CA2037818C - High strength amorphous alloy - Google Patents
High strength amorphous alloyInfo
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- CA2037818C CA2037818C CA002037818A CA2037818A CA2037818C CA 2037818 C CA2037818 C CA 2037818C CA 002037818 A CA002037818 A CA 002037818A CA 2037818 A CA2037818 A CA 2037818A CA 2037818 C CA2037818 C CA 2037818C
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C45/00—Amorphous alloys
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Abstract
A high strength amorphous alloy comprises an amorphous phase containing a predominant metal element, a first additive element consisting rare earth element(s), and a second additive element consisting of element(s) other than rare earth elements and forming a matrix, and a crystalline phase containing the predominant metal element and the first and second additive elements and dispersed homogeneously in the amorphous phase with the first and second additive elements formed into a supersaturated solid solution. The content of the predominant metal element in the crystalline phase is set in a range of at least 85% by atom to at most 99.8%
by atom. If the rare earth element ratio value CR in the crystalline phase is defined as being CR = a / a + b wherein a represents the content, % by atom, of a rare earth element which is the first additive element, and k represents the content, % by atom, of the second additive element, and the rare earth element ratio value CR is set at 0.5 or less.
by atom. If the rare earth element ratio value CR in the crystalline phase is defined as being CR = a / a + b wherein a represents the content, % by atom, of a rare earth element which is the first additive element, and k represents the content, % by atom, of the second additive element, and the rare earth element ratio value CR is set at 0.5 or less.
Description
~IGH BTRENGTH AMORPHO~8 ALLOY
8ACR~ROUND OF THE l~.v~ ON
FIELD OF THB lNV~ lON
The field of the present invention is high strength amorphous alloys, and more particularly, improvements of high strength amorphous alloys comprising an amorphous phase containing a predominant metal element, a first additive element consisting of rare earth element(s), and a second additive element consisting of element(s) other than rare earth elements.
There are various conventionally known amorphous Al alloys of this type, such as described in Japanese Patent Application Laid-open No.47831/89. Any of such amorphous alloys are aimed at the formation of a single phase in order to promote an increase in strength.
However, the prior art amorphous alloys suffer from a problem that if a crystalline phase is partially incorporated due to conditions of production when the intent is to form a single amorphous phase as in the prior art amorphous alloy, the resulting entire alloy may be reduced in strength and toughness due to the appearance of such crystalline phase.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an amorphous alloy of the type described above, wherein a crystalline phase is incorporated in a matrix consisting of an amorphous phase, the content of a predominant metal element in the crystalline phase and the ratio value (which depends upon a relationship with the content of a second additive element) of a rare earth element are controlled, thereby preventing a reduction in strength of the entire alloy and permitting the strength to be increased more than that of an amorphous single-phase alloy.
To achieve the above object, according to the present invention, there is provided an amorphous alloy comprising an amorphous matrix-forming phase containing a predominant metal element, at least one first additional element selected from rare earth elements, and at least one second additional element selected from elements other than rare earth elements, and a crystalline phase homogeneously dispersed in the amorphous phase, the crystalline phase comprising the predominant metal element and the first and second additional elements with the first and second additive elements formed into a supersaturated solid solution, wherein the content of the predominant metal element in the crystalline phase is in the range of at least 85 atom % to at most 99.8 atom %, and wherein the rare earth element ratio CR
in the crystalline phase defined by the formula CR = a / (a + b) (wherein a represents the atom % content of the first additional element, and b represents the atom % content of the second additional element), is 0.5 or less.
If the content of the predominant metal element in the crystalline phase dispersed in the amorphous matrix phase and the rare earth element ratio CR are controlled in the above manner, it is possible to further increase the strength of the entire amorphous alloy and to improve the hot plastic workability of such alloy.
However, if the content of the predominant metal element is less than 85 atom %, compounds are liable to be produced in the crystalline phase in production of the amorphous alloy, and any such compound is liable to appear alone, causing the embrittlement of the entire resulting amorphous alloy. On the other hand, if the content exceeds 99.8 atom %, it is difficult to provide a mixture of an amorphous phase and a crystalline phase at a normal cooling rate. If the cooling rate is significantly increased, the mass productivity is considerably detracted. Moreover, there is also a problem of a degraded heat resistance of the amorphous alloy itself. The term "predominant metal element"
used herein refers to Al and Mg in a preferred embodiment.
A rare earth element is an element required for achieving the non-crystallization, i.e., formation of an amorphous phase, but if the rare earth element is incorporated in a content more than a specified content into a crystal lattice of the predominant metal element forming the crystalline phase, the lattice constant of the crystal lattice is increased, resulting in an embrittlement of the amorphous alloy.
Therefore, the ratio CR of the rare earth element in the crystalline phase has to be 0.5 or less. ~y setting the ratio CR in this manner, it is possible to provide a lattice constant of the crystal lattice approximating that of a pure predominant metal element.
With such a configuration, a relatively soft crystalline phase is dispersed in an amorphous phase having a higher hardness. Therefore, it is believed that the tough-ness of the entire amorphous alloy is improved, because the crystalline phase absorbs the strain in an interface between the crystalline phase and the amorphous phase.
The above and other objects, features and advantages of the invention will become apparent from a reading of the following description of the preferred embodiments, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic view of an apparatus for producing an amorphous alloy;
Fig. 2 is a diagram of an X-ray diffraction pattern for an amorphous single-phase Al alloy;
Fig. 3 is a diagram of an X-ray diffraction pattern for an amorphous Al alloy containing a crystalline phase having a content of 9% by volume;
Fig. 4 is a diagram of an X-ray diffraction pattern 2a37sl&
for an amorphous Al alloy containing a crystalline phase having a content of 29% by volume;
Fig. 5 is a diagram of an X-ray diffraction pattern for an amorphous Al alloy containing a crystalline phase having a content of 37% by volume;
Fig. 6 is a graph illustrating a relationship between the content of a crystalline phase in an amorphous Al alloy and the tensile strength;
Fig. 7 is a graph illustrating a relationship between the Y ratio value CR and the lattice constant;
Fig. 8 is a graph illustrating a relationship between the Y ratio value CR and the tensile strength;
Fig. 9 is a graph illustrating a relationship between the Y ratio value CR and the Young's modulus;
Fig. 10 is a graph illustrating a relationship between the Y content and the lattice constant in a crystalline phase;
Fig. 11 is a thermocurve of a differential thermal analysis for an amorphous single-phase Al alloy;
Fig. 12 is a thermocurve of a differential thermal analysis for an amorphous Al alloy containing a crystalline phase having a content of 26% by volume; and Fig. 13 is a thermocurve of a differential thermal analysis ~or an amorphous Al alloy containing a crystalline phase having a content of 37% by volume.
