JP2965774B2 - High-strength wear-resistant aluminum alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Al--Si alloy which is produced by a rapid solidification method, has high strength, is excellent in toughness, and has high wear resistance.

[0002]

2. Description of the Related Art Conventionally, an aluminum-based alloy having high strength and high heat resistance has been manufactured by a liquid quenching method or the like.
In particular, it is disclosed in Japanese Patent Application Laid-Open No. 1-275732. The aluminum-based alloy obtained by the liquid quenching method is amorphous or microcrystalline, and has high strength, high heat resistance,
It is an excellent alloy with high corrosion resistance.

However, the above-mentioned aluminum-based alloy is an excellent alloy exhibiting high strength, high heat resistance and high corrosion resistance. Although it is excellent in workability as a high-strength material, materials requiring high toughness include: There is room for improvement in toughness. Further, generally, an alloy produced by the rapid solidification method is susceptible to thermal effects during processing, and has a problem that when subjected to such thermal effects, excellent properties such as strength are rapidly lost. The above alloys are no exception, and there is still room for improvement in this respect. Also, regarding the wear resistance,
There is still room for improvement.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, the present invention has been made in consideration of the volume ratios of a main metal element and an additive element and / or various intermetallic compounds formed by an additive element mixed in an Al matrix. Focusing on the volume fraction of Si particles and Si particles, it has improved strength and high toughness at room temperature, and can maintain the characteristics produced by the rapid solidification method even if it is affected by the heat during processing. An object of the present invention is to provide a high-strength wear-resistant aluminum alloy having excellent properties.

[0005]

Means for Solving the Problems The constitution of the present invention for solving the above-mentioned problems is as follows: (1) Al-Si composed of Al which is a main metal element, an additional element added to this, and a Si element In the base alloy, the average crystal grain size of the Al matrix is 40 to 100.
0 nm, the average particle size of the stable phase or the metastable phase of Al and the additional element containing Si is various intermetallic compounds generated and / or the intermetallic compound generated by the additional elements is 10 to 800 nm, The size of a single Si particle is 10 μm or less, and the particles of the intermetallic compound are 18 to 35% by volume in the matrix made of Al.
The high-strength wear-resistant aluminum alloy, in which a single Si particle is distributed in a volume ratio of 15 to 40% in the matrix composed of Al and has the following structure, and the high-strength wear-resistant aluminum alloy, _{formula; Al 100-abc X a M} b Si c , however, X; La, Ce, Mm , Zr, Ti, at least one element selected from Y, M; Ni, 1 kind or 2 kinds selected from Co A, b, and c are atomic percentages of 0.3 ≦ a ≦ 4, 3 ≦ b ≦ 8, and 15 ≦
c ≦ 40, where the volume ratio of AlX-based intermetallic compound is 1 to 18% and the volume ratio of AlM-based intermetallic compound is 17 to 29%, (2) AlX-based intermetallic compound Are Ce ₃ Al ₁₁ , Al ₄ C
e, Mm ₃ Al ₁₁ , Al ₃ Ti, and Al ₃ Zr;
The high-strength, wear-resistant aluminum alloy according to (1), wherein the M-based intermetallic compound is Al ₃ Ni, Al ₉ Co ₂ , (3) Al as a main metal element, and an additive added thereto. In an Al-Si alloy composed of an additive element and an Si element, the average crystal grain size of the Al matrix is 40 to 100.
0 nm, the average particle size of the stable phase or the metastable phase of Al and the additional element containing Si is various intermetallic compounds generated and / or the intermetallic compound generated by the additional elements is 10 to 800 nm, The size of a single Si particle is 10 μm or less, and the particles of the intermetallic compound are 18 to 35% by volume in the matrix made of Al.
A high-strength abrasion-resistant aluminum alloy, characterized in that single Si particles are distributed in a volume ratio of 15 to 40% in the matrix composed of Al, and have the following structure. The high strength wear-resistant aluminum alloy represented by the general _{formula; Al 100-abcd X a M} b Q d Si c However, X; La, Ce, Mm, at least one or more elements selected Zr, Ti, from Y, M: one or two elements selected from Ni and Co; Q; at least one element selected from Mg, Cu, Zn, and a, b, c, and d are 0.3 atomic percent. ≦ a ≦ 4, 3 ≦ b ≦ 8, 15 ≦ c ≦ 40, 0.1
≦ d ≦ 1.5, mainly comprising: AlX-based intermetallic compound having a volume ratio of 1 to 18%, and AlM-based intermetallic compound having a volume ratio of 17 to 29%. Wear-resistant aluminum alloy; (4) AlX-based intermetallic compound is Ce ₃ Al ₁₁ , Al ₄ C
e, Mm ₃ Al ₁₁ , Al ₃ Ti, and Al ₃ Zr;
The high-strength wear-resistant aluminum alloy according to (3), wherein the M-based intermetallic compound is Al ₃ Ni, Al ₉ Co ₂ .

