EP1171643B1 - Magnesiumlegierungen hoher duktilität, verfahren zu deren herstellung und deren verwendung - Google Patents
Magnesiumlegierungen hoher duktilität, verfahren zu deren herstellung und deren verwendung Download PDFInfo
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- EP1171643B1 EP1171643B1 EP00920534A EP00920534A EP1171643B1 EP 1171643 B1 EP1171643 B1 EP 1171643B1 EP 00920534 A EP00920534 A EP 00920534A EP 00920534 A EP00920534 A EP 00920534A EP 1171643 B1 EP1171643 B1 EP 1171643B1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Definitions
- the invention relates to magnesium alloys of high ductility, processes for their Production and their use, in particular those containing calcium and / or strontium Magnesium alloys.
- magnesium alloys in the range from 1.2 to 1.9 g / cm 3 are of great interest as metallic construction materials, above all for vehicle and aircraft construction. In the future, they will be used more and more for the lightweight construction of motor vehicles and airplanes, in order to be able to compensate for the weight of additional elements due to increasing comfort and safety standards, especially in new low-emission automobiles. They are also of interest for transportable devices or systems that are particularly light-weight for other reasons.
- the lightweight construction enables the construction of energy-saving vehicles and planes, such as the 3-liter motor vehicle, to a particular extent.
- the cold formability of the commercially available magnesium alloys is due to the hexagonal crystal structure and the associated low ductility limited. Polycrystalline magnesium and most magnesium alloys behave becomes brittle at room temperature. For a number of applications or for certain Manufacturing process of semi-finished products from magnesium alloys is in addition to good ones mechanical properties such as high tensile strength require ductile behavior. On improved forming, energy absorption and deformation behavior requires a higher one Ductility and possibly also higher strength and toughness. For this are To develop magnesium alloys with these properties or their To further develop manufacturing processes because many material variants match the manufacturing condition have widely varying material properties.
- Ductility is the ability of a material to undergo a permanent change in shape, which, in the uniaxial state according to the stress-strain diagram, is ideally without any elastic component. This property is limited by the occurrence of the break. In general, the permanent elongation achieved in the tensile test up to fracture is considered ductility. The degree of ductility can also be seen as the constriction of fracture, impact work and notched impact work, each with a slightly different statement. These properties can be determined in accordance with EN 10 002, Part 1, or in accordance with DIN 50115 and 50116.
- a highly plastic material is called ductile.
- the elasticity denotes the elastic part of the stress-strain diagram according to Hook's law, where with ideal linear-elastic relationships no permanent change in shape occurs.
- the impact work is above all a measure of the energy consumption of a semi-finished product and for plastic behavior, i.e. for deformability and rate of deformation.
- a high impact work is therefore essential for the use of deformation elements such as Crash elements, impact absorbers, impact shields and impact carriers.
- the impact work - measured on notched samples - is, among other things due to higher absolute values for Magnesium alloys are more meaningful than the impact energy and affects one largely uniaxial load.
- the impact work, which is always on notched samples is determined also indicates the susceptibility of a material to triaxial failure Burden. Their informative value is particularly low if the execution of the Notch significantly affects the values of the impact energy.
- the values listed below measured on samples in a particular The state of manufacture therefore reflects the current material properties. she provide an indication of the forming behavior that previously occurred during the forming process was. In this state it is a conclusion about the characteristics and behavior of a person Semi-finished product or even a component with this semi-finished product, which may be further refined later use possible. Furthermore, there is a conclusion about the material properties formed alloys possible, e.g. by bending, pressing, pressure rolling, Stretch drawing, deep drawing, hydroforming or roll forming processed semi-finished products are to be shaped. Because the change in Material properties from cast to extruded condition similar to that Change in material properties from cast to forged, rolled or a similar reshaped state is therefore also an inference to one other forming condition possible.
- the elastic is usually used Properties (rigidity) lifted, unless it is e.g. in the event of an accident
- Properties rigidity
- These properties are typically for use on the respective ambient temperature, in extreme cases in the range from -40 ° C to +90 ° C individual points in the vehicle or plane, however, to the locally lower or higher Turn off temperatures.
- the load state is usually multi-axis. The Conclusion from uniaxial to multiaxial load conditions is all the more possible, ever more of an isotropic structure.
- the manufacture is particularly suitable by die casting or extrusion, forging and / or rolling.
- requirement for the use of semi-finished products made of magnesium alloys or from them or with them Components manufactured in automobiles can meet certain property profiles depending after application such as for deformation elements, seat and door frames one Tensile strength of the light material of at least 100 MPa, preferably at least 130 MPa, together with an elongation at break measured at room temperature of at least 10%, preferably at least 15%.
- higher strength values and higher ductility are also one Relief and partly also a prerequisite for the forming of cast blanks or for the further forming of already formed blanks or semi-finished products.
- the higher the higher these properties are in the cast or powder-compacted state are usually also in the deformed state.
- a higher ductility can do that Forming or reshaping, especially extrusion, easier. Therefore an elongation at break of at least 10% is also for the following ones Manufacturing steps for elements made of magnesium alloys helpful. Therefore, from tensile strength of at least 150 MPa measured for several reasons Room temperature, preferably at least 180 MPa, or an elongation at break of at least 18%, preferably at least 20%, particularly preferably of at least 25%, recommended.
- the elongation at break is usually commercial Common magnesium alloys measured at room temperature less than 12%.
- alloys based on Mg-Al-Zn such as AZ31, AZ61 and AZ80, based on Mg-Zn-Zr such as ZK40 and ZK60 or based on Mg-Mn such as M1.
- Neite describes in Materials Science and Technology, Vol. 8, ED .: K. H. Matucha, 199 ?, in Chapter 4.3.2 Manufacturing processes and mechanical properties of typical Magnesium alloys.
