JPS63483A - Activating solution for electroless nickel plating - Google Patents
Activating solution for electroless nickel platingInfo
- Publication number
- JPS63483A JPS63483A JP14395686A JP14395686A JPS63483A JP S63483 A JPS63483 A JP S63483A JP 14395686 A JP14395686 A JP 14395686A JP 14395686 A JP14395686 A JP 14395686A JP S63483 A JPS63483 A JP S63483A
- Authority
- JP
- Japan
- Prior art keywords
- electroless nickel
- nickel plating
- alkali metal
- activating
- hydroxide
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000007747 plating Methods 0.000 title claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 17
- 230000003213 activating effect Effects 0.000 title abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- -1 alkali metal gold cyanide Chemical class 0.000 claims abstract description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 7
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000001994 activation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000010931 gold Substances 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は無電解ニッケルめっき用活性化液に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an activating solution for electroless nickel plating.
（従来の技術）
無電解ニッケルめっきにおいては、無電解ニッケルめっ
き反応をスタートさせるため素材に前処理としての活性
化処理を行っている。すなわち無電解ニッケルめっきに
おいては、素材をいきなりめっき液中にｉ％ ｉ７２し
ても反応が起こらず、活性化処理を行って素材表面上に
反応の核となる金属を付着させる必要があり、めっき膜
はこの核となる金属を中心として成長するのである。こ
の核となる金属は＾Ｕ、八ｇへ Ｐｄ、 Ｐｔ等の貴金
属である。(Prior Art) In electroless nickel plating, activation treatment is performed on the material as a pretreatment in order to start the electroless nickel plating reaction. In other words, in electroless nickel plating, even if the material is suddenly immersed in the plating solution at i% i72, no reaction occurs, and it is necessary to perform an activation treatment to attach the metal that will become the nucleus of the reaction on the surface of the material. The film grows around this core metal. The core metals are noble metals such as Pd and Pt.
上記の活性化処理のための活性化液は、Ｓｎ２＋を主成
分とするセンシタイザ−と称する液と、Ｐｄ”を主成分
とするアクチベーターと称する液との２液がある。There are two types of activating solutions for the above-mentioned activation process: a solution called a sensitizer containing Sn2+ as a main component, and a solution called an activator containing Pd'' as a main component.
活性化処理を行うには、まず素材をセンシタイザ−に浸
漬する。するとセンシタイザ−中のＳｎ ２＋がめっき
すべき金属部分に選択的に付着する。次いで素材をアク
チベーターに浸漬すれば、アクナベ−ター中のＰｄ２＋
が上記のＳｎ２＋と置換してめっきすべき金属部分に付
着するのである。To carry out the activation treatment, the material is first immersed in a sensitizer. Then, Sn 2+ in the sensitizer selectively adheres to the metal portion to be plated. Next, if the material is immersed in an activator, the Pd2+ in the activator
is attached to the metal part to be plated, replacing the above-mentioned Sn2+.
なお活性化液にはＳｎ２＋とＰｄ２＋とが混在する１液
のものもある。Note that there is also a one-liquid activating solution in which Sn2+ and Pd2+ are mixed.
このようにＳｎ２＋が選択性を有するから、例えばセラ
ミック基板上に形成したタングステンメタライズの配線
パターン上に無電解ニッケルめっきを行うのに好適であ
る。Since Sn2+ has such selectivity, it is suitable for performing electroless nickel plating on, for example, a tungsten metallized wiring pattern formed on a ceramic substrate.
（発明が解決しようとする問題点）
しかし上記従来の活性化液にも次のような問題点がある
。(Problems to be Solved by the Invention) However, the above conventional activating solution also has the following problems.
すなわち、センシタイザ−とアクチベーターの２液を準
備するのは厄介である。また上記のようにＳｎ２＋とＰ
ｄ２＋とが混在する１液のものもあるが、Ｓｎ２＋とＰ
ｄ２＋のイオン濃度のバランスを保つための液管理が厄
介である。That is, it is troublesome to prepare two liquids, a sensitizer and an activator. Also, as mentioned above, Sn2+ and P
There are one-liquid products that contain a mixture of Sn2+ and P.
Liquid management to maintain the balance of d2+ ion concentration is difficult.
さらには、Ｓｎ２＋は選択性を有してめっきすべき金属
部分のみに付着するが、Ｐｄ２＋は選択性を有さないの
で、非金属部分にも若干付着して該部位に無電解ニッケ
ルめっき膜が形成されるおそれがある。Furthermore, Sn2+ has selectivity and adheres only to the metal parts to be plated, but Pd2+ does not have selectivity, so it adheres to some non-metallic parts and forms an electroless nickel plating film on those parts. There is a risk of formation.
