The present invention relates to an alloy material, particularly, to an alloy material such as a Mg alloy having improved mechanical characteristics and corrosion resistance and a method of manufacturing the same, and more particularly, to an alloy material such as a Mg alloy having improved mechanical characteristics, corrosion characteristics and the like by homogenization heat treatment, unlike the common idea, and a method of manufacturing the same.
Mg is an environmental friendly material that has a density of 1. 74 g/cm3 which is merely ⅕ of Fe and ⅔ of Al, generally has superior strength and can be easily recycled. Mg is also evaluated as an ultra-lightweight structural material, the specific strength and elastic coefficient of which are comparable to those of other lightweight materials, such as Al. In addition, Mg exhibits a superior ability to absorb vibration, impact, electromagnetic wave and the like, and has superior electrical and thermal conductivities.
However, Mg and Mg alloys have the fundamental problem of poor corrosion resistance despite of the above-mentioned excellent characteristics. Since it is known that Mg rapidly corrodes under electromotive force (EMF) and in a galvanic reaction due to its high reactivity, the use of Mg is limited to internal parts in which corrosion environment conditions are not strict or regions in which strength, thermal resistance or corrosion resistance is not highly required. Therefore, although a technology for fundamentally improving the corrosion resistance of Mg and Mg alloys is still required, this requirement is not satisfied by present technologies.
In the meantime, there are attempts to compensate for the drawbacks of Mg by inputting oxide particles of, for embodiment, Ca oxide, into a Mg material (e.g., Korean Patent Publication No. 10-2009-78039). However, when the Ca oxide is strongly stirred or exposed for a long time in a molten metal, oxygen floats on a surface of the molten metal, thereby forming impurities. Such impurities must be removed, which is problematic. When the Ca oxide is added to Mg, it is known that Mg and Ca form a compound and O bonds with Mg to form impurities. Such impurities (e.g. MgO) lower the corrosion resistance of Mg.
In addition, heat treatment is generally performed when manufacturing a material. That is, when homogenization heat treatment such as O-tempering is performed, elongation increases as eutectic structures disappear. Precipitates are created (precipitation hardening) by low-temperature heat treatment in addition to such homogenization heat treatment, thereby improving mechanical characteristics, such as the strength or hardness, of the material. In the meantime, while the homogenization heat treatment increases elongation, strength is decreased as the second phase disappears. In the related art, the decrease in strength due to the homogenization heat treatment was accepted as being natural, and there have been no attempts to improve this strength.
The present invention has been made to solve the foregoing problems with the prior art, and therefore an object of the present invention is to provide an alloy material in which the mechanical characteristics and corrosion resistance of a matrix metal are improved using metal oxide particles.
Another object of the present invention is to provide an alloy material in which the mechanical characteristics as well as the corrosion characteristics can be improved by homogenization heat treatment using metal oxide nano-particles and a method of manufacturing the same.
In order to realize the foregoing object, the present invention provides a cast material including a matrix metal wherein particles of an oxide are decomposed in the matrix metal, such that a metal element and oxygen (O) atoms which are components of the oxide are dispersed in the matrix metal, and the oxygen atoms do not form an oxide with the matrix metal.
According to the present invention, the cast material includes no particles of the oxide.
According to the present invention, the oxygen atoms of the oxide particles may be preferentially dispersed in the matrix metal, and the metal element of the oxide particles may be subsequently dispersed in the matrix metal, thereby mixing with the matrix metal.
According to an embodiment of the present invention, the matrix metal may be Mg or a Mg alloy, and the oxide particles may be particles of at least one oxide selected from among Ti oxides (TiOx), Mn oxides (MnOx), Zr oxides (ZrOx), Cr oxides (CrOx) and Fe oxides (FeOx).
In another aspect of the present invention, provided is a method of manufacturing a cast material that includes the following steps of: preparing a molten metal of a matrix metal; and inputting oxide particles into the molten metal and decomposing the oxide particles, so that the oxygen atoms that are a component of the oxide particles are primarily dispersed into the matrix metal and the metal element which is a component of the oxide particles is subsequently dispersed into the matrix metal, thereby manufacturing a cast material in which the oxygen atoms and the metal element are dispersed in the matrix metal, wherein the oxygen atoms do not form an oxide with the matrix metal.
