JP2007302997A - Method of producing metallic material, and metallic material - Google Patents
Method of producing metallic material, and metallic material Download PDFInfo
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- JP2007302997A JP2007302997A JP2007102132A JP2007102132A JP2007302997A JP 2007302997 A JP2007302997 A JP 2007302997A JP 2007102132 A JP2007102132 A JP 2007102132A JP 2007102132 A JP2007102132 A JP 2007102132A JP 2007302997 A JP2007302997 A JP 2007302997A
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Abstract
Description
本発明は金属材の製造方法に関し、特に金属材に添加材を混入することによって硬度を上昇させた金属材の製造方法およびこの製造方法によって製造された金属材に関する。 The present invention relates to a method for manufacturing a metal material, and more particularly to a method for manufacturing a metal material whose hardness is increased by mixing an additive into the metal material, and a metal material manufactured by this manufacturing method.
従来、金属材に大きさが数〜数百ｎｍ程度の添加材を混入させることによって、金属材を強化する技術が提案されている。例えば、特許文献１には、Ｔｉ合金を溶解させ、溶解金属中にフラーレン（Fullerene）またはカーボンナノチューブ（Carbon Nanotube；ＣＮＴ）を混入させた金属材をゴルフクラブヘッドのフェース部に用い、フェース部の強度を高めて、その薄肉化を可能とした技術が記載されている。また、非特許文献１には、粉末状にしたＡｌ試料またはＴｉ試料とカーボンナノチューブ粉末とを三軸振動式ミルによって混合し、ホットプレスを行った後に熱間押出することによって、複合材料を得ることが記載されている。
しかしながら、上記のような添加材を混入させた金属材料に対しては、産業界からさらなる高強度化の要請がある。ところが、上記の手法により添加材を混入された金属材の機械的特性は、添加材となるフラーレン等の特性から期待されるほど向上せず、さらなる改善が望まれている。 However, there is a demand for higher strength from the industry for metal materials mixed with the above-described additives. However, the mechanical properties of the metal material mixed with the additive by the above-described method are not improved as expected from the properties of fullerene or the like as the additive, and further improvement is desired.
本発明は、斯かる実情に鑑み、添加材を混入することによって金属材の硬度を上昇させる金属材の製造方法において、金属材の硬度を一層向上させることができる金属材の製造方法およびこの製造方法によって硬度を上昇された金属材を提供しようとするものである。 In view of such circumstances, the present invention provides a method for producing a metal material that can further improve the hardness of the metal material and a method for producing the same in a method for producing a metal material that increases the hardness of the metal material by mixing an additive. An object of the present invention is to provide a metal material whose hardness is increased by the method.
本発明は、最小部分の一次粒径が０．５μｍ未満である粒子からなる添加材を金属材の表面部位に供給し、表面部位に棒状の回転ツールを当接させつつ回転させて、表面部位に添加材を混入させて硬度を上昇させた金属材の製造方法である。 In the present invention, an additive comprising particles having a primary particle size of less than 0.5 μm is supplied to the surface portion of the metal material, and the surface portion is rotated by bringing a rod-shaped rotary tool into contact with the surface portion. This is a method for producing a metal material in which the additive material is mixed in to increase the hardness.
この構成によれば、最小部分の一次粒径が０．５μｍ未満である微細な粒子を添加材として金属材の表面部位に供給し、粒子を供給した表面部位に棒状の回転ツールを当接させつつ回転させる摩擦攪拌処理（Friction Stir Processing；ＦＳＰ）を施すため、金属材中に添加材をより均一に混入することができる。また、摩擦攪拌処理における動的再結晶により、金属材の結晶粒が微細化される。このため、金属材の硬度を一層上昇させることができる。 According to this configuration, fine particles having a minimum primary particle size of less than 0.5 μm are supplied to the surface portion of the metal material as an additive, and the rod-shaped rotary tool is brought into contact with the surface portion to which the particles are supplied. Since the friction stir processing (FSP) that rotates while rotating is performed, the additive can be more uniformly mixed in the metal material. Moreover, the crystal grain of a metal material is refined | miniaturized by the dynamic recrystallization in a friction stirring process. For this reason, the hardness of a metal material can be raised further.
なお、本発明における粒子の「最小部分の…粒径」とは、粒子の直径を任意の部位で測定した場合における最小の径を意味する。例えば、外径が２５ｎｍであり長さが２５０ｎｍの円筒状であるカーボンナノチューブの場合、粒径は２５ｎｍとなる。また、本発明における粒子の「一次粒径」とは、それぞれの粒子の粒ひとつひとつ(一次粒子)の径を意味し、「一次粒径が０．５μｍ未満」とは、一次粒子の径が０．５μｍ未満であれば良く、一次粒子同士が互いの凝集力によって凝集した二次粒子等、高次の凝集構造を取る物の径が０．５μｍ以上となる物をも含むものとする。 The “minimum portion... Particle diameter” of the particles in the present invention means the minimum diameter when the diameter of the particles is measured at an arbitrary site. For example, in the case of a carbon nanotube having an outer diameter of 25 nm and a length of 250 nm, the particle diameter is 25 nm. Further, the “primary particle size” of the particles in the present invention means the diameter of each particle (primary particle), and “the primary particle size is less than 0.5 μm” means that the primary particle size is 0. It may be less than 5 μm, and includes particles whose primary particle size is 0.5 μm or more, such as secondary particles in which primary particles are aggregated by mutual cohesive force.
この場合、添加材は炭素を含むことが、金属材の硬度を上昇させるために好適である。 In this case, it is preferable that the additive contains carbon in order to increase the hardness of the metal material.
