Patent Application
20100068089
The present invention relates to a method for manufacturing an Mg or Al alloy to which a carbon nanomaterial has been added as a reinforcing material, and to a method for using the resulting Mg or Al alloy to manufacture an article formed from a composite metal.
Over the past several years, attention has been directed on a special carbon fiber called a “carbon nanofiber” as a reinforcing material, and methods for utilizing this fiber have been proposed. A carbon nanofiber is a sheet rolled into a cylindrical shape containing carbon atoms arranged in the form of a hexagonal mesh, and having a diameter of 1.0 nm (nanometers) to 150 nm. Carbon nanofibers are also called carbon nanotubes, and shall be generically referred to as carbon nanomaterials hereinafter. Carbon nanomaterials are from several to 100 μm in length.
Since carbon nanomaterials are very small, they tend to aggregate and do not readily mix uniformly with a matrix metal used as a base material.
Accordingly, techniques for mixing a ceramic material or a carbon nanomaterial with a low-melting metallic material that is in a semi-molten state and creating a composite are known, as disclosed in JP 06-238422 A and JP 2004-136363 A.
According to the method for manufacturing a composite metal member disclosed in JP 06-238422 A, a metal material with which a reinforcing material has been admixed is heated and dissolved into a semi-molten state, and then stirred and mixed. The material is then further heated and melted into a liquid state, and stirred and mixed. The material is then returned, to a semi-molten state, again stirred and mixed, and subsequently caused to solidify.
Specifically, the method for manufacturing a composite metal member disclosed in JP 06-238422 A is characterized in that a reinforcing material (a ceramic material) is admixed with a metal material in a semi-molten state.
According to the composite forming method disclosed in JP 2004-136363 A, a melted low-melting metal material is cooled to a semi-molten state having a thixotropic property in which a liquid phase and a solid phase are both present. The low-melting metal material is kneaded in this state with a carbon nanomaterial, and a composite material is obtained. A metal forming machine provided with heating means is used to inject the composite material into a die while maintaining the thixotropic property; and an article formed from composite metal is formed using the die.
Specifically, the composite forming method disclosed in JP 2004-136363 A is characterized in that a reinforcing material (carbon nanomaterial) is kneaded with a low-melting metal material in a semi-molten state.
In either method the metal material is in a semi-molten state; therefore, movement of the added reinforcing material is limited, and aggregation of the reinforcing material can be prevented. As a result, the reinforcing material can be uniformly distributed on the metal material.
However, since the metal material is in a semi-molten state, the added reinforcing material moves at a slow rate, and some time is required before the reinforcing material is moved to all parts of the metal material.
In processes of this type, stirring is generally performed in the presence of argon gas or another inert gas in order to prevent the metal material from oxidizing. Increasing the stirring time heightens the risk that the inert gas will be entrained in the metal material, and leads to a deterioration in the quality of the formed article.
An object of the present invention is to provide a manufacturing method that can reduce the kneading time performed when a reinforcing material is added.
According to one aspect of the present invention, a method for manufacturing a composite metal alloy is provided, comprising a step for preparing an Mg material or an Al material for constituting an alloy base material, at least one type of alloying material to be added to the Mg material or Al material, and a carbon nanomaterial to be added to the Mg material or Al material; a mixing step for admixing the carbon nanomaterial with the Mg material or the Al material and at least one of the alloying materials, and thereby obtaining a mixture; and a dissolving step for dissolving the mixture and remaining materials together.
According to the abovementioned aspect of the invention, the carbon nanomaterial is admixed with the metal material before the dissolving step. In the dissolving step, the carbon nanomaterial moves through the melt while adhering to the metal material. As a result, the metal material can be dissolved while aggregation of the carbon nanomaterial is minimized. In the dissolving step, the metal material is brought to a completely molten state. As long as the material is in a molten state, the carbon nanomaterial can be dispersed in the melt more rapidly than when in a semi-molten state. The dissolving step can be completed in a short time; therefore, the inert gas is entrained in the melt to a lesser extent, and the quality of the article can be improved.