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~378~
DESCRIPTION OF THF PREFERRED EMBODIMENTS
Fig.l schematically illustrates an amorphous alloy producing apparatus using a single-roller process. The apparatus comprises a cooling roller l made of a pure copper and adapted to be rotated in a clockwise direction as viewed in Fig.l, a quartz nozzle 2 fixedly mounted above the cooling roller 1 with its outlet being in proximity to an outer peripheral surface of the cooling roller 1, and a high frequency heating coil 3 disposed to surround a lower end of the nozzle 2. The cooling roller l has a diameter set at 200 mm, and the nozzle 2 has a bore diameter set at 0.3 mm at the outlet. The gap between the outlet and the outer peripheral surface of the cooling roller 1 is set at 0.3 mm.
In producing an amorphous Al alloy as an amorphous alloy, a molten alloy m containing a predominant metal element consisting of Al, a first additive element consisting of a rare earth element(s), and a second additive element consisting of an element(s) other than a rare earth element is ejected from the outlet of the nozzle 2 onto the outer peripheral surface of the cooling roller 1 under a pressure of argon gas (for example, 0.4 kg/cm2), and spread on the outer peripheral surface of the roller l from between the nozzle 2 and the cooling roller 1 as the cooling roller l is rotated.
Thus, it is drawn into a thin ribbon form, while at the same time being quenched, thereby providing an amorphous Al alloy.
In this case, if the rotational speed of the cooling roller l is reduced below a speed that forms an amorphous single-phase Al alloy (i.e., an alloy having a volume fraction of an amorphous phase of 100%), thereby providing a reduced cooling rate for the molten alloy, a crystalline phase is produced in the molten metal.
The use of such a procedure provides a high strength amorphous Al alloy comprising an amorphous phase which forms a matrix, containing a predominant metal element and first and second additive elements, and a fine crystalline phase which is dispersed homogeneously in the amorphous phase, containing the predominant metal element and the first and second additive elements with the first and second additive elements formed into a supersaturated solid solution.
The content of Al as the predominant metal element in the crystalline phase is in the range of from 85 atom % to 99.8 atom %. If the Al content is less than 85 atom %, compounds (such as A13Y, A13Ni, AlNimYn, etc.) are liakle to be produced in the crystalline phase in the production of the amorphous Al alloy, and any such compound is liable to appear alone, resulting in an embrittlement of the entire amorphous Al alloy. On the other hand, if the Al content exceeds 99.8 atom %, it is difficult to provide a mixture Gf an amorphous phase and a crystalline phase at a normal cooling rate. If the cooling rate is significantly increased, the mass productivity is considerably detracted. Moreover, the heat resistance of the resulting amorphous Al alloy itself is degraded.
Examples of the rare earth elements that may be used as the first additive element include Y, La, Ce, Sm, Nd, and mixtures thereof such as Mm (Misch metal which is a mixture of rare earth elements of the cerium group containing 40-50%
Ce and 20-40% La), and the content thereof in the crystalline phase is preferably in the range of from 0.1 atom % to 5 atom %. If the content of the rare earth element is too low, it is impossible to provide a mixture of amorphous and crystalline phases. On the other hand, if the content is too high, the resulting crystalline phase is embrittled and as a result the amorphous Al alloy itself is brittle.
Examples of the second additive elements that may be used include Ni, Fe and Co, and mixtures thereof. The content thereof in the crystalline phase is preferably at most 10 atom %. If the content of the second additive element is too high, compounds are liable to appear in the resulting crystalline phase, and the amorphous phase forming ability for the entire alloy is reduced from its interrelation with the content of the rare earth element. The lower limit of the content of the second additive element is preferably of 5 atom %. Too low a content of the second additive element may result in undesirable conditions during production.
It is preferable that the contents of the predominant metal element and the first and second additive elements in the amorphous matrix phase are greater than those in the crystalline phase. If this relationship of the contents is reversed, compounds are liable to appear in the crystalline phase, causing the embrittlement of the entire alloy. Thus, the crystalline phase preferably forms 5-40%, especially 15-25%, by volume of the amorphous alloy.
:i, ._ Using the above-described procedure with varied rotational speeds of the cooling roller 1, amorphous Al alloy specimens A to D having A189Y5Ni6 (wherein numeral values represent atom % which is true with each of the alloy specimens) were produced, and the relationship between the rotational speed of the cooling roller 1 and the content of the crystalline phase was examined. The results are given in the table below. The crystal structure of the crystalline phase was of a fcc (a face-centered cubic structure) due to Al, and the average diameter of the crystalline phase was in the range of from 300 A to 800 A.
AmorphousRotational speed ofContent of crystalline Al alloycooling roller (rpm) phase (% by volume) A 4,000 0 B 3,000 9 C 2,000 29 D 1,500 37 Figs. 2 to 5 illustrate diagrams of X-ray diffraction patterns of the amorphous Al alloys A to Dl respectively. The anticathode of the X-ray tube used for measurement was made of Cu, and Ka-ray was used.
The amorphous Al alloy A is an amorphous single-phase Al alloy because of a more rapid cooling speed, and a halo-pattern having no steep peak, which is peculiar to the amorphous phase, can be seen in Fig. 2.
