The invention relates to a method for producing a wear-resistant aluminum alloy, to aluminum alloys produced according to the method, and to the use thereof.
Engine sliding couples having sliding elements produced from aluminum base alloy are found e.g. in a piston-piston ring-cylinder face assembly or a crankshaft-bearing shell assembly, especially in the form of crankshaft bearing shells, cylinder faces, piston rings, pistons and valve guides.
In addition, the sliding surfaces of the sliding elements can be coated or thermo-chemically treated. Since the thirties of the past century, cylinder faces made of eutectic AlSi alloys (“Silumin”) with coarse Si primary crystals have been known and used in engines. They may include up to 1.3 wt % iron. The material matrix in these concepts is based on aluminum and silicon. With regard to the functional design of the cylinder face surface, an essential point is to recess the aluminum matrix by 0.5-2 μm by subjecting the faces to chemical or mechanical treatment, so that the hard silicon crystals (Hv ˜12-14 GPa) would form the supporting component.
The lowest system wear (piston ring and cylinder face) is achieved with AlSi faces against nitrided piston rings, which can be identical with or in some cases even better than the expected wear of high-carbon gray iron cylinder faces (3.3-3.8 wt % C). The patent document U.S. Pat. No. 6,030,577 discloses AlSi (17-35 wt % Si) with 3-5 wt % Fe.
In total, however, it has been found that this well-tried couple of AlSi alloys can no longer withstand the load of new or future supercharged and/or hydrogen-operated engines in tribological terms. As it turned out, this applies to both AlSi17 (Alusil) and AlSi25 alloys (“SILITEC”). Regarding the tribological high-pressure properties, the AlSi alloys are also limited in their tribological OK load or scuffing load.
The highly castable material system Al—Si—Mg, e.g. Al-9.0Si-0.5Mg (A359) is remarkable for a strength rapidly decreasing with temperature and for the following eutectic equilibria at low temperature:
a. Al—Mg2Si—Mg with a melting temperature of 555° C.,
b. Al—Mg2Si—Al3Mg2 with a melting temperature of 451° C., or
c. Al30.9Mg69.1Mg+Mg17Al12+Mg2Si with a melting temperature of 437° C.
Similar phase equilibria also exist in the material system Al—Cu—Zn.
The heat resistance of AlSi alloys can be improved by ceramic fibers, particles and/or platelets, such as AlSiMg 30 vol. % SiCp (Lanxide Corp., Al-7.0Si-0.3Mg) or A359 20 vol. % SiCp (p=platelet), or enhanced by particles of silicon carbide, such as DURALCAN F3S.20S, 20 wt % SiC) or AA6061+40 vol. % Al2O3 (Al-1% Mg+30 wt % Al2O3 (PRIMEX™). However, the ceramic phases have a highly adverse effect on the piston ring wear.
For optimum establishment of combustion in H2-operated engines, the high thermal diffusivity of aluminum (KRT ˜60-80 mm2/s) is essential, thereby ruling out cylinder face coatings with engineered ceramics, ceramets or hard metals, despite established improved wear resistance. For comparison: a lamellar gray iron including 3.7 wt % C has KRT=16.6 mm2/s.
The patent document U.S. Pat. No. 4,948,558 discloses an AlFeXY material system. Apart from intermetallic phases, the structural morphology of the rapidly solidified Al special alloys is characterized by amorphous and crystalline aluminum phases. To date, these heat-resistant special alloys, e.g. Al88.5Fe8.5V1.3Si1.7 or Al84.5Fe7Cr6Ti2.5, have been rapidly solidified by melt spinning in a technological complex manner and subsequently compacted and extruded, or produced using powder metallurgy. Up to now, the alloys have neither been mentioned in the context with components subject to wear, nor produced using “classical” casting under the influence of gravity or under pressure in molds or ingot molds.
The patent document U.S. Pat. No. 5,318,641 by ALCOA discloses the alloy X8019 of an Al—Fe—Ce material system, which has a tensile strength of up to 1,600 MPa at RT and crystalline nanoparticles deposited in a partially amorphous matrix. The amorphous or partially amorphous structure recrystallizes above 300-450° C. (Al90.8Fe6.2Nb1.0Si2.0 (at. %), at 450° C.), causing loss of the high strengths and entailing grain coarsening. Using powder spinning, melt spinning or spray compacting with subsequent compacting and/or extruding, economic large-scale production of cylinder faces or engine blocks is not possible, especially when compared to competitive solutions such as thermal spraying or laser nitriding of gray iron.
All ultrahigh-strength Al special alloys with 800 MPa<σtensRT=1,600 MPa are produced using either powder metallurgy or powder spinning or a melt spinning process or spray compacting. They have a high volume share of intermetallic phases which, owing to rapid solidifying, are present in the form of fine dispersoids smaller than 50-100 nm in size.
