EP2732061B1 - Alliage chrome-molybdène - Google Patents

Alliage chrome-molybdène Download PDF

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Publication number
EP2732061B1
EP2732061B1 EP12710674.8A EP12710674A EP2732061B1 EP 2732061 B1 EP2732061 B1 EP 2732061B1 EP 12710674 A EP12710674 A EP 12710674A EP 2732061 B1 EP2732061 B1 EP 2732061B1
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weight
amount
alloy
temperature
range
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German (de)
English (en)
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EP2732061A1 (fr
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Matthias Kuntz
Friedrich Muehleder
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Robert Bosch GmbH
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Robert Bosch GmbH
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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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium

Definitions

  • the present invention relates to a chromium-molybdenum alloy. More particularly, the present invention relates to an alloy based on 42CrMo4 or 18CrNiMo7-6 which has an alloy of manganese and a microalloy of aluminum, niobium and nitrogen.
  • high-strength materials are needed.
  • a significant limitation of the use of high-strength materials is given for example by their mechanical properties.
  • the component manufacturing route may impose limitations. Especially for large-sized components, a high strength of importance, since often act large forces and a replacement of damaged parts is very expensive.
  • an alloyed steel which can be used in a motor vehicle and in particular in an internal combustion engine, for example as a piston or as a piston component.
  • This steel is based on an AFP steel and has the following composition, each in weight%: carbon: 0.35-0.50; Silicon: 0.15-0.80; Manganese: 1.20-2.00; Phosphorus: 0.00-0.0025; Nitrogen: 0.010-0.035; Chromium: 0.00-0.50; Molybdenum: 0.00-0.050; Nickel: 0.00-0.15; Copper: 0.00-0.40; Vanadium: 0.13-0.40; Titanium: 0.001-0.004; Aluminum: 0.00-0.04; Niobium: 0.00-0.05; in which at least two of the elements vanadium, aluminum and niobium are included. It is stated that a low titanium content of 0.001 wt.% To 0.004 wt.% Is a decisive factor in order to obtain mechanical properties which are
  • the invention relates to a chromium-molybdenum alloy selected from the group consisting of an alloy comprising carbon in an amount of ⁇ 0.38 wt .-% to ⁇ 0.45 wt .-%; Silicon in an amount of ⁇ 0.40 wt .-%; Manganese in an amount of ⁇ 1.0 wt% to ⁇ 1.3 wt%; Phosphorus in an amount of ⁇ 0.025 wt%; Sulfur in an amount of ⁇ 0.035 wt%; Chromium in an amount of ⁇ 0.90 wt .-% to ⁇ 1.20 wt .-%; Molybdenum in an amount of ⁇ 0.15 wt% to ⁇ 0.30 wt%; Aluminum in an amount of> 0 wt .-% to ⁇ 0.05 wt .-%; Niobium in an amount of> 0 wt .-% to ⁇ 0.04 wt .-%, nitrogen in an
  • the alloy according to the invention has a defined composition of characteristic alloying elements.
  • the basis for the alloy according to the invention is the tempered steel 42CrMo4 or the case hardening steel 18CrNiMo7-6.
  • the composition of such alloys is for known in the art.
  • a 42CrMo4 alloy and an 18CrNiMo7-6 alloy comprise in particular the following metallic compounds in the following concentrations, the concentrations being given in percent by weight (% by weight) (Table 1): element 42CrMo4 18CrNiMo7-6 C ⁇ 0.38 to ⁇ 0.45 ⁇ 0.15 to ⁇ 0.20 Si ⁇ 0.40 ⁇ 0.40 Mn ⁇ 0.60 to ⁇ 0.90 ⁇ 0.35 to ⁇ 0.70 P ⁇ 0.025 - S ⁇ 0.035 - Cr ⁇ 0.90 to ⁇ 1.20 ⁇ 1.50 to ⁇ 1.80 Not a word ⁇ 0.15 to ⁇ 0.30 ⁇ 0.25 to ⁇ 0.35 Ni - ⁇ 1.40 to ⁇ 1.70
