AU2005238479A1 - Heat treatable Al-Zn-Mg-Cu alloy for aerospace and automotive castings - Google Patents

Description

WO 2005/106058 PCTIUS2005/013769 Heat Treatable Al-Zn-Mg-Cu Alloy for Aerospace and Automotive Castings Cross Reference to Related Applications [0001] This application claims the benefit of U.S. Provisional Application Serial No. 60/564,813 filed on April 22, 2004, which is fully incorporated herein by reference thereto. It is also closely related to the patent application "Heat Treatable Al-Zn-Mg Alloy for Aerospace and Automotive Castings" filed concurrently with this application, and which is also incorporated herein by reference thereto. Field of the Invention [0002] This invention is an aluminum alloy for aerospace and automotive shaped castings, castings comprised of the alloy, and methods of making cast components of the alloy. Background of the Invention [00031 Cast aluminum parts are used in structural applications in automobile suspensions to reduce weight. The most commonly used group of alloys, Al-Si 7 -Mg, has well established strength limits. In order to obtain lighter weight parts, higher strength material is needed with established material properties for design. At present, cast materials made of A3 56.0, the most commonly used Al-Si 7 -Mg alloy, can reliably guarantee ultimate tensile strength of 290 MPa (42,060 psi), and tensile yield strength of 220 MPa (31,908 psi) with elongations of 8% or greater. [0004] A variety of alternate alloys exist and are registered that exhibit higher strength than the Al-Sig-Mg alloys. However, these exhibit problems in castability, corrosion potential or fluidity that are not readily overcome. The alternate alloys are therefore less suitable for use. [0005] Where high strength is required, forged products are often used. These are usually more expensive than cast products. There exists the potential for considerable cost savings if cast products can be used to replace forged products with no loss of strength, elongation, corrosion resistance, fatigue strength, etc. This is true in both automotive and aerospace applications. [0006] Casting alloys exhibiting higher tensile strength and fatigue resistance than the A-Si- 7 -Mg material are desirable. Such improvements could be used to reduce weight in new parts or in existing parts which can be redesigned to use the improved material properties to great advantage.

WO 2005/106058 PCTIUS2005/013769 Introduction to the Invention [00071 The alloy of the present invention is an Al-Zn-Mg base alloy for low pressure permanent or semi-permanent mold, squeeze, high pressure die, pressure or gravity casting, lost foam, investment casting, V-mold, or sand mold casting with the following composition ranges (all in weight percent): Zn: about 3.5-5.5%, Mg: about 1-3%, Cu: about 0.05-0.5%, Si: less than about 1.0%, Fe and other incidental impurities: less than about 0.30%, Mn: less than about 0.30%. [0008] Silicon up to about 1.0% may be employed to improve castability. Lower levels of silicon may be employed to increase strength. For some applications, manganese up to about 0.3% may be employed to improve castability. In other alloys, manganese is to be avoided. [00091 The alloy may also contain grain refiners such as titanium diboride, TiB 2 or titanium carbide, TiC and/or anti-recrystallization agents such as zirconium or scandium. If titanium diboride is employed as a grain refiner, the concentration of boron in the alloy may be in a range from 0.0025% to 0.05%. Likewise, if titanium carbide is employed as a grain refiner, the concentration of carbon in the alloy may be in the range from 0.0025% to 0.05%. Typical grain refiners are aluminum alloys containing TiC or TiB 2 . [0010] Zirconium, if used to prevent grain growth during solution heat treatment, is generally employed in a range below 0.2%. Scandium may also be used in a range below 0.3%. [0011] In the T6 temper, the alloy demonstrated 50% higher tensile yield strength than is obtainable from A356.0-T6, while maintaining similar elongations. This will allow part designs requiring higher strength than alloys which are readily available today in Al-Si-Mg alloys such as A356.0-T6 or A357.0-T6. Fatigue performance in the T6 temper is increased over the A356.0-T6 material by 30%. Summary of the Invention [0012] In one aspect, the present invention is an aluminum alloy including from about 3.5-5.5% Zn, from about 1-3%Mg, about 0.05-0.5% Cu and it contains less than about 1% Si.