The patent application US 2003/0185701 (K. L. Sahoo et al.) discloses casting parameters for the Al—Fe—V—Si material system. The casting temperatures mentioned therein are 800-1,000° C., with casting being effected in an ingot mold preheated to 350-500° C. The inoculum for grain refinement consists of <1.0 wt % Mg/Ni. A relation to tribologically loaded surfaces is neither made obvious nor disclosed, which also applies to the casting temperatures according to the invention.
The publication by Sahoo et al., J. of Materials Processing Technology 135 (2003) 253-257, presents the mechanical properties and structural morphologies of an Al-8.3Fe-0.8V-0.9Si alloy, grain-refined with 0.18 wt % Mg, which solidified with 1 K/s to 14 K/s.
The Al-8.3Fe-0.8V-0.9Si alloys produced according to US 2003/0185701, with and without grain refinement by means of 0.1-1.0 wt % Mg, achieved a Vickers hardness between 43 and 143, which is significantly lower than that of the alloys according to the invention.
The Chinese publication by Z. H. Chen et al., J. Cent. South Univ. Technol. Vol. 7, No. 4, December 2000, presents the production of components of an AA8009 alloy according to the OSPREY process. A relation to tribologically loaded surfaces is neither made obvious nor disclosed.
The patent application US 2004/0156739 discloses aluminum alloys with up to 20 wt % rare earths for turbine uses, cast with cooling rates of 10-100 K/s. A relation to tribologically loaded surfaces is neither made obvious nor disclosed.
The patent application US 2004/0261916 discloses a dispersion-solidifying Al—Ni—Mn material system, wherein the alloys consisting of 0.5-6.0 wt % Ni and 1.0-3.0 wt % Mn with up to 0.3 wt % Zr and/or Sc can be grain-refined. A relation to tribologically loaded surfaces is neither made obvious nor disclosed.
The patent application US 2004/0140019 discloses a dispersion-solidifying Al+<11 wt % (Mg, Li, Si, Ti, Zr) material system enriched with up to 0.3 wt % nitrogen by low-temperature grinding. It is used in US 2004/0255460 for the production of tubes conducting cryogenic media. A relation to casting technologies or tribologically loaded surfaces is neither made obvious nor disclosed.
Accordingly, there is a continuing demand for a material which overcomes the above-described limitations of the prior art.
A first aspect of the invention that contributes to a solution of the problem being posed lies in providing a method for producing a wear-resistant aluminum alloy. The method according to the invention comprises the steps of:
The present invention improves the wear resistance, the tribological load-bearing capacity and the heat resistance of aluminum base alloys. This may be caused by intermetallic phases deposited within the structure, such as AlFe3, Al3Fe (HV ˜9.8 GPa, , Al5Fe2 (η, HV˜10.5 GPa), Al6Fe, Al13Fe4, Al5Fe2 (η, HV˜10.5 GPa), Al3(Ti, Cr), Al3Ti, Al4(Cr, Fe), Al10(Cr, Fe), AlSi2 or Al8Fe2Si having microhard-nesses of from 4,000 to 8,000 MPa.
Eutectic melting equilibria with liquids temperatures below 600-620° C. are not formed in the metallurgy according to the invention. Therefore, the silicon content preferably should not be higher than 2.0 wt %, more preferably not higher than 1.0 wt % Si. The intermetallic phases are formed from eutectic (α—AlAl3Fe) and peritectic phase equilibria.
A predominant morphological difference of the alloys according to the invention is the form of the dendrites generated from intermetallic phases compared to the silicon crystals deposited in well-known AlSi alloys. The silicon crystals in aluminum alloys are present as individual single crystals, while a dendritic network allows excellent incorporation in the matrix to absorb shear stress from tribological load. Unambiguous characterization of the alloys according to the invention is possible via the production process thereof.
Furthermore, a specific object of the present invention is to prepare the alloy elements, such as Fe, Ti, Cr, Mo or V, which, in solid state, are insoluble or barely soluble in aluminum, in the form of homogeneous structures free of segregation, using straightforward casting technology. More specifically, this is achieved by grain refinement using an element selected from the group of B, Ce, Sr, Sc, Mg, Nb, Mn and Zr and by using specific casting temperatures.
A mold form in the meaning of the invention may encompass any form suitable for metal casting technology. For test purposes, graphite ingot molds can be used, for example.
