JPH0657364A - Mn-zn alloy for anode of alloy electroplating and its production - Google Patents
Mn-zn alloy for anode of alloy electroplating and its productionInfo
- Publication number
- JPH0657364A JPH0657364A JP23159692A JP23159692A JPH0657364A JP H0657364 A JPH0657364 A JP H0657364A JP 23159692 A JP23159692 A JP 23159692A JP 23159692 A JP23159692 A JP 23159692A JP H0657364 A JPH0657364 A JP H0657364A
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- alloy
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Abstract
(57)【要約】
【目的】 合金電気メッキのアノード用Mn-Zn 合金とそ
の製法の提供
【構成】 Ｍｎ粉末とＺｎ粉末の混合粉末を加圧焼結し
て製造され、Ｍｎ−Ｚｎ固溶体のβ1 相およびβ相を主
体とする合金相を有し、相対密度が７０〜９７重量％で
ある合金電気メッキのアノード用Ｍｎ−Ｚｎ合金、およ
び、８０〜６０重量％のＭｎ粉末と２０〜４０重量％の
Ｚｎ粉末とを３００〜９００℃の温度下で５Kg／cm2 以
上の圧力で加圧焼結することを特徴とするＭｎ−Ｚｎ合
金の製造方法。
【効果】 上記Ｍｎ−Ｚｎ焼結合金は、Ｍｎ−Ｚｎ合金
電気メッキのアノードとして用いた場合、ＭｎとＺｎが
均一に溶出するので、容易にメッキ浴中のＭｎ／Ｚｎ比
を一定に保持することができ、また溶解効率も高く、ス
ラッジも発生しない。(57) [Abstract] [Purpose] Providing Mn-Zn alloy for anode of alloy electroplating and manufacturing method thereof [Composition] Manufactured by pressure sintering of mixed powder of Mn powder and Zn powder, and Mn-Zn solid solution An Mn-Zn alloy for an electroplated anode having an alloy phase mainly composed of β 1 phase and β phase and a relative density of 70 to 97% by weight, and 80 to 60% by weight of Mn powder and 20 to 40 A method for producing an Mn-Zn alloy, which comprises press-compacting with a Zn powder of wt% at a temperature of 300 to 900 ° C. at a pressure of 5 kg / cm 2 or more. [Effect] When the above Mn-Zn sintered alloy is used as an anode for Mn-Zn alloy electroplating, Mn and Zn are uniformly eluted, so that the Mn / Zn ratio in the plating bath can be easily kept constant. In addition, the melting efficiency is high and no sludge is generated.
Description
【０００１】[0001]
【産業上の利用分野】本発明はＭｎ−Ｚｎ合金電気メッ
キの可溶性Ｍｎ−Ｚｎアノードとして用いることができ
るＭｎ−Ｚｎ焼結合金に関する。Ｍｎ−Ｚｎ合金メッキ
は優れた耐食性を有することからＭｎ−Ｚｎ合金メッキ
鋼板は主に自動車用防錆鋼板として用いられている。本
発明はメッキ浴中のＭｎイオン濃度およびＺｎイオン濃
度を一定に保つことができる可溶性Ｍｎ−Ｚｎアノー
ド、もしくは、液濃度調節用の合金ショットとして好適
なＭｎ−Ｚｎ焼結合金に関する。FIELD OF THE INVENTION This invention relates to Mn-Zn sintered alloys that can be used as soluble Mn-Zn anodes for Mn-Zn alloy electroplating. Since the Mn-Zn alloy plating has excellent corrosion resistance, the Mn-Zn alloy plated steel sheet is mainly used as an anticorrosion steel sheet for automobiles. The present invention relates to a soluble Mn-Zn anode capable of keeping the Mn ion concentration and Zn ion concentration in a plating bath constant, or to a Mn-Zn sintered alloy suitable as an alloy shot for adjusting the liquid concentration.
