EP3425074B1 - Substantially pb-free aluminum alloy composition - Google Patents

Substantially pb-free aluminum alloy composition Download PDF

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EP3425074B1
EP3425074B1 EP17181963.4A EP17181963A EP3425074B1 EP 3425074 B1 EP3425074 B1 EP 3425074B1 EP 17181963 A EP17181963 A EP 17181963A EP 3425074 B1 EP3425074 B1 EP 3425074B1
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aluminum alloy
alloy composition
composition
temper
ksi
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French (fr)
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EP3425074A1 (en
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Emre Ildeniz
Robert A. Matuska
Dave J. SHOEMAKER
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Kaiser Aluminum Fabricated Products LLC
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Kaiser Aluminum Fabricated Products LLC
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/18—Alloys based on aluminium with copper as the next major constituent with zinc
    • 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
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with copper as the next major constituent

Definitions

  • the present invention relates to a substantially Pb-free aluminum alloy composition, and method for making said alloy composition, while achieving the machinability characteristics of their Pb-containing counterparts.
  • Pb-containing aluminum alloys such as 2011 and 6262 (registered with the Aluminum Association in 1954 and 1960, respectively) have been used for demanding machinability applications. These applications require an alloy that can be machined at high material removal rates while maintaining good machined surface finishes and producing machine chips that are small and easily removed from the work area to prevent jamming the machine tools.
  • Aluminum alloys containing Pb met this need by providing intermetallic phases that acted as chip breakers in the material which enabled faster material removal rates, small machine chips and good machined surfaces. While Pb does provide an effective solution, it is a heavy metal and considered a hazardous material.
  • Pb-free alternative alloys that are still available are often restricted in their availability and often have limits placed on the machining parameters that do not achieve the same levels of performance as the Pb-containing alternatives.
  • Pb-containing alloy 2011-T3 has a minimum yield strength of 38 KSI / 262 MPa.
  • the substantially Pb-free aluminum alloy composition of the present invention provides a free machining product that achieves the same or superior machining performance in terms of high material removal rates, machining chip size and machined surface finish as their incumbent Pb-containing predecessors.
  • the substantially Pb-free aluminum alloy composition of the present invention is not susceptible to cracking in thin wall, complex machining under severe material removal conditions. This is a critical distinction that has not been achieved in other inventions attempting to solve the afore-mentioned technical problem. Materials that are susceptible to such cracking conditions render the machining performance irrelevant either by requiring substantially lower material removal rates or disqualifying the material altogether to ensure the integrity of the final part.
  • the substantially Pb-free aluminum alloy composition of the present invention substantially meets or exceeds the material property requirements of the current free machining materials. Specifically, in a preferred embodiment, the substantially Pb-free aluminum alloy composition meets the minimum material properties for AA2011-T3 including Ultimate Tensile Strength ⁇ 45.0 KSI / 311 MPa, Yield Strength ⁇ 38.0 KSI / 262 MPa, and % Elongation minimum ⁇ 10%.
  • the substantially Pb-free aluminum alloy composition consists of the following components (in weight percent): Si ⁇ 0.40; Fe ⁇ 0.70; Cu 5.0 - 6.0; Zn ⁇ 0.30; Bi 0.20 - 0.80; Sn 0.10 - 0.50 wherein Si, Fe, Cu, Zn, Bi, and Sn are the only components intentionally added to the alloy composition such that any other material exist only as incidental impurities, with the remainder being aluminum and the incidental impurities
  • the substantially Pb-free aluminum alloy composition maintains a Bi/Sn ratio of less than 1.32/1 (in terms of weight percent; 1.32/1 being the eutectic ratio for Bi-Sn).
  • T8 temper provides specific advantages for machining applications that are sensitive to machining cracks because of their high material removal rates and thin wall geometries. Conversely, specific machining applications that are not sensitive to machining cracks because of more robust part geometries, but which would benefit from even higher material removal rates can be produced in a T6 temper.
  • the substantially Pb-free aluminum alloy composition consists of the following components (in weight percent): Si ⁇ 0.40; Fe ⁇ 0.70; Cu 5.0 - 6.0; Zn ⁇ 0.30; Bi 0.20 - 0.80; Sn 0.10 - 0.50 with the remainder being aluminum and incidental impurities.
  • Si, Fe, Cu, Zn, Bi, and Sn are the only components intentionally added to the alloy composition such that any other material exists only as the incidental impurities.
