ALUMINUM-ALLOY INGOT AND MANUFACTURING METHOD THEREOF

Information

  • Patent Application
  • 20230075358
  • Publication Number
    20230075358
  • Date Filed
    February 05, 2021
    3 years ago
  • Date Published
    March 09, 2023
    a year ago
Abstract
An aluminum-alloy ingot contains TiB2 aggregates (2) dispersed in an aluminum matrix (1). The TiB2 aggregates (2) are formed by aggregation of TiB2 particles (3). The average value of the circle-equivalent diameters of the TiB2 aggregates (2) in the state in which the TiB2 aggregates (2) are exposed at a surface of the aluminum matrix (1) is 3.0 μm or less and the average value of the circularities is 0.20 or more.
Description
TECHNICAL FIELD

The present invention relates to an aluminum-alloy ingot and to a manufacturing method thereof.


BACKGROUND ART

When an ingot is to be manufactured by casting an aluminum alloy, a crystal-grain refining agent is sometimes added to the melt of the aluminum alloy for the purpose of refining the crystal particles in the ingot. An Al—Ti—B refining agent, in which a Ti—B (titanium-boron) compound, such as TiB2, has been dispersed in a base composed of aluminum, is used as the crystal-grain refining agent (Patent Document 1).


When a solid solution of the Al—Ti—B refining agent is formed in the melt of an aluminum alloy, a state results in which solid Ti—B compound has been dispersed in the melt. When the melt is caused to solidify in this state, the Ti—B compound functions as heterogenous nuclei, and therefore crystal particles can be caused to grow in the aluminum matrix, with the Ti—B compound serving as the starting points. As a result, the crystal particles in the aluminum matrix can be refined.


PRIOR ART LITERATURE
Patent Document



  • Patent Document 1 Japanese Laid-open Patent Publication 2001-191654



SUMMARY OF THE INVENTION
Problems to be Solved by the Invention

However, with regard to existing aluminum-alloy ingots, in which the crystal particles are refined using an Al—Ti—B refining agent, linear defects sometimes occur when performing flattening work, such as rolling or extruding, and there is a risk that it will lead to degradation in the surface quality of the final product.


The present invention was conceived considering this background, and an object of the present invention is to provide an aluminum-alloy ingot, comprising fine grain sizes and in which the occurrence of linear defects when performing flattening work can be curtailed, and a manufacturing method thereof.


Means for Solving the Problems

One aspect of the present invention is an aluminum-alloy ingot comprising: an aluminum matrix; and


TiB2 aggregates, which are dispersed in the aluminum matrix and in which TiB2 particles are aggregated;


wherein the average value of the circle-equivalent diameters of the TiB2 aggregates in the state in which the TiB2 aggregates are exposed from the aluminum matrix is 3.0 μm or less and the average value of the circularities is 0.20 or more.


Another aspect of the present invention is a method of manufacturing the aluminum-alloy ingot of the above-mentioned aspect, comprising:


a melting step, in which a crystal-grain refining agent, in which a base composed of aluminum contains TiB2 particles and the average value of the center-to-center distances between adjacent TiB2 particles is 0.60 μm or more, is melted in a melt of aluminum alloy; and


a casting step, in which, after the melting step, the melt is cast.


Yet another aspect of the present invention is a method of manufacturing the aluminum-alloy ingot according to the above-mentioned aspect, comprising:


a melting step, in which a crystal-grain refining agent, in which a base composed of aluminum contains TiB2 aggregates in which TiB2 particles are aggregated, is melted in a melt of an aluminum alloy; and


a casting step, in which, after the melting step, the melt is cast;


wherein, in the situation in which projection-surface areas of 2,000 or more TiB2 aggregates have been measured in the state in which TiB2 aggregates were exposed from the base, the TiB2 aggregates in the crystal-grain refining agent have a particle-size distribution in which the average value of the circle-equivalent diameters of TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, is 3.0 μm or less.


Effects of the Invention

The aluminum-alloy ingot has TiB2 aggregates, in which TiB2 particles are the primary particles, in an aluminum matrix. In addition, the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates are within the above-mentioned specific ranges, respectively. This means that the aluminum-alloy ingot will be manufactured by casting a melt that contains the above-mentioned specific TiB2 aggregates.


The performance of the TiB2 aggregates, in which the average value of the circle-equivalent diameters and the average value of the circularities are within the respective specific ranges, in refining the crystal particles in the aluminum matrix is high. Consequently, by forming the TiB2 aggregates in the melt, the crystal particles in the aluminum matrix can be sufficiently refined. In addition, because the particle sizes of the TiB2 aggregates are comparatively small, the occurrence of linear defects when performing flattening work on the aluminum-alloy ingot can be curtailed.


