EP3272888B1 - Matière à base d'alliage de zinc/cuivre, procédé de fabrication d'une telle matière et élément coulissant constitué d'une telle matière - Google Patents

Matière à base d'alliage de zinc/cuivre, procédé de fabrication d'une telle matière et élément coulissant constitué d'une telle matière Download PDF

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EP3272888B1
EP3272888B1 EP17001112.6A EP17001112A EP3272888B1 EP 3272888 B1 EP3272888 B1 EP 3272888B1 EP 17001112 A EP17001112 A EP 17001112A EP 3272888 B1 EP3272888 B1 EP 3272888B1
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Prior art keywords
manganese
material according
forming
phosphide
phosphides
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German (de)
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EP3272888A1 (fr
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Volker Voggeser
Jeremy Bell
Hans-Achim Kuhn
Maher Ababneh
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Wieland Werke AG
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Wieland Werke AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

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  • the invention relates to a material made of a copper-zinc alloy, a method for producing such a material and a sliding element made of such a material.
  • the proportions of silicon, manganese, iron and nickel are set so that that in the structure of the material there are both iron-nickel-manganese-containing mixed silicides with a stalked shape and mixed silicides enriched with iron and nickel with a globular shape.
  • the structure of the material consists of an ⁇ matrix, in which at least 5% by volume and up to 50% by volume of the ⁇ phase is embedded in addition to the silicides. The globular silicides are seen as the reason why the ⁇ phase stabilizes.
  • the processing of the alloy includes extrusion presses in a temperature range from 600 to 800 ° C. This hot forming is favored in that the structure in the as-cast state has up to 50% by volume of the ⁇ phase. Pipes made from these alloys have elongation at break values of up to approximately 13%.
  • the publication US 2011/0211 781 A1 discloses a Cu-Zn alloy containing 25 to 45 wt% Zn, 0.3 to 2.0 wt% Si, 1.5 to 6.0 wt% Mn and optionally other elements.
  • the alloy contains manganese silicides and is used for plain bearings.
  • a copper-zinc alloy known for plain bearings contains 66 to 90 wt% Cu, 1.0 to 8.0 wt% Mn, 0.3 to 0.7 wt% AI, 0.3 to 2.0 wt% P and balance zinc.
  • Manganese phosphides are contained in the structure in eutectic form. The eutectic excretion can be controlled by the amount of aluminum added. The ratio of phosphorus to aluminum is important for the processability of this alloy. Silicon is not used in this alloy. Materials made from this alloy can reach a hardness of up to 207 HB.
  • the invention has for its object to provide a material that Due to its strength, hardness, ductility and wear properties it is suitable for plain bearings and has a high forming capacity for economical production.
  • the material should have high heat resistance up to over 300 ° C.
  • the invention is also based on the object of a production method for such a material and one in particular with regard to temperature resistance and manufacturing costs to provide improved sliding element.
  • the invention is based on the consideration of choosing the composition of a copper-zinc alloy in such a way that a wrought material with high cold-forming properties and good wear properties is formed.
  • the material can preferably be a strip material. Such a strip material is suitable as a semi-finished product for the production of rolled plain bearing bushes or half-shells.
  • the material according to the invention is based on a copper-zinc alloy with a comparatively low proportion of zinc for bearing materials.
  • the zinc content should not fall below 21% by weight, otherwise the strength of the material is insufficient.
  • the zinc content should not exceed 27% by weight. otherwise the cold forming capacity is limited.
  • the material has a structure with an alpha-phase matrix, which is favorable for high cold formability.
  • the zinc content is preferably at least 22.6% by weight. From this zinc content, the material has very favorable properties in terms of strength and hardness.
  • the zinc content is preferably at most 25.2% by weight. Up to this upper limit of the zinc content, the cold forming capacity of the material is excellent.
  • the copper-zinc alloy of the material according to the invention also contains 0.2 to 0.8% by weight of Si, 1.1 to 1.9% by weight of Mn and 0.005 to 0.2% by weight of P. Alloys of similar composition known from the prior art describe the formation of manganese silicides. Surprisingly, manganese-containing phosphides are present in the material according to the invention in a significant amount and with a characteristic distribution, while the expected manganese silicides cannot be detected in the alloy, although the proportion of silicon in relation to the proportion of phosphorus is comparatively high. It can be assumed that in the material according to the invention, manganese silicides, which are formed as precipitates when the melt solidifies and cools, are redissolved in a subsequent heat treatment.
