JP2001181773A - Mg ALLOY-COATED Mg ALLOY PRODUCT - Google Patents
Mg ALLOY-COATED Mg ALLOY PRODUCTInfo
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- JP2001181773A JP2001181773A JP36739399A JP36739399A JP2001181773A JP 2001181773 A JP2001181773 A JP 2001181773A JP 36739399 A JP36739399 A JP 36739399A JP 36739399 A JP36739399 A JP 36739399A JP 2001181773 A JP2001181773 A JP 2001181773A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】Ｍｇ合金で被覆され耐食性に
優れたＭｇ合金製品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Mg alloy product coated with a Mg alloy and having excellent corrosion resistance.
【０００２】[0002]
【従来の技術】従来、Ｍｇ合金製品の耐食性改善のため
に、陽極酸化処理、化成処理、塗装、Ｃｕめっき、Ｎｉ
めっき等が行われてきた。しかしながら、これらの手法
による耐食性の改善効果は、充分でない上に、製品のリ
サイクルを考慮するならば、リサイクル時に陽極酸化
膜、化成処理膜、塗膜、めっき膜等の被膜を除去しなけ
ればならないという欠点があった。すなわち、リサイク
ルの際には、まずＭｇ合金スクラップを再溶解するが、
その時に、陽極酸化被膜の酸化物、化成処理膜の化合
物、塗膜顔料の酸化物は、そのまま残存することが多
く、鋳造の際に巻き込まれて介在物となる。また、めっ
き膜を構成する金属元素は、溶湯中に混入して合金中の
不純物となる。さらに、塗膜に含まれる有機物は、燃焼
して有害なガスとなる恐れがある。それゆえ、再溶解に
先立って、これら被膜を除去する必要が生じるが、機械
的または化学的いずれの手段によって除去するにしても
リサイクルに関しては余分なエネルギーであり、また、
有害ガスの処理に対しても余分なエネルギーを消費しな
ければならない。これら余分なエネルギーは、リサイク
ルに要する費用を上昇させることになり、Ｍｇ合金のリ
サイクル性を阻害する。2. Description of the Related Art Conventionally, in order to improve the corrosion resistance of Mg alloy products, anodizing treatment, chemical conversion treatment, painting, Cu plating, Ni plating,
Plating has been performed. However, the effect of improving corrosion resistance by these methods is not sufficient, and if recycling of products is considered, it is necessary to remove films such as anodic oxide films, chemical conversion films, coating films, and plating films during recycling. There was a disadvantage. That is, at the time of recycling, the Mg alloy scrap is first redissolved,
At that time, the oxide of the anodic oxide coating, the compound of the chemical conversion treatment film, and the oxide of the coating pigment often remain as they are, and are involved during casting to become inclusions. Further, the metal elements constituting the plating film are mixed in the molten metal and become impurities in the alloy. Furthermore, the organic matter contained in the coating film may burn and become a harmful gas. Therefore, it is necessary to remove these films prior to re-dissolution, but removing them by mechanical or chemical means is an extra energy for recycling, and
Extra energy must be consumed for the treatment of harmful gases. These extra energies increase the cost required for recycling and hinder the recyclability of the Mg alloy.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、Ｍｇ合金製
品の耐食性を改善すると共にリサイクル性を向上させる
ことができるＭｇ合金を被覆したＭｇ合金製品を提供す
ることを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a Mg alloy product coated with a Mg alloy which can improve the corrosion resistance of the Mg alloy product and improve the recyclability.
【０００４】[0004]
【課題を解決するための手段】本発明のＭｇ合金被覆Ｍ
ｇ合金製品は、化学成分として、Ｆｅ、Ｎｉ、Ｃｏ、Ｃ
ｒの各元素を０．０５重量％以下、Ｃｕ元素を０．５重
量％以下、Ａｌ、Ｚｎ、Ｍｎ、Ｓｉの各元素を２０〜
０．０００１重量％含有し、残部がＭｇおよび不可避的
不純物からなるＭｇ合金により表面が被覆されているこ
とを特徴とする。According to the present invention, a Mg alloy coating M of the present invention is provided.
g alloy products are Fe, Ni, Co, C
Each element of r is 0.05% by weight or less, Cu element is 0.5% by weight or less, and each element of Al, Zn, Mn, and Si is 20 to
It is characterized in that the surface is coated with a Mg alloy containing 0.0001% by weight, with the balance being Mg and unavoidable impurities.