- extruded magnesium alloys based on AZ in shape of bars especially increasing with the aluminum content - tensile strengths of 204 up to 340 MPa and elongations at break of 9 to 17% indicated by an artificial Aging could be increased up to a tensile strength of 380 MPa, but the Elongation at break decreased to 6 to 8%.
- Alloy M1 typically had a tensile strength in the extruded state 225 MPa and an elongation at break of 12%.
- For the ZE10 alloy in rolled and annealed dynamically recrystallized state will be 215 to 230 MPa tensile strength and 18 to 23% elongation at break specified.
- GB 2,296,256 A gives values of elongation at break of 17.2 and 18% for alloys MgAl0.5-1.1Mn0.10-0.12, which, however, had a rather low flexural strength.
- WO 89/11552 describes so-called super-plastic moldings Magnesium alloys based on ZnALSE or AlMn. The alloys were over spontaneous quenching of melt droplets obtained.
- the sample 5 in Table 1 said composition based on has contents of Al of 11% by weight and of Mn of 1 % By weight. It also only shows an elongation at break of 3.5%, which is comparatively low ductility, i.e. high brittleness, suggests.
- the highest Elongation at room temperature in all other examples is 18% and was for a magnesium alloy with the composition MgZn2Al15Nd1 was determined.
- EP-A-0 414 620 also teaches magnesium alloys, the Al, Zn, Mn, Ca or / and SE contain.
- the alloys based on AlZn have significantly different compositions than AZ 31.
- EP-A-0 791 662 provides information on magnesium alloys which contain Al, Mn, Ca, SE and possibly Zn contain.
- the alloys of the examples and comparative examples have one Elongation at break in the range from 0.3 to 6.9%.
- No. 5,681,403 teaches magnesium alloys based on AlMn, which may contain SE, Ca, Cu or / and Zn contain.
- the diagrams show an elongation at break of less than for the alloys 12% off.
- US 4,675,157 protects magnesium alloys with up to 11% Al, up to 4% Zn, from 0.5 to 4% of elements selected from Si, Ge, Co, Ti and Sb, the sum of Al and Zn Is 2 to 13% and a mixed crystal phase occurs in a certain way.
- This Magnesium alloys were made by quenching melt droplets. The Elongation at break of various examples and comparative examples varies between 0.8 and 11%.
- JP-A-09/316586 published on December 9, 1997 teaches wear and heat resistant Magnesium alloys with up to 4% SE, up to 5% Si and possibly ⁇ 1% Mn, ⁇ 1% Zr, ⁇ 4% Ca, ⁇ 10% Al, ⁇ 5% Zn and ⁇ 5% Ag. These alloys are characterized by high tensile strength Room temperature and at 200 ° C, but not optimized for high ductility.
- EP-A-0 799 901 discloses heat-resistant magnesium alloys with good creep properties based on 2 to 6% Al and 0.5 to 4% Ca with a Ca: Al ratio of ⁇ 0.8. However, the elongation at break of these samples should only be 0.8 to 7%.
- US 5,071,474 carries out a process for forging magnesium alloys on the Basis of quenched melt droplets, the alloys in addition to Al and Zn Mn, Ce, Nd, Pr and Y can contain.
- the elongation at break of the examples and Comparative examples fluctuate between 0 and 11%.
- GB 831,638 describes the mechanical properties of magnesium alloys Basis of Th and Mn and, if applicable, of Zn and / or SE disclosed. The elongation at break of the Examples are only 3.5 and 4%.
- JP-A-62/00348 published on July 19, 1994 teaches high-strength heat-resistant Magnesium alloys with up to 5% lanthanides and possibly ⁇ 5% Ca, ⁇ 1.5% Mn, ⁇ 1.5 % Zr or / and contents of Ag, Al, Sc, Sr, Y or Zn.
- the alloys are apparently only on Tensile strength optimized at room temperature and at elevated temperature.
- DE-A-42 08 504 protects machine components from a containing 2 to 8% SE Magnesium alloy, which has a high proportion of samarium and a good creep and Fatigue strength and good tensile strength at elevated temperature should. The specimens mentioned were neither reshaped nor deformed.
- US 3,024,108 discloses magnesium alloys based on ZnMn, the SE and / or Th contain.
- the mechanical properties of the rolled samples are each for the Direction of rolling and specified transversely thereto, with averaging over all directions Elongation at break of approx. 9 to 13%.
- A. Raman describes in Uses of Rare Earth Metals and Alloys in Metallurgy, Z. Metallischen 68, 1977, 3, 163 - 172, SE-containing magnesium alloys. Even if occasionally by one Increase in ductility due to the addition of at least one rare earth element the only explicitly stated values of the elongation at break are between 2 and 8% or below Reference to JP-A-72/07973 (March 1972) for La-containing magnesium alloys at about 25%.
- T. Mohri et al. describe in Microstructure and mechanical properties of a Mg-4Y-3RE alloy processed by thermo-mechanical treatment in Materials Science and Engineering A257, 1998, 287-294, magnesium alloys with 4% Y, 0.41% Zr, 0.15% Li and 3.2% SE, of which 2.2% are Nd.
- the extruded samples showed one Elongation at room temperature of about 13% or about 20%.
- WO-A-96/25529 describes magnesium alloys with a content of 2 to 6% by weight aluminum and with 0.1 to 0.8% by weight calcium. In addition to other components, the alloys can also contain up to about 0.5% by weight of manganese. These are cast alloys that are made from a magnesium-aluminum alloy and a calcium-magnesium alloy. The alloys contain the intermetallic compound Al 2 Ca and have an increased creep resistance. Forming after casting is not intended.
- Japanese patent abstract JP-A-9271919 describes heat-resistant Magnesium alloys with a content of 2 to 10 wt .-% aluminum and 1 to 10 % By weight calcium, which in addition to other elements also contains less than 2% May contain manganese.
- the alloys are formed from metal grains or pellets by injection molding at the liquidus temperature or by molding in the semi-melted State from a mixture between solid phase and liquid phase. It will be one Elongation at break of 14% and a tensile strength of 200 MPa are given for the products.
