CA1304607C - High strength, heat resistant aluminum alloys and method of preparingwrought article therefrom - Google Patents
High strength, heat resistant aluminum alloys and method of preparingwrought article therefromInfo
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- CA1304607C CA1304607C CA000573600A CA573600A CA1304607C CA 1304607 C CA1304607 C CA 1304607C CA 000573600 A CA000573600 A CA 000573600A CA 573600 A CA573600 A CA 573600A CA 1304607 C CA1304607 C CA 1304607C
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/08—Amorphous alloys with aluminium as the major constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S420/00—Alloys or metallic compositions
- Y10S420/902—Superplastic
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Abstract
HIGH STRENGTH, HEAT RESISTANT ALUMINUM ALLOYS AND
METHOD OF PREPARING WROUGHT ARTICLES THEREFROM
ABSTRACT OF THE DISCLOSURE
The present invention provides high-strength, heat resistant aluminum alloys having a composition represented by the general formula:
AlaMbXd or AlaMbQcXe (wherein M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe; Q is at least one metal element selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr; X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y ; and a, b, c, d and e are atomic percentages falling within the following ranges:
45? a ? 90, 5 ? b ? 40, 0 < c ? 12, 0.5 ? d? 20 and 0.5 ? e ? 10, the aluminum alloy containing at least 50% by volume of amorphous phase. The aluminum alloys are especially useful as high strength, high heat resistant materials in various applications and since they exhibit a superplasticity in the vicinity of their crystallization temperature, they provide high-strength and heat resistant wrought materials by extrusion, pressing or hot-forging at the temperatures within the range of the crystallization temperature ? 100°C.
METHOD OF PREPARING WROUGHT ARTICLES THEREFROM
ABSTRACT OF THE DISCLOSURE
The present invention provides high-strength, heat resistant aluminum alloys having a composition represented by the general formula:
AlaMbXd or AlaMbQcXe (wherein M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe; Q is at least one metal element selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr; X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y ; and a, b, c, d and e are atomic percentages falling within the following ranges:
45? a ? 90, 5 ? b ? 40, 0 < c ? 12, 0.5 ? d? 20 and 0.5 ? e ? 10, the aluminum alloy containing at least 50% by volume of amorphous phase. The aluminum alloys are especially useful as high strength, high heat resistant materials in various applications and since they exhibit a superplasticity in the vicinity of their crystallization temperature, they provide high-strength and heat resistant wrought materials by extrusion, pressing or hot-forging at the temperatures within the range of the crystallization temperature ? 100°C.
Description
HIGH STRENGTH, HEAT RESISTANT ALUMINUM ALLOYS AND
METHOD OF PREPARING WROUGHT ARTICLES THEREFROM
BACKGROUND OF THE INVENTION
.
1. Field of the Invention The present invention relates to aluminum alloys ~ having a desired combination of properties of high hardness, high strength, high wear-resistance and superior heat-resistance and to a method for preparlng wrought articles from such aluminum alloys by extrusion, press working or hot-forging.
METHOD OF PREPARING WROUGHT ARTICLES THEREFROM
BACKGROUND OF THE INVENTION
.
1. Field of the Invention The present invention relates to aluminum alloys ~ having a desired combination of properties of high hardness, high strength, high wear-resistance and superior heat-resistance and to a method for preparlng wrought articles from such aluminum alloys by extrusion, press working or hot-forging.
2. Description of the Prior Art As conventional aluminum alloys~ there have been known various types of aluminum-based alloys such as Al-Cuf Al-Si, Al-Mg, Al-Cu-Si, Al-Zn-Mg alloys, etc These aluminum alloys have been extensively used in a variety of applications, such as structural materials for aircraft , cars, ships or the like; structural materials used in external portions of buildings, sash, roof, etc.; marine apparatus materials and nuclear reactor materials, etc., according to their proparties.
In general, the aluminum alloys heretofore known have a low hardness and a low heat resistance. In recent years, attempts have been made to achieve a fine structure by rapidly solidifying aluminum alloys and thereby improve the mechanical properties, such as strength, and chemical properties, such as corrosion resistance, of the resulting aluminum alloys. But none of the rapid solidified aluminum alloys known here~ofore has been satisfactory in the properties, 130~60'd especially with regard to strength and heat resistance.
SUMMARY OF THE INVENTION
In view of the foregoing, it is an object of the present invention to provide novel aluminum alloys which have a good combination of properties of high hardness, high strength and superior corrosion resistance.
An another object of the present invention is to provide novel high strength, heat resistant aluminum alloys which can be successfully subjected to operations such as extrusion, press working, hot-forging or a high degree of bending because of their good workability.
A further object of the invention is to provide a method for preparing wrought articles from the novel aluminum alloys specified above by extrusion, press working or hot-forging without deteriorating their properties.
According to the present invention, there are provided high-strength, heat resistant aluminum-based alloys having a composition represented by the following general formula ~I) or (II) and the aluminum alloys contain at least 50% by volume of - amorphous phase.
AlaMbXd ____- (I) Al MbQ Xe -~--- (II) wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
Q is at least one metal element 6elected fxom the group Consisting of Mn, Cr, Mo, W, ,~
V, Ti and zr;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y; and a, b, c, d and e are atomic percentages falling within the following ranges:
45< a < 90, 5 < b < 40, 0 < c < 12, 0.5 < d < 20 and 0~5 < e < 10.
