JPS63121629A - Manufacture of shape memory alloy - Google Patents
Manufacture of shape memory alloyInfo
- Publication number
- JPS63121629A JPS63121629A JP26562986A JP26562986A JPS63121629A JP S63121629 A JPS63121629 A JP S63121629A JP 26562986 A JP26562986 A JP 26562986A JP 26562986 A JP26562986 A JP 26562986A JP S63121629 A JPS63121629 A JP S63121629A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- powder
- coated
- shape memory
- shape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000843 powder Substances 0.000 claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 31
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001000 nickel titanium Inorganic materials 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000009703 powder rolling Methods 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、Ｎｉ−７ｉ系形状記憶合金成形体の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for manufacturing a Ni-7i shape memory alloy compact.
従来の技術
Ｎｉ−７ｉ系形状記憶合金は、優れた形状記憶性を有す
るため、ばね、パイプ接手、その他店範囲の用途に用い
られており、粉末冶金によって製造されている。また、
Ｎｉ−１”’ｉ金合金第３の金属を加えて、変態点を移
動させることも提案されている。BACKGROUND OF THE INVENTION Ni-7i shape memory alloys have excellent shape memory properties and are used in springs, pipe joints, and other commercial applications, and are manufactured by powder metallurgy. Also,
It has also been proposed to add a third metal to the Ni-1''i gold alloy to shift the transformation point.
発明が解決しようとする問題点
しかしながら、Ｎｒ−ｒ；形状記憶合金は、全屈間化合
物であるため、成形加工性が悪い。即ち、ｘｒ−Ｔｉ合
金粉末は、変形しにくく、粉末をそのまま直接、圧延あ
るいはプレス成形しても、通常の条件では成形されず、
所望の形状のものが得られ難い。また、得られた成形製
品も機械加工性が悪く、したがって、価格も非常に高い
ものになっている。又、Ｎｉ−Ｔｉ合金に、第３の金属
を添加すると、変態点を変化させることができるが、第
３の金属を合金の溶解の段階で加えると、熱間加工性が
悪くなり、Ｒ造で割れを生じるという問題があった。Problems to be Solved by the Invention However, since the Nr-r shape memory alloy is a total bending compound, it has poor formability. In other words, the xr-Ti alloy powder is difficult to deform, and even if the powder is directly rolled or press-formed, it will not be molded under normal conditions.
It is difficult to obtain the desired shape. Furthermore, the resulting molded product also has poor machinability and is therefore very expensive. Also, adding a third metal to the Ni-Ti alloy can change the transformation point, but adding the third metal at the stage of melting the alloy will worsen hot workability and reduce R-forming. There was a problem of cracks occurring.
本発明は、上記従来の技術の問題点に鑑みてなされたも
ので、その目的は、成形加工性の悪いＮｉ−Ｔｉ合金粉
末を用いて、直接最終製品、又はそれに近い形状のもの
を容易に得る方法を提供することにある。The present invention has been made in view of the above-mentioned problems of the conventional technology, and its purpose is to easily produce final products directly or products with shapes similar to them using Ni-Ti alloy powder with poor moldability. The purpose is to provide a way to obtain
問題点を解決するための手段
本発明のＮｉ−Ｔｉ形状記憶合金の製造方法は、Ｎｉ−
７ｉ合金の粉末粒子を、Ｃｕ、Ｃｏ及びＰｄから選択さ
れた１種又はそれ以上の金属で被覆し、被覆処理された
Ｎｉ−Ｔｉ合金の粉末を成形し、焼結することを特徴と
する。Means for Solving the Problems The method for producing a Ni-Ti shape memory alloy of the present invention is a method for producing a Ni-Ti shape memory alloy.
The method is characterized in that 7i alloy powder particles are coated with one or more metals selected from Cu, Co, and Pd, and the coated Ni-Ti alloy powder is molded and sintered.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
Ｎｉ−１ｉ合金インゴットを先ず粉砕して、例えば粒径
１００μ程度の粉末粒子を得る。Ｎｉ−Ｔｉ合金として
は、一般に、Ｎｉが５３〜５７重量％で、残部がＴｉよ
りなるものが用いられる。A Ni-1i alloy ingot is first pulverized to obtain powder particles having a particle size of, for example, about 100 microns. As the Ni-Ti alloy, generally used is one containing 53 to 57% by weight of Ni and the remainder being Ti.