In the above alloy, the average crystal grain size of the Al matrix is the average crystal grain size of the matrix of the Al element or a supersaturated solid solution of the Al element.
The reason why the thickness is limited to the range of ~ 1000 nm is that when the thickness is less than 40 nm, the strength is strong but the ductility is insufficient.
If it exceeds nm, the strength is sharply reduced, and a high-strength alloy cannot be obtained.

The average particle size of the intermetallic compound is determined by the size of various intermetallic compounds generated by the matrix element and other alloy elements and / or various intermetallic compounds generated by other alloy elements. It is the average particle size of particles composed of a stable phase or a metastable phase,
The reason for limiting to the range of 800 nm is that outside this range, it does not work as a reinforcing element of the main metal element matrix. That is, if it is less than 10 nm, it does not contribute to strengthening the matrix, and if it is dissolved more than necessary in the matrix, there is a danger of embrittlement. Also, when it exceeds 800 nm,
The particles become too large to maintain strength and not work as reinforcing elements.

Therefore, the Young's modulus, high-temperature strength and fatigue strength can be improved by setting the average crystal grain size of the Al element and the average particle size of the intermetallic compound within the above ranges. In order to achieve the above object, it is necessary to disperse and mix various intermetallic compound particles in a matrix made of an Al element.

The reason why the volume ratio of the intermetallic compound particles to be mixed in the matrix of Al is limited to 18 to 35% is that, when the Al-Si alloy content is less than 18%, the strength at room temperature and the rigidity are reduced. If the reinforcement is not sufficient and the wear resistance is not sufficient, and if it exceeds 35%, the ductility at room temperature is inferior, so that the obtained material cannot be processed sufficiently and the object of the present invention is achieved. Because you can't.

Further, a single Si particle is added in a volume ratio of 15 to 4
The reason why the content is limited to 0% is that if it is less than 15%, the abrasion resistance is not sufficiently improved, and if it exceeds 40%, the material becomes brittle. By controlling the amount of Si within this range, the coefficient of thermal expansion can be adjusted, which is advantageous in terms of design when replacing the steel material with a lightweight material and a sliding member.

The above-mentioned additional elements include a first additional element made of at least one element selected from rare earth elements (including Y), Zr and Ti, and a transition element excluding the elements contained in the first additional element and iron. It is preferable that the second additive element is at least one element selected from a transfer element, Li, and Mg. Among the rare earth elements of the first additive element, the main elements are La and Ce, and in addition, rare earth elements (lanthanoid series) other than the above La and Ce and unavoidable impurities (Si, Fe, Mg, Al, etc.) ), Which is a complex containing Mm (mish metal). The first additive element contributes to stabilization of the fine crystal structure, and the second additional element contributes to improvement of mechanical properties (hardness, strength, rigidity, heat resistance, etc.) and stabilization of the fine crystal structure.

