EP0383934A1 - Giessform für kontinuierlich gegossenen stahl - Google Patents

Giessform für kontinuierlich gegossenen stahl Download PDF

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Publication number
EP0383934A1
EP0383934A1 EP89908510A EP89908510A EP0383934A1 EP 0383934 A1 EP0383934 A1 EP 0383934A1 EP 89908510 A EP89908510 A EP 89908510A EP 89908510 A EP89908510 A EP 89908510A EP 0383934 A1 EP0383934 A1 EP 0383934A1
Authority
EP
European Patent Office
Prior art keywords
mold
nickel
layer
plating layer
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.)
Granted
Application number
EP89908510A
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English (en)
French (fr)
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EP0383934B1 (de
EP0383934A4 (en
Inventor
Takayuki Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Satosen Co Ltd
Original Assignee
Satosen Co Ltd
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Filing date
Publication date
Application filed by Satosen Co Ltd filed Critical Satosen Co Ltd
Publication of EP0383934A1 publication Critical patent/EP0383934A1/de
Publication of EP0383934A4 publication Critical patent/EP0383934A4/en
Application granted granted Critical
Publication of EP0383934B1 publication Critical patent/EP0383934B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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

Definitions

  • the present invention relates to a mold for continuous casting of steel, such as low carbon steel, high carbon steel, stainless steel, special steel, etc. and more particularly to a mold for continuous casting of steel which has an extended useful life.
  • the mold for continuous casting of steel is so designed that molten steel poured from its top end is solidified by cooling and the resulting product is withdrawn from its lower end in a continuous sequence. As such, from productivity points of view, the mold is required to have a long service life.
  • the long-life continuous casting mold heretofore known is the one disclosed in Japanese Examined Patent Publication No. 40341/1980.
  • This mold comprises a copper or copper alloy body and as formed on the internal surface thereof which is to be exposed to molten steel, (A) an intermediate plating layer comprising at least one member selected from the group consisting of nickel and cobalt and (B) a surface alloy plating layer formed from either 3 to 20 weight % of phosphorus or 2 to 15 weight % of boron or both and the balance of at least one member selected from the group consisting of nickel and cobalt.
  • A an intermediate plating layer comprising at least one member selected from the group consisting of nickel and cobalt
  • B a surface alloy plating layer formed from either 3 to 20 weight % of phosphorus or 2 to 15 weight % of boron or both and the balance of at least one member selected from the group consisting of nickel and cobalt.
  • said intermediate layer (A) serves to flatten the gradient of hardness between the copper or copper alloy mold body which is very low in hardness and the alloy layer (B) which has a high hardness to thereby increase the bond between the three members, viz the body metal, intermediate layer and alloy layer.
  • the alloy layer has high resistances to heat and wear at high temperature.
  • the mold carrying a chromium plating layer in superimposition on said alloy layer (B) Japanese Examined Patent Publication No. 50734/1977
  • the mold carrying an oxide layer as formed by oxidizing said alloy layer (B) Japanese Examined Patent Publication No. 50733/1977.
  • the chromium plating layer and the oxide layer in these molds serve to preclude deposition of molten steel splashes evolved at the start of casting on the mold surface and eliminates chances for breakout troubles.
  • the above-mentioned molds carrying two or three protective layers essentially have an intermediate layer comprising at least one member of the group consisting of nickel and cobalt and, as disposed thereon, an alloy layer and, in the case of three-layer molds, further a chromium plating layer or an oxide layer, and, as such, require complicated manufacturing procedures and high production costs.
  • the present inventor conducted an intensive research to develop a protective layer which is structurally simple and easy to manufacture and which is to be formed over a substrate mold body (a plate or tube of copper or copper alloy which constitutes the internal surface of a mold).
  • a nickel-boron alloy plating layer with a low boron content in a certain specific range has a good ability to bond to the substrate copper or copper alloy and serves on its own as an excellent protective layer even without the provision of an intermediate layer used in the foregoing prior art mold, thus providing for the manufacture of a mold having a life at least equal to or even longer t.han the lives of the above-mentioned mold having two or three superposed protective layers.
  • the further research by the inventor led to the finding that a mold having a long life, which is unexpected from the conventional knowledge, can also be produced by forming an under plating layer consisting essentially of at least one of nickel and cobalt and, in superimposition thereon, a nickel-boron alloy plating layer with a low boron content.
  • the present invention is predicated on the above findings.
  • the present invention provides a mold for continuous casting of steel which is characterized in that the mold has a nickel-boron alloy plating layer containing 0.05 to 1.5 weight % of boron on its inner surface.
  • the simple structure of a substrate mold body and a nickel-boron alloy plating layer with a boron content in the above specific range as formed over the substrate mold body assures a mold life which is at least comparable or even longer than the lives of the conventional molds having two or three superposed protective layers.
  • the nickel-boron alloy layer containing 0.05 to 1.5 weight % of boron has a high ability to bond to the substrate copper or copper alloy of the mold and has a coefficient of thermal expansion similar to that of the substrate copper or copper alloy, and this alloy layer has a microvickers hardness of about 500 to 800 HV, high wear resistance at high temperature, high lubricating property at high temperature, remarkably high heat conductivity to allow a rapid dissipation of heat which prevents formation of a major temperature gradient, and a low affinity for molten steel which tends to preclude deposition of splashes.
  • the substrate body of the mold is made of copper or copper alloy.
  • This copper alloy may be virtually any of the alloys heretofore used in the art.
  • alloys of copper with small amounts, particularly about 0.02 to 0.12 weight %, of at least one element selected from the group consisting of silver, iron, tin, zirconium, phosphorus, etc. can be mentioned.
  • Particularly preferred copper alloys are deoxidized coppers containing small amounts of phosphorus and copper alloys containing 0.1 weight % of iron, 0.04 weight % of tin and 0.03 weight % of phosphorus.
  • the foregoing specific nickel-boron alloy layer is formed on the above-mentioned substate mold body.
  • the method usable for this purpose is not limited but includes the following as an example.
  • the surface of the mold body is pretreated in the conventional manner. This pretreatment may, for example, be conducted by serially conducting electrolytic degreasing for 30 minutes at lOA/dm using an . iron plate as the cathode, rinsing with water, rinsing with 50% hydrochloric acid, rinsing with water and rinsing with 3% sulfamic acid.
  • the above-mentioned nickel-boron alloy plating layer with a specified low boron content is formed.
  • the boron content of the alloy layer is less than 0.05 weight %, the microvickers hardness of the layer is reduced and the wear resistance and lubricating property at high temperature also tend to be lowered. Conversely if the boron content exceeds 1.5 weight %, the coefficient of thermal expansion tends to be decreased to cause inadequate bond to the substrate metal, and the resulting decreased thermal conductivity and poor dissipation of heat tends to increase internal stress of the alloy layer and consequent likelihood of cracking. From the standpoints of high temperature wear resistance, lubricating property, thermal conductivity and resistance to cracking, the boron content is preferably in the range of about 0.05 to 0.7 weight % and more preferably in the range of about 0.06 to 0.3 weight %.
  • the thickness of this alloy layer can be chosen from a broad range according to the particular application of the mold, and the like. Generally, it is about 50 ⁇ m to 2 mm, preferably about 50 ⁇ m to 1.5 mm, and more preferably about 100 ⁇ m to 1 mm uniformly throughout the whole surface area of the substrate mold body. If the thickness of the alloy layer is less than 50 ⁇ m, local wear may develop due to operational damage to adversely affect the mold life. On the other hand, increasing the thickness beyond 2 mm is not rewarded with further improved effect but is uneconomical.
  • the thickness of said nickel-boron alloy plating layer of the mold of the invention may be about 50 ⁇ m to about 2 mm, preferably about 50 ⁇ m to about 1.5 mm, and more preferably about 100 ⁇ m to about 1 mm in the lower half of the inner surface of the mold body.
  • the thickness of the alloy plating layer may be less than 50 ⁇ m or even there may be no alloy layer with the substrate copper or copper alloy remaining exposed.
  • the gradient of the taper can be chosen from a broad range but it is generally preferable to assure that the thickness of the alloy layer of the invention is about 0 to about 100 ⁇ m at the top end, and about 150 ⁇ m to about 2 mm and preferably about 200 ⁇ m to about 1 mm at the bottom end. More desirably, the alloy plating layer has a taper such that the difference between its top end thickness and its bottom end thickness is about 500 to 1000 ⁇ m.
  • the alloy layer (2) may be formed in such a fashion that it is thin in the upper half and thick in the lower half of the mold. Furthermore, as shown in Figs. 4 and 5, the alloy layer (2) may be formed only in the area corresponding to the lower half of the mold body. In any case, the alloy layer (2) may be formed in such a manner that as in the case illustrated in Fig. 1, its thickness is about 50 ⁇ m to 2 mm in the area corresponding to the lower half of the mold body.
  • the formation of the above nickel-boron alloy plating layer may be effected by the conventional electroplating technique or the conventional non-electrolytic plating technique.
  • the electroplating process is more advantageous.
  • the following plating bath may, for example, be employed.
  • the following plating bath for instance, may be employed.
  • any other plating bath capable of yielding a nickel-boron alloy plating layer with the specified boron content can also be employed.
  • the above nickel-boron alloy plating layer varying in thickness from the top end to the bottom end can be formed, for example, by carrying out the plating procedure with the anode inclined and, then, finishing the resulting plating layer by machining if necessary.
  • a long-life mold to which splashes are difficult to adhere can also be obtained by forming a plating layer consisting essentially of at least one of nickel and cobalt on the copper or copper alloy substrate and, then, forming on said plating layer a nickel-boron alloy plating layer with a boron content of about 0.05 to about 0.5 weight %, preferably about 0.05 to about 0.30 weight %.
  • the present invention provides a copper- or copper alloy-based mold for continuous casting of steel which has a plating layer formed on the inner surface of said mold and consisting essentially of at least one of nickel and cobalt, and a nickel-boron alloy plating layer formed on said plating layer and containing about 0.05 to 0.5 weight %, preferably about 0.05 to 0.30 weight %, of boron.
  • the plating layer comprising at least one of nickel and cobalt (hereinafter referred to as "under layer”) has a good ability to bond to both of the above-mentioned alloy plating layer and the copper or copper alloy substrate, thus serving as a protective film of good bonding ability as a whole, and this good bonding ability coupled with the excellent high-temperature wear resistance and lubricating property, good heat-dissipating property and good splash-repellency of the alloy plating layer appears to synergistically assure an extended life of the resulting mold.
  • the mold of the present invention which has the above-mentioned under layer and alloy layer has not only the above-mentioned advantage of extended mold life but also the advantage that even if the alloy layer is damaged to a certain extent by external physical forces, etc., the mold can still be serviceable because of the presence of the under layer.
  • the above-mentioned under layer consisting essentially of at least one of nickel and cobalt can be easily provided by pretreating the surface of the mold body in the conventional manner and, then, electroplating the surface in the usual manner.
  • the alloy layer it is exactly the same as the nickel-boron alloy layer mentioned hereinbefore and formed, after the formation of said under layer, by the aforementioned electroplating or non-electrolytic plating technique.
  • the thickness of the under layer and that of the alloy layer can also be chosen from broad ranges as mentioned hereinbefore. Generally, the minimum thickness of the alloy layer is about 50 ⁇ m and the total thickness of the under layer and alloy layer is about 100 ⁇ m to about 3 mm and preferably about 100 ⁇ m to about 2 mm.
  • the thickness of the boron alloy plating layer may be at least about 50 ⁇ m in the lower half of the mold body, with the total thickness of the under layer and alloy layer being about 100 ⁇ m to about 3 mm and preferably about 100 ⁇ m to about 2 mm.
  • the total thickness may be less than 100 ⁇ m and there may be neither the under layer nor the alloy layer, with the substrate copper or copper alloy being exposed. Therefore, in the present invention, the above-mentioned under layer (3) and alloy layer (2) may be formed in a tapered fashion as illustrated in Fig. 6. In this connection, the gradient of the taper may be chosen from a broad range.
  • the total thickness of the under layer and alloy layer is about 50 ⁇ m to about 300 ⁇ m at the top end and about 150 ⁇ m to about 2 mm and preferably about 200 um to about 1.5 mm at the bottom end.
  • the under layer (3) and alloy layer (2) may be thin in the area corresponding to the upper half of the mold body and thick in the area corresponding to the lower half of the mold body.
  • the under layer (3) and alloy layer (2) may be formed only in the area corresponding to the lower half of the mold body. In any case, in the area corresponding to the lower half of the mold body, the thickness of the alloy layer (2) should be at least about 50 ⁇ m and the total thickness of the under layer (3) and alloy layer (2) be about 100 ⁇ m to about 3 mm.
  • the mold of the invention having, on its substrate copper or copper alloy mold body, either a nickel-boron alloy plating layer alone or an under layer consisting essentially of at least one of nickel and cobalt and a nickel-boron alloy plating layer can be used in the continuous casting of steel into slabs, blooms, billets and other products and invariably assures an extended life.
  • a short side mold body (250 mm wide x 900 mm high) made of pure copper for continuously casting steel whose section perpendicular to its horizontal axis is substantially rectangular and having a tapered configuration with the thickness at the bottom end thereof being smaller than that at the top end by 300 ⁇ m was masked over the surface thereof except the area to be exposed to molten steel and then subjected to 30-minute electrolytic degreasing at 10 A/dm 2 using an iron plate as the anode.
  • the degreased mold body was rinsed with water, 50% hydrochloric acid, water, and 3% sulfamic acid in the order mentioned for pretreatment.
  • the mold body was finally rinsed with water and, then, using the following plating bath, a tapered nickel-boron alloy plating layer with a boron content of 0.3 weight % was formed on the mold body at a current density of 1 to 3 A/dm 2 , pH 3.0 - 4.0 and a temperature of 40 to 45°C.
  • the thickness of the alloy layer was 100 ⁇ m at the top end and 400 ⁇ m at the bottom end (See Fig. 1). Then, the masking was removed.
  • a long side mold body (2200 mm wide x 900 mm high) for continuously casting steel whose section perpendicular to its horizontal axis is substantially rectangular and having a tapered configuration with the thickness at its bottom end being smaller than that at the top end by 150 ⁇ m was masked over the surface thereof except the area to be exposed to molten steel and, then, using the following nickel plating bath, a nickel plating layer having a thickness of 300 ⁇ m was formed as an under layer over the entire surface of the mold body at a bath temperature of 50°C, pH 3.0 and a cathode current density of 2.0 A/dm 2 .
  • a tapered nickel-boron alloy plating layer with a boron content of 0.3 weight % was formed in a tapered fashion using the same nickel-boron alloy plating bath as used for the plating of the short side mold body above.
  • the thickness of this alloy plating layer was 50 ⁇ m at the top end and 200 ⁇ m at the bottom end. The masking was then removed.
  • a 300 ⁇ m-thick nickel plating layer was formed by electroplating using a nickel sulfamate plating bath of the following composition at a temperature of 50°C, pH 3.0 and a cathode current density of 2.0 A/dm for 18 hours.
  • the nickel plating surface was finished so as to adjust its degree of precision by means of a stretch gauge, filler gauge and disk grinder.
  • a tapered nickel-boron alloy plating layer with a boron content of 0.3 weight % was formed using a plating bath of the following composition under the conditions of pH 3.0 - 4.0, bath temperature 40 - 45°C and current density 1.5 A/dm 2 .
  • the thickness of the alloy plating layer was 50 ⁇ m at the top end and 200 ⁇ m at the bottom end. The masking was then removed.
  • the mold used in this example was a continuous bloom casting mold (inside dimension: 612 mm x 392 mm, 900 mm high) which was made of copper alloy containing 0.1 weight % of iron, 0.04 weight % of tin and 0.03 weight % of phosphorus and which had substantially a rectangular section perpendicular to its horizontal axis and had a taper with the thickness at the bottom end being smaller than that at the top end by 400 ⁇ m.
  • the inside cavity of the mold was filled with an electrolytic degreasing solution and electrolytic degreasing was carried out in the same manner as Example 1.
  • the degreased mold was rinsed with water, 50% hydrochloric acid, water and 3% sulfamic acid in the order mentioned for pretreatment.
  • a plating bath of the following composition was circulated into the cavity of the mold and electroplating was carried out at a current density of 3.0 A/dm 2 , bath temperature of 40°C and pH 4.0.
  • a nickel-boron alloy layer with a boron content of 0.06 weight % was formed in a tapered fashion with the thickness increasing from the top end to the lower end. Then, the surface was finished by machining to provide a tapered nickel-boron alloy layer with an evenly increasing thickness from 100 ⁇ m at the top end to 500 ⁇ m at the bottom end.
  • a plating bath of the following composition was circulated and electroplating was carried out at a current density of 2.0 A/dm 2 , bath temperature of 40°C and pH 4.0.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Electroplating Methods And Accessories (AREA)
EP19890908510 1988-07-22 1989-07-20 Giessform für kontinuierlich gegossenen stahl Expired - Lifetime EP0383934B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP184145/88 1988-07-22
JP18414588 1988-07-22

Publications (3)

Publication Number Publication Date
EP0383934A1 true EP0383934A1 (de) 1990-08-29
EP0383934A4 EP0383934A4 (en) 1991-01-23
EP0383934B1 EP0383934B1 (de) 1993-09-29

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EP19890908510 Expired - Lifetime EP0383934B1 (de) 1988-07-22 1989-07-20 Giessform für kontinuierlich gegossenen stahl

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EP (1) EP0383934B1 (de)
JP (1) JPH0459064B2 (de)
WO (1) WO1990000945A1 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4039230A1 (de) * 1990-12-08 1992-06-11 Schloemann Siemag Ag Verfahren zum beschichten der innenflaechen einer durchlaufkokille und eine dergestalt beschichtete kokille
EP0492264A1 (de) 1990-12-24 1992-07-01 Sms Schloemann-Siemag Aktiengesellschaft Stahlstranggiesskokille
GB2318314A (en) * 1996-10-15 1998-04-22 Davy Distington Ltd Continuous casting mould with a coating of varying thickness
WO1998021379A1 (en) * 1996-11-08 1998-05-22 Monitor Coatings And Engineers Limited Coating of continuous casting machine components
DE19919777C2 (de) * 1998-10-24 2001-07-26 Sms Demag Ag Verfahren zum Herstellen von Breitseitenplatten für Durchlaufkokillen
EA008676B1 (ru) * 2005-08-22 2007-06-29 Республиканское Унитарное Предприятие "Белорусский Металлургический Завод" Способ нанесения двухслойного гальванического покрытия на медные гильзы и плиты кристаллизаторов
CN104120461A (zh) * 2013-04-28 2014-10-29 上海宝钢工业技术服务有限公司 薄带连铸结晶辊表面梯度合金镀层的制备方法及电镀液

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2314001A1 (fr) * 1975-06-13 1977-01-07 Sumitomo Chemical Co Moules de fonderie
JPS55100851A (en) * 1979-01-26 1980-08-01 Kawasaki Steel Corp Mold for continuous casting of bloom, billet and beam blank
JPS5954444A (ja) * 1982-09-01 1984-03-29 Nippon Steel Corp 鉄鋼連続鋳造用鋳型

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62270249A (ja) * 1986-05-17 1987-11-24 Fujiki Kosan Kk 連続鋳造用鋳型の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2314001A1 (fr) * 1975-06-13 1977-01-07 Sumitomo Chemical Co Moules de fonderie
JPS55100851A (en) * 1979-01-26 1980-08-01 Kawasaki Steel Corp Mold for continuous casting of bloom, billet and beam blank
JPS5954444A (ja) * 1982-09-01 1984-03-29 Nippon Steel Corp 鉄鋼連続鋳造用鋳型

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 4, no. 147 (M-36)[629], 16th October 1980; & JP-A-55 100 851 (KAWASAKI SEITETSU K.K.) 01-08-1980 *
PATENT ABSTRACTS OF JAPAN, vol. 8, no. 158 (M-311)[1595], 21st July 1984; & JP-A-59 054 444 (SHIN NIPPON SEITETSU K.K.) 29-03-1984 *
See also references of WO9000945A1 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4039230A1 (de) * 1990-12-08 1992-06-11 Schloemann Siemag Ag Verfahren zum beschichten der innenflaechen einer durchlaufkokille und eine dergestalt beschichtete kokille
DE4039230C2 (de) * 1990-12-08 2000-02-17 Schloemann Siemag Ag Verfahren zum Beschichten der Innenflächen einer Durchlaufkokille und eine dergestalt beschichtete Kokille
EP0492264A1 (de) 1990-12-24 1992-07-01 Sms Schloemann-Siemag Aktiengesellschaft Stahlstranggiesskokille
GB2318314A (en) * 1996-10-15 1998-04-22 Davy Distington Ltd Continuous casting mould with a coating of varying thickness
US6176298B1 (en) 1996-10-15 2001-01-23 Davy Distington Limited Continuous casting mould
WO1998021379A1 (en) * 1996-11-08 1998-05-22 Monitor Coatings And Engineers Limited Coating of continuous casting machine components
DE19919777C2 (de) * 1998-10-24 2001-07-26 Sms Demag Ag Verfahren zum Herstellen von Breitseitenplatten für Durchlaufkokillen
EA008676B1 (ru) * 2005-08-22 2007-06-29 Республиканское Унитарное Предприятие "Белорусский Металлургический Завод" Способ нанесения двухслойного гальванического покрытия на медные гильзы и плиты кристаллизаторов
CN104120461A (zh) * 2013-04-28 2014-10-29 上海宝钢工业技术服务有限公司 薄带连铸结晶辊表面梯度合金镀层的制备方法及电镀液

Also Published As

Publication number Publication date
EP0383934B1 (de) 1993-09-29
WO1990000945A1 (en) 1990-02-08
JPH0459064B2 (de) 1992-09-21
EP0383934A4 (en) 1991-01-23

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