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BACKGROUND OF THE INVENTION
This invention relates to improved wrought zinc alloys and more particularly to eutectic and near eutectic zinc alloys which are eutectic and near eutectic compositions consisting essentially of zinc, aluminum, copper and magnesium, having highly favorable castability, tensile strength, tensile strength stability, shear strength, and platability characteristics. The zinc alloys of the present invention are ideally suited to continuous casting operations and in this regard are superior to eutectoid and near eutectoid compositions comprising zinc, aluminum, copper and magnesium. This is due in large measure to the small freezing range of the eutectic and near eutectic alloys of this invention.
Eutectoid and near eutectoid alloys, i.e., those containing about 20-25% aluminum have been found to present continuously casting difficulties attributable to segregation and shrinkage. Further, it has been found that casting high aluminum content alloys involves high energy requirements because of their relatively high pouring temperatures. Moreover the eutectoid and near eutectoid alloy systems generally precluded the implementation of relatively simple, efficient and economic procedures conventionally employed with eutectic and near eutectic alloy systems.
SUMMARY OF THE INVENTION
It has now been discovered that the disadvantages of known eutectoid and near eutectoid zinc alloys can be overcome by the present invention which is directed to low-aluminum content zinc alloys which are near eutectic compositions consisting essentially of zinc, aluminum, copper and magnesium. In particular, the alloy compositions of the subject invention relate to improved continuously castable zinc base alloys comprising about 4-10 weight percent aluminum, about 1-6 weight percent copper and about 0.02-0.04 weight percent magnesium, the balance being zinc.
The alloy composition of this invention may also possibly include, as impurities, the following elements in the amounts indicated: Cd -- 0.005 wt % max; Fe -- 0.100 wt % max; Pb -- 0.007 wt % max; and Sn -- 0.005 wt % max. Thus, in the alloy composition of this invention the impurities content does not exceed 0.117 weight percent thereof.
In one embodiment of the present invention, the zinc base alloy consists essentially of 9-10 percent by weight aluminum, 5-6 percent by weight copper, 0.02-0.04 percent by weight magnesium, the balance being zinc. The above indicated impurities may possibly also be present. A more preferred alloy composition of this embodiment consists essentially of 9.4-9.6 percent by weight aluminum, 5.4-5.6 percent by weight copper, 0.028-0.032 percent by weight magnesium, the balance being zinc. Again the above indicated impurities, not exceeding 0.117 weight percent of the alloy composition, may possibly be present. An optimal alloy composition of this embodiment consists essentially of 9.5 percent by weight aluminum, 5.5 percent by weight copper, 0.03 percent by weight magnesium, the balance being zinc, with the possible presence of said impurities not exceeding the amounts indicated above.
In another preferred embodiment of the present invention, the zinc base alloy consists essentially of 6.4-6.6 percent by weight aluminum, 3.7-3.9 percent by weight copper, 0.02-0.04 percent by weight magnesium, the balance being zinc. The above indicated impurities may also be present. An optimal alloy composition of this embodiment consists essentially of 6.5 percent by weight aluminum, 3.8 percent by weight cooper, 0.03 percent by weight magnesium, the balance being zinc, with the possible presence of the said impurities not exceeding the amounts indicated above.
It is therefore a principal object of the present invention to provide novel zinc-based alloys which exhibit improved tensile strength, tensile strength stability, shear strength, continuous casting properties and plating deposition characteristics which are at least comparable to, if not improved over, those of known zinc alloys.
It is another object of this invention to produce a zinc base alloy composition having improved wrought characteristics.
As is generally known, the eutectic alloys including zinc base alloys are known to possess suitable casting properties. On the other hand, these particular alloy systems do not often yield suitable tensile properties, especially in the order of about 50,000 psi and still have suitable stability over a given extended period of time. As a general rule, zinc base alloys are not particularly noted for these high tensile properties. In essence, it was surprising, therefore, to find that the alloys of the subject invention not only exhibited high tensile strength and tensile strength stability, but they also exhibited the advantageous casting characteristics of standard die-cast grade zinc alloys.
EXAMPLE 1
A zinc alloy having the following composition was prepared: 9.5% Al, 5.50% Cu and 0.03% Mg, the balance being zinc from 2.375 lbs of aluminum, 1.375 lbs of copper, 0.381 lbs of magnesium and 20 lbs 13.9 ounces of zinc.
