JPH0459064B2 - - Google Patents
Info
- Publication number
- JPH0459064B2 JPH0459064B2 JP50792489A JP50792489A JPH0459064B2 JP H0459064 B2 JPH0459064 B2 JP H0459064B2 JP 50792489 A JP50792489 A JP 50792489A JP 50792489 A JP50792489 A JP 50792489A JP H0459064 B2 JPH0459064 B2 JP H0459064B2
- Authority
- JP
- Japan
- Prior art keywords
- mold
- nickel
- alloy
- copper
- boron
- 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.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 50
- 229910000521 B alloy Inorganic materials 0.000 claims description 31
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 claims description 30
- 229910000831 Steel Inorganic materials 0.000 claims description 25
- 239000010959 steel Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 22
- 229910052796 boron Inorganic materials 0.000 claims description 22
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 17
- 238000009749 continuous casting Methods 0.000 claims description 11
- 239000010410 layer Substances 0.000 description 71
- 229910045601 alloy Inorganic materials 0.000 description 32
- 239000000956 alloy Substances 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000005266 casting Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011253 protective coating Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229940074439 potassium sodium tartrate Drugs 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/059—Mould materials or platings
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Continuous Casting (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、鉄鋼、例えば低炭素銅、高炭素鋼、
ステンレス鋼、特殊鋼等の連続鋳造用鋳型、より
詳しくは長い寿命を有する鉄鋼連続鋳造用鋳型に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is applicable to steel, such as low carbon copper, high carbon steel,
The present invention relates to a mold for continuous casting of stainless steel, special steel, etc., and more specifically to a mold for continuous casting of steel with a long life.
従来の技術
鉄鋼連続鋳造用鋳型は、その上部から溶鋼を注
入し、下部から冷却により固化した鋳片を引き抜
いて連続的に鋳造を行う鋳型であり、生産性向上
の観点から長寿命が要求される。従来、長寿命の
鉄鋼連続鋳造用鋳型としては、特公昭55−40341
号に記載の鋳型が知られている。この鋳型は、鋳
型を構成する銅又は銅合金の溶鋼注入面に(A)ニッ
ケル及びコバルトの少なくとも１種からなる中間
めっき層及び(B)リン３〜20重量％及びホウ素２〜
15重量％の少なくとも１種と残部ニツケル及びコ
バルトの少なくも１種からなる合金めつき層を順
次施したものである。この鋳型が長寿命を有する
理由は、上記中間層Ａの使用により、硬度の極め
て低い銅又は合金からなる鋳型基体と高硬度の合
金層Ｂとの硬度勾配をなだらかなものとすること
により鋳型基体、中間層及び合金層の三者の相互
の密着性が高くなっていること、並びに合金層の
高温における耐熱性及び耐摩耗性が高いことに基
づくものとされている。Conventional technology Continuous steel casting molds are molds that perform continuous casting by injecting molten steel into the upper part and pulling out the solidified slab from the lower part, and are required to have a long life from the perspective of improving productivity. Ru. Conventionally, as a long-life continuous steel casting mold, the
The mold described in this issue is known. This mold has (A) an intermediate plating layer consisting of at least one of nickel and cobalt on the molten steel injection surface of copper or copper alloy constituting the mold, and (B) 3 to 20% by weight of phosphorus and 2 to 20% by weight of boron.
An alloy plating layer consisting of 15% by weight of at least one metal and the balance of at least one of nickel and cobalt is sequentially applied. The reason why this mold has a long life is because the use of the intermediate layer A makes the hardness gradient between the mold base made of extremely low hardness copper or alloy and the high hardness alloy layer B gentle. This is based on the high adhesion between the intermediate layer and the alloy layer, and the high heat resistance and wear resistance of the alloy layer at high temperatures.
また上記鋳型の改良として、上記合金層Ｂの上
に更にクロムめっき層を設けた鋳型（特公昭52−
50734号）及び上記合金層Ｂを酸化して酸化被膜
層を形成した鋳型（特公昭52−50733号）も知ら
れている。これ等鋳型においては、そのクロムめ
っき層又は酸化被膜層により、溶鋼の鋳込開始初
期に発生する溶鋼飛沫（スプラッシュ）の鋳型表
面への固着を無くし、いわゆるブレークアウト事
故を確実に防止するものであり、上記鋳型基体、
中間層及び合金層の三者相互の高い密着性及び合
金層の高温における耐摩耗性とあいまつて、上記
特公昭55−40341号に記載の鋳型よりも更に長い
鋳型寿命を達成している。 In addition, as an improvement to the above mold, a mold in which a chromium plating layer was further provided on the above alloy layer B (Special Publication No. 52-
No. 50734) and a mold in which an oxide film layer is formed by oxidizing the alloy layer B (Japanese Patent Publication No. 52-50733) are also known. In these molds, the chrome plating layer or oxide layer prevents the molten steel splash that occurs in the early stages of pouring of molten steel from sticking to the mold surface, thereby reliably preventing so-called breakout accidents. Yes, the above mold base,
Combined with the high adhesion between the intermediate layer and the alloy layer and the wear resistance of the alloy layer at high temperatures, this mold achieves a longer mold life than the mold described in Japanese Patent Publication No. 55-40341.