Furthermore, if specific examples for the above, (I) the general _{formula; Al 100-abc X a M} b Si c ( however, X; La least, Ce, Mm, Zr, Ti, selected from Y One or more elements, M; one or two elements selected from Ni and Co, and a, b, and c are represented by atomic percentages of 0.3 ≦ a ≦ 4, 3 ≦ b ≦ 8, and 15 ≦ c. ≤
40), (II) General formula: Al _100-abcd X _a M _b Q _d Si
_c (however, X: at least one or more elements selected from La, Ce, Mm, Zr, Ti, and Y; M; one or two elements selected from Ni and Co; Q; Mg, Cu,
At least one element selected from Zn,
a, b, c, and d are atomic percentages of 0.3 ≦ a ≦ 4, 3
≦ b ≦ 8, 15 ≦ c ≦ 40, 0.1 ≦ d ≦ 1.5) are more preferable.

In the above general formula, a
0.3-4%, b 3-8%, c 15-40%, d
Is limited to the range of 0.1% to 1.5%, respectively. If it is within the range, the strength from room temperature to 300 ° C. is higher than that of a conventional (commercially available) high-strength aluminum alloy and can withstand practical processing. This is because it has only ductility.
Further, the wear resistance is enhanced mainly by the fine Si and intermetallic compounds precipitated.

Further, since the workability is not affected even if the amount of Si is increased, warm working becomes possible, and the structure is not coarsened even during warm working. Further, since the coefficient of thermal expansion can be controlled by the amount of Si, it is easy to match the coefficient of thermal expansion of the mating material when used for a sliding member, for example.

The X element is La, Ce, Mm, Ti,
One or two elements selected from Zr, the X element is an element having a small diffusivity in an Al matrix,
It forms various metastable or stable intermetallic compounds and contributes to stabilization of the microcrystalline structure.

In the above description, the M element is one or two elements selected from Ni and Co, and the X element is A
l is an element with relatively low diffusivity in the matrix,
Dispersing finely as an intermetallic compound in an Al matrix has the effect of strengthening the matrix and controlling the growth of crystal grains. That is, the hardness, strength and rigidity of the alloy are remarkably improved, the fine crystalline phase is stabilized at normal temperature as well as at high temperature, and heat resistance is imparted.

Further, the combination of the above-mentioned elements can impart the required ductility in existing processing.

The Q element is at least one element selected from the group consisting of Mg, Si, Cu, and Zn. The Q element forms a compound of Al and a compound or a combination of the Q elements to strengthen the matrix and improve heat resistance. Let it. In addition, specific strength and specific elasticity are improved.

The Si element is dispersed in a fine single particle of 10 μm or less, and has an effect of increasing the wear resistance and hardness of the alloy. Further, by adjusting the amount of dispersion (content) of the Si particles, the coefficient of thermal expansion of the alloy can be adjusted.

In the above-mentioned general formula,
As described above, the average crystal grain size of the matrix of Al or a supersaturated solid solution of Al is 40 to 1000 nm, and various intermetallic compounds and / or other alloy elements formed by the matrix element and other alloy elements are formed. The average particle size of the particles composed of the stable phase or metastable phase of the various intermetallic compounds is 10 to 800 nm, and the particles of the intermetallic compound mixed in the Al matrix have a volume fraction of 18 to 35%. It is necessary that the volume of a single Si particle of 10 μm or less be 15 to 40 in volume ratio.

In the general formulas further exemplified, the volume ratio of the AlX-based compound is preferably 1 to 18%, and if it is less than 1%, the matrix becomes coarse,
This is because the strength is reduced, and if it exceeds 18%, the ductility is extremely reduced. The AlM-based compound has a volume ratio of 1%.
This is because 7 to 29% is preferable, and if it is less than 17%, the strength at room temperature decreases, and if it exceeds 29%, ductility decreases.

In particular, in the compounds represented by the above general formula, the preferred M-type compound dispersed is A
l ₃ Ni, Al ₉ Co ₂ , and as an X-based compound,
Ce ₃ Al ₁₁ , Al ₄ Ce, La ₃ Al ₁₁ , Mm ₃ Al ₁₁ ,
Al ₃ Ti, Al ₃ Zr, etc. are desirable, and Al ₃ Ti, Al ₃
As for Zr, a metastable phase compound has a higher effect of contributing to fine dispersion.