得られたＮｉ−Ｔｉ合金粉末粒子をＣｕ、Ｃｏ及びＰｄ
のいずれか一種又はそれ以上の金属を用いて被覆する。The obtained Ni-Ti alloy powder particles were mixed with Cu, Co and Pd.
coated with one or more of the following metals:
被覆は、どのような方法で行ってもよく、例えば、無電
解メッキ、蒸着、スパッタリング、湿式メッキ等によっ
て行われる。被覆される迅は、合金に対して２〜２０重
量％の範囲で、最終製品に求められる性質に応じて適宜
設定される。The coating may be performed by any method, for example, electroless plating, vapor deposition, sputtering, wet plating, etc. The amount of coating to be applied is in the range of 2 to 20% by weight based on the alloy, and is appropriately set depending on the properties required for the final product.
被覆処理された合金粉末は次に所定の形状、例えば、板
状あるいは円筒状に成形され、１０００°Ｃ前後の温度
で焼結される。この場合、合金粉末に熱間静水圧をかけ
て、例えば、９００’Ｃで’１０００気圧の条件のもと
で、成形と焼結とを同時に行ってもよい。また、合金粉
末をロール間に供給して直接圧延する粉末直接圧延法に
よって成形してもよい。The coated alloy powder is then formed into a predetermined shape, such as a plate or cylinder, and sintered at a temperature of about 1000°C. In this case, hot isostatic pressure may be applied to the alloy powder to simultaneously perform molding and sintering under conditions of, for example, 900'C and 1,000 atm. Alternatively, the molding may be performed by a powder direct rolling method in which alloy powder is supplied between rolls and directly rolled.
得られたＮｉ−’ｌ’−ｉ合金焼結体は、必要に応じて
、更に加工、例えば、冷間加工した後、所望の形状に拘
束して４５０〜５００℃に加熱し、形状記憶処理を行う
。The obtained Ni-'l'-i alloy sintered body is further processed, for example, cold worked, if necessary, and then constrained to a desired shape and heated to 450 to 500°C to undergo shape memory treatment. I do.
本発明において、Ｎｉ−Ｔｉ合金の粉末粒子をＣＵ、Ｃ
ｏあるいはＰｄで被覆したものを使用すると、加工性が
改善されるほか、これらの金属がｘｉ−Ｔｒ金合金添加
されることによるＮｉ−Ｔｉ合金の性状の改変効果もあ
る。すなわち、Ｃｕで被覆すると、Ｎｉ−１”ｉ合金の
Ｎｉ＠量の変化による変態点の変化が小さくなる。また
、ＣＯで被覆すると、変態点Ｏ′Ｃ前後のものが得られ
、Ｐｄで被覆すると、１２０〜２００℃の範囲の変態点
を有するものが得られる。In the present invention, Ni-Ti alloy powder particles are CU, C
The use of a Ni-Ti alloy coated with O or Pd not only improves workability but also has the effect of modifying the properties of the Ni-Ti alloy by adding these metals to the xi-Tr gold alloy. That is, when coated with Cu, the change in the transformation point due to the change in the amount of Ni in the Ni-1"i alloy becomes smaller. When coated with CO, a transformation point around O'C is obtained, and when coated with Pd, Then, a material having a transformation point in the range of 120 to 200°C is obtained.
なお、Ｎ ｉ −Ｔ ｉ合金の粉末粒子の被覆を、上記
金属の変わりにＮｉを用いて行うと、Ｎｉ−Ｔｉ合金の
Ｎｉ含量の調整が容易になる。即ち、Ｎｉ含量の低いＮ
ｉ−４ｒ合金を製造した後、Ｎｉで被覆することによっ
て、所定量のＮｉ含量の合金を製造することが可能にな
る。Note that if the powder particles of the Ni--Ti alloy are coated with Ni instead of the above-mentioned metal, the Ni content of the Ni--Ti alloy can be easily adjusted. That is, N with low Ni content
After producing the i-4r alloy, coating it with Ni makes it possible to produce an alloy with a certain amount of Ni content.
作用
本発明においては、Ｎｒ−Ｔｒ金合金粉末粒子をＣｕ、
ＣｏあるいはＰｄ等の金属によって被覆するから、粉末
粒子を成形し、焼結する際に、上記の金属が粉末粒子間
を満たし、粉末粒子の成形性を向上すると共に、焼結に
際してバインダーとしての役割を果たす。しかもそれ等
Ｃｕ、Ｃ：、ｏ及びＰｄ等の金属は、Ｎｉ−Ｔｉ合金の
変態点を変化させる作用も示す。Function In the present invention, Nr-Tr gold alloy powder particles are made of Cu,
Since it is coated with a metal such as Co or Pd, when the powder particles are formed and sintered, the above metal fills the space between the powder particles, improving the formability of the powder particles, and also plays a role as a binder during sintering. fulfill. Furthermore, metals such as Cu, C:, O, and Pd also exhibit the effect of changing the transformation point of the Ni-Ti alloy.
