MONOTECTIC ALUMINUM PLAIN BEARING ALLOY, METHOD FOR PRODUCING SAME, AND PLAIN BEARING PRODUCED THEREWITH

Abstract

The invention relates to a monotectic aluminum plain bearing alloy having bismuth inclusions, which alloy is suitable for plastic deformation and consists of 1 to 20 wt % bismuth, at least one element selected from 0.05 to 7 wt % copper, 0.05 to 15 wt % silicon, 0.05 to 3 wt % manganese, 0.05 to 5 wt % zinc as a primary alloying element and, in combination, 0.005 to 0.4 wt % titanium, 0.005 to 0.7 wt % zirconium, 0.001 to 0.1 wt % boron as additional alloying elements, and optionally one or more further additional elements, the remainder aluminum. The plain bearing alloy is ultra-fine-grained and has superplastic-like properties.

Claims

1. A monotectic aluminum plain bearing alloy having bismuth inclusions which is suitable for plastic deformation, comprising: from 1 to 20% by weight of bismuth, at least one main alloying element selected from the group consisting of from 0.05 to 7% by weight of copper, from 0.05 to 15% by weight of silicon, from 0.05 to 3% by weight of manganese, from 0.05 to 5% by weight of zinc, at least one additional alloying element that acts in combination with at least one main alloying element selected from the consisting of from 0.005 to 0.4% by weight of titanium, from 0.005 to 0.7% by weight of zirconium, from 0.001 to 0.1% by weight of boron, optionally one or more further additional elements, and a balance of aluminum.

2. The plain bearing alloy as claimed in claim 1, wherein the one or more further additional elements are present and are selected from the following groups: group 1: tantalum, niobium, hafnium, vanadium, tungsten, molybdenum, antimony, scandium, cerium, calcium in a total proportion of not more than 0.5% by weight; group 2: nickel, cobalt, iron, chromium in a total proportion of not more than 1% by weight; group 3: carbon, nitrogen in a total proportion of not more than 0.1% by weight; group 4: silver, germanium, lithium in a total proportion of not more than 1.0% by weight; group 5: tin, lead in a total proportion of not more than 0.5% by weight.

3. The plain bearing alloy as claimed in claim 1 wherein a proportion of bismuth in the plain bearing alloy is from 4.5 to 15.5% by weight.

4. The plain bearing alloy as claimed in claim 1 wherein the at least one main alloying element is manganese and/or copper and/or silicon and/or zinc in a proportion from 0.5 to 2.8% by weight.

5. The plain bearing alloy as claimed in claim 1 further comprising up to 3% by weight of Al—Ti—B or Al—Ti—C grain refining agent.

6. A process for producing an aluminum plain bearing alloy having the composition as claimed in claim 1 wherein the bismuth, aluminium, and main and additional alloying elements are combined to give the aluminium plain bearing alloy in a casting process in which a cooling rate is in a range from 5 to 300 K/s.

7. The process as claimed in claim 6, wherein the casting process is a continuous casting process.

8. The process as claimed in claim 6 wherein the aluminium plain bearing alloy is provided with at least one support layer to provide a semifinished part.

9. The process as claimed in claim 6 further comprising subjecting the aluminium plain bearing alloy to at least one heat treatment at temperatures of from 200° C. to 400° C. during subsequent forming processes.

10. The process as claimed in claim 9, wherein the at least one heat treatment is carried out in a rolling operation and/or roll cladding operation.

11. A plain bearing element comprising a support layer and a plain bearing alloy as claimed in claim 1 applied to the support layer.

12. A plain bearing formed with at least one plain bearing element as claimed in claim 11.

13. The plain bearing alloy as claimed in claim 1 wherein a proportion of bismuth in the plain bearing alloy is from 5 to 8% by weight.

14. The plain bearing alloy as claimed in claim 4 wherein the at least one main alloying element is manganese and/or copper and/or silicon and/or zing in a proportion from 0.7 to 1.5% by weight.

