CA2417546A1 - Age-hardenable copper alloy - Google Patents
Age-hardenable copper alloy Download PDFInfo
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- CA2417546A1 CA2417546A1 CA002417546A CA2417546A CA2417546A1 CA 2417546 A1 CA2417546 A1 CA 2417546A1 CA 002417546 A CA002417546 A CA 002417546A CA 2417546 A CA2417546 A CA 2417546A CA 2417546 A1 CA2417546 A1 CA 2417546A1
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- 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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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
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0637—Accessories therefor
- B22D11/0648—Casting surfaces
- B22D11/066—Side dams
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- Moulds For Moulding Plastics Or The Like (AREA)
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Abstract
An age-hardenable copper alloy made of 1.2 to 2.7 % cobalt, which is able to be partially replaced by nickel, 0.3 to 0.7 % beryllium, 0.01 to 0.5 % zirconium, optionally 0.005 to 0.1 % magnesium and/or iron and in some instances up to a maximum of 0.15 % of at least one element from the group including niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium.
The remainder is copper and includes production-conditioned impurities and usual processing additives. This copper alloy is used as the material for producing mold blocks for the side dams of continuous strip-casting installations.
The remainder is copper and includes production-conditioned impurities and usual processing additives. This copper alloy is used as the material for producing mold blocks for the side dams of continuous strip-casting installations.
Description
(364 j 104) BAC GEOUND 4F THE INVE_~TION, , Field of the Inve~,tion The invention relates to an age-hardenable copper allay as material for producing blocks for the side dams of continuous strip-casting installations.
Description of Rg~,~ted Art The worldwide aim, especially in ~~he steel and copper industzies, to cast semifinished material to as close'tb the final dimensions as possible, in order to save hot forming and/or cold forming steps, led even before 1970 to the development of the so-called,I-~a elettsp-casting installations, in which the molten metal solidifies in the gap :between two bands guided in parallel. The side dams. in, for example, the strip-casting instahation known from ~T.S:
Patent No. 3,865, 3?6, are made of metallic mold blocks or dam blocks having a T
groove, which are lined up on a fl~e~i,ble continuous band such as one made of steel, and which move .in the: longitudin~- direction, synchronously wifih the casting bands: In this contexts. the :daxn blocks. bound the casting mold cavity formed by the casting bands, : . _ , Also known, from EP 0 9?4 413 A1 are dam i~lock chains for continuous strip-casting, formed by,blocks having_a slot. and key, The advantage of these fiu~ther developed mold blocks <lzaving: ~ slob and key comes about. due to a more exact alignment. and. guidance of the:'T~~ooks. during the casting process, and leads to an improvexner~t of the surface qu~ty of the cast strip. In order to prevent premature wear of the side edges-. of the blocks by plastic deformation and the formation of cracks, a suitable material has to have great hardness and strength, a fine-grained anicrostructure and a good long-term resistance to softening. In order to remove the heat of solidif cataon from the liquid molten material, a high thermal conductivity, of the gnold block material is additionally required.
Finally, optimum fatigue behavioa- of the material is of .the most decisive significance, which wall ensure that, after leaving the casting segment, the thermal stresses appearing during the cooling off of the blocks do not lead to crackzng of the blocks at fine corners of the T gzoove incorporated for the accommodation of the steel band. In this context, particularly great thermal stresses are to be expected in dam blocks having the design using slot and key, on .account of the unfavorable geometry and mass distribution.
If such cracks caused by thermal shock appear, the respective mold block will fall out of the dam block chain of the continuous strip-casting machine after even a short period, anolten metal being able to run uncontrollably from the casting mold cavity and to damage pats of .the installation, For the purpose of exchanging the damaged moldblocks; . he'entire strip-casting installation has to .
b.e stopped and the casting process .has td be interrupted:
A testing method has proven itself for checking the tendsnc~ to crack, in which the mold blocks are submitted to heat treatment for two hours at 500 °C
and are subsequently quenched in water at 20 to 25 °C. den if this thermal shock test is repeated several times; in.the c~se'of a suitable mateaial no cracks may appear in the T groove surface. . : .
1~rP 0 345 645 B1 describes an age-hardenable copper-based alloy which is made of 1.6 to 2.4 % nickel, 0:5 tb 0.8 % silicon, 0.01, to 0,2 % zirconium, optionally up to 0.4 % chromium and/or up to 0.2 % iron, the remainder being copper including production-caused impurities. This known copper alloy basically satisfies the pxerequisites~..for a long. service life, if used as the material for producing standard mold blocks for the side dams of continuous strip-casting installations. The following combination of properties is given for this copper alloy:
Rm at 20 °C: 635 to'660 MPs Rm at 500 °C: . 286 to 372 MPs Brinell hardness: 185 for 1.91:HB, (corresponds to about 195 to 210 Conductivity: 41.4 to 42.4 % IACS.
No cracks are to appear during the thermal shock test. i7ne advantage compared to beryllium-containing, copper-based alloys is the possibility of 'being able to regrind the mold blocks rnenually; si~ice rto beryllium is contained in the grinding dust. .The reproeessirlg-.of used dam blocks having slot acid key is considerably more costly and, as a rule, requires machine (wet) cleaning of the T
groove and the casting surfaces (e. g. in closed chambersJ, whereby the liberation of grinding dusts is prevented, Thus, using beryllium-containing ahoys would basically be possible under these circumstances.