A sintering step for sintering the mixture and obtaining a sintered compact is preferably included between the mixing step and the dissolving step. As long as a powdered mixture is used, scattering will be a problem. According to the present invention, however, as long as the mixture is sintered and made into a sintered compact, scattering can be prevented and safety during storage can be improved. With a sintered compact, furthermore, no concern is presented in regard to movement of the carbon nanomaterial, and aggregation of the carbon nanomaterial can be reliably minimized. Moreover, sintering the mixture and obtaining a sintered compact makes it possible to reduce the surface area. As long as the surface area is small, oxidation and the like can be minimized and the quality can be prevented from deteriorating.
The carbon nanomaterial is preferably composed of a metal-deposited carbon nanomaterial on whose surface a carbide-forming metal including an element that reacts with carbon and generates a compound is caused to adhere. The wettability of the carbon nanomaterial is low; however, the wettability of the carbide-forming element is high. Using a metal-deposited carbon nanomaterial on whose surface this type of carbide-forming element has been caused to adhere allows the wettability of the carbon nanomaterial to be enhanced.
The metal-deposited carbon nanomaterial is preferably obtained by mixing a carbon nanomaterial with a carbide-forming metal, introducing the resulting mixture into a vacuum furnace, and causing the carbide-forming metal to evaporate under a high-temperature vacuum and adhere to the surface of the carbon nanomaterial. The carbide-forming metal generates carbon and a compound, and the compound exhibits a bonding action; therefore, the carbide-forming metal can be securely joined to the carbon nanomaterial.
The carbide-forming metal is preferably Ti or Si. Si and Ti are both metals having melting points allowing vapor deposition to be performed in a vacuum, and have satisfactory wettability with regard to molten matrix metals. Si and Ti are both readily available, and Si in particular is inexpensive; therefore, both enable the method of the present invention to be used more widely, and are preferred.
According to another aspect of the present invention, there is provided a method for manufacturing an article formed from composite metal, comprising a step for directly supplying to a metal forming machine a composite metal alloy, the composite metal alloy being manufactured by a step for preparing an Mg material or an Al material for constituting an alloy base material, at least one type of alloying material to be added to the Mg material or Al material, and a carbon nanomaterial to be added to the Mg material or Al material; a mixing step for admixing the carbon nanomaterial with the Mg material or Al material and at least one of the alloying materials and thereby obtaining a mixture; and a dissolving step for dissolving the mixture and remaining materials together; and a step for bringing the composite metal material into a semi-molten state, and forming the composite metal material in a cavity of a die.
In the method of the present invention according to another aspect, a composite metal material having high wettability is used, and an article formed from composite metal is manufactured. The mechanical and thermal characteristics of the resulting article formed from composite metal can be enhanced. This aspect of the invention is particularly preferred for high-volume production because the composite metal material is directly supplied to a metal forming machine; therefore, production efficiency increases and productivity can be increased.
According to yet another aspect of the present invention, there is provided a method for manufacturing an article formed from composite metal, comprising a step for cooling a composite metal alloy and obtaining a solid composite metal material, the composite metal alloy being manufactured by a step for preparing an Mg material or an Al material for constituting an alloy base material, at least one type of alloying material to be added to the Mg material or Al material, and a carbon nanomaterial to be added to the Mg material or Al material; a mixing step for admixing the carbon nanomaterial with the Mg material or Al material and at least one of the alloying materials and thereby obtaining a mixture; and a dissolving step for dissolving the mixture and remaining materials together; a step for supplying the solid composite metal material to a metal forming machine; a step for heating the solid composite metal material to a semi-molten state; and a step for forming the semi-molten composite metal material in a cavity of a die.
In the method for manufacturing an article formed from composite metal according to this aspect of the invention as well, a composite metal material having high wettability is used, and an article formed from composite metal is manufactured. The mechanical and thermal characteristics of the resulting article formed from composite metal can be enhanced. This aspect of the invention is particularly preferred for low-volume production because the composite metal material is maintained in solid form and supplied to a metal forming machine when necessary; therefore, the degree of latitude in production increases.