- the problem is solved with a magnesium alloy, the additives or traces of Cd less than 1.8% by weight and the traces of up to 0.1% by weight of Cu, up to 0.05% by weight of Fe and can contain up to 0.005% by weight of Ni and 0.2 to 4% by weight of Mn and 0.2 to 6 Wt .-% Ca or / and 0.1 to 6 wt .-% Sr, the remaining contents of Magnesium alloy consist of magnesium and unavoidable impurities, their compressive strength is at least 300 MPa, their impact energy measured notched specimens at least 20 J and their elongation at break measured on tensile specimens is at least 15% and it is made from high purity alloys Extrusion or forging with a degree of deformation of at least 1.5 under dynamic recrystallization and with the formation of a fine-grained structure with a average grain size of at most 25 ⁇ m.
- the task is also solved with a corresponding magnesium alloy, the one Alloy based on AM (aluminum / manganese) or MA (manganese / aluminum) which is 0.5 to 10 wt .-% Al and 0.1 to 4 wt .-% Mn and 0.1 to 6 wt .-% Ca or / and Sr contains, with the remaining contents of the magnesium alloy of magnesium and unavoidable impurities, with a compressive strength of at least 320 MPa, their impact energy measured on unslotted specimens at least 40 J and their Elongation at break measured on tensile specimens is at least 16% and where it is produced is made of high purity alloys by extrusion or forging with one Degree of deformation of at least 1.5 with dynamic recrystallization and with training a fine-grained structure with an average grain size of at most 25 ⁇ m.
- AM aluminum / manganese
- MA manganesese / aluminum
- These magnesium alloys preferably have a plastic portion of the stress determined in the tensile test according to the stress-strain diagram from the difference of Tensile stress and yield stress of at least 40 MPa, particularly preferably of at least 60 MPa, very particularly preferably from 80 to 120 MPa.
- All of these magnesium alloys can include be made by extrusion. However, there are other forming processes instead of or together with the Extrusion is an advantage, especially forging. They are preferably formed, in particular extruded and / or forged, and have a fine-grained, dynamic recrystallized structure, in particular with an average grain size of not more than 20 ⁇ m, and a precipitation phase content of not more than 5% by volume is preferred of not more than 2% by volume. You can use a structure with a medium Grain size of at most 25 microns, especially preferably of at most 15 ⁇ m, very particularly preferably of at most 8 ⁇ m. The average grain size is obtained on bevels with conventional stereometric methods certainly.
- the chemical composition of the magnesium alloys varied only slightly or almost not at all from the composition of the melt to the composition before or after extrusion to the composition of the semi-finished product made from it.
- the invention further relates to a method for producing such Magnesium alloy, in which a shaped or compacted molded body is produced and is dynamically recrystallized by shaping and / or shaping.
- the molded body can therefore have been produced via the melt or / and via powder.
- At the Forming especially during extrusion, results in a degree of forming of at least 1.5 chosen, preferably from at least 2 or even from at least 3, to be dynamic To achieve recrystallization and a fine-grained structure.
- the degree of deformation characterizes the degree of cross-sectional reduction when reshaping and is considered more natural Logarithm of the ratio of the initial cross section to the cross section according to the Forming specified.
- the aim is to create a structure that is as fine-grained as possible Magnesium alloys require high ductility.
- the reshaped and / or deformed shaped body can then be a semi-finished product and / or a component made from or with this semi-finished product are processed or processed.
- the semi-finished product or the component made from or with the semi-finished product can directed, e.g. by bending, pressing, pressure rolling, stretch drawing, deep drawing, Internal high pressure forming or roll forming further deformed, e.g. by cutting, drilling, Milling, grinding, lapping, polishing, machining, joining and / or e.g. by etching, pickling, Painting or other coating are surface treated.
- the semi-finished product or the component made therefrom or with it can pass through at least one low-heat joining process such as Gluing, riveting, plugging, pressing, Pressing in, clinching, folding, shrinking or screwing and / or at least one heat-generating joining process such as Composite casting, composite forging, Composite extrusion, composite rolling, soldering or welding, in particular Beam welding or fusion welding, with a similar or different type Semi-finished product or component can be connected.
- the different semi-finished product or component can likewise essentially of a magnesium alloy or of another alloy or also consist of a non-metallic material. It can be the same or one have a different geometry than the semi-finished product or component according to the invention.
- the Joining methods can serve in particular to create a housing from several elements, to manufacture an apparatus, a system, a profile construction and / or a cladding.
- semi-finished products are understood to be shaped articles which have not yet are completed and ready for use for their respective application.
- the molded articles are suitable for the intended purpose designated.
- both terms flow smoothly into one another, since it is the same shaped body for one purpose around a semi-finished product, but for the other can already be a component.
- Simplification does not strictly differentiate between semi-finished products and components throughout the text or both mentioned at the same time or only spoken of magnesium alloy, although both can be meant.
- the semifinished products made of magnesium alloys according to the invention or those thereof or therewith manufactured components can be used as rims, gear housings, Steering wheel skeletons, wishbones, frame elements, elements of vehicle cells or Vehicle outer skins, vehicle cell, vehicle outer skin, cockpit support, cockpit skin, Housing, floor elements, floors, lids, tank elements, tank flaps, brackets, Supports, beams, angles, hollow profiles, pipes, deformation elements, crash elements, Crash absorbers, impact absorbers, impact shields, impact carriers, small parts such as Gears than Impellers and other types of wheels, as welded profile constructions, for the Vehicle body, for seat, window and / or door frames, as semi-finished products, components or Connections on or in the automobile or airplane.
- high-purity alloys are alloyed with additives.
- the high-purity alloys can absorb small amounts of contaminants from the crucible during the melting process.
- the alloys can be melted, for example, in a nickel and chromium-free steel crucible under a protective gas atmosphere, for example Ar or / and SF 6 .