It should be noted that predicting the formation of intermetallic phases or dendrites during casting is not possible, but it is precisely the presence thereof that has a considerable influence on the tribological material properties. Lacking predictability of intermetallic phases, morphology and composition of the individual components in the structure, as well as problems arising from the formation of eutectic phases lead to the conclusion that purely theoretical considerations are not suitable for predicting suitable materials. It has now been found in experiments that holding the temperature of the melt above 650° C. causes establishment of a phase equilibrium over the entire volume of the material within a period of time reasonable for commercial applications.
Following melting and homogenizing, between 0.5 and 0.8 wt % of one or more elements selected from the group of B, Ce, Sr, Sc, Mg, Nb, Mn or Zr can preferably be alloyed for grain refinement. Grain refinement predominantly reduces the size of the dendrites of intermetallic phases deposited during solidification, but also results in an increase of the crystal germ number/density during primary crystallization of aluminum.
A higher cooling rate of >100 K/s achieves the same effect, so that grain refinement can be used with advantage to obtain a uniform structural pattern when the wall thickness of the cast parts is larger. The dendrites, still being relatively large, are favorable to the tribological sliding load and binding of the intermetallic phases within the structure, but unfavorable in supplementing the solidification front with melt. For this reason, the size thereof must be optimized by grain-refining elements, optionally with the aid of magnetic stirring.
Formation of dendrites from the intermetallic phases can also be prevented by magnetic stirring. In this way, magnetic stirring improves feeding the solidification front with fresh melt and aids in preventing voids (pores).
The casting temperature in step (iii) is preferably in the range of 1° C. to 80° C., particularly in the range of 10° C. to 50° C. above the melting temperature of the alloy. The casting temperatures are preferably below 800° C.
According to another preferred variant of the method, an alloy having 4-8 wt % Fe and/or 3-5 wt % X is provided. It is also preferred to preset X for the combination of elements (a) in such a way that the share of Si is smaller than or equal to 2 wt %, particularly smaller than or equal to 1 wt %. The measures mentioned above result in aluminum alloys having particularly favorable tribological behavior.
In a preferred fashion, the steps (ii) and (iii) form part of a metallurgic melt casting process selected from the group of sand casting, pressure casting, continuous casting, thin-strip casting, centrifugal casting and cold crucible process. The above-mentioned processes are particularly easy to accomplish in cooperation with the method according to the invention. In a preferred fashion, the workpiece consisting of the alloy can be treated by die-forging wherein the workpiece is completely surrounded by the closed mold, i.e. the forging die, and the cavity incorporated in the forging die determines the shape of the finished molding.
Finally, the temperature of the casting mold preferably ranges from 450° C. to 600° C. In this way, it is possible to produce aluminum alloys having particularly favorable tribological behavior.
A second aspect of the invention relates to an aluminum alloy produced or obtainable according to the method described above.
A third aspect of the invention relates to the use of the above-mentioned aluminum alloy in the production of sliding elements in crankshaft bearing shells, cylinder faces, piston rings, pistons, valve guides, bearing bushes or bearing shells.
With reference to the examples and associated drawings, the invention will be illustrated in more detail below.
The following
As seen in
In addition to deposition of primary dendrites of Al3Fe (001-1265) and Al80V12Fe7.5 (JCPDS No. 040-1229) in the 88.5Al8.5Fe1.3V1.7Si alloy, the REM images of
Similarly, the Al84.4Fe7.0Cr6.0Ti2.5 alloy system deposits a dense, yet closed, primary dendrite network (see
As is the case with the 88.5Al8.5Fe1.3V1.7Si alloy, the AlFeCrTi alloy shows a fine, “perlite-like” pattern from eutectic decomposition of the residual melt of the Al84.4Fe7.0Cr6.0Ti2.5 alloy (
By reducing the difference between the casting and ingot mold temperatures to 250 K and grain refining using 0.1 wt % Mg, the dendrite network in an Al84.4Fe7.0Cr6.0Ti2.5Mg0.1 alloy appears somewhat finer (
In total, it has also been found that the AlFeXY alloys according to the invention can be cast with advantage at a slightly excessive temperature of 150 K at maximum above the melting temperature of the alloy.
The outside-engine characterization of the tribological behavior of the AlFeXY alloys according to the invention was performed according to the BAM testing methodology which has been described in detail in the citation “Woydt M. and N. Kelling, Characterization of the tribological behaviour of lubricants and materials for the tribosystem piston ring/cylinder liner, in: ASTM STP 1404, “Bench testing of industrial fluid lubrication and wear properties used in machinery applications”, June 2000, Seattle, ISBN 0-8031-2867-3, p. 153”.