  • the known alloys 42CrMo4 or the insert steel 18CrNiMo7-6 are modified according to the invention by an addition of manganese, whereby the amount of manganese according to the invention no longer corresponds to the amounts given in Table 1, but are higher, in particular in a range of ⁇ 1, 0 to ⁇ 1.3% by weight. Furthermore, the alloys according to the invention have a microalloy of niobium, aluminum and nitrogen.
  • aluminum is present in an amount of> 0% by weight to ⁇ 0.05% by weight; Niobium in an amount of> 0 wt .-% to ⁇ 0.04 wt .-% and nitrogen in an amount of> 0 wt .-% to ⁇ 0.015 wt .-% before.
  • aluminum is present in an amount of from ⁇ 0.01% by weight to ⁇ 0.025% by weight; Niobium in an amount of ⁇ 0.01 wt .-% to ⁇ 0.02 wt .-% and nitrogen in an amount of ⁇ 0.005 wt .-% to ⁇ 0.010 wt .-% before.
  • a niobium content of ⁇ 0.03 wt% may be sufficient.
  • microalloys produces an initial state in the alloy which, in further processing and / or heat treatment steps, leads to a grain-fine effect in the alloy structure.
  • the micro-alloying elements prevent grain growth in a heat treatment. Therefore, according to the invention, it is possible to obtain an ASTM grain size in a range of ⁇ 12 to ⁇ 13 with a heat treatment route in an alloy based on 42CrMo 4. Further, according to the present invention, in an 18CrNiMo7-6 based alloy, an ASTM grain size in a range of ⁇ 13 to ⁇ 14 can be obtained.
  • ASTM grain size ASTM: American Society for Testing Materials
  • ASTM straightening series of stylized grain boundary nets of sizes 1 (16 grains / mm 2 ) to 8 (about 200 grains / mm 2 ) hundred times magnification compared.
  • microalloyed alloying partners can form aluminum and niobium according to the invention with the likewise added micro-alloyed nitrogen carbonitrides.
  • These intermetallic compounds attach themselves to the grain boundaries and can thus prevent grain growth and thus lead to smaller particle sizes.
  • the added manganese in particular stabilizes the austenitic high-temperature phase and thus delays, for example in a heat treatment, the conversion of this phase into the martensitic low-temperature phase. This enhances the grain-refining effect.
  • a fine grain can ensure a more uniform distribution of the impurities, more perfect isotropy, greater strength, hardness, toughness and impact energy.
  • the alloy according to the invention makes it possible, in particular, to make it possible to increase the cyclic resistance and the resistance to rolling fatigue, whereby the component production route can essentially remain unchanged. As a result, an improvement in the reliability of the components can be made possible without significant additional costs or at no extra cost. Due to the improved mechanical properties, for example, the power density of large gearboxes can be improved.
  • existing component production routes based on the alloy according to the invention can remain unchanged. Changes to the processes are not or only insignificantly necessary in negligible effort.
  • the alloy according to the invention in a simple and cost-effective manner without the need for costly conversions and associated downtime in existing manufacturing processes are integrated.
  • the alloy according to the invention can also be used without difficulty in existing processes in a wide range, which makes possible a wide range of application of the invention. This is particularly advantageous in the case of large transmission components, since here the component production route is severely limited due to the dimensioning of the components.
  • the alloy may further comprise phosphorus and / or sulfur and / or oxygen. These elements can occur as accompanying elements and can have a concentration in a conventional range known to the person skilled in the art.