Description

[0032] The present invention is based on the recognition that the combination of the additional elements titanium, zirconium and boron leads to an ultra-fine-grained, superplastic-like monotectic aluminum plain bearing alloy having small bismuth inclusions, which is suitable for high-degree plastic forming. However, an increase in the element concentrations above 7% by weight in the case of copper or zinc, above 15% by weight in the case of silicon and above 3% by weight in the case of manganese leads to a coarsening of the structure and a deterioration in the alloy properties. The content of zinc is preferably up to 2.5% by weight, more preferably in the range from 0.5 to 2% by weight. The content of silicon is preferably in the range from 1.2 to 15% by weight, with proportions of from 1.5 to 5% by weight and from 10 to 15% by weight being particularly preferred.

[0033] An explanation of the ultra-fine-grained structure of the plain bearing alloy of the invention is the formation of specific clusters having a high packing density.

[0034] Manganese has an only insignificantly smaller atomic radius (Mn.sub.atomic radius=127 μm) than aluminum (Al.sub.atomic radius=143 μm). The ratio of the atomic radii is Mn.sub.atomic radius/−Al.sub.atomic radius=0.8881 [D.B. Miracle, Candidate Atomic Cluster Configurations in Metallic Glass Structures. Materials Transactions, Vol. 47, No. 7 (2006) pp. 1737 to 1742].

[0035] This is very close to the optimum ratio of the atomic radii of 0.9 for the formation of icosahedral clusters having the coordination number 12.

[0036] Silicon has an only insignificantly smaller atomic radius (Si.sub.atomic radius=110 μm) than aluminum (Al.sub.atomic radius=143 μm). The ratio of the atomic radii is Si.sub.atomic radius/−Al.sub.atomic radius=0.769 [D.B. Miracle, Candidate Atomic Cluster Configurations in Metallic Glass Structures. Materials Transactions, Vol. 47, No. 7 (2006) pp. 1737 to 1742].

[0037] Copper and zinc likewise have an only insignificantly smaller atomic radius (Cu(Zn).sub.atomic radius=135 μm) than aluminum (Al.sub.atomic radius=143 μm). The ratio of the atomic radii is Cu(Zn).sub.atomic radius/Al.sub.atomic radius=0.94 [D.B. Miracle, Candidate Atomic Cluster Configurations in Metallic Glass Structures. Materials Transactions, Vol. 47, No. 7 (2006) pp. 1737 to 1742].

[0038] This is very close to the optimum ratio of the atomic radii of 0.9 for the formation of icosahedral clusters having the coordination number 12.

[0039] Titanium has an only insignificantly smaller atomic radius (Ti.sub.atomic radius=140 μm) than aluminum (Al.sub.atomic radius=143 μm). The ratio of the atomic radii is Ti.sub.atomic radius/−Al.sub.atomic radius=0.979 [D.B. Miracle, Candidate Atomic Cluster Configurations in Metallic Glass Structures. Materials Transactions, Vol. 47, No. 7 (2006) pp. 1737 to 1742].

[0040] This is very close to the optimum ratio of the atomic radii of 1.0 for the formation of octahedral, FCC (face-centered) or cuboctahedral clusters having the coordination number 12.

[0041] Zirconium has an only insignificantly greater atomic radius (Zr.sub.atomic radius=155 μm) than aluminum (Al.sub.atomic radius=143 μm). The ratio of the atomic radii is Ti.sub.atomic radius/−Al.sub.atomic radius=1.08 [D.B. Miracle, Candidate Atomic Cluster Configurations in Metallic Glass Structures. Materials Transactions, Vol. 47, No. 7 (2006) pp. 1737 to 1742].

[0042] Boron has a significantly smaller atomic radius (B.sub.atomic radius=85 μm) than aluminum (Al.sub.atomic radius=143 μm). The ratio of the atomic radii is Ti.sub.atomic radius/Al.sub.atomic radius=0.594 [D.B. Miracle, Candidate Atomic Cluster Configurations in Metallic Glass Structures. Materials Transactions, Vol. 47, No. 7 (2006) pp. 1737 to 1742].

[0043] This is very close to the optimum ratio of the atomic radii of 0.591 for the formation of icosahedral clusters having the coordination number 7.

[0044] Boron in combination with titanium and/or aluminum plays an important role in the formation of the structure of the alloy during crystallization.