また、添加材はフラーレンを含むことが、金属材の硬度を上昇させるために一層好適である。 Further, it is more preferable that the additive contains fullerene in order to increase the hardness of the metal material.
加えて、粒子はＣ６０を含むことが、金属材の硬度を上昇させるためにさらに好適である。 In addition, it is more preferable that the particles contain C 60 in order to increase the hardness of the metal material.
一方、本発明の別の態様は、本発明の金属材の製造方法によって硬度を上昇された金属材である。この構成によれば、金属材は、最小部分の一次粒径が０．５μｍ未満である微細な粒子からなる添加材を摩擦攪拌処理によって表面部位に混入されており、添加材が金属材中に均一に混入され、かつ金属材の結晶粒が摩擦攪拌処理によって微細化されているため、その硬度を一層上昇された物とできる。 On the other hand, another aspect of the present invention is a metal material whose hardness has been increased by the method for producing a metal material of the present invention. According to this configuration, the metal material is mixed with an additive material composed of fine particles having a primary particle size of less than 0.5 μm at the minimum portion in the surface portion by friction stir processing, and the additive material is contained in the metal material. Since the metal particles are uniformly mixed and the crystal grains of the metal material are refined by the friction stir processing, the hardness can be further increased.
本発明の金属材の製造方法によれば、金属材の硬度を一層上昇させることができる。また、本発明の金属材は、その強度を一層上昇された物とできる。 According to the method for producing a metal material of the present invention, the hardness of the metal material can be further increased. In addition, the metal material of the present invention can be made to have a further increased strength.
以下、本発明の実施の形態について添付図面を参照して説明する。 Embodiments of the present invention will be described below with reference to the accompanying drawings.
以下、金属材の製造方法について説明する。図１は、本発明に係る金属材の製造方法の一実施形態を示す斜視図である。図１（ａ）および（ｂ）に示すように、本実施形態の金属材の製造方法では、金属材１０の表面部位に供給した添加材１４を、回転ツール１６を用いた摩擦攪拌処理によって金属材１０中に混入させる。金属材１０としては、例えば、Ａｌ材、Ｆｅ材、Ｍｇ材を適用することができる。 Hereinafter, the manufacturing method of a metal material is demonstrated. FIG. 1 is a perspective view showing an embodiment of a method for producing a metal material according to the present invention. As shown in FIGS. 1A and 1B, in the method for manufacturing a metal material according to the present embodiment, the additive 14 supplied to the surface portion of the metal material 10 is made into a metal by a friction stirring process using a rotary tool 16. It mixes in the material 10. As the metal material 10, for example, an Al material, an Fe material, or an Mg material can be applied.
本実施形態では、まず図１（ａ）に示すように、金属材１０の表面部位に溝１２を形成し、その溝に添加材１４を充填する。添加材１４は、最小部分の一次粒径が０．５μｍ未満である粒子である。より具体的には、添加材１４として、最小部分の一次粒径が０．５μｍ未満であって、炭素を含む黒鉛粉末やＳｉＣ粉末等のシリコンカーバイドや金属カーバイドを適用することができる。より好ましくは、添加材１４として、カーボンナノチューブ（炭素繊維または炭素ファイバーと呼ばれることもある）を適用することができ、カーボンナノチューブとしては、外径が２ｎｍ以下の炭素原子からなる単層の円筒である単層カーボンナノチューブ（SingleWalled Carbon NanoTube；ＳＷＣＮＴ）、炭素原子からなる二層の円筒である二層カーボンナノチューブ（DoubleWalled Carbon NanoTube；ＤＷＣＮＴ）、および外径が２０〜２５ｎｍであり長さが２５０ｎｍ以下の炭素原子からなる複数の円筒が入れ子状に多層をなしている多層カーボンナノチューブ（MultiWalled Carbon NanoTube；ＭＷＣＮＴ）からなる群から選択される１または２種以上を適用することができる。さらに好ましくは、添加材１４として、炭素原子が球状をなしているＣ６０、Ｃ７０、Ｃ７６、Ｃ７８、Ｃ８２およびＣ８４からなる群から選択される１または２種以上のフラーレン（炭素クラスターまたは球状炭素分子と呼ばれることもある）を適用することができ、最も好ましくは、添加材１４として、炭素原子が直径０．７ｎｍ以下のサッカーボール状の球形をなしているＣ６０を適用することができる。 In this embodiment, first, as shown in FIG. 1A, the groove 12 is formed in the surface portion of the metal material 10, and the additive material 14 is filled in the groove. The additive 14 is a particle having a primary particle size of a minimum portion of less than 0.5 μm. More specifically, as the additive 14, silicon carbide or metal carbide such as graphite powder or SiC powder containing carbon having a minimum primary particle size of less than 0.5 μm can be applied. More preferably, carbon nanotubes (sometimes referred to as carbon fibers or carbon fibers) can be applied as the additive 14, and the carbon nanotubes are single-layer cylinders having carbon atoms with an outer diameter of 2 nm or less. A single-walled carbon nanotube (SWCNT), a double-walled carbon nanotube (DWCNT) that is a double-layered cylinder made of carbon atoms, and an outer diameter of 20 to 25 nm and a length of 250 nm or less One or more selected from the group consisting of multiwalled carbon nanotubes (MWCNTs) in which a plurality of cylinders made of carbon atoms are nested in multiple layers can be applied. More preferably, the additive 14 is one or more fullerenes (carbons) selected from the group consisting of C 60 , C 70 , C 76 , C 78 , C 82 and C 84 in which the carbon atoms are spherical. Most preferably, as the additive 14, C 60 having a soccer ball-like sphere shape with a carbon atom diameter of 0.7 nm or less is applied as the additive 14. be able to.