A dam block nnade of the CuNiSiZr alloy described in EP 0 346 645 8 Z, however, disadvantageously tends to premature wear of the side edges and casting surfaces, at very high mechanical and thermal stresses in the castixig opera.~ion of a continuous strip-casting installation. As the results of investigations have shown, this wear may be attributed to a material softening of the casting edges and surfaces to a value below 160 H T. F'urthexmore, the thermal shock resistance of the known CuNiSiZr alloy is not always sufficient for eil'ectively preventing the formation of cracks ix~ the 'T groove during. casting use, when the alloy is used for a dam block having: -a slot and key.
~UMMARY~F THE INVENTION
It is an object of the invention to create axe age-hardenable copper alloy as a material fox producing dam blocks .for continuous strip-casting installations, especially 'in a slot and key embodiment, ~ which is stable to changing temperature stresses even at high casting speeds, and which has a great resistance to wear and resistance to softening, as well as great resistance to crack formation in the T groove.
These and other objects of the invention are achieved by an age-hardenable copper alloy made of 1..2 to 2,~7 % cobalt, 0,3 to 0.? % berylliiun, 0.07. to 0.5 zirconium, optionally 0.005 to 0.2 % magnesium and/or 0.005 to 0.2 % iron and, in some instances, up to a. maximum of 0, 35 % of at least one element from the group including niobium, tantalum, vanadiurri, hafnium, chromium?
manganese, titanium and cerium, the remainder being copper including production-caused impurities and the usual processing additives. This alloy is used as the material for producing bloek.for the side dams of strip-casting installations.
D LE DE CRl it3 OF THE NVE TIO
By using a copper-based alloy made of 1.2 to 2.7 wt.% cobalt, 0.3 to 0.7 wt.%
beryllium, O.Ol to 0.5 wt.% zirconium, optionally 0,005 to 0,2 wt.% magnesium and/or iron and of the reanainder copper, including production-caused impurities and the usual. processing additives, on the one hand, a sufficient age-hardenability of the material for achieving great strength, hardness and conductivity rnay be ensured. On the other hand, only a'relatively slight cold working of up to a anaximurn of ~0 °/n is required fox establishing a fine-grained microstructure having a sufficient plasticity. Because ,of the deliberately graduated zirconium content, both the fatigue resistance and the heat resistance properties are improved.
A further improvement of the mechanical properties of the dam blocks, especially an increase .in tensile strength, rnay-advantageoiasly be achieved by having the copper alloy contaih,° 1.:8: to 2:4'wt:% cobalt, 0.45 to 0.65 wt:°Jo beryllium, 0.15 to 0.3 urt.% zirconium; up to 0.05 wt.°/a magnesium and/or up t0 ~. ~. % 1T'Ori.
The invention permits that, in the copper alloy up to 80 % of the cobalt content may be replaced by nickel.
Farther improvements of the mechanical properties of a dam block may be achieved if the copper alloy contains up to a maximum of 0,15 wt.% of at least one elements of the group including.niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium. Usual deoxidants such as boron, lithium.; potassium an;d phosphonx~ may also be added up to a maximum of 0.03 wt.%, without negativelyinfluencing the mechanical properties of the copper alloy of the present invention.
According to another specific embodiment, a part of the zirconium content may be replaced by. up to 0,15 wt.% by afi, least a~ie element of the group includirsg ceriuxn, hafnium, . niobium; tantalum; vanadium, chromium; manganese and titanium.
Advantageously; the blocks for the side dams of double strip-casting installations are produced using the age-hardenable copper alloy, by the method steps: casting, hot forming, cold forming up to. 40 ~ %, solution treating at a temperature in the range of 850 to 970 ~~, as well as a 0.5 to 16-hour age-haxdenzng treatrnerzt at 400 ao 55d~ °G, : .
As a particular advaxrta~e, the copper alloy may be .cold formed by 5 to 3Q
after hot forming. A cold fob degree of 10 to 15 % lying within this range is particularly preferred in this context.
It i,s especially advantageous if the datn blocks in .the age-hardened condition have a tensile strength ~f at least ~Si~ :l~Epa,. particularly ?4~0 to 900 Mpa, a Vickers hardness of at least X10 H~', .~artaculariy 230 to 28Q HV, an electrical .. 5.
conductivity of at least 40 ~% IACS; pai~ticuiarly 45 to 50 % IACS, a hot tensile strength at 500 °C of at Least 400 Mpa, particularly of at least 450 Mpa, a minimum hardness of 160 HV after 500-hour ageing at 500 °C, and a maximum grain size according to ASTM E 312 of 0.5 mrn:
Particularly preferred are dam blocks made of the copper ~.lloy, if, in the age-hardened condition they have a graiin size, ascertaixiecl according to ASTM ~
1~2, between 30 and 90 Nrri. ~ .
in a preferred embodiment, the copper alloy, after the hot forming of the.
