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(11) | EP 0 688 880 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | High-strength aluminum alloy and method of manufacturing same |
| (57) A high-strength aluminum alloy has an aluminum-base matrix, ultra-fine TiB-base particles
dispersed in the aluminum-base matrix and having a maximum particle diameter of 50nm,
and fine TiB-base particles dispersed in the aluminum-base matrix and having a maximum
particle diameter of 1.2 µm. The aluminum-base matrix is composed of Al and Ti, the
fine TiB-base particles are composed of Ti and B and free of Fe or Fe and Si, and
the ultra-fine TiB-base particles are composed of Ti and B and contain Fe or Fe and
Si. |
FIG. 1 is a schematic diagram showing a metallic structure of a high-strength aluminum alloy according to the present invention;
FIG. 2 is a microscopic representation of the metallic structure of the high-strength aluminum alloy;
FIG. 3 is a schematic diagram of the metallic structure shown in FIG. 2;
FIG. 4 is a graph showing the result of an elemental analysis conducted on an aluminum-base matrix by energy dispersive X-ray spectroscopy (EDX);
FIG. 5 is a graph showing the result of an elemental analysis conducted on an ultra-fine TiB-base particle by EDX;
FIG. 6 is a graph showing the result of an elemental analysis conducted on another ultra-fine TiB-base particle by EDX;
FIG. 7 is a graph showing the result of an elemental analysis conducted on a fine TiB-base particle by EDX;
FIG. 8 is a graph showing the 0.2 %-offset yield strengths of an aluminum alloy I according to Inventive Example 1 and an aluminum alloy I according to Comparative Example 1;
FIG. 9 is a graph showing the 0.2 %-offset yield strengths of an aluminum alloy II according to Inventive Example 2 and an aluminum alloy II according to Comparative Example 2; and
FIG. 10 is a graph showing the 0.2 %-offset yield strengths of an aluminum alloy III according to Inventive Example 3 and an aluminum alloy III according to Comparative Example 3.
[Inventive Example 1]
(a) Using a crucible, a molten aluminum alloy composed of 0.17 g of Fe, 0.17 g of Si, and 380 g of Al was prepared at 700°C in an argon (Ar) gas atmosphere.
(b) To the molten aluminum alloy, there were simultaneously added 480 g of K₂TiF₆
powder having a particle diameter of 500 µm or less and 504 g of KBF₄ powder having
a particle diameter of 500 µm or less. Then, the molten aluminum alloy was stirred
using a stirring rod. The ratio
was 0.004. After confirming the end of a temperature rise of the molten aluminum
alloy due to a chemical reaction, the molten aluminum alloy was left so as to be solidified
in the crucible, and cooled into an ingot made of an aluminum alloy I.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using a transmission electron microscope (TEM). As a result, it was confirmed,
as shown in FIGS. 2 and 3, that countless ultra-fine TiB-base particles 2 (2₁, 2₂)
and countless fine TiB-base particles 3 (3₁) were dispersed in an aluminum-base matrix
1. The ultra-fine TiB-base particles 2 had a maximum particle diameter of 50 nm and
an average particle diameter of 20 nm, and the fine TiB-base particles 3 had a maximum
particle diameter of 1.2 µm and an average-particle diameter of 0.4 µm.
The specimen was subjected to elemental analyses by energy dispersive X-ray spectroscopy
(EDX). The results of the elemental analyses are shown in FIGS. 4 through 7.
FIG. 4 shows the results of the elemental analysis of the aluminum-base matrix 1,
and indicates that the aluminum-base matrix 1 is composed of Al and Ti.
FIG. 5 shows the results of the elemental analysis of one 2₁ of the ultra-fine TiB-base
particles 2 shown in FIGS. 2 and 3. It can seen from FIG. 5 that the ultra-fine TiB-base
particle 2₁ is composed of Ti and B and contains Fe and Si. The peak indicated by
Al in FIG. 5 represents a measurement error.