For this reason, according to the above-mentioned aspect, an aluminum-alloy ingot, having a fine grain size and in which the occurrence of linear defects during flattening work can be curtailed, can be provided.


In addition, in a method of manufacturing the aluminum-alloy ingot, after the crystal-grain refining agent has been melted in the melt of the aluminum alloy, the ingot is manufactured by solidifying the melt. In a method of manufacturing the aluminum-alloy ingot, by melting the crystal-grain refining agent, which has the above-mentioned specific composition, into the melt in the melting step, TiB2 aggregates for which the average value of the circle-equivalent diameters and the average value of the circularities are within the respective specific ranges, can be formed in the melt. Furthermore, by solidifying such a melt, the crystal particles of the ultimately obtained aluminum-alloy ingot can be easily refined, and the occurrence of linear defects when performing flattening work on the aluminum-alloy ingot can be curtailed.


In addition, in a method of manufacturing the aluminum alloy, because the quality of the aluminum-alloy ingot can be improved by using methods performed in the past, that is, by melting the crystal-grain refining agent in the melt of the aluminum alloy, there is no need to add special steps or equipment to refine the crystal particles of the aluminum matrix. Therefore, according to a method of manufacturing the aluminum alloy, an aluminum-alloy ingot having excellent quality can be obtained while avoiding an increase in the cost of manufacturing the aluminum-alloy ingot.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is an enlarged photograph of TiB2 particles, which are contained in an aluminum-alloy ingot, of Working Example 1.



FIG. 2 is an enlarged photograph of TiB2 particles, which are contained in an aluminum-alloy ingot, of Comparative Example 1.





MODES FOR CARRYING OUT THE INVENTION

The chemical composition of the above-mentioned aluminum-alloy ingot is not particularly limited and may be any kind of aluminum alloy. It is noted that the “aluminum alloy” described above is a concept that encompasses pure aluminum. For example, the above-mentioned aluminum-alloy ingot may have a chemical composition classified as A1000-series aluminum or may have a chemical composition classified as A2000-series alloys, A3000-series alloys, A4000-series alloys, A5000-series alloys, A6000-series alloys, A7000-series alloys, or A8000-series alloys.


From the viewpoint of curtailing the aggregation of TiB2 particles during casting and making the average value of the circle-equivalent diameters of TiB2 aggregates small, the above-mentioned aluminum-alloy ingot preferably has a chemical composition that contains one or two or more of elements selected from the group consisting of Si (silicon): 0.01 mass % or more and 14.0 mass % or less, Fe (iron): 0.01 mass % or more and 2.0 mass % or less, Cu (copper): 0.01 mass % or more and 7.0 mass % or less, Mg (magnesium): 0.01 mass % or more and 7.0 mass % or less, Mn (manganese): 0.01 mass % or more and 2.0 mass % or less, and Ti (titanium): 0.003 mass % or more and 0.3 mass % or less, the remainder being Al (aluminum) and unavoidable impurities.


The aluminum-alloy ingot contains an aluminum matrix and TiB2 aggregates. Depending on the chemical composition, the aluminum-alloy ingot may contain crystallized products. In addition, the aluminum-alloy ingot may contain unaggregated TiB2 particles.


The aluminum matrix contains aluminum atoms and solid-solution elements in accordance with the chemical composition of the above-mentioned aluminum-alloy ingot. In addition, the aluminum matrix is composed of numerous crystal particles. The crystal-particle sizes of the aluminum matrix vary in accordance with the chemical composition of the above-mentioned aluminum-alloy ingot; in an aluminum-alloy ingot that contains the above-mentioned specific TiB2 aggregates, the mean particle size of the aluminum matrix is usually within the range of 50 μm or more and 5,000 μm or less.


The TiB2 aggregates are dispersed in the aluminum matrix, in which aggregates of the TiB2 particles serve as primary particles. The particle size of each individual TiB2 particle contained in the TiB2 aggregates may be, for example, 0.1 μm or more and 5.0 μm or less.


The average value of the circle-equivalent diameters of the above-mentioned TiB2 aggregates in the state in which the TiB2 aggregates are exposed from the above-mentioned aluminum matrix is 3.0 μm or less. By setting the average value of the circle-equivalent diameters of the TiB2 aggregates to 3.0 μm or less, the occurrence of linear defects when performing flattening work, such as rolling or extruding, on the above-mentioned aluminum-alloy ingot can be curtailed.


In the situation in which the average value of the circle-equivalent diameters of the TiB2 aggregates is larger than 3.0 μm, the possibility that coarse TiB2 aggregates will be present in the aluminum-alloy ingot becomes high. For that reason, in this situation, when flattening work has been performed on aluminum-alloy ingots, there is a risk that linear defects originating at the coarse TiB2 aggregates will tend to occur.