  • Said incidental impurities are present in a total amount of less than 1 wt.%, or less than 0.5 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.%.
  • the substantially Pb-free aluminum alloy composition maintains a Bi/Sn ratio of less than 1.32/1 (in terms of weight percent; 1.32 being the eutectic ratio for Bi-Sn).
  • the substantially Pb-free aluminum alloy composition of the present invention substantially meets or exceeds the material property requirements of the current free machining materials.
  • the substantially Pb-free aluminum alloy composition meets the minimum material properties for AA2011-T3 including Ultimate Tensile Strength ⁇ 45.0 KSI / 311 MPa, Yield Strength ⁇ 38.0 KSI / 262 MPa, and % Elongation minimum ⁇ 10%.
  • the phrase "substantially Pb-free" is defined as having no intentional additions of Pb to the aluminum alloy composition as it is being produced.
  • any Pb that may be contained in the aluminum alloy composition is the result of tramp contamination.
  • the aluminum alloy composition of the present invention contains ⁇ 0.05 wt.% Pb.
  • the aluminum alloy composition of the present invention contains ⁇ 0.01 wt.% Pb.
  • the aluminum alloy composition of the present invention contains ⁇ 0.005 wt.% Pb.
  • the aluminum alloy composition of the present invention contains ⁇ 0.003 wt.% Pb.
  • the ranges identified above for the substantially Pb-free aluminum alloy composition include the upper or lower limits for the element selected and every numerical range and fraction provided within the range may be considered an upper or lower limit.
  • the upper or lower limit for Si may be selected from 0.30, 0.25, 0.20, 0.15, and 0.10 wt.%.
  • the amount of Si ranges from ⁇ 0.20 wt.%.
  • the amount of Si ranges from ⁇ 0.16 wt.%.
  • the amount of Si ranges from 0.10-0.16 wt.%.
  • the upper or lower limit for Fe may be selected from 0.60, 0.50, 0.40, 0.30, 0.20, and 0.10 wt.%. In one embodiment, the amount of Fe ranges from 0.30-0.50 wt.%. In another embodiment, the amount of Fe ranges from 0.33-0.44 wt.%.
  • the upper or lower limit for Cu may be selected from 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, and 5.9. In one embodiment, the amount of Cu ranges from 5.1-5.8 wt.%.
  • the amount of Cu ranges from 5.13-5.63 wt.%.
  • the upper or lower limit for Zn may be selected from 0.20, 0.10, 0.05, 0.01, and 0.005 wt.%
  • the amount of Zn ranges from 0.002-0.05.
  • the amount of Zn ranges from 0.002-0.044.
  • the upper or lower limit for Bi may be selected from 0.30, 0.40, 0.50, 0.60, and 0.70.
  • the amount of Bi ranges from 0.40-0.80.
  • the amount of Bi ranges from 0.20-0.40.
  • the upper or lower limit for Sn may be selected from 0.20, 0.30, and 0.40. In one embodiment, the amount of Sn ranges from 0.20-0.50. Additionally, for example, it is also understood that within the range of Bi/Sn ratio of less than 1.32/1, the upper or lower limit for Bi/Sn ratio may be selected from 1.30/1, 1.25/1, 1.20/1, 1.15/1,1.10/1, 1.05/1, 1.00/1, and 0.80/1. In one embodiment, the Bi/Sn ration may be between 1.32/1-0.80/1. It is further understood that any and all permutations of the ranges identified above are included within the scope of the present invention.
  • the substantially Pb-free aluminum alloy composition may consist of the following components (in weight percent): Si ⁇ 0.16; Fe ⁇ 0.50; Cu 5.1-5.8; Zn ⁇ 0.05; Bi 0.20 - 0.50; Sn 0.20 - 0.50 with the remainder being aluminum and incidental impurities, while maintaining a Bi/Sn ratio of less than 1.32/1 (in terms of weight percent; 1.32/1 being the eutectic ratio for Bi-Sn) or a Bi/Sn ratio from 1.32/1 to 0.80/1, having incidental impurities present in a total amount of less than 1 wt.%, or less than 0.5 wt.%, or less than 0.1 wt.%, or less than 0.05 wt.%.
  • a free machining, machining crack insensitive aluminum alloy may be produced.
  • the aluminum alloy product has been homogenized to improve the recrystallization for improved grain size control.
  • the alloy has a Bi/Sn ratio (in weight percent) of less than 1.32/1.