  • phosphorus for example, can increase the strength, in particular the tensile strength, and the hardness, and at the same time improve the corrosion resistance against atmospheric influences, in particular at a carbon content of from about 0.1%.
  • sulfur can reduce ductility, allowing for greater component stability, particularly in rolling contact.
  • the manganese is present in an amount of ⁇ 1.0 wt .-% to ⁇ 1.2 wt .-%, and / or the aluminum is in an amount of> 0.04 wt % to ⁇ 0.05% by weight, and / or the nitrogen is present in an amount of ⁇ 0.010% by weight.
  • the alloy comprises in addition to the alloying constituents carbon, silicon, manganese, chromium, molybdenum and optionally nickel, phosphorus and sulfur as further alloy constituents exclusively: aluminum, niobium, nitrogen and optionally oxygen.
  • the alloying constituents are in particular in the above-described concentrations before, wherein the alloy components are present together with a residue of iron and add up to 100% by weight.
  • the term "alloying component" refers in particular to substances which form mixed crystals with one another.
  • the inventive method can be produced in a particularly simple manner, a component which consists of the alloy according to the invention or is constructed essentially of this.
  • an alloy according to the invention is first provided, which can be carried out by a conventional method known to the person skilled in the art.
  • the alloy may be provided in a conventional steelmaking process with the actual alloying adjustment in secondary metallurgy.
  • the alloy is shaped, that is brought into a shape corresponding to the component to be produced.
  • the molded alloy is subjected to a heat treatment.
  • the heat treatment can have several functions.
  • the individual constituents of the alloy can be homogenized by a heat treatment.
  • a heat treatment is used in particular to harden the alloy.
  • the alloy according to the invention is based on an 18CrNiMo7-6 alloy, by a conventional multiple hardening.
  • the shaped alloy can be repeatedly heated to a temperature in a range of ⁇ 800 ° C to ⁇ 1200 ° C and quenched after a short time of holding the temperature. This method is known to those skilled in the art.
  • the heat treatment is thus a heat treatment comprising four steps.
  • the four steps can also be carried out individually and independently of each other as a single heat treatment or in a suitable combination of the individual steps.
  • heating ramps in a range of ⁇ 2 ° C / s to ⁇ 4 ° C / s, in particular of 3.3 ° C / s are preferably used for each heating, whereas for each cooling quench ramps in a range of ⁇ 25 ° C / s to ⁇ 75 ° C / s, in particular of 50 ° C / s used.
  • a solution annealing is carried out, which serves in particular to homogenize the individual alloy components.
  • This solution heat treatment is carried out in particular in a temperature range from ⁇ 1000 ° C to ⁇ 1400 ° C, preferably at 1200 ° C for a period of ⁇ 3 minutes to ⁇ 7 minutes, preferably 5 minutes.
  • a second step the alloy is subjected to a two-stage heat treatment without intermediate quenching.
  • This step is a so-called FP annealing (ferritic-pearlitic) and serves in particular to set a defined strength.
  • This step will be more particularly with respect to the first stage in a temperature range from ⁇ 800 ° C to ⁇ 1000 ° C, preferably at 900 ° C for a period of ⁇ 20 minutes to ⁇ 45 minutes, preferably for 30 minutes and then with reference to the second stage in a temperature range of ⁇ 550 ° C to ⁇ 790 ° C, preferably at 680 ° C for a period of ⁇ 60 minutes to ⁇ 120 minutes, preferably for 90 minutes performed.
  • a so-called pendulum annealing takes place.