The aluminum ailoys of the present invention are very useful as high-hardness material, high-strength matexial, high ~lectrical-resistant material, wear-resistant material and brazing material.
Further, since the aluminum alloys specified above exhibit a superplasticity in the vicinity of their crystallization temperature, they can be readily processed into bulk by extrusion, press working or hot forging at the temperatures within the range of the crystallization temperature ~ 100C. The wrought articles thus obtained can be used as high strength, high heat-resistant material in many practical applications because of their high hardness and high tensile strength. The present invention also provides a method for preparing such wrought articles by extrusion, press working or hot-forging.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of a single roller-melting apparatus employed to prepare ribbons from the alloys of the present invention by a rapid solidification process;
FIG. 2 is a graph showing the relationship between the Vickers hardness (Hv) and the content of the element X (X = Ta, Hf, Nb or Y) for the rapidly .~ ~
6~
solidified ribbons of A185_xNi10Cu5Xx alloys a g to the present invention; and FIG. 3 is a graph showing the relationship between the crystallization temperature (Tx) and the content of the element X (X = Ta, Hf, Nb or Y) for the rapidly solidified ribbons of the Alg5-xNi10Cu5xx allo~s according to the present invention~
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The aluminum alloys of the present invention can be obtained by rapidly solidifying melt of the alloy having the composition as specified above by means of a liquid quenching technique. The liquid quenching technique is a method for rapidly cooling molten alloy and, particularly, the single-roller melt-spinning technique, twin roller melt-spinning technique and in-rotating-water melt-spinning technique are mentioned as effective examples of such a technique. In these techniques, a cooling rate of about 104 to 1 o6 K/sec can be obtained. In order to produce ribbon materials by the single-roller melt-spinning technique or twin roller melt-spinning technique, molten alloy is ejected from the opening of a nozzle to a roll of, for example, copper or steel, with a diameter of about 30 - 3000 mm, which is rotating at a constant rate of about 300 -10000 rpm. In these techniques, various ribbon materials with a width of about 1 - 300 mm and a thickness of about 5 - 500 ~m can be readily obtained.
Alternatively, in order to produce wire materials by the in-rotating-water melt-spinning technique, a jet of molten alloy is directed , under application of the back pressure of argon gas, through a nozzle into a liquid refrigerant layer with a depth of about 1 to 10 ~3~
cm which is formed by centrifugal force in a drum rotating at a rate of about 50 to 500 rpm. In such a mannerj fine wire materials can be readily obtained.
In this technique, the angle between the molten alloy ejecting from the nozzle and the liquid refrigerant surface is preferably in the range of about 60 to 90 and the ratio of the velocity of the ejected molten alloy to the velocity of the liquid refrigerant is preferably in the range of about 0.7 to 0.9.
Besides the above process, the alloy of the present invention can be also obtained ln the form of thin film by a sputtering process. Further, a rapidly solidified powder of the alloy composition of the present invention can be obtained by various atomizing processes, for example, a high pressure gas atomizing process or spray process Whether the rapidly solidified alloys thus obtained above are amorphous or not can be known by checking the presence of the characteristic halo pattern of an amorphous structure using an ordinary X-ray diffraction method. The amorphous structure is transformed into a crystalline structure by heating to a certain temperature (called "crystallization temperature") or higher temperatures.
In the aluminum alloys of the present invention represented by the general formula (I), a is limited to the range of 45 to 90 atomic % and b is limited to the range of 5 to 40 atomic ~. The reason for such limitations is that when a and b stray from the respective ranges, it is difficult to form an amorphous region in the resulting alloys and the intended alloys having at least 50 volume % of amorphous region can not be obtained by industrial cooling techniques using the above-mentioned liquid quenching, etc. The reason why ~ ~ I
. .
~3~
d is limited to the range of 0.5 to 20 atomic % is that when the elements represented by X (i.e~, Nb, Ta, Hf and Y~ are added singly or in combination of two or more thereof in the specified range, considerably improved hardness and heat resistance can be achieved.
When d is beyond 20 atomic %, it is impossible to obtain alloys having at least 50 volume % of an amorphous phase.
In the aluminum alloys of the present invention represented by the general formula tII)t a is limited to the range of 45 to 90 atomic % and b is limited to the range of 5 to 40 atomic %. The reason or such limitations is that when a and b stray from the respective ranges, it is difiicult to develop an amorphous region in the resulting alloys and the intended alloys having at least 50 volume % of amorphous region can not be obtained by industrial cooling techniques using the above-mentioned liquid quenching, etc. The reason why c and e are limited to the range of not more than 12 atomic % and the range of 0.5 to 10 atomic %, respectively, is that at least one metal element Q selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr and at least one metal element X selected from the group consisting of Nb, Ta, Hf and Y remarkedly improve the hardness and heat resistance properties of the alloys in combination thereof.
The raason why the upper limits of c and e are 12 atomic % and 10 atomic %, respectively, is that addition of Q and X exceeding the respective upper limits make impossible the attainment of the alloys containing at least 50 % by volume of an amorphous region.
Further, since the aluminum alloys of the present invention exhibit superplasticity in the vicinity of ~3~ 7 their crystallization temperatures (crystallization temperature + 100 C), they can be readily subjected to extrusion, press working, hot forging, etc. Therefore, the aluminum alloys of the present invention obtained in the form of ribbon, wire, sheet or powder can be successfully processed into bulk by way of extrusion, pressing, hot forging, etc., at the temperature range of their crystallization temperature ~ 100 C.
