EP0910489B1 - Stranggusskokilleteil mit einer metalbeschichter, gekühlter wand aus kupfer oder kupferlegierung und verfahren zu seiner herstellung - Google Patents

Stranggusskokilleteil mit einer metalbeschichter, gekühlter wand aus kupfer oder kupferlegierung und verfahren zu seiner herstellung Download PDF

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Publication number
EP0910489B1
EP0910489B1 EP97930592A EP97930592A EP0910489B1 EP 0910489 B1 EP0910489 B1 EP 0910489B1 EP 97930592 A EP97930592 A EP 97930592A EP 97930592 A EP97930592 A EP 97930592A EP 0910489 B1 EP0910489 B1 EP 0910489B1
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EP
European Patent Office
Prior art keywords
silver
wall
copper
coating
metal
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 - Lifetime
Application number
EP97930592A
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English (en)
French (fr)
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EP0910489A1 (de
Inventor
Jean-Michel Damasse
Jean-Claude Catonne
Christian Allely
Guido Stebner
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Thyssen Stahl AG
USINOR SA
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Thyssen Stahl AG
USINOR SA
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Publication of EP0910489A1 publication Critical patent/EP0910489A1/de
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/67—Electroplating to repair workpiece

Definitions

  • the invention relates to the continuous casting of metals. More specifically, it concerns the coating of the external surface of copper or alloy walls copper ingot molds in which the solidification of metals such as steel (DE-A-3,211,199).
  • the faces of these walls which are intended to be in contact with the liquid metal are coated with a layer of nickel whose initial thickness can reach up to 3 mm. It constitutes for copper a protective layer which avoids being overheated thermally and mechanically.
  • This nickel layer wears out over the use of the mold. She must therefore be restored periodically by total removal of the remaining thickness and then depositing a new layer, but such restoration obviously costs a lot cheaper than a complete replacement of worn copper walls.
  • the complete nickel removal operation of the ferrule which must precede the restoration of the nickel layer is also fundamental. On the one hand, its good completion largely determines the quality of the nickel layer which will be then deposited, in particular its adhesion to the shell, because it is very difficult to deposit a new layer of strongly adherent nickel on a layer of nickel older. On the other hand, this nickel removal operation must be carried out without very significant consumption of copper from the ferrule which is an extremely expensive, and the duration of use should be extended as much as possible. This last requirement, in particular, practically excludes the use of a purely method mechanical for this nickel plating, because its precision would not be sufficient to guarantee both a total elimination of nickel and a safeguard of copper on the whole of the shell surface.
  • the aim of the invention is to propose a method of coating the surface outside of the copper or copper alloy wall of a continuous casting mold overall more economical than the usual methods where a layer is deposited of nickel on this surface.
  • This method should also provide the walls of the ingot mold with characteristics and quality at least comparable to those obtained by depositing a layer of nickel. It should also include a step of periodic regeneration of this surface.
  • This method should be particularly suitable for the coating of cylinder ferrules for a casting machine between cylinders or on a single cylinder.
  • the invention relates to an element of an ingot mold for casting metal continuous, including a cooled wall of copper or copper alloy intended to be brought into contact with liquid metal and comprising on its external surface a metallic coating, characterized in that said coating consists of a silver layer.
  • this wall is a cylinder ferrule for continuous casting machine for thin metal strips between two cylinders or on a single cylinder.
  • the invention also relates to a method of coating with a layer metal of the external surface of a wall cooled in copper or copper alloy of a ingot mold element for continuous casting of metals, characterized in that this is achieved coating by depositing a layer of silver on said surface preferably by electrolytic.