発明が解決しようとする課題
上記２層又は３層の保護被膜を有する鋳型は、
いずれも、ニッケル及びコバルトの少なくとも１
種からなる中間層を必須とし、その上に合金層を
設け、３層構造のものにあっては、更にクロムめ
っき層又は酸化被膜層を設けるため、製造工程が
繁雑であり、コストの高いものとなっている。Problems to be Solved by the Invention The mold having the above-mentioned two-layer or three-layer protective coating,
At least one of nickel and cobalt
An intermediate layer consisting of a seed is essential, an alloy layer is provided on top of that, and in the case of a three-layer structure, a chromium plating layer or an oxide film layer is additionally provided, making the manufacturing process complicated and costly. It becomes.
課題を解決するための手段
本発明者は、上部から溶鋼を注入し、下部から
鋳片を引き抜くタイプの鋳型に関し、構造的に単
純であつて、製造が容易な鋳型基体（鋳型内面を
構成する銅または銅合金製のプレート又はチユー
ブ）の保護被膜を開発すべく、鋭意研究を重ね
た。その結果、ニツケル−ホウ素合金めつき被膜
は基体銅又は銅合金と密着性が乏しいとされてい
たにも拘らず、特定範囲の低いホウ素含量を有す
るニツケル−ホウ素合金めつき被膜は、基体銅又
は銅合金との密着性に優れ、上記従来の鋳型の中
間層を使用しなくとも単独でそのまま極めて優れ
た保護被膜層となり、前記２層又は３層の保護被
膜を有する鋳型と同等又はそれ以上の長寿命を有
する鋳型が得られるという驚くべき事実を見出だ
した。本発明は、この新知見に基づき完成された
ものである。Means for Solving the Problems The present inventor has proposed a mold base (constituting the inner surface of the mold) that is structurally simple and easy to manufacture, regarding a type of mold in which molten steel is injected from the upper part and a slab is pulled out from the lower part. Intensive research was conducted to develop a protective coating for copper or copper alloy plates (plates or tubes). As a result, although nickel-boron alloy plating films were said to have poor adhesion to the base copper or copper alloy, it was found that nickel-boron alloy plating films with a low boron content within a specific range were It has excellent adhesion to the copper alloy, and even without using the intermediate layer of the conventional mold mentioned above, it becomes an extremely excellent protective coating layer as it is, and is equivalent to or better than the mold having two or three layers of protective coating. We have discovered the surprising fact that a mold with a long life can be obtained. The present invention was completed based on this new knowledge.
本発明は、銅又は銅合金からなる鉄鋼連続鋳造
用鋳型であつて、その銅又は銅合金からなる鋳型
基体上に、ホウ素0.05重量％から0.5重量％未満
を含有し、50μｍ〜２mmの厚さを有するニツケル
−ホウ素合金めつき層を形成したことを特徴とす
る鉄鋼連続鋳造用鋳型を提供するものである。 The present invention is a mold for continuous casting of steel made of copper or copper alloy, which contains boron from 0.05% by weight to less than 0.5% by weight on the mold base made of copper or copper alloy, and has a thickness of 50 μm to 2 mm. The present invention provides a mold for continuous casting of steel, characterized in that a nickel-boron alloy plating layer is formed thereon.
本発明では、鋳型基体上に単に上記特定のホウ
素含量のニツケル−ホウ素合金めつき層を設ける
という簡単な構成により、従来の２層又は３層の
保護被膜を有する鋳型と同等又はそれ以上の鋳型
寿命を達成するものである。このことは、従来の
技術において、ニツケル−ホウ素合金めつき被膜
が、基体銅又は銅合金との密着性が乏しいとされ
ていたこと、ホウ素含量が２重量％よりも低いと
耐熱性及び硬度の点で不充分であると考えられて
いたこと、スプラツシユ固着を確実に防止するた
めには合金層上にクロムめつき層を設けるか又は
合金層を酸化して酸化被膜を形成することが必要
とされていたこと等を考慮すると、極めて予想外
なことである。 In the present invention, by simply providing a nickel-boron alloy plating layer with the above-mentioned specific boron content on the mold base, the mold is equivalent to or better than the conventional mold having two or three layers of protective coating. It is something that achieves longevity. This is because, in the prior art, it was believed that the nickel-boron alloy plating film had poor adhesion to the base copper or copper alloy, and that if the boron content was less than 2% by weight, the heat resistance and hardness would deteriorate. In order to reliably prevent splash sticking, it is necessary to provide a chrome plating layer on the alloy layer or to oxidize the alloy layer to form an oxide film. Considering what had happened, this was extremely unexpected.
本発明鋳型がこのように長寿命を有する理由
は、必ずしも完全に解明された訳ではないが、上
記ホウ素含量0.05重量％から0.5重量％未満のニ
ツケル−ホウ素合金層が、鋳型基体の銅又は銅合
金に対し高い密着性を有すると共に基体銅又は銅
合金との熱膨張係数が近似していること、該合金
層がかなり高い硬度を有していると共に高温にお
ける耐摩耗性に優れていること、該合金層が高温
に於ける潤滑性に優れていること、該合金層の熱
伝導性が極めて高く、抜熱性がよいので、大きな
温度勾配の発生がないこと、該合金層が溶鋼と馴
染みにくくスプラツシユが固着し難いこと等に基
づくものと思われる。 The reason why the mold of the present invention has such a long life is not completely elucidated. It has high adhesion to the alloy and has a coefficient of thermal expansion similar to that of the base copper or copper alloy; the alloy layer has fairly high hardness and has excellent wear resistance at high temperatures; The alloy layer has excellent lubricity at high temperatures, the alloy layer has extremely high thermal conductivity and good heat removal properties, so there is no large temperature gradient, and the alloy layer does not mix well with molten steel. This seems to be due to the fact that the splash is difficult to stick.