次に、図１（ｂ）に示すような回転ツール１６を用意する。回転ツール１６は、略円筒状をなし、先端に本体より小径の略円柱状のプローブ１８を備えている。なお、プローブは必ず必要なものではなく、場合によってはプローブを有しない略円筒状の回転ツールを用いても良い。回転ツール１６の材質は、例えば、ＪＩＳに規格されているＳＫＤ６１鋼等の工具鋼や、タングステンカーバイト（ＷＣ）、コバルト（Ｃｏ）からなる超硬合金、またはＳｉ３Ｎ４等のセラミックスからなるものとすることができる。図１（ｂ）に示すように、金属材１０の添加材１４を充填した溝１２上に、回転ツール１６のプローブ１８を当接させつつ回転させ、さらに溝１２の長手方向に沿って回転ツール１６を移動させることにより、溝１２に充填した添加材１４を回転ツール１６によって攪拌させ、添加材１４を金属材１０中に混入させることができる。なお、添加材を十分に混入させるため、回転ツール１６を、添加材１４を充填した溝１２上で回転させつつ往復動させることもできる。あるいは、回転ツール１６を移動させずに同じ場所で回転させ続けることによっても、添加材１４を金属材１０中に混入させることができる。この場合、添加材１４を連続した複数箇所で混入させることにより、金属材１０上の広い領域を強化することができる。 Next, a rotating tool 16 as shown in FIG. The rotary tool 16 has a substantially cylindrical shape, and includes a substantially cylindrical probe 18 having a smaller diameter than the main body at the tip. Note that a probe is not necessarily required, and in some cases, a substantially cylindrical rotating tool having no probe may be used. The material of the rotary tool 16 is made of, for example, tool steel such as SKD61 steel standardized by JIS, cemented carbide made of tungsten carbide (WC) or cobalt (Co), or ceramics such as Si 3 N 4. Can be. As shown in FIG. 1 (b), the probe 18 of the rotary tool 16 is rotated on the groove 12 filled with the additive 14 of the metal material 10, and further rotated along the longitudinal direction of the groove 12. By moving 16, the additive 14 filled in the groove 12 can be stirred by the rotary tool 16, and the additive 14 can be mixed into the metal material 10. In order to sufficiently mix the additive, the rotary tool 16 can be reciprocated while rotating on the groove 12 filled with the additive 14. Alternatively, the additive material 14 can be mixed into the metal material 10 by continuing to rotate the same at the same place without moving the rotary tool 16. In this case, a wide region on the metal material 10 can be strengthened by mixing the additive material 14 at a plurality of continuous locations.
以下、本実施形態の金属材の製造方法の作用効果について説明する。本実施形態においては、金属材１０の表面部位に最小部分の一次粒径が０．５μｍ未満の粒子からなる添加材１４を供給し、添加材１４を摩擦攪拌処理により金属材１０中に混入させる。このため、カーボンナノチューブ等の金属材１０中に均一に分散しにくい物質を添加材１４とした場合であっても、添加材１４を金属材１０中に均一に混入させることができる。さらに、摩擦攪拌処理における動的再結晶により、金属材１０の結晶粒が微細化される。このため、金属材１０の強度を一層向上させることができる。 Hereinafter, the effect of the manufacturing method of the metal material of this embodiment is demonstrated. In the present embodiment, the additive material 14 made of particles having a primary particle size of less than 0.5 μm is supplied to the surface portion of the metal material 10, and the additive material 14 is mixed into the metal material 10 by friction stir processing. . For this reason, even when a material that is difficult to disperse uniformly in the metal material 10 such as carbon nanotubes is used as the additive material 14, the additive material 14 can be uniformly mixed in the metal material 10. Furthermore, the crystal grains of the metal material 10 are refined by dynamic recrystallization in the friction stir processing. For this reason, the strength of the metal material 10 can be further improved.
尚、本発明の金属材の製造方法は、上記した実施の形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。例えば、金属材１０の表面部位に添加材１４を供給する方法としては、図１（ａ）に示す方法の他、ノズルから添加材１４を金属材１０の表面に噴射する方法や、回転ツール１６に設けた噴出孔から添加材１４を金属材１０の表面に噴出する方法を用いることができる。また、回転ツール１６を構成する材料に添加材１４を含有させておき、回転ツール１６を金属材１０に当接させつつ回転させることにより、回転ツール１６を磨耗させつつ金属材１０に添加材を供給することができる。この方法では、金属材１０に添加材１４をより均一に供給することができる。あるいは、添加材１４を含有させた粘着テープを金属材１０に貼付し、当該粘着テープ上に回転ツール１６を当接させつつ回転させることによっても、金属材１０に添加材を供給することができる。この方法では、金属材１０上の強化したい部位に、一層容易に添加材１４を供給することができる。 In addition, the manufacturing method of the metal material of this invention is not limited to above-described embodiment, Of course, a various change can be added in the range which does not deviate from the summary of this invention. For example, as a method of supplying the additive material 14 to the surface portion of the metal material 10, in addition to the method shown in FIG. 1A, a method of spraying the additive material 14 from the nozzle onto the surface of the metal material 10, A method of jetting the additive 14 to the surface of the metal material 10 from the jet holes provided in the metal plate 10 can be used. Further, the additive 14 is contained in the material constituting the rotary tool 16, and the rotary tool 16 is rotated while being in contact with the metal material 10, whereby the additive is added to the metal material 10 while the rotary tool 16 is worn. Can be supplied. In this method, the additive 14 can be more uniformly supplied to the metal material 10. Alternatively, the additive material can be supplied to the metal material 10 by applying an adhesive tape containing the additive material 14 to the metal material 10 and rotating the adhesive tool 16 while abutting the rotating tool 16 on the adhesive tape. . In this method, the additive 14 can be more easily supplied to the portion on the metal material 10 to be strengthened.