In the BAM test procedure, nitrided rings against AlSi17 (AlSi17Cu4Mg, “Alusil”, from Kolbenschmidt) or AlSi25Ni4 (“Silitec” from PEAK Werkstoff GmbH) are regarded as low-wearing up to 25 N normal force, i.e., a low-wear condition, passing to a high-wear condition above ˜25 N (oil-dependent!). The mixed/boundary friction coefficients of AlSi alloys (subjected to chemical exposure) in the BAM test procedure (T=170° C.; s=24 km; v=0.3 m/s) compared to Al84.4Fe7Cr6Ti2.5Mg0.1 can be inferred from the following table.
Using more than 200 tests with GGL20HCN high-carbon gray iron on an average, the mean wear coefficient of GGL20HCN in the BAM test procedure was 4.8×10−8 mm3/Nm at FN=50 N. The wear resistance of the Al84.4Fe7Cr6 Ti2.5Mg0.1 alloy grain-refined with 0.1 wt % Mg against the molybdenum-based MKP81A piston ring was comparable to the wear resistance and load-bearing/carrying capacity of high-carbon gray iron.
The higher friction coefficients with the SAE 5W-30 initial-fill oil under mixed/boundary friction of the AlFeXY alloys compared to GGL20HCN represent a remarkable feature in the table.
The relatively high mixed friction coefficients can be reduced by using a polyalkylene glycol (PAG46-4+2.6 Phopani, HTHS=3.6 mPas) or a polypropylene glycol monobutyl ether (PPG32-2+2.6 Phopani; HTHS=2.87 mPas) (see
Referring to the nitrided piston ring only,
Crankshaft slide bearing shells made of “eutectic” AlSi12CuNiMg (Karl Schmidt GmbH, KS 1275 (material number: 3210.9), now Kolbenschmidt AG, with 11-13.5% Si, 0.5-1.3 Cu, 0.8-1.3 Mg, 0.5-1.3 Ni, ˜0.25 Zn, ˜0.1% Cr, balance Al) were used in the BMW 801 double-row radial aircraft engine (Ing. Buske, Die Abhängigkeit der Lagerbelastbarkeit von der Lagerbauform, Report of the Schmierstoff-Tagung, Part 1: Reibung und Verschleiβ, Kälteverhalten, Dec. 11/12, 1941, Berlin Adlershof, pp. 119-148), wherein the crankshaft journal was made of a nitrided steel with HRC 58. Since then, such a material solution has been unusual in the automotive and construction machinery industries. Current faces of slide bearing shells made of AlSn14Cu8, AlSn20, PbSn10Cu3, GZ-CuSn7ZnPb or lead bronzes, as well as friction-reducing lacquer coatings, require anti-corrosion additives for non-ferrous metals in the lubricants, significantly deteriorating the ecotoxicological properties. On the whole, AlSi or AlFeXY alloys are less endangered by corrosion, so that anti-corrosion additives are dispensable or can be used at significantly lower concentrations. Also well-known in the prior art is an Al96(Ni,Mn) alloy (Glyco-172) with a maximum allowable geometrical bearing load of 80 MPa, which is fatigue- and corrosion-resistant, but tends to show adhesive failure in the event of lacking lubrication, which is suppressed by virtue of the AlFeXY metallurgy.
The tribological load-bearing capacity limit of 100 MPa (geometrical surface load) of the sliding couple AlSi12CuNiMg/nitrided steel in the BMW 801 double-row radial engine at an oil inlet temperature of 99° C. of the fully synthetic lubricant “SS-1600” based on an adipic ester and ethylene oil is remarkable because, having a kinematic viscosity η100C˜6.2 mm2/s, it was significantly “thinner” than current high-lubricity oils having η100C˜9-12 mm2/s.
Another advantage to an AlFeXY system is that the anti-wear and high-pressure additives in engine and transmission oils—also as a consequence of the metallurgy of the specimen in tribometers—have been adjusted to iron rather than silicon.
Dissipating the heat from the valve shaft into the cylinder head, valve guides require high thermal diffusivity in association with an appropriate wear resistance. For this reason, valve guides are preferably made of copper base alloys such as CuZn36Mn3Al2SiPb (≅CuZn40Al2 according to DIN 17660 or CW713R) with λRT˜63 W/mK or KRT˜19.7 mm2/s. Temperatures of 500° C. are not unusual on the surfaces of the lower part of the outlet valve guide. The aluminum alloys according to the invention offer a thermal diffusivity increased by 3-4 times, in association with the required temperature resistance and without melting equilibria up to >600° C.
Aluminum piston materials consist of eutectic AlSi2CuXX alloys or hypereutectic AlSi18CuXX alloys, likewise with up to 0.85 wt % iron. The thermal diffusivities range between 55 mm2/s<KRT<61.7 mm2/s.
Number | Date | Country | Kind |
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10 2005 047 037.8 | Sep 2005 | DE | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/EP2006/065258 | 8/11/2006 | WO | 00 | 3/30/2008 |