JPWO2008140062A1 - Mg-based alloy - Google Patents
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Abstract
本発明のMg基合金は、Zn以外の添加材として、Agが1.98at%以下含有されていることを特徴とする。実用上十分な強度のみならず、室温での延性が従来には望むことが出来ないほど良好で、かつ強度特性の異方性が小さいMg基合金が提供される。The Mg-based alloy of the present invention is characterized in that Ag is contained in an amount of 1.98 at% or less as an additive other than Zn. There is provided an Mg-based alloy that not only has a practically sufficient strength, but also has a ductility at room temperature that is so good that it cannot be desired in the past and has a small anisotropy in strength properties.
Description
本発明は、Alに変わる軽量材としてその実現が望まれてMgを主材とするMg基合金に関する。 The present invention relates to a Mg-based alloy containing Mg as a main material, which is desired to be realized as a lightweight material replacing Al.
このMg基合金については、従来より、下記特許文献1〜8に示された各種のものが開発されてきた。
特許文献2、3、4、6、8においては、強度改善を図るため、希土類元素やスカンジウム、リチウムが添加されている。しかし、これら希土類元素は、地球上では得にくい希少元素であるので合金の価格が高くなり、汎用性が低くなる。
特許文献1ではCaを0.3〜3質量%含有し、同時にAl、Sr、Mnを含有した5元系の合金である。このような合金では、Mgの結晶粒界に析出(晶出)物が形成される。特許文献2では、Zrを0.3%以上1.0%以下、Caを含む場合には0.2%以上2.0%以下含むMg合金である。(%は質量%)
特許文献8の合金はZnを3〜8重量%、Caを0.8〜5重量%含む鋳造材として開発されたMg合金が示されている。As for this Mg-based alloy, conventionally, various alloys shown in Patent Documents 1 to 8 below have been developed.
In Patent Documents 2, 3, 4, 6, and 8, rare earth elements, scandium, and lithium are added to improve the strength. However, since these rare earth elements are rare elements that are difficult to obtain on the earth, the price of the alloy increases, and the versatility decreases.
Patent Document 1 is a ternary alloy containing 0.3 to 3% by mass of Ca and simultaneously containing Al, Sr, and Mn. In such an alloy, precipitates (crystallizations) are formed at the grain boundaries of Mg. In Patent Document 2, it is an Mg alloy containing 0.3% or more and 1.0% or less of Zr, and 0.2% or more and 2.0% or less when Ca is contained. (% Is mass%)
The alloy of Patent Document 8 is an Mg alloy developed as a casting material containing 3 to 8 wt% Zn and 0.8 to 5 wt% Ca.
本発明の実験の過程で、Caの含有量が過剰であることが原因で、粒界析出物が形成され、室温での延性が低くなることが判明し、このことから前記特許文献の1、2、8の何れにおいても室温での延性が乏しくなるものである。
特許文献7の合金は鋳造材として開発された合金であり、具体的にはCaがゼロまたは0.5重量%で、Znが1重量%〜7重量%、ゼロの組み合わせにおいて、Caがゼロ又は0.5重量%でZnがゼロの時は75MPa未満、Znが1重量%〜7重量%の場合は75MPa〜100MPa未満の0.2%耐力を有するとしていることから、構造材料として使用するには不十分な強度であることを示している。また、延性については、本発明者等が本発明の実験において得た上記知見からすれば、Caを高濃度含有するものは、低いものであると推察する他はない。
特許文献5でMnとZnを添加物の主体とするMg基合金が示されており、高強度を得るために溶体化処理が示されているが、2段時効の付加的な熱処理を必要とするなどの、工程が複雑化する問題を有しているものである。
文献8において、Cuを10重量%以下添加した合金を開発しているが、Cuの添加はMg合金の耐食性を著しく低下させる欠点がある。In the course of the experiment of the present invention, it was found that due to the excessive Ca content, grain boundary precipitates were formed, resulting in low ductility at room temperature. In both cases 2 and 8, the ductility at room temperature becomes poor.