The said alloy, having a heat of transformation of 5.2 cal/gm at 556.degree. K. and heat of fusion of 27.5 cal/gm at 625.degree. K., was subjected to the following rolling treatment: homogenization for 5-18 hours at 650.degree. F.; air cooled to 550.degree. F.; initial reduction to 0.250 inches at 550.degree. F.; air cooled to room temperature; re-heat to 425.degree. F. for 30 minutes; final reduction to 0.100 inch at 425.degree. F.; and air cooled to room temperature.
The thus treated alloy was initially tested in accordance with ASTM E8-69 to determine its tensile strength (TS), yield strength (YS) and percent elongation (%El) characteristics. Thereafter the thus tested alloy was heat aged to 200.degree. F. for 10 days and the said ASTM E8-69 test procedures were repeated to determine, principally the tensile strength stability characteristics of the said alloy. The results of these tests are reported in Table I below.
TABLE I
______________________________________
Alloy: 9.5% Al; 5.5% Cu; 0.03% Mg; balance Zn
Sam- As Rolled YS Heat Aged at 200.degree. F for 10 days
ple TS (lbs/ % Loss
No. (lbs/in.sup.2)
in.sup.2)
%El TS YS %El of TS
______________________________________
1 68,519 58,375 12 63,275
43,120
10
2 68,812 58,151 8 62,317
43,171
5
Avg. 68,665 58,263 10 62,796
43,146
7 8.56%
______________________________________
EXAMPLE 2
A zinc alloy having the following composition: 9.5% Al, 5.50% Cu, and 0.03% Mg, the balance being zinc was prepared essentially as described in Example 1.
The said alloy was subjected to the following rolling treatment: homogenization at 650.degree. F. (5-18 hours); air cooled to 550.degree. F.; initial reduction to 0.250 inch at 550.degree. F.; air cooled to room temperature; homogenization at 500.degree. F. (30 min - 1 hr), and final reduction to 0.100 inch at the following temperatures: 450.degree. F., 425.degree. F., 400.degree. F., 375.degree. F., 350.degree. F., 325.degree. F. and 300.degree. F., followed by air cooling to room temperature in each instance.
The thus treated alloy was initially tested in accordance with ASTM E8-69 to determine its tensile strength (TS), yield strength (YS) and percent elongation (%El) characteristics Thereafter the tested alloy was heat aged for 10 days at 200.degree. F. and the said ASTM test procedures were repeated to determine principally the tensile strength stability characteristics of the said alloy. The results of these tests are reported in Table II, below.
TABLE II
__________________________________________________________________________
Temp
Heat Aged
Sample
As Rolled Final % Loss
No. TS YS % El
Roll
TS YS % El
in TS
__________________________________________________________________________
3a 60,728
43,109
21 300.degree. F
60,051
41,414
8
3b 60,469
42,253
17 300.degree. F
58,333
39,941
10
3c 60,436
43,168
17 300.degree. F
58,824
40,149
4
3 avg.
60,544
42,844
18 300.degree. F
59,069
40,502
7 2.4%
4a 62,210
46,845
20 325.degree. F
58,891
41,668
4
4b 61,752
44,707
17 325.degree. F
58,046
40,412
13
4c 61,369
44,565
19 325.degree. C
58,200
41,440
2
4 avg.
61,777
45,372
18 325.degree. F
58,379
41,173
6 5.5%
5a 61,273
45,954
11 350.degree. F
58,487
41,913
6
5b 61,364
48,090
17 350.degree. F
59,163
40,078
11
5c 61,842
47,348
17 350.degree. F
58,476
44,616
4
5 avg.
61,493
47,131
15 350.degree. F
58,709
42,202
7 4.5%
6a 62,787
50,783
16 375.degree. F
58,421
41,925
7
6b 63,119
50,346
15 375.degree. F
58,553
43,507
6
6c 63,585
48,410
14 375.degree. F
58,269
40,716
7
6 avg.
63,164
49,846
15 375.degree. F
58,414
42,049
6 7.5%
7a 64,014
52,629
15 400.degree. F
58,017
42,496
7
7b 63,909
51,279
13 400.degree. F
58,638
45,608
6
7c 63,646
51,783
12 400.degree. F
57,934
44,492
4
7 avg.
63,857
51,897
13 400.degree. F
58,196
44,198
5 8.8%
8a 65,107
53,946
15 425.degree. F
59,277
44,009
6
8b 64,497
55,761
12 425.degree. F
59,366
43,942
7
8c 64,660
56,998
14 425.degree. F
58,264
42,654
4
8 avg.