  • the mass ratio of manganese to phosphorus is between 2.7 and 3.3.
  • the quantitative composition of the particles is determined by means of energy dispersive X-ray spectroscopy (EDXS).
  • EDXS energy dispersive X-ray spectroscopy
  • particles can be detected in the material according to the invention which contain phosphorus, manganese and oxygen.
  • the mass-related manganese content of these particles is significantly reduced compared to the manganese-containing phosphides. It is approximately at the same level as the oxygen content of these particles.
  • the manganese-containing phosphides are globular-shaped as phosphide particles educated.
  • globular shape means not only the exact sphere, but also all shapes that can be approximately described as ellipsoids of revolution.
  • At least 90% of the phosphide particles have a size of at most 2.0 ⁇ m.
  • the maximum size of the phosphide particles is 4 ⁇ m.
  • the diameter of the particle is defined as a measure of the size of the particle.
  • size is understood to mean the volume-equivalent diameter, that is to say the diameter of a sphere of the same volume as the particle.
  • the average size of all phosphide particles which can be seen by light microscopy in the etched structure at 1000x magnification, is between 0.8 and 1.5 ⁇ m.
  • the smallest particles still visible by light microscopy have a size of 0.5 ⁇ m.
  • the averaging therefore begins only with particles with a size of at least 0.5 ⁇ m. From the globular form it can be concluded that the phosphide particles are not fragments of originally larger particles.
  • the phosphide particles are compact and there are no cracks within the particles.
  • the density of the phosphide particles embedded in the matrix is inhomogeneous. There are first areas in which the matrix is almost free of phosphide particles, while second areas are rich in phosphide particles.
  • the manganese-containing phosphides hinder the recrystallization of the structure at elevated temperatures and thus improve the wear resistance of the material.
  • the manganese content in the material according to the invention is preferably 1.3 to 1.6% by weight.
  • the silicon content in the material according to the invention is preferably 0.3 up to 0.6% by weight.
  • the phosphorus content in the material according to the invention is preferably 0.03 to 0.08% by weight.
  • nickel can be added to the copper-zinc alloy. Together with phosphorus, nickel forms precipitates that increase the strength of the material.
  • the copper content of the copper-zinc alloy of the material according to the invention can be between 72 and 76% by weight, depending on the precise composition.
  • the copper-zinc alloy of the material according to the invention can contain unavoidable impurities.
  • impurities are understood to mean elements that are unavoidable and are present in the alloy in such a small proportion that they do not significantly influence the properties of the material.
  • the degree of deformation q is the decrease in the cross-sectional area of the formed material in relation to its initial cross-sectional area.
  • the material according to the invention enables degrees of cold forming of over 65%, even over 85%, without intermediate annealing. This allows inexpensive production of thin strips, which can be used, for example, as a semi-finished product for the production of rolled plain bearing bushes.
  • the material according to the invention shows a significant tempering effect.
  • the strength and hardness of the material can be increased further by annealing at 300 ° C for 1 to 3 hours. This enables the tensile strength R m from 740 MPa to at least 780 MPa, the yield strength R p0.2 from 650 MPa to at least 720 MPa and the hardness from 200 HB 2.5 / 62.5 to at least 230 HB 2.5 / 62. 5 can be raised.
  • the elongation at break in this state is approximately 5%.
  • the material can be subjected to a further heat treatment at temperatures above 300 ° C.
  • the elongation at break can be increased to 16% to 25% by heat treatment between 380 and 420 ° C.
  • the tensile strength of the material only decreases by 13 to 24% based on the initial value.
  • the material is therefore very temperature-resistant. In particular, its strength and hardness decrease less strongly with increasing temperature than is the case with similar materials that are known from the prior art. For example, at temperatures above 440 ° C the hardness is only 20% below the value at 25 ° C. This temperature resistance is particularly important for slide bearings in modern internal combustion engines.
  • Another advantage of the material according to the invention is its high wear resistance. This is due to the manganese-containing phosphides, which are embedded in the ductile matrix as small hard particles with a globular shape. On the other hand, the ductile matrix gives the material a high dynamic resilience.