  • the restoration of said silver layer is carried out by leaving a residual silver layer on said wall, and by carrying out a resilvering of said layer by placing said cathode wall in a bath electrolysis consisting, for example, of an aqueous solution of silver cyanide, cyanide of an alkali metal and carbonate of an alkali metal.
  • a bath electrolysis consisting, for example, of an aqueous solution of silver cyanide, cyanide of an alkali metal and carbonate of an alkali metal.
  • the invention consists first of all in replacing by silver nickel traditionally used to form the external coating of walls of copper ingot molds for continuous casting of metals such as steel. Contrary to what one might think at first glance since solid silver is considered a precious metal, this solution has multiple advantages economical, and it is perfectly technically viable. This is particularly the case when silvering is carried out by an electrolytic method using a bath with alkaline cyanides. It turned out that such baths are suitable for carrying out silver deposits on copper having properties of use well adapted to the protection of the walls of ingot molds for continuous casting.
  • the particular method of coating the surface of the mold which is also described and claimed includes a silvering step, and also possibly a step of silvering said surface when it is desired to restore the coating a used ingot mold.
  • This silvering may be only partial, while in the in the case of a nickel coating, the nickel removal of copper must almost imperatively be total, at the risk of consuming part of the copper from the wall.
  • Silver and silvering can both be achieved by electrolytic means.
  • the silver removed from the ferrule is recovered in metallic form on the silver cathode in the silver reduction reactor. Said cathode can in turn be recycled as an anode in the silvering reactor.
  • the silvering can be carried out at least in partly by chemical or mechanical means.
  • the invention will now be described in detail in one of its forms of realization, applied to the coating of a ferrule in copper or copper alloy of cylinder for continuous steel casting machine between two cylinders or on a single cylinder.
  • the example described can easily be adapted to other types of ingot molds with copper or copper alloy walls, such as ingot molds with fixed walls for the continuous casting of slabs, blooms or billets.
  • the silvering or de-silvering method can implement various other electrolytic processes such as pad or pad coatings spraying, as well as electrolytes different from those given in example.
  • We can also provide for complete immersion of the copper wall in a bath silvering, and under these conditions the invention can be applied to a ferrule in permanent or intermittent rotation, or on a ferrule kept stationary in an electrolyte in forced circulation.
  • the new ferrule is generally in the form of a hollow cylinder of copper or copper alloy, such as a copper-chromium alloy (1%) - zirconium (0.1%).
  • Its outside diameter is, for example, of the order of 1500 mm and its length is equal to the width of the strips that it is desired to pour, ie of the order of 600 to 1500 mm.
  • Its thickness can be, for information, of the order of 180 mm, but varies locally depending, in particular, on the method of attachment of the shell to the core of the cylinder that was adopted.
  • the ferrule is crossed by channels intended to be traversed by a cooling fluid such as water, when using the machine of casting.
  • the silvering / de-silvering workshop treatment stations each consisting of a tank containing a solution suitable for carrying out a given stage of treatment, above which one can place said shaft with its horizontal axis and rotate it around its axis. So we dip the bottom of the shell in the solution, and the rotation of the shaft / ferrule assembly makes it possible to carry out the processing of the entire ferrule (it being understood that the ferrule normally performs several turns on itself during the same treatment, at a speed of about 10 rpm, for example).
  • the bare ferrule (in the case of the first silvering of a new ferrule, or the silvering of a used ferrule whose copper surface would have been exposed) undergoes first, preferably, a mechanical preparation by polishing its surface. Then we performs chemical degreasing in an alkaline medium, which has the function of ridding the surface of the shell of organic matter which can pollute it. It is carried out at hot, at a temperature of about 40 to 70 ° C for about fifteen minutes, and followed by a water rinse. We can substitute or even add a step of electrolytic degreasing which would provide an even better surface quality.