64,755
55,568
13 425.degree. F
58,969
43,535
5 8.9%
9a 64,665
56,394
12 450.degree. F
9b 64,237
55,858
13 450.degree. F
59,604
45,210
9c 63,866
56,187
11 450.degree. F
59,000
44,250
9 avg.
64,254
56,148
12 450.degree. F
59,302
44,730 7.7%
__________________________________________________________________________
EXAMPLE 3
Shear strength tests were conducted on a zinc alloy having the following composition: 9.5% Al; 5.5% Cu and 0.03% Mg, the balance being Zn, and compared to values achieved under essentially identical conditions, using CDA 353 Brass. The results of these tests are reported below in Table III.
TABLE III
______________________________________
Key Blank
Press Shear
Test Temp Gauge Shear Area
Load Strength
Material
(.degree. F)
(in) (in.sup.2)
(lbs) (lbs/in.sup.2)
______________________________________
Zinc Alloy
25 0.074 0.421 19,334
45,923
150 0.074 0.421 18,547
44,054
200 0.074 0.421 17,026
40,441
CDA 353 25.degree.
0.078 0.444 21,274
47,915
Brass
______________________________________
EXAMPLE 4
A zinc alloy of the present invention having the following composition: 9.5% Al, 5.5% Cu and 0.03% Mg, the balance being zinc, was compared to a conventional high aluminum containing zinc alloy having the following composition: 25% Al, 1% Cu, 0.03% Mg, the balance being zinc and to brass Ford key blanks to illustrate their torque properties. A 1/8 inch testing standard was utilized. The Ford key was in the unmilled condition and the tests were carried out at room temperature. The results, reported in Table IV below, are an average of 10 torque tests except where otherwise indicated.
TABLE IV
______________________________________
Maxi-
Starting 30.degree.
Maximum mum
Gauge Torque Torque Rotation
Torque
Material
(in.) (in. lbs.)
(in. lbs)
(0.degree.)
(in. lbs.)
______________________________________
Zn alloy
of this
invention
0.075 45 57 44 64
High
Aluminum
Zinc alloy
0.075 41 53 42 55
*CDA 353
Brass 0.078 58 77 52 88
______________________________________
*15 tests
EXAMPLE 5
A zinc alloy having the following composition was prepared: 6.5% Al; 3.8% Cu; and 0.03% Mg, the balance being zinc.
The said alloy, having a heat of fusion of 2.1 cal/gm at 556.degree. K. and 23.7 cal/gm at 652.degree. K., was subjected to the following rolling treatment: homogenization for 5 hours at 650.degree. F.; furnace cooled to 550.degree. F.; initial reduction to 0.250 inch at 550.degree. F.; air cooled to room temperature; re-heat to 425.degree. F. for 30 minutes; final reduction to 0.100 inch at 425.degree. F.; and air cooled to room temperature.
The thus treated alloy was initially tested in accordance with ASTM E8-69 to determine its tensile strength (TS), yield strength (YS) and percent elongation (%El) characteristics. Thereafter, the thus treated alloy was heat aged at 200.degree. F. for 10 days and the said ASTM E8-69 test procedures were repeated to determine principally the tensile strength stability characteristics of the said alloy. The results of these tests are reported in Table V, below.
TABLE V
______________________________________
Alloy: 6.5% Al; 3.8% Cu; 0.03% Mg; balance Zn
Heat Aged at 200.degree. F for
As Rolled Ten Days
% % % Loss
Sample No.
TS YS E1 TS YS E1 of TS
______________________________________
10a 65,023 57,093 4 53,747
41,563
8
10b 66,147 59,804 3 56,336
37,483
7
10c 65,406 60,182 6 55,708
41,781
10
10 avg. 65,525 59,026 4 55,264
40,275
8 15.7%
______________________________________
The above Zn-Al-Cu-Mg alloy was then compared to other Zn-Al alloys containing in addition to copper and magnesium, either titanium and/or manganese. Sample 11 is an alloy having the following composition: 7.40% Al; 3.75% Cu; 0.029% Mg; 0.01% Ti; the balance being Zn. Sample 12 is an alloy having the following composition: 7.40% Al; 3.80% Cu; 0.03% Mg; 0.08% Mn; the balance being Zn. Sample 13 is an alloy having the following composition: 7.30% Al; 3.67% Cu; 0.032% Mg; 0.08% Mn; 0.01% Ti; the balance being Zn. Following essentially the same procedures given above, the following results were achieved:
______________________________________
Heat Aged at 200.degree. F
As Rolled for Ten Days
% % % Loss
Sample No.