The alloy of Patent Document 7 is an alloy developed as a cast material. Specifically, in a combination of zero or 0.5% by weight of Ca and 1% to 7% by weight of Zn and zero, When it is 0.5 wt% and Zn is zero, it has a 0.2% proof stress of less than 75 MPa, and when Zn is 1 wt% to 7 wt%, it has a 0.2% proof stress of 75 MPa to less than 100 MPa. Indicates insufficient strength. In addition, regarding the ductility, there is no other way than to infer that those containing a high concentration of Ca are low based on the above findings obtained by the present inventors in the experiment of the present invention.
Patent Document 5 shows an Mg-based alloy mainly composed of Mn and Zn, and shows solution treatment in order to obtain high strength, but requires an additional heat treatment with two-stage aging. This has a problem that the process is complicated.
In Reference 8, an alloy to which Cu is added in an amount of 10% by weight or less is developed. However, the addition of Cu has a drawback that the corrosion resistance of the Mg alloy is remarkably lowered.
以上要するに、現在、Mg合金が利用される部材の大部分は、鋳造、ダイカスト法で製造されている。将来、自動車、航空機などの輸送機器へのMg合金の応用が期待されるが、鋳造法では材料の組織が粗大になり延性が低くなる、サイズに制限があり板材、棒材、パイプ材等に適用できないという欠点がある。一方、展伸用実用Mg合金にはMg‐Al‐Zn(AZ系合金)、あるいはMg‐Zn‐Zr(ZK系合金)があるが、それらの展伸用Mg合金の強度は不十分であり、しかも熱間加工時に形成される集合組織の影響により強度設計に使用する耐力が、引張荷重が負荷される場合と圧縮荷重が負荷される場合で大きく異なる(市販のAZ31合金圧延材では圧縮耐力は引張耐力の約50%)ため、そのまま使用することは困難である。これまでに、Mg合金の高強度化を図るため、希土類元素の添加および多量の合金元素の添加する方法がとられてきた。 In short, most of the members using Mg alloys are currently manufactured by casting and die casting. In the future, it is expected that Mg alloys will be applied to transportation equipment such as automobiles and airplanes. However, the casting method makes the material structure coarser and lowers ductility. There is a disadvantage that it cannot be applied. On the other hand, there are Mg-Al-Zn (AZ alloy) or Mg-Zn-Zr (ZK alloy) as practical Mg alloys for extension, but the strength of these extension Mg alloys is insufficient. In addition, the yield strength used for the strength design is greatly different between the case where a tensile load is applied and the case where a compressive load is applied due to the influence of the texture formed during hot working (compressive strength in a commercially available AZ31 alloy rolled material). Is about 50% of the tensile strength), so it is difficult to use as it is. In the past, in order to increase the strength of Mg alloys, methods of adding rare earth elements and adding a large amount of alloy elements have been employed.
しかし、希土類元素は高価であることから汎用性は低く、さらに多量合金元素の添加は粗大な化合物相の形成をともない、高強度は得られるが延性が損なわれるという欠点がある。そこで、希土類元素フリーで、安価な合金元素添加による強度と延性に優れた新しい展伸用Mg合金の開発が求められている。
本発明は、このような実情に鑑み、実用上十分な強度のみならず、室温での延性が従来には望むことが出来ないほど良好で、かつ強度特性の異方性が小さいMg基合金を提供することを目的とする。 In view of such circumstances, the present invention provides an Mg-based alloy having not only a sufficient strength for practical use but also a ductility at room temperature that is so good that it cannot be conventionally desired and has a small anisotropy in strength properties. The purpose is to provide.