From the viewpoint of curtailing the occurrence of linear defects, the lower limit of the average value of the circle-equivalent diameters of the TiB2 aggregates is not particularly limited, but the average value of the circle-equivalent diameters of the TiB2 aggregates formed by the manufacturing method of the above-mentioned aspect is usually 1.0 μm or more.


The average value of the circle-equivalent diameters of the TiB2 aggregates described above is a value that is calculated by the following method. First, a test piece is collected from the interior of the aluminum-alloy ingot. Subsequently, the aluminum matrix on the surface of the test piece is removed by a method such as dip etching. By observing the surface of the test piece using an electron microscope or the like, an enlarged photograph of the TiB2 aggregates is taken. The circle-equivalent diameter of each individual TiB2 aggregate is calculated based on the projection-surface area of the TiB2 aggregate in the enlarged photograph that was taken. By performing the above operation on a plurality of randomly selected TiB2 aggregates and calculating the arithmetic mean of the circle-equivalent diameters thereof, the average value of the circle-equivalent diameters of the TiB2 aggregates can be obtained. The number of TiB2 aggregates used when calculating the average value of the circle-equivalent diameters should be, for example, 3 or more.


In addition, the average value of the circularities of the above-mentioned TiB2 aggregates in the state in which the TiB2 aggregates are exposed from the above-mentioned aluminum matrix is 0.20 or more. The circularity of a TiB2 aggregate is a value that becomes an indication of whether the shape of the TiB2 aggregate is close to a sphere and means that, the closer the circularity is to 1, the closer the shape of the TiB2 aggregate is to a sphere.


In casting processes of the above-mentioned aluminum-alloy ingot, TiB2 aggregates having a variety of shapes are usually formed in the melt. Furthermore, the more that the TiB2 aggregates in the melt have a shape in which the circularity is large and therefore the shape is close to a sphere, the more the TiB2 aggregates have the property of tending to function as heterogenous nuclei. Accordingly, by setting the average value of the circularities of the TiB2 aggregates to 0.20 or more, it is possible to increase the proportion of the TiB2 aggregates, among the TiB2 aggregates formed during casting, that can function as heterogenous nuclei.


In the situation in which the average value of the circularities of the TiB2 aggregates is less than 0.20, the proportion of the TiB2 aggregates, among the TiB2 aggregates formed during casting, that can function as heterogenous nuclei tends to become low. Consequently, in this situation, there is a risk that the refinement of the crystal particles in the aluminum matrix will become insufficient.


From the viewpoint of increasing the effect of refining the crystal particles of the TiB2 aggregates, the upper limit of the average value of the circularities of the TiB2 aggregates is not particularly limited, but the average value of the circularities of the TiB2 aggregates formed by the manufacturing method of the above-mentioned aspect is usually 0.8 or less.


The average value of the circularities of the TiB2 aggregates described above specifically is a value that is calculated by the following method. First, the method of calculating the circle-equivalent diameters is the same, and an enlarged photograph of the TiB2 aggregates is taken. The circularity of each individual TiB2 aggregate is described by the equation below, using the surface area S [μm2] and the circumferential length L [μm] of each TiB2 aggregate in the enlarged photograph that was taken.





Circularity=4πS/L2


By performing the above operation on a plurality of randomly selected TiB2 aggregates and calculating the arithmetic mean of the circularities thereof, the average value of the circularities of the TiB2 aggregates can be obtained. The number of TiB2 aggregates used when calculating the average value of the circularities should be, for example, 3 or more.


In addition, by setting the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates contained in the above-mentioned aluminum-alloy ingot to within the above-mentioned specific ranges, respectively, the functions and effects thereof described above can be increased, and the amount of the crystal-grain refining agent added in the casting process can be decreased while ensuring the effect of refining the crystal particles.


That is, in casting processes of the above-mentioned aluminum-alloy ingot as described above, by setting the average value of the circle-equivalent diameters of the TiB2 aggregates formed in the melt to within the above-mentioned specific range, the number of coarse TiB2 aggregates can be decreased and the total number of TiB2 aggregates in the melt can be made large. In addition, by setting the average value of the circularities of the TiB2 aggregates to within the above-mentioned specific range, the proportion of the TiB2 aggregates in the melt that can function as heterogenous nuclei can be increased.


Accordingly, in casting processes of the above-mentioned aluminum-alloy ingot, by setting the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates to within the above-mentioned specific ranges, respectively, the number of TiB2 aggregates that can function as heterogenous nuclei can be made large and, in turn, the effect of refining the crystal particles in the aluminum matrix can be increased.