Further, since the aluminum alloys of the present lO invention have a high degree of toughness, some of them can be bent by 180 without fracture.
As set forth above, the aluminum alloys of the present invention have the foregoing two types of compositions, namely, an aluminum~based composition with lS addition of the element M ( one or more elements of Cu, Ni, Co and Fe) and the element X (one or more elements of Nb, Ta, Hf and Y~ and an aluminum-based composition with addition of the element Mj the element X and the element Q (one or more elements of Mn, Cr, Mo, W, V, Ti and Zr). In the alloys, the element M has an effect in improving the capability to form an amorphous structure. The elements Q and X not only provide significant improvements in the hardness and strength without deteriorating the capability to form an amorphous structure, but also considerably increase the crystallization temperature, thereby resulting in a significantly improved heat resistance.
Now, the advantageous features of the aluminum alloys of the present invention will be described with reference to the following examples.
Example 1 Molten alloy 3 having a predetermined alloy ~3~
composition was prepared hy a high-frequency melting process and was charged into a quartz tube 1 having a small opening 5 with a diameter of 0.5 mm at the tip thereof, ~s shown in FIG. 1. After heating and melting the alloy 3, the quartz tube 1 was disposed right above a copper roll 2l 20 cm in diameter. Then, the molten alloy 3 contained in the quartz tube 1 was ejected from the small opening 5 of the quartz-tube 1 under the application of an argon gas pressure of 0.7 kg/cm2 and brought into contact with the surface of the roll 2 rapidly rotating at a rate of 5,000 rpm. The molten alloy 3 is rapidly solidified and an alloy ribbon 4 was obtained.
According to the processing conditions as described above/ 51 different kinds of alloys having the compositions given in Table 1 were obtained in a ribbon form, 1 mm in width and 20 ~m in thickness, and wexe subjected to X-ray diffraction analysis. In all of the alloys halo patterns characteristic of amorphous metal were confirmed.
Further, the hardness (Hv), electrical resistance (p) and crystallization temperature (Tx) were measured for aach test specimen of the alloy ribbons and there were obtained the results as shown in Table 1. The hardness (Hv) is indicated by values (DPN) measured using a Vickers microhardness tester under load of 25 g. The electrical resistance (p) is values (~Q.cm) measured by a conventional foux-probe technigue. The crystallization temperature (Tx) is the starting temperature (K) of the first exothermic peak on the differential scanning calorimetric curve which was conducted for each test specimen at a heatiny rate of 40 K/min. In the column of "Structure", characters "a"
and "b" represent an amorphous structure and a ., ~3~
.9 crystalline structure, respectively, and subscripts of the character "c'l show volume percentages of "c".
Table 1 No. Composition Structure Hv P Tx (by at.%) (DPN) (~Q.cm) (K) _ 1. Al7oFe2oNb1o a 750 460 788 2. A17oFe2oHf1o a 900 570 827 3. Al7oFe2oTa1o a+C10970 630 860 4, Al70Fe2oy1o a~c80990 670 875 5, Al70co2oTa1o a 880 620 780 6. A170C20Nb10 a 740 580 760 7, Al7oco2oHf1o a 850 530 758 8. Al7oco2oy1o a 720 590 720 9, AlgsNi10Nb5 a 550 560 607 10. Al70Ni20Nb10 a 590 720 755 11. Al85Ni10Hf5 a 540 550 612 12. Al7oNi2oHf1o a 810 470 755 13. Al75Ni20Y5 a 520 520 590 14. Al70Ni20Y10 620 560 685 15. Al70Ni20Ta10 a1040 710 820 16. Al7ocu2oHf1o a 630 520 623 17. Al70cu2oTa1o a 975 690 768 18. Al70CU20Nb10 a855 590 692 19. Al70CU20Y10 a~c10 860 595 688 20. Al70Ni20Cr8Hf2 a820 550 663 21. Al7oNi2oMo8Hf2 a850 630 755 22. A170Ni20W8Hf2 a880 550 821 23. Al7ocu2oTi8Hf2 a870 480 660 24. Al7ocu2ozr8Hf2 a670 520 650 _ ~3~
Table 1 (continued) No. Composition Structure Hv P Tx (by atO%) (DPN) (~Q.cm) (K) 25. Al85CU5V8Nb2 a 540 470 605 26. Al7SCU15V8Nb2 a 700 560 719 27. Al65cu25v8Nb2 a 1000 450 705 28. Al60CU30V8Nb2 a1040 460 642 29. Al7sCU15V5Y5 a 620 510 705 30. Al7ocu15v1oy5 a+c10870 570 773 31. Al7ocu2ocr8Ta2 a 885 715 626 32. Al7ocu2oMo8Ta2 a 810 700 715 33. Al7ocu2oMn8Ta2 a 615 490 642 34. Al7oNi2oMn8Hf2 a 705 512 701 35. Al65Ni20Cr5M5Hf5 a 730 540 ~ 723 36. Al6sJ~20zrsNb5Hf5a+c20 825 610 796 37. Al8scoszr5Nb5 a 428 530 654 38. Alg4coscr3Y8 a 422 550 640 39. Al75Fe10M5Hf10 a 778 630 720 40. Alg4Fescr3y8 a 450 560 670 41. Al70Ni1s Fe5Hf10 a 860 510 786 42. Al70Ni15co5y1o a 820 490 755 43. ALgoFesco5Hf5 a 680 460 620 44. Al80cusco5Nb1o a 880 630 770 45, Al70Ni1oTi1o~If1o a 850 550 635 46. Al80Fesw5y1o a 920 625 830 47~ AL70Ni1scosMo5Ta5 a 860 635 785 48. Al70Ni1 oNb10Y10 a 780 730 810 49, Al7oNi1oHf1oy1o a 730 680 725 50, AlgoFe5Nb5y1o a750 530 710 51. Al80Niszr5Hf5y5 a 720 620 730 _ ~3~6~7 As shown in Table 1, the aluminum alloys of the present invention have an extremely high hardness of the order of about 450 to 1050 DPN, in comparison with the hardness of the order of 50 to 100 DPN of ordinary aluminum-based alloys. Further, with respect to the electrical resistance, ordinary aluminum alloys have resistivity on the order of 100 to 300 ~Q.cm, while the amorphous aluminum alloys of the present invention have a high degree of resistivity of at least about 400 ~Q
.cm. A further surprising effect is that the aluminum-based alloys of the present invention have very high crystallization temperatures Tx of at least 600 K and exhibit a greatly improved heat resistance.
