EP0250001B1 - Copper alloy - Google Patents
Copper alloy Download PDFInfo
- Publication number
- EP0250001B1 EP0250001B1 EP87108853A EP87108853A EP0250001B1 EP 0250001 B1 EP0250001 B1 EP 0250001B1 EP 87108853 A EP87108853 A EP 87108853A EP 87108853 A EP87108853 A EP 87108853A EP 0250001 B1 EP0250001 B1 EP 0250001B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- copper
- copper alloy
- production
- phosphorus
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Definitions
- the invention is therefore based on the object of specifying a copper alloy which has a high thermal conductivity, a high mechanical strength, in particular at temperatures above 300 ° C. and a high degree of hot plasticity.
- the material should be used in particular for the production of continuous casting molds.
- a copper alloy consisting of 0.05 to 0.4% zinc, 0.02 to 0.3% magnesium, 0.02 to 0.2% phosphorus, the rest copper and production-related impurities, the alloy can optionally contain 0 to 0.2% silicon and / or 0 to 0.15% zirconium.
- silicon up to 0.2%, preferably up to 0.1%, has a positive effect on the hardness and thus on the wear resistance.
- the invention further relates to a method for producing a copper alloy as described above.
- the alloy is then hot worked at 300 to 550 ° C for 1 to 5 hours and finally cold worked by at least 10%.
- Cold working of at least 10% between hot working and aging at 300 to 550 ° C has a positive effect on the state of homogenization and the combination of properties.
- the alloy is particularly advantageous for the alloy to be thermoformed above the temperature of the maximum solubility of the alloy components and then to be quenched by at least 750 ° C. With this measure, an additional curing effect can be achieved. However, solution annealing can also be carried out separately from hot working.
- the technological properties of the alloy are somewhat more favorable if the hot working at solution annealing temperature is heard and quenched and then the operations described above are followed. By eliminating intermediate phases from the copper matrix, even more favorable strength and conductivity values can be achieved.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
- Continuous Casting (AREA)
- Error Detection And Correction (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
- Transmission Systems Not Characterized By The Medium Used For Transmission (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Metal Extraction Processes (AREA)
- Molds, Cores, And Manufacturing Methods Thereof (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
Als Werkstoff zur Herstellung von Stranggießkokillen zum Stranggießen von hochschmelzenden Metallen wie Stahl wird seit langem Kupfer vorwiegend des Typs SF-Cu verwendet, welches aufgrund seiner hohen thermischen Leitfähigkeit sehr schnell die Wärme aus der Schmelze abzuleiten vermag. Die Wandstärke der Kokillen wird so groß gewählt, daß sie in ausreichender Weise den zu erwartenden mechanischen Beanspruchungen genügt.As a material for the production of continuous casting molds for the continuous casting of refractory metals such as steel, copper of the SF-Cu type has long been used, which due to its high thermal conductivity is able to dissipate the heat from the melt very quickly. The wall thickness of the molds is chosen so large that it sufficiently meets the mechanical loads to be expected.
Zur Erhöhung der Warmfestigkeit ist vorgeschlagen worden, Stranggießkokillen aus einer Legierung mit mindestens 85 % Kupfer und wenigstens einem weiteren eine Ausscheidungshärtung bewirkenden Legierungselement herzustellen. Als Legierungselement werden bis zu 3 % Chrom, Silizium, Silber und Beryllium vorgeschlagen. Auch die aus diesem Werkstoff hergestellten Stranggießkokillen konnten noch nicht vollauf befriedigen, da insbesondere die Legierungskomponenten Silizium und Beryllium die thermische Leitfähigkeit stark herabsetzen (AT-PS 234 930).To increase the heat resistance, it has been proposed to produce continuous casting molds from an alloy with at least 85% copper and at least one further alloy element which effects precipitation hardening. Up to 3% chromium, silicon, silver and beryllium are proposed as alloying elements. Even the continuous casting molds made from this material have not yet been completely satisfactory, since the alloy components silicon and beryllium in particular greatly reduce the thermal conductivity (AT-PS 234 930).
Alle diese Lösungen haben als Werkstoffe für Stranggießkokillen noch nicht vollauf befriedigen können.All of these solutions have not yet been completely satisfactory as materials for continuous casting molds.
Der Erfindung liegt von daher die Aufgabe zugrunde, eine Kupferlegierung anzugeben, die eine hohe thermische Leitfähigkeit, eine hohe mechanische Festigkeit insbesondere bei Temperaturen oberhalb 300° C und eine hohe Warmplastizität aufweist. Der Werkstoff soll insbesondere zur Herstellung von Stranggießkokillen verwendbar sein.The invention is therefore based on the object of specifying a copper alloy which has a high thermal conductivity, a high mechanical strength, in particular at temperatures above 300 ° C. and a high degree of hot plasticity. The material should be used in particular for the production of continuous casting molds.