さらに、本発明の金属材の製造方法では、２つの金属材同士を接合部において突き合わせるか、あるいは重ね合わるかした後に、接合部に添加材を供給し、回転ツールを接合部に挿入して回転させる摩擦攪拌接合（Friction Stir Welding；ＦＳＷ）を行うことによっても、接合部周辺の金属材の硬度を上昇させることができる。 Furthermore, in the method for producing a metal material of the present invention, after two metal materials are abutted or overlapped at the joint, an additive is supplied to the joint, and a rotary tool is inserted into the joint. The hardness of the metal material around the joint can also be increased by performing friction stir welding (FSW).
次に、本発明者が本発明の金属材の製造方法により、実際に金属材の硬度を上昇させた実験結果を説明する。 Next, an experimental result in which the inventor actually raised the hardness of the metal material by the method for producing the metal material of the present invention will be described.
実験例１
厚さ６ｍｍのＡＺ３１材（Ａｌを３％、Ｚｎを１％含有するＭｇ合金）を用意した。用意したＡＺ３１材の表面に、図１（ａ）に示すような幅１ｍｍ、深さ２ｍｍの溝１２を形成した。形成した溝１２に、図２に示すような炭素原子２４が直径０．７ｎｍ以下のサッカーボール状の球形をなしているＣ６０（２２）を添加材１４として充填した。図３に示すようにＣ６０の集合体２６は、直径１０〜５０μｍ程度の粒径となる。Ｃ６０の充填後、図１（ｂ）に示すように、直径４ｍｍ、長さ１．８ｍｍのプローブ１８を有し、本体の直径１２ｍｍのＳＫＤ６１からなる回転ツール１６によって摩擦攪拌処理を行った。回転ツールの回転速度は１５００ｒｐｍとし、回転ツールの移動速度は５０ｍｍ／ｍｉｎとした。
Experimental example 1
An AZ31 material (Mg alloy containing 3% Al and 1% Zn) having a thickness of 6 mm was prepared. A groove 12 having a width of 1 mm and a depth of 2 mm as shown in FIG. 1A was formed on the surface of the prepared AZ31 material. The formed grooves 12 were filled with C 60 (22) having carbon balls 24 having a diameter of 0.7 nm or less as shown in FIG. As shown in FIG. 3, the C 60 aggregate 26 has a diameter of about 10 to 50 μm. After filling of the C 60, as shown in FIG. 1 (b), has a diameter 4 mm, length 1.8mm probe 18, was subjected to friction stir processing by the rotational tool 16 consisting of SKD61 having a diameter of 12mm of the body. The rotating speed of the rotating tool was 1500 rpm, and the moving speed of the rotating tool was 50 mm / min.
図４は本実験例の摩擦攪拌処理を施した部位の状態を示す縦断面図であり、図５はＣ６０を含む部位の状態を示す図である。図４および５により、回転ツール１６によって攪拌された金属材１０の表面に近い部位Ａおよび表面から深い部位Ｂにおいては、金属材１０中に白く見えるＣ６０が混入していることが判る。一方、図４により、金属材１０の表面から境界２８より深い部位Ｃにおいては、金属材１０中にＣ６０が混入していないことが判る。 Figure 4 is a longitudinal sectional view showing a state of a portion subjected to friction stir processing of the present experimental example, FIG. 5 is a diagram showing a state of a portion including a C 60. 4 and 5, it can be seen that C 60 that appears white in the metal material 10 is mixed in the portion A near the surface of the metal material 10 and the portion B deep from the surface stirred by the rotary tool 16. On the other hand, FIG. 4, the deeper portion C than the boundary 28 from the surface of the metal member 10, it is understood that the C 60 in the metal member 10 is not contaminated.
図６は本実験例のＣ６０を含まない部位の結晶粒を示す図であり、図７はＣ６０を含む部位の結晶粒を示す図であり、図８はＣ６０を含む部位と含まない部位との境界を示す図である。図６および８に示すように、Ｃ６０が混入していない部位Ｃにおける金属材１０の結晶粒径は２０μｍ以上と大きいのに対し、図７および８に示すように、Ｃ６０が混入している部位Ｂにおける結晶粒径は５００ｎｍ以下と微細化されていることが判る。 Figure 6 is a diagram showing the crystal grains of the site without the C 60 of this Example, Figure 7 is a diagram showing a crystal grain of a portion including a C 60, FIG. 8 does not include a site containing the C 60 It is a figure which shows the boundary with a site | part. As shown in FIGS. 6 and 8, the crystal grain size of the metal material 10 in the portion C where C 60 is not mixed is as large as 20 μm or more, whereas as shown in FIGS. 7 and 8, C 60 is mixed. It can be seen that the crystal grain size in the portion B is reduced to 500 nm or less.