  • the next step is a pickling operation in an oxidizing acid medium, which has function of removing surface oxides, taking care to dissolve only one thickness very minimal of the shell.
  • An aqueous solution is used for this purpose, for example sulfuric acid at 100 ml / l, to which 50 ml / l of a 30% solution of hydrogen peroxide or a solution of another compound.
  • This pickling operation in an oxidizing acid medium has maximum efficiency when the electrolyte temperature is understood between 40 and 55 ° C. It is advantageous to maintain this temperature at the interface by a circulation of hot water inside the channels of the rotating shell. The operation lasts about 5 minutes and is followed by a water rinse.
  • the purpose of the pre-silvering operation is intended to be placed under chemical conditions intended to prevent a displacement of silver by copper during silvering, which would be detrimental to the adhesion deposit money. It is particularly useful even if the ferrule is not pure copper, but a Cu-Cr-Zr alloy. It lasts 4 to 5 minutes and is preferably done at room temperature, the ferrule being placed as a cathode in an electrolyte consisting of an aqueous solution of sodium cyanide (50 to 90 g / l approximately) and silver cyanide sufficiently diluted in dissolved metal (30 to 50 g / l). You can also replace sodium cyanide with potassium cyanide (65 to 100 g / l).
  • the optimal operating temperature is 40 to 45 ° C
  • the potassium carbonate is necessary to obtain a homogeneous corrosion of the anodes. It can be replaced by sodium carbonate, with the disadvantage that sodium carbonate has a lower solubility. Potash can be replaced by soda. They ensure the conductivity of the electrolyte, as well as the stability of the anionic complex under which the silver is found (Ag (CN) 4 2- ).
  • the silver plating operation is generally carried out using a direct current source, which can advantageously be replaced by a source of transient currents, which make it possible to increase the fineness of the crystallization.
  • the crystallization can also be advantageously modified by lowering the temperature of the shell / electrolyte interface, for example by circulating cold water through the channels of the shell. Under these conditions, the silver electrolyte is a hot source and the ferrule is a cold source. A temperature gradient is established and the interface then offers a greater activation overvoltage, favorable to the increase in the hardness of the coating.
  • the anode (s) are soluble anodes formed by one or more baskets titanium anodics containing silver beads or metallic silver under any other form, for example berlingots. These titanium panodes are used as dimensionally stable electrodes. Their shape matches that of the ferrule in its submerged part, which makes it possible to homogenize the distribution of current densities cathodics on the ferrule. As the anode-cathode distance does not vary in these conditions, the panodes keep the current densities constant on the cathode.
  • the silver layer is attacked and mechanical wear which leads to its progressive consumption.
  • the surface of the ferrule should be cleaned, and the silver layer may, at least occasionally time, undergo a slight machining intended to compensate for the possible heterogeneities of its wear which could compromise the homogeneity of the thermomechanical behavior of the shell over its entire surface. It is also important to restore the initial roughness of the ferrule whenever necessary.
  • the thickness mean of the silver layer of the shell reaches a predetermined value, which one generally estimated at around 1 mm, use of the cylinder is interrupted, the ferrule is disassembled and can undergo a complete silver removal treatment or only partial, which must precede the restoration of the silver layer of the shell. To this end, the ferrule can be again mounted on the axis which supported it during operations silver plating. If the silver removal is complete, we then proceed to restore the silver layer according to the whole process which has just been described.
  • a way to shorten the silver removal operation would consist of preceding it with a removal operation silver mechanics which would aim to reduce its residual thickness without, however, reach copper.
  • This operation would also have the advantage of homogenizing this thickness and to remove various surface impurities (especially residues that could locally slow the onset of dissolution. We would avoid still being still dissolving the money in certain areas of the shell then even as in other areas the copper has already been exposed.