The alloy No. 12 given in Table 1 was further examined for the strength using an'~nstro~'-type tensile testing machine. The tensile strength was about 95 kg/mm2 and the yield strength was about 80 kg/mm2.
These values are 2.1 times of the maximum tensile strength (about 45 kg/mm2) and maximum yield strength (about 40 kg/mm2) of conventional age-hardened Al-Si-Fe ; aluminum allovs.
Example 2 Master alloys A70Fe20Hf1o and Al70Ni20Hf10 were each melted in a vacuum high-freguency melting furnace and were formed into amorphous powder by a high-pressure gas atomization process. The powder thus obtained from each alloy was sintered at a temperature of100 to 550 C for 30 minutes under pressure of 940 MPa to provide a cylindrical material with a diameter of 5 mm and a heightof 5 mm. Each cylindrical material was hot-pressed at a temperature of 400 C near the ~- * Trademark crystallization temperature of each alloy for 30 minutes. The resulting hot-pressed sintered bodies had a density of about 95 % of the theoretical density, hardness of about 850 DPN and electrical resistivity of 500 ~Q ~cm. Further, the wear resistance of the hot-pressed bodies was approximately 100 times as high as that of conventional aluminum alloys.
Example 3~
Alloy ribbons, 3 mm in width and 25 ~m in thickness, were obtained from A185_xNi10Cu5xx alloys within the compositional range of the present invention by the same rapid solidification process as described in Example 1. Hardness and crystallization temperature were measured for each test piece of the rapidly solidified ribbons. As the element X o the A185_ xNi10Cu5Xx alloys, Ta, Hf, Nb or Y was chosen. The results of the measurements are summarized with the contents of the element X in FIGS. 2 and 3.
The A185Ni10Cu5 alloy had a structure mainly composed of crystalline. As apparent from the results shown in FIGS. 2 and 3, while the~hardness and the crystallization temperature are only about 460 DPN and about 410 K, respectively, these values are markedly - increased by addition of Ta, Hf, Nb or Y to the alloy and thereby high hardness and heat resistance can be obtained. Particularly, Ta and Hf have a prominent effect on these properties.
Example 4 AlloY ribbons of A170CU20Zr8Hf2' A175 20 5 A175Ni20Ta5 alloys of the invention were each placed on ~3~
A12O3 and heated at 650 C in a vacuum furnace to test wettability with A12O3. The alloys all melted and exhibited good wettability. Using the above alloys, an A12O3 sheet was bonded to an aluminum sheet. The two sheets could be strongly bound together and it has been found that the alloys of the present invention are also useful as brazing materials.
As described above, the aluminum alloys of the present invention are very useful as high-hardness material, high-strength material, high electrical-resistant material, wear-resistant material and brazing material. Further, the aluminum alloys can be easily sub;ected to extrusion, pressing, hot-forging because of theix superior workability, thereby resulting in high strength and high heat-resistant bulk materials which are very useful in a variety of applications.
In general, the aluminum alloys heretofore known have a low hardness and a low heat resistance. In recent years, attempts have been made to achieve a fine structure by rapidly solidifying aluminum alloys and thereby improve the mechanical properties, such as strength, and chemical properties, such as corrosion resistance, of the resulting aluminum alloys. But none of the rapid solidified aluminum alloys known here~ofore has been satisfactory in the properties, 130~60'd especially with regard to strength and heat resistance.
SUMMARY OF THE INVENTION
In view of the foregoing, it is an object of the present invention to provide novel aluminum alloys which have a good combination of properties of high hardness, high strength and superior corrosion resistance.
An another object of the present invention is to provide novel high strength, heat resistant aluminum alloys which can be successfully subjected to operations such as extrusion, press working, hot-forging or a high degree of bending because of their good workability.
A further object of the invention is to provide a method for preparing wrought articles from the novel aluminum alloys specified above by extrusion, press working or hot-forging without deteriorating their properties.
According to the present invention, there are provided high-strength, heat resistant aluminum-based alloys having a composition represented by the following general formula ~I) or (II) and the aluminum alloys contain at least 50% by volume of - amorphous phase.