図９は、図４における各測定点の組成を示す表であり、各数値は原子％を示す。図９に示すように、部位Ｃにおいては炭素Ｃの含有量がＡＺ３１母材と大きな差がないのに対し、部位ＡおよびＢにおいては、炭素Ｃが多く含有されていることが判る。 FIG. 9 is a table showing the composition of each measurement point in FIG. 4, and each numerical value represents atomic%. As shown in FIG. 9, it can be seen that the carbon content in the part C is not significantly different from that of the AZ31 base material, whereas the carbons are contained in the parts A and B in a large amount.
上記Ｃ６０を混入させて摩擦攪拌処理を行ったＡＺ３１材と、Ｃ６０を混入させずに摩擦攪拌処理を行ったＡＺ３１材と、摩擦攪拌処理を行っていないＡＺ３１母材について硬度試験を行った。図１０に示すようにＣ６０を混入させて摩擦攪拌処理を行ったＡＺ３１材は測定痕３０が小さいのに対し、図１１に示すようにＣ６０を混入させずに摩擦攪拌処理を行ったＡＺ３１材は測定痕３０が大きいことが判る。さらに、図１２に示すように、摩擦攪拌処理を行っていないＡＺ３１母材の微小硬度が４０〜５０Ｈｖであり、Ｃ６０を混入させずに摩擦攪拌処理を行ったＡＺ３１材の微小硬度が５０〜６０Ｈｖであるのに対し、Ｃ６０を混入させて摩擦攪拌処理を行ったＡＺ３１材のＣ６０が存在する領域（ナノ複合層）の微小硬度は最大で１２８Ｈｖと硬度が大幅に向上していることが判る。 The a C 60 AZ31 material subjected to friction stir processing is mixed, it was performed and AZ31 material friction stir process is performed without mixing the C 60, a hardness test for AZ31 base material not subjected to friction stir processing . FIG whereas AZ31 material measurement marks 30 subjected to friction stir processing by mixing C 60 is small as shown in 10 and subjected to friction stir processing without mixing the C 60 as shown in FIG. 11 AZ31 It can be seen that the material has a large measurement mark 30. Furthermore, as shown in FIG. 12, the micro hardness of the AZ31 base material not subjected to the friction stir processing is 40 to 50 Hv, and the micro hardness of the AZ 31 material subjected to the friction stir processing without mixing C 60 is 50 to 50 In contrast to 60 Hv, the microhardness of the region (nanocomposite layer) where C 60 of the AZ31 material mixed with C 60 and subjected to friction stir processing is 128 Hv is greatly improved. I understand.
上記と同様にして、添加材１４として粒径０．５μｍ未満の黒鉛粉末とＳｉＣ粉末を用い、摩擦攪拌処理を行った。図１３は本実験例におけるＣ６０を含むＡＺ３１材の結晶粒を示す図であり、図１４は黒鉛粉末を含むＡＺ３１材の結晶粒を示す図であり、図１５はＳｉＣを含むＡＺ３１材の結晶粒を示す図である。また、図１６は摩擦攪拌処理を施していないＡＺ３１材の結晶粒を示す図であり、図１７は摩擦攪拌処理を施したＡＺ３１材の結晶粒を示す図である。図１６に示すように、摩擦攪拌処理を施していないＡＺ３１材の結晶粒径は平均で７９．１μｍと大きく、微小硬度も４６Ｈｖと低い。図１７に示すように、摩擦攪拌処理を施すと結晶粒径は平均で１２．９μｍに微細化されるが、微小硬度は５９Ｈｖまでしか向上しない。一方、図１４に示すように、黒鉛粉末を混入させて摩擦攪拌処理を行った場合は、結晶粒径は平均２．５μｍまで微細化され、微小硬度は６４Ｈｖまで向上することが判る。また図１５に示すように、ＳｉＣを混入させて摩擦攪拌処理を行った場合は、結晶粒径は平均６．０μｍまで微細化され、微小硬度は７４Ｈｖまで向上することが判る。しかし、図１３に示すように、Ｃ６０を混入させて摩擦攪拌処理を行った場合に、結晶粒径は最も微細化され、微小硬度は１２８Ｈｖと大幅に向上することが判る。 In the same manner as described above, a friction stir treatment was performed using graphite powder and SiC powder having a particle size of less than 0.5 μm as additive 14. Figure 13 is a diagram showing the crystal grains of AZ31 material containing C 60 in this experimental example, FIG 14 is a diagram showing the crystal grains of AZ31 material containing graphite powder, 15 crystals of AZ31 material containing SiC It is a figure which shows a grain. FIG. 16 is a diagram showing crystal grains of the AZ31 material not subjected to the friction stir processing, and FIG. 17 is a diagram showing crystal grains of the AZ31 material subjected to the friction stir processing. As shown in FIG. 16, the crystal grain size of the AZ31 material not subjected to the friction stir processing is as large as 79.1 μm on average, and the micro hardness is as low as 46 Hv. As shown in FIG. 17, when the friction stir processing is performed, the crystal grain size is refined to 12.9 μm on average, but the micro hardness is improved only to 59 Hv. On the other hand, as shown in FIG. 14, when the graphite powder is mixed and the friction stirring process is performed, the crystal grain size is refined to an average of 2.5 μm, and the microhardness is improved to 64 Hv. Further, as shown in FIG. 15, when the friction stir processing is performed with SiC mixed, the crystal grain size is refined to an average of 6.0 μm, and the micro hardness is improved to 74 Hv. However, as shown in FIG. 13, it can be seen that when the friction stir processing is performed with C 60 mixed, the crystal grain size is most refined and the micro hardness is greatly improved to 128 Hv.