TS YS E1 TS YS E1 of TS
______________________________________
11a 68,039 53,821 6 55,188
39,245
12
11b 67,621 53,567 6 56,251
42,541
11
11c 67,295 55,300 3 55,327
41,852
11
11 avg. 67,651 54,229 5 55,588
41,213
11 17.8%
12a 66,052 52,922 8 55,613
46,512
12
12b 67,103 55,851 5 53,744
40,459
10
12c 66,008 54,669 9 56,007
43,425
6
12 avg. 66,387 54,481 7 55,121
43,466
9 17%
13a 66,062 59,143 2 53,182
40,707
4
13b 66,546 59,226 5 53,072
40,841
6
13c 65,806 60,676 2 54,984
42,935
2
13 avg. 66,138 59,682 3 53,746
41,495
4 18.7%
______________________________________
It can thus be seen that the addition to the near-eutectic Zn-Al-Cu-Mg alloy composition of this invention of other alloying elements disadvantageously reduces the tensile strength stability of the alloy.
EXAMPLE 6
A zinc alloy having the following composition: 6.5% Al; 3.8% Cu; 0.03% Mg; balance Zn was again prepared and was subjected to the following rolling treatment: homogenization at 650.degree. F. (5 hours); furnace cooled to 550.degree. F.; initial reduction to 0.250 inch at 550.degree. F.; air cooled to room temperature; reheat to 425.degree. F. for 30 minutes; final reduction to 0.100 inch at the following temperatures: 450.degree. F., 425.degree. F., 400.degree. F., 375.degree. F., 350.degree. F., 325.degree. F. and 300.degree. F., followed by air cooling to room temperature in each instance.
The thus treated alloy was initially tested in accordance with ASTM E8-69 to determine its tensile strength (TS), yield strength (YS) and percent elongation (%El) characteristics. Thereafter, the tested alloy was heat aged for 10 days at 200.degree. F. and the said ASTM test procedures were repeated to determine, principally, the tensile strength stability characteristics of the said alloy. The results of these tests are reported in Table VI, below.
TABLE VI
__________________________________________________________________________
Temp
Heat Aged
Sample
As Rolled Final % Loss
No. TS YS % El
Roll
TS YS % El
in TS
__________________________________________________________________________
14a 58,308
33,299
20 300.degree. F
51,765
36,975
13
14b 58,743
39,968
19 300.degree.F
51,352
38,142
14
14c 58,268
41,086
18 300.degree. F
51,355
35,765
14
14 avg.
58,440
40,117
19 300.degree. F
51,491
36,960
13 11.8%
15a 60,146
44,621
17 325.degree. F
53,529
36,916
5
15b 59,757
44,818
4 325.degree. F
53,609
35,800
6
15c 59,845
51,878
12 325.degree. F
53,603
38,091
6
15 avg.
59,916
47,106
11 325.degree. F
53,580
36,936
5 10.6%
16a 62,758
48,349
14 350.degree. F
55,387
39,018
4
16b 62,476
49,523
14 350.degree. F
54,675
36,891
3
16c 62,676
49,531
12 350.degree. F
55,582
40,646
8
16 avg.
62,637
49,134
13 350.degree. F
55,214
38,852
5 11.8%
17a 62,717
51,049
10 375.degree. F
53,853
38,984
6
17b 61,591
49,460
10 375.degree. F
53,234
37,502
6
17c 60,932
48,007
11 375.degree. F
53,923
40,078
5
17 avg.
61,747
49,505
10 375.degree. F
53,670
38,855
5 13.1%
18a 64,377
53,189
8 400.degree. F
53,853
38,984
6
18b 400.degree. F
53,234
37,502
6
18c 64,123
53,436
7 400.degree. F
53,923
40,078
5
18 avg.
64,250
53,312
8 400.degree. F
53,670
38,855
5 13.1%
19a 61,574
55,719
6 425.degree. F
53,390
39,202
11
19b 63,155
55,614
6 425.degree. F
54,998
39,679
12
19c 62,486
54,693
6 425.degree. F
53,708
39,545
7
19 avg.
62,385
55,342
6 425.degree. F
54,032
39,476
10 13.3%
20a 62,584
56,018
9 450.degree. F
54,393
41,627
6
20b 62,726
55,236
6 450.degree. F
55,004
41,952
12
20c 62,225
55,458
8 450.degree. F
55,051
42,776
9
20 avg.