The alloy of the present invention may be subjected to a liquid quenching method such as a single roll method, a gas or water atomizing method, or a submerged spinning method, and the cooling rate of an ordinary solidification process may be appropriately adjusted within a range of 10 ⁷ to 10 ² K / sec. Thin ribbon directly by controlling,
It can be manufactured as a material such as powder and fine wire. Alternatively, it can be directly produced as a foil-like material by using a vapor phase vapor deposition means such as a sputtering method, an ion beam sputtering method, and a vapor deposition method. Similarly, a powder can be produced by a mechanical alloying method (mechanical alloying; MA method).

Further, even if a two-stage solidifying means as disclosed in JP-A-3-253525 is used, the alloy solidified material of the present invention can be directly produced by appropriately controlling the cooling rate. Can be. In the case of manufacturing as a solidified material, materials obtained as described above, such as a ribbon, a powder, a fine wire, and a foil, can be assembled and processed by ordinary plastic deformation means.

At this time, it is desirable that the powder, flake, etc. having a fine structure produced by rapid solidification or the like undergo plastic deformation at a warm temperature of 50 to 500 ° C., more preferably 320 to 440 ° C. Depending on the history, a more suitable crystal structure can be obtained.

When a mechanical alloying method is used in the above, oxides, nitrides, and the like are formed, and a solidified material produced by assembling the oxides and nitrides can be more excellent in high-temperature strength.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.

Example 1 An aluminum-based alloy powder (Al _bal Ni _4-5 Ce _1-3 Si) having a predetermined component composition by a gas _{atomizer
20-37} ). After filling the produced aluminum-based alloy powder into a metal capsule, a billet for extrusion is produced while degassing. This billet is extruded with an extruder
Each sample was produced by extruding at a temperature of 0 to 440 ° C.

The relationship between the mechanical properties (tensile strength) at room temperature and 200 ° C. of each sample (extruded material; solidified material) obtained under the above manufacturing conditions and the volume fraction of the precipitated intermetallic compound were examined. Here, the volume ratio of the single fine Si particles was fixed at 20%.

FIG. 1 shows the results.

The volume ratio of the above-mentioned intermetallic compound and Si
The volume ratio of the particles was measured using an image analysis technique by TEM of the obtained solidified material. The intermetallic compounds precipitated from the above sample were mainly Al ₃ Ni, Ce ₃ Al _{11 and the} like. Further, as a result of TEM observation, the sample is a matrix of aluminum or a supersaturated solid solution of aluminum having an average crystal grain size of 40 to 1000 nm, and various intermetallic compounds and / or other alloys generated from the matrix element and other alloy elements. Particles consisting of a stable phase or a metastable phase of various intermetallic compounds generated from alloy elements are uniformly distributed in the matrix, the average particle size of the intermetallic compound is 10 to 800 nm, and the matrix The size of the single fine Si particles uniformly distributed therein was 10 μm or less.

According to FIG. 1, the high-temperature strength at room temperature and 200 ° C. indicates that the intermetallic compound particles rapidly increase in volume ratio from 18%, and rapidly decrease in excess of 35%.

The ductility of the sample at room temperature decreases as the volume of the intermetallic compound particles increases with the volume ratio, and the ductility at room temperature becomes 3%.
Over 5%, lower than the minimum required for general processing (2%).

The relationship between the mechanical properties (tensile strength) at room temperature and 200 ° C. and the volume fraction of the precipitated single Si particles was examined for each sample obtained under the above manufacturing conditions. The volume ratio of the intermetallic compound deposited here was fixed at 25% for Al ₃ Ni and 7% for Ce ₃ Al ₁₁ .

FIG. 2 shows the result.

FIG. 2 shows that the high-temperature strength at room temperature and 200 ° C. decreases with the increase in the fine Si particles alone. Further, when examining ductility at room temperature, when the volume ratio exceeded 40%, it was lower than the minimum required for general processing (2%). Further, the effect of wear resistance was remarkably exhibited at a volume ratio of 15% or more.

Further, for each of the samples obtained under the above manufacturing conditions, the main intermetallic compound, Al ₃ Ni, C
With respect to e ₃ Al ₁₁ , changes in the high-temperature strength at room temperature and 200 ° C. due to the change in the particles of each intermetallic compound were examined. Here, the volume ratio of the single fine Si particles is 20%.
And fixed.