実験例２
厚さ６ｍｍのＡＺ３１材（Ａｌを３％、Ｚｎを１％含有するＭｇ合金）を用意した。用意したＡＺ３１材の表面に、図１（ａ）に示すような幅１ｍｍ、深さ２ｍｍの溝１２を形成した。形成した溝１２に、図１８に示すような外径が２０〜２５ｎｍであり長さが２５０ｎｍ以下の炭素原子からなる複数の円筒が入れ子状に多層をなしている多層カーボンナノチューブ３２を添加材１４として充填した。多層カーボンナノチューブ３２の充填後、図１（ｂ）に示すように、直径４ｍｍ、長さ１．８ｍｍのプローブ１８を有し、本体の直径１２ｍｍのＳＫＤ６１からなる回転ツール１６によって摩擦攪拌処理を行った。回転ツールの回転速度は１５００ｒｐｍとし、回転ツール１６の移動速度は１００ｍｍ／ｍｍ，５０ｍｍ／ｍｉｎおよび２５ｍｍ／ｍｉｎで行った。
Experimental example 2
An AZ31 material (Mg alloy containing 3% Al and 1% Zn) having a thickness of 6 mm was prepared. A groove 12 having a width of 1 mm and a depth of 2 mm as shown in FIG. 1A was formed on the surface of the prepared AZ31 material. A multi-walled carbon nanotube 32 in which a plurality of cylinders made of carbon atoms having an outer diameter of 20 to 25 nm and a length of 250 nm or less as shown in FIG. As filled. After filling the multi-walled carbon nanotubes 32, as shown in FIG. 1 (b), the friction stir processing is performed by the rotary tool 16 having the probe 18 having a diameter of 4 mm and a length of 1.8 mm and comprising the SKD 61 having a diameter of 12 mm. It was. The rotating speed of the rotating tool was 1500 rpm, and the moving speed of the rotating tool 16 was 100 mm / mm, 50 mm / min, and 25 mm / min.
図１９〜２１は、それぞれ本実験例において回転ツール１６の移動速度１００ｍｍ／ｍｉｎ，５０ｍｍ／ｍｉｎおよび２５ｍｍ／ｍｉｎで摩擦攪拌処理を施した部位の縦断面図である。図１９に示すように、回転ツール１６の移動速度が１００ｍｍ／ｍｉｎでは、多層カーボンナノチューブ３２が凝集している部分が図中に黒く残るが、図２０〜２１に示すように、回転ツール１６の移動速度が５０ｍｍ／ｍｉｎおよび２５ｍｍ／ｍｉｎでは、多層カーボンナノチューブ３２がほぼ均一に分散されていることが判る。 FIGS. 19 to 21 are longitudinal sectional views of portions subjected to the friction stir processing at the moving speeds of 100 mm / min, 50 mm / min, and 25 mm / min of the rotary tool 16 in this experimental example, respectively. As shown in FIG. 19, when the moving speed of the rotary tool 16 is 100 mm / min, a portion where the multi-walled carbon nanotubes 32 are aggregated remains black in the drawing, but as shown in FIGS. It can be seen that when the moving speed is 50 mm / min and 25 mm / min, the multi-walled carbon nanotubes 32 are almost uniformly dispersed.
図２２，２４および２６はそれぞれ本実験例において回転ツール１６の移動速度１００ｍｍ／ｍｉｎ，５０ｍｍ／ｍｉｎおよび２５ｍｍ／ｍｉｎで摩擦攪拌処理を施した部位の平面図であり、図２３，２５および２７はそれぞれの破線部における拡大図である。図２２〜２７に示すように、回転ツール１６の移動速度が１００ｍｍ／ｍｉｎから２５ｍｍ／ｍｉｎへと遅くなるにつれて、図中で白く見える多層カーボンナノチューブが均一に分散されていることが判る。 22, 24 and 26 are plan views of portions subjected to the friction stir processing at the moving speeds of 100 mm / min, 50 mm / min and 25 mm / min of the rotary tool 16 in this experimental example, respectively. It is an enlarged view in each broken line part. As shown in FIGS. 22 to 27, it can be seen that the multi-walled carbon nanotubes that appear white in the drawing are uniformly dispersed as the moving speed of the rotary tool 16 decreases from 100 mm / min to 25 mm / min.
上記多層カーボンナノチューブを混入させて摩擦攪拌処理を行ったＡＺ３１材と摩擦攪拌処理を行っていないＡＺ３１母材について硬度試験を行った。図２８に示すように摩擦攪拌処理を行っていないＡＺ３１母材の微小硬度は４１Ｈｖであるのに対し、図２９に示すように多層カーボンナノチューブを混入させて摩擦攪拌処理を行ったＡＺ３１材の微小硬度は７８Ｈｖと向上していることが判る。 A hardness test was performed on the AZ31 material mixed with the multi-walled carbon nanotubes and subjected to the friction stirring treatment and the AZ31 base material not subjected to the friction stirring treatment. As shown in FIG. 28, the fine hardness of the AZ31 base material not subjected to the friction stir processing is 41 Hv, whereas as shown in FIG. 29, the minute hardness of the AZ31 material subjected to the friction stir processing by mixing multi-walled carbon nanotubes. It can be seen that the hardness is improved to 78 Hv.