As described above, by setting the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates contained in the above-mentioned aluminum-alloy ingot to within the above-mentioned specific ranges, respectively, the effect due to the decrease in the circle-equivalent diameters and the effect due to the increase in circularity can be made to function synergistically. As a result, when manufacturing the above-mentioned aluminum-alloy ingot, the amount of the crystal-grain refining agent added during casting can be decreased more than in the past while maintaining the effect of refining the crystal particles.


For example, the content of the TiB2 aggregates in the above-mentioned aluminum-alloy ingot can be set to 0.0001 mass % or more and 0.0010 mass % or less based on the boron atoms.


With regard to the manufacture of the above-mentioned aluminum-alloy ingot, a method can be used that comprises: a melting step, in which the crystal-grain refining agent is caused to melt in the melt of the aluminum alloy; and, after the melting step, a casting step that casts the melt.


The crystal-grain refining agent added into the melt in the above-mentioned manufacturing method has a base composed of aluminum. The shape of the base is not particularly limited and may have, for example, a rod shape, a plate shape, or the like.


In addition, the base contains TiB2 particles. The TiB2 particles are dispersed within the base and may exist in an unaggregated state. In addition, TiB2 aggregates may be formed in the base by aggregation of a plurality of the TiB2 particles. More specifically, all the TiB2 particles in the base may exist in an unaggregated state, or all the TiB2 particles in the base may exist in a TiB2 aggregate state. Furthermore, both TiB2 particles and TiB2 aggregates may exist in the base in an unaggregated state.


With regard to at least some of the TiB2 particles in the base, after the crystal-grain refining agent has melted into the melt in the melting step, the TiB2 particles aggregate in the melt to form TiB2 aggregates. In addition, with regard to the TiB2 aggregates in the base, when the crystal-grain refining agent has melted in the melt in the melting step, the TiB2 aggregates migrate into the melt while maintaining the aggregated state. For that reason, by causing the crystal-grain refining agent, which contains TiB2 particles, to melt in the aluminum melt, TiB2 aggregates can be formed in the melt.


In the above-mentioned melting step, for example, the crystal-grain refining agent according to any of the aspects below can be melted in the melt. That is, in a first aspect of the crystal-grain refining agent, the average value of the center-to-center distances of adjacent TiB2 particles is 0.60 μm or more in an arbitrary cross section of the above-mentioned crystal-grain refining agent. By setting the center-to-center distances of the TiB2 particles in the crystal-grain refining agent to within the above-mentioned specific range, the aggregation of TiB2 particles and the growth of TiB2 aggregates when the crystal-grain refining agent has been melted in the melt can be curtailed. As a result, the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates formed in the melt can be easily set to within the above-mentioned specific ranges, respectively.


In the situation in which the average value of the center-to-center distances of adjacent TiB2 particles is less than 0.60 μm, it becomes easy for aggregates to form between TiB2 particles when the crystal-grain refining agent has been melted in the melt. As a result, there is a risk that coarse TiB2 aggregates will tend to be formed in the melt, which will lead to a decrease in the effect of refining the crystal particles and to an increase in the occurrence frequency of linear defects during flattening work.


It is noted that the average value of the center-to-center distances of the TiB2 particles described above is a value that is calculated by the following method. First, the crystal-grain refining agent is cut to expose a cut surface. This cut surface is observed using an electron microscope or the like, and an enlarged photograph of the cut surface is taken. With regard to the enlarged photograph that was taken, the center of gravity of each TiB2 particle present in the enlarged photograph is determined. It is noted that both the TiB2 particles present in an undispersed state and the TiB2 particles that constitute a portion of the TiB2 aggregates are included in the TiB2 particles present in the enlarged photograph.


Next, the TiB2 particles that will become the objects to be measured for the center-to-center distances are determined from among the TiB2 particles present in the enlarged photograph. Furthermore, the distance between the center of gravity of the TiB2 particle that is the object to be measured and the center of gravity of the TiB2 particle closest to the TiB2 particle that is the object to be measured is measured, and that value is set as the center-to-center distance of the TiB2 particle that is the object to be measured. By performing the above operation on all TiB2 particles present in the enlarged photograph, the arithmetic-mean value of the obtained center-to-center distances is set as the average value of the center-to-center distances of the TiB2 particles.


In a second aspect of the crystal-grain refining agent, in the situation in which the projection-surface areas of 2,000 or more TiB2 aggregates have been measured in the state in which the TiB2 aggregates are exposed from the base, the TiB2 aggregates in the crystal-grain refining agent have a particle-size distribution in which the average value of the circle-equivalent diameters of the TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, is 3.0 μm or less. In crystal-grain refining agents containing TiB2 aggregates, the TiB2 aggregates having large circle-equivalent diameters effectively function as heterogenous nuclei in the aluminum melt.