cast blank, is cold formed up.to 40%~, is then solution treated at a temperature lying in the temperature range of 850 tc 9'70°C; .arid is subsequently submitted to a 0.5 to 16-hour age-Hardening roatmentvat 400 to 550°.C -~n a surprisingly simple way one azay..succeed. in getting rid of the bad recxystallization behavior observed in the known CuCoBe alloys during the hot fornzing and solution treatment. The bad recrystallization behavior, in the production of mold blocks made of CuCoBe alloys, in the hot formed, solution treated and age-hardened condition leads to a coarse microstructure:, that is not acceptable for the application purposes having grain. sizes: up-to snore than :l mm, However, if, between the hot forming and the solution treatment; the material is submitted to cold forming up to .a :maximum of ~0 °!o; preferably up tn a maximum of 15 %, this aEddi,tionaa, processing step leads tc~ aconsiderably more fine-gz~ained microstructure. Relevant investigative series have confirmed that materials for mold blocks for the side dams of strip-casting machines, which are cold formed below the recr3rstalliza,tion tornperature, and are subsequently.solution treated, have a clearly finer microstructure at grain sizes below 0:5 mm, while higher degrees of cold forming,. above. approximately 40 %; lead during subsequent solution treatment to a coarsening of the grain by secondary recrystatlization, at grain sizes above Z mm.
. ": 6.
°'EX.~,MPLES
The invention is explained below in greater detail, with the aid of exemplary embodiments. The advantages of the copper alloys are demonstrated using three alloys according.to the invention (A, B and C) and three alloys for reference (D, E and F) , The composition of the copper alloys in wt.% is given below in Table 1.
Ta - ~ 1:~, Alloy Co (%) Ni (%)'Be (%) ~~2t Si (%) Cr (%) Cu (%j ' (%) A 2.1 - 0.54 0,18 - - Remainder B 2.2 - 0:56 0.24 - - Remainder C 1.3 1.0 0.48 0.15 - - Remainder D - 2:0 , X7:1 0.62 0.34 Remainder C
E 2.1 - 0.55 ~ - - Remainder F 1.0 1:1 0:62 ~ - - - Remainder In the case of the composition of alloy D, a known CuNiSi-based alloy is involved, whereas E and F are normalized CuCo2Be or CuCoNiBe materials.
All the copger alloys were smelted: is an induction crucible oven and were cast by the continuous strip-casting methad to round billets.having a diameter of 280 mm. The round ballets of exemplary alloy A, B and C were extruded on an extrusion press at a temperature above 900 °C to flat bar of a dimension y9 x 59 mxn, and subsequently were drawza, at a loss in cross section of 12 %, to a dimension of 75 x 55 mm. The blocks of the ,reference alloys D, E and F were , extruded at the sayne temperature; directly to the dimension ~5 x 55 rnm, and were not submitted to additional cold forming. The CuCoBe and CuCoNiBe materials were subsequently solution=treated at 900 to.950 °C and were age-hardened at a temperature .range between 450 and 550 °C for 0.5 to hours.
The CuNiSi-based alloy was solution-treated at 800 to 850 °C and age-hardened under the same conditioa~s. In the age-hardened condition, tine tensile strength Rm, the Vickers hardness HVIO,. the electrical conductivity (as substitute quantity for the heat conductivity), the grain size according to ASTM E112, the heat resistance Rm at 500 °C and the resistance to softening via Vickers hardness measurement (HV 10) after ageing at S00 °C after 500 hours were ascertained, The thermal shock behavior was finally tested on mold blocks ( 1 ) of dimensions ?0 x 50 x 40 mm and mold blocks (2j; having slat and key; of dimensions 70 x 50 x 47 mm. For this, the mold blocks were t-ust annealed for two hours at 500 °C and then quenched in water at,20 to 25 °C. The T groove of the blocks were then searched for cracks wzth the naked eye and a microscope at 10-fold magnification.
All the test results are summarized in Table 2 below.
Table 2 AlloyTensiteVirkas Co~ductiviryGraia 'reaeile~ckess FiardaeasHeheariaa~
s~mgth Hardncsa(docu3cal)Siu Streagth1 o ARer Aita ~!o Ag~r~g at l7ieratoshack Teat ~10 ~rs ~ ~~J~A .5~~ C OVGT H~ llt ~i? rJ~' ~ 1 t MPa h A $01 254 -SO .30-90523 1?3 ~sck-Freectacls-free B 804 24S 51.5 45-.9n464 1?S crack-freeQerk free C 812 255 49.6 4S-90 4S5 16? ~~-~ a~-~
D 652 205 ~3 45-90 38? 118 cs~ck-~Breecracked E 786 260 S0. S to 423 150 ~d F 807 248 4$.5 to 434 152 p~$~ age In the mold blocks classified as mcracked", the, extension of determined cracks in '8 the groove was 2 , to 5 mrn, and in individual cases, the length o~ the crack was up to 10 mm. One may see from the reference that, as compared to materials E
and F, only copper alloys A, B and C, and produced using slight cold working, at optimum properties, have a surprisingly uniform and fine-grained microstructure, and have the necessary resistance to the formation of cracks when used as mold block having lot and key. Even when used in a usual mold block, the copper alloys in accordance with the invention have a clearly better resistance to softening compared to the known CuNiSi alloys D, and a somewhat better resistance to softening when compared to alloys E and F.
Therefore, the copper alloy in accordance with the invention is eminently suitable as the material for producing all mold blocks, that are submitted to typically changing temperature stress during the casting process, for the side darns of strip-casting installations. These .are both the mold blocks used up ~o the present and the mold blocks.embodied with slot and key as in EP0974413A1.