発明1のMg基合金は、Zn以外の添加材として、Agが1.98at%以下含有されていることを特徴とする。
発明2は、発明1に記載のMg基合金において、Zn、Ag以外の添加材として、さらにCaが0.61at%以下含有されていることを特徴とする。
発明3は、発明2に記載のMg基合金において、Zn、Ag及びCa以外の添加材として、さらにZrが0.17at%以下含有されていることを特徴とする。
発明4は、発明1から3の何れかに記載のMg基合金において、その結晶粒径が0.1μm〜25μmであることを特徴とする。The Mg-based alloy of the invention 1 is characterized in that Ag is contained in an amount of 1.98 at% or less as an additive other than Zn.
Invention 2 is characterized in that, in the Mg-based alloy described in Invention 1, Ca is further contained in an amount of 0.61 at% or less as an additive other than Zn and Ag.
Invention 3 is characterized in that, in the Mg-based alloy described in Invention 2, Zr is further contained in an amount of 0.17 at% or less as an additive other than Zn, Ag and Ca.
Invention 4 is characterized in that in the Mg-based alloy according to any one of Inventions 1 to 3, the crystal grain size is 0.1 μm to 25 μm.
発明1から4により、安価な合金元素のみを添加することにより、強度と延性に双方が従来には望むことができない程に優れ、かつ強度の異方性が少ないMg基合金を提供できるようになった。
さらにCu等の耐食性を損なう合金元素を使用していないので、優れた耐久性をも期待できるものである。
本発明合金は、荷重負荷方向に対する底面すべり方向の平均シュミット因子が0.2以上であり、実用Mg合金である既存のAZ91合金(Mg−9質量%Al−1質量%Zn合金)押出し材と比較しても、シュミット因子の一様な分布を有する。つまり、本発明合金は押出し方向に平行な底面の集積度が弱いことを特徴とする。
本発明合金は、圧縮耐力が引張耐力の75%以上であり、強度の異方性が少ない優れた機械的性質を有する。
According to Inventions 1 to 4, by adding only an inexpensive alloy element, it is possible to provide an Mg-based alloy that is superior in strength and ductility to the extent that both cannot be desired in the past and has low strength anisotropy. became.
Furthermore, since an alloy element such as Cu that impairs corrosion resistance is not used, excellent durability can be expected.
The alloy of the present invention has an average Schmid factor in the bottom slip direction with respect to the load direction of 0.2 or more, and an existing AZ91 alloy (Mg-9 mass% Al-1 mass% Zn alloy) extruded material which is a practical Mg alloy Even in comparison, it has a uniform distribution of Schmid factors. That is, the alloy of the present invention is characterized in that the degree of integration of the bottom surface parallel to the extrusion direction is weak.
The alloy of the present invention has excellent mechanical properties such that the compressive strength is 75% or more of the tensile strength and the strength anisotropy is small.
下記実施例より、本願発明では、希土類元素フリーで比較的入手しやすい元素であるAg、Ca、Zrを微量添加することにより時効硬化性が向上することがわかる。また、その合金を熱間押出するだけでも微細析出物が分散した微細結晶粒組織が形成され、強度だけでなく延性にも優れ、従来合金より強度の異方性も少ないMg基合金であることがわかる。また、実施例及び技術的な常識からすれば下記の範囲で上記効果を発揮することが予測できる。
Znについて:Mg中へのZnの最大固溶量は2.4at%である。
0.75at%以上の組成範囲であれば時効硬化が行われるが、Mg−Zn系合金の強化相として作用する棒状のβ′析出物を分散させ高強度化を図るには、Zn含有量はできるだけ多くする必要があり、1.52at%以上が好ましい。
この棒状のβ′析出物をさらに大量に且つ微細に分散させるには、1.92at%以上とするのが好ましい。
Agについて:Mg中へのAgの溶解度は大きく、その最大固溶量は3.82at%である。From the following examples, it can be seen that in the present invention, age hardening is improved by adding a small amount of Ag, Ca, Zr, which are rare earth element-free and relatively easily available elements. In addition, it is a Mg-based alloy that forms a fine grain structure in which fine precipitates are dispersed just by hot extrusion of the alloy, has excellent strength as well as ductility, and has less strength anisotropy than conventional alloys. I understand. Further, from the examples and technical common sense, it can be predicted that the above-described effects will be exhibited within the following range.