However, when the circle-equivalent diameters of the TiB2 aggregates in the crystal-grain refining agent become excessively large, coarse TiB2 aggregates tend to mix into the aluminum melt when the crystal-grain refining agent has been melted in the aluminum melt. As a result, when flattening work is performed on the aluminum-alloy ingot after it has been cast, there is a risk that linear defects originating from the coarse TiB2 aggregates will tend to occur.


Accordingly, by setting the particle-size distribution of the TiB2 aggregates in the crystal-grain refining agent to the above-mentioned specific aspect, the possibility that the crystal-grain refining agent will contain coarse TiB2 aggregates can be made low and, in turn, the mixing of the coarse TiB2 aggregates into the melt can be curtailed. As a result, the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates formed in the melt can be set easily to within the above-mentioned specific ranges, respectively.


In the situation in which the average value of the circle-equivalent diameters of the TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, is larger than 3.0 μm, the possibility that the crystal-grain refining agent will contain coarse TiB2 aggregates becomes high. Consequently, when the crystal-grain refining agent has been melted in the melt, the coarse TiB2 aggregates tend to mix into the melt, and there is a risk that this will lead to a decrease in the effect of refining the crystal particles and to an increase in the occurrence frequency of linear defects during flattening work.


It is noted that the average value of the circle-equivalent diameters of the TiB2 aggregates described above is a value calculated by the following method. First, the crystal-grain refining agent is cut to expose a cut surface. The cutting direction of the crystal-grain refining agent is not particularly limited. For example, in the situation in which the crystal-grain refining agent is rod shaped, the crystal-grain refining agent should be cut through its center in a plane perpendicular to the longitudinal direction.


Next, after polishing the cut surface of the crystal-grain refining agent, the TiB2 aggregates are exposed from the base by removing a peripheral portion of the TiB2 aggregates at the base. For example, a method such as dip etching can be used as the method of removing the base.


Subsequently, the TiB2 aggregates that have been exposed from the base are observed using an electron microscope or the like, and an enlarged photograph of the TiB2 aggregates is taken. The surface area of each TiB2 aggregate in the enlarged photograph is taken as the projection-surface area of the TiB2 aggregate. It is noted that an image-analyzing apparatus or the like can be used in the calculation of the projection-surface area and the calculation of the circle-equivalent diameter of each TiB2 aggregate.


The above operation is performed for 2,000 or more TiB2 aggregates randomly selected from the TiB2 aggregates present at the cut surface of the crystal-grain refining agent. Based on the projection-surface areas of the TiB2 aggregates obtained in this manner, the 95th percentile of the projection-surface areas is calculated. It is noted that, in the situation in which a plurality of numerical values is sorted in order from the smallest numerical value to the largest numerical value, the percentile is a numerical value in which the number of numerical values counting from the smallest numerical value is the desired percentage of the total number of numerical values. In the situation in which there is no such numerical value, the largest value of the values, in which the number of numerical values counting from the smallest numerical value is less than the desired percentage of the total number of the numerical values, is taken as the percentile. More specifically, the 95th percentile of the projection-surface areas is the value in which the number of TiB2 aggregates having a projection-surface area in the 95th percentile or higher is 5% of the total number of TiB2 aggregates for which the projection-surface area was measured.


After the 95th percentile of the projection-surface areas has been determined as described above, the circle-equivalent diameters of the TiB2 aggregates having a projection-surface area in the 95th percentile or higher are calculated. It is noted that a circle-equivalent diameter is the diameter of a circle having a surface area equal to the projection-surface area of a TiB2 aggregate. Furthermore, by calculating the mean average of the circle-equivalent diameters of the obtained TiB2 aggregates, the average value of the circle-equivalent diameters of the TiB2 aggregates having a projection-surface area in the 95th percentile or higher can be obtained.


The content of the TiB2 particles in the crystal-grain refining agent can be set to, for example, 0.5 mass % or more and 3.2 mass % or less. In this situation, the average value of the center-to-center distances of adjacent TiB2 particles tends to become large. As a result, the effect of curtailing the aggregation of the TiB2 particles when the crystal-grain refining agent has been melted in the melt can be exhibited more reliably.


In the above-mentioned manufacturing method, the above-mentioned crystal-grain refining agent is melted in the melt of an aluminum alloy having a desired chemical composition. At this time, the melt may be stirred as needed to evenly disperse the TiB2 particles in the crystal-grain refining agent in the melt.