Description of Rg~,~ted Art The worldwide aim, especially in ~~he steel and copper industzies, to cast semifinished material to as close'tb the final dimensions as possible, in order to save hot forming and/or cold forming steps, led even before 1970 to the development of the so-called,I-~a elettsp-casting installations, in which the molten metal solidifies in the gap :between two bands guided in parallel. The side dams. in, for example, the strip-casting instahation known from ~T.S:
Patent No. 3,865, 3?6, are made of metallic mold blocks or dam blocks having a T
groove, which are lined up on a fl~e~i,ble continuous band such as one made of steel, and which move .in the: longitudin~- direction, synchronously wifih the casting bands: In this contexts. the :daxn blocks. bound the casting mold cavity formed by the casting bands, : . _ , Also known, from EP 0 9?4 413 A1 are dam i~lock chains for continuous strip-casting, formed by,blocks having_a slot. and key, The advantage of these fiu~ther developed mold blocks <lzaving: ~ slob and key comes about. due to a more exact alignment. and. guidance of the:'T~~ooks. during the casting process, and leads to an improvexner~t of the surface qu~ty of the cast strip. In order to prevent premature wear of the side edges-. of the blocks by plastic deformation and the formation of cracks, a suitable material has to have great hardness and strength, a fine-grained anicrostructure and a good long-term resistance to softening. In order to remove the heat of solidif cataon from the liquid molten material, a high thermal conductivity, of the gnold block material is additionally required.
Finally, optimum fatigue behavioa- of the material is of .the most decisive significance, which wall ensure that, after leaving the casting segment, the thermal stresses appearing during the cooling off of the blocks do not lead to crackzng of the blocks at fine corners of the T gzoove incorporated for the accommodation of the steel band. In this context, particularly great thermal stresses are to be expected in dam blocks having the design using slot and key, on .account of the unfavorable geometry and mass distribution.
If such cracks caused by thermal shock appear, the respective mold block will fall out of the dam block chain of the continuous strip-casting machine after even a short period, anolten metal being able to run uncontrollably from the casting mold cavity and to damage pats of .the installation, For the purpose of exchanging the damaged moldblocks; . he'entire strip-casting installation has to .
b.e stopped and the casting process .has td be interrupted:
A testing method has proven itself for checking the tendsnc~ to crack, in which the mold blocks are submitted to heat treatment for two hours at 500 °C
and are subsequently quenched in water at 20 to 25 °C. den if this thermal shock test is repeated several times; in.the c~se'of a suitable mateaial no cracks may appear in the T groove surface. . : .
1~rP 0 345 645 B1 describes an age-hardenable copper-based alloy which is made of 1.6 to 2.4 % nickel, 0:5 tb 0.8 % silicon, 0.01, to 0,2 % zirconium, optionally up to 0.4 % chromium and/or up to 0.2 % iron, the remainder being copper including production-caused impurities. This known copper alloy basically satisfies the pxerequisites~..for a long. service life, if used as the material for producing standard mold blocks for the side dams of continuous strip-casting installations. The following combination of properties is given for this copper alloy:
Rm at 20 °C: 635 to'660 MPs Rm at 500 °C: . 286 to 372 MPs Brinell hardness: 185 for 1.91:HB, (corresponds to about 195 to 210 Conductivity: 41.4 to 42.4 % IACS.
No cracks are to appear during the thermal shock test. i7ne advantage compared to beryllium-containing, copper-based alloys is the possibility of 'being able to regrind the mold blocks rnenually; si~ice rto beryllium is contained in the grinding dust. .The reproeessirlg-.of used dam blocks having slot acid key is considerably more costly and, as a rule, requires machine (wet) cleaning of the T
groove and the casting surfaces (e. g. in closed chambersJ, whereby the liberation of grinding dusts is prevented, Thus, using beryllium-containing ahoys would basically be possible under these circumstances.
A dam block nnade of the CuNiSiZr alloy described in EP 0 346 645 8 Z, however, disadvantageously tends to premature wear of the side edges and casting surfaces, at very high mechanical and thermal stresses in the castixig opera.~ion of a continuous strip-casting installation. As the results of investigations have shown, this wear may be attributed to a material softening of the casting edges and surfaces to a value below 160 H T. F'urthexmore, the thermal shock resistance of the known CuNiSiZr alloy is not always sufficient for eil'ectively preventing the formation of cracks ix~ the 'T groove during. casting use, when the alloy is used for a dam block having: -a slot and key.
~UMMARY~F THE INVENTION
It is an object of the invention to create axe age-hardenable copper alloy as a material fox producing dam blocks .for continuous strip-casting installations, especially 'in a slot and key embodiment, ~ which is stable to changing temperature stresses even at high casting speeds, and which has a great resistance to wear and resistance to softening, as well as great resistance to crack formation in the T groove.
These and other objects of the invention are achieved by an age-hardenable copper alloy made of 1..2 to 2,~7 % cobalt, 0,3 to 0.? % berylliiun, 0.07. to 0.5 zirconium, optionally 0.005 to 0.2 % magnesium and/or 0.005 to 0.2 % iron and, in some instances, up to a. maximum of 0, 35 % of at least one element from the group including niobium, tantalum, vanadiurri, hafnium, chromium?
manganese, titanium and cerium, the remainder being copper including production-caused impurities and the usual processing additives. This alloy is used as the material for producing bloek.for the side dams of strip-casting installations.