[0045] It is known that icosahedral or decahedral clusters, in particular with the coordination number 7, have a particular tendency to a high degree of subcooling of the melt. In the subcooled state, icosahedral or decahedral short-range order arises and clusters having a high packing density are formed. Icosahedral short-range order and the solid body have significantly different packing. The increase in the packing density in the event of strong subcooling inhibits diffusion of the atoms for crystallization and for other phase transformations. In the case of a high degree of subcooling, the melt has a large excess of free energy which the system can utilize for a variety of solidification routes far outside equilibrium in various metastable phases. Thus, metastable solids which can consist of supersaturated mixed phases, grain-refined alloys, disordered superlattice structures, metastable crystallographic phases can be formed. This leads to considerable strengthening of the alloy.

[0046] Based on these calculations, manganese, copper and zinc, zirconium and titanium lead to formation of particularly dense and stable clusters with aluminum having the coordination number 12, the configuration of which can be decahedral, icosahedral or octahedral, FCC (face-centered) or cuboctahedral. This leads to a particularly effective interaction between aluminum and copper and zinc, zirconium, titanium and manganese atoms, with copper and zinc, zirconium, titanium and manganese being initiators for dense packing both in the liquid state and the solid state.

[0047] The decahedral or icosahedral packing and the solid body have significantly different packing. The increase in the packing density in the case of a high degree of subcooling inhibits diffusion of the atoms for crystallization and for other phase transformations. In the case of great subcooling, the melt has a large excess of free energy which the system can utilize for a variety of solidification routes far outside equilibrium in various metastable phases. Thus, metastable solids which can consist of supersaturated mixed phases, grain-refined alloys, disordered superlattice structures, metastable crystallographic phases can be formed. The grain refinement achieved by cluster formation leads to a change in the morphology of a coarse-grained dendritic microstructure to an equiaxial grain-refined microstructure having a typical grain size of less than 100 microns. This also leads to significant refinement of a bismuth phase down to an average size of 20 microns.

[0048] Excessively large amounts of additional alloying elements can increase the crystallization interval and hinder optimum interaction between aluminum and copper, silicon, manganese, zinc, titanium, zirconium, boron. This contributes to development of segregations and to enlarging of the bismuth inclusions, as a result of which the properties of the alloy deteriorate. To ensure the positive influence of copper and zinc, zirconium, titanium and manganese, it is useful for the amount of additional elements to be less than 1.0% by weight.

[0049] In the plain bearing alloy of the invention, bismuth serves as sole soft phase former, i.e. there is no combination of bismuth with lead and/or tin present for this purpose. Lead and/or tin should occur in the plain bearing alloy of the invention in at most small amounts with a total proportion of less than 0.5% by weight, if at all.

[0050] Further additional alloying elements make it possible to specifically adjust the properties of the alloy of the invention to a particular use.

[0051] The eligible additional alloying elements can be divided into five groups:

[0052] Group 1:

[0053] Tantalum, niobium, hafnium, vanadium, tungsten, molybdenum, antimony, scandium, cerium, calcium in a total proportion of not more than 0.5% by weight.

[0054] Group 2:

[0055] Nickel, cobalt, iron, chromium in a total proportion of not more than 1% by weight.

[0056] Group 3:

[0057] Carbon, nitrogen in a total proportion of not more than 0.1% by weight.

[0058] Group 4:

[0059] Silver, germanium, lithium in a total proportion of not more than 1.0% by weight.

[0060] Group 5:

[0061] Tin, lead in a total proportion of not more than 0.5% by weight.

[0062] In the individual groups, lower limits are in each case 0.001% by weight, i.e. essentially the detection limit.

[0063] The additional alloying elements of group 1 display two mechanisms of action. These mechanisms generally act simultaneously, but in some cases one predominates over the other.

[0064] Mechanism of Action 1:

[0065] The elements tantalum, niobium, hafnium, vanadium, tungsten, molybdenum, antimony, scandium, cerium have a larger or at least not significantly smaller atomic radius than aluminum and lead to formation of particularly dense and stable clusters having the coordination number 12—decahedral or octahedral and cuboctahedral clusters. The decahedral packing and the solid body have significantly different packing. An increase in the packing density in the case of a high degree of subcooling inhibits diffusion of the atoms for crystallization and for other phase transformations. In the case of great subcooling, the melt has a large excess of free energy which the system can utilize for a variety of solidification routes far outside equilibrium in various metastable phases. Thus, metastable solids which can consist of supersaturated mixed phases, grain-refined alloys, disordered superlattice structures, metastable crystallographic phases can be formed. The grain refinement achieved by cluster formation leads to a change in the morphology from a coarse-grain dendritic microstructure to an equiaxial grain-refined microstructure having a typical grain size of less than 100 microns. This also leads to significant refining of the bismuth phase down to an average size of 20 microns. During the formation of octahedral and cuboctahedral clusters, crystal growth predominates. The packings of the octahedral and cuboctahedral clusters and of the solid body have similarities. In this case, only a very small degree of subcooling occurs in front of the solidification front and a trans-crystalline microstructure having a typical grain size of less than 500 microns with small inclusions of bismuth to an average size of 10 microns within the trans-crystalline grains is formed.

[0066] Mechanism of Action 2:

[0067] The elements tantalum, niobium, hafnium, vanadium, tungsten, molybdenum, scandium react peritectically with aluminum and lead to formation of additional crystal nuclei composed of an Al.sub.xM1 phase, where M1 is one of the abovementioned metals. The additional crystallization nuclei lead to refinement of the matrix (αA1). This also leads to refinement of the bismuth phase down to an average size of 40 microns. The additional crystallization nuclei can be composed of Al.sub.3V, Al.sub.3Nb, Al.sub.3Ta phase. The grain refinement by nucleus formation changes the morphology from a coarse-grain dendritic microstructure to a fine-grain dendritic microstructure having a typical grain size of more than 100 microns. If the second mechanism dominates strongly, which is often the case when a high concentration of additional alloying elements of group 1 forms a coarse intermetallic phase, the bismuth phase is coarsened up to a grain size of 100 microns. Since the increase in the Al.sub.xM1 phase can in this case, too, lead to a decrease in the plasticity and coarsening of the bismuth phase, an upper limit of 0.5% by weight should be imposed on the total proportion.

[0068] Sc, Hf, Nb, Zr, Ti, V, Mn form supersaturated a mixed crystals, particularly in the case of high solidification rates. A subsequent heat treatment converts the dissolved Sc, Zr, Ti, V, Mn in a targeted manner into Al.sub.3XYZ, where XYZ is Sc, Hf, Nb, Zr, Ti, V, for example: Al.sub.3(Sc, Zr) or Al.sub.3(Ti, Zr) Al.sub.12Mn.sub.2CU nanophases. The high density of these nanostructured phases brings about a significant increase in strength combined with greater toughness. These nanostructured phases inhibit the recrystallization process and lead to formation and retention of ultra-fine-grained grain structures. These ultimately lead to the particular properties of the ultra-fine-grained superplastic-like monotectic aluminum plain bearing alloy having small bismuth inclusions, which is suitable for high-degree plastic forming.

[0069] The additional alloying elements of group 2, namely nickel, cobalt, iron, chromium, which have a significantly smaller atomic radius than aluminum, lead to the formation of particularly dense and stable clusters with coordination numbers 12, 11, 10, 9 of the icosahedral cluster type which display a eutectic transformation with aluminum. The additional alloying elements of group 2, namely silicon, zinc, copper, nickel, cobalt, iron, chromium, form the eutectic e(αAl+Al.sub.xM2.sub.y) with aluminum, where M2 is one of the elements from this group. The eutectic thus consists of two phases, namely αAl mixed crystal and the intermetallic phase Al.sub.xM2.sub.y. Alloying atoms dissolved in the αAl mixed crystals brought about mixed crystal hardening. Al.sub.xM2.sub.y particles finely dispersed in the matrix represent obstacles for the migrating dislocations and bring about particle hardening. It is known that eutectic alloys have a particular tendency to a high degree of subcooling. In the subcooled state, an icosahedral close-range order arises and clusters having a high packing density are formed. Icosahedral close-range order and the solid body have significantly different packing. The increase in the packing density in the case of a high degree of subcooling inhibits diffusion of the atoms for crystallization and for other phase transformations. In the case of great subcooling, the melt has a large excess of free energy which the system can utilize for a variety of solidification routes far outside equilibrium in various metastable phases. Thus, metastable solids which can consist of supersaturated mixed phases, grain-refined alloys, disordered superlattice structures, metastable crystallographic phases can be formed. This leads to considerable strengthening of the alloy. Since a high proportion of eutectic can contribute to a lowering of the plasticity, an upper limit of 1.0% by weight should be imposed on the total proportion.