- a protective gas atmosphere for example Ar or / and SF 6 .
- the powder-metallurgical production of green compacts possibly with subsequent annealing, can also be used.
- the process steps are known in principle, but require a different modification or optimization depending on the alloy.
- a bolt with a very large diameter can be cast are then turned into round bolts using a high-performance extrusion press can be pressed with a diameter that corresponds to the recipient diameter.
- the segregation is reduced by the thermomechanical treatment.
- the cast bolts can first be subjected to heat treatment depending on the Alloy composition in e.g. 350 ° C homogenized in the range from 6 h to 12 h to eliminate segregations in the structure, some of which heterogeneous structure too improve and increase the pressability. Then the homogenized bolts machined to the required dimensions.
- the extrusion of the magnesium alloys can be carried out in the same extrusion plants take place, which are used for the extrusion of aluminum alloys, both via direct as well as indirect extrusion. Only with the Tool design (die), the deformation behavior must be specifically taken into account. There are sharp-edged inlets, such as those used in aluminum alloys Avoid magnesium alloys, otherwise there is a risk of surface cracks. In many cases e.g. for matrices of round profiles an entry angle of approx. 50 ° for Magnesium alloys used.
- the most important parameter besides the extrusion temperature is the extrusion speed, because they have the properties and surface quality of the Extruded profiles significantly influenced.
- a high pressure also means a high one Extrusion speed, which is aimed for economic reasons.
- a high Extrusion speed is usually with an even better surface quality connected.
- the pressability of the magnesium alloys is comparable to that heavy-duty aluminum alloys.
- a high extrusion speed is true Desired from an economic point of view, but is not the case with magnesium alloys always feasible.
- Magnesium alloys usually need the parameters for extrusion in detail be worked out because there is a huge potential for optimization.
- the extrusion is advantageously followed by a heat treatment.
- This Heat treatment is usually not of great interest since the Alloys according to the invention are usually not strong through this heat treatment be improved.
- the semi-finished products can be straightened, further deformed, processed, joined or / and surface treated.
- semi-finished products can be improved, components are also manufactured.
- a Al, E indicates at least one of the alloy designations used Rare earth element SE, whereby La and Y are also classified as rare earth elements, M or MN Mn, S Si and Z Zn - usually with content in% by weight, insofar as nothing other is noted.
- alloy information such as AZ31 are only of the order of magnitude as usual for the respective alloy Levels indicated that can vary to a relatively wide extent as is customary in the industry. additionally can in the starting alloy used in the examples and the so produced modified alloys based on AZ have a low manganese content. All Examples showed traces of less than 0.1 wt% Cd, less than 0.05 wt% Cu, less than 0.04 wt% Fe and less than 0.003 wt% Ni.
- the alloys were made as high-purity, commercially available alloys or usually from high-purity starting alloys such as, for example, AM, AS or AZ alloys or by adding high-purity magnesium HP-Mg, a rare earth element-containing pre-alloy with a ratio of Nd to other rare earths, including yttrium of 0.92, a zirconium-containing master alloy, alloyed with calcium or strontium.
- the standard alloys contained an Mn content of up to about 0.2% by weight.
- the alloys were melted in a steel crucible under the protective gas atmosphere of an Ar-SF 6 mixture. The melt was kept and poured at a temperature in the range from 780 to 820 ° C, once at 750 ° C.
- the blanks required for the subsequent extrusion were cast in a cylindrical steel mold with machining allowance.
- the mold had a diameter of 90 or 110 mm and a mold temperature in the range from 80 to 320 ° C.
- the element contents achieved were checked spectroscopically. With all alloys, care was taken to ensure that the structure of the cast body is as homogeneous and free of impurities as possible, as this can have a sensitive effect on ductility. All alloys could be melted, poured off and processed into bolts without any problems.
- the castings were then homogenized at 350 ° C. for 12 h.
- Bolts usually made 70 mm in diameter and 120 mm in length; with 6 samples for the AZ31Ca0.3 alloy, however, a diameter of 74 mm was chosen.
- the homogenized and twisted bolts were then well prepared for extrusion.
- the bolts were then brought to the respective extrusion temperature in the range from 200 to Heated to 450 ° C, warmed for 60 to 150 minutes and in a 400 t horizontal press extruded.
- the temperature of the bolt is therefore the temperature that the bolt at Has entry into the extrusion press.
- extrusion pressures that occurred varied depending on the alloy used and set parameters in a wide range.
- the final pressures reached were for Alloys without Ca, SE or Zr addition in the range around 10 ⁇ 2 MPa Extrusion temperatures greater than 300 ° C and in the case of alloys containing Ca, SE or Zr up to 4 MPa higher.
- Cause for the higher extrusion pressures and thus for the increased Resistance to deformation of magnesium alloys with Ca, SE or Zr addition is a higher proportion of stable precipitates than with magnesium alloys without it Additive.
- extrusion pressures were generally somewhat higher determined.
- the strength values determined on the cast and extruded samples were much higher than expected.
- the deformability was also surprising of these alloys very high. It was also surprising that the The material properties of the modified alloys are surprisingly little dependent varied from the extrusion conditions, which is advantageous for production. Furthermore was it is surprising that the impact energy of the ZE10 alloy was so high.
- the measurement results of the Brinell hardness determinations did not allow any special ones Statement.
- the Brinell hardness of the extruded samples was found to be 7 to 22% greater than the cast samples. The hardness increased with the aluminum content.
- extruded alloy AM20Ca0.2 and AM50Ca0.5 compared to extruded alloy AM20 or AM50 higher in compression and impact tests mechanical properties with a comparably high ductility, with the lower Alloys containing aluminum also in tensile tests. Because the examined extruded samples that have not yet had the best structural homogeneity can be found here even better properties can be achieved.
- the extruded alloy AZ31Ca0.3 or AS41 Ca0.4 the results of the compressive strength were higher than for the extruded AZ31 or AS41 alloy. With these Ca-modified alloys the highest determined compressive strengths occurred.