  • Plain bearings made from this material have a coefficient of friction of less than 0.1.
  • the manganese-containing phosphides can be arranged in the manner of pearl strings.
  • the phosphide particles are arranged along virtual lines like pearls on a string.
  • the lines extend essentially longitudinally to the forming direction, but they are not completely straight. There may be slight curvatures and kinks. There are also deviations from the forming direction with regard to the alignment of the lines.
  • the lines along which the particles line up follow the flow behavior of the matrix structure.
  • the manganese-containing phosphides are arranged along the sliding lines and shear bands of the material. Adjacent phosphide particles are spaced apart with a few exceptions.
  • the phosphide particles arranged like pearl strings do not form a coherent structure such as a chain or a stem-like or needle-like conglomerate.
  • the characteristic arrangement of the manganese-containing phosphides results from the stretching of the structure during forming.
  • the phosphides that are interdendritically stored as a collection during the solidification process are essentially distributed in the forming direction.
  • the length of the individual pearl string-like arrangements of phosphide particles is 10 to 60 ⁇ m.
  • the length of the pearl cord-like arrangement is related to the degree of deformation that is applied during the deformation of the material. The greater the degree of deformation, the greater the length of the pearl cord-like arrangements. Since the individual phosphide particles are predominantly embedded in the matrix at a distance from neighboring particles, they are completely enclosed by the matrix structure and their anchoring in the matrix is particularly strong. This effectively prevents the phosphides from breaking out of the matrix.
  • the manganese-containing Phosphides can be arranged so that in at least 50% of all pearl-string-like arrangements of manganese-containing phosphides there is a section of 20 ⁇ m in length, in which 7 to 30 phosphide particles with a size of 0.5 to 2.0 ⁇ m are arranged.
  • the phosphide particles have a size distribution which is influenced, among other things, by the conditions which prevail when the melt solidifies.
  • the density with which the phosphide particles are arranged along a line correlates with the degree of deformation with which the material was formed. The stronger the deformation, the further the phosphide particles are distributed.
  • the arrangement of the phosphide particles described is created by appropriate process control in the manufacture of the material.
  • this arrangement of the manganese-containing phosphide particles typical of the material is, so to speak, the characteristic "fingerprint" that the manufacturing process leaves in the material.
  • the manganese-containing phosphide particles arranged in this way ensure that the material is particularly resistant to wear.
  • the good suitability of the material for sliding elements is consequently not a property that the alloy has solely on the basis of its composition, but only the combination of alloy composition and manufacturing process result in the inventive material.
  • the structure of the material according to the invention can advantageously have first regions that are recrystallized and second regions that are not recrystallized.
  • the structure is therefore incompletely recrystallized after the final annealing.
  • the melt solidifies, almost phosphide-free dendrites are formed.
  • the phosphides accumulate in the areas between the dendrites and are pushed together to form clusters as the dendrites grow.
  • the almost phosphide-free dendrites become almost phosphide-free, that is to say low-phosphide, areas in the reshaped structure, while the interdendritic accumulations of the phosphides become areas with a large phosphide density in the reshaped structure.
  • the low-phosphide areas recrystallize at a lower temperature than the high-phosphide areas because the manganese-containing phosphides inhibit recrystallization in the high-phosphide areas.
  • the low-phosphide, recrystallized areas are advantageous for the ductility of the material, the phosphide-rich, non-recrystallized areas are advantageous for its wear resistance. In other words, there are quasi two very different material components side by side, which complement each other in their properties.
  • the copper-zinc alloy of the material according to the invention can contain at least 0.03% by weight of Ni. Together with phosphorus, nickel forms nickel phosphides, which are embedded in the structure. The nickel phosphides are so small that they are barely visible under light microscopy. They fix the grain boundaries and thus increase the strength of the material.
  • the ratio of the proportions of nickel (in% by weight) and phosphorus (in% by weight) is particularly preferably between 0.8 and 1.2. With such an alloy composition, there are particularly favorable conditions for the simultaneous formation of manganese-containing phosphides and of nickel phosphides. The former contribute to the wear resistance of the material, the latter increase the strength of the material.
  • an alloy according to the composition described is first melted.
  • the alloy can also have a restricted composition, as specified above in the description of the material according to the invention.