AlaMbXd ____- (I) Al MbQ Xe -~--- (II) wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
Q is at least one metal element 6elected fxom the group Consisting of Mn, Cr, Mo, W, ,~
V, Ti and zr;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y; and a, b, c, d and e are atomic percentages falling within the following ranges:
45< a < 90, 5 < b < 40, 0 < c < 12, 0.5 < d < 20 and 0~5 < e < 10.
The aluminum ailoys of the present invention are very useful as high-hardness material, high-strength matexial, high ~lectrical-resistant material, wear-resistant material and brazing material.
Further, since the aluminum alloys specified above exhibit a superplasticity in the vicinity of their crystallization temperature, they can be readily processed into bulk by extrusion, press working or hot forging at the temperatures within the range of the crystallization temperature ~ 100C. The wrought articles thus obtained can be used as high strength, high heat-resistant material in many practical applications because of their high hardness and high tensile strength. The present invention also provides a method for preparing such wrought articles by extrusion, press working or hot-forging.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic view of a single roller-melting apparatus employed to prepare ribbons from the alloys of the present invention by a rapid solidification process;
FIG. 2 is a graph showing the relationship between the Vickers hardness (Hv) and the content of the element X (X = Ta, Hf, Nb or Y) for the rapidly .~ ~
6~
solidified ribbons of A185_xNi10Cu5Xx alloys a g to the present invention; and FIG. 3 is a graph showing the relationship between the crystallization temperature (Tx) and the content of the element X (X = Ta, Hf, Nb or Y) for the rapidly solidified ribbons of the Alg5-xNi10Cu5xx allo~s according to the present invention~
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The aluminum alloys of the present invention can be obtained by rapidly solidifying melt of the alloy having the composition as specified above by means of a liquid quenching technique. The liquid quenching technique is a method for rapidly cooling molten alloy and, particularly, the single-roller melt-spinning technique, twin roller melt-spinning technique and in-rotating-water melt-spinning technique are mentioned as effective examples of such a technique. In these techniques, a cooling rate of about 104 to 1 o6 K/sec can be obtained. In order to produce ribbon materials by the single-roller melt-spinning technique or twin roller melt-spinning technique, molten alloy is ejected from the opening of a nozzle to a roll of, for example, copper or steel, with a diameter of about 30 - 3000 mm, which is rotating at a constant rate of about 300 -10000 rpm. In these techniques, various ribbon materials with a width of about 1 - 300 mm and a thickness of about 5 - 500 ~m can be readily obtained.
Alternatively, in order to produce wire materials by the in-rotating-water melt-spinning technique, a jet of molten alloy is directed , under application of the back pressure of argon gas, through a nozzle into a liquid refrigerant layer with a depth of about 1 to 10 ~3~
cm which is formed by centrifugal force in a drum rotating at a rate of about 50 to 500 rpm. In such a mannerj fine wire materials can be readily obtained.
In this technique, the angle between the molten alloy ejecting from the nozzle and the liquid refrigerant surface is preferably in the range of about 60 to 90 and the ratio of the velocity of the ejected molten alloy to the velocity of the liquid refrigerant is preferably in the range of about 0.7 to 0.9.
Besides the above process, the alloy of the present invention can be also obtained ln the form of thin film by a sputtering process. Further, a rapidly solidified powder of the alloy composition of the present invention can be obtained by various atomizing processes, for example, a high pressure gas atomizing process or spray process Whether the rapidly solidified alloys thus obtained above are amorphous or not can be known by checking the presence of the characteristic halo pattern of an amorphous structure using an ordinary X-ray diffraction method. The amorphous structure is transformed into a crystalline structure by heating to a certain temperature (called "crystallization temperature") or higher temperatures.
In the aluminum alloys of the present invention represented by the general formula (I), a is limited to the range of 45 to 90 atomic % and b is limited to the range of 5 to 40 atomic ~. The reason for such limitations is that when a and b stray from the respective ranges, it is difficult to form an amorphous region in the resulting alloys and the intended alloys having at least 50 volume % of amorphous region can not be obtained by industrial cooling techniques using the above-mentioned liquid quenching, etc. The reason why ~ ~ I
. .
~3~
d is limited to the range of 0.5 to 20 atomic % is that when the elements represented by X (i.e~, Nb, Ta, Hf and Y~ are added singly or in combination of two or more thereof in the specified range, considerably improved hardness and heat resistance can be achieved.
When d is beyond 20 atomic %, it is impossible to obtain alloys having at least 50 volume % of an amorphous phase.
In the aluminum alloys of the present invention represented by the general formula tII)t a is limited to the range of 45 to 90 atomic % and b is limited to the range of 5 to 40 atomic %. The reason or such limitations is that when a and b stray from the respective ranges, it is difiicult to develop an amorphous region in the resulting alloys and the intended alloys having at least 50 volume % of amorphous region can not be obtained by industrial cooling techniques using the above-mentioned liquid quenching, etc. The reason why c and e are limited to the range of not more than 12 atomic % and the range of 0.5 to 10 atomic %, respectively, is that at least one metal element Q selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr and at least one metal element X selected from the group consisting of Nb, Ta, Hf and Y remarkedly improve the hardness and heat resistance properties of the alloys in combination thereof.
The raason why the upper limits of c and e are 12 atomic % and 10 atomic %, respectively, is that addition of Q and X exceeding the respective upper limits make impossible the attainment of the alloys containing at least 50 % by volume of an amorphous region.