The amorphous alloy B was produced at a cooling rate 23378 1 ~
._ 1,000 rpm lower than when the alloy A was produced. As shown in Fig. 3, in the amorphous alloy B, a peak pl was observed as a result of the appearance of a slight crystalline phase. This peak pl corresponds to a (111) plane of the fcc.
The amorphous Al alloy C was produced at a cooling rate half of when the alloy A was produced, and about 30% of the entire amorphous Al alloy was a crystalline phase. Hence, a higher peak pl and lower peaks p2 to p4 have appeared as a result of the appearance of a crystalline phase, as shown in Fig. 4. Among these peaks p2 to p4, the peak p2 corresponds to a (200) plane of the fcc, the peak p3 corresponds to a (220) plane of the fcc, and the peak p4 corresponds to a (311) plane of the fcc.
The amorphous Al alloy D was produced at a cooling rate lower than when the alloy C was produced, and about 40%
of the entire amorphous Al alloy was a crystalline phase.
Therefore, higher peaks pl and p2 and lower peaks p3 and p4 have appeared as a result of the appearance of a crystalline phase, as shown in Fig. 5.
Fig. 6 illustrates a relationship between the content of a crystalline phase in each cf three amorphous Al alloys and the tensile strength. In Fig. 6, a line xl corresponds to the above-described A189Y5Ni6 alloy, a line x2 corresponds to an A188Y2Nilo alloy, and a line x3 corresponds to an AlgoY6Ni4 alloy-As apparent from Fig. 6, in each alloy, the strength is increased as the content of the crystalline phase is increased, as compared with an amorphous single-phase (the content of a crystalline phase = 0). Therefore, the content of the crystalline phase is preferred to be in the range of from 5% by volume to 40% by volume.
In this case, in the A189Y5Ni6 and A188Y2Nilo alloys indicated by the lines xl and x2, an embrittlement begins at a crystalline phase content near 40% by volume. On the other hand, in the AlgoY6Ni4 alloy indicated by the line x3, an embrittlement begins at a crystalline phase content near 20%
by volume, and hence, this alloy is compositionally not included in the present invention.
The average diameter of the crystalline phase is preferably in the range of from 300 A to 800 A. If the average diameter is too low, the meaning of the appearance of the crystalline phase is lost. If the average diameter is too high, the stabilization of the crystalline phase is not provided and a homogeneous dispersion is impossible, resulting in a reduced strength of the entire amorphous Al alloy.
The rare earth element is an element required for achieving a non-crystallization or formation of an amorphous phase, but if a rare earth element in an amount more than a specified amount is incorporated in a crystal lattice (fcc) of Al forming a crystalline phase, the lattice constant (~ =
4.05 A) of the crystal lattice is increased, resulting in a embrittlement of the amorphous alloy, because the rare earth element has a relatively large atomic radius (e.g., Y has a radius of 1.8 A).
~3781 a The ratio CR of the rare earth element component in the crystalline phase is defined by the formula or equation:
CR = a / (a + b) (wherein a and b are as defined above) and is 0.5 or less.
By setting the ratio CR of the rare earth element component in the crystalline phase in the above manner, it is possible to provide a lattice constant of the crystal lattice approximating that of pure Al.
Such a configuration results in a relatively soft crystalline phase dispersed in an amorphous phase having a higher hardness. Therefore, it is believed that the entire amorphous alloy has an improved toughness, because the crystalline phase absorbs the strain in an interface between the crystalline phase and the amorphous phase.
Figs. 7 to 9 illustrate relationships between the ratio CR[a / (a + b), wherein a represents a Y content and b represents a Ni content] of Y in an Al-Y-Ni based amorphous alloy having a crystalline phase content of 20% by volume and the lattice constant of a crystal lattice in a crystalline phase, the tensile strength and the Young's modulus, respectively.
As is apparent from Fig. 7, by setting the ratio CR of Y at no greater than 0.5, it is possible to provide a lattice constant approximating that (4.05 A) of pure Al.
In addition, as apparent from Figs. 8 and 9, both the tensile strength and the Young's modulus can be maintained at high values by setting the ratio CR of Y at no greater than 0.5.
The relation, a _ b, is established from the above-described relation a / (a * b) < 0.5. This means that the content of an expensive rare earth element such as Y, La, Ce, etc., can be reduced, which is effective for reducing the cost of an amorphous A1 alloy.
Fig. 10 illustrates the relationship between the Y
content and the lattice constant of a crystal lattice in a crystalline phase in each of Alloo xYX based amorphous alloy (indicated by line yl) and an A198_xYxNi2 based amorphous alloy (indicated by line y2) when the contents of the crystalline phase are set in the range of 5 to 40% by volume.
It can be seen from the lines yl and y2 in Fig. 10 that the lattice constant is substantially constant if the Y
content is equal to or less than 2% by atom, but the lattice constant is increased if the Y content exceeds 2% by atomic weight.
Therefore, in the A198 XYxNi2 based amorphous alloy, the Y content in the crystalline phase is set in the range of from 0.5 atom % to 2 atom % in order to ensure that the required strength is achieved.
Figs. 11 to 13 illustrate differential thermal analysis thermocurves for three A189Y5Ni6 alloys which are amorphous Al alloys. Fig. 11 corresponds to the alloy having a single amorphous phase, Fig. 12 corresponds to the alloy having a crystalline phase content of 26% by volume, and Fig. 13 corresponds to the alloy having a crystalline phase content of 37% by volume.
The crystallization temperature Tx of the amorphous single-phase Al alloy shown in Fig. 11 is 89~C, but tends to be gradually raised as the crystalline phase content is increased. For this reason, the crystallization temperature Tx of the amorphous Al alloy shown in Fig. 12 is raised to 99~C, and the crystallization temperature Tx of the amorphous Al alloy shown in Fig. 13 is raised to 109~C.