Regarding Zn: The maximum solid solution amount of Zn in Mg is 2.4 at%.
If the composition range is 0.75 at% or more, age hardening is performed. However, in order to disperse the rod-shaped β ′ precipitate that acts as a strengthening phase of the Mg—Zn alloy, It is necessary to increase as much as possible, and 1.52 at% or more is preferable.
In order to disperse this rod-like β ′ precipitate in a larger amount and finely, it is preferably 1.92 at% or more.
About Ag: The solubility of Ag in Mg is large, and the maximum solid solution amount is 3.82 at%.
鋳造後の溶体化熱処理を400℃で行う場合には、Ag含有量が1.98at%を超えると粗大な析出物が形成され、機械的性質を劣化させる恐れがある。
0.2at%を超えると添加量を増加しても時効硬化性はあまり変化しないから、構成元素であるZn或いはCaやZrとの化合物相形成を阻止するためには、できるだけ含有量を抑える意味で上限を0.2at%とするのが好ましい。
また、0.08at%以上であると、析出物の核形成を促す働きをするので、下限値を0.08at%以上とするのが好ましい。
Caについて:MgへのCaの最大固溶量は0.82at%である。
鋳造後溶体化熱処理を400℃で行う場合には、Ca含有量が0.61at%を超えると、粗大な粒界析出物が形成され、機械的性質を損なう。
それ故に、上限を0.61at%以下とした。When the solution heat treatment after casting is performed at 400 ° C., if the Ag content exceeds 1.98 at%, coarse precipitates may be formed and the mechanical properties may be deteriorated.
If it exceeds 0.2 at%, the age hardening does not change much even if the addition amount is increased. Therefore, in order to prevent the compound phase formation with the constituent elements Zn, Ca and Zr, the content should be suppressed as much as possible. And the upper limit is preferably 0.2 at%.
Moreover, since it works to promote the nucleation of precipitates when it is 0.08 at% or more, the lower limit is preferably 0.08 at% or more.
About Ca: The maximum solid solution amount of Ca in Mg is 0.82 at%.
When the solution heat treatment after casting is performed at 400 ° C., if the Ca content exceeds 0.61 at%, coarse grain boundary precipitates are formed and the mechanical properties are impaired.
Therefore, the upper limit was made 0.61 at% or less.
また、実施例1の図2、図3に示すように、Caの添加量を2倍にしても時効硬化特性には変化は認められない。それ故、構成元素であるZn或いはAgやZrとの化合物相形成を阻止するためには、できるだけ含有量を抑える意味で上限を0.2at%とするのが好ましい。
また、0.08at%以上であると、析出物の核形成を促す働きをするので、下限値を0.08at%以上とするのが好ましい。
Zrについて:MgへのZrの最大固溶量は1.04at%である。
しかし、0.17at%を超えると650℃付近に包晶反応が存在しており、粗大な析出物が形成されることから0.17at%以下とした。
0.08at%以上であると、微細な析出物、あるいはZr原子自身により、溶体化および熱間押出における結晶粒粗大化抑制効果が期待されることから、下限を0.08at%以上とするのが好ましい。
以上のような各元素の具体的な添加量は、以下の実施例の結果に基づき、微細結晶粒組織の平均粒径を出来るだけ小さくし、結晶粒の配向性を弱めるように配分されることとなる。Further, as shown in FIGS. 2 and 3 of Example 1, no change is observed in the age-hardening characteristics even when the amount of Ca added is doubled. Therefore, in order to prevent the formation of a compound phase with the constituent elements Zn, Ag, and Zr, the upper limit is preferably set to 0.2 at% in order to suppress the content as much as possible.
Moreover, since it works to promote the nucleation of precipitates when it is 0.08 at% or more, the lower limit is preferably 0.08 at% or more.