- the mean grain sizes with the extrusion temperature e.g.
- the alloy was AM50Ca0.5 the average grain size in the range of 4.5 to 9 ⁇ m and therefore due to the addition of Ca. lower, the mean grain sizes proportional to the extrusion temperature also increased slightly.
- the extruded alloy MN150Ca0.2 showed a very strong increase in most mechanical properties compared to the extruded alloy MN150. Adding Zr0.7 to the extruded MN150 base alloy had little effect out.
- the properties of the ZE10 alloy become essential from the rare earths influenced and can vary in the variation of rare earth elements including lanthanum and Yttrium and their contents can be further optimized. Occurred with the alloy ZE10 average grain sizes in the range of 6.5 to 13 microns, which again with the Extrusion temperature tend to increase; however, this alloy also warmed up increasing extrusion speed relatively strong, which at higher Extrusion speed also led to somewhat larger average grain sizes.
- magnesium alloys in particular were found to be suitable, in which a Ca content in the range of about 0.05 to 0.2% by weight Ca was added to each 1% by weight Al present in order to separate out the Al 2 Ca. Phase.
- the Al 2 Ca phase proved to be more temperature stable than the Mg 17 Al 12 phase and was therefore able to hinder the grain growth during extrusion better than the Mg 17 Al 12 phase.
- the Mg 2 Si precipitation phase also prevented grain growth during extrusion better than the Mg 17 Al 12 phase.
- the addition of Ca to Al-free alloys led to the formation of Mg 2 Ca or Ca 5 Zn 2 precipitates.
- phase Mg 17 Al 12 which normally appears in magnesium alloys containing Al, does cause a somewhat increased strength, but is also responsible for a lower elongation at break. Since this phase is even more brittle than the pure hexagonal Mg phase, higher levels of Mg 17 Al 12 should be avoided.
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Description
Ergebnisse der Vorversuche zur Ermittlung der Strangpreßparameter mit der Legierung AZ31 bei einer Strangpreßtemperatur von 400 °C, einem Matrizendurchmesser von 16 mm, einem Rezipientendurchmesser von 74 mm und einem Verpressungsverhältnis von 1 : 21 | |||||
Preßgeschwindigkeit | Mittlerer Korndurchmesser | Zugfestigkeit Rm | Streckgrenze RP0,2 | Bruchdehnung A | Brucheinschnürung |
m/min | µm | MPa | MPa | % | % |
4 | 8,8 | 277 | 134 | 12,5 | 29,2 |
5 | 9,3 | 281 | 141 | 12,7 | 29,3 |
8,4 | 9,0 | 282 | 137 | 15,6 | 35,2 |
Einfluß des Verpressungsverhältnisses auf die mittleren Korngrößen und die mechanischen Eigenschaften aus dem Zugversuch bei einer Strangpreßtemperatur von 400 °C bei den Vorversuchen zum Ermitteln der Strangpreßparameter | |||||||
Matrizendurchmesser | Preßverhältnis | Preßgeschwindigkeit | mittlerer Korndurchmesser | Zugfestigkeit Rm | Streckgrenze RP0,2 | Bruchdehnung A | Brucheinschnürung |
mm | m/min | µm | MPa | MPa | % | % | |
16 | 1 : 21 | 4 | 8,8 | 277 | 134 | 12,5 | 29,2 |
12 | 1 : 38 | 5 | 9,3 | 281 | 141 | 12,7 | 29,3 |
Mittelwerte der Meßergebnisse der mechanischen Versuche an verschiedenen Proben der Ca-. Sr-, SE- und Zr-haltigen Magnesiumlegierungen und deren Ausgangslegierungen: | ||||||||||
Probe | Legierung | Zugversuch | Druckversuch | Schlagvers. | ||||||
BE % | Rm MPa | RP0,2 MPa | A % | RDm MPa | Rstauch MPa | AD % | CG J | CUG J | ||
VB 10 | AM20 extr. | 32,5 | 274 | 230 | 17,9 | 325 | 129 | 7,8 | 8,6 | 46 |
B 11 | AM20Ca0.2 extr. | 30,9 | 283 | 233 | 16,6 | 394 | 168 | 13,9 | 6,8 | 51 |
VB 12 | AM50 Guß | 14,0 | 178 | 69 | 11,0 | 338 | 73 | 26,0 | 6,2 | 13 |
B 13 | AM50Ca0.5 extr. | 30,1 | 287 | 197 | 18,3 | 373 | 166 | 15,8 | 7,3 | 66 |
B 13a | AM50Ca1.5Sr0.2 extr. | 27,6 | 268 | 186 | 17,8 | n.b. | n.b. | n.b. | 7,7 | 63 |
VB 14 | AS41 extr. | 19,0 | 292 | 202 | 14,2 | 355 | 138 | 9,3 | 5,2 | 52 |
B 15 | AS41Ca0.4 extr. | 18,0 | 275 | 188 | 13,4 | 406 | 150 | 16,0 | 4,8 | 51 |
VB 16a | AZ31 extr. | 33,1 | 282 | 215 | 17,6 | 342 | 124 | 8,9 | 10,8 | 65 |
B 17 | AZ31Ca0.3 extr. | 30,9 | 280 | 199 | 18,2 | 389 | 143 | 12,5 | 8,6 | 59 |