D LE DE CRl it3 OF THE NVE TIO
By using a copper-based alloy made of 1.2 to 2.7 wt.% cobalt, 0.3 to 0.7 wt.%
beryllium, O.Ol to 0.5 wt.% zirconium, optionally 0,005 to 0,2 wt.% magnesium and/or iron and of the reanainder copper, including production-caused impurities and the usual. processing additives, on the one hand, a sufficient age-hardenability of the material for achieving great strength, hardness and conductivity rnay be ensured. On the other hand, only a'relatively slight cold working of up to a anaximurn of ~0 °/n is required fox establishing a fine-grained microstructure having a sufficient plasticity. Because ,of the deliberately graduated zirconium content, both the fatigue resistance and the heat resistance properties are improved.
A further improvement of the mechanical properties of the dam blocks, especially an increase .in tensile strength, rnay-advantageoiasly be achieved by having the copper alloy contaih,° 1.:8: to 2:4'wt:% cobalt, 0.45 to 0.65 wt:°Jo beryllium, 0.15 to 0.3 urt.% zirconium; up to 0.05 wt.°/a magnesium and/or up t0 ~. ~. % 1T'Ori.
The invention permits that, in the copper alloy up to 80 % of the cobalt content may be replaced by nickel.
Farther improvements of the mechanical properties of a dam block may be achieved if the copper alloy contains up to a maximum of 0,15 wt.% of at least one elements of the group including.niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium. Usual deoxidants such as boron, lithium.; potassium an;d phosphonx~ may also be added up to a maximum of 0.03 wt.%, without negativelyinfluencing the mechanical properties of the copper alloy of the present invention.
According to another specific embodiment, a part of the zirconium content may be replaced by. up to 0,15 wt.% by afi, least a~ie element of the group includirsg ceriuxn, hafnium, . niobium; tantalum; vanadium, chromium; manganese and titanium.
Advantageously; the blocks for the side dams of double strip-casting installations are produced using the age-hardenable copper alloy, by the method steps: casting, hot forming, cold forming up to. 40 ~ %, solution treating at a temperature in the range of 850 to 970 ~~, as well as a 0.5 to 16-hour age-haxdenzng treatrnerzt at 400 ao 55d~ °G, : .
As a particular advaxrta~e, the copper alloy may be .cold formed by 5 to 3Q
after hot forming. A cold fob degree of 10 to 15 % lying within this range is particularly preferred in this context.
It i,s especially advantageous if the datn blocks in .the age-hardened condition have a tensile strength ~f at least ~Si~ :l~Epa,. particularly ?4~0 to 900 Mpa, a Vickers hardness of at least X10 H~', .~artaculariy 230 to 28Q HV, an electrical .. 5.
conductivity of at least 40 ~% IACS; pai~ticuiarly 45 to 50 % IACS, a hot tensile strength at 500 °C of at Least 400 Mpa, particularly of at least 450 Mpa, a minimum hardness of 160 HV after 500-hour ageing at 500 °C, and a maximum grain size according to ASTM E 312 of 0.5 mrn:
Particularly preferred are dam blocks made of the copper ~.lloy, if, in the age-hardened condition they have a graiin size, ascertaixiecl according to ASTM ~
1~2, between 30 and 90 Nrri. ~ .
in a preferred embodiment, the copper alloy, after the hot forming of the.
cast blank, is cold formed up.to 40%~, is then solution treated at a temperature lying in the temperature range of 850 tc 9'70°C; .arid is subsequently submitted to a 0.5 to 16-hour age-Hardening roatmentvat 400 to 550°.C -~n a surprisingly simple way one azay..succeed. in getting rid of the bad recxystallization behavior observed in the known CuCoBe alloys during the hot fornzing and solution treatment. The bad recrystallization behavior, in the production of mold blocks made of CuCoBe alloys, in the hot formed, solution treated and age-hardened condition leads to a coarse microstructure:, that is not acceptable for the application purposes having grain. sizes: up-to snore than :l mm, However, if, between the hot forming and the solution treatment; the material is submitted to cold forming up to .a :maximum of ~0 °!o; preferably up tn a maximum of 15 %, this aEddi,tionaa, processing step leads tc~ aconsiderably more fine-gz~ained microstructure. Relevant investigative series have confirmed that materials for mold blocks for the side dams of strip-casting machines, which are cold formed below the recr3rstalliza,tion tornperature, and are subsequently.solution treated, have a clearly finer microstructure at grain sizes below 0:5 mm, while higher degrees of cold forming,. above. approximately 40 %; lead during subsequent solution treatment to a coarsening of the grain by secondary recrystatlization, at grain sizes above Z mm.
. ": 6.
°'EX.~,MPLES
The invention is explained below in greater detail, with the aid of exemplary embodiments. The advantages of the copper alloys are demonstrated using three alloys according.to the invention (A, B and C) and three alloys for reference (D, E and F) , The composition of the copper alloys in wt.% is given below in Table 1.