WO 2005/106058 PCTIUS2005/013769 [0013] In another aspect, the present invention is a heat treatable shaped casting of an aluminum alloy including from about 3.5-5.5% Zn, from about 1-3% Mg, from about 0.05 0.5% Cu, and less than about% Si. [0014] In another aspect, the present invention is a method of preparing a heat treatable aluminum alloy shaped casting. The method includes preparing a molten mass of an aluminum alloy including from about 3.5-5.5% Zn, from about 1-3% Mg, from about 0.05 0.5% Cu, and less than about 1% Si. The method further includes casting at least a portion of the molten mass in a mold configured to produce the shaped casting, permitting the molten mass to solidify, and removing the shaped casting from the mold. Brief Description of the Drawings [00151 Figure 1 is a photograph of a cut surface of a cut sample of prior art A356.0 alloy cast in a shrinkage mold showing the shrinkage cracking tendency of the prior art A356.0 alloy; [00161 Figure 2 is a photograph, similar to Figure 1, of a cut surface of a second sample of prior art A356.0 cast in a shrinkage mold showing the shrinkage cracking tendency of the prior art A356.0 alloy; [00171 Figure 3 is a photograph of a cut surface of a sample of the alloy of the present invention cast in a shrinkage mold showing a lack of shrinkage cracking; [00181 Figure 4 is a photograph, similar to Figure 3, of a cut surface of a second sample of the alloy of the present invention cast in a shrinkage mold showing a lack of shrinkage cracking; [00191 Figure 5 presents strength and elongation data for directionally solidified samples of the present invention in T6 condition; [00201 Figure 6 is a photograph of a front knuckle casting of an alloy according to the present invention, showing locations from which tensile test samples were obtained; [00211 Figure 7 is a plot of strength and elongation data for tensile test samples cut from the casting shown in Figure 6 after T5 and also after T6 heat treatments; [00221 Figure 8 is a graph showing the S-N fatigue response (ASTM E 466 testing, R=-1) of the present alloy in T6 condition compared to the response of prior art A356.0-T6; [00231 Figure 9 is a graph showing staircase fatigue testing of the present alloy in T6 condition compared to the response of prior art A356.0-T6 with the mean fatigue strength for A356.0-T6; WO 2005/106058 PCTIUS2005/013769 [0024] Figure 10 is a graph showing depth of attack after an intergranular corrosion test of the alloy of the present invention compared to the prior art alloy A356; [0025] Figure 11 is a photomicrograph of an alloy according to the present invention after an intergranular corrosion test, on the as cast side of the sample; [00261 Figure 12 is a photomicrograph of an alloy according to the present invention after an intergranular corrosion test, on a machined side of the sample; [0027] Figure 13 is a photomicrograph of the prior art alloy A356 after an intergranular corrosion test; [00281 Figure 14 is a graph presenting results of a stress corrosion test on alloys of the present invention, with varied levels of copper; and [0029] Figure 15 is a graph showing the effect of copper and magnesium levels on stress corrosion cracking for alloys of the present invention. Detailed Description of Preferred Embodiments and Comparison with Prior Art Alloys [0030] When referring to any numerical range of values herein, such ranges are understood to include each and every number and/or fraction between the stated range minimum and maximum. A range of about 3.5 to 5.5 wt% zinc, for example, would expressly include all intermediate values of about 3.6, 3.7, 3.8 and 3.9%, all the way up to and including 5.3, 5.35, 5.4, 5.475 and 5.499% Zn. The same applies to each other numerical property and/or elemental range set forth herein. [00311 Table I presents composition data for the alloys which were tested. The first and third lines showing compositions are for directionally solidified castings. The second line is for the composition used in a shaped casting. The shaped casting was the front knuckle shown in Fig. 6. Table I: Alloy Composition Composition of test samples (Weight %) Zn Mg Si Cu Mn Fe Ti B DS Casting 4.28 1.99 0.04 0.01 0.00 0.04 0.00 0.0005 Cast Knuckle 4.2 2 <0.1 0.2 0.05 <0.1 0.06 0.02 DS Casting 4.57 2.03 0.04 0.31 0.04 0.05 0.06 0.02 [0032] Table II presents room temperature mechanical properties of the directionally solidified alloys having the compositions shown in the first and third data lines of Table I. The WO 2005/106058 PCTIUS2005/013769 first data line in Table II is for a directionally solidified casting comprised of the alloy of the first data line in Table I after five weeks of natural ageing. The second data line in Table 2 is for the same alloy after T5 heat treatment, and the third data line is for that alloy after T6 heat treatment. The fourth and fifth data lines in Table II are for the alloy in the bottom line of Table 1, which is a high copper alloy. This alloy, also, was subjected to a T6 heat treatment. Table II: DS casting room temperature mechanical properties Temper TYS (MPa) UTS (MPa) El % F 5 (5 weeks natural ageing) 185 322 18 T5 245 323 14 T6 338 359 7 T6 (H1igh Cu) 382 424 12 Cooling rate: 1"C/sec I T6 (High Cu) 372 412 9 Cooling rate: 0.2 0 C/sec [0033] The development of mechanical properties of directionally solidified samples of the present invention during heat treatment is presented in Figure 5. The composition of these samples was presented in the first data row in Table 1. The solution heat treatment was at 1030 'F (554 'C) for 8 hours, which was followed by the cold water quench, and then artificial ageing. Samples were taken out of the oven and subjected to mechanical testing after various amounts of artificial ageing. The properties measured were TYS, UTS and percent elongation. The duration of the artificial ageing was 15 hours. During the first 6 hours, the temperature was 250 'F (121 'C). For the subsequent 9 hours, the temperature was 320 'F (160 'C). Values for the TYS and UTS are referenced to the scale on the left; values of percent elongation are referenced to the scale on the right. [0034] Table III presents data for front knuckle castings as shown in Fig. 6. This is an alloy according to the present invention, and has the composition presented in the second data row in Table 1. The locations of tensile test samples 1, 2 and 3 are indicated in Fig. 6. Tests were performed on one casting subjected to a T5 heat treatment consisting of 160 "C for 6 hours, and one casting subjected to a T6 heat treatment consisting of solution heat treatment at 554 "C for 8 hours followed by a cold water quench, then by artificial ageing at 121 *C for 6 hours and 160 "C for 6 hours.