【０００５】Ｆｅ、Ｎｉ、Ｃｏ、Ｃｒの各々の元素の含
有量を０．０５重量％以下、Ｃｕ元素を０．５重量％以
下としたのは、０．０５重量％若しくは０．５重量％を
越えて含有する場合は、著しく耐食性が低下し、これら
の元素の含有量は低いほど耐食性が向上するからであ
る。これは被覆材としてのＭｇ合金に、Ｍｇ合金のスク
ラップを使用する場合を考慮したものであり、Ｍｇ合金
のスクラップにはＦｅ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒの各元
素を含有する場合が多く、この制限の範囲内に調整すれ
ばスクラップを使用可能である。従って、Ｆｅ、Ｃｕ、
Ｎｉ、Ｃｏ、Ｃｒは０重量％であってもよい。Ａｌ、Ｚ
ｎ、Ｍｎ、Ｓｉの各々の元素を２０〜０．０００１重量
％としたのは、耐食性を向上させるためのものであり、
２０重量％を越えて含有する場合に耐食性はあるが、被
膜の機械的特性が低下し、脆くなるため、実使用上は２
０重量％以下であることが好ましく、また、０．０００
１重量％よりも少なく含有する場合は、前記元素を含有
することによる耐食性の効果がそれほど認められないか
らである。The reason why the content of each element of Fe, Ni, Co, and Cr is set to 0.05% by weight or less and the Cu element is set to 0.5% by weight or less is 0.05% by weight or 0.5% by weight. When the content exceeds the above range, the corrosion resistance is significantly reduced, and the lower the content of these elements, the higher the corrosion resistance. This considers the case of using Mg alloy scrap for the Mg alloy as the coating material, and the Mg alloy scrap often contains each element of Fe, Cu, Ni, Co, and Cr. Scrap can be used if it is adjusted within this limit. Therefore, Fe, Cu,
Ni, Co, and Cr may be 0% by weight. Al, Z
The reason that each element of n, Mn, and Si is set to 20 to 0.0001% by weight is to improve corrosion resistance.
When the content exceeds 20% by weight, there is corrosion resistance, but the mechanical properties of the coating deteriorate and the coating becomes brittle.
0% by weight or less.
If the content is less than 1% by weight, the effect of corrosion resistance due to the inclusion of the above elements is not so noticeable.
【０００６】[0006]
【発明の実施の形態】本発明の実施の形態は、Ｍｇ合金
被覆した素地が、純度９９．９％の純マグネシウム板で
あり、素地の耐食性は市販のＭｇ−Ａｌ−Ｚｎ合金など
に比較すると劣るものである。これはＭｇ合金被覆の有
効性を確認するために純マグネシウムとしたが、一般的
にはより耐食性の優れたＭｇ合金を素地としてもよい。
この素地にＭｇ合金を被覆した実施例１−１〜実施例１
９−５、および同じ素地に他の被膜を形成した比較例１
〜５の夫々の耐食性を調べるための浸漬試験と、被膜の
機械的特性を調べるための曲げ試験とを行った結果を表
１〜表４に示す。各実施例の化学組成に記載している元
素含有重量割合の残部はＭｇと不可避的不純物である。
浸漬試験は３．５％ＮａＣｌ溶液に１００時間浸漬した
後の腐食状況の目視評価で、曲げ試験は９０°曲げ試験
を行った際の被膜の割れ目の目視評価である。同表中の
「浸漬試験後の腐食状況」欄の記号は３段階評価したも
のであり、◎は試料の形状変化が無い、○は試料の形状
変化があるが僅少、×は試料の形状変化が著しい、を示
す。「曲げ試験後の表面状況」欄の記号も３段階評価し
たものであり、◎は被覆層のクラック無し、剥離無し、
○は被覆層のクラックあり、剥離無し、×は被覆層の剥
離有り、を示す。BEST MODE FOR CARRYING OUT THE INVENTION The embodiment of the present invention is based on the fact that the substrate coated with a Mg alloy is a pure magnesium plate having a purity of 99.9%, and the corrosion resistance of the substrate is lower than that of a commercially available Mg-Al-Zn alloy. Inferior. This is pure magnesium in order to confirm the effectiveness of the Mg alloy coating, but in general, a Mg alloy having more excellent corrosion resistance may be used as a base material.