  • the electrolytic silver plating method presents the disadvantage of requiring for its implementation a special, incompatible solution for reasons of toxicity with other operations carried out in the workshop silvering-silvering of the ferrules where cyanide solutions are also used.
  • the inventors therefore recommend practicing the restoration of the coating of silver from the shell by direct recharging in a silver plating bath (advantageously the one used for the first silvering described above), without obligation completely or almost completely remove the residual silver coating.
  • a this is possible because it is easy to electrochemically deposit a new silver layer over an older silver layer and get good adhesion of the new layer on the old, while this is not possible for nickel.
  • it considerably simplifies the management of the ferrule packaging workshop, and on the other hand it shortens their maintenance, and therefore downtime.
  • the silver top-up does not have the defects generally attributed to other forms of demetallization in general and nickel removal in particular, due of the natural alkalinity of the silver plating bath.
  • This alkalinity can, in fact, be used as a means of natural passivation of the silver station infrastructure if it is made of uncoated steel.
  • Another advantage of the invention is that it never require to carry in anodic situation said steel infrastructures, which would promote their corrosion and would be detrimental to their durability.
  • Another benefit of direct recharge silver compared to almost electrochemical silver reduction total followed by resilvering is to avoid the total dissolution of money in certain preferential areas (such as the edges of the ferrule) during the silvering, which would lead to localized copper exposures.
  • the refill silvering carried out in conditions avoiding any dissolution of the copper from the ferrule makes it possible not to attack the surface of the shell, therefore extending its service life.
  • Refill silver can be preceded by a light machining of the used silver layer, to homogenize its thickness and remove the impurities which would be detrimental to the adhesion of the new layer of silver on the old.
  • a workshop of ferrule silver would therefore be distinguished in that it would not include necessarily installation for the dissolution of a used coating by way chemical or electrochemical. It would therefore be more economical to build. He would also more economical to operate, because it would consume less electricity: the money is deposited three times faster than nickel at an equal current density, especially because it is monovalent while nickel is bivalent.
  • this advantage is offset partially in that, to obtain equivalent thermal protection of the shell with a silver deposit and a nickel deposit, a silver layer must be deposited about twice as thick as the corresponding nickel layer. But in counterpart, this layer of silver provides mechanical protection of the shell higher than the thinner nickel layer.
  • the cost of salts silver used is in fact not very different from that of the nickel salts employed for the traditional nickel plating of the mold walls. Overall, the cost of a silver coating is therefore not much superior to that of a nickel coating, and especially the repair of a used casting cylinder ferrule is much faster and economical.
  • Cyanide effluents from the workshop can be treated with bleach to destroy cyanides.
  • these effluents can be treated slightly chlorinated by continuous electrolysis: metallic silver is recovered at the cathode and directly destroys ammonium carbonate cyanides on anodes dimensionally stable. Simple and economical solutions can therefore be found to the environmental problems that can arise from the use of cyanide.
  • the invention particularly finds its application in the packaging of ferrules of cylinders for continuous steel casting installations between cylinders or on a single cylinder, because of the large dimensions and the high manufacturing cost of these parts, the life of which is important to prolong as much as possible. But it goes without saying that we can envisage its transposition to the treatments of the walls of casting molds made of copper or copper alloy of all shapes and sizes, intended for the casting of all supporting metals to be brought into liquid state in contact with silver under the conditions of casting.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Coating With Molten Metal (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (13)