According to an embodiment of the present invention, the cast material may not include the oxide particles.
In a further aspect of the present invention, provided is a cast alloy material. The cast alloy material includes a matrix metal and an alloy element. Oxide particles in the nanometer scale are decomposed in the matrix metal, so that a new phase including a metal element that is a component of the oxide particles and the alloy element forms a band or network structure. The metal element and the alloy element have a relationship of a negative heat of mixing. Oxygen atoms formed by decomposition of the oxide particles are dispersed in the matrix metal and do not form an oxide with the matrix metal.
According to an embodiment of the present invention, the metal element and the matrix metal may have a relationship of a positive heat of mixing or a relationship of a negative heat of mixing, an absolute value of the negative heat of mixing being smaller than that of the negative heat of mixing between the metal element and the alloy element.
According to an embodiment of the present invention, a compound of the metal element that is a component of the oxide particles and the matrix metal may not be formed.
According to an embodiment of the present invention, the new phase may be formed during a process of homogenization heat treatment, so that mechanical characteristics and corrosion characteristics are improved, compared to those before heat treatment. The homogenization heat treatment may be O-tempering.
According to an embodiment of the present invention, the matrix metal may be Mg, the alloy element may be Al, and the oxide particles may be particles of at least one oxide selected from among Ti oxides (TiOx), Mn oxides (MnOx), Cr oxides (CrOx), Zr oxides (ZrOx) and Fe oxides (FeOx).
In further another aspect of the present invention, provided is a method of manufacturing a cast alloy material. The method includes the following steps of: preparing a molten metal of a matrix metal; inputting an alloy element that has a relationship of a negative heat of mixing with the matrix metal; inputting oxide particles in the nanometer scale into the molten metal, the oxide particles including an alloy element that has a relationship of a negative heat of mixing with the alloy element, and thus decomposing the oxide particles, thereby manufacturing a cast material in which the metal element is preferentially distributed around the alloy element; and performing homogenization heat treatment for the cast material so that a new phase including the metal element and the alloy element forms a band or network structure, thereby improving mechanical characteristics and corrosion characteristics of the cast material, compared to those of a cast material which did not undergo the homogenization heat treatment. In the cast alloy material, oxygen atoms formed by decomposition of the oxide particles are dispersed in the matrix metal and do not form an oxide with the matrix metal.
According to an embodiment of the present invention, the mechanical characteristics may be further improved as the heat treatment time increases.
According to an embodiment of the present invention, the homogenization heat treatment may be O-tempering.
According to an embodiment of the present invention, the metal element and the matrix metal may have a relationship of a positive heat of mixing or a relationship of a negative heat of mixing, an absolute value of the negative heat of mixing being smaller than that of a negative heat of mixing between the metal element and the alloy element.
According to an embodiment of the present invention, the matrix metal may be Mg, the alloy element may be Al, and the oxide particles may be particles of at least one oxide selected from among Ti oxides (TiOx), Mn oxides (MnOx), Cr oxides (CrOx), Zr oxides (ZrOx) and Fe oxides (FeOx).
In yet another aspect of the present invention, provided is a Mg alloy material that includes a Mg matrix metal and an alloy element having a relationship of a negative heat of mixing with the Mg matrix metal. Oxide particles in the nanometer scale including a metal element that has a relationship of a positive heat of mixing with the Mg and a relationship of a negative heat of mixing with the alloy element are decomposed, so that a new phase including the metal element that is a component of the oxide particles and the alloy element forms a band or network structure. Oxygen atoms formed by decomposition of the oxide particles are dispersed in the Mg matrix metal and do not form an oxide with the Mg.
According to the present invention, it is possible to manufacture a cast material by decomposing particles of an oxide in a molten metal to thus disperse a metal element and oxygen atoms, which compose the oxide, into a matrix metal. As the oxygen atoms are dispersed, the cast alloy material exhibits superior mechanical characteristics and corrosion resistance, compared to the other alloys. In addition, even though homogenization heat treatment is performed, a new phase including the alloy element and the metal element which is formed by the decomposition of the oxide particles forms a band or network structure, thereby improving the mechanical characteristics such as strength and corrosion characteristics of the alloy material.