そこで本発明は上記問題点を解消すべくなされたもので
あり、その目的とするところは、１液でよく、かつ選択
性に優れ、目的とする部位のみに確実にめっきを行える
無電解ニッケルめっき用活性化液を提供するにある。Therefore, the present invention was made to solve the above problems, and its purpose is to provide electroless nickel plating that requires only one liquid, has excellent selectivity, and can reliably plate only the target areas. To provide an activating solution for use.
（発明の構成） 本発明は上記問題点を解消するため次の構成を備える。(Structure of the invention) The present invention has the following configuration to solve the above problems.
すなわち、シアン化金アルカリ金属と水酸化アルカリ金
属とジメチルチオ尿素等の錯化剤と必要に応じてＰＨ緩
衝剤とを含むことを特徴とする。That is, it is characterized by containing an alkali metal cyanide, an alkali metal hydroxide, a complexing agent such as dimethylthiourea, and, if necessary, a PH buffer.
シアン化金アルカリ金属は金の供給源で１〜１０ｇｅｌ
で有効である。水酸化アルカリ金属は、ＫＯＨｌＮ ａ
Ｏｔｌ等が有効であり、めっき部位の金属、例えばタ
ングステンを若干溶解し、Ｗ６＋とじて液中に存在させ
る。水酸化アルカリ金属は５０〜２００ｇ／ １で用い
られ、液をＰＨＩＯ〜１４の強アルカリにする。Gold alkali metal cyanide is a gold source with 1-10 gel
is valid. Alkali metal hydroxide is KOHlNa
Otl or the like is effective, as it slightly dissolves the metal in the plating area, such as tungsten, and makes it exist in the solution as W6+. Alkali metal hydroxide is used at 50-200g/1 to make the liquid a strong alkaline with a PHIO~14.
このＷ６＋と置換してＡｕがめつき部位の金属に付着す
るのである。ジメチルチオ尿素等の錯化剤は液中に熔解
したＷ６＋を錯化し、安定に保持する。錯化剤は尿素等
のイオウを含む化合物が好適であり、濃度は１０〜３０
ｇ／ １程度が良好である。Au replaces this W6+ and adheres to the metal at the plating site. A complexing agent such as dimethylthiourea complexes W6+ dissolved in the liquid and stably maintains it. The complexing agent is preferably a compound containing sulfur such as urea, and the concentration is 10 to 30.
About g/1 is good.
なお好適には、ＰＨの変動を抑えるためクエン酸ニアン
モニウム等の緩衝剤を１０〜４０ｇ／ ４２程度加える
。クエン酸ニアンモニウムは緩衝作用の他に、液中に含
まれ、あるいは液中にもち込まれる不純物金属の錯化作
用も有する。ｆｆｔ 衝剤としてはクエン酸アンモニウ
ムと併用して、あるいは単独で酒石酸アンモニウム、Ｅ
ＤＴＡニナトリウム、ＥＤＴＡ三ナトリウム等を用いる
ことができる。Preferably, about 10 to 40 g/42 of a buffer such as ammonium citrate is added to suppress pH fluctuations. In addition to its buffering effect, ammonium citrate also has a complexing effect on impurity metals contained in or brought into the liquid. fft Ammonium tartrate, E
DTA disodium, EDTA trisodium, etc. can be used.
（実施例）
シアン化金カリウム ２ｇ／ｌクエン酸
ニアンモニウム ２０ｇ／ １ジメチルチオ尿
素 ２５ｇ／ １水酸化カリウム
１００ｇ／β液温
８０℃セラミック基板上にタングステンメタライズ
配線パターンを形成したものを、アルカリ脱脂、水洗、
酸浸漬、水洗したのち、上記組成の活性化液に浸漬し、
タングステンメタライズ配線パターン上にＡｕを付着さ
せた。次いでセラミック基板を無電解ニッケルめっき浴
中に浸漬したところ、タングステンメタライズ配線パタ
ーン上に緻密で、かつ密着性に優れた無電解ニッケルめ
っき膜を得た。(Example) Potassium gold cyanide 2g/l Niammonium citrate 20g/1 dimethylthiourea 25g/potassium hydroxide
100g/β liquid temperature
A tungsten metallized wiring pattern was formed on an 80°C ceramic substrate, which was then degreased with alkaline, washed with water,
After immersion in acid and washing with water, immersion in an activation solution with the above composition,
Au was deposited on the tungsten metallized wiring pattern. Next, the ceramic substrate was immersed in an electroless nickel plating bath, and a dense electroless nickel plating film with excellent adhesion was obtained on the tungsten metallized wiring pattern.