  • the alloy has a Bi/Sn ratio (in weight percent) ranging from 1.32/1 to 0.8/1.
  • the alloy has a Bi/Sn ratio (in weight percent) ranging from 1.20/1 to 1/1.
  • the aluminum alloy product has been homogenized to improve the recrystallization for improved grain size control.
  • the alloy has a Bi/Sn ratio (in weight percent) is less than 1.32/1.
  • the alloy has a Bi/Sn ratio (in weight percent) ranging from 1.32/1 to 0.8/1.
  • the alloy has a Bi/Sn ratio (in weight percent) ranging from 1.20/1 to 1/1.
  • the preferred process in accordance with the present application does not include any naturally aging beyond that which is inherent in the described processes disclosed herein. Specifically, the present invention does not include any T3 or T4 naturally aging of the alloy composition.
  • the alloy may initially be cast into ingots and the ingots homogenized at a temperature ranging from about 482-571°C (900° to 1170° F) for at least 1 hour but generally not more than 24 hours, optionally followed either by fan or air cooling.
  • the ingot is soaked at about 548.8 ° C (1020° F) for about 4 hours and then cooled to room temperature.
  • the ingots are cut into shorter billets, heated to a temperature ranging from about 260° to 382.2° C (500° to 720° F) and then extruded into a desired shape.
  • a temperature ranging from about 260° to 382.2° C 500° to 720° F
  • the extruded alloy shapes are then thermomechanically treated to obtain the desired mechanical and physical properties.
  • solution heat treatment is conducted at a temperature ranging from about 498.9° to 554.4 ° C (930° to 1030° F), preferably at about 537.8° C (1000° F), for a time period ranging from about 0.5 to 2 hours, water quenched to room temperature, cold worked, and artificial aged at a temperature ranging from about 121.1° to 204.4° C (250° to 400° F) for about 2 to 12 hours.
  • solution heat treatment is conducted at a temperature ranging from about 498.9° to 554.4 ° C (930° to 1030° F), preferably at about 537.8° C (1000° F), for a time period ranging from about 0.5 to 2 hours, water quenched to room temperature, cold worked, and artificial aged at a temperature ranging from about 121.1° to 204.4° C (250° to 400° F) for about 2 to 12 hours.
  • the billets are homogenized at a temperature ranging from about 510° to 565.6° C (950° to 1050° F) and then extruded to a near desired size.
  • the rod or bar is then straightened using any known straightening operation such as stress relieved stretching of about 1 to 3 %.
  • the alloy is heat treated by precipitation artificial age hardening. Generally, this may be accomplished at a temperature ranging from about 121.1° to 204.4° F (250° to 400° F) for a time period from about 2 to 12 hours.
  • a temperature ranging from about 121.1° to 204.4° F (250° to 400° F) for a time period from about 2 to 12 hours.
  • it should be understood that one of ordinary skill in the art may select different times, quenching conditions, and temperatures and still remain within the scope of the present invention.
  • Billets were produced in 254 mm (10 inch) diameter with the target compositions found in Table 1. These billets were extruded and processed into T3, T4, T6 and T8 tempers using the process parameters shown in FIG.1 to produce 25.4 mm (1.000 inch) diameter rod. Casting of the billets was done using conventional direct chill casting techniques. The 6040 alloy variants were produced in both press quenched (T6511 temper) and separate solution heat treatment (T651 temper) processes. Homogenization, extrusion, solution heat treatment, quenching, drawing and artificial aging operations were all completed using typical industry practices. Samples from this material were evaluated for tensile properties and machinability. The tensile property results are shown in Table 2.