Example 1-1 to Example 1 in which this substrate was coated with a Mg alloy
9-5, and Comparative Example 1 in which another coating was formed on the same substrate
Tables 1 to 4 show the results of the immersion test for examining the corrosion resistance and the bending test for examining the mechanical properties of the coating. The balance of the element content weight ratio described in the chemical composition of each example is Mg and unavoidable impurities.
The immersion test is a visual evaluation of the corrosion state after immersion in a 3.5% NaCl solution for 100 hours, and the bending test is a visual evaluation of a crack in the coating when a 90 ° bending test is performed. The symbols in the column “Corrosion status after immersion test” in the table were evaluated on a three-point scale. ◎ indicates no change in sample shape, ○ indicates slight but slight change in sample shape, and × indicates change in sample shape. Is remarkable. The symbols in the column “Surface condition after bending test” were also evaluated on a three-point scale, and ◎ indicates no cracks in the coating layer, no peeling,
○ indicates that the coating layer had cracks and no peeling, and x indicates that the coating layer had peeled.
【０００７】[0007]
【表１】 [Table 1]
【０００８】[0008]
【表２】 [Table 2]
【０００９】[0009]
【表３】 [Table 3]
【００１０】[0010]
【表４】 [Table 4]
【００１１】実施例のＭｇ合金被覆は真空蒸着によるも
ので、その条件は、蒸発側合金の加熱温度が５００〜６
００°Ｃ、蒸着側合金の加熱温度が２００〜３００°
Ｃ、真空度が１．３３３２２×１０-1〜１．３３３２２
×１０-4Ｐａである。The Mg alloy coating of the embodiment is formed by vacuum evaporation, and the condition is that the heating temperature of the evaporation side alloy is 500 to 6
00 ° C, heating temperature of vapor deposition side alloy is 200 ~ 300 °
C, the degree of vacuum is 1.333222 × 10 −1 to 1.33322
× 10 -4 Pa.
【００１２】表１において、実施例１−１〜１−７は、
Ｆｅの含有量を単独で変化させ、他の元素含有量を一定
にしたものである。実施例１−１、１−２に見られるよ
うにＦｅの含有量が４９０ｐｐｍに増加すると、機械的
強度は良いが、耐食性の低下が認められ、６６０ｐｐｍ
に増加すると、機械的強度の低下及び耐食性の更なる低
下が認められる。In Table 1, Examples 1-1 to 1-7 are
The content of Fe is changed alone and the content of other elements is kept constant. As seen in Examples 1-1 and 1-2, when the Fe content was increased to 490 ppm, the mechanical strength was good, but the corrosion resistance was reduced, and 660 ppm.
, A decrease in mechanical strength and a further decrease in corrosion resistance are observed.
【００１３】実施例２−１〜２−７は、Ｃｕの含有量を
単独で変化させ、他の元素含有量を一定にしたものであ
る。実施例２−１〜２−７に見られるようにＣｕの含有
量が４８００ｐｐｍに増加すると、機械的強度は良い
が、耐食性の低下が認められ、６５００ｐｐｍに増加す
ると、機械的強度の低下及び耐食性の更なる低下が認め
られる。In Examples 2-1 to 2-7, the content of Cu is changed alone and the content of other elements is kept constant. As seen in Examples 2-1 to 2-7, when the Cu content increased to 4800 ppm, the mechanical strength was good, but a decrease in corrosion resistance was observed. When the Cu content increased to 6500 ppm, the mechanical strength decreased and the corrosion resistance increased. Is further reduced.