Further, since the aluminum alloys of the present invention exhibit superplasticity in the vicinity of ~3~ 7 their crystallization temperatures (crystallization temperature + 100 C), they can be readily subjected to extrusion, press working, hot forging, etc. Therefore, the aluminum alloys of the present invention obtained in the form of ribbon, wire, sheet or powder can be successfully processed into bulk by way of extrusion, pressing, hot forging, etc., at the temperature range of their crystallization temperature ~ 100 C.
Further, since the aluminum alloys of the present lO invention have a high degree of toughness, some of them can be bent by 180 without fracture.
As set forth above, the aluminum alloys of the present invention have the foregoing two types of compositions, namely, an aluminum~based composition with lS addition of the element M ( one or more elements of Cu, Ni, Co and Fe) and the element X (one or more elements of Nb, Ta, Hf and Y~ and an aluminum-based composition with addition of the element Mj the element X and the element Q (one or more elements of Mn, Cr, Mo, W, V, Ti and Zr). In the alloys, the element M has an effect in improving the capability to form an amorphous structure. The elements Q and X not only provide significant improvements in the hardness and strength without deteriorating the capability to form an amorphous structure, but also considerably increase the crystallization temperature, thereby resulting in a significantly improved heat resistance.
Now, the advantageous features of the aluminum alloys of the present invention will be described with reference to the following examples.
Example 1 Molten alloy 3 having a predetermined alloy ~3~
composition was prepared hy a high-frequency melting process and was charged into a quartz tube 1 having a small opening 5 with a diameter of 0.5 mm at the tip thereof, ~s shown in FIG. 1. After heating and melting the alloy 3, the quartz tube 1 was disposed right above a copper roll 2l 20 cm in diameter. Then, the molten alloy 3 contained in the quartz tube 1 was ejected from the small opening 5 of the quartz-tube 1 under the application of an argon gas pressure of 0.7 kg/cm2 and brought into contact with the surface of the roll 2 rapidly rotating at a rate of 5,000 rpm. The molten alloy 3 is rapidly solidified and an alloy ribbon 4 was obtained.
According to the processing conditions as described above/ 51 different kinds of alloys having the compositions given in Table 1 were obtained in a ribbon form, 1 mm in width and 20 ~m in thickness, and wexe subjected to X-ray diffraction analysis. In all of the alloys halo patterns characteristic of amorphous metal were confirmed.
Further, the hardness (Hv), electrical resistance (p) and crystallization temperature (Tx) were measured for aach test specimen of the alloy ribbons and there were obtained the results as shown in Table 1. The hardness (Hv) is indicated by values (DPN) measured using a Vickers microhardness tester under load of 25 g. The electrical resistance (p) is values (~Q.cm) measured by a conventional foux-probe technigue. The crystallization temperature (Tx) is the starting temperature (K) of the first exothermic peak on the differential scanning calorimetric curve which was conducted for each test specimen at a heatiny rate of 40 K/min. In the column of "Structure", characters "a"
and "b" represent an amorphous structure and a ., ~3~
.9 crystalline structure, respectively, and subscripts of the character "c'l show volume percentages of "c".
Table 1 No. Composition Structure Hv P Tx (by at.%) (DPN) (~Q.cm) (K) _ 1. Al7oFe2oNb1o a 750 460 788 2. A17oFe2oHf1o a 900 570 827 3. Al7oFe2oTa1o a+C10970 630 860 4, Al70Fe2oy1o a~c80990 670 875 5, Al70co2oTa1o a 880 620 780 6. A170C20Nb10 a 740 580 760 7, Al7oco2oHf1o a 850 530 758 8. Al7oco2oy1o a 720 590 720 9, AlgsNi10Nb5 a 550 560 607 10. Al70Ni20Nb10 a 590 720 755 11. Al85Ni10Hf5 a 540 550 612 12. Al7oNi2oHf1o a 810 470 755 13. Al75Ni20Y5 a 520 520 590 14. Al70Ni20Y10 620 560 685 15. Al70Ni20Ta10 a1040 710 820 16. Al7ocu2oHf1o a 630 520 623 17. Al70cu2oTa1o a 975 690 768 18. Al70CU20Nb10 a855 590 692 19. Al70CU20Y10 a~c10 860 595 688 20. Al70Ni20Cr8Hf2 a820 550 663 21. Al7oNi2oMo8Hf2 a850 630 755 22. A170Ni20W8Hf2 a880 550 821 23. Al7ocu2oTi8Hf2 a870 480 660 24. Al7ocu2ozr8Hf2 a670 520 650 _ ~3~
Table 1 (continued) No. Composition Structure Hv P Tx (by atO%) (DPN) (~Q.cm) (K) 25. Al85CU5V8Nb2 a 540 470 605 26. Al7SCU15V8Nb2 a 700 560 719 27. Al65cu25v8Nb2 a 1000 450 705 28. Al60CU30V8Nb2 a1040 460 642 29. Al7sCU15V5Y5 a 620 510 705 30. Al7ocu15v1oy5 a+c10870 570 773 31. Al7ocu2ocr8Ta2 a 885 715 626 32. Al7ocu2oMo8Ta2 a 810 700 715 33. Al7ocu2oMn8Ta2 a 615 490 642 34. Al7oNi2oMn8Hf2 a 705 512 701 35. Al65Ni20Cr5M5Hf5 a 730 540 ~ 723 36. Al6sJ~20zrsNb5Hf5a+c20 825 610 796 37. Al8scoszr5Nb5 a 428 530 654 38. Alg4coscr3Y8 a 422 550 640 39. Al75Fe10M5Hf10 a 778 630 720 40. Alg4Fescr3y8 a 450 560 670 41. Al70Ni1s Fe5Hf10 a 860 510 786 42. Al70Ni15co5y1o a 820 490 755 43. ALgoFesco5Hf5 a 680 460 620 44. Al80cusco5Nb1o a 880 630 770 45, Al70Ni1oTi1o~If1o a 850 550 635 46. Al80Fesw5y1o a 920 625 830 47~ AL70Ni1scosMo5Ta5 a 860 635 785 48. Al70Ni1 oNb10Y10 a 780 730 810 49, Al7oNi1oHf1oy1o a 730 680 725 50, AlgoFe5Nb5y1o a750 530 710 51. Al80Niszr5Hf5y5 a 720 620 730 _ ~3~6~7 As shown in Table 1, the aluminum alloys of the present invention have an extremely high hardness of the order of about 450 to 1050 DPN, in comparison with the hardness of the order of 50 to 100 DPN of ordinary aluminum-based alloys. Further, with respect to the electrical resistance, ordinary aluminum alloys have resistivity on the order of 100 to 300 ~Q.cm, while the amorphous aluminum alloys of the present invention have a high degree of resistivity of at least about 400 ~Q