【０００２】[0002]
【従来技術とその課題】Ｍｎ−Ｚｎ合金電気メッキ時に
は、メッキ浴中のＭｎイオン濃度およびＺｎイオン濃度
を一定に調節することが必要である。このメッキ浴中の
イオン濃度を調節する方法として、ＭｎやＺｎの炭酸
塩、硫酸塩、塩化物、水酸化物、酸化物などを供給する
方法や、可溶性アノードを用いる方法が知られている
が、炭酸塩などを供給する方法では、不溶性アノードを
用いるためにアノードで酸素が発生して電解効率が低下
し、また金属塩を添加するための装置が必要であり、さ
らに余分な陰イオン（SO4 ，Cl- など）を除去しなけれ
ばならないなどの問題がある。また可溶性アノードを用
いる方法は、ＭｎアノードとＺｎアノードの２種のアノ
ードを用いた場合、ＭｎとＺｎは溶解効率が異なるため
メッキ浴中のＭｎイオン濃度とＺｎイオン濃度を所定の
割合に制御するのが難しい。また、ＭｎアノードとＺｎ
アノードの２種のアノードを用いる方法に代えて、可溶
性Ｍｎ−Ｚｎ合金をアノードに用いる方法が考えられる
が、ＭｎとＺｎは融点および蒸気圧の差が大きく、通常
の溶解方法では所定の組成比を有するＭｎ−Ｚｎ族合金
を製造するのは難しい。因みに従来の溶解方法では、Ｍ
ｎの含有量が多いとＭｎを完全に溶解する温度まで加熱
するとＺｎの蒸発が激しくなるので、４０重量％以上の
Ｍｎ含有量を有するＭｎ−Ｚｎ合金を得るのは極めて困
難である。2. Description of the Related Art Mn-Zn alloy electroplating requires constant adjustment of the Mn ion concentration and the Zn ion concentration in the plating bath. As a method of adjusting the ion concentration in the plating bath, a method of supplying carbonates, sulfates, chlorides, hydroxides, oxides, etc. of Mn and Zn, and a method of using a soluble anode are known. In the method of supplying carbonate, etc., since an insoluble anode is used, oxygen is generated at the anode to lower the electrolysis efficiency, and a device for adding a metal salt is required. 4, Cl - there are problems such as the need to remove the like). In the method using a soluble anode, when two types of anodes, that is, a Mn anode and a Zn anode are used, Mn and Zn have different dissolution efficiencies, so that the Mn ion concentration and the Zn ion concentration in the plating bath are controlled to a predetermined ratio. Is difficult. In addition, Mn anode and Zn
Although a method of using a soluble Mn—Zn alloy for the anode can be considered instead of the method of using two types of anodes, Mn and Zn have a large difference in melting point and vapor pressure, and a normal composition method has a predetermined composition ratio. It is difficult to produce a Mn-Zn group alloy having By the way, in the conventional dissolution method, M
When the content of n is large, the evaporation of Zn becomes severe when heated to a temperature at which Mn is completely dissolved. Therefore, it is extremely difficult to obtain an Mn-Zn alloy having a Mn content of 40% by weight or more.
【０００３】本発明者等はＭｎ−Ｚｎ合金電気メッキに
おける可溶性アノードの開発を試み、粉末加圧焼結法
（ホットプッレス法）によって製造した高密度Ｍｎ−Ｚ
ｎ焼結合金は、多量のＭｎを含有させることができ、ま
たその金属組織がＭｎ−Ｚｎ固溶体の高温相であるβ相
およびβ1 相の単相またはこれらの混合相を主体とする
ものはＭｎ−Ｚｎ合金電気メッキのアノードに用いた場
合、ＭｎおよびＺｎが均一に溶解し、溶解効率も高くメ
ッキ浴中にスラッジも残留しないことを見出した。本発
明は上記知見に基づきＭｎ−Ｚｎ合金電気メッキの可溶
性アノードとして最適な高密度Ｍｎ−Ｚｎ焼結合金を提
供することを目的とする。The inventors of the present invention tried to develop a soluble anode for electroplating of Mn-Zn alloy, and produced a high density Mn-Z produced by the powder pressure sintering method (hot press method).