  • Table 1 Compositions for Example 1 (weight percent) Alloy Cast Si Fe Cu Mn Mg Zn Cr Pb Bi Sn Ti Zr B Ni BISN-01 0969 0.11 0.36 5.22 0.00 0.00 0.044 0.020 0.001 0.40 0.35 0.020 0.003 0.001 0.00 BISN-03 0971 0.11 0.38 5.32 0.00 0.00 0.003 0.000 0.002 0.49 0.27 0.025 0.002 0.001 0.00 BISN-31 0973 0.12 0.42 5.40 0.00 0.00 0.004 0.000 0.002 0.63 0.49 0.019 0.002 0.001 0.00 BISN-31 0975 0.12 0.39 5.47 0.00 0.00 0.003 0.000 0.002 0.60 0.42 0.022 0.002 0.001 0.00 BISN-31 0977 0.11 0.40 5.40 0.00 0.00 0.003 0.000 0.002 0.60 0.42 0.021 0.002 0.001 0.00 BISN-04 0978 0.12 0.44 5.63 0.00 0.00 0.00
  • Table 2 Mechanical Properties of Material Evaluated in Example 1 Lot ID Cast # Alloy Temper Yield MPa (KSI) Ultimate MPa (KSI) % Elongation 299 969 BISN-01 T3 317 (45.9) 361 (52.3) 17.2 300 985 BISN-02 T3 318 (46.1) 363 (52.5) 15.0 301 971 BISN-03 T3 313 (45.3) 355 (51.5) 16.5 302 978 BISN-04 T3 319 (46.3) 363 (52.6) 15.3 303 975 BISN-31 T3 317 (46.0) 362 (52.4) 16.5 304 973 BISN-31 T451 169 (24.5) 303 (43.9) 33.8 306 979 BISN-06 T3 307 (44.5) 346 (50.2) 16.8 307 983 2111-31 T3 302 (43.8) 342 (49.6) 17.3 308 981 2111-06 T3 314 (45.5) 355 (51.4) 15.8 310 989 BISN
  • Machinability testing was conducted by producing a representative part that utilizes several machining operations. This part is depicted conceptually in FIG. 2 . Material removal rates were kept constant between materials by keeping the cutting speed and feed rate constant for all machining operations. The chip size is evaluated by determining the number of clean, dry chips per gram. The results from this evaluation are shown in FIG.3 and are compared with current Pb-containing free machining material, 2011-T3, as a benchmark comparison. This shows that the alloy / temper combinations tested were better or comparable to the incumbent material. Also tested in this matrix were Pb-free 6040 compositions that are currently available in the market. These have historically not performed as well as 2011-T3, and this test validated their inferior performance.
  • the BISN-31 is designated with the different tempers (T3, T4 and T8) in this figure for simplification. This shows that the 2011 (incumbent Pb-containing alloy) consistently passed, as expected, as well as the Pb-free 6040 alloy variants (note these alloy variants did not perform well from a chip size perspective, however). The only experimental alloy that passed was BISN-31-T4, but unfortunately this failed the tensile property requirements.
  • BISN-01 forms part of the present invention.
  • Billets were cast in 254 mm (10") diameter and processed into 25.4 mm (1") rod using the process depicted in FIG.1 and the compositions listed in Table 4.
  • the % ROA (reduction of area) during the drawing operation was evaluated in this study, particularly in the T3 temper.
  • the effect of homogenization was also evaluated with cast 1110 being homogenized and compared to the unhomogenized cast 1108.
  • the 25.4 mm (1") rod was evaluated for mechanical properties, machinability, and machining crack susceptibility using the same techniques described in Example 1.
  • Table 4 Compositions of the present invention and Tempers for Example 2 (weight percent) Alloy Cast Bi Sn Cu Mg Fe Si Ni Mn Pb Cr Bi/Sn Bi+Sn Temper % ROA BI26 1102 0.27 0.24 5.31 0.00 0.42 0.15 0.00 0.00 0.00 1.13 0.51 T3 20.3 BI26 1103 0.28 0.23 5.40 0.00 0.35 0.13 0.00 0.00 0.08 1.22 0.51 T3 15.8 BI26 1104 0.27 0.24 5.35 0.00 0.36 0.14 0.00 0.00 0.00 1.13 0.51 T3 9.3 BI26 1105 0.26 0.24 5.36 0.00 0.38 0.15 0.00 0.00 0.00 1.08 0.50 T8 15.8 BI26 1106 0.26 0.24 5.34 0.00 0.35 0.14 0.00 0.00 0.00 1.08 0.50 T651 17.4 BI39 1111 0.39 0.36 5.37 0.00 0.41 0.14 0.00 0.00 0.00 0.00 0.00 1.08 0.75 T3 20.3 BI39
  • the mechanical properties are shown in Table 5. This shows that all of the composition and temper combinations were capable of achieving the minimum 2011-T3 target mechanical properties (Yield Strength 262 MPa (38 KSI); Ultimate Strength 311 MPa (45.0 KSI); 10% Elongation). The addition of Mg was successful in achieving these properties as well in the T4 temper.