.cm. A further surprising effect is that the aluminum-based alloys of the present invention have very high crystallization temperatures Tx of at least 600 K and exhibit a greatly improved heat resistance.
The alloy No. 12 given in Table 1 was further examined for the strength using an'~nstro~'-type tensile testing machine. The tensile strength was about 95 kg/mm2 and the yield strength was about 80 kg/mm2.
These values are 2.1 times of the maximum tensile strength (about 45 kg/mm2) and maximum yield strength (about 40 kg/mm2) of conventional age-hardened Al-Si-Fe ; aluminum allovs.
Example 2 Master alloys A70Fe20Hf1o and Al70Ni20Hf10 were each melted in a vacuum high-freguency melting furnace and were formed into amorphous powder by a high-pressure gas atomization process. The powder thus obtained from each alloy was sintered at a temperature of100 to 550 C for 30 minutes under pressure of 940 MPa to provide a cylindrical material with a diameter of 5 mm and a heightof 5 mm. Each cylindrical material was hot-pressed at a temperature of 400 C near the ~- * Trademark crystallization temperature of each alloy for 30 minutes. The resulting hot-pressed sintered bodies had a density of about 95 % of the theoretical density, hardness of about 850 DPN and electrical resistivity of 500 ~Q ~cm. Further, the wear resistance of the hot-pressed bodies was approximately 100 times as high as that of conventional aluminum alloys.
Example 3~
Alloy ribbons, 3 mm in width and 25 ~m in thickness, were obtained from A185_xNi10Cu5xx alloys within the compositional range of the present invention by the same rapid solidification process as described in Example 1. Hardness and crystallization temperature were measured for each test piece of the rapidly solidified ribbons. As the element X o the A185_ xNi10Cu5Xx alloys, Ta, Hf, Nb or Y was chosen. The results of the measurements are summarized with the contents of the element X in FIGS. 2 and 3.
The A185Ni10Cu5 alloy had a structure mainly composed of crystalline. As apparent from the results shown in FIGS. 2 and 3, while the~hardness and the crystallization temperature are only about 460 DPN and about 410 K, respectively, these values are markedly - increased by addition of Ta, Hf, Nb or Y to the alloy and thereby high hardness and heat resistance can be obtained. Particularly, Ta and Hf have a prominent effect on these properties.
Example 4 AlloY ribbons of A170CU20Zr8Hf2' A175 20 5 A175Ni20Ta5 alloys of the invention were each placed on ~3~
A12O3 and heated at 650 C in a vacuum furnace to test wettability with A12O3. The alloys all melted and exhibited good wettability. Using the above alloys, an A12O3 sheet was bonded to an aluminum sheet. The two sheets could be strongly bound together and it has been found that the alloys of the present invention are also useful as brazing materials.
As described above, the aluminum alloys of the present invention are very useful as high-hardness material, high-strength material, high electrical-resistant material, wear-resistant material and brazing material. Further, the aluminum alloys can be easily sub;ected to extrusion, pressing, hot-forging because of theix superior workability, thereby resulting in high strength and high heat-resistant bulk materials which are very useful in a variety of applications.
Claims (4)
1. A high strength, heat resistant aluminum alloy having a composition represented by the general formula:
AlaMbXd wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y; and a, b and d are atomic percentages falling within the following ranges:
45 ? a ? 90, 5 ? b ? 40 and 0.5 ? d ? 20, said aluminum alloy containing at least 50% by volume of an amorphous phase.
AlaMbXd wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y; and a, b and d are atomic percentages falling within the following ranges:
45 ? a ? 90, 5 ? b ? 40 and 0.5 ? d ? 20, said aluminum alloy containing at least 50% by volume of an amorphous phase.
2. A high strength, heat resistant aluminum alloy having a composition represented by the general formula:
AlaMbQcXe wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
Q is at least one metal element selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y;
and a, b, c and e are atomic percentages falling within the following ranges:
45? a ? 90, 5 ? b ? 40, 0 < c ? 12 and 0.5 ? e ? 10, said aluminum alloy containing at least 50% by volume of an amorphous phase.