実施例 以下、本発明を実施例によって説明する。Example Hereinafter, the present invention will be explained by examples.
実施例１
Ｎｉ５５％−Ｔｉ４５％合金粉末（粒度≦１００μｍ）
を、５Ａ酸銅水溶液に入れ、ホルムアルデヒドで還元す
る無電解メッキを実施した。Example 1 55% Ni-45% Ti alloy powder (particle size ≦100 μm)
was placed in a 5A acid copper aqueous solution, and electroless plating was performed by reducing it with formaldehyde.
被覆した銅の割合は、重量％で１０％であった。The proportion of coated copper was 10% by weight.
この粉末を、ロール径１５０ｍの圧延機により、加圧力
５ ｔｏｎ／ｃｆｆｌで加圧して、直接圧延により、厚
み１．０、幅５０＃の薄板を得た。この薄板は、ｆで変
形が可能であるが、未だ、空隙が認められるため、１０
５０℃で３時間真空焼結を実施した。This powder was pressed with a pressure of 5 ton/cffl using a rolling mill with a roll diameter of 150 m, and a thin plate having a thickness of 1.0 and a width of 50# was obtained by direct rolling. This thin plate can be deformed at f, but voids are still observed, so 10
Vacuum sintering was performed at 50° C. for 3 hours.
焼結後、冷間圧延によって０．５ｍ厚の薄板とし、−・
部切断してＵ字型に曲げ、固定して５００’Ｃの形状記
憶処理を施した。After sintering, it is made into a thin plate of 0.5m thickness by cold rolling, and -
It was cut into parts, bent into a U shape, fixed, and subjected to 500'C shape memory treatment.
これを室温で直線に変形し、加熱したところ、元の形に
完全に回復した。この時の回復温度は、６５°Ｃであっ
た。When this was deformed into a straight line at room temperature and heated, it completely recovered to its original shape. The recovery temperature at this time was 65°C.
以上の変形−回復を繰返し実施しても、へたり、破断は
みられず、溶製月と全く同一でおることがわかった。Even when the above deformation-recovery process was repeated, no wear or breakage was observed, and it was found that the moon was exactly the same as the melted moon.
実施例２
Ｎｉ５５．５％−Ｔｉ４４．５％合金粉末（粒度≦２０
０μｍ）を、塩化コバルト水溶液に入れ、次亜リン酸ナ
トリウムによって還元して、ＣＯを析出させた。被覆し
たコバルトの量は、重量％で、２．２％であった。Example 2 Ni55.5%-Ti44.5% alloy powder (particle size ≦20
0 μm) was placed in an aqueous cobalt chloride solution and reduced with sodium hypophosphite to precipitate CO. The amount of cobalt coated was 2.2% by weight.
この粉末を用いて、内径１５Ｊ７１ｆｆｉ、外径２５ｍ
の二重化の中に入れ、二重化の中を脱気、封孔して、１
０００’Ｃで１時間、１０００気圧で熱間静水圧プレス
を行った。焼結後の試料を、スェージングにより外径１
２ｍ（内径１０ｍ＞まで加工した後、二重化を機械加工
で除去して、パイプ継手を作成した。この継手は、−４
０’Ｃぐらいで軟化し、０℃以上で元の形に戻ることが
わかった。Using this powder, the inner diameter is 15J71ffi and the outer diameter is 25m.
Put it in the duplex, deaerate and seal the inside of the duplex, 1
Hot isostatic pressing was carried out at 1000 atm for 1 hour at 000'C. After sintering, the sample is swaged to reduce the outer diameter to 1
2 m (inner diameter 10 m>), the duplication was removed by machining to create a pipe joint. This joint was -4
It was found that it softens at about 0'C and returns to its original shape at temperatures above 0C.
実施例３
Ｎｉ５４％−Ｔｉ４６％粉末（粒径≦２００μ′ｒｒＬ
）を容器に入れ、塩化パラジウムと水素気流中で、化学
蒸着を行い、粉末の表面に、パラジウム膜を形成した。Example 3 Ni54%-Ti46% powder (particle size ≦200μ'rrL
) was placed in a container, and chemical vapor deposition was performed in a flow of palladium chloride and hydrogen to form a palladium film on the surface of the powder.
被覆パラジウム母は、重囲で３％でめった。The coated palladium matrix was found to be 3% heavy.
この粉末をプレス成型してφ２５Ｘ３００．Ｑの棒状に
し、１０５０’Ｃで５時間真空焼結を行った。This powder was press-molded to a diameter of φ25×300. It was made into a Q rod shape and vacuum sintered at 1050'C for 5 hours.