VB 18 | ME10 Guß | 15,3 | 192 | 75 | 7,9 | 328 | 83 | 27,0 | 7,3 | 19 |
VB 19 | MN150 extr. | 15,2 | 225 | 177 | 15,2 | 309 | 119 | 14,1 | 5,1 | 22 |
B 20 | MN150Ca0.2 extr. | 27,3 | 264 | 242 | 18,3 | 354 | 194 | 14,6 | 2,5 | 34 |
Mittelwerte der aus dem Spannungs-Dehnungs-Diagramm der Zugversuche für modifizierte Magnesiumlegierungen und deren Ausgangslegierungen bestimmbare Werte. F = RP02 = Fließspannung = elastischer Anteil der Spannung. V = Streckgrenzenverhältnis = F : Z. Rm = Zugspannung Z = elastischer + plastischer Anteil der Spannung: | ||||||
Nr. | Legierung | Spannungen | Dehnung | |||
Fließ-F MPa | Z - F MPa | Zug-Z MPa | V = F:Z | Aplast = A % | ||
VB 10 | AM20 extr. | 230 | 44 | 274 | 0,84 | 17,9 |
B 11 | AM20Ca0.2 extr. | 233 | 50 | 283 | 0,82 | 16,6 |
VB 12 | AM50 Guß | 69 | 109 | 178 | 0,39 | 11,0 |
B 13 | AM50Ca0.5 extr. | 197 | 90 | 287 | 0,69 | 18,3 |
B 13a | AM50Ca1.5Sr0.2 extr. | 186 | 82 | 268 | 0,69 | 17,8 |
VB 14 | AS41 extr. | 202 | 90 | 292 | 0,69 | 14,2 |
B 15 | AS41Ca0.4 extr. | 188 | 87 | 275 | 0,68 | 13,4 |
VB 16a | AZ31 extr. | 215 | 67 | 282 | 0,76 | 17,6 |
B 17 | AZ31Ca0.3 extr. | 199 | 81 | 280 | 0,71 | 18,2 |
VB 18 | ME10 Guß | 75 | 117 | 192 | 0,39 | 7,9 |
VB 19 | MN150 extr. | 177 | 48 | 225 | 0,79 | 15,2 |
B 20 | MN150Ca0.2 extr. | 242 | 22 | 264 | 0,92 | 18,3 |
Höchste Mittelwerte der Meßergebnisse der mechanischen Eigenschaften ausgewählt aus verschiedenen Einzelproben der modifizierten Magnesiumlegierungen: | ||||||||||
Probe | Legierung | Zugversuch | Druckversuch | Schlagvers. | ||||||
BE % | Rm MPa | RP0,2 MPa | A % | RDm MPa | Rstauch MPa | AD % | CG J | CUG J | ||
VB 10 | AM20 extr. | 36,6 | 278 | 238 | 20,5 | 352 | 150 | 8,4 | 9,3 | 50,8 |
B 11 | AM20Ca0.2 extr. | 36,0 | 294 | 254 | 20,8 | 425 | 209 | 15,6 | 8,0 | 58,0 |
VB 12 | AM50 extr. | 21,6 | 287 | 212 | 21,6 | 365 | 140 | 11,2 | 10,0 | 85,0 |
B 13 | AM50Ca0.5 extr. | 32,0 | 295 | 215 | 20,3 | 421 | 186 | 16,7 | 7,5 | 68,5 |
B 13a | AM50Ca1.5Sr0.2 extr. | 32,7 | 284 | 207 | 18,3 | n.b. | n.b. | n.b. | 11,2 | 68,7 |
VB 14 | AS41 extr. | 16,8 | 284 | 227 | 16,8 | 372 | 148 | 10,4 | 5,5 | 56,3 |
B 15 | AS41Ca0.4 extr. | 20,7 | 279 | 204 | 16,1 | 430 | 169 | 18,0 | 5,0 | 55,0 |
B 17 | AZ31Ca0.3 extr. | 35,3 | 286 | 214 | 21,8 | 407 | 162 | 15,3 | 9,0 | 63,7 |
VB 19 | MN150 extr. | 17,8 | 230 | 196 | 17,8 | 342 | 150 | 23,8 | 5,5 | 34,8 |
B 20 | MN150Ca0.2 extr. | 33,9 | 291 | 286 | 23,8 | 383 | 226 | 16,5 | 2,5 | 42,2 |
Vorwiegend auftretende Korngrößen im Gußzustand nach dem Homogenisieren bei 350 °C 4 h bzw. nach dem Strangpressen bei den modifizierten Magnesiumlegierungen und deren Ausgangslegierungen. | ||
Probe | Legierung | mittlere Korngrößen, µm |
VB 12 | AM50 Guß | 95 |
VB 13 | AM50Ca0,5 Guß | 124 |
B 13 | AM50Ca0,5 extr. | 4,6 - 9,2 |
B 13a | AM50Ca1,5Sr0,2 extr. | 8,9 - 17,8 |
VB 16 | AZ31 Guß | 130 |
VB 16a | AZ31 extr. | 3,5 - 6,8 |
VB 18 | ME10 Guß | 103 |
Verfahrensparameter zu verschiedenen Proben der modifizierten Magnesiumlegierungen und deren Ausgangslegierungen. | |||||||
Probe | Legierung | Schmelztemperatur | Temperatur des Bolzens | Umformgrad ϕ= In(Ao/A) | Anfangspreßdruck | Preßgeschwindigkeit | Probenzahl |
°C | °C | MPa | m/min | ||||
VB 10 | AM20 extr. | 780 - 800 | 340 - 390 | 2,8 - 3,3 | 10,7 - 15,0 | 4,2 - 9,9 | 9 |
B 11 | AM20Ca0.2 extr. | 780 | 200 - 390 | 2,8 - 3,1 | 16,7 - 22,2 | 3,5 - 9,1 | 11 |
VB 12 | AM50 Guß | 800 | 1 | ||||
B 13 | AM50Ca0.5 extr. | 780 | 250 - 340 | 2,8 - 3,1 | 15,7 - 23,5 | 3,4 - 9,2 | 8 |
B 13a | AM50Ca1.5Sr0.2 extr. | 780 | 300 - 400 | 3,1 | 11,4 - 18,0 | 3,8 - 4,5 | 3 |
VB 14 | AS41 HP extr. | 780 | 250 - 390 | 2,8 - 3,3 | 10,7 - 21,4 | 4,3 - 10,2 | 10 |
B 15 | AS41 Ca0.4 extr. | 780 | 250 - 340 | 2,8 - 3,1 | 15,5 - 23,0 | 3,4 - 9,3 | 8 |
VB 16 | AZ31 Guß | 800 | 1 | ||||
VB 16a | AZ31 extr. | 780 - 800 | 250 - 390 | 2,8 - 3,2 | 10,6 - 20,8 | 4,2 - 10,6 | 17 |
B 17 | AZ31Ca0.3 extr. | 780 | 250 - 365 | 2,8 - 3,1 | 15,9 - 21,7 | 3,4 - 9,1 | 9 |
B17a | AZ31Ca0.5 extr. | 780 | 250 - 365 | 2,8 - 3,1 | 14,7 - 21,2 | 3,5 - 9,1 | 9 |
VB 18 | ME10 Guß | 800 | 340 | 1 | |||