  • the alloy is heated alternately to a temperature in a range of, in particular, ⁇ 750 ° C to ⁇ 1000 ° C, preferably 850 ° C, and following a temperature in a range of, in particular, ⁇ 550 ° C to ⁇ 745 ° C,
  • the respective upper temperature is maintained for a period in a range of ⁇ 10 seconds to ⁇ 45 seconds, preferably 30 seconds
  • the respective lower temperature for a period in a range of ⁇ 5 seconds to ⁇ 10 Seconds, preferably 7.5 seconds is held.
  • the fourth step includes heating the alloy to a temperature in a range of ⁇ 750 ° C to ⁇ 1000 ° C, particularly 850 ° C, and maintaining the temperature for a period in a range of ⁇ 5 minutes to ⁇ 15 minutes. This step is used in particular for curing the alloy.
  • the invention further relates to a component comprising an alloy according to the invention.
  • the invention includes in particular components that a Cyclic stress are exposed and in particular those experiencing a Wälzbe retailung.
  • components according to the invention include gearboxes and, in particular, large gearboxes or gearboxes whose components, such as toothed wheels or stationary components in general.
  • the invention further relates to the use of an alloy according to the invention for producing a component.
  • a use in particular for the production of such components is advantageous, as described with respect to the component according to the invention.
  • Fig. 1 a schematic timing diagram for illustrating a production method according to the invention for a component comprising an alloy according to the invention.
  • FIG. 1 a timing diagram of a method according to the invention for producing a component is shown.
  • the inventive method is based on the use of a chromium-molybdenum alloy according to the invention, selected from the group consisting of an alloy comprising carbon in an amount of ⁇ 0.38 wt .-% to ⁇ 0.45 wt .-%; Silicon in an amount of ⁇ 0.40 wt .-%; Manganese in an amount of ⁇ 1.0 wt% to ⁇ 1.3 wt%; Phosphorus in an amount of ⁇ 0.025 wt%; Sulfur in an amount of ⁇ 0.035 wt%; Chromium in an amount of ⁇ 0.90 wt .-% to ⁇ 1.20 wt .-%; Molybdenum in an amount of ⁇ 0.15 wt% to ⁇ 0.30 wt%; Aluminum in an amount of> 0 wt .-% to ⁇ 0.05 wt .-
  • the heat treatment involves four steps and is in FIG. 1 in a non-limiting embodiment in the form of a time chart shown schematically.
  • a solution annealing designated by a) is carried out, wherein the alloy is heated to a temperature range of 1200 ° C with a heating ramp of 3.3 ° C / s, where it remains for a period of 5 minutes and to a temperature of 0 ° C is cooled or quenched using a quench ramp of 50 ° C / s.
  • an FP annealing designated by b) is carried out, wherein the alloy is heated to a temperature of 900 ° C. with a heating ramp of 3.3 ° C./s and remains at this temperature for a period of 30 minutes. Subsequently, the alloy is cooled to a temperature of 680 ° C using a quench ramp of 50 ° C / s and left at this temperature for a period of 90 minutes, after which the alloy is heated to a temperature using a quench ramp of 50 ° C / s is cooled or quenched from 0 ° C.
  • a pendulum annealing there is a pendulum annealing called c).
  • the alloy is heated a total of three times with a heating ramp of 3.3 ° C / s to a temperature of 850 ° C and remains at that temperature for a period of 30 seconds.
  • each alloy is cooled to a temperature of 660 ° C using a quench ramp of 50 ° C / s and left there for 7.5 minutes each time is heated again to 850 ° C using the above-described Aufhardrampe.
  • a quench ramp 50 ° C / s to a temperature of 0 ° C.
  • the fourth step is a hardening referred to as d), wherein the alloy is heated to a temperature range of 850 ° C with a heating ramp of 3.3 ° C / s, there for a period of 10 minutes and to a temperature of 0 ° C below Using a Abschreckrampe of 50 ° C / s is cooled or quenched.