また、本発明では、鋳型が長寿命であることに
加えて、更に次の如き優れた効果も奏される。 Further, in addition to the long life of the mold, the present invention also provides the following excellent effects.
(a) 前記従来の特公昭55−40341号等に記載の鋳
型にあつては、合金層のホウ素含量が２〜15重
量％と高く、極めて高硬度であるため応力歪み
が生じる、熱伝導性が低く、大きな温度勾配が
生じる等により、クラツクが発生する虞れがあ
つた。これに対し、本発明の合金めつき層は、
その様なクラツクが発生する虞れが小さく、従
つて鋳型の信頼性が高い。(a) In the case of the conventional mold described in Japanese Patent Publication No. 55-40341, etc., the boron content of the alloy layer is as high as 2 to 15% by weight, and the extremely high hardness causes stress distortion and thermal conductivity. There was a risk of cracks occurring due to the low temperature and large temperature gradients. In contrast, the alloy plating layer of the present invention
There is little risk of such cracks occurring, and therefore the reliability of the mold is high.
(b) 本発明の合金層の熱伝導性が極めて高いの
で、冷却効率が極めて良好である。(b) Since the alloy layer of the present invention has extremely high thermal conductivity, the cooling efficiency is extremely good.
本発明の鋳鋼連続鋳造用鋳型において、鋳型を
構成する鋳型基体は、銅または銅合金からなる。
該銅合金としては、この分野で従来から慣用され
ているものが特に制限なく使用でき、例えば、銅
に少量の、特に0.02〜0.12重量％程度の銀、鉄、
スズ、ジルコニウム、リン等から選ばれた少なく
とも１種の元素を含有するものが例示される。特
に好ましい銅合金としては、銅に微量のリンを含
有させた脱酸銅、銅に鉄0.1重量％、スズ0.04重
量％および0.03重量％を含有させた銅合金等が挙
げられる。 In the mold for continuous casting of cast steel of the present invention, the mold base forming the mold is made of copper or a copper alloy.
As the copper alloy, those conventionally used in this field can be used without particular restriction. For example, copper with a small amount, especially about 0.02 to 0.12% by weight of silver, iron,
Examples include those containing at least one element selected from tin, zirconium, phosphorus, and the like. Particularly preferred copper alloys include deoxidized copper in which copper contains a trace amount of phosphorus, copper alloys in which copper contains 0.1% by weight of iron, 0.04% by weight and 0.03% by weight of tin, and the like.
本発明では、このような鋳型基体上に、前記特
定のニツケル−ホウ素合金層を形成する。その方
法としては、特に限定されず、各種の方法が採用
できるが、例えば、次の方法が挙げられる。ま
ず、鋳型基体表面を常法に従い前処理する。前処
理は、例えば、鉄板を陰極とし、10A／ｄm2にて
30分間電解脱脂を行ない、水洗後、50％塩酸でリ
ンスし、再び水洗し、次いで、３％スルフアミン
酸でリンスすることにより行なうことができる。
この様にして前処理した後、上記特定のホウ素含
量を有するニツケル−ホウ素合金めつき層を施
す。合金層のホウ素含量が、0.05重量％を下回る
と、マイクロビツカーズ硬度が低下し、高温にお
ける耐摩耗性、潤滑性が低下する傾向が生じる。
他方、1.5重量％を上回ると熱膨張係数が小さく
なり、基体との密着性が不十分となる、熱伝導性
の低下、抜熱性の低下と共に合金皮膜の内部応力
も上昇し、クラツクが発生し易くなる等の傾向が
生じるが、本発明では、高温における耐摩耗性、
耐熱性、潤滑性、熱伝導性、クラツク発生防止等
の観点からホウ素含量を、0.05重量％から0.5重
量％未満とする。該ホウ素含量は、0.06〜0.03重
量％とするのが好ましい。 In the present invention, the specific nickel-boron alloy layer is formed on such a mold substrate. The method is not particularly limited, and various methods can be employed, including, for example, the following method. First, the surface of the mold substrate is pretreated according to a conventional method. For example, pretreatment is performed at 10A/ dm2 using an iron plate as a cathode.
This can be carried out by performing electrolytic degreasing for 30 minutes, washing with water, rinsing with 50% hydrochloric acid, washing with water again, and then rinsing with 3% sulfamic acid.
After pretreatment in this manner, a nickel-boron alloy plating layer having the specified boron content is applied. When the boron content of the alloy layer is less than 0.05% by weight, the microvitkers hardness tends to decrease, and the wear resistance and lubricity at high temperatures tend to decrease.
On the other hand, if it exceeds 1.5% by weight, the coefficient of thermal expansion becomes small, resulting in insufficient adhesion to the substrate, a decrease in thermal conductivity, a decrease in heat removal performance, and an increase in the internal stress of the alloy film, causing cracks. However, in the present invention, wear resistance at high temperatures,
From the viewpoint of heat resistance, lubricity, thermal conductivity, crack prevention, etc., the boron content is from 0.05% by weight to less than 0.5% by weight. The boron content is preferably 0.06 to 0.03% by weight.