  • the cast format cast in step b) is preferably slab or ribbon-shaped. After casting, the surface of the cast format can be milled. For homogenization, a heat treatment between 610 ° C and 800 ° C, preferably between 655 ° C and 695 ° C, is carried out on the cast format. The duration of this heat treatment is between 1 and 6 hours. In order to get from the cast format to the final dimension of the material, forming steps are carried out.
  • At least one sequence of cold forming steps is carried out without intermediate annealing with a total degree of forming of at least 50%.
  • the total degree of deformation is the accumulated cross-sectional decrease related to the initial cross-section over the sequence of the forming steps. It is also possible to achieve a degree of deformation of at least 50% in a single cold forming step.
  • the cold forming operations can preferably be rolling steps for producing a strip-like material.
  • the high degree of cold forming leads to the formation of a structure in which in an alpha-phase matrix inhomogeneously distributed, manganese-containing phosphides with a globular shape and a maximum size of 4 ⁇ m are embedded.
  • the total degree of deformation of the cold deformations carried out without intermediate annealing is preferably at least 65%.
  • the material is subjected to a heat treatment at a temperature of at least 280 ° C and at most 440 ° C with a duration of 1 to 3 hours. If the temperature is between 280 ° C and 320 ° C, the strength and hardness of the material increase above the initial values of the work-hardened material.
  • the temperature during the heat treatment is preferably at least 370 ° C. and at most 420 ° C. Such a final heat treatment reduces the strength and hardness of the material only slightly, while at the same time increasing the ductility of the material to a level that is favorable for dynamically loaded plain bearings.
  • a band-shaped casting format can be cast in process step b) and after process step c) and before process step d) at least one cold forming, which begins with the casting format and has a degree of deformation of at least 20%, and at least one further one Heat treatment take place.
  • the heat treatment is carried out at a temperature of at least 610 ° C. and at most 800 ° C., preferably between 655 ° C. and 695 ° C., with a duration of 1 to 6 hours.
  • a band-shaped casting format is understood to mean a casting format that has a thickness of at most 20 mm, preferably at most 15 mm.
  • the casting format can be cold formed immediately after the homogenization annealing.
  • the degree of deformation is at least 20%, preferably at least 30%.
  • This first cold forming follows another heat treatment as intermediate annealing.
  • this heat treatment can optionally be used for further cold forming with a degree of deformation of at least 30% and a further heat treatment.
  • the last stage of cold forming is then carried out as described in process step d) with a degree of deformation of at least 50%, preferably at least 65%.
  • a slab or plate-shaped casting format can be cast in process step b).
  • the heat treatment in process step c) is followed by hot forming at a temperature of at least 720 ° C. and at most 830 ° C.
  • the degree of deformation during hot forming is at least 60%. It is chosen so that the dimension of the intermediate product after hot forming is as small as possible, so that the final dimension of the material can be achieved by a sequence of cold forming.
  • Another aspect of the invention includes a sliding member from one above described material according to the invention. Because of its properties, the material according to the invention is very well suited for use as a material for sliding elements.
  • the sliding element can preferably be produced from a band-shaped material. An example of this are rolled bushings for plain bearings.
  • Another example are half shells for the storage of crankshafts in internal combustion engines. Such half-shells can be made of a solid material of the material according to the invention or the material according to the invention is applied as a thin metal layer on a steel back. In the latter case, the thickness of the metal layer is 0.3 to 0.8 mm.
  • the excellent cold forming capacity of the material according to the invention enables the cost-effective production of such thin strips.
  • Table 1 shows the chemical composition of particularly preferred samples in% by weight. The two samples differ essentially in the zinc content and consequently also in the copper content. Sample 1 has about 23 wt% Zn, Sample 2 has about 25 wt% Zn. A sample made from the alloy CuZn31Si1 is used as a comparison sample. This alloy is known as an alloy for sliding elements from the prior art. Table 1: Composition of the samples in% by weight Cu Zn Mn Si P Fe Ni rest Sample 1 75.12 22.92 1.38 0.42 0.05 0.01 0.08 0.02 Sample 2 73.18 24.88 1.36 0.40 0.07 0.01 0.08 0.02
  • the alloys were cast into strips with the thickness of 13 mm using the band casting process. After milling the surface and homogenizing annealing at 690 ° C / 3 hours, a three-stage cold rolling was carried out with degrees of deformation of 25% in the first stage, 35% in the second stage and 65% in the third stage to the final dimension of 2 mm thickness. Between the individual forming steps, the alloys were annealed at 690 ° C for 3 hours. After the last cold working, a heat treatment was carried out on each alloy at different temperatures between 300 ° C and 460 ° C in order to determine the temperature resistance of the materials. The result of this investigation is documented in Table 2.