図３０はＡＺ３１材の結晶粒を示す図であり、図３１は多層カーボンナノチューブを混入させずに摩擦攪拌処理を施したＡＺ３１材の結晶粒を示す図であり、図３２は本実験例における多層カーボンナノチューブを混入させて摩擦攪拌処理を施したＡＺ３１材の結晶粒を示す図であり、図３３は図３２の破線部分の拡大図である。図３０および３１に示すように、摩擦攪拌処理をほどこしただけでは結晶粒はあまり微細化されないが、図３２および３３に示すように、多層カーボンナノチューブを混入させて摩擦攪拌処理を施すことにより、結晶粒を極めて微細化できることが判る。 FIG. 30 is a diagram showing crystal grains of the AZ31 material, FIG. 31 is a diagram showing crystal grains of the AZ31 material that has been subjected to the friction stirring process without mixing multi-walled carbon nanotubes, and FIG. It is a figure which shows the crystal grain of AZ31 material which mixed the carbon nanotube and performed the friction stirring process, and FIG. 33 is an enlarged view of the broken-line part of FIG. As shown in FIGS. 30 and 31, the crystal grains are not made very fine just by applying the friction stirring process, but as shown in FIGS. 32 and 33, by mixing the multi-walled carbon nanotubes and performing the friction stirring process, It can be seen that the crystal grains can be made extremely fine.
実験例３
Ａ５０８３材（Ｍｇを約４．５％含有するＡｌ合金）を用意した。用意したＡ５０８３材の表面に、図１（ａ）に示すような幅１ｍｍ、深さ２ｍｍの溝１２を形成した。形成した溝１２にＣ６０とＣ７０との混合物（以下、ＭＦ（Mixed Fullerene）と呼ぶ）の粉末を添加材１４として充填した。ＭＦの充填後、図１（ｂ）に示すように、直径４ｍｍ、長さ１．８ｍｍのプローブ１８を有し、本体の直径１２ｍｍのＳＫＤ６１からなる回転ツール１６によって摩擦攪拌処理を行った。回転ツール１６の移動速度は５０ｍｍ／ｍｉｎとし、回転速度は５００ｒｐｍ、１０００ｒｐｍ、１５００ｒｐｍ及び２０００ｒｐｍで行った。
Experimental example 3
A5083 material (Al alloy containing about 4.5% Mg) was prepared. A groove 12 having a width of 1 mm and a depth of 2 mm as shown in FIG. 1A was formed on the surface of the prepared A5083 material. The formed groove 12 was filled with powder of a mixture of C 60 and C 70 (hereinafter referred to as MF (Mixed Fullerene)) as an additive 14. After filling with MF, as shown in FIG. 1 (b), a friction stir processing was performed with a rotary tool 16 having a probe 18 having a diameter of 4 mm and a length of 1.8 mm and made of SKD 61 having a diameter of 12 mm. The moving speed of the rotating tool 16 was 50 mm / min, and the rotating speed was 500 rpm, 1000 rpm, 1500 rpm, and 2000 rpm.
また、同様にしてＡ５０８３材に溝１２を形成した後、形成した溝１２にＭＦをより高密度に充填するため、ＭＦの粉末をスターチをバインダーとしてペースト状にしたＭＦペーストを添加材１４として充填した。ＭＦペーストの充填後、同様にして摩擦攪拌処理を行った。回転ツール１６の移動速度は５０ｍｍ／ｍｉｎとし、回転速度は１５００ｒｐｍで行った。 Similarly, after forming the groove 12 in the A5083 material, in order to fill the formed groove 12 with higher density of MF, the MF paste made of paste of MF powder with starch as a binder is filled as the additive 14 did. After filling with the MF paste, a friction stirring process was performed in the same manner. The moving speed of the rotating tool 16 was 50 mm / min, and the rotating speed was 1500 rpm.
さらに、Ｃ１０２０材（純銅）を用意した。同様にしてＣ１０２０材に溝１２を形成した後、形成した溝１２にＭＦの粉末を添加材１４として充填した。ＭＦの充填後、同様にして摩擦攪拌処理を行った。回転ツール１６の移動速度は５０ｍｍ／ｍｉｎとし、回転速度は１５００ｒｐｍで行った。また、同様に形成した溝にＭＦペーストを添加材１４として充填したＣ１０２０材についても、同様にして摩擦攪拌処理を行った。 Furthermore, C1020 material (pure copper) was prepared. Similarly, after forming the groove 12 in the C1020 material, the formed groove 12 was filled with MF powder as the additive 14. After filling with MF, a friction stirring process was performed in the same manner. The moving speed of the rotating tool 16 was 50 mm / min, and the rotating speed was 1500 rpm. Further, the friction stir processing was similarly performed on the C1020 material in which the groove formed in the same manner was filled with the MF paste as the additive 14.
図３４〜３７は、それぞれ本実験例において回転ツール１６の回転速度５００ｒｐｍ，１０００ｒｐｍ，１５００ｒｐｍおよび２０００ｒｐｍで摩擦攪拌処理を施した部位の縦断面図である。図中のＡＳは回転ツール１６の前進側（Advancing Side）を示し、ＲＳは回転ツール１６の後退側（Retreating Side）を示す。図３４〜３７中で黒く見える領域にＭＦが分散している。図３４〜３７から、回転ツール１６の回転速度が上昇するにつれて、ＭＦが比較的均一に分散していることが判る。 34 to 37 are longitudinal cross-sectional views of portions subjected to the friction stirring process at the rotation speeds of 500 rpm, 1000 rpm, 1500 rpm, and 2000 rpm of the rotary tool 16 in this experimental example, respectively. In the figure, AS indicates the advancing side of the rotary tool 16, and RS indicates the retreating side of the rotary tool 16. MF is dispersed in a region that looks black in FIGS. 34 to 37, it can be seen that the MF is relatively uniformly dispersed as the rotational speed of the rotary tool 16 increases.