また、該合金層の厚さは、鋳型の使用目的等に
応じて広い範囲から適宜選択できるが、一般に鋳
型基体の表面の全面に均一厚さで50μｍ〜２mm程
度、好ましくは50μｍ〜1.5mm程度、より好ましく
は100μｍ〜１mm程度とすればよい。厚さが、50μ
ｍを下回ると、操業上の傷から部分的な摩耗が発
生し、鋳型寿命に影響を与えることもあり、ま
た、厚さを２mm以上としても一層の効果上の向上
は期待できず、経済的ではないことが多い。 The thickness of the alloy layer can be appropriately selected from a wide range depending on the purpose of use of the mold, but generally the thickness is uniform over the entire surface of the mold base, and is about 50 μm to 2 mm, preferably about 50 μm to 1.5 mm. , more preferably about 100 μm to 1 mm. Thickness is 50μ
If the thickness is less than 2 mm, partial wear may occur due to operational scratches, which may affect the life of the mold.Also, even if the thickness is 2 mm or more, further improvement in effectiveness cannot be expected, and it is not economical. Often not.
また、本発明者の研究によれば、本発明の鋳型
では前記ニツケル−ホウ素合金めつき層の厚さ
は、鋳型基体の下半分の領域において、50μｍ〜
２mm程度、好ましくは50μｍ〜1.5mm程度、より好
ましくは100μｍ〜１mm程度の範囲となつておれ
ばよく、鋳型基体の上半分の領域においては、
50μｍを下回つても良いし、また、全く合金層が
存在せず鋳型基体の銅または銅合金が露出した状
態であつてもよい。従つて、本発明では、第１図
に示すように鋳型基体１をその厚さが上端から下
端にかけて連続的に減少するように加工し、その
上に本発明の合金層２をそのその厚さが上端から
下端にかけて連続的に増加するようにテーパー状
に形成することもできる。この場合、テーパーの
勾配は広い範囲から適宜選択できるが、一般に本
発明の合金層の厚さが、上端において０〜100μ
ｍ程度、下端において150μｍ〜２mm程度、好ま
しくは200μｍ〜１mm程度とするのが望ましい。
より好ましくは、上端と下端とにおける厚さの差
が500〜1000μｍ程度になるようにテーパー状の
合金めつき層を形成する。また、第２図および第
３図に示す如く、鋳型基体の上半分の領域で薄
く、下半分の領域で厚くなるように合金層２を施
すこともでできる。また、第４図および第５図に
示す如く、鋳型基体の下半分の領域にのみ合金層
２を施すこともできる。いずれの場合も、合金層
２の厚さは、上記第１図の場合に準じて、鋳型基
体の下半分の領域において50μｍ〜２mm程度とな
るように適宜決定すれば良い。 Further, according to the research of the present inventor, in the mold of the present invention, the thickness of the nickel-boron alloy plating layer is 50 μm to 50 μm in the lower half region of the mold base.
The range may be about 2 mm, preferably about 50 μm to 1.5 mm, more preferably about 100 μm to 1 mm, and in the upper half region of the mold base,
The thickness may be less than 50 μm, or the copper or copper alloy of the mold base may be exposed without any alloy layer. Therefore, in the present invention, the mold base 1 is processed so that its thickness decreases continuously from the upper end to the lower end, as shown in FIG. It can also be formed into a tapered shape so that the number increases continuously from the upper end to the lower end. In this case, the slope of the taper can be appropriately selected from a wide range, but generally the thickness of the alloy layer of the present invention is 0 to 100μ at the upper end.
It is desirable that the thickness is approximately 150 μm to 2 mm, preferably approximately 200 μm to 1 mm at the lower end.
More preferably, the tapered alloy plating layer is formed so that the difference in thickness between the upper end and the lower end is about 500 to 1000 μm. Alternatively, as shown in FIGS. 2 and 3, the alloy layer 2 can be applied so that it is thinner in the upper half region of the mold base and thicker in the lower half region. Alternatively, as shown in FIGS. 4 and 5, the alloy layer 2 can be applied only to the lower half region of the mold base. In either case, the thickness of the alloy layer 2 may be appropriately determined to be approximately 50 μm to 2 mm in the lower half region of the mold base, as in the case of FIG. 1 above.
上記ニツケル−ホウ素合金めつき層の形成は、
従来から慣用されている電解めつき法及び無電解
めつき法のいずれによつても行うことができる。
合金層の厚さを厚くする場合は電解めつき法が有
利である。無電解めつき法により上記合金層を形
成する場合、例えば、
硫酸ニツケル 20〜30ｇ／
酒石酸カリウムナトリウム 30〜40ｇ／
水素化ホウ素ナトリウム 2.0〜2.5ｇ／
PH 12.0〜12.5
温 度 45〜50℃
のごときめつき浴を用いることができる。また、
電解めつき法による場合は、例えば、
硫酸ニツケル 250〜300ｇ／
塩化ニツケル 20〜25ｇ／
硼 酸 30〜40ｇ／
ジメチルアミンボラン 0.01〜0.3ｇ／
応力減少剤 ０〜適量
界面活性剤 ０〜1.5ｇ／
PH 3.0〜4.0
浴 温 40〜45℃
電流密度 １〜3A／ｄm2
のごときめつき浴を使用できる。これらめつき浴
に限らず、前記特定のホウ素含量のニツケル−ホ
ウ素合金めつき層を形成し得るめつき浴はいずれ
も使用可能である。 The formation of the nickel-boron alloy plating layer is as follows:
The plating can be carried out by either an electrolytic plating method or an electroless plating method which has been conventionally used.