  • the yield strength R p0.2 and the tensile strength R m in MPa are shown after a two-hour heat treatment at the temperature indicated in the first column.
  • the values at 25 ° C are the strength values of the material immediately after the last cold forming, i.e. without a final one Heat treatment.
  • Table 2 Strength values after the final heat treatment.
  • the examples marked with (*) are comparative examples with regard to the inventive production process.
  • Sample 1 Sample 2 Comparative sample CuZn23Mn1.4Si0.4NiP CuZn25Mn1.4Si0.4NiP CuZn31Si1 T in ° C R p0.2 in MPa R m in MPa R p0.2 in MPa R m in MPa R p0.2 in MPa R m in MPa R p0.2 in MPa R m in MPa 25 (*) 654 740 654 748 690 800 300 714 779 735 796 730 800 340 666 738 678 747 418 588 380 566 651 569 652 322 523 420 459 571 460 570 290 501 460 (*) 385 522 398 530 250 473
  • the elongation at break of the two samples according to the invention is approximately 4% in the cold-rolled state and after the heat treatment at 300 ° C.
  • Annealing at 340 ° C increases it to approximately 7%.
  • a further increase in the annealing temperature by 40 ° C in each case leads to a further increase in the elongation at break by 10 percentage points each, so that after annealing at 460 ° C an elongation at break of almost 32% is achieved.
  • Fig. 3 shows a sketch of the structure 1 of the sample 1 according to the invention after a heat treatment at 420 ° C.
  • Fig. 4 shows a sketch of the structure 1 of the sample 2 according to the invention after a heat treatment at 420 ° C.
  • the sketches were created from light microscopic images of sections of the respective structure.
  • the manganese-containing phosphides can be seen as globular particles 2 in both figures.
  • the phosphides are distributed inhomogeneously.
  • First regions 31 can be seen in the structure which are low in phosphide.
  • the structure is recrystallized in these regions 31.
  • second regions 32 can be seen in the structure which are rich in phosphide. In these areas 32, the structure is not recrystallized.
  • the phosphide particles 2 are arranged in the manner of pearl strings, as indicated by reference number 21. Especially in Fig. 3 it becomes clear that the phosphide particles 2 are arranged along virtual lines which essentially extend in the rolling direction. Also in Fig. 4 arrange most of the phosphide particles 2 along lines that are oriented essentially in the rolling direction. In addition, in Fig. 4 however, a few phosphide particles 2 are visible, the arrangement 21 of which differs significantly from the rolling direction. In the Figures 3 and 4 corresponds to the rolling direction of the horizontal.
  • Fig. 5 shows schematically the sequence of an inventive manufacturing process in the event that a band-shaped casting format is cast after melting the alloy.
  • a degree of deformation of at least 30% may be provided. This preferably follows the intermediate annealing after the first cold rolling stage. Before the last cold rolling stage with a degree of deformation of at least 50%, intermediate annealing is carried out again.
  • Fig. 6 shows schematically the sequence of an inventive manufacturing process in the event that a slab or plate-shaped casting format is cast after melting the alloy by means of continuous casting.
  • only one cold rolling stage is shown after hot rolling.
  • a further cold rolling stage with a degree of deformation of at least 30% can be provided. This then follows the hot rolling.
  • An intermediate annealing is then carried out before the last cold rolling stage with a degree of deformation of at least 50%.

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  • Engineering & Computer Science (AREA)
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Claims (9)

  1. Matériau à base d'alliage de zinc/cuivre ayant la composition suivante, en % en poids : Zn : 21 à 27 %, Si : 0,2 à 0,8 %, Mn : 1,1 à 1,9 %, P : 0,005 à 0,2 %, sélectivement Ni : jusqu'à 0,2 % au maximum,
    le reste de Cu et d'impuretés inévitables,
    caractérisé en ce que
    le matériau comporte une structure (1) ayant une matrice à phase alpha, dans laquelle sont incrustés des phosphures contenant du manganèse, les phosphures contenant du manganèse étant conçus sous la forme de particules de phosphures (2) de forme globulaire et au moins 90 % de ces particules de phosphures (2) comportant une taille de 2,0 µm au maximum.