Ta - ~ 1:~, Alloy Co (%) Ni (%)'Be (%) ~~2t Si (%) Cr (%) Cu (%j ' (%) A 2.1 - 0.54 0,18 - - Remainder B 2.2 - 0:56 0.24 - - Remainder C 1.3 1.0 0.48 0.15 - - Remainder D - 2:0 , X7:1 0.62 0.34 Remainder C
E 2.1 - 0.55 ~ - - Remainder F 1.0 1:1 0:62 ~ - - - Remainder In the case of the composition of alloy D, a known CuNiSi-based alloy is involved, whereas E and F are normalized CuCo2Be or CuCoNiBe materials.
All the copger alloys were smelted: is an induction crucible oven and were cast by the continuous strip-casting methad to round billets.having a diameter of 280 mm. The round ballets of exemplary alloy A, B and C were extruded on an extrusion press at a temperature above 900 °C to flat bar of a dimension y9 x 59 mxn, and subsequently were drawza, at a loss in cross section of 12 %, to a dimension of 75 x 55 mm. The blocks of the ,reference alloys D, E and F were , extruded at the sayne temperature; directly to the dimension ~5 x 55 rnm, and were not submitted to additional cold forming. The CuCoBe and CuCoNiBe materials were subsequently solution=treated at 900 to.950 °C and were age-hardened at a temperature .range between 450 and 550 °C for 0.5 to hours.
The CuNiSi-based alloy was solution-treated at 800 to 850 °C and age-hardened under the same conditioa~s. In the age-hardened condition, tine tensile strength Rm, the Vickers hardness HVIO,. the electrical conductivity (as substitute quantity for the heat conductivity), the grain size according to ASTM E112, the heat resistance Rm at 500 °C and the resistance to softening via Vickers hardness measurement (HV 10) after ageing at S00 °C after 500 hours were ascertained, The thermal shock behavior was finally tested on mold blocks ( 1 ) of dimensions ?0 x 50 x 40 mm and mold blocks (2j; having slat and key; of dimensions 70 x 50 x 47 mm. For this, the mold blocks were t-ust annealed for two hours at 500 °C and then quenched in water at,20 to 25 °C. The T groove of the blocks were then searched for cracks wzth the naked eye and a microscope at 10-fold magnification.
All the test results are summarized in Table 2 below.
Table 2 AlloyTensiteVirkas Co~ductiviryGraia 'reaeile~ckess FiardaeasHeheariaa~
s~mgth Hardncsa(docu3cal)Siu Streagth1 o ARer Aita ~!o Ag~r~g at l7ieratoshack Teat ~10 ~rs ~ ~~J~A .5~~ C OVGT H~ llt ~i? rJ~' ~ 1 t MPa h A $01 254 -SO .30-90523 1?3 ~sck-Freectacls-free B 804 24S 51.5 45-.9n464 1?S crack-freeQerk free C 812 255 49.6 4S-90 4S5 16? ~~-~ a~-~
D 652 205 ~3 45-90 38? 118 cs~ck-~Breecracked E 786 260 S0. S to 423 150 ~d F 807 248 4$.5 to 434 152 p~$~ age In the mold blocks classified as mcracked", the, extension of determined cracks in '8 the groove was 2 , to 5 mrn, and in individual cases, the length o~ the crack was up to 10 mm. One may see from the reference that, as compared to materials E
and F, only copper alloys A, B and C, and produced using slight cold working, at optimum properties, have a surprisingly uniform and fine-grained microstructure, and have the necessary resistance to the formation of cracks when used as mold block having lot and key. Even when used in a usual mold block, the copper alloys in accordance with the invention have a clearly better resistance to softening compared to the known CuNiSi alloys D, and a somewhat better resistance to softening when compared to alloys E and F.
Therefore, the copper alloy in accordance with the invention is eminently suitable as the material for producing all mold blocks, that are submitted to typically changing temperature stress during the casting process, for the side darns of strip-casting installations. These .are both the mold blocks used up ~o the present and the mold blocks.embodied with slot and key as in EP0974413A1.
Claims (19)
1. An age-hardenable copper alloy suitable as a material for producing block for the side dams of strip-casting installations, comprising: 1.2 to 2.7 %
cobalt, 0.3 to 0.7 % beryllium, 0,01 to 0.5 % zirconium, and a balance of copper.
cobalt, 0.3 to 0.7 % beryllium, 0,01 to 0.5 % zirconium, and a balance of copper.
2. The copper alloy according to Claim 1, further comprising 0.005 to 0.2 %
magnesium.
magnesium.
3. The copper alloy according to Claim 1, further comprising 0.005 to 0.2 %
iron.
iron.
4. The copper alloy according to Claim 2, further comprising 0.005 to 0.2 %
iron.
iron.
5. The copper alloy according to Claim 1, further comprising up to a maximum of 0.15 % of at least one element selected from the group consisting of niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium.
6. The copper alloy according to Claim 2, further comprising up to a maximum of 0.15 % of at least one element selected from the group consisting of niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium.
7. The copper alloy according to Claim 3, further comprising up to a maximum of 0.15 % of at yeast one element selected from the group consisting of niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium.
8. The copper alloy according to Claim 4, further comprising up to a maximum of 0.15 % of at least one element selected from the group consisting of niobium, tantalum, vanadium, hafnium, chromium, manganese, titanium and cerium.