[0070] The elements carbon and nitrogen of group 3, or a combination of carbon, nitrogen with titanium, zirconium, tantalum, niobium, vanadium, result in formation of mainly additional crystallization nuclei. These additional crystallization nuclei can be AlTiC, AlTiB, TaC, TiC phase. Since an increase in the abovementioned phases can contribute to lowering of the plasticity, an upper limit of 0.1% by weight is imposed on the total proportion of these alloying elements.

[0071] The additional alloying elements of group 4, namely silver, germanium, lithium, are soluble in the aluminum matrix and form αAl mixed crystals. This brings about mixed crystal hardening. The total proportion should be limited to 1.0% by weight.

[0072] It has been found that the addition of titanium and boron can also be effected by use of the commercial grain refining agent AlTi5B1 or AlTi3C0.15 in added amounts of from about 0.3 to 2% by weight. This produces a strong grain-refining action on the alloy of the invention and hot cracking in continuous casting using various cooling rates is reliably prevented. The addition of the grain refining agents mentioned also brings about a significant reduction in the size of the minority phase. The maximum diameter of the bismuth droplets has been able to be reduced to less than 30 microns by use of grain refining additives in the cast state, even at relatively low cooling rates of about 5 K/s.

[0073] The invention further provides a process for producing an aluminum plain bearing alloy using the composition according to the invention as described above. The alloy constituents are preferably combined to form an alloy in a casting process in which the cooling rate is from 5 to 300 K/s. The cooling rate can be increased up to 1000 K/s when the abovementioned grain refining agents are added. The alloy can otherwise be produced using other conventional production processes, in particular by means of other casting processes. At present, production by continuous casting is preferred. The conditions should be adapted so that preferably droplet-shaped bismuth inclusions are formed. During continuous casting, the offtake velocity is preferably from 2 to 15 mm/s. The alloy obtained by casting is, in a particular embodiment of the present invention, subjected to at least one heat treatment at temperatures in the range from about 230 to 400° C. during the course of subsequent forming processes. Such a heat treatment preferably follows a rolling operation and/or roll cladding operation with a plurality of rolling and/or cladding operations being able to be carried out within the manufacturing process between casting of the alloy and the end product and at least one heat treatment following the last rolling operation and/or roll cladding operation or else a plurality or all of these operations.

[0074] To provide a semifinished product or during the course of production of products such as plain bearings, the cast alloy can be provided with at least one support layer. The support layer can be, in particular, a steel layer. Further layers, e.g. bonding promoting layers or coatings, can be added thereto.

[0075] The invention further provides a plain bearing shell which contains an alloy according to the invention as one of the materials used therein, or consists of such an alloy. Finally, the invention provides a plain bearing comprising such a plain bearing shell and also the use of the alloy according to the invention in a plain bearing.

[0076] The invention will be illustrated below with the aid of a working example.

[0077] To produce the plain bearing material, cast strips having a cross section of 10 mm×130 mm are produced on a continuous casting plant in this example. To produce the strips, the offtake speed is 8 mm/s and the cooling rate is 100 K/s. The strips are firstly horizontally milled at the broad sides to a thickness of about 8 mm. A brushed and degreased bonding agent composed of an aluminum alloy is subsequently applied by cladding in the first rolling pass to the likewise brushed and degreased AlBi7Mn1.4Cu0.5Ti0.15Zr0.3B0.005, AlBi7Mn2.3Cu1.6Cr0.35Ti0.15Zr0.15B0.003, AlBi5Cu1.5Mn0.45Ti0.25Zr0.23B0.004, AlBi5Cu2.5Zn2Si1Mn0.45Ti0.25Zr0.25B0.002, or AlSi11Bi7Cu0.5Ti0.17Zr0.22B0.009 alloy in a roll stand.

[0078] In order to improve the cladability of the aluminum bearing material strip, the latter is subjected to a recovery heat treatment at 370° C. for up to 3 hours. The thickness of the clad precursor material strip is 4 mm. This is subsequently rolled down to 1.3 mm in only one rolling pass and joined to steel strip on a cladding rolling mill.