In addition, from a comparison of the calorific values after the heating temperature exceeds the crystallization temperature Tx, i.e., the heights of the peaks, it can be seen that the height of the peak for the amorphous single phase Al alloy of Fig. ll is largest, and the height of the peak is reduced with increasing Gf the crystalline phase content. This means that the amount of the crystalline phase produced by crystallization is smaller.
Thus, when a material is formed from an amorphous Al alloy having a thermal characteristic as shown in Figs. 12 and 13 and such material is subjected to a hot plastic working, e.g., a hot extrusion, the thermal contrcl for the material is relatively easy.
It should be noted that a crystalline phase appears even when an amorphous single-phase Al alloy is subjected to a thermal treatment, but the crystalline phase in this case is coalesced because of an increased rate of growth of crystalline particles. In addition, the strength and tough-ness are reduced as compared with those of the amorphous Al alloy according to the present invention, because the 2~37~3l a dispersion of the crystalline phase is heterogeneous and moreover, a segregation of the crystalline phase is produced.
It wi]l be understood that amorphous Mg alloys containing Mg as a predominant metal element rather than Al are also included in the scope of the present invention.
It will also be appreciated that a further aspect of the present invention provides a process for the prepara-tion of the a~ove-descrlbed alloys. ~ preferred embodiment of this aspect comprises ejecting a molten alloy of the composition defined from a nozzle onto an outer peripheral surface of a cooling roller and spreading the molten alloy on the peripheral surface while rotating the cooling roller, thereby drawing the alloy into a thin ribbon form and quenching it at the same time, wherein the roller is rotated at a speed so controlled that it is ~elow a speed -c~a~
forms an amorphous single-phase alloy.
8ACR~ROUND OF THE l~.v~ ON
FIELD OF THB lNV~ lON
The field of the present invention is high strength amorphous alloys, and more particularly, improvements of high strength amorphous alloys comprising an amorphous phase containing a predominant metal element, a first additive element consisting of rare earth element(s), and a second additive element consisting of element(s) other than rare earth elements.
There are various conventionally known amorphous Al alloys of this type, such as described in Japanese Patent Application Laid-open No.47831/89. Any of such amorphous alloys are aimed at the formation of a single phase in order to promote an increase in strength.
However, the prior art amorphous alloys suffer from a problem that if a crystalline phase is partially incorporated due to conditions of production when the intent is to form a single amorphous phase as in the prior art amorphous alloy, the resulting entire alloy may be reduced in strength and toughness due to the appearance of such crystalline phase.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an amorphous alloy of the type described above, wherein a crystalline phase is incorporated in a matrix consisting of an amorphous phase, the content of a predominant metal element in the crystalline phase and the ratio value (which depends upon a relationship with the content of a second additive element) of a rare earth element are controlled, thereby preventing a reduction in strength of the entire alloy and permitting the strength to be increased more than that of an amorphous single-phase alloy.
To achieve the above object, according to the present invention, there is provided an amorphous alloy comprising an amorphous matrix-forming phase containing a predominant metal element, at least one first additional element selected from rare earth elements, and at least one second additional element selected from elements other than rare earth elements, and a crystalline phase homogeneously dispersed in the amorphous phase, the crystalline phase comprising the predominant metal element and the first and second additional elements with the first and second additive elements formed into a supersaturated solid solution, wherein the content of the predominant metal element in the crystalline phase is in the range of at least 85 atom % to at most 99.8 atom %, and wherein the rare earth element ratio CR
in the crystalline phase defined by the formula CR = a / (a + b) (wherein a represents the atom % content of the first additional element, and b represents the atom % content of the second additional element), is 0.5 or less.
If the content of the predominant metal element in the crystalline phase dispersed in the amorphous matrix phase and the rare earth element ratio CR are controlled in the above manner, it is possible to further increase the strength of the entire amorphous alloy and to improve the hot plastic workability of such alloy.
However, if the content of the predominant metal element is less than 85 atom %, compounds are liable to be produced in the crystalline phase in production of the amorphous alloy, and any such compound is liable to appear alone, causing the embrittlement of the entire resulting amorphous alloy. On the other hand, if the content exceeds 99.8 atom %, it is difficult to provide a mixture of an amorphous phase and a crystalline phase at a normal cooling rate. If the cooling rate is significantly increased, the mass productivity is considerably detracted. Moreover, there is also a problem of a degraded heat resistance of the amorphous alloy itself. The term "predominant metal element"
used herein refers to Al and Mg in a preferred embodiment.
A rare earth element is an element required for achieving the non-crystallization, i.e., formation of an amorphous phase, but if the rare earth element is incorporated in a content more than a specified content into a crystal lattice of the predominant metal element forming the crystalline phase, the lattice constant of the crystal lattice is increased, resulting in an embrittlement of the amorphous alloy.
Therefore, the ratio CR of the rare earth element in the crystalline phase has to be 0.5 or less. ~y setting the ratio CR in this manner, it is possible to provide a lattice constant of the crystal lattice approximating that of a pure predominant metal element.
With such a configuration, a relatively soft crystalline phase is dispersed in an amorphous phase having a higher hardness. Therefore, it is believed that the tough-ness of the entire amorphous alloy is improved, because the crystalline phase absorbs the strain in an interface between the crystalline phase and the amorphous phase.
The above and other objects, features and advantages of the invention will become apparent from a reading of the following description of the preferred embodiments, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic view of an apparatus for producing an amorphous alloy;
Fig. 2 is a diagram of an X-ray diffraction pattern for an amorphous single-phase Al alloy;
Fig. 3 is a diagram of an X-ray diffraction pattern for an amorphous Al alloy containing a crystalline phase having a content of 9% by volume;
Fig. 4 is a diagram of an X-ray diffraction pattern 2a37sl&
for an amorphous Al alloy containing a crystalline phase having a content of 29% by volume;
Fig. 5 is a diagram of an X-ray diffraction pattern for an amorphous Al alloy containing a crystalline phase having a content of 37% by volume;
Fig. 6 is a graph illustrating a relationship between the content of a crystalline phase in an amorphous Al alloy and the tensile strength;
Fig. 7 is a graph illustrating a relationship between the Y ratio value CR and the lattice constant;
Fig. 8 is a graph illustrating a relationship between the Y ratio value CR and the tensile strength;
Fig. 9 is a graph illustrating a relationship between the Y ratio value CR and the Young's modulus;
Fig. 10 is a graph illustrating a relationship between the Y content and the lattice constant in a crystalline phase;
Fig. 11 is a thermocurve of a differential thermal analysis for an amorphous single-phase Al alloy;
Fig. 12 is a thermocurve of a differential thermal analysis for an amorphous Al alloy containing a crystalline phase having a content of 26% by volume; and Fig. 13 is a thermocurve of a differential thermal analysis ~or an amorphous Al alloy containing a crystalline phase having a content of 37% by volume.