VB 19 | MN150 extr. | 780 - 800 | 250 - 390 | 2,8 - 3,3 | 8,7 - 14,6 | 4,5 - 10,8 | 10 |
B 20 | MN150Ca0.2extr. | 780 | 250 - 340 | 2,8 - 3,1 | 16,4 - 21,5 | 3,2 - 8,7 | 8 |
Claims (12)
- Magnesiumlegierung, die 0,2 bis 4 Gew.-% Mn sowie 0,2 bis 6 Gew.-% Ca oder/und 0,1 bis 6 Gew.-% Sr enthält und Zusätze oder Spuren an Cd kleiner als 1,8 Gew.-% und Spuren von bis zu 0,1 Gew.-% Cu sowie, bis zu 0,05 Gew.-% Fe und bis zu 0,005 Gew.-% Ni enthalten kann, wobei die restlichen Gehalte der Magnesiumlegierung aus Magnesium und unvermeidbaren Verunreinigungen bestehen, hergestellt durch Strangpressen oder Schmieden mit einem Umformgrad von mindestens 1,5 unter dynamischer Rekristallisation und unter Ausbildung eines feinkörnigen Gefüges mit einer mittleren Korngröße von höchstens 25 µm, wobei ihre Druckfestigkeit mindestens 300 MPa, ihre Schlagarbeit gemessen an ungekerbten Proben mindestens 20 J und ihre Bruchdehnung gemessen an Zugproben mindestens 15 % beträgt.
- Magnesiumlegierung auf Basis AM (Aluminium/Mangan) oder MA (Mangan/Aluminium), die 0,5 bis 10 Gew.-% Al und 0,1 bis 4 Gew.-% Mn sowie jeweils 0,1 bis 6 Gew.-% Ca oder/und Sr enthält und Zusätze oder Spuren an Cd kleiner als 1,8 Gew.-% und Spuren von bis zu 0,1 Gew.-% Cu sowie, bis zu 0,05 Gew.-% Fe und bis zu 0,005 Gew.-% Ni enthalten kann, wobei die restlichen Gehalte der Magnesiumlegierung aus Magnesium und unvermeidbaren Verunreinigungen bestehen, hergestellt durch Strangpressen oder Schmieden mit einem Umformgrad von mindestens 1,5 unter dynamischer Rekristallisation und unter Ausbildung eines feinkörnigen Gefüges mit einer mittleren Korngröße von höchstens 25 µm, wobei ihre Druckfestigkeit mindestens 320 MPa, ihre Schlagarbeit gemessen an ungekerbten Proben mindestens 40 J und ihre Bruchdehnung gemessen an Zugproben mindestens 16 % beträgt.
- Magnesiumlegierung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie einen plastischen Anteil der Spannung bestimmt im Zugversuch nach dem Spannungs-Dehnungs-Diagramm aus der Differenz von Zugspannung und Fließspannung von mindestens 40 MPa aufweist.
- Magnesiumlegierung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie ein Gefüge mit einer mittleren Korngröße von nicht mehr als 20 µm aufweist.
- Magnesiumlegierung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie umgeformt ist und ein feinkörniges, dynamisch rekristallisiertes Gefüge und einen Gehalt an Ausscheidungsphasen von nicht mehr als 5 Vol.-% aufweist.
- Verfahren zum Herstellen einer Magnesiumlegierung nach mindestens einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass ein urgeformter oder kompaktierter Formkörper hergestellt und durch Umformen oder/und Verformen dynamisch rekristallisiert wird.
- Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass der umgeformte oder/und verformte Formkörper zu einem Halbzeug oder/und einem aus oder mit diesem Halbzeug gefertigten Bauteil bearbeitet bzw. verarbeitet wird.
- Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass das hergestellte Halbzeug bzw. das aus oder mit dem Halbzeug hergestellte Bauteil gerichtet, z. B. durch Biegen, Drücken, Druckwalzen, Streckziehen, Tiefziehen, Innenhochdruckumformen oder Walzprofilieren weiter verformt, bearbeitet, gefügt oder/und oberflächenbehandelt wird.
- Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, dass das Halbzeug oder das daraus oder damit hergestellte Bauteil durch mindestens ein wärmearmes Fügeverfahren wie z. b. Kleben, Nieten, Strecken, Anpressen, Einpressen, Clinchen, Falzen, Schrumpfen oder Schrauben oder/und mindestens ein wärmeeinbringendes Fügeverfahren wie z. B. Verbundgießen, Verbundschmieden, Verbundstrangpressen, Verbundwalzen, Löten oder Schweißen, insbesondere Strahlschweißen oder Schmelzschweißen, mit einem gleichartigen oder andersartigen Halbzeug oder Bauteil verbunden wird.
- Halbzeug aus einer Magnesiumlegierung oder daraus oder damit hergestelltes Bauteil oder Verbund mit einem solchen Halbzeug oder Bauteil, dadurch gekennzeichnet, dass es/er nach mindestens einem der vorstehenden Ansprüche hergestellt wurde.