Electrolytic plating is advantageous when increasing the thickness of the alloy layer. When forming the above alloy layer by electroless plating, for example, nickel sulfate 20-30g/potassium sodium tartrate 30-40g/sodium borohydride 2.0-2.5g/PH 12.0-12.5 Temperature 45-50°C. Texture baths can be used. Also,
In the case of electrolytic plating, for example, nickel sulfate 250-300g/nickel chloride 20-25g/boric acid 30-40g/dimethylamineborane 0.01-0.3g/stress reducer 0-appropriate surfactant 0-1.5g/ A glittering bath having a pH of 3.0 to 4.0, a bath temperature of 40 to 45°C, and a current density of 1 to 3 A/dm 2 can be used. In addition to these plating baths, any plating bath capable of forming a nickel-boron alloy plating layer having the specific boron content can be used.
なお、前記の如く、鋳型基体の上端から下端に
かけて厚さが変化するニツケル−ホウ素合金めつ
き層は、例えば、陽極を傾斜させてめつきを行な
い、次いで必要に応じて得られためつき被膜を機
械加工により仕上げる等の方法で形成できる。 As mentioned above, the nickel-boron alloy plating layer whose thickness changes from the upper end to the lower end of the mold substrate is, for example, plated by tilting the anode, and then, if necessary, the resulting plating film is applied. It can be formed by a method such as finishing by machining.
本発明に従い、銅または銅合金からなる鋳型基
体表面に、前記ニツケル−ホウ素合金めつき層単
独を形成した鉄鋼連続鋳造用鋳型は、スラブ、ブ
ルーム、ビレツト等の製造に使用でき、いずれの
場合も、長い寿命を達成する。 According to the present invention, a steel continuous casting mold in which the nickel-boron alloy plating layer alone is formed on the surface of a mold base made of copper or copper alloy can be used for manufacturing slabs, blooms, billets, etc. , achieve long service life.
以下、実施例を掲げて本発明をより詳しく説明
する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
純銅からなり、その垂直断面が長方形状であつ
て、その下端の厚さが上端の厚さよりも300μｍ
小さくなるようにテーパーを付けた鉄鋼連続鋳造
用鋳型基体の短辺（幅250mm×高さ900mm）の溶鋼
接触面以外のめつき不用部分をマスキングし、鉄
板を陽極として10A／ｄm2にて30分間電解脱脂を
行ない、水洗後50％塩酸でリンスし、再び水洗後
３％スルフアミン酸でリンスして前処理を行なつ
た。Example 1 Made of pure copper, its vertical cross section is rectangular, and its lower end is 300 μm thicker than its upper end.
Mask off the parts that are not needed for plating other than the molten steel contact surface on the short side (width 250 mm x height 900 mm) of the small tapered mold base for continuous steel casting, and use the iron plate as an anode at 10 A/dm 2 for 30 min. Pretreatment was carried out by performing electrolytic degreasing for a minute, washing with water, rinsing with 50% hydrochloric acid, washing with water again, and rinsing with 3% sulfamic acid.
水洗後、
硫酸ニツケル 250ｇ／
塩化ニツケル 20ｇ／
硼 酸 30ｇ／
ジメチルアミンボラン 0.2ｇ／
からなる浴を用いて電流密度１〜3A／ｄm2，PH
3.4〜4.0、温度40〜45℃にてホウ素含量0.3重量％
のニツケル−ホウ素合金めつきを、鋳型基体の上
端で100μｍ、下端で400μｍのテーパー状（第１
図参照）に施し、マスキングを除去した。After washing with water, a current density of 1 to 3 A/dm 2 , PH was applied using a bath consisting of 250 g of nickel sulfate, 20 g of nickel chloride, 30 g of boric acid, and 0.2 g of dimethylamine borane.
3.4-4.0, boron content 0.3% by weight at temperature 40-45℃
Nickel-boron alloy plating of 100 μm at the upper end of the mold base and 400 μm at the lower end (first
(see figure) and the masking was removed.
尚、長辺鋳型としては、純銅からなり、その垂
直断面が長方形状であつて、下端の厚さが上端の
厚さより150μｍ小さくなるようにテーパーを付
けた鉄鋼連続通造用鋳型基体の長辺（幅2200mm×
高さ900mm）の溶鋼と接触する面以外のめつき不
要部分をマスキングし、
これに、
スルフアミン酸ニツケル 250ｇ／
臭化ニツケル（50％） 10c.c.／
硼 酸 20ｇ／
なるニツケルめつき浴を用いて浴温50℃、PH3.0、
陰極電流密度2.0A／ｄm2にて全面に300μｍの厚
さのニツケル層を下地層として施した。 The long side mold is made of pure copper, has a rectangular vertical cross section, and is tapered so that the thickness at the lower end is 150 μm smaller than the thickness at the upper end. (width 2200mm x
900mm in height), mask off unnecessary parts of the plate other than the surfaces that come into contact with the molten steel, and apply a nickel plating bath containing 250g of nickel sulfamate/10c.c. of nickel bromide (50%)/20g of boric acid. Using bath temperature 50℃, PH3.0,
A 300 μm thick nickel layer was applied as an underlayer over the entire surface at a cathode current density of 2.0 A/dm 2 .