図３８は、ＭＦペーストを用いてＡ５０８３材の摩擦攪拌処理を施した部位の縦断面図である。図３８から、ＭＦペーストを用いて摩擦攪拌処理を施した場合、図中で黒く見えるＭＦが分散している領域が密に存在していることが判る。また、図３９は、図３８の拡大図であり、Ａ５０８３材の結晶粒を示すＴＥＭ（Transmission Electoron Microscope：透過電子顕微鏡）写真である。図中でＭＦをＭＦ３４として示す。図３９より、母材であるＡ５０８３材の結晶粒がｎｍオーダーまで微細化されていることが判る。 FIG. 38 is a vertical cross-sectional view of a portion where the friction stir processing of the A5083 material is performed using MF paste. From FIG. 38, it can be seen that when the friction stir processing is performed using the MF paste, there are densely dispersed regions of MF that appear black in the drawing. FIG. 39 is an enlarged view of FIG. 38 and is a TEM (Transmission Electron Microscope) photograph showing the crystal grains of the A5083 material. In the figure, MF is shown as MF34. From FIG. 39, it can be seen that the crystal grains of the A5083 material, which is the base material, are miniaturized to the nm order.
図４０は、実験例３におけるＭＦを含むＡ５０８３材の硬度試験の結果を示すグラフ図であり、Ａ５０８３材にＭＦを分散させた試料の表面から深さ方向への硬度分布を示す。図４０より、Ａ５０８３材にＭＦを分散させた場合、ＭＦを含まないＡ５０８３母材と比較して著しく硬度が上昇していることが判る。図４１は実験例３におけるＭＦを含まないＡ５０８３母材の硬度試験の様子を示す図であり、図４２は実験例３におけるＭＦペーストを用いて摩擦攪拌処理を施されたＡ５０８３材の硬度試験の様子を示す図である。図４１に示すようにＭＦを混入させずに摩擦攪拌処理を行ったＡ５０８３材は測定痕３０が大きいのに対し、図４２に示すようにＭＦを混入させて摩擦攪拌処理を行ったＡ５０８３材は測定痕３０が小さいことが判る。 FIG. 40 is a graph showing the results of the hardness test of the A5083 material containing MF in Experimental Example 3, and shows the hardness distribution in the depth direction from the surface of the sample in which MF is dispersed in the A5083 material. FIG. 40 shows that when MF is dispersed in the A5083 material, the hardness is remarkably increased as compared with the A5083 base material not containing MF. FIG. 41 is a diagram showing a state of a hardness test of an A5083 base material not containing MF in Experimental Example 3, and FIG. 42 is a diagram of a hardness test of an A5083 material subjected to friction stirring using the MF paste in Experimental Example 3. It is a figure which shows a mode. As shown in FIG. 41, the A5083 material subjected to the friction stir processing without mixing MF has a large measurement mark 30, whereas the A5083 material subjected to the friction stirring processing mixed with MF as shown in FIG. It can be seen that the measurement mark 30 is small.
図４３は実験例３においてＣ１０２０材の摩擦攪拌処理を施した部位の縦断面図であり、図４４は実験例３においてＭＦペーストを用いてＣ１０２０材の摩擦攪拌処理を施した部位の縦断面図である。図４３及び４４に示すように、図中で黒くＭＦが分散している領域が確認できる。 FIG. 43 is a longitudinal sectional view of a portion where the friction stir processing of the C1020 material was performed in Experimental Example 3, and FIG. 44 is a longitudinal sectional view of a portion where the friction stir processing of the C1020 material was performed using MF paste in Experimental Example 3. It is. As shown in FIGS. 43 and 44, black regions in which MFs are dispersed can be confirmed.
図４５は、実験例３における硬度試験で得られた試料の最大微小硬度を示すグラフ図である。図中でＭＦ−Ｐ／Ａ１０５０及びＭＦ−Ｐ／Ａ５０８３は、それぞれＡ１０５０材及びＡ５０８３材にＭＦペーストを用いて摩擦攪拌処理を施した試料を示す。また、図中でＭＦ／Ｃ１０２０は、Ｃ１０２０材にＭＦの粉末を用いて摩擦攪拌処理を施した試料を示す。図４５に示すように、Ａ１０５０材、Ａ５０８３材及びＣ１０２０材のいずれの試料についても、ＭＦを分散させると硬度が上昇することが判る。 FIG. 45 is a graph showing the maximum micro hardness of the sample obtained in the hardness test in Experimental Example 3. In the figure, MF-P / A1050 and MF-P / A5083 indicate samples obtained by subjecting the A1050 material and the A5083 material to friction stirring treatment using MF paste, respectively. In the figure, MF / C1020 indicates a sample obtained by subjecting the C1020 material to a friction stirring process using MF powder. As shown in FIG. 45, it can be seen that the hardness of any sample of A1050 material, A5083 material, and C1020 material increases when MF is dispersed.
１０…金属材、１２…溝、１４…添加材、１６…回転ツール、１８…プローブ、２０…攪拌部、２２…Ｃ６０、２４…炭素原子、２６…Ｃ６０の集合体、２８…境界、３０…測定痕、３２…カーボンナノチューブ、３４…ＭＦ。 10 ... metal member, 12 ... groove, 14 ... additional material, 16 ... rotary tool, 18 ... probe, 20 ... stirring unit, 22 ... C 60, 24 ... carbon atoms, a collection of 26 ... C 60, 28 ... boundary, 30 ... measurement mark, 32 ... carbon nanotube, 34 ... MF.
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