Certain preferred embodiments of the present invention will be described in detail below, by way of example only, with reference to the accompanying drawings, in which:
a)-(g) are views showing a mixing stop and a sintering step for processing a base material according to an embodiment of the present invention;
a)-(g) are views showing a mixing step and a sintering step for processing an alloying material according to an embodiment of the present invention;
a)-(f) are views showing a process according to an embodiment of the present invention, starting from a dissolving step to a step where an article formed from a composite metal is obtained;
a)-(f) show a modification of the process starting from the dissolving step to the step where the article formed from composite metal is obtained, as shown in
a)-(f) show another embodiment of the step for obtaining the article formed from composite metal, as shown in
a)-(e) are views showing a step for surface-treating the carbon nanomaterial;
Reference is now made to
MDC1D is a magnesium alloy made from about 9 mass % of Al, 0.5 mass % or less of Mn, and 1.0 mass % or less of Zn as alloying materials; and the remaining approximately 90 mass % of Mg as a base material.
Described below is a method for manufacturing a composite metal alloy having a material that is about 90 mass % Mg (base material); about 9 mass % of Al, 0.5 mass % or less of Mn, and 1.0 mass % of Zn as alloying materials; and a suitable amount of a carbon nanomaterial used as a starting material.
Drawings (a) to (g) of
a): First, a carbon nanomaterial 11 having a fiber diameter (average value) of 10 nm to 200 nm is prepared, and a powdery Mg material 12 having a grain size (average value) of 200 μm is prepared.
b): Premixing is performed. The premixing is performed by introducing suitable amounts of the carbon nanomaterial 11 and the Mg material 12 into a container and stirring the contents.
c): The carbon nanomaterial 11 and the Mg material 12 are thoroughly kneaded by mechanical alloying. Mechanical alloying is a mechanical mixing method in a broad sense, and refers to a “solid-state alloying method using a high-energy attritor or a ball mill” as stipulated in JIS Z2500, or a “method for using a high-energy mill to mechanically stir, mix, and pulverize a variety of types of starting powders; and use a solid-state reaction to achieve an alloyed state,” which is a mechanical alloying method as stipulated by JIS H7004. These methods are universally known); therefore, a description of the apparatus and principles has been omitted.
d): The preceding processes cause the carbon nanomaterial 11 to deaggregate, and yield a mixture 13 in a form in which the Mg material 12 is covered with innumerable particles of the carbon nanomaterial 11. Specifically,
e): A die 15 is positioned on a bottom punch 14 of a sintering device, and the mixture 13 is filled into the die 15. A conduction-heating sintering device or a hot press is suitably used for the sintering device.
f): A top punch 16 is inserted into the die 15, and the mixture 13 is compacted, into a solid, while the sintering temperature of the Mg (500° C.) is maintained.
g): An Mg sintered compact 17 including the carbon nanomaterial can thereby be obtained.
e) and (f) are sintering steps.
(a) to (g) of
a): The carbon nanomaterial 11 having a fiber diameter (average value) of 10 nm to 200 nm is prepared, powdery Al—Mn alloying material 12B having a grain size (average value) of 200 μm is prepared as an alloying material, and powdery Zn material 12C having a grain size (average value) of 200 μm is prepared as an alloying material. Mn-series aluminum having 90 mass % of Al and 10 mass % of Mn is suitably used for the Al—Mn alloying material 12B.
b): Premixing is performed using a combination of the carbon nanomaterial 11 and the Al—Mn alloying material 12B. Premixing is performed using a combination of the carbon nanomaterial 11 and the Zn material 12C.
c): The carbon nanomaterial 11 and the Al—Mn alloying material 12B are thoroughly kneaded by mechanical alloying. The carbon nanomaterial 11 and the Zn material 12C are thoroughly kneaded by mechanical alloying.
d): The preceding processes cause the carbon nanomaterial 11 to deaggregate, and yield a mixture 13B or 13C in a form in which the Al—Mn material 12B or the Zn material 12C is covered with innumerable particles of the carbon nanomaterial 11. Specifically,
e): The die 15 is positioned on the bottom punch 14 of a sintering device, and the mixture 13B or the mixture 13C is filled into the die 15.
f): The top punch 16 is inserted into the die 15, and the mixture 13 is compacted into a solid while the sintering temperature of Al—Mn (500° C.) or the sintering temperature of Zn (300° C.) is maintained.
g): An Al—Mn sintered compact 17B including the carbon nanomaterial, or a Zn sintered compact 17C including the carbon nanomaterial, can thereby be obtained.
e) and (f) show the sintering step.