次いでこの下地層上に前記短辺のめつきに用い
たものと同一のニツケル−ホウ素合金めつき液を
用いて、鋳型基体の上端で50μｍ、下端で200μｍ
のテーパー状にホウ素含有量0.3重量％のニツケ
ル−ホウ素合金めつき層を施し、次いでマスキン
グを除去した。 Next, using the same nickel-boron alloy plating solution as that used for plating the short sides, the base layer was coated with a thickness of 50 μm at the upper end of the mold base and 200 μm at the lower end.
A nickel-boron alloy plating layer with a boron content of 0.3% by weight was applied to the tapered shape, and then the masking was removed.
こうして得られた本発明の短辺及び上記長辺を
組合せた鋳型を用いることにより、ブレークアウ
トは全くなく、1300チヤージの製品のスラブが欠
陥なく生産された。この鋳型は尚使用可能と思わ
れたが、安全のためこの時点で生産を中止した。
使用後の上記鋳型の本発明に従い保護皮膜を形成
した短辺上の合金層の状態は、わずかに擦傷が認
められるが尚使用可能な状態を保持していた。 By using the thus obtained mold in which the short side of the present invention and the above-mentioned long side were combined, there was no breakout and a product slab with a charge of 1300 was produced without any defects. Although this mold was considered usable, production was discontinued at this point for safety reasons.
After use, the alloy layer on the short side of the mold on which the protective film was formed according to the present invention was slightly scratched, but remained usable.
実施例 ２
本実施例で用いた鋳型は、鉄0.1重量％、スズ
0.04重量％及びリン0.03重量％を含有する銅合金
からなり、その垂直断面が長方形状であつて、そ
の下端の厚さが上端の厚さよりも400μｍ小さく
なるようにテーパーを付けた鋳型基体から構成さ
れたブルーム用鉄鋼連続鋳造用鋳型（内径612mm
×392mm、高さ900mm）である。Example 2 The mold used in this example was made of 0.1% iron and tin.
Consisting of a mold base made of a copper alloy containing 0.04% by weight and 0.03% by weight of phosphorus, the vertical cross section of which is rectangular, and tapered so that the thickness of the lower end is 400 μm smaller than the thickness of the upper end. Continuous steel casting mold for bloom (inner diameter 612 mm)
×392mm, height 900mm).
該鋳型の内部に、電解脱脂液を充填し、鉄板を
陰極として10A／ｄm2にて30分間電解脱脂を行な
い、水洗後、50％塩酸でリンスし、水洗後３％ス
ルフアミン酸でリンスし、前処理を行なつた。 Fill the inside of the mold with an electrolytic degreasing solution, perform electrolytic degreasing at 10 A/dm 2 for 30 minutes using an iron plate as a cathode, wash with water, rinse with 50% hydrochloric acid, rinse with water and rinse with 3% sulfamic acid, Pretreatment was performed.
次いで、該鋳型の内部に外部サービスタンクか
ら、下記組成のめつき浴を循環させつつ、電流密
度3.0A／ｄm2、浴温40℃、PH4.0の条件下で電解
めつきを行つた。 Next, electrolytic plating was performed under the conditions of a current density of 3.0 A/dm 2 , a bath temperature of 40° C., and a pH of 4.0 while circulating a plating bath having the composition shown below from an external service tank inside the mold.
硫酸ニツケル 250ｇ／
塩化ニツケル 20ｇ／
ホウ酸 30ｇ／
ジメチルアミンボラン 0.1ｇ／
経時的にめき浴の液面レベルを下げて行くこと
により、ホウ素含量0.06重量％のニツケル−ホウ
素合金めつき層を、上端に薄く、下端に近付くに
つれて厚くなるように形成し、次いで、機械加工
により表面仕上げを行い、鋳型基体の上端で
100μｍ、下端で500μｍ、その間平均的に厚さが
増加するテーパー状のニツケル−ホウ素合金めつ
き層を施した。Nickel sulfate 250g / Nickel chloride 20g / Boric acid 30g / Dimethylamine borane 0.1g / By lowering the liquid level of the plating bath over time, a nickel-boron alloy plating layer with a boron content of 0.06% by weight was applied to the upper end. The mold base is formed thinner and thicker toward the bottom edge, and then machined to finish the surface.
A tapered nickel-boron alloy plating layer of 100 μm thick and 500 μm thick at the lower end with an average thickness increasing therebetween was applied.
こうして得られた鋳型を、鋳込み速度0.6〜0.7
ｍ／minで用いることにより、ブレークアウトは
全くなく、1000チヤージもの製品ブルームが欠陥
なく生産された。 The mold thus obtained was poured at a casting speed of 0.6 to 0.7.
When used at m/min, there were no breakouts and 1000 charges of product bloom were produced without defects.