- Verwendung einer Magnesiumlegierung, hergestellt nach mindestens einem der Ansprüche 6 bis 9, als Felge, Getriebegehäuse, Lenkradskelett, Querlenker, Rahmenelement, Element von Fahrzeugzellen oder Fahrzeugaußenhaut, Fahrzeugzelle oder Fahrzeugaußenhaut, Cockpitträger, Cockpithaut, Gehäuse, Bodenelement, Boden, Deckel, Tankelement, Tankklappe, Halterung, Stütze, Träger, Winkel, Hohlprofil, Rohr, Deformationselement, Crashelement, Crashabsorber, Pralldämpfer, Prallschild, Prallträger, Kleinteil, als geschweißte Profilkonstruktion, für die Fahrzeugkarosserie, für Sitz-, Fenster- oder/und Türrahmen, als Halbzeug, Bauteil oder Verbund am oder im Automobil oder Flugzeug.
- Verwendung eines Halbzeuges aus einer Magnesiumlegierung nach einem der Ansprüche 1 bis 9, eines daraus oder damit hergestellten Bauteiles oder/und eines Verbundes mit mindestens einem derartigen Halbzeug oder/und Bauteil als Felge, Getriebegehäuse, Lenkradskelett, Querlenker, Rahmenelement, Element von Fahrzeugzellen oder Fahrzeugaußenhaut, Cockpitträger, Gehäuse, Bodenelement, Deckel, Tankelement, Tankklappe, Halterung, Stütze, Träger, Winkel, Hohlprofil, Rohr, Deformationselement, Crashelement, Crashabsorber, Pralldämpfer, Prallschild, Prallträger, Kleinteil, als geschweißte Profilstruktionen, für die Fahrzeugkarosserie, für Sitz-, Fenster- oder/und Türrahmen, als Halbzeug, Bauteil oder Verbund am oder im Automobil oder Flugzeug.
Applications Claiming Priority (3)
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DE19915277A DE19915277A1 (de) | 1999-04-03 | 1999-04-03 | Magnesiumlegierungen hoher Duktilität, Verfahren zu deren Herstellung und deren Verwendung |
DE19915277 | 1999-04-03 | ||
PCT/EP2000/002524 WO2000063452A1 (de) | 1999-04-03 | 2000-03-22 | Magnesiumlegierungen hoher duktilität, verfahren zu deren herstellung und deren verwendung |
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EP1171643A1 EP1171643A1 (de) | 2002-01-16 |
EP1171643B1 true EP1171643B1 (de) | 2004-06-02 |
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Country Status (4)
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EP (1) | EP1171643B1 (de) |
AT (1) | ATE268391T1 (de) |
DE (2) | DE19915277A1 (de) |
WO (1) | WO2000063452A1 (de) |
Cited By (2)
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CN109937263A (zh) * | 2017-01-16 | 2019-06-25 | 镁电子有限公司 | 可腐蚀的井下制品 |
US11890004B2 (en) | 2021-05-10 | 2024-02-06 | Cilag Gmbh International | Staple cartridge comprising lubricated staples |
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DE10049579B4 (de) * | 2000-10-06 | 2006-09-14 | Audi Ag | Verfahren zur Herstellung einer dekorativen Oberfläche |
WO2002099147A1 (en) * | 2001-06-06 | 2002-12-12 | Noranda, Inc. | Magnesium-based casting alloys having improved elevated temperature properties |
DE10221720A1 (de) * | 2002-05-16 | 2003-11-27 | Bayerische Motoren Werke Ag | Magnesiumlegierung |
JP2004162090A (ja) * | 2002-11-11 | 2004-06-10 | Toyota Industries Corp | 耐熱性マグネシウム合金 |
CN100386175C (zh) * | 2005-09-08 | 2008-05-07 | 于克儒 | 用镁合金型材制作自行车轮辋的方法 |
US8333924B2 (en) * | 2006-03-20 | 2012-12-18 | National University Corporation Kumamoto University | High-strength and high-toughness magnesium alloy and method for manufacturing same |
DE102006015457A1 (de) | 2006-03-31 | 2007-10-04 | Biotronik Vi Patent Ag | Magnesiumlegierung und dazugehöriges Herstellungsverfahren |
DE102010006502B4 (de) * | 2010-01-28 | 2023-08-03 | Dr. Ing. H.C. F. Porsche Aktiengesellschaft | Fahrzeugaufbau |
DE112017001307T5 (de) | 2016-07-15 | 2018-11-29 | National University Corporation University Of Toyama | Magnesiumlegierung |
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-
1999
- 1999-04-03 DE DE19915277A patent/DE19915277A1/de not_active Withdrawn
-
2000
- 2000-03-22 EP EP00920534A patent/EP1171643B1/de not_active Expired - Lifetime
- 2000-03-22 DE DE50006687T patent/DE50006687D1/de not_active Expired - Lifetime
- 2000-03-22 AT AT00920534T patent/ATE268391T1/de not_active IP Right Cessation
- 2000-03-22 WO PCT/EP2000/002524 patent/WO2000063452A1/de active IP Right Grant
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109937263A (zh) * | 2017-01-16 | 2019-06-25 | 镁电子有限公司 | 可腐蚀的井下制品 |
US11890004B2 (en) | 2021-05-10 | 2024-02-06 | Cilag Gmbh International | Staple cartridge comprising lubricated staples |
US11998192B2 (en) | 2021-05-10 | 2024-06-04 | Cilag Gmbh International | Adaptive control of surgical stapling instrument based on staple cartridge type |
Also Published As
Publication number | Publication date |
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DE50006687D1 (de) | 2004-07-08 |
DE19915277A1 (de) | 2000-10-05 |
WO2000063452A8 (de) | 2001-02-01 |
EP1171643A1 (de) | 2002-01-16 |
WO2000063452A1 (de) | 2000-10-26 |
ATE268391T1 (de) | 2004-06-15 |
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