【００１４】実施例３−１〜３−７、実施例４−１〜４
−７、実施例５−１〜５−７は、夫々Ｎｉ、Ｃｏ、Ｃｒ
の含有量を単独で変化させ、他の元素の含有量を一定に
したものであり、実施例１−１〜１−７と同様に、略同
様に各元素が４９０ｐｐｍに増加すると、機械的強度は
良いが、耐食性の低下が認められ、６４０〜６６０ｐｐ
ｍに増加すると、機械的強度の低下及び耐食性の更なる
低下が認められる。Examples 3-1 to 3-7, Examples 4-1 to 4
-7, Examples 5-1 to 5-7 correspond to Ni, Co, and Cr, respectively.
Is changed alone and the contents of other elements are kept constant. As in Examples 1-1 to 1-7, when each element increases to 490 ppm substantially in the same manner, the mechanical strength Is good, but a decrease in corrosion resistance is observed, and 640-660 pp
When it is increased to m, a decrease in mechanical strength and a further decrease in corrosion resistance are observed.
【００１５】従って、Ｆｅ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒの
各元素は、機械的強度の向上及び耐食性に関して略無効
な元素と見做すことができ、その含有量は、Ｆｅ、Ｎ
ｉ、Ｃｏ、Ｃｒを５００ｐｐｍ以下に、またＣｕを５０
００ｐｐｍ以下に抑え、できれば０ｐｐｍに近づけるこ
とが適切である。Therefore, the elements Fe, Cu, Ni, Co, and Cr can be regarded as elements that are substantially ineffective with respect to improvement in mechanical strength and corrosion resistance.
i, Co, Cr to 500 ppm or less and Cu to 50 ppm
It is appropriate to keep the content below 00 ppm and, if possible, close to 0 ppm.
【００１６】表２において、実施例６−１〜６−７、・
・・・、実施例９−１〜９−７も、前記実施例と同様に
夫々Ａｌ、Ｚｎ、Ｍｎ、Ｓｉの含有量を単独で変化さ
せ、他の元素含有量を一定にしたものである。実施例６
−１〜６−７、・・・・、実施例９−１〜９−７も、各
元素Ａｌ、Ｚｎ、Ｍｎ、Ｓｉが、夫々１．１〜１．３％
以上になると耐食性は良いが、少し強度の低下が認めら
れ、１８．９〜１９．１％以上になると強度及び耐食性
の双方に少し低下が認められ、２５．６〜２７．０％以
上になると更に強度の低下が認められる。従って、Ａ
ｌ、Ｚｎ、Ｍｎ、Ｓｉの各元素は、機械的強度の向上及
び耐食性に関して一応略２０％以下で有効な元素と認め
られるから、２０％以下に抑えることが適切である。In Table 2, Examples 6-1 to 6-7,.
..., in Examples 9-1 to 9-7, similarly to the above-described examples, the contents of Al, Zn, Mn, and Si were independently changed, and the contents of other elements were kept constant. . Example 6
-1 to 6-7,..., And Examples 9-1 to 9-7 also show that each of the elements Al, Zn, Mn, and Si is 1.1 to 1.3%, respectively.
When it is above, the corrosion resistance is good, but a slight decrease in strength is recognized, and when it becomes 18.9 to 19.1% or more, both strength and corrosion resistance are slightly reduced, and when it becomes 25.6 to 27.0% or more, Further, a decrease in strength is observed. Therefore, A
Since each element of l, Zn, Mn, and Si is recognized as an effective element at about 20% or less for improvement in mechanical strength and corrosion resistance, it is appropriate to suppress it to 20% or less.