~, , ., , ., ~ .
~378~
DESCRIPTION OF THF PREFERRED EMBODIMENTS
Fig.l schematically illustrates an amorphous alloy producing apparatus using a single-roller process. The apparatus comprises a cooling roller l made of a pure copper and adapted to be rotated in a clockwise direction as viewed in Fig.l, a quartz nozzle 2 fixedly mounted above the cooling roller 1 with its outlet being in proximity to an outer peripheral surface of the cooling roller 1, and a high frequency heating coil 3 disposed to surround a lower end of the nozzle 2. The cooling roller l has a diameter set at 200 mm, and the nozzle 2 has a bore diameter set at 0.3 mm at the outlet. The gap between the outlet and the outer peripheral surface of the cooling roller 1 is set at 0.3 mm.
In producing an amorphous Al alloy as an amorphous alloy, a molten alloy m containing a predominant metal element consisting of Al, a first additive element consisting of a rare earth element(s), and a second additive element consisting of an element(s) other than a rare earth element is ejected from the outlet of the nozzle 2 onto the outer peripheral surface of the cooling roller 1 under a pressure of argon gas (for example, 0.4 kg/cm2), and spread on the outer peripheral surface of the roller l from between the nozzle 2 and the cooling roller 1 as the cooling roller l is rotated.
Thus, it is drawn into a thin ribbon form, while at the same time being quenched, thereby providing an amorphous Al alloy.
In this case, if the rotational speed of the cooling roller l is reduced below a speed that forms an amorphous single-phase Al alloy (i.e., an alloy having a volume fraction of an amorphous phase of 100%), thereby providing a reduced cooling rate for the molten alloy, a crystalline phase is produced in the molten metal.
The use of such a procedure provides a high strength amorphous Al alloy comprising an amorphous phase which forms a matrix, containing a predominant metal element and first and second additive elements, and a fine crystalline phase which is dispersed homogeneously in the amorphous phase, containing the predominant metal element and the first and second additive elements with the first and second additive elements formed into a supersaturated solid solution.
The content of Al as the predominant metal element in the crystalline phase is in the range of from 85 atom % to 99.8 atom %. If the Al content is less than 85 atom %, compounds (such as A13Y, A13Ni, AlNimYn, etc.) are liakle to be produced in the crystalline phase in the production of the amorphous Al alloy, and any such compound is liable to appear alone, resulting in an embrittlement of the entire amorphous Al alloy. On the other hand, if the Al content exceeds 99.8 atom %, it is difficult to provide a mixture Gf an amorphous phase and a crystalline phase at a normal cooling rate. If the cooling rate is significantly increased, the mass productivity is considerably detracted. Moreover, the heat resistance of the resulting amorphous Al alloy itself is degraded.
Examples of the rare earth elements that may be used as the first additive element include Y, La, Ce, Sm, Nd, and mixtures thereof such as Mm (Misch metal which is a mixture of rare earth elements of the cerium group containing 40-50%
Ce and 20-40% La), and the content thereof in the crystalline phase is preferably in the range of from 0.1 atom % to 5 atom %. If the content of the rare earth element is too low, it is impossible to provide a mixture of amorphous and crystalline phases. On the other hand, if the content is too high, the resulting crystalline phase is embrittled and as a result the amorphous Al alloy itself is brittle.
Examples of the second additive elements that may be used include Ni, Fe and Co, and mixtures thereof. The content thereof in the crystalline phase is preferably at most 10 atom %. If the content of the second additive element is too high, compounds are liable to appear in the resulting crystalline phase, and the amorphous phase forming ability for the entire alloy is reduced from its interrelation with the content of the rare earth element. The lower limit of the content of the second additive element is preferably of 5 atom %. Too low a content of the second additive element may result in undesirable conditions during production.
It is preferable that the contents of the predominant metal element and the first and second additive elements in the amorphous matrix phase are greater than those in the crystalline phase. If this relationship of the contents is reversed, compounds are liable to appear in the crystalline phase, causing the embrittlement of the entire alloy. Thus, the crystalline phase preferably forms 5-40%, especially 15-25%, by volume of the amorphous alloy.
:i, ._ Using the above-described procedure with varied rotational speeds of the cooling roller 1, amorphous Al alloy specimens A to D having A189Y5Ni6 (wherein numeral values represent atom % which is true with each of the alloy specimens) were produced, and the relationship between the rotational speed of the cooling roller 1 and the content of the crystalline phase was examined. The results are given in the table below. The crystal structure of the crystalline phase was of a fcc (a face-centered cubic structure) due to Al, and the average diameter of the crystalline phase was in the range of from 300 A to 800 A.
AmorphousRotational speed ofContent of crystalline Al alloycooling roller (rpm) phase (% by volume) A 4,000 0 B 3,000 9 C 2,000 29 D 1,500 37 Figs. 2 to 5 illustrate diagrams of X-ray diffraction patterns of the amorphous Al alloys A to Dl respectively. The anticathode of the X-ray tube used for measurement was made of Cu, and Ka-ray was used.
The amorphous Al alloy A is an amorphous single-phase Al alloy because of a more rapid cooling speed, and a halo-pattern having no steep peak, which is peculiar to the amorphous phase, can be seen in Fig. 2.