  2. Matériau selon la revendication 1, caractérisé en ce qu'au moins une partie des phosphures contenant du manganèse est disposée à la manière d'un chapelet.
  3. Matériau selon la revendication 2, caractérisé en ce que les phosphures de manganèse sont disposés de sorte que, dans au moins 50 % de tous les ensembles (21) de type chapelet de phosphures contenant du manganèse, il existe une partie de tronçon de 20 µm de longueur dans laquelle sont disposées 7 à 30 particules de phosphores (2) d'une taille de 0,5 à 2,0 µm.
  4. Matériau selon l'une des revendications précédentes, caractérisé en ce que la structure comprend des premières régions (31) qui sont recristallisées et des deuxièmes régions (32) qui ne sont pas recristallisées.
  5. Matériau selon l'une des revendications précédentes, caractérisé en ce que l'alliage de zinc/cuivre comprend au moins 0,03 % en poids de Ni.
  6. Procédé de fabrication d'un matériau selon l'une des revendications 1 à 5,
    le procédé comprenant les étapes suivantes dans l'ordre cité :
    a) fusion de l'alliage
    b) coulée d'une forme de coulée
    c) traitement à chaud de la forme de coulée à une température d'au moins 610°C et d'au maximum 800°C pendant une durée de 1 à 6 heures,
    d) déformation à froid à un degré de déformation total d'au moins 50 %
    e) traitement à chaud à une température d'au moins 280°C et d'au maximum 440°C pendant une durée de 1 à 3 heures.
  7. Procédé selon la revendication 6, caractérisé en ce que, à l'étape de procédé b), une forme de coulée en bande est coulée et en ce que, après l'étape de procédé c) et avant l'étape de procédé d), au moins une déformation à froid qui commence avec la forme de coulée et présente un degré de déformation d'au moins 20 % et au moins un autre traitement thermique sont effectués, le traitement thermique étant réalisé à une température d'au moins 610°C et d'au maximum 800°C pendant une durée de 1 à 6 heures.
  8. Procédé selon la revendication 6, caractérisé en ce que, à l'étape de procédé b), une forme de coulée en brame est coulée et en ce qu'une déformation à chaud s'adjoint au traitement thermique à l'étape de procédé c) à une température d'au moins 720°C et d'au maximum 830°C.
  9. Élément coulissant constitué d'un matériau selon l'une des revendications 1 à 5.
EP17001112.6A 2016-07-21 2017-06-29 Matière à base d'alliage de zinc/cuivre, procédé de fabrication d'une telle matière et élément coulissant constitué d'une telle matière Active EP3272888B1 (fr)

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DE102016008928.8A DE102016008928A1 (de) 2016-07-21 2016-07-21 Werkstoff aus einer Kupfer-Zink-Legierung, Verfahren zur Herstellung eines solchen Werkstoffs und Gleitelement aus einem solchen Werkstoff

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EP3272888B1 true EP3272888B1 (fr) 2020-03-04

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EP3992318A1 (fr) 2020-10-29 2022-05-04 Otto Fuchs - Kommanditgesellschaft - Produit d'alliage fabriqué à partir d'alliage de cuivre-zinc sans plomb et son procédé de fabrication
EP3992319A1 (fr) 2020-10-29 2022-05-04 Otto Fuchs - Kommanditgesellschaft - Produit d'alliage fabriqué à partir d'alliage de cuivre-zinc sans plomb et son procédé de fabrication
DE102022122831A1 (de) 2022-09-08 2024-03-14 Diehl Brass Solutions Stiftung & Co. Kg Bleifreie Messinglegierung und daraus hergestelltes Maschinenelement
DE102022122830A1 (de) 2022-09-08 2024-03-14 Diehl Brass Solutions Stiftung & Co. Kg Bleifreie Messinglegierung und daraus hergestelltes Lagerbauteil

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DE3626435A1 (de) 1986-08-05 1988-03-10 Diehl Gmbh & Co Kupfer-zink-legierung
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