Diese Aufgabe wird durch eine Kupferlegierung gelöst, die aus 0,05 bis 0,4 % Zink, 0,02 bis 0,3 % Magnesium, 0,02 bis 0,2 % Phosphor, Rest Kupfer und herstellungsbedingten Verunreinigungen besteht, wobei die Legierung wahlweise noch 0 bis 0,2 % Silizium und/oder 0 bis 0,15 % Zirkon enthalten kann.This object is achieved by a copper alloy consisting of 0.05 to 0.4% zinc, 0.02 to 0.3% magnesium, 0.02 to 0.2% phosphorus, the rest copper and production-related impurities, the alloy can optionally contain 0 to 0.2% silicon and / or 0 to 0.15% zirconium.
Es ist bekannt, daß Zusätze von Zink oder Magnesium die Leitfähigkeit des Kupfers geringfügig herabsetzen, während Phosphorzusätze zu einem starken Leitfähigkeitsabfall führen. Die Festigkeit wird durch den Zusatz von Zink, Magnesium oder Phosphor heraufgesetzt. Völlig überraschend hat sich jedoch herausgestellt, daß der gemeinsame Zusatz aller drei Elemente in den beanspruchten Bereichen die Leitfähigkeit verglichen mit einem handelsüblichen SF-Kupfer gar nicht oder nur geringfügig herabsetzt. Die Festigkeit ist infolge einer Mischkristallhärtung sowie durch zusätzliche Aushärtungseffekte durch Phosphidbildung, die ausscheidungsfähig sind,gegenüber SF-Kupfer wesentlich höher. Insbesondere die Warmfestigkeit zeigt wesentlich höhere Werte als SF-Kupfer. Als besonders vorteilhaft hat sich eine Legierung erwiesen, die aus 0,1 bis 0,25 % Zink, 0,05 bis 0,15 % Magnesium, 0,05 bis 0,1 % Phosphor, Rest Kupfer und herstellungsbedingte Verunreinigungen besteht.It is known that additions of zinc or magnesium slightly reduce the conductivity of the copper, while additions of phosphorus lead to a sharp drop in conductivity. The strength is increased by the addition of zinc, magnesium or phosphorus. Completely surprisingly, however, it has been found that adding all three elements together in the claimed areas does not reduce the conductivity at all, or only slightly, in comparison with a commercially available SF copper. The strength is significantly higher than that of SF copper due to mixed crystal hardening and additional hardening effects due to phosphide formation, which can be precipitated. The heat resistance in particular shows significantly higher values than SF copper. An alloy which has been found to be particularly advantageous is composed of 0.1 to 0.25% zinc, 0.05 to 0.15% magnesium, 0.05 to 0.1% phosphorus, the remainder copper and production-related impurities.
Ein Zusatz von Silizium bis zu 0,2 % vorzugsweise bis 0,1 % wirkt sich positiv auf die Härte und damit auf die Verschleißfestigkeit aus.The addition of silicon up to 0.2%, preferably up to 0.1%, has a positive effect on the hardness and thus on the wear resistance.
Zusätze von bis zu 0,15 % Zirkon führen zu einer Verbesserung der Warmplastizität.Additions of up to 0.15% zircon lead to an improvement in the warm plasticity.
Sie ermöglichen ferner in Kombination mit einer gezielten Wärmebehandlung eine weitere Verbesserung des Erweichungsverhaltens. Beide Zusätze führen in den angegebenen Konzentrationen zu keiner wesentlichen Verringerung der Wärmeleitfähigkeit.In combination with targeted heat treatment, they also enable a further improvement in the softening behavior. Both additives do not lead to a significant reduction in the thermal conductivity in the stated concentrations.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung einer Kupferlegierung wie sie oben beschrieben ist.The invention further relates to a method for producing a copper alloy as described above.
Danach wird die Legierung nach dem Gießen warmverformt bei 300 bis 550° C 1 bis 5 Stunden geglüht und abschließend um mindestens 10 % kaltverformt.After the casting, the alloy is then hot worked at 300 to 550 ° C for 1 to 5 hours and finally cold worked by at least 10%.
Eine Kaltverformung um mindestens 10 % zwischen der Warmverformung und der Auslagerung bei 300 bis 550° C wirkt sich positiv auf den Homogenisierungszustand und die Eigenschaftskombination aus.Cold working of at least 10% between hot working and aging at 300 to 550 ° C has a positive effect on the state of homogenization and the combination of properties.
Mit besonderem Vorteil wird die Legierung oberhalb der Temperatur der maximalen Löslichkeit der Legierungskomponenten warmverformt und danach von mindestens 750° C abgeschreckt. Durch diese Maßnahme kann ein zusätzlicher Aushärtungseffekt erzielt werden. Ein Lösungsglühen kann jedoch auch getrennt von der Warmverformung vorgenommen werden.It is particularly advantageous for the alloy to be thermoformed above the temperature of the maximum solubility of the alloy components and then to be quenched by at least 750 ° C. With this measure, an additional curing effect can be achieved. However, solution annealing can also be carried out separately from hot working.