  • Table 5 Mechanical Properties of Material Evaluated in Example 2 Lot ID Cast # Alloy % ROA Temper Yield MPa (KSI) Ultimate MPa (KSI) % Elongation 338 1102 BI26 20.3 T3 313 (45.3) 348 (50.5) 15.0 341 1103 BI26 15.8 T3 302 (43.8) 344 (49.8) 18.0 344 1104 BI26 9.3 T3 275 (39.8) 322 (46.6) 18.0 345 1105 BI26 15.8 T8 270 (39.2) 371 (53.8) 15.0 347 1106 BI26 17.4 T651 277 (40.2) 406 (58.8) 23.0 339 1111 BI39 20.3 T3 324 (46.9) 355 (51.4) 14.0 342 1108 BI39 15.8 T3 302 (43.8) 343 (49.7) 18.5 343 1109 BI39 9.3 T3 265 (38.4) 325 (47.1) 12.0 346 1112 BI39 15.8 T8 270 (39
  • the T651 temper material regardless of alloy composition, performed very well, with small chip size.
  • the T8 tempers generally performed better than the T3 counterparts for a given alloy, particularly the BI26 composition.
  • Billets were cast in 254 mm (10") diameter and processed into 25.4 mm (1") and 50.8 mm (2") T3 and T8 rod using the process depicted in FIG. 1 and the compositions listed in Table 6.
  • the rods were evaluated for mechanical properties, machinability, and machining crack susceptibility using the same techniques described in Example 1.
  • Table 6 Compositions of the present invention and Tempers for Example 3 (weight percent) Alloy Cast Si Fe Cu Mn Mg Zn Cr Pb Bi Sn Ti Bi+Sn Bi/Sn SN01 1172 0.16 0.45 5.76 0.03 0.00 0.00 0.002 0.25 0.21 0.009 0.46 1.21 SN01 1173 0.14 0.36 5.32 0.03 0.02 0.00 0.00 0.000 0.24 0.20 0.010 0.44 1.20 SN02 1175 0.15 0.39 5.55 0.03 0.00 0.01 0.00 0.002 0.35 0.21 0.013 0.56 1.65 SN02 1176 0.15 0.36 5.25 0.03 0.02 0.00 0.06 0.002 0.34 0.19 0.010 0.53 1.83 SN03 1178 0.10 0.38 5.77 0.03 0.02 0.00 0.01 0.000 0.26 0.33 0.005 0.59 0.80 SN03 1182 0.16 0.39 5.37 0.03 0.01 0.00 0.01 0.003 0.24 0.30 0.009 0.55 0.81 SN04 1180 0.15 0.36 5.
  • Table 7 Mechanical Properties of Material Evaluated in Example 3 Alloy / Temper Cast Lot ID Diameter mm (inch) Yield MPa (KSI) Ultimate MPa (KSI) % Elongation SN01-T3 1172 402 25.4 (1.000) 311 (45.0) 348 (50.4) 14.0 SN02-T3 1175 403 25.4 (1.000) 306 (44.4) 347 (50.3) 16.0 SN03-T3 1182 404 25.4 (1.000) 307 (44.5) 350 (50.7) 15.0 SN04-T3 1184 405 25.4 (1.000) 303 (43.9) 342 (49.6) 16.0 SN01-T8 1173 398 50.8 (2.000) 305 (44.2) 391 (56.6) 13.0 SN02-T8 1175 399 50.8 (2.000 290 (42.1) 388 (56.2) 14.0 SN03-T8 1182 400 50.8 (2.000) 299 (43.3) 392 (56.8) 14.0 SN04-T8 1184 401 50.8 (2.000) 309
  • the machinability test relative to chip size was evaluated with the results depicted in FIG. 9 for the 25.4 mm (1.000") diameter material.
  • the results show that the T8 performed superior to the Pb-containing 2011 material, while the T3 material, which still performed acceptably, was not as good as the Pb-containing 2011 material.
  • the test was replicated with the 50.8 mm (2.000") diameter to ensure the material machined well over a wider range of diameters. While the 50.8 mm (2.000") diameter results were slightly worse than the Pb-containing 2011 incumbent material in this test, it must be noted that from a chips per gram basis, it was better than any of the 25.4 mm (1.000") diameter test results. Thus it can be concluded that the material performs well throughout these diameter ranges.

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TWI776910B (zh) 2022-09-11
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US20200270731A1 (en) 2020-08-27
US20190003025A1 (en) 2019-01-03
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