FIG. 6 shows the results of the elemental analysis of another one 2₂ of the ultra-fine
TiB-base particles 2 shown in FIGS. 2 and 3. It can seen from FIG. 6 that the ultra-fine
TiB-base particle 2₂ is composed of Ti and B and contains Fe and Si. The peak indicated
by Al in FIG. 6 represents a measurement error.
FIG. 7 shows the results of the elemental analysis of one 3₁ of the fine TiB-base
particles 3 shown in FIGS. 2 and 3. It can seen from FIG. 7 that the fine TiB-base
particle 3₁ is composed of Ti and B and does not contain Fe and Si. The peak indicated
by Al in FIG. 5 represents a measurement error.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS (Japanese Industrial Standards) 14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength σ0.2 of 644 MPa.
[Comparative Example 1]
(a) Using a crucible, 380 g of molten aluminum composed of pure aluminum having a purity of 99.99 % was prepared at 700°C in an Ar gas atmosphere.
(b) To the molten aluminum, there were simultaneously added 480 g of K₂TiF₆ powder
having a particle diameter of 500 µm or less and 504 g of KBF₄ powder having a particle
diameter of 500 µm or less. Then, the molten aluminum was stirred using a stirring
rod. The ratio
was 0. After confirming the end of a temperature rise of the molten aluminum due
to a chemical reaction, the molten aluminum was left so as to be solidified in the
crucible, and cooled into an ingot made of an aluminum alloy I.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using a TEM. As a result, it was confirmed that no ultra-fine TiB-base
particles 2 were present, but only countless fine TiB-base particles 3 were scattered,
in an aluminum-base matrix 1. The fine TiB-base particles 3 had a maximum particle
diameter of 1.2 µm and an average particle diameter of 0.4 µm.
The specimen was subjected to elemental analyses by EDX. The results of the elemental
analyses indicate that the aluminum-base matrix 1 is composed of Al and Ti, and the
fine TiB-base particles 3 are composed of Ti and B and do not contain Fe and Si.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS
14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile
test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength
σ0.2 of 307 MPa.
FIG. 8 shows a comparison between the 0.2 %-offset yield strengths σ0.2 of the aluminum alloy I according to Inventive Example 1 and the aluminum alloy I
according to Comparative Example 1. It can be understood from FIG. 8 that the 0.2
%-offset yield strength σ0.2 of the aluminum alloy I according to Inventive Example 1 is about 2.1 times that
of the aluminum alloy I according to Comparative Example 1.
[Inventive Example 2]
(a) Using a crucible, a molten aluminum alloy composed of 0.1 g of Fe, 0.05 g of Si, and 200 g of Al was prepared at 900°C in an Ar gas atmosphere.
(b) To the molten aluminum alloy, there were simultaneously added 96 g of Ti powder
having a particle diameter of 100 µm or less and 43 g of B powder having a particle
diameter of 44 µm or less. Then, the molten aluminum alloy was stirred using a stirring
rod. The ratio
was 0.001. After confirming the end of a temperature rise of the molten aluminum
alloy due to a chemical reaction, the molten aluminum alloy was left so as to be solidified
in the crucible, and cooled into an ingot made of an aluminum alloy II.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using TEM. As a result, it was confirmed, as is the case with the specimen
as shown in FIGS. 2 and 3, that countless ultra-fine TiB-base particles 2 and countless
fine TiB-base particles 3 were dispersed in an aluminum-base matrix 1. The ultra-fine
TiB-base particles 2 had a maximum particle diameter of 50 nm and an average particle
diameter of 20 nm, and the fine TiB-base particles 3 had a maximum particle diameter
of 1.2 µm and an average particle diameter of 0.8 µm.