9. The copper alloy according to Claim 4, comprising: 1.8 to 2.4 % cobalt, 0.45 to 0.65 % beryllium, 0.15 to 0.3 % zirconium, up to 0.05 % magnesium, up to 0.1 % iron, and a balance of copper.
10. The copper alloy according to Claim 1, wherein up to 80 % of the cobalt content is replaced by nickel.
11. The copper alloy according to Claim 2, wherein up to 80 % of the cobalt content is replaced by nickel.
12. The copper alloy according to Claim 1, wherein a part of the zirconium content is replaced by up to 0.15 wt.% of at least one element selected from the group consisting of cerium, hafnium, niobium, tantalum, chromium, manganese, titanium and vanadium.
13. The copper alloy according to Claim 2, wherein a part of the zirconium content is replaced by up to 0.15 wt.% of at least one element selected from the group consisting of cerium, hafnium, niobium, tantalum, chromium, manganese, titanium and vanadium.
14. The copper alloy according to Claim 1, which, after hot forming of the cast blank, is cold formed up to 40 %, is then solution treated at a temperature lying in the temperature range of 850 to 970 °C, and is subsequently submitted to a 0.5 to 16-hour age-hardening treatment at 400 to 550 °C.
15. The copper alloy according to Claim 14, which, after the hot forming, is cold formed by 5 to 30 %.
16. The copper alloy according to Claim 14, which, after hot forming, is cold formed by 10 to 15 %.
17. The copper alloy according to Claim 1, which, in the age-hardened state, has a tensile strength of at least 650 Mpa, a Vickers hardness of at least 210 HV, an electrical conductivity of at least 40 % IACS, a hot tensile strength at 500 °C of at least 400 Mpa, a minimum hardness of 160 HV after 500 hours of constant ageing at 500 °C and a maximum grain size according to ASTM
of 0.5 mm.
of 0.5 mm.
18. The copper alloy according to Claim 1, which, in the age-hardened state, has a tensile strength of at least 700 to 900 Mpa, a Vickers hardness of 230 to 280 HV, an electrical conductivity of 45 to 60 % IACS, a hot tensile strength at 500 °C of at least 450 Mpa and a minimum hardness of 160 HV after 500 hours of constant ageing at 500 °C.
19. The copper alloy according to Claim 1, which has a grain size between 30 and 90 µm, ascertained according to ASTM E112.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10206597A DE10206597A1 (en) | 2002-02-15 | 2002-02-15 | Hardenable copper alloy used as a material for blocks for the sides of strip casting mills contains alloying additions of cobalt, beryllium, zirconium, and magnesium and/or iron |
| DE10206597.7 | 2002-02-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2417546A1 true CA2417546A1 (en) | 2003-08-15 |
| CA2417546C CA2417546C (en) | 2015-03-31 |
Family
ID=27635063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2417546A Expired - Fee Related CA2417546C (en) | 2002-02-15 | 2003-01-28 | Age-hardenable copper alloy |
Country Status (15)
| Country | Link |
|---|---|
| US (2) | US20030159763A1 (en) |
| EP (1) | EP1340564B1 (en) |
| JP (1) | JP4472933B2 (en) |
| KR (1) | KR100967864B1 (en) |
| CN (1) | CN1271228C (en) |
| AT (1) | ATE367229T1 (en) |
| BR (1) | BR0300445B1 (en) |
| CA (1) | CA2417546C (en) |
| DE (2) | DE10206597A1 (en) |
| DK (1) | DK1340564T3 (en) |
| ES (1) | ES2288572T3 (en) |
| MX (1) | MXPA03000218A (en) |
| PL (1) | PL198565B1 (en) |
| PT (1) | PT1340564E (en) |
| RU (1) | RU2301844C2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060086437A1 (en) * | 2004-10-22 | 2006-04-27 | Russell Nippert | Method for manufacturing copper alloys |
| JP2008151270A (en) * | 2006-12-18 | 2008-07-03 | Kitz Sct:Kk | Metal diaphragm valve |
| CN101333609B (en) * | 2007-06-28 | 2011-03-16 | 周水军 | Low copper beryllium mold material for gravitation and low-pressure casting and production process thereof |
| DE102008015096A1 (en) * | 2008-03-19 | 2009-09-24 | Kme Germany Ag & Co. Kg | Process for producing molded parts and molded parts produced by the process |
| CN101643867B (en) * | 2009-08-28 | 2011-11-23 | 镇江汇通金属成型有限公司 | High performance copper casting alloy and preparation method thereof |
| JP2011081764A (en) * | 2009-09-14 | 2011-04-21 | Panasonic Corp | Content receiver, content reproducer, content reproducing system, content writing method, expiration date determining method, program, and recording medium |