【００１７】実施例１０−１〜１０−９は、前記実施例
１−１〜実施例９−７を踏まえて、Ｆｅ、Ｎｉ、Ｃｏ、
Ｃｒを４９０〜０．１１ｐｐｍの範囲で同程度に含むよ
うに変化させ、Ｃｕを４９００〜０．１１ｐｐｍの範囲
で含むように変化させ、Ａｌ、Ｚｎ、Ｍｎ、Ｓｉを１９
００〜１．１ｐｐｍの範囲で含むように変化させたもの
である。実施例１０−１〜１０−９では、各元素の含有
割合について機械的強度の向上及び耐食性に関して、前
述したように、Ｆｅ、Ｎｉ、Ｃｏ、Ｃｒを５００ｐｐｍ
以下に、またＣｕを５０００ｐｐｍ以下に抑え、できれ
ば０ｐｐｍに近づけることが適切で、Ａｌ、Ｚｎ、Ｍ
ｎ、Ｓｉを略２０％以下に抑えることが、有効であるこ
とが確認できる。Examples 10-1 to 10-9 are based on Examples 1-1 to 9-7, and are based on Fe, Ni, Co,
Cr was changed so as to contain the same amount in the range of 490 to 0.11 ppm, Cu was changed so as to contain the same in the range of 4900 to 0.11 ppm, and Al, Zn, Mn, and Si were changed to 19 to 19 ppm.
It was changed so as to be contained in the range of 00 to 1.1 ppm. In Examples 10-1 to 10-9, regarding the content ratio of each element, regarding the improvement of mechanical strength and corrosion resistance, as described above, 500 ppm of Fe, Ni, Co, and Cr were added.
In addition, it is appropriate to suppress Cu to 5000 ppm or less, and to approach 0 ppm if possible.
It can be confirmed that it is effective to suppress n and Si to approximately 20% or less.
【００１８】表３、表４において、実施例１１−１〜１
１−５、・・・・、実施例１８−１〜１８−５は（実施
例１１〜１８は）、順次各元素Ｆｅ、Ｃｕ、Ｎｉ、Ｃ
ｏ、Ｃｒの許容できる範囲、また、Ａｌ、Ｚｎ、Ｍｎ、
Ｓｉの有効であると認めた範囲内で変化させたものであ
り、機械的強度の向上及び耐食性の有効性を確認でき
る。Tables 3 and 4 show that Examples 11-1 to 11-1
1-5,..., Examples 18-1 to 18-5 (Examples 11 to 18) are sequentially Fe, Cu, Ni, C
o, the acceptable range of Cr, and Al, Zn, Mn,
It was changed within the range in which Si was considered to be effective, and the improvement of mechanical strength and the effectiveness of corrosion resistance can be confirmed.
【００１９】実施例１９−１〜１９−５は、前記無効な
元素Ｆｅ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒを許容できる最多含
有量付近と前記有効な元素Ａｌ、Ｚｎ、Ｍｎ、Ｓｉの有
効範囲の最少含有量付近とを組み合わせた場合、前記無
効な元素Ｆｅ、Ｃｕ、Ｎｉ、Ｃｏ、Ｃｒを許容できる最
少含有量付近と前記有効な元素Ａｌ、Ｚｎ、Ｍｎ、Ｓｉ
の有効範囲の最多含有量付近とを組み合わせた場合、及
びその間でも、機械的強度の向上及び耐食性の有効性を
確認できる。Examples 19-1 to 19-5 show that the ineffective elements Fe, Cu, Ni, Co, and Cr are in the vicinity of the maximum allowable content and the effective ranges of the effective elements Al, Zn, Mn, and Si. When combined with the minimum content, the ineffective elements Fe, Cu, Ni, Co, and Cr can be allowed near the minimum content and the effective elements Al, Zn, Mn, Si
In the case where the maximum content in the effective range is combined with, and during that period, the improvement of mechanical strength and the effectiveness of corrosion resistance can be confirmed.
【００２０】[0020]
【発明の効果】以上の実施例から明らかなように、本発
明によるＭｇ合金被覆Ｍｇ合金製品は、耐食性に優れる
上に、本質的にＭｇ合金上にＭｇ合金を被覆したもので
あるため、素地と被膜の密着性が損なわれることがない
ので、加工性も良好であり、さらに製品をリサイクルす
る際に、被覆膜、素地ともにＭｇ又はＭｇ合金であるた
め、被覆膜を除去する必要がなく、リサイクルに要する
エネルギーを低減できる効果を奏する。As is apparent from the above examples, the Mg alloy-coated Mg alloy product according to the present invention has excellent corrosion resistance and is essentially obtained by coating the Mg alloy on the Mg alloy. The workability is also good because the adhesion of the coating and the coating is not impaired, and when the product is recycled, the coating and the base are both Mg or an Mg alloy, so the coating must be removed. In addition, there is an effect that the energy required for recycling can be reduced.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高谷 泰之 兵庫県加古川市平岡町新在家1192−330 Ｆターム(参考） 4F100 AB02A AB09A AB09B AB10A AB11A AB13A AB14A AB15A AB16A AB18A AB31A AB31B BA02 JB02 JL16 4K029 AA02 AA24 BA21 BB01 BC01 CA01 DB04 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuyuki Takaya 1192-330 F-term (reference) 4F100 AB02A AB09A AB09B AB10A AB11A AB13A AB14A AB15A AB16A AB18A AB31A AB31B BA02 JB02 JL16 4K029 AA02A BC01 CA01 DB04
Claims (1)
ｒの各元素を０．０５重量％以下、Ｃｕ元素を０．５重
量％以下、Ａｌ、Ｚｎ、Ｍｎ、Ｓｉの各元素を２０〜
０．０００１重量％含有し、残部がＭｇおよび不可避的
不純物からなるＭｇ合金により表面が被覆されているこ
とを特徴とするＭｇ合金被覆Ｍｇ合金製品。1. The chemical component is Fe, Ni, Co, C
Each element of r is 0.05% by weight or less, Cu element is 0.5% by weight or less, and each element of Al, Zn, Mn, and Si is 20 to
A Mg alloy-coated Mg alloy product comprising 0.0001% by weight, the remainder being coated with a Mg alloy comprising Mg and unavoidable impurities.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36739399A JP2001181773A (en) | 1999-12-24 | 1999-12-24 | Mg ALLOY-COATED Mg ALLOY PRODUCT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36739399A JP2001181773A (en) | 1999-12-24 | 1999-12-24 | Mg ALLOY-COATED Mg ALLOY PRODUCT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001181773A true JP2001181773A (en) | 2001-07-03 |
Family
ID=18489207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36739399A Pending JP2001181773A (en) | 1999-12-24 | 1999-12-24 | Mg ALLOY-COATED Mg ALLOY PRODUCT |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001181773A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348660A (en) * | 2001-05-18 | 2002-12-04 | Katsuhiro Nishiyama | Method for manufacturing product of magnesium or magnesium alloy |
| JP2009501845A (en) * | 2005-07-20 | 2009-01-22 | テヒニッシェ・ウニベルジテート・クラウシュタール | Magnesium alloy |
| KR101167155B1 (en) | 2004-12-24 | 2012-07-24 | 재단법인 포항산업과학연구원 | Method for improving the corrosion resistance of magnesium melting crucible |
-
1999
- 1999-12-24 JP JP36739399A patent/JP2001181773A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002348660A (en) * | 2001-05-18 | 2002-12-04 | Katsuhiro Nishiyama | Method for manufacturing product of magnesium or magnesium alloy |
| JP4651854B2 (en) * | 2001-05-18 | 2011-03-16 | 勝廣 西山 | Manufacturing method of magnesium and magnesium alloy products |
| KR101167155B1 (en) | 2004-12-24 | 2012-07-24 | 재단법인 포항산업과학연구원 | Method for improving the corrosion resistance of magnesium melting crucible |
| JP2009501845A (en) * | 2005-07-20 | 2009-01-22 | テヒニッシェ・ウニベルジテート・クラウシュタール | Magnesium alloy |
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