In the manufacturing method, after the crystal-grain refining agent has been melted in the melt, the aluminum-alloy ingot can be manufactured by casting the melt. The casting method is not particularly limited; for example, methods such as semicontinuous casting, continuous casting, and the like can be used. An aluminum-alloy ingot manufactured by these methods can be used in the manufacture of flattened materials such as rolled plates, extruded materials, and the like. In addition, by cooling the aluminum-alloy melt described above after the melt has been poured into a mold or a sand mold, it is also possible to obtain an ingot having a desired article shape or a shape close to the desired article shape.


In the above-mentioned manufacturing method, after the crystal-grain refining agent has been melted into the melt, it is preferable to cast the melt within 30 min. The specific gravity of the TiB2 particles is greater than that of the melt. Consequently, when the elapsed time since the point in time when the crystal-grain refining agent was melted into the melt becomes long, the TiB2 particles precipitate owing to their intrinsic weight, and the TiB2 particles tend to aggregate at the lower portion of the crucible. As a result, there is a risk that coarse TiB2 aggregates will tend to be formed. By setting the time from the point in time at which the crystal-grain refining agent was melted into the melt until the casting to within 30 min, such problems can be avoided more easily.


When viewed from another viewpoint, it is noted that the aluminum-alloy ingot and the manufacturing method thereof described above can also be understood as the invention of a crystal-grain refining agent in which the distribution state of TiB2 particles is specified.


That is, a first aspect of the crystal-grain refining agent comprises:


a base composed of aluminum; and


TiB2 particles, which are present in the base;


wherein the average value of center-to-center distances of the TiB2 particles that are adjacent in an arbitrary cross section is 0.60 μm or more.


In addition, a second aspect of the crystal-grain refining agent comprises:


a base composed of aluminum; and


TiB2 aggregates, in which TiB2 particles are aggregated and present in the base; and


in the situation in which the projection-surface areas of 2,000 or more of the TiB2 aggregates have been measured in the state in which the TiB2 aggregates are exposed from the base, the TiB2 aggregates have a particle-size distribution in which the average value of the circle-equivalent diameters of the TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, is 3.0 μm or less.


It is assumed that such a crystal-grain refining agent can be manufactured by, for example, the following manufacturing method.


That is, in the manufacturing method of the crystal-grain refining agent, a melt of aluminum, which will become the base, is prepared;


the TiB2 particles are dispesed in the melt by blowing the TiB2 particles, together with an inert gas, into the melt; and


the melt is subsequently solidified. The crystal-grain refining agent can be obtained by the above.


It is preferable to use TiB2 particles having a narrow particle-size distribution range as the TiB2 particles that are blown into the melt, and it is more preferable to use TiB2 particles having a particle-size standard deviation of 0.5 μm or less. In addition, for example, nitrogen gas, argon gas, or the like can be used as the inert gas. It is noted that the standard deviation of the particle sizes of the TiB2 particles is a value that is calculated based on the particle-size distribution on a volume basis. To acquire the particle-size distribution on a TiB2-particle volume basis, specifically, a laser-diffracting, particle-size-distribution measuring apparatus can be used.


WORKING EXAMPLES

Working examples of the aluminum-alloy ingot and the manufacturing method thereof will be explained below. It is noted that the specific aspects of the aluminum-alloy ingot and the manufacturing method thereof according to the present invention are not limited to the aspects of the working examples, and the configuration can be modified as appropriate within a range that does not impair the gist of the present invention.


Working Examples 1, 2 and Comparative Examples 1, 2

Working Examples 1, 2 and Comparative Examples 1, 2 are examples of aluminum-alloy ingots composed of pure aluminum. In these examples, first, a melt was prepared by melting aluminum metal having a purity of 99.7 mass %. After the temperature of the melt was set to 718° C., a crystal-grain refining agent, in which TiB2 particles are dispersed in a base composed of aluminum, was added such that the boron atoms reached 10 mass ppm.


Crystal-grain refining agents used in the present example specifically had a chemical composition containing Ti: 1.0 mass % or more and 5.5 mass % or less and B: 0.1 mass % or more and 1.5 mass % or less, the remainder being Al and unavoidable impurities, and had a base composed of aluminum and TiB2 particles present in the base. Some of the TiB2 particles existed in an unaggregated state, the remainder being composed of TiB2 aggregates.


The center-to-center distances between adjacent TiB2 particles in an arbitrary cross section of the crystal-grain refining agent of the present example are the values shown in Table 1. In addition, in the situation in which the projection-surface areas of 2,000 or more TiB2 aggregates were measured in the state in which the TiB2 aggregates were exposed from the base, the TiB2 aggregates in the crystal-grain refining agent had particle-size distributions in which the average values of the circle-equivalent diameters of the TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, are the values shown in Table 1.


After the crystal-grain refining agent was added into the melt, the melt was stirred for 30 seconds using a graphite rod in the state in which the temperature of the melt was maintained at 718° C., and the crystal-grain refining agent was sufficiently melted. In addition, at the point in time at which 9 minutes 15 seconds had elapsed since the point in time when the crystal-grain refining agent was added, the melt was once again stirred for 15 seconds using a graphite rod.