The n-sintered alloy can contain a large amount of Mn, and its metallic structure is mainly composed of a single phase of β phase and β 1 phase which are high temperature phases of Mn-Zn solid solution or a mixed phase thereof is Mn. It has been found that when used as an anode for electroplating of Zn alloy, Mn and Zn are uniformly dissolved, the dissolution efficiency is high, and no sludge remains in the plating bath. An object of the present invention is to provide a high-density Mn-Zn sintered alloy that is optimal as a soluble anode for Mn-Zn alloy electroplating based on the above findings.
【０００４】[0004]
【課題の解決手段：発明の構成】本発明によれば、Ｍｎ
粉末とＺｎ粉末の混合粉末を加圧焼結して製造され、Ｍ
ｎ−Ｚｎ固溶体のβ相およびβ1 相を主体とする合金相
を有し、相対密度が７０〜９７重量％である合金電気メ
ッキのアノード用Ｍｎ−Ｚｎ合金が提供される。また本
発明によれば、８０〜６０重量％のＭｎ粉末と２０〜４
０重量％のＺｎ粉末とを３００〜９００℃の温度下で５
Kg／cm2 以上の圧力で加圧焼結することを特徴とするＭ
ｎ−Ｚｎ合金の製造方法が提供される。According to the present invention, Mn
It is manufactured by pressure sintering a mixed powder of powder and Zn powder.
Provided is an Mn-Zn alloy for an anode of alloy electroplating, which has an alloy phase mainly composed of a β phase and a β 1 phase of an n-Zn solid solution and has a relative density of 70 to 97% by weight. Also according to the present invention, 80-60 wt% Mn powder and 20-4
5% by weight of Zn powder at a temperature of 300 to 900 ° C.
M characterized by pressure sintering at a pressure of Kg / cm 2 or more
A method of making an n-Zn alloy is provided.
【０００５】本発明は、従来の溶解法に代えて粉末加圧
焼結法（ホットプレス法）により、Ｍｎ粉末とＺｎ粉末
の混合粉末を加圧焼結して合金化する。なお加圧焼結法
によらず常圧焼結法を用いると、亜鉛の蒸気圧が高いた
め焼結体の密度が上がらず相対密度が６０％以下にな
る。加圧焼結法を利用することにより、高圧のため原料
粉末の焼結が促進され同時に亜鉛の蒸発も抑えられるの
で相対密度７０〜１００％の緻密な強度の大きい焼結体
が得らる。In the present invention, a mixed powder of Mn powder and Zn powder is pressure-sintered and alloyed by a powder pressure sintering method (hot pressing method) instead of the conventional melting method. When the atmospheric pressure sintering method is used instead of the pressure sintering method, since the vapor pressure of zinc is high, the density of the sintered body does not increase and the relative density becomes 60% or less. By using the pressure sintering method, the sintering of the raw material powder is promoted due to the high pressure and the evaporation of zinc is suppressed at the same time, so that a dense sintered body having a relative density of 70 to 100% and a high strength can be obtained.
【０００６】本発明で用いるＭｎ粉末およびＺｎ粉末の
粒度は２０〜１００μｍが好ましい。これらの粉末の粒
径が２０μｍ未満であると取込まれる酸素量が多くな
り、アノードとして用いたときにスラッジを発生する。
また上記粉末の粒径が１００μｍより大きいと合金化し
たときに組成が不均一になり易い。The particle size of Mn powder and Zn powder used in the present invention is preferably 20 to 100 μm. If the particle size of these powders is less than 20 μm, the amount of oxygen taken in is large and sludge is generated when used as an anode.
If the particle size of the powder is larger than 100 μm, the composition tends to be nonuniform when alloyed.
【０００７】Ｍｎ含有量は８０〜６０重量％であり、Ｚ
ｎ含有量は２０〜４０重量％である。具体的なＭｎとＺ
ｎの組成比はメッキ浴の合金組成に応じて適宜定められ
る。一般にＺｎ含有量が２０重量％より少なく、また４
０重量％より多いとメッキ膜の耐蝕性が低下するので好
ましくない。The Mn content is 80 to 60% by weight and Z
The n content is 20 to 40% by weight. Specific Mn and Z
The composition ratio of n is appropriately determined according to the alloy composition of the plating bath. Zn content is generally less than 20% by weight, and 4
If it is more than 0% by weight, the corrosion resistance of the plated film is deteriorated, which is not preferable.