About Zr: The maximum solid solution amount of Zr in Mg is 1.04 at%.
However, if it exceeds 0.17 at%, a peritectic reaction exists at around 650 ° C., and a coarse precipitate is formed, so that it is set to 0.17 at% or less.
If it is 0.08 at% or more, fine precipitates or Zr atoms themselves are expected to suppress the grain coarsening in solution and hot extrusion, so the lower limit is made 0.08 at% or more. Is preferred.
Based on the results of the following examples, the specific amount of each element as described above is allocated so as to make the average grain size of the fine grain structure as small as possible and weaken the orientation of the grain. It becomes.
表1に示す合金組成になるように各元素を配合し、アルゴン雰囲気下で鉄製のるつぼを用いて高周波溶解炉で溶製した。
オイル浴を使って160℃、200℃の温度で時効した。時効による硬度はビッカース硬度計により荷重1kg、保持時間15秒の条件で測定した。
透過型電子顕微鏡(TEM)を用いて組織観察を実行した。実験手順の詳細を図1に示す。
図2,図3は160℃、200℃時効における硬度変化を示している。これらの図から160℃時効では100h前後に、200℃時効では10h前後に最高硬度に達する。
時効硬化性はMg−2.3Zn合金にAg、Ag+Ca、Ag+Ca+Zrと添加することにより良好になる。
Mg−2.3Zn合金にAg+Ca+Zr添加をした合金の最高硬度がもっとも高く100Hvにまで達している。
Ag+Ca添加合金において、それぞれの元素添加量を0.2at%に増やした合金の時効硬度を調べている。
しかし、添加量を増やしても時効特性の明らかな違いは認められない。Each element was blended so as to have the alloy composition shown in Table 1, and melted in a high-frequency melting furnace using an iron crucible under an argon atmosphere.
Aging was performed at 160 ° C. and 200 ° C. using an oil bath. The hardness by aging was measured with a Vickers hardness tester under the conditions of a load of 1 kg and a holding time of 15 seconds.
Tissue observation was performed using a transmission electron microscope (TEM). Details of the experimental procedure are shown in FIG.
2 and 3 show changes in hardness at 160 ° C. and 200 ° C. aging. From these figures, the maximum hardness is reached around 100 h at 160 ° C., and around 10 h at 200 ° C.
Age hardening is improved by adding Ag, Ag + Ca, Ag + Ca + Zr to the Mg-2.3Zn alloy.
The highest hardness of the alloy obtained by adding Ag + Ca + Zr to the Mg-2.3Zn alloy is as high as 100 Hv.
In the Ag + Ca-added alloy, the aging hardness of the alloy in which each element addition amount is increased to 0.2 at% is examined.
However, no obvious difference in aging characteristics is observed even when the amount added is increased.
図4、図5、図6、図8に示したそれぞれの合金について、切片法(ASTM standardE112)により結晶粒径を測定した。平均結晶粒径は図4に示すMg−2.3Zn2元合金で約100μm、図5に示すMg−2.3Zn−0.1Ag合金で約50μm、図6に示すMg−2.3Zn−0.1Ag−0.1Ca合金で約50μm、図8に示すMg−2.3Zn−0.1Ag−0.1Ca−0.17Zr合金で約10μmであった。Agの添加、Ag+Caの複合添加により結晶粒径は小さくなり、Zrの添加によりさらに結晶粒径が細かくなることがわかる。
図4から図9にそれぞれの合金の160℃時効におけるピーク時効段階のTEM組織を示している。
いずれの時効組織において、Mgのc軸方向に伸びた棒状の析出物が観察される。
Mg−2.3Zn合金にAg、Ag+Ca、Ag+Ca+Zrと添加することでその析出物は微細になっている。
この析出物の微細化がピーク時効硬さの上昇に起因していると考えられる。
結論として、Ag+CaおよびAg+Ca+Zrを複合添加した合金において、良好な時効硬化性が得られる。For each of the alloys shown in FIGS. 4, 5, 6, and 8, the crystal grain size was measured by the intercept method (ASTM standard E112). The average crystal grain size is about 100 μm for the Mg-2.3Zn binary alloy shown in FIG. 4, about 50 μm for the Mg-2.3Zn-0.1Ag alloy shown in FIG. 5, and Mg-2.3Zn-0. The thickness was about 50 μm for the 1Ag-0.1Ca alloy, and about 10 μm for the Mg-2.3Zn-0.1Ag-0.1Ca-0.17Zr alloy shown in FIG. It can be seen that the addition of Ag and the combined addition of Ag + Ca makes the crystal grain size smaller, and the addition of Zr makes the crystal grain size smaller.