After the second stirring was completed, a ladle, which was made of iron and prepared in accordance with the AA-TP1 standard, was immersed into the melt, and the cup portion of the ladle was filled with the melt. Furthermore, at the point in time when 10 min had elapsed since the point in time when the crystal-grain refining agent was added, the ladle was lifted up from the melt, thereby scooping up the melt in the cup portion. Subsequently, the cup portion of the ladle was cooled using a water-cooling apparatus that is compliant with the AA-TP1 standard, and the melt was caused to solidify. The aluminum-alloy ingots for Working Examples 1, 2 and Comparative Examples 1, 2 were obtained by the above. These aluminum-alloy ingots all exhibited a circular, truncated-cone shape.


The methods of calculating the average values of the circle-equivalent diameters and the average values of the circularities of the TiB2 aggregates in the aluminum-alloy ingots of Working Examples 1, 2 and Comparative Examples 1, 2 were as follows. These values for the aluminum-alloy ingots of Working Examples 1, 2 and Comparative Examples 1, 2 are shown in Table 1.


Average Value of Circle-Equivalent Diameters and Average Value of Circularities of TiB2 Aggregates


The aluminum-alloy ingot was cut at a cross section, from among the circular end surfaces of the aluminum-alloy ingot, at which the height from the plane having a small diameter (that is, the plane that is adjacent to the bottom surface of the ladle) was 38 mm, thereby exposing the cut surface. After this cut surface was polished, aluminum matrix was removed by performing dip etching, thereby exposing the entirety of the TiB2 aggregates.


Subsequently, enlarged photographs of the TiB2 aggregates were taken using an electron microscope. As one example, FIG. 1 shows an enlarged photograph of TiB2 aggregates contained in an aluminum-alloy ingot of Working Example 1, and FIG. 2 shows an enlarged photograph of TiB2 aggregates contained in an aluminum-alloy ingot of Comparative Example 2. As shown in FIG. 1 and FIG. 2, a TiB2 aggregate 2 in the aluminum matrix 1 exhibits a lump shape, in which numerous TiB2 particles 3 are aggregated.


The surface area of each of the TiB2 aggregates 2 in the enlarged photographs was calculated using image-analyzing software, and the circle-equivalent diameter of each TiB2 aggregate was calculated based on the surface area of the TiB2 aggregate 2. The above operation was performed on eight randomly selected TiB2 aggregates, and the value of the arithmetic mean of these circle-equivalent diameters was taken as the average value of the circle-equivalent diameters of the TiB2 aggregates. Table 1 shows the average value of the circle-equivalent diameters of the TiB2 aggregates for each of the aluminum-alloy ingots.


In addition, the circumferential length, i.e., the length of the contour, of each of the TiB2 aggregates 2 in the enlarged photograph described above was calculated using image-analyzing software. Furthermore, the circularity of each of the TiB2 aggregates was calculated based on the surface area and the circumferential length of each of the TiB2 aggregates 2. The above operation was performed on three or more randomly selected TiB2 aggregates, and the value of the arithmetic mean of these circularities was taken as the average value of the circularities of the TiB2 aggregates. Table 1 shows the average value of the circularities of the TiB2 aggregates for each of the aluminum-alloy ingots.


Working Example 3

Working Example 3 is an example of an aluminum-alloy ingot composed of an A3000-series alloy. In Working Example 3, first, a melt composed of an A3000-series alloy was prepared using a heating furnace, after which a crystal-grain refining agent was added to the melt such that the boron atoms reached 10 mass ppm. The crystal-grain refining agent used in the present example is the same as that in Working Example 1 except for: the point that it had a chemical composition containing Ti: 5.0 mass % and B: 1.0 mass %, the remainder being Al and unavoidable impurities; the point that the center-to-center distances between adjacent TiB2 particles at an arbitrary cross section of the crystal-grain refining agent are the values shown in Table 1; and the point that the average value of the circle-equivalent diameters of the TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, is the value shown in Table 1.


After the crystal-grain refining agent was added to the melt, the melt was stirred for 30 seconds using a graphite rod. Subsequently, the melt was cast using a DC-casting method. Thus, the aluminum-alloy ingot of Working Example 3 was obtained. The aluminum-alloy ingot of Working Example 3 exhibits a rectangular-parallelepiped shape.