Reference will now be made in detail to various embodiments of the present invention with reference to the accompanying drawings. In the following description of the present invention, detailed descriptions of well-known technologies will be omitted. However, the following embodiments will enable a person having ordinary skill in the art to easily understand the characteristic constitutions and effects of the present invention and put the present invention into practice with no significant difficulties.
The inventors selected Mg and titania (TiO2, 50 nm) as a metal matrix and nano oxide particles, manufactured a material according to the following process and then evaluated its properties.
First, the inventors achieved an extraordinary result of dissolving oxygen atoms by decomposing/dispersing the oxide particles into a matrix metal using a typical casting method. Specifically, pure Mg was melted using an electric melting furnace, and then titania (TiO2, 50 nm) was inputted by a volume ratio of 1% into the molten metal. At this time, the titania powder was prepared in the form of a compact at room temperature so that the titania particles could be inputted into the molten metal. The temperature of the molten metal was increased to 820° C., which was maintained for 30 minutes such that the particles could be decomposed. Afterwards, casting was performed, thereby manufacturing a cast material, which is shown in
In order to analyze a microstructure of the Mg material that was manufactured as above, the Mg material before and after etching was observed using an optical microscope, and the results are presented in
After the cast material was etched using picric acid, the surface thereof was observed using an optical microscope. The result is presented at the left part of
The inventors observed the microstructure using a scanning electron microscope (SEM) and performed a composition analysis by energy dispersive X-ray spectroscopy (EDS) in order to analyze the microstructure in detail, and the results are presented in
The inventors selected Mg, Al and titania (TiO2, 50 nm) as a metal matrix, an alloy element and nano oxide particles, manufactured a material according to the following process and then evaluated its properties.
In the meantime, the inventors analyzed the selected metal matrix, the alloy element and the nano oxide particles from the viewpoint of the heat of mixing. The heat of mixing is a parameter that shows a difference between enthalpies unique to two different elements when the two elements are present in the liquid form. When the enthalpy difference between the liquids of the two different elements is negative (−), mixing occurs through a mutual reaction between molecules of the two elements. The greater the difference, the easier becomes the mixing (That is, the two different elements tend to aggregate together). In contrast, when the enthalpy difference is positive (+), mixing does not occur since the two elements do not react with each other (That is, the two different elements tend to remain separate from each other). The difference in the heat of mixing between Mg and Ti is +16, the difference in the heat of mixing between Al and Ti is −30, and the difference in the heat of mixing between Mg and Al is −2. Therefore, it can be said that Ti tends to preferentially bond with Al rather than Mg.
First, the inventors achieved an extraordinary result of dissolving oxygen atoms by decomposing/dispersing the oxide particles inside the matrix metal using a typical casting method. Specifically, pure Mg was melted using an electric melting furnace, Al was added by mass ratios of 6, 9 and 12%, and then titania was inputted by a volume ratio of 1% into each molten metal. At this time, the titania powder was prepared in the form of a compact at room temperature so that the titania particles could be inputted into each molten metal. The temperature of the molten metal was increased to 820° C., which was maintained for 30 minutes such that the particles could be decomposed. Afterwards, casting was performed, thereby manufacturing cast materials. A protective gas (SF6+CO2) was used throughout the production process in order to prevent oxidation.
Meanwhile, in the present invention, the grain size of the oxide particles that are inputted is in the nanometer scale (50 nm in this embodiment), and a compact of the oxide particles in the nanometer scale was inputted into the molten metal. Although not specifically shown in the specification, according to the observation of the inventors, when the size of the oxide particles exceeds the nanometer scale, for embodiment, when the oxide particle size was increased to the micrometer scale, even though the oxide particles were inputted into the molten metal, the phenomenon in which the oxide is divided into the metal element and the oxygen atoms was not observed, as will be described later.