FIG. 4 to FIG. 9 show the TEM structures at the peak aging stage in each alloy at 160 ° C. aging.
In any aging structure, a rod-like precipitate extending in the c-axis direction of Mg is observed.
By adding Ag, Ag + Ca, Ag + Ca + Zr to the Mg-2.3Zn alloy, the precipitates become fine.
This refinement of the precipitate is considered to be caused by an increase in peak age hardness.
In conclusion, good age-hardening properties can be obtained in an alloy to which Ag + Ca and Ag + Ca + Zr are added in combination.
実験手順の詳細を図10に示す。表1の合金組成になるように合金元素を配合し、CO2+SF6混合ガス雰囲気下で溶解し、鋳造した。その後、Arガスを流しながら350℃で48h均質化熱処理を施した。その後、300℃、350℃で熱間押出しした。熱間押出の条件は押出比20、ラム速度0.1mm/sであった。押出し後の材料を400℃で0.5から4hの溶体化処理を施し、160℃,200℃の温度で時効処理を行い、ビッカース硬度測定を行った。
また、押出し後の試料について光学顕微鏡およびTEMによる組織観察を行った。Details of the experimental procedure are shown in FIG. Alloy elements were blended so as to have the alloy composition shown in Table 1, and were melted and cast in a CO 2 + SF 6 mixed gas atmosphere. Thereafter, homogenization heat treatment was performed at 350 ° C. for 48 hours while flowing Ar gas. Then, it hot-extruded at 300 degreeC and 350 degreeC. The conditions for hot extrusion were an extrusion ratio of 20 and a ram speed of 0.1 mm / s. The extruded material was subjected to a solution treatment at 400 ° C. for 0.5 to 4 hours, an aging treatment was performed at 160 ° C. and 200 ° C., and Vickers hardness was measured.
Moreover, the structure | tissue observation by an optical microscope and TEM was performed about the sample after extrusion.
図11、図12は160℃,200℃におけるMg−2.3%Zn−0.1%Ag−0.1%Ca合金の時効曲線を示している。
鋳造後、溶体化処理した材料と熱間押出後溶体化処理した材料の比較を行ったところ、最高硬度および時効硬化特性はほぼ同じである。
図13,図14は160、200℃におけるMg−2.3%Zn−0.1%Ag−0.1%Ca−0.17%Zr合金の時効曲線を示している。
鋳造後、溶体化処理した材料と熱間押出後溶体化処理した材料の比較を行ったところ、最高硬度および時効硬化特性に明らかな違いはない。
図15は350℃で熱間押出しMg−2.3%Zn−0.1%Ag−0.1%Ca合金の光学顕微鏡組織である。この写真を使って切片法により結晶粒径を測定したところ、平均結晶粒径は20μmであった。11 and 12 show the aging curves of Mg-2.3% Zn-0.1% Ag-0.1% Ca alloy at 160 ° C and 200 ° C.
When a comparison was made between the solution-treated material after casting and the material that was solution-treated after hot extrusion, the maximum hardness and age-hardening characteristics were almost the same.
FIG. 13 and FIG. 14 show the aging curves of Mg-2.3% Zn-0.1% Ag-0.1% Ca-0.17% Zr alloy at 160 and 200 ° C.