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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 Articles (AREA)
  • Powder Metallurgy (AREA)

Claims (7)

  1. Alliage chrome-molybdène, choisi dans le groupe constitué par :
    - un alliage, comprenant du carbone en une quantité de ≥ 0,38 % en poids à ≤ 0,45 % en poids ; du silicium en une quantité de 0,40 % en poids ; du manganèse en une quantité de ≥ 1,0 % en poids à ≤ 1,3 % en poids ; du phosphore en une quantité de ≤ 0,025 % en poids ; du soufre en une quantité de ≤ 0,035 % en poids ; du chrome en une quantité de ≥ 0,90 % en poids à ≤ 1,20 % en poids ; du molybdène en une quantité de ≥ 0,15 % en poids à ≤ 0,30 % en poids ; de l'aluminium en une quantité de > 0 % en poids à ≤ 0,05 % en poids ; du niobium en une quantité de > 0 % en poids à 0,04 % en poids ; de l'azote en une quantité de > 0 % en poids à ≤ 0,015 % en poids ; du phosphore et/ou du soufre et/ou de l'oxygène pouvant être présents en tant qu'éléments accompagnateurs, les composants de l'alliage étant présents conjointement avec un résidu de fer et leur somme étant de 100 % en poids, et
    - un alliage comprenant du carbone en une quantité de ≥ 0,15 % en.poids à ≤ 0,20 % en poids ; du silicium en une quantité de 0,40 % en poids ; du manganèse en une quantité de ≥ 1,0 % en poids à ≤ 1,3 % en poids ; du chrome en une quantité de ≥ 1,50 % en poids à ≤ 1,80 % en poids ; du molybdène en une quantité de ≥ 0,25 % en poids à ≤ 0,35 % en poids ; du nickel en une quantité de ≥ 1,40 % en poids à ≤ 1,70 % en poids ; de l'aluminium en une quantité de > 0 % en poids à 0,05 % en poids ; du niobium en une quantité de > 0 % en poids à ≤ 0,04 % en poids ; de l'azote en une quantité de > 0 % en poids à ≤ 0,015 % en poids ; du phosphore et/ou du soufre et/ou de l'oxygène pouvant être présents en tant qu'éléments accompagnateurs, les composants de l'alliage étant présents conjointement avec un résidu de fer et leur somme étant de 100 % en poids.
  2. Alliage selon la revendication 1, caractérisé en ce que le manganèse est présent en une quantité de ≥ 1,0 % en poids à < 1,2 % en poids, et/ou l'aluminium est présent en une quantité de > 0,04 % en poids à ≤ 0,05 % en poids, et/ou l'azote est présent en une quantité de < 0,010 % en poids.
  3. Alliage selon la revendication 1 ou 2, caractérisé en ce que l'alliage comprend en plus des constituants d'alliage carbone, silicium, manganèse, chrome, molybdène et éventuellement nickel, phosphore et soufre en tant qu'autres constituants d'alliage exclusivement : de l'aluminium, du niobium, de l'azote et éventuellement de l'oxygène.
  4. Procédé de fabrication d'un composant, comprenant les étapes suivantes :
    - la préparation d'un alliage selon l'une quelconque des revendications 1 à 3,
    - le façonnage de l'alliage,
    - la réalisation d'un traitement thermique de l'alliage façonné.
  5. Procédé selon la revendication 4, caractérisé en ce que
    - l'alliage comprend du carbone en une quantité de ≥ 0,38 % en poids à ≤ 0,45 % en poids ; du silicium en une quantité de ≤ 0,40 % en poids ; du manganèse en une quantité de ≥ 1,0 % en poids à ≤ 1,3 % en poids ; du phosphore en une quantité de ≤ 0,025 % en poids ; du soufre en une quantité de ≤ 0,035 % en poids ; du chrome en une quantité de ≥ 0,90 % en poids à ≤ 1,20 % en poids. ; du molybdène en une quantité de ≥ 0,15 % en poids à ≤ 0,30 % en poids ; de l'aluminium en une quantité de > 0 % en poids à ≤ 0,05 % en poids ; du niobium en une quantité de > 0 % en poids à ≤ 0,04 % en poids ; de l'azote en une quantité de > 0 % en poids à ≤ 0,015 % en poids ; du phosphore et/ou du soufre et/ou de l'oxygène pouvant être présents en tant qu'éléments accompagnateurs, les composants de l'alliage étant présents conjointement avec un résidu de fer et leur somme étant de 100 % en poids,
    - le traitement thermique comprend les étapes suivantes :
    - le chauffage de l'alliage à une température dans une plage allant de ≥ 1 000 °C à ≤ 1 400 °C, le maintien de la température pendant une durée dans une plage allant de ≥ 3 minutes à ≤ 7 minutes, et la trempe de l'alliage en une durée ≤ 1 minute à une température dans une plage ≤ 50 °C ;
    - le chauffage de l'alliage à une température dans une plage allant de ≥ 800 °C à 1 000 °C, le maintien de la température pendant une durée dans une plage allant de ≥ 20 minutes à ≤ 45 minutes, et le refroidissement de l'alliage en une durée ≤ 1 minute à une température dans une plage allant de ≥ 550 °C à ≤ 790 °C, le maintien de la température pendant une durée dans une plage allant de ≥ 60 minutes à ≤ 120 minutes, et le refroidissement de l'alliage en une durée ≤ 1 minute à une température dans une plage ≤ 50 °C ;
    - à plusieurs reprises, le chauffage de l'alliage à une température dans une plage allant de ≥ 750 °C à ≤ 1 000 °C, et le maintien de la température pendant une durée dans une plage allant de ≥ 10 secondes à ≤ 45 secondes, et le refroidissement de l'alliage à une température dans une plage allant de ≥ 550 °C à ≤ 745 °C, et le maintien de la température pendant une durée dans une plage allant de ≥ 5 secondes à ≤ 10 secondes, puis le refroidissement de l'alliage en une durée ≤ 1 minute à une température dans une plage ≤ 50 °C,
    - le chauffage de l'alliage à une température dans une plage allant de ≥ 750 °C à ≤ 1 000 °C, le maintien de la température pendant une durée dans une plage allant de ≥ 5 minutes à ≤ 15 minutes, et la trempe de l'alliage en une durée ≤ 1 minute à une température dans une plage ≤ 50 °C.
  6. Composant, comprenant un alliage selon l'une quelconque des revendications 1 à 3.
  7. Utilisation d'un alliage selon l'une quelconque des revendications 1 à 3 pour la fabrication d'un composant.
EP12710674.8A 2011-05-12 2012-03-13 Alliage chrome-molybdène Active EP2732061B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011075697A DE102011075697A1 (de) 2011-05-12 2011-05-12 Chrom-Molybden-Legierung
PCT/EP2012/054363 WO2012152477A1 (fr) 2011-05-12 2012-03-13 Alliage chrome-molybdène