この鋳型は尚使用可能と思われたが、安全のめ
この時点で生産を打切つたものである。使用後の
上記鋳型の内面を観察したところ、僅かに擦傷が
認められるだけであり、ニツケル−ホウ素合金め
つき層の剥離やクラツクは全く認められず、尚使
用可能な状態を保持していた。 Although it was thought that this mold could still be used, production was discontinued at this point for safety reasons. When the inner surface of the mold was observed after use, only slight scratches were observed, and no peeling or cracking of the nickel-boron alloy plating layer was observed, indicating that the mold was still usable.
実施例 ３
微量のリンを含有する脱酸銅からなる丸型チユ
ーブラー鋳型（内径213mmφ、高さ900mm、鋳型基
体の肉厚は上端14.02mm、下端15.17mm）の内部
に、下記組成のめつきを循環させつつ、電流密度
2.0A／ｄm2、浴温40℃、PH4.0の条件下で電解め
つきを行つた。Example 3 A round tubular mold made of deoxidized copper containing a trace amount of phosphorus (inner diameter 213 mmφ, height 900 mm, thickness of the mold base 14.02 mm at the top end, 15.17 mm at the bottom end) was plated with the following composition inside. While circulating, the current density
Electrolytic plating was performed under the conditions of 2.0 A/dm 2 , bath temperature of 40° C., and pH of 4.0.
硫酸ニツケル 250ｇ／
塩化ニツケル 20ｇ／
ホウ酸 30ｇ／
ジメチルアミンボラン 0.2ｇ／
こうして、上端から下端まで75μｍの均一厚さ
でニツケル−ホウ素合金めつき層（ホウ素含量
0.18重量％）を形成した。250 g of nickel sulfate / 20 g of nickel chloride / 30 g of boric acid / 0.2 g of dimethylamine borane / In this way, a nickel-boron alloy plating layer (boron content
0.18% by weight).
得られた鋳型を鋳込み速度1.9ｍ／minで用い
ることにより、ブレークアウトは全くなく、300
チヤージの炭素鋼ビレツトが欠陥なく生産され
た。この鋳型は尚使用可能と思われたが、安全の
ためこの時点で生産を打切ったものである。 By using the obtained mold at a casting speed of 1.9 m/min, there was no breakout and 300 m/min was achieved.
Charge carbon steel billets were produced without defects. Although it was thought that this mold could still be used, production was discontinued at this point for safety reasons.
使用後の上記鋳型の内面を観察したところ、僅
かに擦傷が認められるだけであり、ニツケル−ホ
ウ素合金めつき層の剥離やクラツクは全く認めら
れず、尚使用可能な状態を保持していた。 When the inner surface of the mold was observed after use, only slight scratches were observed, and no peeling or cracking of the nickel-boron alloy plating layer was observed, indicating that the mold was still usable.
なお、上記ニツケル−ホウ素合金めつき層をニ
ツケルめつき層に置換える以外は上記と同一の鋳
型を上記と同一の条件下で用いると、わずか120
チヤージの炭素鋼ビレツトが生産されるに過ぎ
ず、使用後の鋳型はニツケルめつき層が摩耗し、
一部基体銅が露出し、もはや使用を継続できる状
態ではなかつた。 In addition, if the same mold as above is used under the same conditions as above, except that the nickel-boron alloy plating layer is replaced with a nickel plating layer, it will be only 120
Only a charge carbon steel billet is produced, and the nickel plating layer of the mold is worn out after use.
Part of the base copper was exposed and it was no longer in a condition where it could be continued to be used.
試験例 １
ニツケル−ホウ素合金めつき被膜中のホウ素含
量が異なる被膜を４種作成した。ニツケル−ホウ
素合金めつきは、銅板（200×50×５mm）に２mm
の厚さで形成した。このめつき銅板に１Kgの加重
の下で鋼球を接触させ、約300℃に加熱しながら、
銅板を30分間往復運動させ、鋼球によるめつき面
の窪み深さを測定した。Test Example 1 Four types of nickel-boron alloy plating films with different boron contents were prepared. Nickel-boron alloy plating is 2mm on copper plate (200 x 50 x 5mm)
It was formed with a thickness of . A steel ball is brought into contact with this plated copper plate under a load of 1 kg, and heated to approximately 300°C.
The copper plate was reciprocated for 30 minutes, and the depth of the depression in the plated surface by the steel balls was measured.
なお、ニツケル−ホウ素合金めつき皮膜中のホ
ウ素含量は、同一めつき浴内でステンレス板上に
作成した同皮膜を剥離し、剥離した皮膜の溶解分
析により測定した。 The boron content in the nickel-boron alloy plating film was measured by peeling off the same film created on a stainless steel plate in the same plating bath and dissolving the peeled film.
この試験は、ニツケル−ホウ素合金めつき被膜
の耐久性を示す加速試験であり、窪み深さの測定
できないものは、鉄鋼連続鋳造用鋳型の保護被膜
として有効性が高いと考えられる。結果を下記に
示す。 This test is an accelerated test that shows the durability of nickel-boron alloy plating coatings, and those whose dent depth cannot be measured are considered to be highly effective as protective coatings for molds for continuous steel casting. The results are shown below.
ホウ素含量 窪み深さ 備考
0.04％ 0.5mm 比較例
0.06％ 測定できず 本発明
0.45％ 測定できず 本発明
0.55％ 0.2mm 比較例
なお、ホウ素含量が0.55％の場合、めつき面に
微小なクラツクの発生が認められた。Boron content Hollow depth Notes 0.04% 0.5mm Comparative example 0.06% Cannot be measured Invention 0.45% Cannot be measured Invention 0.55% 0.2mm Comparative example If the boron content is 0.55%, there will be minute cracks on the plated surface. Occurrence was observed.