The amorphous alloy B was produced at a cooling rate 23378 1 ~
._ 1,000 rpm lower than when the alloy A was produced. As shown in Fig. 3, in the amorphous alloy B, a peak pl was observed as a result of the appearance of a slight crystalline phase. This peak pl corresponds to a (111) plane of the fcc.
The amorphous Al alloy C was produced at a cooling rate half of when the alloy A was produced, and about 30% of the entire amorphous Al alloy was a crystalline phase. Hence, a higher peak pl and lower peaks p2 to p4 have appeared as a result of the appearance of a crystalline phase, as shown in Fig. 4. Among these peaks p2 to p4, the peak p2 corresponds to a (200) plane of the fcc, the peak p3 corresponds to a (220) plane of the fcc, and the peak p4 corresponds to a (311) plane of the fcc.
The amorphous Al alloy D was produced at a cooling rate lower than when the alloy C was produced, and about 40%
of the entire amorphous Al alloy was a crystalline phase.
Therefore, higher peaks pl and p2 and lower peaks p3 and p4 have appeared as a result of the appearance of a crystalline phase, as shown in Fig. 5.
Fig. 6 illustrates a relationship between the content of a crystalline phase in each cf three amorphous Al alloys and the tensile strength. In Fig. 6, a line xl corresponds to the above-described A189Y5Ni6 alloy, a line x2 corresponds to an A188Y2Nilo alloy, and a line x3 corresponds to an AlgoY6Ni4 alloy-As apparent from Fig. 6, in each alloy, the strength is increased as the content of the crystalline phase is increased, as compared with an amorphous single-phase (the content of a crystalline phase = 0). Therefore, the content of the crystalline phase is preferred to be in the range of from 5% by volume to 40% by volume.
In this case, in the A189Y5Ni6 and A188Y2Nilo alloys indicated by the lines xl and x2, an embrittlement begins at a crystalline phase content near 40% by volume. On the other hand, in the AlgoY6Ni4 alloy indicated by the line x3, an embrittlement begins at a crystalline phase content near 20%
by volume, and hence, this alloy is compositionally not included in the present invention.
The average diameter of the crystalline phase is preferably in the range of from 300 A to 800 A. If the average diameter is too low, the meaning of the appearance of the crystalline phase is lost. If the average diameter is too high, the stabilization of the crystalline phase is not provided and a homogeneous dispersion is impossible, resulting in a reduced strength of the entire amorphous Al alloy.
The rare earth element is an element required for achieving a non-crystallization or formation of an amorphous phase, but if a rare earth element in an amount more than a specified amount is incorporated in a crystal lattice (fcc) of Al forming a crystalline phase, the lattice constant (~ =
4.05 A) of the crystal lattice is increased, resulting in a embrittlement of the amorphous alloy, because the rare earth element has a relatively large atomic radius (e.g., Y has a radius of 1.8 A).
~3781 a The ratio CR of the rare earth element component in the crystalline phase is defined by the formula or equation:
CR = a / (a + b) (wherein a and b are as defined above) and is 0.5 or less.
By setting the ratio CR of the rare earth element component in the crystalline phase in the above manner, it is possible to provide a lattice constant of the crystal lattice approximating that of pure Al.
Such a configuration results in a relatively soft crystalline phase dispersed in an amorphous phase having a higher hardness. Therefore, it is believed that the entire amorphous alloy has an improved toughness, because the crystalline phase absorbs the strain in an interface between the crystalline phase and the amorphous phase.
Figs. 7 to 9 illustrate relationships between the ratio CR[a / (a + b), wherein a represents a Y content and b represents a Ni content] of Y in an Al-Y-Ni based amorphous alloy having a crystalline phase content of 20% by volume and the lattice constant of a crystal lattice in a crystalline phase, the tensile strength and the Young's modulus, respectively.
As is apparent from Fig. 7, by setting the ratio CR of Y at no greater than 0.5, it is possible to provide a lattice constant approximating that (4.05 A) of pure Al.
In addition, as apparent from Figs. 8 and 9, both the tensile strength and the Young's modulus can be maintained at high values by setting the ratio CR of Y at no greater than 0.5.
The relation, a _ b, is established from the above-described relation a / (a * b) < 0.5. This means that the content of an expensive rare earth element such as Y, La, Ce, etc., can be reduced, which is effective for reducing the cost of an amorphous A1 alloy.
Fig. 10 illustrates the relationship between the Y
content and the lattice constant of a crystal lattice in a crystalline phase in each of Alloo xYX based amorphous alloy (indicated by line yl) and an A198_xYxNi2 based amorphous alloy (indicated by line y2) when the contents of the crystalline phase are set in the range of 5 to 40% by volume.
It can be seen from the lines yl and y2 in Fig. 10 that the lattice constant is substantially constant if the Y
content is equal to or less than 2% by atom, but the lattice constant is increased if the Y content exceeds 2% by atomic weight.
Therefore, in the A198 XYxNi2 based amorphous alloy, the Y content in the crystalline phase is set in the range of from 0.5 atom % to 2 atom % in order to ensure that the required strength is achieved.
Figs. 11 to 13 illustrate differential thermal analysis thermocurves for three A189Y5Ni6 alloys which are amorphous Al alloys. Fig. 11 corresponds to the alloy having a single amorphous phase, Fig. 12 corresponds to the alloy having a crystalline phase content of 26% by volume, and Fig. 13 corresponds to the alloy having a crystalline phase content of 37% by volume.
The crystallization temperature Tx of the amorphous single-phase Al alloy shown in Fig. 11 is 89~C, but tends to be gradually raised as the crystalline phase content is increased. For this reason, the crystallization temperature Tx of the amorphous Al alloy shown in Fig. 12 is raised to 99~C, and the crystallization temperature Tx of the amorphous Al alloy shown in Fig. 13 is raised to 109~C.