焼結後、熱間圧延−伸線加工により、１．０＃径の線材
を製造した。この線材を、直線に固定して、５００’Ｃ
で熱処理を実施した。室温で変形した後、加熱して行く
と、１４５℃で元の直線形状へ回復した。After sintering, a wire rod with a diameter of 1.0# was manufactured by hot rolling and wire drawing. Fix this wire in a straight line and heat it to 50'C.
Heat treatment was carried out. After being deformed at room temperature, when heated, it recovered to its original linear shape at 145°C.
発明の効果
本発明は、前記のようにＣｕ、ＣＯ及びＰｄから選択さ
れた金属で被覆したＮｉ−Ｔｉ合金粉末粒子を成形し、
焼結するものであるから、成形加工性の悪いＮｉ−Ｔｉ
合金を、その粉末から直接、最終製品又はそれに近い形
状のものにすることができる。したがって、所望の形状
及び変態点を有するＮｉ−Ｔｉ形状記憶合金を容易に！
！造することが可能になる。Effects of the Invention The present invention forms Ni-Ti alloy powder particles coated with a metal selected from Cu, CO and Pd as described above,
Ni-Ti has poor moldability because it is sintered.
The alloy can be made directly from the powder into a final product or a shape close to it. Therefore, it is easy to create a Ni-Ti shape memory alloy with a desired shape and transformation point!
! It becomes possible to build.
Claims (2)
ｄから選択された１種又はそれ以上の金属で被覆し、被
覆処理されたＮｉ−Ｔｉ合金の粉末を成形し、焼結する
ことを特徴とするＮｉ−Ｔｉ系形状記憶合金成形体の製
造方法。(1) Ni-Ti alloy powder particles are mixed with Cu, Co and P.
A method for producing a Ni-Ti-based shape memory alloy molded body, which comprises coating with one or more metals selected from d, molding and sintering the coated Ni-Ti alloy powder. .
接圧延法によって成形する特許請求の範囲第１項に記載
のＮｉ−Ｔｉ系形状記憶合金成形体の製造方法。(2) The method for producing a Ni-Ti-based shape memory alloy molded body according to claim 1, wherein the coated Ni-Ti alloy powder is molded by a direct powder rolling method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26562986A JPS63121629A (en) | 1986-11-10 | 1986-11-10 | Manufacture of shape memory alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26562986A JPS63121629A (en) | 1986-11-10 | 1986-11-10 | Manufacture of shape memory alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63121629A true JPS63121629A (en) | 1988-05-25 |
Family
ID=17419789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26562986A Pending JPS63121629A (en) | 1986-11-10 | 1986-11-10 | Manufacture of shape memory alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63121629A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0297696A (en) * | 1988-10-04 | 1990-04-10 | Shinko Kosen Kogyo Kk | Ni-ti-based alloy material and production thereof |
| CN107008905A (en) * | 2017-02-25 | 2017-08-04 | 河北工业大学 | The preparation method of TiNiCu marmem based damping composite materials |
| CN112760511A (en) * | 2020-12-24 | 2021-05-07 | 先导薄膜材料（广东）有限公司 | Preparation method of titanium-nickel-palladium alloy |
Citations (3)
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|---|---|---|---|---|
| JPS5073803A (en) * | 1973-11-01 | 1975-06-18 | ||
| JPS5893803A (en) * | 1981-11-12 | 1983-06-03 | テイツセン・イングウストリ−・アクチエンゲゼルシヤフト | Production of press article by press-forming fregile granular alloy powder |
| JPS60138029A (en) * | 1983-12-27 | 1985-07-22 | Daido Steel Co Ltd | Production of metallic powder molding |
-
1986
- 1986-11-10 JP JP26562986A patent/JPS63121629A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5073803A (en) * | 1973-11-01 | 1975-06-18 | ||
| JPS5893803A (en) * | 1981-11-12 | 1983-06-03 | テイツセン・イングウストリ−・アクチエンゲゼルシヤフト | Production of press article by press-forming fregile granular alloy powder |
| JPS60138029A (en) * | 1983-12-27 | 1985-07-22 | Daido Steel Co Ltd | Production of metallic powder molding |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0297696A (en) * | 1988-10-04 | 1990-04-10 | Shinko Kosen Kogyo Kk | Ni-ti-based alloy material and production thereof |
| CN107008905A (en) * | 2017-02-25 | 2017-08-04 | 河北工业大学 | The preparation method of TiNiCu marmem based damping composite materials |
| CN112760511A (en) * | 2020-12-24 | 2021-05-07 | 先导薄膜材料（广东）有限公司 | Preparation method of titanium-nickel-palladium alloy |
| CN112760511B (en) * | 2020-12-24 | 2022-07-12 | 先导薄膜材料（广东）有限公司 | Preparation method of titanium-nickel-palladium alloy |
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