WO 2005/106058 PCTIUS2005/013769 Table I: CS front knuckde room temperature mechanical properties Sample Temper TYS MPa US MPa Elongation (%) Location 1 163.4 237.9 6 2 T5 189.6 259.2 5 3 170.3 253.0 10 1 357.8 388.9 6 2 T6 375.8 419.9 11 3 356.5 400.6 13 [00351 It is noted that in Table III, extremely high tensile strength values and good elongation are obtained for the alloy in both T5 and T6 tempers. It is noted, again, that the composition was as presented in the second data line in Table I. The data presented in Table III are plotted in Fig. 7. [00361 The graph in Figure 8 shows the S-N fatigue response of the alloy of the present invention in comparison to the response of the prior art alloy A356.0-T6. This test was ASTM E466, R=-1. It can be seen that after 100,000 cycles, the alloy of the present invention is markedly superior to the prior art alloy. [00371 Figure 9 is a graph showing staircase fatigue testing of the alloy of the present invention in T6 condition compared to the response of the prior art alloy, A356.0-T6 with a calculated mean value for A356.0-T6. The composition of the alloy of the present invention was as presented in the second data row of Table 1. [0038] The samples were solution heat treated at 526 'C or 554 'C, quenched and artificially aged at 160 *C for 6 hours. As seen earlier, the fatigue response of these samples is appreciably improved when compared to A3 56.0-T6 material. [00391 The mean fatigue strength of the alloy of the present invention was 109.33 MPa with a standard deviation of 9.02 MPa. The standard deviation of the mean fatigue strength was 3.01 MPa. The calculated mean fatigue strength at 107 cycles of A356.0 T6 is 70MPa. [0040] Corrosion resistance of the alloy of the present invention was tested using the ASTM GI 10 corrosion test, which is the "Standard Practice for Evaluating Intergranular Corrosion Resistance of Heat Treatable Aluminum Alloys by Immersion in Sodium Chloride ± Hydrogen Peroxide Solution".