  1. Stranggusskokilleteil, das eine gekühlte Wand aus Kupfer oder einer Kupferlegierung umfasst, die vorgesehen ist, in Kontakt mit dem schmelzflüssigen Metall gebracht zu werden, und an ihrer Außenfläche eine Metallbeschichtung aufweist, dadurch gekennzeichnet, dass die Beschichtung aus einer Silberschicht besteht.
  2. Stranggusskokilleteil nach Anspruch 1, dadurch gekennzeichnet, dass die Wand ein Walzenring für eine Maschine für den Strangguss dünner Metallbänder zwischen zwei Walzen oder auf einer einzigen Walze ist.
  3. Stranggusskokilleteil nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Silberschicht mit einem elektrolytischen Verfahren aufgebracht wurde.
  4. Verfahren zum Beschichten der Außenfläche einer gekühlten Wand aus Kupfer oder einer Kupferlegierung eines Stranggusskokilleteils mit einer Metallschicht, dadurch gekennzeichnet, dass diese Beschichtung durch Aufbringen einer Silberschicht auf diese Fläche erfolgt.
  5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass die Silberschicht mit einem elektrolytischen Verfahren aufgebracht wird.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass es auf eine nackte Wand aus Kupfer oder einer Kupferlegierung angewandt wird und nacheinander folgende Schritte umfasst:
    eine Entfettung der Wand;
    ein Dekapieren der Wand in oxidierendem, sauren Milieu;
    einen Arbeitsschritt, bei dem die Wand vorversilbert wird, wobei diese als Kathode in ein Elektrolysebad gebracht wird, das aus einer wässrigen Lösung aus Silbercyanid und Alkalimetallcyanid besteht, so dass eine Silberschicht von einigen um Stärke aufgebracht wird;
    einen Arbeitsschritt, bei dem die Wand versilbert wird, wobei diese als Kathode in ein Elektrolysebad gebracht wird, das aus einer wässrigen Lösung aus Silbercyanid, einem Alkalimetallcyanid, einem Alkalimetallhydroxid und einem Alkalimetallkarbonat besteht.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass es auch ein weiches Dekapieren der Wand zwischen dem Dekapieren und Vorversilbern umfasst.
  8. Verfahren zur Wiederherstellung einer auf die Außenwand einer Wand aus Kupfer oder einer Kupferlegierung eines Stranggusskokilleteils aufgebrachten Silberschicht, dadurch gekennzeichnet, dass man auf der Wand eine Restsilberschicht bestehen lässt, sowie dadurch, dass man eine erneute Versilberung dieser Schicht vornimmt, indem man die Wand als Kathode in ein Elektrolysebad bringt, das ein Silbersalz enthält.
  9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das Elektrolysebad aus einer wässrigen Lösung aus Silbercyanid, einem Alkalimetallcyanid und einem Alkalimetallkarbonat besteht.
  10. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass man vor der erneuten Versilberung eine leichte Bearbeitung der Restsilberschicht vornimmt, ohne diese gänzlich wegzunehmen.
  11. Verfahren zur Wiederherstellung einer auf die Außenwand einer Wand aus Kupfer oder einer Kupferlegierung eines Stranggusskokilleteils aufgebrachten Silberschicht, dadurch gekennzeichnet, dass man eine partielle oder tolale Entsilberung der Wand vornimmt, indem man die Wand als Anode in ein Elektrolysebad auf Basis von Salpetersäure bringt, das einen Inhibitor für Kupfer enthält, und dass man anschließend eine erneute Versilberung der Wand oder der Restsilberschicht vornimmt, indem man die Wand als Kathode in ein Elektrolysebad bringt, das aus einer wässrigen Lösung aus Silbercyanid, einem Alkalimetallcyanid und einem Alkalimetallkarbonat besteht.
  12. Verfahren nach einem der Ansprüche 6 bis 11, dadurch gekennzeichnet, dass man während der Versilberung oder erneuten Versilberung einen Temperaturgradienten zwischen der Wand und dem Elektrolysebad durch Kühlen der Wand erzeugt.
  13. Verfahren nach einem der Ansprüche 6 bis 12, dadurch gekennzeichnet, dass man während der Versilberung oder erneuten Versilberung einen transienten Strom verwendet.
EP97930592A 1996-07-11 1997-06-26 Stranggusskokilleteil mit einer metalbeschichter, gekühlter wand aus kupfer oder kupferlegierung und verfahren zu seiner herstellung Expired - Lifetime EP0910489B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9608658A FR2750903B1 (fr) 1996-07-11 1996-07-11 Element d'une lingotiere pour la coulee continue des metaux, comprenant une paroi refroidie en cuivre ou en alliage de cuivre comportant sur sa surface externe un revetement metallique et procede pour son revetement
FR9608658 1996-07-11
PCT/FR1997/001139 WO1998002263A1 (fr) 1996-07-11 1997-06-26 Element d'une lingotiere pour la coulee continue des metaux, comprenant une paroi refroidie en cuivre ou en alliage de cuivre comportant sur sa surface externe un revetement metallique, et procede pour son revetement