Working Example 4

Working Example 4 is an example of an aluminum-alloy ingot composed of an A1000-series aluminum. In Working Example 4, the melt of the aluminum alloy was cast using the same method as that in Working Example 3, except for the point that the melt composed of the A1000-series aluminum was prepared using a heating furnace. Thereby, the aluminum-alloy ingot of Working Example 4 was obtained. The aluminum-alloy ingot of Working Example 4 exhibited a rectangular-parallelepiped shape, the same as in Working Example 3.


With regard to the aluminum-alloy ingots of Working Example 3 and Working Example 4, the methods of calculating the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates were as follows.


Average Value of Circle-Equivalent Diameters and Average Value of Circularities of the TiB2 Aggregates


The aluminum-alloy ingot is cut and a test piece is collected from a center portion in the width direction and the thickness direction. A surface of the test piece is polished, after which the test piece is subject to dip etching to remove aluminum matrix, thereby exposing the entirety of the TiB2 aggregates. Thereafter, the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates should be calculated using the same method as in Working Example 1, etc. Table 1 shows these values for the aluminum-alloy ingots of Working Examples 3, 4.












TABLE 1









Crystal-Grain Refining Agent
TiB2 Aggregates in Ingot














Center-to-
Average Value of Circle-
Average





Center
Equivalent Diameters of
Value of





Distances
TiB2 Aggregates Having
Circle-





between
a Projection Surface in
Equivalent
Average




Adjacent TiB2
the 95th Percentile or
Diameters
Value of



Alloy Type
Particles (μm)
Higher (μm)
(μm)
Circularities





Working
Al: 99.7 mass %
0.68
2.95
2.4
0.3


Example 1







Working
Al: 99.7 mass %
0.62
2.64
2.2
0.2


Example 2







Working
A3000-series
0.68
2.95
2.6
0.3


Example 3
alloy






Working
A1000-series
0.63
2.73
2.3
0.2


Example 4
aluminum






Comparative
Al: 99.7 mass %
0.58
3.01
3.8
0.2


Example 1







Comparative
Al: 99.7 mass %
0.48
3.97
3.5
0.2


Example 2














As shown in Table 1, the average value of the circle-equivalent diameters and the average value of the circularities of the TiB2 aggregates contained in the aluminum-alloy ingots of Working Examples 1-4 were within the above-mentioned specific ranges, respectively. For this reason, with regard to these aluminum-alloy ingots, the crystal particles in the aluminum matrix were sufficiently refined, there were few coarse TiB2 aggregates, and the occurrence of linear defects when performing processing such as rolling could be curtailed.


The average value of the circle-equivalent diameters of the TiB2 aggregates contained in the aluminum-alloy ingots of Comparative Examples 1, 2 were above the above-mentioned specific ranges, respectively. Consequently, these aluminum-alloy ingots tended to contain coarse TiB2 aggregates, and linear defects tended to occur during flattening work.

Claims
  • 1. An aluminum-alloy ingot comprising: an aluminum matrix; andTiB2 aggregates, which are dispersed in the aluminum matrix and are formed of aggregated TiB2 particles;wherein the average value of the circle-equivalent diameters of the TiB2 aggregates in the state in which the TiB2 aggregates are exposed from the aluminum matrix is 3.0 μm or less and the average value of the circularities is 0.20 or more.
  • 2. The aluminum-alloy ingot according to claim 1, wherein the content of the TiB2 aggregates in the aluminum matrix is 0.0001 mass % or more and 0.0010 mass % or less based on the boron atoms.
  • 3. A method of manufacturing the aluminum-alloy ingot according to claim 1, comprising: melting a crystal-grain refining agent, which contains TiB2 particles in a base composed of aluminum and has an average value of center-to-center distances between adjacent TiB2 particles in an arbitrary cross section that is 0.60 μm or more, in a melt of aluminum alloy; andafter the melting step, casting the melt.
  • 4. A method of manufacturing the aluminum-alloy ingot according to claim 1, comprising: melting a crystal-grain refining agent, which contains TiB2 particles in a base composed of aluminum in which the TiB2 particles are aggregated, in a melt of an aluminum alloy; andafter the melting step, casting the melt;wherein, when projection-surface areas of 2,000 or more TiB2 aggregates are measured in the state in which TiB2 aggregates are exposed from the base, the TiB2 aggregates in the crystal-grain refining agent have a particle-size distribution in which the average value of the circle-equivalent diameters of TiB2 aggregates, which have a projection-surface area in the 95th percentile or higher, is 3.0 μm or less.
  • 5. The method of manufacturing the aluminum-alloy ingot according to claim 3, wherein the melt is cast within 30 min after the crystal-grain refining agent has been melted in the melt.
Priority Claims (2)
Number Date Country Kind
2020-018896 Feb 2020 JP national
2020-109517 Jun 2020 JP national
PCT Information
Filing Document Filing Date Country Kind
PCT/JP2021/004225 2/5/2021 WO