In addition, from a comparison of the calorific values after the heating temperature exceeds the crystallization temperature Tx, i.e., the heights of the peaks, it can be seen that the height of the peak for the amorphous single phase Al alloy of Fig. ll is largest, and the height of the peak is reduced with increasing Gf the crystalline phase content. This means that the amount of the crystalline phase produced by crystallization is smaller.
Thus, when a material is formed from an amorphous Al alloy having a thermal characteristic as shown in Figs. 12 and 13 and such material is subjected to a hot plastic working, e.g., a hot extrusion, the thermal contrcl for the material is relatively easy.
It should be noted that a crystalline phase appears even when an amorphous single-phase Al alloy is subjected to a thermal treatment, but the crystalline phase in this case is coalesced because of an increased rate of growth of crystalline particles. In addition, the strength and tough-ness are reduced as compared with those of the amorphous Al alloy according to the present invention, because the 2~37~3l a dispersion of the crystalline phase is heterogeneous and moreover, a segregation of the crystalline phase is produced.
It wi]l be understood that amorphous Mg alloys containing Mg as a predominant metal element rather than Al are also included in the scope of the present invention.
It will also be appreciated that a further aspect of the present invention provides a process for the prepara-tion of the a~ove-descrlbed alloys. ~ preferred embodiment of this aspect comprises ejecting a molten alloy of the composition defined from a nozzle onto an outer peripheral surface of a cooling roller and spreading the molten alloy on the peripheral surface while rotating the cooling roller, thereby drawing the alloy into a thin ribbon form and quenching it at the same time, wherein the roller is rotated at a speed so controlled that it is ~elow a speed -c~a~
forms an amorphous single-phase alloy.
Claims (13)
1. An amorphous alloy comprising an amorphous matrix-forming phase containing a predominant metal element Al or Mg, at least one first additional element selected from rare earth elements, and at least one second additional element selected from the group consisting of Ni, Fe and Co, and a crystalline phase homogeneously dispersed in the amorphous phase, the crystalline phase comprising the predominant metal element and the first and second additional elements with the first and second additional elements formed into a supersaturated solid solution, wherein the content of the predominant metal element in the crystalline phase is in the range of from 85 atom % to z 99.8 atom %, and wherein the rare earth element ratio CR in the crystalline phase defined by the formula CR = a/ (a + b) (wherein a represents the atom percent content of the first additional element, and b represents the atom percent content of the second additional element) is no greater than 0.5.
2. An alloy according to claim 1, wherein the first additional element in the crystalline phase is selected from the group consisting of Y, La, Ce, Sm, Nd and Misch metal and is present in a content of from 0.1 atom % to 5 atom %.
3. An alloy according to claim 1 or 2, wherein the second additional element in the crystalline phase is present in a content of no greater than 10 atom %.
4. An alloy according to claim 1 or 2, wherein the second additional element in the crystalline phase is present in a content of 5 to 10 atom %.
5. A high strength amorphous alloy according to any one of claims 1 to 4, wherein the content of the crystalline phase is in the range of from 5 to 40% by volume.
6. A high strength amorphous alloy according to any one of claims 1 to 5, wherein the average diameter of the crystalline phase has an average diameter in the range of from 300 .ANG. to 800 .ANG..
7. A high strength amorphous alloy according to any one of claims 1 to 6, wherein the predominant metal element is Al, the first additional element is Y and the second additional element is Ni.
8. An amorphous alloy comprising:
an amorphous phase that forms a matrix and contains a predominant metal element selected from the group consisting of Al and Mg, a first additive element consisting of at least one rare earth element and a second additive element selected from the group consisting of Ni, Fe and Co; and a crystalline phase that contains the predominant element and the first and second additive elements and is dispersed homogeneously in the amorphous phase with the first and second additive elements formed into a super-saturated solid solution, wherein:
the content of the predominant metal element in the crystalline phase is from 85 atom % to 99.8 atom %; and the rare earth element ratio CR in the crystalline phase that is defined by the equation:
CR = a / (a + b) [where: a represents the content of the rare earth in the crystalline phase in atom % and is from 0.1 to 5, and b represents the content of the second additive element in the crystalline phase in atom % and is up to 10]
is no greater than 0.5.
an amorphous phase that forms a matrix and contains a predominant metal element selected from the group consisting of Al and Mg, a first additive element consisting of at least one rare earth element and a second additive element selected from the group consisting of Ni, Fe and Co; and a crystalline phase that contains the predominant element and the first and second additive elements and is dispersed homogeneously in the amorphous phase with the first and second additive elements formed into a super-saturated solid solution, wherein:
the content of the predominant metal element in the crystalline phase is from 85 atom % to 99.8 atom %; and the rare earth element ratio CR in the crystalline phase that is defined by the equation:
CR = a / (a + b) [where: a represents the content of the rare earth in the crystalline phase in atom % and is from 0.1 to 5, and b represents the content of the second additive element in the crystalline phase in atom % and is up to 10]
is no greater than 0.5.
9. An alloy according to claim 8, wherein the predominant metal element is Al, and b is from 2 to 10.
10. An alloy according to claim 9, wherein the content of the crystalline phase is from 5 to 40% by volume.
11. An alloy according to claim 10, wherein the crystalline phase has an average diameter of from 300 to 800 A.
12. An alloy according to claim 11, wherein the second additive element is Ni and is contained in an amount of 2 to 10 atom %.