Publications (2)

Publication Number Publication Date
EP0910489A1 EP0910489A1 (de) 1999-04-28
EP0910489B1 true EP0910489B1 (de) 2000-05-17

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EP97930592A Expired - Lifetime EP0910489B1 (de) 1996-07-11 1997-06-26 Stranggusskokilleteil mit einer metalbeschichter, gekühlter wand aus kupfer oder kupferlegierung und verfahren zu seiner herstellung

Country Status (23)

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EP (1) EP0910489B1 (de)
JP (1) JP2000514361A (de)
KR (1) KR20000022396A (de)
CN (1) CN1072047C (de)
AT (1) ATE192951T1 (de)
AU (1) AU710657B2 (de)
BR (1) BR9710229A (de)
CA (1) CA2258927A1 (de)
CZ (1) CZ6499A3 (de)
DE (1) DE69702064T2 (de)
DK (1) DK0910489T3 (de)
ES (1) ES2148994T3 (de)
FR (1) FR2750903B1 (de)
GR (1) GR3034001T3 (de)
PL (1) PL331180A1 (de)
PT (1) PT910489E (de)
RO (1) RO119994B1 (de)
RU (1) RU2181315C2 (de)
SK (1) SK299A3 (de)
TR (1) TR199900041T2 (de)
TW (1) TW438911B (de)
WO (1) WO1998002263A1 (de)
ZA (1) ZA975970B (de)

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CN102672437A (zh) * 2012-06-04 2012-09-19 无锡市三方轧辊有限公司 热轧铝板轧辊再生利用的加工工艺

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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
DE202009013126U1 (de) * 2009-09-29 2009-12-10 Egon Evertz Kg (Gmbh & Co.) Kokille zum Stranggießen
EP2942168B1 (de) 2014-05-09 2018-02-07 Fiskars Finland Oy Ab Vorrichtung für Hauklötze
CN107254697B (zh) * 2017-06-06 2020-02-14 秦皇岛瀚丰长白结晶器有限责任公司 结晶器铜板镍钴合金镀层钴的梯度分布工艺及电镀装置

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JPS5570452A (en) * 1978-11-20 1980-05-27 Nishio Metaraijingu:Kk Continuous casting mold
DE3211199A1 (de) * 1982-03-26 1983-09-29 Egon 5650 Solingen Evertz Verfahren zum vernickeln von kokillenwaenden
FR2622901B1 (fr) * 1987-11-05 1990-02-09 Snecma Procede electrolytique d'argentage en couche mince et application a des chemins de roulement

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Publication number Priority date Publication date Assignee Title
CN102672437A (zh) * 2012-06-04 2012-09-19 无锡市三方轧辊有限公司 热轧铝板轧辊再生利用的加工工艺
CN102672437B (zh) * 2012-06-04 2014-07-30 无锡市三方轧辊有限公司 热轧铝板轧辊再生利用的加工工艺

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SK299A3 (en) 1999-05-07
WO1998002263A1 (fr) 1998-01-22
JP2000514361A (ja) 2000-10-31
CN1225046A (zh) 1999-08-04
FR2750903B1 (fr) 1998-09-18
EP0910489A1 (de) 1999-04-28
FR2750903A1 (fr) 1998-01-16
GR3034001T3 (en) 2000-11-30
DE69702064T2 (de) 2001-01-11
TR199900041T2 (xx) 1999-06-21
DE69702064D1 (de) 2000-06-21
PL331180A1 (en) 1999-06-21
AU710657B2 (en) 1999-09-23
BR9710229A (pt) 1999-08-10
ZA975970B (en) 1998-01-30
PT910489E (pt) 2000-10-31
CN1072047C (zh) 2001-10-03
AU3448897A (en) 1998-02-09
ATE192951T1 (de) 2000-06-15
RU2181315C2 (ru) 2002-04-20
DK0910489T3 (da) 2000-10-09
RO119994B1 (ro) 2005-07-29
TW438911B (en) 2001-06-07
CA2258927A1 (fr) 1998-01-22
CZ6499A3 (cs) 1999-10-13
KR20000022396A (ko) 2000-04-25
ES2148994T3 (es) 2000-10-16

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