[0079] Subsequently, the material composite produced is subjected to a heat treatment at a temperature of 360° C. for 3 hours, with the bonding between the steel and the aluminum bearing material being increased by a diffusion process and the bismuth threads which are greatly elongated in the aluminum-zinc-copper matrix after cladding being transformed predominantly into fine spherical droplets having a size of up to 20 μm. The high hardness of at least

55 HB (2.5/62. 5/30) in the case of AlBi7Mn1.4Cu0.5Ti0.15Zr0.3B0.005,
62 HB in the case of AlBi7Mn2.3Cu1.6Cr0.35Ti0.15Zr0.15B0.003,
60 HB in the case of AlBi5Cu1.5Mn0.45Ti0.25Zr0.23B0.004,
63 HB in the case of AlBi5Cu2.5Zn2Si1Mn0.45Ti0.25Zr0.025B0.002, and
82 HB in the case of AlSi11Bi7Cu0.5Ti0.17Zr0.22B0.009 (table 1) which likewise results from the heat treatment is advantageous. After this heat treatment, the clad strip can be cut up and shaped to give bearing shells.

[0080] Comparison of the technological and mechanical properties (table 1) of the AlZn5Cu3Bi7 alloy as per WO2006131129A1 and the newly developed alloys AlBi7Mn1.4Cu0.5Ti0.15Zr0.3B0.005 and AlBi7Mn2.3Cu1.6Cr0.35Ti0.15Zr0.15B0.003; AlBi5Cu1.5Mn0.45Ti0.25Zr0.23B0.004; AlBi5Cu2.5Zn2Si1Mn0.45Ti0.25Zr0.23B0.002, AlSi11Bi7Cu0.5Ti0.17Zr0.22B0.009 shows that the newly developed alloys have the better technological and mechanical properties.

TABLE-US-00001 TABLE 1 See comparison of the technological and mechanical properties (table 1) of the AlZn5Cu3Bi7 alloy as per WO2006131129A1 and the newly developed alloys Hardness Rolling passes 2.5/62.5/30 after required to heat treatment for achieve 1.3 mm Alloy 3 hours at 360° C. after cladding AlZn5Cu3Bi7, from WO2006131129A1 43 5 AlBi7Mn1.4Cu0.5Ti0.15Zr0.3B0.005 55 1 AlBi7Mn2.3Cu1.6Cr0.35Ti0.15Zr0.15B0.003 62 1 AlBi5Cu1.5Mn0.45Ti0.25Zr0.23B0.004 60 1 AlBi5Cu2.5Zn2Si1Mn0.45Ti0.25Zr0.25B0.002 63 1 AlSi11Bi7Cu0.5Ti0.17Zr0.22B0.009 72 1

[0081] The plain bearing alloy of the invention is preferably continuously cast and as early as in the cast state has a fine distribution of the bismuth phase which is largely independent of the offtake speed and cooling rate. Long bismuth plates formed in the course of a further treatment involving rolling and roll cladding can subsequently be completely recoagulated by a heat treatment at temperatures of from 270° C. to 400° C. to give finely distributed spherical droplets which under appropriate process conditions are smaller than 20 μm. The alloy preferably contains from about 7 to 12% by weight of bismuth. The proportion of manganese is in the range from 1 to 5% by weight, in particular from about 1.3 to 4.5% by weight. The proportions of the various elements can be varied independently of one another within the limits indicated.

[0082] The attached pictures of the microstructure clarify the structure of working examples.

[0083] FIGS. 1 and 2 show the microstructure of AlBi7Mn1.4Cu0.5Ti0.15Zr0.3B0.005 and AlBi7Mn2.3Cu1.6Cr0.35Ti0.15Zr0.15B0.003 alloys after casting and after applying to steel strip by cladding. The bismuth phase appears dark.

[0084] FIG. 3 shows the microstructure of the AlBi7Mn1.4Cu0.5Ti0.15Zr0.3B0.005 alloy (etched) clad to steel strip.

[0085] FIG. 4 shows the microstructure of the AlSi11Bi7Cu0.5Ti0.17Zr0.22B0.009 alloy (etched).

[0086] It should be pointed out that the examples serve solely for the purposes of illustration and do not restrict the invention. A person skilled in the art will also know how plain bearings and bearing shells are produced and how the production of the alloy according to the invention can be incorporated into conventional bearing production processes.