A comparison between the solution-treated material after casting and the material that was solution-treated after hot extrusion revealed no obvious differences in maximum hardness and age-hardening properties.
FIG. 15 is an optical microstructure of a hot-extruded Mg-2.3% Zn-0.1% Ag-0.1% Ca alloy at 350 ° C. When the crystal grain size was measured by the intercept method using this photograph, the average crystal grain size was 20 μm.
図16は350℃で熱間押出しMg−2.3%Zn−0.1%Ag−0.1%Ca−0.17%Zr合金の光学顕微鏡組織である。図17、図18は同合金のTEM組織である。
図16の光学顕微鏡写真において、押出し後の組織は粗大な未再結晶粒(A)、微細で等軸な再結晶粒(B)、および不明瞭な領域(C)の3つに分けられる。不明瞭な領域(C)は図17のTEM写真に対応すると考えられ、サブミクロンの微細粒再結晶粒組織であることがわかる。
図18はそのサブミクロンの微細結晶内部を拡大した組織であり、Mgのc軸に沿った挿入数十nm程度の微細な棒状析出物が観察される。FIG. 16 is an optical microstructure of an Mg-2.3% Zn-0.1% Ag-0.1% Ca-0.17% Zr alloy hot extruded at 350 ° C. 17 and 18 are TEM structures of the same alloy.
In the optical micrograph of FIG. 16, the structure after extrusion is divided into three, coarse unrecrystallized grains (A), fine equiaxed recrystallized grains (B), and unclear regions (C). The indistinct region (C) is considered to correspond to the TEM photograph of FIG. 17, and it can be seen that it is a submicron fine grain recrystallized grain structure.
FIG. 18 shows an enlarged structure of the inside of the submicron fine crystal, and a fine rod-like precipitate having an insertion of about several tens of nanometers along the c-axis of Mg is observed.
図16と図17より熱間押出しMg−2.3%Zn−0.1%Ag−0.1%Ca−0.17%Zr合金の結晶粒径を測定した。なお、得られた組織が均一でないため、切片法ではなくそれぞれの領域の結晶に対して長軸と短軸を測定し、その平均値を結晶粒径とした。また、未再結晶粒(A)と等軸な再結晶粒(B)については図16の光学顕微鏡写真、サブミクロンの微細結晶領域(C)は図17のTEM写真を使用した。その結果、(A)の未再結晶粒は約5〜25μmのサイズ分布で平均粒径11μm、(B)の等軸再結晶粒は約1〜5μmのサイズ分布で平均粒径2.8μm、(C)のサブミクロン微細粒領域は約0.1〜1μmのサイズ分布で平均粒計0.75μmであることがわかった。
時効硬化性に優れるMg−2.3%Zn−0.1%Ag−0.1%Ca合金およびMg−2.3%Zn−0.1%Ag−0.1%Ca−0.17%Zr合金について室温引張試験および室温圧縮試験を押出し方向に平行に実行した。引張試験片はJIS14B試験片、標点間距離20mmであった。圧縮試験片は直径9.5mm、高さ14.3mmであった。引張試験および圧縮試験は初期ひずみ速度10−3 s−1の条件下で行った。From FIG. 16 and FIG. 17, the crystal grain size of the hot-extruded Mg-2.3% Zn-0.1% Ag-0.1% Ca-0.17% Zr alloy was measured. In addition, since the obtained structure | tissue was not uniform, the major axis and the minor axis were measured with respect to the crystal | crystallization of each area | region instead of the intercept method, and the average value was made into the crystal grain diameter. Further, the non-recrystallized grains (A) and the recrystallized grains (B) that are equiaxed use the optical micrograph of FIG. 16, and the submicron fine crystal region (C) uses the TEM photograph of FIG. As a result, the unrecrystallized grains in (A) have an average particle size of 11 μm with a size distribution of about 5 to 25 μm, and the equiaxed recrystallized grains in (B) have an average particle size of 2.8 μm with a size distribution of about 1 to 5 μm, It was found that the sub-micron fine particle region (C) had a size distribution of about 0.1 to 1 μm and an average particle size of 0.75 μm.