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EP2732061A1 EP2732061A1 (fr) 2014-05-21
EP2732061B1 true EP2732061B1 (fr) 2017-06-21

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CN106312000A (zh) * 2016-10-12 2017-01-11 中原特钢股份有限公司 立式连铸生产齿轮钢用18CrNiMo7‑6连铸圆坯方法
CN106424524B (zh) * 2016-10-14 2018-10-12 太原科技大学 一种17CrNiMo6钢风力发电齿轮的锻造方法
CN109609867A (zh) * 2018-11-05 2019-04-12 南京中船绿洲机器有限公司 一种18CrNiMo7-6材料及其低温冲击热处理方法
CN110565018B (zh) * 2019-09-25 2021-06-01 山东钢铁股份有限公司 一种改善低碳高合金齿轮钢退火态带状组织的控制方法

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JPH0826432B2 (ja) * 1993-03-19 1996-03-13 愛知製鋼株式会社 高品質肌焼鋼
DE102007021101A1 (de) 2007-05-03 2008-11-06 Mahle International Gmbh Legierter Stahl und dessen Verwendung
DE102008004371A1 (de) * 2008-01-15 2009-07-16 Robert Bosch Gmbh Bauelement, insbesondere eine Kraftfahrzeugkomponente, aus einem Dualphasen-Stahl

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ASHLEY G: "Patentability of alloys at the European Patent Office", INTELLECTUAL PROPERTY, BIRMINGHAM, GB, vol. 2, no. 3, 1 May 1997 (1997-05-01), pages 3 - 6, XP007922941, ISSN: 1361-5793 *
SPIEKERMANN P: "Alloys - a special problem of patent law", NONPUBLISHED ENGLISH TRANSLATION OF DOCUMENT, 31 December 2002 (2002-12-31), pages 1 - 20, XP002184689 *

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WO2012152477A1 (fr) 2012-11-15
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