AlaMbQcXe wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
Q is at least one metal element selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y;
and a, b, c and e are atomic percentages falling within the following ranges:
45? a ? 90, 5 ? b ? 40, 0 < c ? 12 and 0.5 ? e ? 10, said aluminum alloy containing at least 50% by volume of an amorphous phase.
3. A method of preparing a wrought article from a high strength, heat resistant aluminum alloy by extrusion, press working or hot-forging at temperatures within the range of the crystallization temperature of sald aluminum alloy ? 100°C, said aluminum alloy having a composition represented by the general formula:
AlaMbXd wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y;
and a, b and d are atomic percentages falling within the following ranges:
45 ? a ? 90, 5 ? b ? 40 and 0.5 ? d ? 20, said aluminum alloy containing at least 50% by volume of an amorphous phase.
AlaMbXd wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y;
and a, b and d are atomic percentages falling within the following ranges:
45 ? a ? 90, 5 ? b ? 40 and 0.5 ? d ? 20, said aluminum alloy containing at least 50% by volume of an amorphous phase.
4. A method of preparing a wrought article from a high strength, heat resistant aluminum alloy by extrusion, press working or hot-forging at temperatures within the range of the crystallization temperature of said aluminum alloy ? 100°C, said aluminum alloy having a composition represented by the general formula:
A1aMbQcXe wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
Q is at least one metal element selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y; and a, b, c and e are atomic percentages falling within the following ranges:
45? a ? 90, 5 ? b ? 40, 0 ? c ? 12, and 0.5 ? e ? 10, said aluminum alloy containing at least 50% by volume of an amorphous phase.
A1aMbQcXe wherein: M is at least one metal element selected from the group consisting of Cu, Ni, Co and Fe;
Q is at least one metal element selected from the group consisting of Mn, Cr, Mo, W, V, Ti and Zr;
X is at least one metal element selected from the group consisting of Nb, Ta, Hf and Y; and a, b, c and e are atomic percentages falling within the following ranges:
45? a ? 90, 5 ? b ? 40, 0 ? c ? 12, and 0.5 ? e ? 10, said aluminum alloy containing at least 50% by volume of an amorphous phase.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62199971A JPS6447831A (en) | 1987-08-12 | 1987-08-12 | High strength and heat resistant aluminum-based alloy and its production |
| JP62-199971 | 1987-08-12 | ||
| JP5083421A JPH0637696B2 (en) | 1987-08-12 | 1993-04-09 | Method for manufacturing high-strength, heat-resistant aluminum-based alloy material |
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| Publication Number | Publication Date |
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| CA1304607C true CA1304607C (en) | 1992-07-07 |
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|---|---|---|---|
| CA000573600A Expired - Lifetime CA1304607C (en) | 1987-08-12 | 1988-08-02 | High strength, heat resistant aluminum alloys and method of preparingwrought article therefrom |
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| Country | Link |
|---|---|
| US (1) | US5053084A (en) |
| EP (1) | EP0303100B1 (en) |
| JP (2) | JPS6447831A (en) |
| KR (1) | KR930006295B1 (en) |
| CA (1) | CA1304607C (en) |
| DE (1) | DE3886845T2 (en) |
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| US4743317A (en) * | 1983-10-03 | 1988-05-10 | Allied Corporation | Aluminum-transition metal alloys having high strength at elevated temperatures |
| US4715893A (en) * | 1984-04-04 | 1987-12-29 | Allied Corporation | Aluminum-iron-vanadium alloys having high strength at elevated temperatures |
| JPS6237335A (en) * | 1985-08-09 | 1987-02-18 | Yoshida Kogyo Kk <Ykk> | Aluminum alloy having high corrosion resistance and strength |
| EP0218035A1 (en) * | 1985-10-02 | 1987-04-15 | Allied Corporation | Rapidly solidified aluminum based, silicon containing, alloys for elevated temperature applications |
-
1987
- 1987-08-12 JP JP62199971A patent/JPS6447831A/en active Granted
-
1988
- 1988-07-26 DE DE3886845T patent/DE3886845T2/en not_active Expired - Fee Related
- 1988-07-26 EP EP88112041A patent/EP0303100B1/en not_active Expired - Lifetime
- 1988-08-02 CA CA000573600A patent/CA1304607C/en not_active Expired - Lifetime
- 1988-08-11 KR KR1019880010324A patent/KR930006295B1/en not_active Expired - Fee Related
-
1990
- 1990-04-30 US US07/515,334 patent/US5053084A/en not_active Expired - Fee Related
-
1993
- 1993-04-09 JP JP5083421A patent/JPH0637696B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR930006295B1 (en) | 1993-07-12 |
| DE3886845D1 (en) | 1994-02-17 |
| JPH0637696B2 (en) | 1994-05-18 |
| DE3886845T2 (en) | 1994-07-21 |
| KR890003976A (en) | 1989-04-19 |
| JPH0673513A (en) | 1994-03-15 |
| JPH0579750B2 (en) | 1993-11-04 |
| EP0303100A1 (en) | 1989-02-15 |
| JPS6447831A (en) | 1989-02-22 |
| US5053084A (en) | 1991-10-01 |
| EP0303100B1 (en) | 1994-01-05 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |