subsequent removal of the binder in the injection molding process, the molding is sintered to the sintered compact in a sintering furnace and, if a nitrogen-free or nitrogen-reduced precursor of the steel of the present invention is used, the desired nitrogen content is established by nitriding.
  • the optimal composition for sintering and optionally for nitriding the furnace atmosphere and the optimum temperature control depend on the exact chemical composition of the steel or its precursor used or its precursor, in particular its nitrogen solubility, and on the grain size of the powder used. In general, both the increase in nitrogen partial pressure in the furnace atmosphere and the decrease in temperature are directly correlated with higher nitrogen contents in the steel. However, since lowering the temperature not only slows down the sintering process itself, but also decreases the diffusion rate of the nitrogen in the steel, the sintering and / or nitridation process lasts lower temperature correspondingly longer.
  • furnace atmosphere in particular the nitrogen partial pressure, temperature and duration of sintering and / or nitriding, to achieve a specific desired nitrogen content in a homogeneous, dense sintered compact, can be easily determined on a case-by-case basis using less routine tests.
  • sintering methods are described, for example, in the publications by Bähre et al. and Wohlfromm et al. described. These two publications are hereby incorporated by reference.
  • nitrogen partial pressures in the furnace atmosphere of at least 0.1, preferably at least 0.25, are used. This nitrogen partial pressure is generally at most 2 bar, preferably at most 1 bar.
  • the furnace atmosphere may consist of pure nitrogen or contain inert gases such as argon and / or reactive gases such as hydrogen. In most cases, it is advantageous to use a mixture of nitrogen and hydrogen as the furnace atmosphere in order to remove possibly interfering oxidic impurities of the metals.
  • the hydrogen content if present, is generally at least 5% by volume, preferably at least 15% by volume, and generally at most 50% by volume, preferably at most 30% by volume. If desired, this furnace atmosphere may additionally contain inert gases, for example argon.
  • the furnace atmosphere should preferably be substantially dry, generally a dew point of -40 ° C is sufficient.
  • the (absolute) pressure in the sintering and / or nitriding furnace is usually at least 100 mbar, preferably at least 250 mbar. It is also generally not more than 2.5 bar, preferably at most 2 bar. In a particularly preferred manner, working is carried out under atmospheric pressure.
  • the sintering and / or nitriding temperature is generally at least 1000 ° C, preferably at least 1050 ° C, and most preferably at least 1100 ° C. It is also generally at most 1450 ° C, preferably at most 1400 ° C and most preferably at most 1350 ° C.
  • the temperature may be varied during the sintering and / or nitriding process, for example, to completely or substantially dense sinter the workpiece only at a higher temperature and then adjust the desired nitrogen content at a lower temperature.
  • the optimum heating rates are readily determined by some routine experimentation, usually at least 1 ° C per minute, preferably at least 2 ° C per minute and in particular preferably at least 3 ° C per minute.
  • the highest possible heating rate is generally desired in order to avoid a negative influence on the quality of the sintering and / or nitriding, but usually a heating rate below 20 ° C. per minute will have to be set.
  • the sintering and / or nitriding time ie the holding time at sintering and / or nitriding temperature, is generally adjusted so that the sintered moldings are sintered both sufficiently dense and sufficiently homogeneously nitrided.
  • the sintering and / or nitridation time is generally at least 30 minutes and preferably at least 60 minutes.
  • This duration of the sintering and / or nitriding process determines the rate of production, so sintering and / or nitriding is preferably carried out so that the sintering and / or nitriding process does not take an unsatisfactorily long time from an economic point of view.
  • the sintering and nitriding process (without the heating and cooling phases) can be completed after a maximum of 10 hours.
  • the sintering and / or nitriding process is terminated by cooling the sintered moldings.
  • a particular cooling process may be required, for example, to cool as quickly as possible to obtain high temperature phases or to prevent segregation of the components of the steel.
  • the upper limit of the cooling rate is reached when occurring in economically unsatisfactory high amount sintered components with due to rapid cooling errors such as cracking, cracking or deformation.
  • the optimum cooling rate is therefore easily determined in a few routine tests.
  • the sintered moldings can be quenched, for example, in cold water or oil.
  • any desired aftertreatment for example solution heat treatment and quenching in water or oil or hot isostatic pressing of the sintered shaped parts, can be carried out.
  • the sintered moldings are solution annealed by keeping for a period of at least 5 minutes, preferably at least 10 minutes and at most 2 hours, preferably at most one hour at a temperature of at least 1000 ° C, preferably at least 1100 ° C and at most 1250 ° C, preferably not more than 1200 ° C under inert gas, for example under nitrogen and / or argon, are heat treated and then quenched, for example in cold water.
  • Example 2 was repeated, but after quenching cold deformation was performed by 92% reduction in section and then tempered. This resulted in an extremely high yield strength of 3100 MPa.
  • the examples show that the steel according to the invention is not only resistant to corrosion, but also has a surprisingly high strength.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Heat Treatment Of Steel (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Materials For Medical Uses (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Dry Shavers And Clippers (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP00941991A 1999-05-26 2000-05-26 Nickelarmer austenitischer stahl Expired - Lifetime EP1198604B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH00981/99A CH694401A5 (de) 1999-05-26 1999-05-26 Nickelarmer, molybdänarmer, biokompatibler, nicht Allergie auslösender, korrosionsbeständiger austenitischer Stahl.
CH98199 1999-05-26
PCT/EP2000/004824 WO2000073528A1 (de) 1999-05-26 2000-05-26 Nickelarmer austenitischer stahl

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EP1198604B1 true EP1198604B1 (de) 2007-10-03

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ES2292445T3 (es) 2008-03-16
CN1129676C (zh) 2003-12-03
CH694401A5 (de) 2004-12-31
CN1351674A (zh) 2002-05-29
CA2372563A1 (en) 2000-12-07
RU2394114C2 (ru) 2010-07-10
EP1198604A1 (de) 2002-04-24
DE50014694D1 (de) 2007-11-15
RU2259420C2 (ru) 2005-08-27
WO2000073528A1 (de) 2000-12-07
AU5676300A (en) 2000-12-18
KR100710092B1 (ko) 2007-04-20
KR20020016631A (ko) 2002-03-04
US6682581B1 (en) 2004-01-27
RU2005112442A (ru) 2006-10-27
JP4610822B2 (ja) 2011-01-12
ATE374845T1 (de) 2007-10-15
CA2372563C (en) 2009-09-29
JP2003500544A (ja) 2003-01-07

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