【０００８】ホットプレスの圧力は５Kg／cm2 以上が好
ましい。５Kg／cm2 未満の圧力では焼結体の相対密度が
６０重量％以下になり、アノードとして用いた場合にス
ラッジが発生する。なお現状ではプレスの耐圧強度が10
00Kg／cm2 であり、従って実用上５〜1000Kg／cm2 のプ
レス圧が好ましい。なお圧力はプレス開始時から負荷し
てもよく、またキープ温度に達した時点から負荷しても
よい。この圧力はキープ温度終了後に解除される。ホッ
トプレスの雰囲気は、不活性ガス、真空、水素ガスなど
何れでもよい。The hot press pressure is preferably 5 kg / cm 2 or more. When the pressure is less than 5 kg / cm 2, the relative density of the sintered body becomes 60% by weight or less, and sludge is generated when it is used as an anode. At present, the pressure resistance of the press is 10
The pressing pressure is 00 kg / cm 2 , and therefore a pressing pressure of 5 to 1000 kg / cm 2 is preferable for practical use. The pressure may be applied from the start of pressing, or may be applied from the time when the keep temperature is reached. This pressure is released after the keep temperature ends. The atmosphere of the hot press may be any of inert gas, vacuum, hydrogen gas and the like.
【０００９】ホットプレスの温度は３００〜９００℃の
範囲が好ましい。加熱温度が３００℃より低いとＭｎと
Ｚｎが合金化せず、９００℃を越えて加熱しても合金化
時間は変わらない。ＭｎとＺｎの融点は各々1244℃、４
２０℃であり上記下限温度より大幅に高いが、本発明に
おいては原料粉末の固相拡散により３００℃〜９００℃
の温度範囲で合金化反応が進行する。上記加圧加熱時間
は１０分〜５時間が好ましい。１０分未満であると焼結
密度が小さく、５時間を越えも合金の相対密度は変わら
ない。また昇温速度は１〜２０℃／分が好ましい。１℃
／分未満では生産性が低く、２０℃／分より大きいと急
激な加熱によりＺｎの蒸発が激しくなるので好ましくな
い。焼結体の相対密度と合金相はホットプレス温度に影
響され、一般にホットプレス温度が高いほど相対密度が
大きく、またＭｎとＺｎの拡散が進む。従ってホットプ
レス温度を調整することにより合金相を制御することが
できる。The hot press temperature is preferably in the range of 300 to 900 ° C. If the heating temperature is lower than 300 ° C, Mn and Zn do not alloy, and even if the heating temperature exceeds 900 ° C, the alloying time does not change. The melting points of Mn and Zn are 1244 ℃ and 4 respectively.
It is 20 ° C., which is significantly higher than the above lower limit temperature, but in the present invention, it is 300 ° C. to 900 ° C. due to solid phase diffusion of the raw material powder
The alloying reaction proceeds in this temperature range. The pressure heating time is preferably 10 minutes to 5 hours. If it is less than 10 minutes, the sintered density is small, and even if it exceeds 5 hours, the relative density of the alloy does not change. The rate of temperature increase is preferably 1 to 20 ° C / minute. 1 ° C
If it is less than / min, the productivity is low, and if it is more than 20 ° C / min, Zn is violently vaporized by rapid heating, which is not preferable. The relative density and alloy phase of the sintered body are affected by the hot pressing temperature. Generally, the higher the hot pressing temperature is, the larger the relative density is, and the diffusion of Mn and Zn proceeds. Therefore, the alloy phase can be controlled by adjusting the hot press temperature.
【００１０】上記製造法によれば、Ｍｎ−Ｚｎ固溶体の
β相およびβ1 相の単相またはこれらの混合相、或いは
これらβ相およびβ1 相の高温相を主体とし、一部にα
相のＭｎ−Ｚｎ固溶体やα'-Ｍｎ−Ｚｎ金属間化合物相
が共存する金属組織からなる高密度Ｍｎ−Ｚｎ焼結合金
が得られる。According to the above manufacturing method, the β phase and the β 1 phase of the Mn—Zn solid solution are single phases or a mixed phase thereof, or the high temperature phases of the β phase and the β 1 phase are mainly contained, and α is partially formed.
A high-density Mn-Zn sintered alloy having a metallic structure in which the Mn-Zn solid solution of the phase and the α'-Mn-Zn intermetallic compound phase coexist is obtained.
【００１１】実施例１〜１０ 平均粒径３０μｍのＭｎ粉末（純度99.9％）とＺｎ粉末
（純度99.9％）を表１の組成になるように調製し均一に
混合した後にＢＮ粉末を塗布した炭素モールド（１２５
φ）に充填し、真空雰囲気中で表１に示す温度、圧力
（１５０Kg／cm2）条件でホットプレスを行なった。得
られた焼結体の密度を水中重量法で測定した。またＸ線
回折により焼結体の合金相を同定した。この結果を表３
に示した。表１および表３の結果から明らかなように、
３００℃〜９００℃の加圧焼結により、Ｍｎ含有量８０
〜６０重量％、β相およびβ1 相のＭｎ−Ｚｎ固溶体を
主体とする相対密度７０〜９７％のＭｎ−Ｚｎ焼結合金
が得られた。次に、上記Ｍｎ−Ｚｎ焼結合金を板状に加
工し、電解槽のアノードとして用い表２に示す電解条件
に従ってＦｅ板にＭｎ−Ｚｎ合金の電気メッキを施し
た。メッキ後、メッキ浴を濾過した後に浴中に残留した
Ｍｎ量およびＺｎ量、カソードのＦｅ板に電着したＭｎ
−Ｚｎ合金メッキ層のＭｎ量とＺｎ量を各々定量し、ア
ノードから溶出した全Ｍｎ量および全Ｚｎ量を調べた。
また通電量と溶出量からアノードの溶解効率を求め、さ
らにスラッジの有無を確認した。これらの結果を表４に
示した。Examples 1 to 10 Mn powder (purity 99.9%) and Zn powder (purity 99.9%) having an average particle size of 30 μm were prepared so as to have the composition shown in Table 1, and were uniformly mixed, and then BN powder was coated on the carbon. Mold (125
φ) and hot-pressed under the conditions of temperature and pressure (150 kg / cm 2 ) shown in Table 1 in a vacuum atmosphere. The density of the obtained sintered body was measured by a weight method in water. The alloy phase of the sintered body was identified by X-ray diffraction. The results are shown in Table 3.
It was shown to. As is clear from the results of Table 1 and Table 3,
Mn content of 80 by pressure sintering at 300 ° C to 900 ° C
A Mn-Zn sintered alloy having a relative density of 70 to 97%, which is composed mainly of a Mn-Zn solid solution of .beta. Next, the above Mn-Zn sintered alloy was processed into a plate shape and used as an anode of an electrolytic cell, and an Fe plate was electroplated with a Mn-Zn alloy according to the electrolysis conditions shown in Table 2. After plating, after filtering the plating bath, the amount of Mn and Zn remaining in the bath, Mn electrodeposited on the cathode Fe plate
The Mn amount and Zn amount of the Zn alloy plated layer were quantified respectively, and the total Mn amount and total Zn amount eluted from the anode were examined.
In addition, the dissolution efficiency of the anode was determined from the amount of electricity and the amount of elution, and the presence or absence of sludge was confirmed. The results are shown in Table 4.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【表２】 [Table 2]
【００１４】[0014]
【表３】 [Table 3]
【００１５】[0015]
【表４】 [Table 4]
【００１６】比較例１〜３ 表５に示す条件以外は上記実施例と同様にＭｎ−Ｚｎ焼
結体を製造し、これをアノードとして用い、実施例と同
一条件でＭｎ−Ｚｎ合金メッキを行なった。この結果を
表６に示した。Comparative Examples 1 to 3 Mn-Zn sintered bodies were produced in the same manner as in the above-mentioned examples except for the conditions shown in Table 5, and this was used as an anode, and Mn-Zn alloy plating was performed under the same conditions as in the examples. It was The results are shown in Table 6.
【００１７】[0017]
【表５】 [Table 5]
【００１８】[0018]
【表６】 [Table 6]
【００１９】[0019]
【発明の効果】本発明のＭｎ−Ｚｎ焼結合金は、Ｍｎ−
Ｚｎ合金電気メッキのアノードとして用いた場合、Ｍｎ
とＺｎが均一に溶出するので容易にメッキ浴中のＺｎ／
Ｍｎ比を一定に保持することができ、また溶解効率も高
く、スラッジも発生しない。The Mn-Zn sintered alloy of the present invention is Mn-Zn.
When used as an anode for Zn alloy electroplating, Mn
And Zn are uniformly eluted, so Zn / Zn in the plating bath can be easily
The Mn ratio can be kept constant, the dissolution efficiency is high, and no sludge is generated.
【表７】 [Table 7]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年９月２２日[Submission date] September 22, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】[0014]
【表３】 [Table 3]
Claims (3)
して製造され、Ｍｎ−Ｚｎ固溶体のβ相およびβ1 相を
主体とする合金相を有し、相対密度が７０〜９７重量％
である合金電気メッキのアノード用Ｍｎ−Ｚｎ合金。1. A mixed powder of Mn powder and Zn powder, which is manufactured by pressure sintering, has an alloy phase mainly composed of β phase and β 1 phase of Mn-Zn solid solution, and has a relative density of 70 to 97 weight. %
Is a Mn-Zn alloy for the anode of alloy electroplating.
量が２０〜４０重量％である請求項１のＭｎ−Ｚｎ合
金。2. The Mn-Zn alloy according to claim 1, wherein the Mn content is 80 to 60% by weight and the Zn content is 20 to 40% by weight.
重量％のＺｎ粉末とを３００〜９００℃の温度下で５Kg
／cm2 以上の圧力で加圧焼結することを特徴とするＭｎ
−Ｚｎ合金の製造方法。3. 80 to 60% by weight Mn powder and 20 to 40
5% by weight of Zn powder at a temperature of 300 to 900 ° C.
Mn characterized by pressure sintering at a pressure of / cm 2 or more
-Zn alloy manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23159692A JPH0657364A (en) | 1992-08-07 | 1992-08-07 | Mn-zn alloy for anode of alloy electroplating and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23159692A JPH0657364A (en) | 1992-08-07 | 1992-08-07 | Mn-zn alloy for anode of alloy electroplating and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0657364A true JPH0657364A (en) | 1994-03-01 |
Family
ID=16925996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23159692A Withdrawn JPH0657364A (en) | 1992-08-07 | 1992-08-07 | Mn-zn alloy for anode of alloy electroplating and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657364A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018016855A (en) * | 2016-07-28 | 2018-02-01 | 山陽特殊製鋼株式会社 | Sputtering target material |
| JP2020111833A (en) * | 2020-03-16 | 2020-07-27 | 山陽特殊製鋼株式会社 | Sputtering target material |
| CN114134378A (en) * | 2021-09-15 | 2022-03-04 | 上海大学 | A kind of high-entropy high-temperature manganese-based damping alloy material and preparation method thereof |
| CN114503306A (en) * | 2019-09-30 | 2022-05-13 | 松下知识产权经营株式会社 | Negative electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
-
1992
- 1992-08-07 JP JP23159692A patent/JPH0657364A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018016855A (en) * | 2016-07-28 | 2018-02-01 | 山陽特殊製鋼株式会社 | Sputtering target material |
| CN114503306A (en) * | 2019-09-30 | 2022-05-13 | 松下知识产权经营株式会社 | Negative electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| JP2020111833A (en) * | 2020-03-16 | 2020-07-27 | 山陽特殊製鋼株式会社 | Sputtering target material |
| CN114134378A (en) * | 2021-09-15 | 2022-03-04 | 上海大学 | A kind of high-entropy high-temperature manganese-based damping alloy material and preparation method thereof |
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| A300 | Withdrawal of application because of no request for examination |
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