セラミック基板上の他の部位に無電解ニッケルめっき膜
が形成されることはなかった。No electroless nickel plating film was formed on other parts of the ceramic substrate.
なお、配線パターンを、モリブデンメタライズ、モリブ
デン−マンガンメタライズでそれぞれ形成した場合にお
いても、上記の活性化処理を行うことで配線パターン上
に上記同様に良好な無電解ニッケルめっき膜を形成する
ことができた。Note that even when the wiring pattern is formed using molybdenum metallization or molybdenum-manganese metallization, it is possible to form a good electroless nickel plating film on the wiring pattern by performing the above activation treatment. Ta.
、核金属の供給源として、シアン化金アルカリ金属の代
りにシアン化銀アルカリ金属を用いた活性化液で活性化
処理を行い、無電解ニッケルめっきを行ったところ、め
っき膜は得られたが素材全屈上への密着度はよくなかっ
た。When electroless nickel plating was performed using an activation solution using alkali metal silver cyanide instead of alkali metal gold cyanide as a source of nuclear metal, a plated film was obtained. The degree of adhesion of the material to the top was not good.
また核金属供給源としてＰｄ含有化合物を用いた場合に
は、やはり選択性に問題があった。Furthermore, when a Pd-containing compound is used as a nuclear metal source, there is still a problem in selectivity.
（発明の効果）
以上のように本発明に係る活性化液によれば、ｌ液で済
み、しかも選択性よく核となるＡｕを素材の所定金泥上
に付着させることができる。しかも得られる無電解ニッ
ケルめっき膜は緻密で、かつ密着度のよいものであった
。(Effects of the Invention) As described above, according to the activating liquid according to the present invention, only one liquid is required, and Au, which serves as a nucleus, can be deposited on a predetermined gold slurry of a material with good selectivity. Moreover, the electroless nickel plating film obtained was dense and had good adhesion.
以上本発明につき好適な実施例を挙げて種々説明したが
、本発明はこの実施例に限定されるものではなく、発明
の精神を逸脱しない範囲内で多くの改変を施し得るのは
もらろんのことである。Although the present invention has been variously explained above with reference to preferred embodiments, the present invention is not limited to these embodiments, and it goes without saying that many modifications can be made without departing from the spirit of the invention. It is about.
Claims (1)
メチルチオ尿素等の錯化剤と必要に応じてＰＨ緩衝剤と
を含む無電解ニッケルめっき用活性化液。1. An activation solution for electroless nickel plating containing alkali metal cyanide, alkali metal hydroxide, a complexing agent such as dimethylthiourea, and optionally a PH buffer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61143956A JPH0765180B2 (en) | 1986-06-19 | 1986-06-19 | Non-electrolytic nickel activating liquid for plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61143956A JPH0765180B2 (en) | 1986-06-19 | 1986-06-19 | Non-electrolytic nickel activating liquid for plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63483A true JPS63483A (en) | 1988-01-05 |
| JPH0765180B2 JPH0765180B2 (en) | 1995-07-12 |
Family
ID=15350962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61143956A Expired - Lifetime JPH0765180B2 (en) | 1986-06-19 | 1986-06-19 | Non-electrolytic nickel activating liquid for plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0765180B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7081172B2 (en) | 2001-03-13 | 2006-07-25 | Aisin Seiki Kabushiki Kaisha | Nodular graphite cast iron with high strength and high toughness |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4829635A (en) * | 1971-08-20 | 1973-04-19 | ||
| JPS53118228A (en) * | 1977-03-25 | 1978-10-16 | Hitachi Ltd | Method of plating |
| JPS54100931A (en) * | 1978-01-27 | 1979-08-09 | Hitachi Ltd | Electroless nickel plating |
-
1986
- 1986-06-19 JP JP61143956A patent/JPH0765180B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4829635A (en) * | 1971-08-20 | 1973-04-19 | ||
| JPS53118228A (en) * | 1977-03-25 | 1978-10-16 | Hitachi Ltd | Method of plating |
| JPS54100931A (en) * | 1978-01-27 | 1979-08-09 | Hitachi Ltd | Electroless nickel plating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7081172B2 (en) | 2001-03-13 | 2006-07-25 | Aisin Seiki Kabushiki Kaisha | Nodular graphite cast iron with high strength and high toughness |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0765180B2 (en) | 1995-07-12 |
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