13. A process for producing the amorphous alloy as defined in any one of claims 1, 2, 3, 4 , 8, 9, 10, 11 and 12, which comprises:
ejecting a molten alloy of the composition defined from a nozzle onto an outer peripheral surface of a cooling roller and spreading the molten alloy on the peripheral surface while rotating the cooling roller, thereby drawing the alloy into a thin ribbon form and quenching it at the same time, wherein the roller is rotated at a speed so controlled that it is below a speed that forms an amorphous single-phase alloy.
ejecting a molten alloy of the composition defined from a nozzle onto an outer peripheral surface of a cooling roller and spreading the molten alloy on the peripheral surface while rotating the cooling roller, thereby drawing the alloy into a thin ribbon form and quenching it at the same time, wherein the roller is rotated at a speed so controlled that it is below a speed that forms an amorphous single-phase alloy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059139A JP2639455B2 (en) | 1990-03-09 | 1990-03-09 | High strength amorphous alloy |
| JP59139/90 | 1990-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2037818A1 CA2037818A1 (en) | 1991-09-10 |
| CA2037818C true CA2037818C (en) | 1998-07-07 |
Family
ID=13104688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037818A Expired - Fee Related CA2037818C (en) | 1990-03-09 | 1991-03-08 | High strength amorphous alloy |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP2639455B2 (en) |
| AU (1) | AU634866B2 (en) |
| CA (1) | CA2037818C (en) |
| DE (1) | DE4107532C2 (en) |
| FR (1) | FR2659355B1 (en) |
| GB (1) | GB2243617B (en) |
| NO (1) | NO180205C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2799642B2 (en) * | 1992-02-07 | 1998-09-21 | トヨタ自動車株式会社 | High strength aluminum alloy |
| JP2945205B2 (en) * | 1992-03-18 | 1999-09-06 | 健 増本 | Amorphous alloy material and manufacturing method thereof |
| DE69321862T2 (en) * | 1992-04-07 | 1999-05-12 | Koji Hashimoto | Temperature resistant amorphous alloys |
| JPH0673479A (en) * | 1992-05-06 | 1994-03-15 | Honda Motor Co Ltd | High strength and high toughness al alloy |
| JPH0617161A (en) * | 1992-06-30 | 1994-01-25 | Honda Motor Co Ltd | Production of metallic material excellent in mechanical characteristic, etc. |
| EP0584596A3 (en) * | 1992-08-05 | 1994-08-10 | Yamaha Corp | High strength and anti-corrosive aluminum-based alloy |
| JP2583718B2 (en) * | 1992-08-05 | 1997-02-19 | 健 増本 | High strength corrosion resistant aluminum base alloy |
| JP3852805B2 (en) * | 1998-07-08 | 2006-12-06 | 独立行政法人科学技術振興機構 | Zr-based amorphous alloy excellent in bending strength and impact strength and its production method |
| EP1111079A1 (en) * | 1999-12-20 | 2001-06-27 | Alcoa Inc. | Supersaturated aluminium alloy |
| WO2005005675A2 (en) * | 2003-02-11 | 2005-01-20 | Liquidmetal Technologies, Inc. | Method of making in-situ composites comprising amorphous alloys |
| US8333924B2 (en) * | 2006-03-20 | 2012-12-18 | National University Corporation Kumamoto University | High-strength and high-toughness magnesium alloy and method for manufacturing same |
| CN103290340B (en) * | 2013-05-30 | 2016-06-22 | 济南大学 | A kind of adjustable rare earth based block metal glass of rare earth composition content |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4743317A (en) * | 1983-10-03 | 1988-05-10 | Allied Corporation | Aluminum-transition metal alloys having high strength at elevated temperatures |
| US4675157A (en) * | 1984-06-07 | 1987-06-23 | Allied Corporation | High strength rapidly solidified magnesium base metal alloys |
| DE3524276A1 (en) * | 1984-07-27 | 1986-01-30 | BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau | Aluminium alloy for producing ultrafine-grained powder having improved mechanical and microstructural properties |
| JPH01127641A (en) * | 1987-11-10 | 1989-05-19 | Takeshi Masumoto | High tensile and heat-resistant aluminum-based alloy |
| JPH01240631A (en) * | 1988-03-17 | 1989-09-26 | Takeshi Masumoto | High tensile and heat-resistant aluminum-based alloy |
| JPH0637695B2 (en) * | 1988-03-17 | 1994-05-18 | 健 増本 | Corrosion resistant aluminum base alloy |
| JPH0621326B2 (en) * | 1988-04-28 | 1994-03-23 | 健 増本 | High strength, heat resistant aluminum base alloy |
| JPH07116482B2 (en) * | 1988-06-17 | 1995-12-13 | 健 増本 | Aluminum alloy powder and paint for paint |
| JP2777416B2 (en) * | 1989-08-15 | 1998-07-16 | 本田技研工業株式会社 | Connecting member |
| JP2762127B2 (en) * | 1989-09-13 | 1998-06-04 | 本田技研工業株式会社 | Method for producing structural member made of amorphous Al alloy and amorphous Al alloy powder |
-
1990
- 1990-03-09 JP JP2059139A patent/JP2639455B2/en not_active Expired - Lifetime
-
1991
- 1991-03-07 NO NO910906A patent/NO180205C/en unknown
- 1991-03-08 DE DE4107532A patent/DE4107532C2/en not_active Expired - Fee Related
- 1991-03-08 AU AU72751/91A patent/AU634866B2/en not_active Ceased
- 1991-03-08 FR FR9102831A patent/FR2659355B1/en not_active Expired - Fee Related
- 1991-03-08 CA CA002037818A patent/CA2037818C/en not_active Expired - Fee Related
- 1991-03-08 GB GB9104956A patent/GB2243617B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU7275191A (en) | 1991-09-12 |
| JPH03260037A (en) | 1991-11-20 |
| FR2659355B1 (en) | 1993-11-26 |
| GB2243617B (en) | 1994-02-09 |
| NO910906D0 (en) | 1991-03-07 |
| AU634866B2 (en) | 1993-03-04 |
| NO910906L (en) | 1991-09-10 |
| CA2037818A1 (en) | 1991-09-10 |
| NO180205C (en) | 1997-03-05 |
| NO180205B (en) | 1996-11-25 |
| GB9104956D0 (en) | 1991-04-24 |
| GB2243617A (en) | 1991-11-06 |
| JP2639455B2 (en) | 1997-08-13 |
| DE4107532A1 (en) | 1991-09-12 |
| FR2659355A1 (en) | 1991-09-13 |
| DE4107532C2 (en) | 1996-08-29 |
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