The specimen was subjected to elemental analyses by EDX. The results of the elemental
analyses indicate that the aluminum-base matrix 1 is composed of Al and Ti, the ultra-fine
TiB-base particles 2 are composed of Ti and B and contains Fe and Si, and the fine
TiB-base particles 3 are composed of Ti and B and do not contain Fe and Si.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS 14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength σ0.2 of 453 MPa.
[Comparative Example 2]
(a) Using a crucible, 200 g of molten aluminum composed of pure aluminum having a purity of 99.99 % was prepared at 900°C in an Ar gas atmosphere.
(b) To the molten aluminum, there were simultaneously added 96 g of Ti powder having
a particle diameter of 100 µm or less and 43 g of B powder having a particle diameter
of 44 µm or less. Then, the molten aluminum was stirred using a stirring rod. The
ratio
was 0. After confirming the end of a temperature rise of the molten aluminum due
to a chemical reaction, the molten aluminum was left so as to be solidified in the
crucible, and cooled into an ingot made of an aluminum alloy II.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using a TEM. As a result, it was confirmed that no ultra-fine TiB-base
particles 2 were present, but only countless fine TiB-base particles 3 were dispersed,
in an aluminum-base matrix 1. The fine TiB-base particles 3 had a maximum particle
diameter of 1.2 µm and an average particle diameter of 0.8 µm.
The specimen was subjected to elemental analyses by EDX. The results of the elemental
analyses indicate that the aluminum-base matrix 1 is composed of Al and Ti, and the
fine TiB-base particles 3 are composed of Ti and B and do not contain Fe and Si.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS
14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile
test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength
σ0.2 of 180 MPa.
FIG. 9 shows a comparison between the 0.2 %-offset yield strengths σ0.2 of the aluminum alloy II according to Inventive Example 2 and the aluminum alloy
II according to Comparative Example 2. A study of FIG. 9 indicates that the 0.2 %-offset
yield strength σ0.2 of the aluminum alloy II according to Inventive Example 2 is about 2.5 times that
of the aluminum alloy II according to Comparative Example 2. Based on this finding,
the lower limit of the range of ratios
is set to 0.001.
[Inventive Example 3]
(a) Using a crucible, a molten aluminum alloy composed of 28 g of Fe, 2.8 g of Si, and 200 g of Al was prepared at 900°C in an Ar gas atmosphere.
(b) To the molten aluminum alloy, there were simultaneously added 96 g of Ti powder
having a particle diameter of 100 µm or less and 43 g of B powder having a particle
diameter of 44 µm or less. Then, the molten aluminum alloy was stirred using a stirring
rod. The ratio
was 0.3. After confirming the end of a temperature rise of the molten aluminum alloy
due to a chemical reaction, the molten aluminum alloy was left so as to be solidified
in the crucible, and cooled into an ingot made of an aluminum alloy III.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using TEM. As a result, it was confirmed, as is the case with the specimen
as shown in FIGS. 2 and 3, that countless ultra-fine TiB-base particles 2 and countless
fine TiB-base particles 3 were dispersed in an aluminum-base matrix 1. The ultra-fine
TiB-base particles 2 had a maximum particle diameter of 50 nm and an average particle
diameter of 20 nm, and the fine TiB-base particles 3 had a maximum particle diameter
of 1.2 µm and an average particle diameter of 0.8 µm.
The specimen was subjected to elemental analyses by EDX. The results of the elemental
analyses indicate that the aluminum-base matrix 1 is composed of Al and Ti, the ultra-fine
TiB-base particles 2 are composed of Ti and B and contain Fe and Si, and the fine
TiB-base particles 3 are composed of Ti and B and do not contain Fe and Si.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS 14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength σ0.2 of 500 MPa.
[Comparative Example 3]
(a) Using a crucible, a molten aluminum alloy composed of 44.7 g of Fe, 5.6 g of Si, and 200 g of Al was prepared at 900°C in an Ar gas atmosphere.