62,508
55,571
7 450.degree. F
54,816
42,118
9 12.3%
__________________________________________________________________________
EXAMPLE 7
Table VII below summarizes a comparative study of some significant properties of standard die-cast grade alloys (AG40A and AG41A), low-aluminum zinc alloys A and B of the present invention and a high aluminum containing zinc alloy C.
TABLE VII
__________________________________________________________________________
Castability -
Ultimate Tensile Strength (TS)
Chemical Composition (wt %) Melting Range - .degree. F
As-Aged
% Loss
Alloy
(Al)
(Cu) (Mg) (Cd)
(Fe)
(Pb)
(Sn)
(Total)/(Range)
As-Cast
As Rolled
(200.degree.
in
__________________________________________________________________________
TS
AG40A
3.5-4.3
0.25 max.
0.03-0.08
0.005
0.100
0.007
0.005
(11)/(717-728.degree. F).sup.(2)
41,000.sup.(1)
28,300.sup.(1),(3)
31%
max
max max max
AG41A
3.5-4.3
0.75-1.25
0.03-0.08
0.005
0.100
0.007
0.005
(10)/(717-727.degree. F).sup.(2)
47,600.sup.(1)
35,100.sup.(1),(3)
26%
max
max max max
A 6.4-6.6
3.7-3.9
0.02-0.04
0.005
0.100
0.007
0.005
(45)/684-729.degree. F)
61,000
54,000.sup.(5)
11%
max
max max max
B 9.4-9.6
5.4-5.6
0.02-0.04
0.005
0.100
0.007
0.005
(68)/(684-752.degree. F)
37,900
63,000
60,200.sup.(5)
4%
max
max max max
C 24-26
0.9-1.1
0.02-0.04
0.005
0.100
0.007
0.005
(223)/(705-928.degree. F).sup.(4)
62,500.sup.(4)
54,500.sup.(4)
13%
max
max max max
__________________________________________________________________________
.sup.(1) ASTM B-86 and "Zinc - The Science and Technology of the Metal,
Its Alloys and Compounds", C. H. Matthewson, Reinhold Publishing Corp.,
1960.
.sup.(2) The Metals Handbook, , Vol. 1, 8th Ed. ASM, 1967.
.sup.(3) Aged at 203.degree. F.
.sup.(4) "Experimental High Strength Zinc Alloy", D. L. Dollar, report,
Aug. 14, 1973.
.sup.(5) Aged at 200.degree. F for 10 days.
From the data reported in Table VII, it can be seen that alloys A and B of the present invention exhibit not only the advantageous casting properties of standard die-cast grade alloys, i.e., AG40A and AG41A, and the high tensile strength properties of high aluminum zinc based alloys, for example alloy C, but they also exhibit, as noted earlier, a higher level of strength stability.
EXAMPLE 8
A zinc alloy of the present invention having the following composition: 6.5% Al, 3.8% Cu and 0.03% Mg, the balance being zinc was compared to a conventional high aluminum containing zinc alloy having the following composition: 25% Al, 1% Cu, 0.03% Mg, the balance being zinc and to CDA 353 brass to illustrate their relative shear strength properties. The shear strength value determined for the zinc alloy of the present invention was 38,424 lbs/in.sup.2 while that for the high aluminum zinc alloy was 38,881 lbs/in.sup.2 and that for brass was 49,422 lbs/in.sup.2.
A processing operation, alternative to that utilized in certain of the above example, which is particularly advantageous for a zinc alloy of the present invention having the following composition: 9.5% Al, 5.5% Cu and 0.03% Mg, the balance being zinc, comprises continuously casting said zinc alloy as an air-cooling strip, generally having a thickness of 0.500 inch and a width ranging from 17 to 27 inches; hot rolling the said air-cooling strip at approximately 550.degree. F. to an initial reduction of 0.250 in. thick; coiling the said initially reduced strip and air cooling it to ambient temperature at a rate of about 3.degree.-5.degree. F./min; heating the said coils to a temperature above 620.degree. F. for about 3 hours; furnace cooling the said coils to about 600.degree. F. for a period of approximately 2 hours at a minimum; hot rolling said coils to a final reduction wherein the entry rolling temperature ranges from about 580.degree. F. to 600.degree. F. and the exit rolling temperature ranges from about 220.degree. F. to 250.degree. F.; cooling to room temperature in forced air; reheating for slitting to a temperature of about 220.degree. F. to 240.degree. F.; slitting said finally reduced coils to, for instance, 3 inch widths; and air cooling the same.
As an alternative, slitting and air cooling can take place immediately after the coil exits from the final rolling operation.
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