Zur Erhöhung der Festigkeit ist es von Vorteil, nach dem letzten Auslagerungsglühen nochmals eine Kaltverformung von mindestens 10 % vorzunehmen.To increase the strength, it is advantageous to perform a cold deformation of at least 10% again after the last aging annealing.
Die Erfindung ist an Hand eines Ausführungsbeispiels näher erläutert.The invention is explained in more detail using an exemplary embodiment.
Eine Legierung bestehend aus 0,19 % Zink, 0,09 % Magnesium, 0,07 % Phosphor, Rest Kupfer und herstellungsbedingte Verunreinigungen, wurde nach dem Gießen durch Strangpressen warmverformt und darauf durch Ziehen um 20 % kaltverformt. Die Legierung wurde dann bei 500° C fünf Stunden geglüht. Es wurden dann Proben hergestellt, die um 10 %, 20 % und 40 % kaltverformt wurden. Die Eigenschaften dieser Proben sind in den Tabellen A, B und C im Vergleich zu SF-Kupfer und einer Kupfer-Chrom-Zirkon-Legierung aufgeführt.An alloy consisting of 0.19% zinc, 0.09% magnesium, 0.07% phosphorus, the rest copper and production-related impurities was cast after extrusion thermoformed and then cold-formed by drawing by 20%. The alloy was then annealed at 500 ° C for five hours. Samples were then made that were cold worked by 10%, 20% and 40%. The properties of these samples are listed in Tables A, B and C compared to SF copper and a copper-chrome-zirconium alloy.
Der Vergleich mit dem für Stranggießkokillen häufig verwendeten Werkstoff SF-Kupfer zeigt deutlich, daß bei vergleichbaren Verformungsgraden die Festigkeitswerte durchweg um ca. 50 % höher liegen. Die Leitfähigkeit ist ebenfalls höher. Wesentlich ist jedoch, daß das Erweichungsverhalten bei hohen Temperaturen erheblich günstiger ist. So erweicht der erfindungsgemäße Werkstoff bei vergleichbarer Leitfähigkeit erst bei Temperaturen von über 500° C. Hinzu kommt eine wesentlich geringere Kriechdehnung bei erhöhten Temperaturen, die eine bessere Verzugsfreiheit gewährleistet. Insgesamt kann erwartet werden, daß sich die Kupferlegierung nach der Lehre der Erfindung hervorragend als Werkstoff für Stranggießkokillen eignet. Im Vergleich mit der Kupfer-Chrom-Legierung schneidet die erfindungsgemäße Legierung ebenfalls sehr gut ab. Da die erfindungsgemäße Legierung jedoch wesentlich einfacher herstellbar ist, und die Legierungselemente preisgünstiger sind, dürften Stranggießkokillen aus dem neuen Werkstoff bei gleichem Standverhalten preisgünstiger sein.A comparison with the material SF copper, which is frequently used for continuous casting molds, clearly shows that, with comparable degrees of deformation, the strength values are consistently around 50% higher. The conductivity is also higher. It is essential, however, that the softening behavior at high temperatures is considerably more favorable. Thus, the material according to the invention, with comparable conductivity, only softens at temperatures above 500 ° C. In addition, there is a significantly lower creep at elevated temperatures, which ensures better freedom from warping. Overall, it can be expected that the copper alloy is outstandingly suitable as a material for continuous casting molds according to the teaching of the invention. In comparison with the copper-chromium alloy, the alloy according to the invention also performs very well. However, since the alloy according to the invention is much easier to manufacture and the alloy elements are less expensive, continuous casting molds made from the new material should be less expensive with the same stability.
Etwas günstiger sind die technologischen Eigenschaften der Legierung, wenn man die Warmverformung bei Lösungsglühtemperatur vernimmt und darauf abschreckt und dann die oben beschriebenen Arbeitsgänge folgen läßt. Durch Ausscheidung von intermediären Phasen aus der Kupfermatrix können noch günstigere Festigkeits- und Leitfähigkeitswerte erzielt werden.
Claims (7)
- A copper alloy composed of 0.05 to 0.4% zinc, 0.02 to 0.3% magnesium, 0.02 to 0.2% phosphorus, optionally 0 to 0.2% silicon, 0 to 0.15% zirconium, the remainder copper and production-related impurities.
- A copper alloy as claimed in Claim 1, composed of 0.1 to 0.25% zinc, 0.05 to 0.15% magnesium, 0.05 to 0.1% phosphorus, the remainder copper and production-related impurities.