(b) To the molten aluminum, there were simultaneously added 96 g of Ti powder having
a particle diameter of 100 µm or less and 43 g of B powder having a particle diameter
of 44 µm or less. Then, the molten aluminum was stirred using a stirring rod. The
ratio
was 0.5. After confirming the end of a temperature rise of the molten aluminum due
to a chemical reaction, the molten aluminum was left so as to be solidified in the
crucible, and cooled into an ingot made of an aluminum alloy III.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using a TEM. As a result, it was confirmed that countless ultra-fine
TiB-base particles 2, countless fine TiB-base particles 3, and countless coarse intermetallic
compound bodies were dispersed in an aluminum-base matrix 1. The ultra-fine TiB-base
particles 2 had a maximum particle diameter of 50 nm and an average particle diameter
of 20 nm. The fine TiB-base particles 3 had a maximum particle diameter of 1.2 µm
and an average particle diameter of 0.8 µm. The coarse intermetallic compound bodies
had longest portions whose length was 500 µm.
The specimen was subjected to elemental analyses by EDX. The results of the elemental
analyses indicate that the aluminum-base matrix 1 is composed of Al and Ti, the ultrafine
TiB-base particles 2 are composed of Ti and B and contain Fe and Si, the fine TiB-base
particles 3 are composed of Ti and B and do not contain Fe and Si, and the coarse
intermetallic compound bodies are composed of Al and Fe.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS
14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile
test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength
σ0.2 of 318 MPa.
FIG. 10 shows a comparison between the 0.2 %-offset yield strengths σ0.2 of the aluminum alloy III according to Inventive Example 3 and the aluminum alloy
III according to Comparative Example 3. A study of FIG. 10 indicates that the 0.2
%-offset yield strength σ0.2 of the aluminum alloy III according to Inventive Example 3 is about 1.5 times that
of the aluminum alloy III according to Comparative Example 3. Based on this finding,
the upper limit of the range of ratios
is set to 0.3.
[Inventive Example 4]
(a) Using a crucible, a molten aluminum alloy composed of 0.15 g of Fe and 380 g of Al was prepared at 700°C in an Ar gas atmosphere.
(b) To the molten aluminum alloy, there were simultaneously added 480 g of K₂TiF₆
powder having a particle diameter of 500 µm or less and 504 g of KBF₄ powder having
a particle diameter of 500 µm or less. Then, the molten aluminum alloy was stirred
using a stirring rod. The ratio
was 0.001. After confirming the end of a temperature rise of the molten aluminum
alloy due to a chemical reaction, the molten aluminum alloy was left so as to be solidified
in the crucible, and cooled into an ingot made of an aluminum alloy IV.
(c) The ingot was taken out of the crucible, and extruded in a hot extrusion process at a temperature of 500°C with an extrusion ratio of 11, thereby producing an extruded round rod having a diameter of 9 mm.
(d) A specimen was produced from the extruded round rod, and its metallic structure
was observed using a TEM. As a result, it was confirmed, as is the case with the specimen
as shown in FIGS. 2 and 3, that countless ultra-fine TiB-base particles 2 and countless
fine TiB-base particles 3 were dispersed in an aluminum-base matrix 1. The ultra-fine
TiB-base particles 2 had a maximum particle diameter of 50 nm and an average particle
diameter of 20 nm, and the fine TiB-base particles 3 had a maximum particle diameter
of 1.2 µm and an average particle diameter of 0.4 µm.
The specimen was subjected to elemental analyses by EDX. The results of the elemental
analyses indicate that the aluminum-base matrix 1 is composed of Al and Ti, the ultra-fine
TiB-base particles 2 are composed of Ti and B and contain Fe, and the fine TiB-base
particles 3 are composed of Ti and B and do not contain Fe.
(e) The extruded round rod was machined into a sample for use in a tensile test JIS 14A. The sample had a gage length L of 22 mm and a diameter D of 4.0 mm. The tensile test conducted on the sample indicated that the sample had a 0.2 %-offset yield strength σ0.2 of 638 MPa.