The results are shown in FIG. 3 and FIG.

In FIG. 3, the composition of the sample was Al
_{Using bal} Ni ₅ Ce _1.2 Si ₂₀ and fixing the volume ratio of the particles of the intermetallic compound of Ce ₃ Al ₁₁ to 5%, the change in strength with the change of the volume ratio of the particles of the intermetallic compound of Al ₃ Ni Was examined. In FIG. 4, the composition of the sample is Al _bal
Using Ni _{4.5 to 5} Ce _{1.5 to 3} Si ₂₀ and fixing the volume ratio of the particles of the intermetallic compound of Al ₃ Ni to 20%, Ce ₃ A
investigating changes in the intensity due to the change in volume of the particles of the intermetallic compound of the l _11.

According to FIG. 3, the high temperature strength at room temperature and 200 ° C. is such that the particles of the intermetallic compound of Al ₃ Ni are 17% by volume.
From the above, it can be seen that the temperature rises sharply and drops sharply exceeding 29%.

According to FIG. 4, the high-temperature strength at room temperature and 200 ° C. rapidly increased from 1% or more by volume of Ce ₃ Al ₁₁ intermetallic compound particles, and suddenly exceeded 18%. Significant decline was observed. For the above sample, the elongation at room temperature is more than 29% in the case of Al ₃ Ni intermetallic compound,
In the case of the intermetallic compound of Ce ₃ Al ₁₁ , if it exceeds 18%, it is lower than the minimum required for general processing (2%).

Example 2 Extruded materials (solidified materials) having the various components shown in Table 1 were prepared in the same manner as in Example 1 above, and the mechanical properties (tensile strength) at room temperature were examined. In the table,
The main precipitated intermetallic compound phase and its volume ratio were specified.

Table 1 shows the results.

[0044]

[Table 1]

Table 1 shows that the extruded material (solidified material) of the present invention has excellent properties in terms of tensile strength at room temperature.

In addition, the extruded materials shown in the table all had the minimum elongation (2%) required for general processing.

It should be noted that the alloy of this embodiment is also a matrix of aluminum or a supersaturated solid solution of aluminum having an average crystal grain size of 40 to 1000 nm, and various intermetallic compounds formed by the matrix element and other alloy elements. And / or particles comprising a stable phase or a metastable phase of various intermetallic compounds generated by other alloying elements are uniformly distributed in the matrix, and the average particle size of the intermetallic compound is 10 to 800 nm. And the size of a single fine Si particle was 10 μm or less.

Example 3 Inventive Examples 1, 2, 3, 4 and Comparative Example 1 (Al
_{bal Si 5 Fe 3 Ce 0.} 2) as well as powder by the alloy high pressure gas atomization having a composition equivalent A390 (average particle size 1
5 μm). This was packed in a copper container and a cap, vacuum degassed (1 × 10 ⁻⁵ Torr), and then pressed by a press to obtain a billet.

The billet was set in a container of an extruder, and was warm-extruded at a temperature of 320 ° C. to 440 ° C. to obtain an extruded round bar. Among the extruded round bars, those of the present invention are:
The structure was the same as that shown in Example 2 above.

The extruded round bar was processed into the shape shown in FIG. 5 and brought into contact with a mating disk (S45C) as shown in FIG. 6 to obtain a pressure of 20 kgf / cm ² and a speed of 0.84 m / cm ² .
The test was performed by the pin-on-disk method under the condition of sec.

FIG. 7 shows the result.

A390 aluminum alloy known as a wear-resistant aluminum alloy and Comparative Example 1 Al _bal
For Si ₅ Fe ₃ Ce _{0. 2} rapidly solidified alloy, the test material and the mating member is worn much less wear of itself and the mating material both in the case of the present invention embodiment, the invention also material It can be seen that is compatible with the partner material.