上記結果から、ホウ素含量が、0.05〜0.5重量
％であることが重要であることが判る。 From the above results, it can be seen that it is important that the boron content is 0.05 to 0.5% by weight.
第１図は、本発明のニツケル−ホウ素合金めつ
き層をテーパー状に施した鋳型の一例を示す縦断
面図であり、第２〜５図は、本発明のニツケル−
ホウ素合金めつき層を施した鋳型の他の例を示す
縦断面図である。
１……鋳型基体、２……ニツケル−ホウ素合金
めつき層。
FIG. 1 is a longitudinal cross-sectional view showing an example of a mold in which a nickel-boron alloy plating layer of the present invention is applied in a tapered shape, and FIGS.
FIG. 3 is a longitudinal cross-sectional view showing another example of a mold provided with a boron alloy plating layer. 1... Mold base, 2... Nickel-boron alloy plating layer.
Claims (1)
あって、その銅又は銅合金からなる鋳型基体上
に、ホウ素0.05重量％から0.5重量％未満を含有
し、50μｍ〜２mmの厚さを有するニッケル−ホウ
素合金めっき層を形成したことを特徴とする鉄鋼
連続鋳造用鋳型。 ２ ニッケル−ホウ素合金めっき層が、ホウ素含
量0.06〜0.3重量％を有する請求項１に記載の鉄
鋼連続鋳造用鋳型。 ３ ニッケル−ホウ素合金めっき層が、鋳型の下
半分の領域において、50μｍ〜２mmの厚さを有す
る請求項１に記載の鉄鋼連続鋳造用鋳型。[Scope of Claims] 1. A mold for continuous casting of steel made of copper or copper alloy, containing 0.05% to less than 0.5% by weight of boron on the mold base made of copper or copper alloy, and having a diameter of 50 μm to 2 mm. 1. A mold for continuous casting of steel, characterized by forming a nickel-boron alloy plating layer having a thickness of . 2. The mold for continuous casting of steel according to claim 1, wherein the nickel-boron alloy plating layer has a boron content of 0.06 to 0.3% by weight. 3. The mold for continuous casting of steel according to claim 1, wherein the nickel-boron alloy plating layer has a thickness of 50 μm to 2 mm in the lower half region of the mold.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18414588 | 1988-07-22 | ||
| PCT/JP1989/000723 WO1990000945A1 (en) | 1988-07-22 | 1989-07-20 | Mold for continuously casting steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0459064B2 true JPH0459064B2 (en) | 1992-09-21 |
Family
ID=16148154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50792489A Expired JPH0459064B2 (en) | 1988-07-22 | 1989-07-20 |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0383934B1 (en) |
| JP (1) | JPH0459064B2 (en) |
| WO (1) | WO1990000945A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4039230C2 (en) * | 1990-12-08 | 2000-02-17 | Schloemann Siemag Ag | Process for coating the inner surfaces of a continuous mold and a mold coated in this way |
| DE4041830A1 (en) | 1990-12-24 | 1992-06-25 | Schloemann Siemag Ag | STEEL MOLDING CHOCOLATE |
| GB9621427D0 (en) | 1996-10-15 | 1996-12-04 | Davy Distington Ltd | Continuous casting mould |
| GB2320034B (en) * | 1996-11-08 | 1998-11-11 | Monitor Coatings & Eng | Coating of continuous casting machine grid plates |
| DE19919777C2 (en) * | 1998-10-24 | 2001-07-26 | Sms Demag Ag | Process for the production of broad side plates for continuous molds |
| EA008676B1 (en) * | 2005-08-22 | 2007-06-29 | Республиканское Унитарное Предприятие "Белорусский Металлургический Завод" | Method for applying two-layer galvanic coating on copper sleeve and crystallizer plate |
| CN104120461A (en) * | 2013-04-28 | 2014-10-29 | 上海宝钢工业技术服务有限公司 | Method for preparing gradient alloy plating layer on surface of thin strip continuous casting crystallization roller and plating solution |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4037646A (en) * | 1975-06-13 | 1977-07-26 | Sumitomo Metal Industries, Ltd. | Molds for continuously casting steel |
| JPS55100851A (en) * | 1979-01-26 | 1980-08-01 | Kawasaki Steel Corp | Mold for continuous casting of bloom, billet and beam blank |
| JPS5954444A (en) * | 1982-09-01 | 1984-03-29 | Nippon Steel Corp | Casting mold for continuous casting of iron and steel |
| JPS62270249A (en) * | 1986-05-17 | 1987-11-24 | Fujiki Kosan Kk | Production of mold for continuous casting |
-
1989
- 1989-07-20 WO PCT/JP1989/000723 patent/WO1990000945A1/en active IP Right Grant
- 1989-07-20 EP EP19890908510 patent/EP0383934B1/en not_active Expired - Lifetime
- 1989-07-20 JP JP50792489A patent/JPH0459064B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0383934B1 (en) | 1993-09-29 |
| WO1990000945A1 (en) | 1990-02-08 |
| EP0383934A4 (en) | 1991-01-23 |
| EP0383934A1 (en) | 1990-08-29 |
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