WO 2005/106058 PCTIUS2005/013769 [0041] In this test, specimens are immersed in a solution that contains 57g/L NaCl and 10 mL/L H202 (30%) for 6-24 hours. The specimens are then cross-sectioned and examined under optical microscope for type (intergranular corrosion or pitting) and depth of corrosion attack. [0042] Figure 10 is a graph presenting the depth of attack following the ASTM G1 10 corrosion test after 6 hours and 24 hours for an alloy according to the present invention and for the alloy A356.0. [0043] Figures 11 and 12 are photomicrographs of an alloy according to the present invention after 24 hours exposure to the ASTM GI 10 corrosion test. Very little intergranular corrosion can be seen in these photomicrographs. [00441 Figure 13 is a photomicrograph of the A356.0 alloy after 24 hours of exposure to the ASTM GI10 corrosion test. Considerable intergranular corrosion can be seen in this photomicrograph. [0045] Corrosion tests were also performed employing the ASTM G44 test, which is the "Standard Practice for Exposure of Metals and Alloys by Alternate Immersion in Neutral 3.5% Sodium Chloride Solution". In this test, stressed specimens are subject to a 1-hour cycle which includes immersion in 3.5% NaCl solution for 10 minutes and then in lab air for 50 minutes. This 1-hour cycle is continuously repeated. During the test, the specimens are regularly inspected for cracks and failures. [0046] Table IV presents the compositions of various alloys according to the present invention, which were employed in ASTM G44 tests.

WO 2005/106058 PCT/US2005/013769 Table IV Sample Number Alloy Composition Zn Mg Cu Ti B Zr 59 4.23 1.5 0.29 0.029 0.0055 <0.001 86 4.41 1.49 0.23 0.036 0.0038 n/a 110 4.39 1.74 0.28 0.057 0.0129 < 0.001 117 4.39 1.74 0.28 0.057 0.0129 <0.001 138 4.19 1.99 0.26 0.073 0.015 <0.001 159 4.31 1.93 0.24 0.105 0.0252 0.1127 A 4.43 2.05 0.06 0.0208 B 4.5 2 0.2 0.06 0.02 n/a C 4.5 1.2 D 4.5 1.2 [0047] Table V presents the test results for the alloy compositions presented in Table IV. Table V: ASTM G44 test of alloys with various Mg and Cu contents Run or S Temper Stress Percentage F/N Days to Failure Number Level(MPa) of TYS 59 (Knuckle) T5 152.37 75% 0/5 86 (Knuckle) T6 239.25 75% 4/5 17, 17, 22, 28 110 (Knuckle) T5 154.44 75% 0/5 117 (Knuckle) T6 196.50 75% 0/5 138 (Knuckle) T6 247.52 75% 2/5 45, 61 159 (Knuckle) T6 270.27 75% 3/5 11, 11, 11 A T5 186.16 75% 5/5 4, 4, 4, 7, 64 B T6 182.02 50% 4/4 7,11, 13, 19 C T5 135.83 75% 0/5 D T6 194.43 75% 0/5 [0048] Figure 14 is a graph presenting the results of these tests. It is seen that, for alloys of the present invention, and at these high magnesium levels, increasing copper provides increased resistance to stress corrosion cracking. [00491 Figure 15 is a graph showing the effect of copper and magnesium levels on stress corrosion cracking for alloys of the present invention. This shows that for alloys WO 2005/106058 PCTIUS2005/013769 according to the present invention which have magnesium in the range from 1.5-2%, it is desirable to include copper in the range from 0.25-0.3%. [0050] Table VI and VII present the results of plant trials in which repeated shots were made from a single liquid metal reservoir. One trial was performed on April 4; one was performed on June 4 and one on September 4. On each day, the composition for all the castings made varied very little. [0051] Table VI presents the ranges of the compositions of samples taken on each of the test days. The compositions contained high levels of magnesium and copper, which were expected to provide exceptionally high strength levels. Table VI: MCC plant trial alloy composition ranges Date Si Fe Mn Cu Mg Zn Ti | Zr Apr-04 0.05- 0.03- 0.03- 0.22- 1.9- 4.1- 0.03- 0.001- 0.00 0.09 0.04 0.04 0.27 2.2 4.7 0.06 0.0007 0.15 Jun-04 0.03- 0.04- 0.04- 0.24- 1.5- 4.6- 0.03- 0.008- 0,00 0.09 0.08 0.05 0.29 2.0 4.9 0.11 0.025 0.12 0.04- 0.14- 0.03- 0.27- 2.1- 4.4- 0.04- 0.0006 0.13 Sep-04 0,05 0.20 0.04 0.32 2.3 4.9 0.07 ~ 0.14 0.0037 100521 Table VII presents the stress data, ultimate tensile strength, tensile yield strength, and elongation for four different locations in each casting. The column for sample numbers labels the individual castings. The column for location defines individual mechanical test samples cut from the castings.