In order to analyze microstructures of the Mg materials that were manufactured as above, the Mg alloy materials before and after etching were observed using an optical microscope, and the results are presented in
This result is a considerably exceptional result. That is, it is known that the dispersion of oxygen atoms in Mg is impossible in the thermodynamically stable state since Mg has substantially no solubility of oxygen at the liquid/solid phase. In addition, when oxygen is forcibly dissolved, MgO must be formed directly in the viewpoint of thermodynamics. However, according to the present invention, the oxygen atoms were dispersed in Mg instead of forming MgO in the molten metal and during solidification, which was empirically observed and the result of which is in
Specifically, in an attempt to form MgO by inputting oxide particles into the Mg molten metal, it can be regarded that MgO particles are formed when oxygen forms several clusters and MgO nuclei are formed and grown to a predetermined size or greater. For the purpose of removing oxygen to prevent it from residing in the molten metal, the related art involves strongly stirring the molten metal while inputting the oxide particles into the molten metal. The strong stirring forms clusters, such that an oxide such as MgO is consequently formed. Unlike the related-art method that is widely performed, the inventors simply inputted the oxide particles in the steady state. That is, the inventors divided the titania particles into Ti and oxygen atoms by simply inputting the titania particles that were prepared as above into the molten metal, and did not perform the operation of strongly stirring the molten metal in order to mix the particles into the molten metal when inputting the titania particles. Accordingly, it is considered that the condition in which the oxygen atoms divided from the titania can form clusters was not satisfied, such that the nucleation of MgO crystals did not occur. Consequently, MgO is not included in the Mg alloys that were finally manufactured.
In the meantime, the inventors performed heat treatment for the materials that were manufactured as above. That is, in a general production process for a material, heat treatment is performed in order to relax strain hardening and improve ductility (for embodiment, O-tempering; see
As apparent from the Mg—Al phase diagram in
As shown in
The inventors compared the materials in which the amounts of Al and titania are different with AZ91 Mg alloy, a commercially available alloy, in relation to hardness values depending on the heat treatment time, and the results are presented in
In addition, the inventors performed a corrosion test on the cast materials that were manufactured as above by polishing their surface and then heat-treating them at 420° C. for 24 hours, and the results are presented in
The results of
The inventors hot-rolled a cast material in which oxygen atoms are dissolved as proposed in the foregoing embodiment at 380° C., and the resultant rolled material is shown in
Although the present invention has been described hereinabove with respect to the preferred embodiments, it should be understood that the present invention is not limited to the foregoing embodiments. Although the foregoing embodiments were described as using ceramic particles, i.e. titania (TiO2), by way of embodiment, the present invention is not limited thereto. For embodiment, it is possible to apply particles of an oxide matrixd on a metal element that has a positive heat of mixing with respect to a matrix metal and a negative heat of mixing with respect to an alloy element, for embodiment, an oxide selected from among Mn oxides (MnOx), Cr oxides (CrOx), Zr oxides (ZrOx) and Fe oxides (FeOx), to the present invention. In addition, even if an oxide is soluble to the matrix metal (e.g., Ca oxides (CaOx), Sr oxides (SrOx), Ba oxides (BaOx), Zn oxides (ZnOx), Si oxides (SiOx), Al oxides (AlOx), Y oxides (YOx), rare earth oxides (REOx) and Sn oxides (SnOx)), when the oxide is inputted by the foregoing production method according to the present invention (i.e. inputted in the static state without being strongly stirred), it can be decomposed and heat-treated according to the present invention in order to form a new phase that makes up a band or network structure across the entire matrix metal, thereby improving the mechanical characteristics of the alloy material. As set forth above, the present invention can be made into various alterations and modifications without departing from the scope of the appended claims, and all such alterations and modifications fall within the scope of the present invention. Therefore, the present invention shall be defined by only the claims and their equivalents.
Number | Date | Country | Kind |
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10-2011-0060963 | Jun 2011 | KR | national |
10-2011-0082532 | Aug 2011 | KR | national |
10-2012-0064752 | Jun 2012 | KR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/KR12/04940 | 6/22/2012 | WO | 00 | 8/21/2013 |