| DE102014224236A1 (en) | 2014-11-27 | 2016-06-02 | Sms Group Gmbh | Device for strip casting of metallic products |
| DE102016006824A1 (en) * | 2016-06-03 | 2017-12-07 | Wieland-Werke Ag | Copper alloy and its uses |
| RU2625193C1 (en) * | 2016-10-10 | 2017-07-12 | Юлия Алексеевна Щепочкина | Copper-based alloy |
| KR101810925B1 (en) * | 2017-10-18 | 2017-12-20 | 주식회사 풍산 | Copper alloy strips having high heat resistance and thermal dissipation properties |
| CN112210692B (en) * | 2020-09-10 | 2021-12-17 | 新余市长城铜产品开发有限公司 | Beryllium bronze long guide rail and manufacturing method thereof |
| CN115233032B (en) * | 2022-08-01 | 2023-06-27 | 河南云锦空天特导新材料有限公司 | Copper alloy wire and preparation method and application thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3865176A (en) * | 1973-09-28 | 1975-02-11 | Hazelett Strip Casting Corp | Casting method for twin-belt continuous metal casting machines |
| US4179314A (en) * | 1978-12-11 | 1979-12-18 | Kawecki Berylco Industries, Inc. | Treatment of beryllium-copper alloy and articles made therefrom |
| US4377424A (en) * | 1980-05-26 | 1983-03-22 | Chuetsu Metal Works Co., Ltd. | Mold of precipitation hardenable copper alloy for continuous casting mold |
| JPS6260879A (en) * | 1985-09-10 | 1987-03-17 | Ngk Insulators Ltd | Wear resistant copper alloy member |
| US4749548A (en) * | 1985-09-13 | 1988-06-07 | Mitsubishi Kinzoku Kabushiki Kaisha | Copper alloy lead material for use in semiconductor device |
| EP0271991B1 (en) * | 1986-11-13 | 1991-10-02 | Ngk Insulators, Ltd. | Production of copper-beryllium alloys |
| JP2869076B2 (en) * | 1988-12-19 | 1999-03-10 | 中越合金鋳工株式会社 | Precipitation hardening mold material for continuous casting |
| DE4142941A1 (en) * | 1991-12-24 | 1993-07-01 | Kabelmetal Ag | USE OF A CURABLE copper alloy |
| US6059905A (en) * | 1993-08-26 | 2000-05-09 | Ngk Metals Corporation | Process for treating a copper-beryllium alloy |
| EP0854200A1 (en) * | 1996-10-28 | 1998-07-22 | BRUSH WELLMAN Inc. | Copper-beryllium alloy |
| DE10156925A1 (en) * | 2001-11-21 | 2003-05-28 | Km Europa Metal Ag | Hardenable copper alloy as a material for the production of casting molds |
-
2002
- 2002-02-15 DE DE10206597A patent/DE10206597A1/en not_active Withdrawn
-
2003
- 2003-01-08 MX MXPA03000218A patent/MXPA03000218A/en active IP Right Grant
- 2003-01-18 PT PT03001084T patent/PT1340564E/en unknown
- 2003-01-18 EP EP03001084A patent/EP1340564B1/en not_active Expired - Lifetime
- 2003-01-18 DE DE50307676T patent/DE50307676D1/en not_active Expired - Lifetime
- 2003-01-18 DK DK03001084T patent/DK1340564T3/en active
- 2003-01-18 ES ES03001084T patent/ES2288572T3/en not_active Expired - Lifetime
- 2003-01-18 AT AT03001084T patent/ATE367229T1/en active
- 2003-01-22 CN CNB031033067A patent/CN1271228C/en not_active Expired - Fee Related
- 2003-01-28 CA CA2417546A patent/CA2417546C/en not_active Expired - Fee Related
- 2003-02-10 US US10/361,660 patent/US20030159763A1/en not_active Abandoned
- 2003-02-11 PL PL358681A patent/PL198565B1/en unknown
- 2003-02-12 JP JP2003033937A patent/JP4472933B2/en not_active Expired - Fee Related
- 2003-02-13 BR BRPI0300445-7A patent/BR0300445B1/en not_active IP Right Cessation
- 2003-02-13 KR KR1020030008977A patent/KR100967864B1/en not_active IP Right Cessation
- 2003-02-14 RU RU2003104534/02A patent/RU2301844C2/en not_active IP Right Cessation
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- 2008-06-02 US US12/156,604 patent/US20080240974A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE10206597A1 (en) | 2003-08-28 |
| ATE367229T1 (en) | 2007-08-15 |
| US20030159763A1 (en) | 2003-08-28 |
| JP2004002967A (en) | 2004-01-08 |
| PL358681A1 (en) | 2003-08-25 |
| DE50307676D1 (en) | 2007-08-30 |
| KR100967864B1 (en) | 2010-07-05 |
| CN1271228C (en) | 2006-08-23 |
| JP4472933B2 (en) | 2010-06-02 |
| PL198565B1 (en) | 2008-06-30 |
| MXPA03000218A (en) | 2004-10-29 |
| EP1340564B1 (en) | 2007-07-18 |
| DK1340564T3 (en) | 2007-11-19 |
| CN1442500A (en) | 2003-09-17 |
| KR20030069066A (en) | 2003-08-25 |
| BR0300445A (en) | 2004-08-17 |
| RU2301844C2 (en) | 2007-06-27 |
| EP1340564A2 (en) | 2003-09-03 |
| ES2288572T3 (en) | 2008-01-16 |
| BR0300445B1 (en) | 2011-07-26 |
| CA2417546C (en) | 2015-03-31 |
| PT1340564E (en) | 2007-09-03 |
| US20080240974A1 (en) | 2008-10-02 |
| EP1340564A3 (en) | 2005-04-27 |
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