Mg-2.3% Zn-0.1% Ag-0.1% Ca alloy and Mg-2.3% Zn-0.1% Ag-0.1% Ca-0.17% which are excellent in age hardening A room temperature tensile test and a room temperature compression test were performed on the Zr alloy parallel to the extrusion direction. The tensile test piece was a JIS 14B test piece and the distance between the gauge points was 20 mm. The compression test piece had a diameter of 9.5 mm and a height of 14.3 mm. The tensile test and the compression test were performed under conditions of an initial strain rate of 10 −3 s −1 .
図19(その基になった測定データを表2に示す)に引張荷重負荷方向、すなわち押出し方向に対する底面すべり方向のシュミット因子の分布を示す。本発明合金のシュミット因子の分布は、押出し方向に平行な底面の集積度が弱いため、既存のAZ91合金(Mg−9質量%Al−1質量%Zn合金)押出し材と比較すると一様に分布し、その平均値は0.20以上となる。
図20は350℃で押出したMg−2.3%Zn−0.1%Ag−0.1%Ca−0.17%Zr合金の室温引張試験および圧縮試験で得られた応力‐ひずみ曲線を示す。表3〜表7は、図20での、引張試験の応力‐ひずみ曲線に対応する測定データを示しており、表8〜表11は、図20での、圧縮試験の応力‐ひずみ曲線に対応する測定データを示している。
(初期ひずみ速度:10−3 s−1。引張試験片形状:JIS14B (標点間距離20mm)、圧縮試験片形状:直径9.5mm、高さ14.3mm)
(Initial strain rate: 10 −3 s −1 . Tensile test piece shape: JIS14B (distance between gauge points 20 mm), compression test piece shape: diameter 9.5 mm, height 14.3 mm)
表12は300℃,350℃で押出したMg−2.3%Zn−0.1%Ag−0.1%Ca、Mg−2.3%Zn−0.1%Ag−0.1%Ca−0.17%Zr合金の引張試験および圧縮試験の結果をまとめたものである。
この高強度・高延性で、強度の異方性が少ない優れた機械的性質の発現は、微細結晶粒、底面集合組織の集積度の低下およびその粒内における微細析出物が関係していると考えられる。Table 12 shows Mg-2.3% Zn-0.1% Ag-0.1% Ca and Mg-2.3% Zn-0.1% Ag-0.1% Ca extruded at 300 ° C. and 350 ° C. -Summarizes the results of the tensile test and compression test of 0.17% Zr alloy.
The expression of excellent mechanical properties with high strength and high ductility and low strength anisotropy is related to the decrease in the degree of accumulation of fine crystal grains, bottom texture, and fine precipitates in the grains. Conceivable.
本発明の材料は、高強度でなおかつ高延性を有しており、Al部材との代替えにより軽量化が期待される輸送機器、例えば自動車、バイク、飛行機などに使用されうる。さらに、本発明材料の機械的性質は、熱間加工後付加的な熱処理を必要としなくても得られることから、現在使用されている展伸用Mg合金に変わる部材としても期待される。また、350℃の熱間押出後の試料において、平均結晶粒径が約500nmの超微細粒組織を呈していることから、超塑性材料として応用される可能性がある。
The material of the present invention has high strength and high ductility, and can be used for transportation equipment such as automobiles, motorcycles, airplanes, and the like that are expected to be reduced in weight by replacement with Al members. Furthermore, since the mechanical properties of the material of the present invention can be obtained without the need for additional heat treatment after hot working, it is also expected as a member that replaces the currently used Mg alloy for extension. Moreover, since the sample after hot extrusion at 350 ° C. exhibits an ultrafine grain structure with an average crystal grain size of about 500 nm, it may be applied as a superplastic material.
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