- A copper alloy as claimed in Claim 1 or 2, characterised by an addition of up to 0.2%, preferably up to 0.1%, of silicon.
- A copper alloy as claimed in one or more of Claims 1 to 3, characterised by an addition of up to 0.15% zirconium.
- A process for the production of a copper alloy as claimed in one or more of Claims 1 to 4, characterised in that after casting the alloy is hot worked, annealed for 1 to 6 hours at approximately 300 to 550°C, and then cold worked by at least 10%.
- A process as claimed in Claim 5, characterised in that after the hot working the alloy is cold worked by at least 10%.
- A process as claimed in Claim 5, characterised in that the hot working is carried out above the temperature of maximum solubility, and the alloy is chilled by at least 750°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT87108853T ATE70858T1 (en) | 1986-06-20 | 1987-06-20 | COPPER ALLOY. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3620654 | 1986-06-20 | ||
DE19863620654 DE3620654A1 (en) | 1986-06-20 | 1986-06-20 | COPPER ALLOY |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0250001A2 EP0250001A2 (en) | 1987-12-23 |
EP0250001A3 EP0250001A3 (en) | 1989-06-07 |
EP0250001B1 true EP0250001B1 (en) | 1991-12-27 |
Family
ID=6303307
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87108853A Expired - Lifetime EP0250001B1 (en) | 1986-06-20 | 1987-06-20 | Copper alloy |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0250001B1 (en) |
JP (1) | JP2530657B2 (en) |
AT (1) | ATE70858T1 (en) |
CA (1) | CA1308940C (en) |
DE (2) | DE3620654A1 (en) |
ES (1) | ES2038620T3 (en) |
FI (1) | FI88623C (en) |
IN (1) | IN168226B (en) |
ZA (1) | ZA874542B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR910004078B1 (en) * | 1987-08-31 | 1991-06-22 | 미쯔비시마테리알 가부시기가이샤 | Mold member and rapidly solidifying water looled rotary roll member kazuhiko tabei |
DE10032627A1 (en) * | 2000-07-07 | 2002-01-17 | Km Europa Metal Ag | Use of a copper-nickel alloy |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3778318A (en) * | 1969-02-24 | 1973-12-11 | Cooper Range Co | Copper base composition |
US4202688A (en) * | 1975-02-05 | 1980-05-13 | Olin Corporation | High conductivity high temperature copper alloy |
GB1562870A (en) * | 1977-03-09 | 1980-03-19 | Louyot Comptoir Lyon Alemand | Copper alloys |
JPS5514128A (en) * | 1978-07-13 | 1980-01-31 | Honda Motor Co Ltd | Heat treatment method of in-furnace brazing |
US4305762A (en) * | 1980-05-14 | 1981-12-15 | Olin Corporation | Copper base alloy and method for obtaining same |
JPS5832220A (en) * | 1981-08-19 | 1983-02-25 | Matsushita Electric Ind Co Ltd | Step-up type magnetic head |
US4605532A (en) * | 1984-08-31 | 1986-08-12 | Olin Corporation | Copper alloys having an improved combination of strength and conductivity |
-
1986
- 1986-06-20 DE DE19863620654 patent/DE3620654A1/en not_active Withdrawn
- 1986-06-23 ZA ZA874542A patent/ZA874542B/en unknown
-
1987
- 1987-06-20 DE DE8787108853T patent/DE3775474D1/en not_active Expired - Fee Related
- 1987-06-20 EP EP87108853A patent/EP0250001B1/en not_active Expired - Lifetime
- 1987-06-20 AT AT87108853T patent/ATE70858T1/en not_active IP Right Cessation
- 1987-06-20 ES ES198787108853T patent/ES2038620T3/en not_active Expired - Lifetime
- 1987-06-22 FI FI872760A patent/FI88623C/en not_active IP Right Cessation
- 1987-06-29 JP JP62159587A patent/JP2530657B2/en not_active Expired - Fee Related
- 1987-07-13 IN IN534/CAL/87A patent/IN168226B/en unknown
- 1987-07-21 CA CA000542572A patent/CA1308940C/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE3620654A1 (en) | 1987-12-23 |
DE3775474D1 (en) | 1992-02-06 |
EP0250001A3 (en) | 1989-06-07 |
FI88623C (en) | 1993-06-10 |
EP0250001A2 (en) | 1987-12-23 |
CA1308940C (en) | 1992-10-20 |
ATE70858T1 (en) | 1992-01-15 |
FI872760A (en) | 1987-12-21 |
FI872760A0 (en) | 1987-06-22 |
FI88623B (en) | 1993-02-26 |
JP2530657B2 (en) | 1996-09-04 |
IN168226B (en) | 1991-02-23 |
JPS648236A (en) | 1989-01-12 |
ZA874542B (en) | 1988-07-27 |
ES2038620T3 (en) | 1993-08-01 |
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