WO 2005/106058 PCTIUS2005/013769 Table VII: Plant trial mechanical properties Sample Location UTS YTS Elong. Sample Location UTS YTS Elong. (MPa) (MPa) (%) (MPa) (MPa) (%) April 2004 tests June 2004 tests 1-019 1 337 269 9.9 86 1 268 216 9.3 1-019 2 386 349 9.5 86 2 359 321 9,2 1-019 3 375 357 3.1 86 3 319 294 6.7 1-019 4 405 365 10.6 86 4 366 339 6.7 1-024 1 345 301 8.1 117 1 238 193 12.3 1-024 2 384 355 8.2 117 2 305 254 14.6 1-024 3 388 359 6.3 117 3 291 244 8.5 1-024 4 406 370 9.7 117 4 331 286 8.4 2-007 1 371 330 4.7 138 1 264 198 8.9 2-007 2 382 340 8.2 138 2 367 320 8.8 2-007 3 381 352 5.5 138 3 343 308 7.5 2-007 4 419 378 9.25 138 4 375 341 8.9 2-024 1 349 301 8.5 138 IL 373 334 6.6 2-024 2 381 340 9.25 138 1U 356 333 6.4 2-024 3 369 342 3.7 159 1 326 265 9.7 2-024 4 408 370 11.7 159 2 392 352 11,7 3-165 1 331 268 10.1 159 3 368 339 7.2 3-165 4 436 382 8.85 159 4 404 369 9.3 1-014 1 371 335 6.1 159 IL 407 359 9.2 1-014 2 392 352 8.4 159 1U 413 375 7.9 1-014 3 348 318 5.1 166 4 393 354 7.2 1-014 4 392 357 7.5 Sep 2004 Tests Sample Location UTS YTS Elong. Sample Location UTS YTS Elong. (MPa) (MPa) (%) (MPa) (MPa) (%) 79 1 326 267 12.4 129 1 330.5 270.5 11 79 2 385 338 9 129 2 351.5 296.5 5 79 3 401 356 9.8 129 3 369 316 11 79 4 387 357 5.6 129 4 387.5 352.5 6 53 1 355 303 12.9 151 1 284 269 4 53 2 396 343 10.8 151 2 349 302 10 53 3 396 349 9.5 151 3 380.5 334.5 10 53 4 404 371 5.7 151 4 378 365.5 4 48 1 361 305 11.6 152 1 364.5 311.5 10 48 2 393 342 11.1 152 2 386 349 6 48 3 395 350 8.85 152 3 351 320 3 48 4 373 332 6.8 152 4 382 347 6 [0053] It is noted that at these high levels of magnesium and copper, excellent strength levels are obtained, with good elongation.