(a) to (f) of
The Mg-sintered compact 17, the Al—Mn-sintered compact 17B, and the Zn-sintered compact 17C shown in
As shown, in
As shown in
In
As shown in
Alternatively, as shown in
The composite metal formed article 35 is additionally hot-rolled and hot-extruded, whereby the metallic texture is made finer, and the mechanical strength and other qualities can be improved.
As shown in
The direct method offers high productivity, and makes it possible to manufacture carbon nano-composite metal formed articles at low cost; however, the direct method does not facilitate such actions as the changing of materials, and is accordingly suited to low mix/high volume production.
The indirect method is disadvantageous from the standpoint of production capacity, but offers a high degree of latitude in regard to production, and is preferred for high mix/low volume production.
Drawings (a) to (f) of
a) shows the preparation of the Mg-sintered compact 17 that includes a carbon nanomaterial, an Al—Mn alloy ingot 37 used as an alloying material, and a Zn ingot 38 used as an alloying material. The ingots 37, 38 are simple cast articles made of alloying materials; therefore, the method for manufacturing the ingots has been omitted.
(b) to (f) of
(a) to (f) of
a) shows the preparation of the mixture 13 obtained in the steps shown in
As shown in
As shown in
As shown in
As shown in
Alternatively, as shown in
The improved technique involving the use of carbon nanomaterial 11 shown in
(a) to (e) of
a): a carbon nanomaterial 41 is prepared in an amount of, e.g., 10 g. The carbon nanomaterial 41 may be the same as the carbon nanomaterial 11 shown in
b): a Si powder 42 is prepared as a carbide-forming element in an amount of, e.g., 1 g.
c): the carbon nanomaterial 41 and the Si powder 42 are placed in a mortar 43, and mixed for 15 to 30 minutes using a pestle 44.
d): a resulting mixture 45 is introduced into an aluminum container 46 that is then covered using an aluminum lid 47. An unsealed lid is used as the aluminum lid 47, whereby air is allowed to pass in and out of the container 46.
e): a vacuum furnace 50 having a sealed furnace 51, heating means 52 for heating the inside of the furnace 51, a stand 53 on which the container 46 is placed, and a vacuum pump 54 for evacuating the interior of the furnace 51 are prepared. The container 46 is introduced into the vacuum furnace 50.
The conditions under which heating and pressurization are performed in the vacuum furnace 50 are shown by
Taken all together,
At a degree of vacuum of 6×10−3 Pa, the furnace temperature is raised from room temperature to 300° C. over five hours.
At a degree of vacuum of 5.3×10−3 to 2.1×102 Pa, the furnace temperature is raised from 300° C. to 1400° C. over four hours.
Conditions are maintained for ten hours at 1400° C. and a degree of vacuum of 2.1×10−2 Pa.
The melting point of Si is 1427° C.; therefore, a temperature just below the melting point (1350° C. to 1400° C.) is maintained, and the Si is held in a state of saturated vapor pressure at this temperature. At 1350° C. the saturated vapor pressure is about 1.3×103 Pa, and at 1400° C. the saturated vapor pressure is about 2.1×10−2 Pa. These approximate degrees of vacuum can be readily attained using a vacuum furnace, and therefore a processing temperature of 1350° C. to 1400° C. is suitable. However, the evaporation rate at 1350° C. is low, and the evaporation rate at 1400° C. is high; therefore, the processing temperature in the present embodiment is 1400° C.
SiC (silicon carbide), which is a compound of Si and carbon, will be described below. The standard free energy of formation of SiC is −39.6 kJ/mol at 1400° C., and since this condition can be met, Si vapor is thought to react with the carbon in the carbon nanomaterial and form SiC.