[0053]

As described above, the high-strength wear-resistant aluminum alloy of the present invention has excellent strength at room temperature and high temperature and also has excellent toughness. Also, even if it is affected by the heat during processing, it is possible to maintain the excellent characteristics produced by the rapid solidification method. Further, the alloy of the present invention has excellent wear resistance and, when used as a sliding member, for example, can reduce the amount of wear of the mating material.

[Brief description of the drawings]

FIG.

FIG. 2

FIG. 3

FIG. 4 is a graph showing the relationship between the volume fraction of fine particles and the tensile strength in the alloys having the compositions shown in Examples of the present invention.

FIG. 5

FIG. 6 is an explanatory diagram showing dimensions of a sample on which a wear test of Example 3 was performed.

FIG. 7 is a graph showing the results of the wear test.

Claims (4)

(57) [Claims] 1. An Al—Si alloy composed of Al as a main metal element, an additive element added thereto, and a Si element, the average crystal grain size of the Al matrix is 40%.
~ 1000 nm, Al and the additional element containing Si
The average particle size of the stable phase or metastable phase of the various intermetallic compounds to be generated and / or the intermetallic compound generated by the additional elements is 10 to 800 nm, and the size of a single Si particle is 10 μm or less, In the matrix composed of Al, particles of the intermetallic compound have a volume fraction of 18 to
35% of the above-mentioned Al
i-particles are distributed in a volume ratio of 15 to 40% , and
A high-strength wear-resistant aluminum alloy having the above structure . The high strength wear-resistant aluminum alloy represented by the general _{formula; Al 100-abc X a M} b Si c , however, X; selection La, Ce, Mm, Zr, Ti, from Y
At least one or more elements, M; one or two elements selected from Ni and Co
A , b, c are in atomic percent 0.3 ≦ a ≦ 4, 3 ≦ b
≦ 8, 15 ≦ c ≦ 40, and the AlX-based intermetallic compound mainly has a volume fraction of 1 to 18
%, AlM-based intermetallic compound is 17-29% by volume.
You. 2. The method according to claim 1, wherein the AlX intermetallic compound is Ce ₃ A.
l ₁₁ , Al ₄ Ce, Mm ₃ Al ₁₁ , Al ₃ Ti, Al ₃ Zr
, And the high strength wear-resistant aluminum alloy according to claim 1, wherein the intermetallic compound of AlM system Al ₃ Ni, an Al ₉ Co _2. 3. The method according to claim 1, wherein the main metal element is Al and
Al-Si compound composed of an additive element and a Si element
In gold, the average crystal grain size of the Al matrix is 40
~ 1000 nm, Al and the additional element containing Si
Various intermetallic compounds and / or additive elements
Of a stable or metastable phase of an intermetallic compound
The average particle size is 10 to 800 nm,
A matrix having a size of 10 μm or less and made of Al
In the box, the particles of the intermetallic compound are 18 to
35% of the above-mentioned Al
i-particles are distributed in a volume ratio of 15 to 40%, and
High-strength abrasion-resistant aluminum characterized by having the above structure
Alloy. The high strength wear-resistant aluminum alloy represented by the general _{formula; Al 100-abcd X a M} b Q d Si c However, X; La, Ce, Mm, at least one or more elements selected Zr, Ti, from Y, M: one or two elements selected from Ni and Co; Q; at least one element selected from Mg, Cu, Zn; a, b, c, and d are 0.3 in atomic percent. ≦ a ≦ 4,3
≤ b ≤ 8, 15 ≤ c ≤ 40, 0.1 ≤ d ≤ 1.5, where the volume ratio of AlX-based intermetallic compound is 1 to 18% and the volume ratio of AlM-based intermetallic compound is mainly High-strength abrasion-resistant aluminum alloy, characterized in that it is 17-29% by weight. 4. The method according to claim 1, wherein the AlX intermetallic compound is Ce ₃ A.
l ₁₁ , Al ₄ Ce, Mm ₃ Al ₁₁ , Al ₃ Ti, Al ₃ Zr
And the AlM-based intermetallic compound is Al ₃ Ni, Al ₉ C
high strength wear-resistant aluminum alloy according to claim 3, characterized in that the o _2.