WO 2005/106058 PCTIUS2005/013769 [0054] Having described the presently preferred embodiments of the present invention, it is to be understood that the invention may be otherwise embodied within the scope of the appended claims.

Claims (27)

1. A heat treatable aluminum alloy for shaped castings, said aluminum alloy comprising, in weight percent, alloying ingredients as follows: Zn: about 3.5-5.5%; Mg: about 1-3%; Cu: about 0.05-0.5%; Si: less than about 1%.

2. An aluminum alloy according to claim 1 further comprising at least one grain refiner selected from the group consisting of boron, carbon and combinations thereof

3. An aluminum alloy according to claim 2 wherein said at least one grain refiner includes boron in a range from about 0.0025 to about 0.05%.

4. An aluminum alloy according to claim 2 wherein said at least one grain refiner includes carbon in a range from about 0.0025 to about 0.05%.

5. An aluminum alloy according to claim 1 further comprising at least one anti-recrystallization agent selected from the group consisting of zirconium, scandium and combinations thereof

6. An aluminum alloy according to claim 5 wherein said at least one anti recrystallization agent includes zirconium in a range below 0.2%.

7. An aluminum alloy according to claim 5 wherein said at least one anti recrystallization agent includes scandium in a range below 0.3%.

8. An aluminum alloy according to claim 1 wherein said zinc is at a concentration of about 4.2 to 4.8%.

9. An aluminum alloy according to claim 1 wherein said magnesium is at a concentration of about 1.7 to 2.3%. WO 2005/106058 PCTIUS2005/013769

370054-00048-1

10. An aluminum alloy according to claim 8 wherein said copper is at a concentration of about 0.25-0.3%.

11. An aluminum alloy according to claim 10 wherein said copper is at a concentration of about 0.27-0.28%.

12. An aluminum alloy according to claim 1 wherein a concentration of iron in said alloy is less than about 0.3%.

13. An aluminum alloy according to claim 1 wherein a concentration of manganese in said alloy is less than about 0.3%.

14. A shaped casting of an aluminum alloy, wherein said alloy comprises alloying ingredients as follows: Zn: about 3.5-5.5%; Mg: about 1-3%; Cu: about 0.05-0.5%; Si: less than about 1%.

15. A shaped casting according to claim 14 after T5 heat treatment.

16. A shaped casting according to claim 14 after T6 heat treatment.

17. A shaped casting according to claim 14 wherein said zinc is at a concentration of about 4.2-4.8%.

18. A shaped casting according to claim 14 wherein said magnesium is at a concentration of about 1.8-2.2%.

19. A shaped casting according to claim 14 wherein said copper is at a concentration of about 0.25-0.3%. WO 2005/106058 PCT/US2005/013769

20. A shaped casting according to claim 14 wherein said copper is at a concentration of about 0.27-0.28%.

21. A method of making an aluminum alloy shaped casting, said method comprising: preparing a molten mass of an aluminum alloy, said alloy comprising alloying ingredients as follows: Zn: about 3.5-5.5%; Mg: about 1-3%; Cu: about 0.05-0.5%; Si: less than about 1%; casting at least a portion of said molten mass in a mold configured to produce said shaped casting; permitting said molten mass in said mold to solidify; removing said shaped casting from said mold.

22. A method according to claim 21 further comprising subjecting said shaped casting to a T5 heat treatment.

23. A method according to claim 21 further comprising subjecting said shaped casting to a T6 heat treatment.

24. A method according to claim 21 wherein said zinc is at a concentration of about 4.2-4.8%.

25. A method according to claim 21 wherein said magnesium is at a concentration of about 1.8-2.2%.

26. A method according to claim 21 wherein said copper is at a concentration of about 0.25-0.3%.

27. A method according to claim 26 wherein said copper is at a concentration of about 0.27-0.28%. 1 A