Therefore, should the mixture be introduced into a semi-sealed container, and the Si powder caused to evaporate, bubble stirring will occur, and Si microparticles can be caused to adhere to the carbon nanomaterial.
The conditions are maintained for long period of time; i.e., 10 hours, in order for stirring and reacting to be adequately performed. It shall be apparent that the time over which the conditions are maintained may be increased or decreased according to the mixture ratio, the throughput, and other conditions.
The heating means shuts down after 19 hours; however, furnace cooling is performed while a degree of vacuum of 1.1×10−3 Pa is maintained. Furnace cooling is a method for gradually cooling the manufactured articles.
A metal-deposited carbon nanomaterial 55 is composed of the deaggregated carbon nanomaterial 41, and numerous Si microparticles 56 that have uniformly adhered to the surface of the carbon nanomaterial 41. As previously described, the Si microparticles 56 are formed by crystallizing Si, which is an element that reacts with carbon and generates a chemical compound.
It is important that the Si microparticles 56 adhere to the carbon nanomaterial 41 with the carbide SiC interposed therebetween. Since the carbon nanomaterial 41 has poor wettability, a concern is presented that the contact strength would be inadequate if the Si microparticles were used alone. In this regard, causing Si microparticles to adhere to the surface of the carbon nanomaterial 41 enables a SiC reation layer to form at the interface, and the Si microparticles 56 can be securely adhered to the carbon nanomaterial 41.
The previously mentioned metal-deposited carbon nanomaterial 55 may be used in place of the carbon nanomaterial 11 shown in
In the present embodiment, even if the Si used as a carbide-forming metal (an element that reacts with metallic carbon and generates a compound) is substituted for Ti, the same effect in terms of an improvement in mechanical strength can be obtained, although a detailed description thereof is omitted. Furthermore, in addition to Si and Ti, Zr (zirconium) and V (vanadium) can be employed for use in forming a carbide.
However, Si and Ti are both readily available, and Si in particular is inexpensive; therefore, both enable the method of the present invention to be used more widely, and are preferred.
In addition to Mg and Mg alloys having a melting point of about 650° C., Al and Al alloys having a melting point of 660° C. are preferred for use as the base material metallic material.
Mg, Al, and alloys formed from each of these elements are light-weight metals, and by including a carbon nanomaterial in these metals and increasing mechanical strength, it becomes possible to provide a light-weight structural material of exceptional strength, thermal conductivity and abrasion resistance.
Based on the above description, the present invention can be summarized in the following manner.
According to a first aspect of the present invention, there is provided a method for manufacturing a composite metal alloy, comprising a material preparation step for preparing an Mg material or an Al material for constituting an alloy base material, at least one type of alloying material to be added to the Mg material or Al material, and a carbon nanomaterial to be added to the Mg material or Al material (see
According to the first aspect of the present invention, a sintering step for sintering the mixture and obtaining a sintered compact is additionally included between the mixing step and the dissolving step (see
According to the first aspect of the present invention, as shown in
According to the first aspect of the present invention, as shown in
According to the first aspect of the present invention, the carbide-forming metal is Ti or Si.
According to a second aspect of the present invention, an article formed from composite metal is manufactured by directly supplying to a metal forming machine the composite metal alloy manufactured according to
According to a third aspect of the present invention, an article formed from composite metal is manufactured through a step for obtaining a solid composite metal material by cooling the composite metal alloy manufactured according to
A step for stirring the composite metal alloy while the alloy is maintained in a semi-molten state may be added after the invention according to the first aspect and before the invention according to the second or third aspect. Adding this step allows even greater dispersion of the carbon nanomaterial to occur.
The [type of] alloying material is determined according to the additive elements required for the desired composite metal alloy, and thus is not limited to Al—Mn and Zn.
The present invention is an Mg alloy or an Al alloy for use in injection molding, and is preferred for use in a method for manufacturing Mg alloy or Al alloy to which a carbon nanomaterial is added.
Obviously, various minor changes and modifications of the present invention are possible in light of the above teaching. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.
