DE1483180A1 - Highly conductive copper-based alloys - Google Patents

Description

The present invention relates to alloys, in particular Copper-based alloys with a unique combination of properties.

Attempts have been made to make highly conductive materials with improved mechanical properties both at room temperature as well as at elevated (temperatures. It is known to contain materials with a high electrical and Thermal conductivity of copper. However, it is also known that ' that alloying constituents, which are added to copper or its alloys for the purpose of strengthening or hardening, usually cause a damaging reduction in conductivity. While increased amounts of alloying constituents reduce the strength can increase, they also slightly deteriorate the electrical and thermal conductivity. The technique was therefore difficult and unusual problems.

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One of the better solutions to the above problems was the development of the copper-zirconium class of alloys, which in U.S. Patents 2,842,438, 3,019,102 and 3,107,998. Each of these alloys brought a clear, valuable advantage in a technique where even minor Improvements are extremely difficult to achieve. For example, the copper-zirconium alloy has a high level of electrical and conductivity along with good strength and support at temperatures up to! ^ 00 C.

An addition of arsenic, for example 0.1-0.5 % to the copper-zirconium ionization system, produced an alloy with improved properties at room temperature and properties which were achieved without adversely affecting the other valuable properties. On the other hand, an addition of hafnium turned out to be ^ .B. from.}, 1-1.2 fo, to the copper-zirconium system as an advantage in another direction. Thus, for example, hafnium alloys have better mechanical properties at 400 ⁰ C. as the copper zirconium or copper-zirconium-arsenic alloys.

Despite the above advantages and improvements, the demand for materials with even better physical properties remained and mechanical properties, especially at elevated temperatures. It is based on the constantly increasing Requirements for structural components for various electrical and electronic uses. Although attempts have been made to make such a material, So far, as far as is known, none has been completely successful when used on an industrial or industrial scale.

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It has now been found that copper-based alloys with high strength at elevated temperatures and excellent electrical and thermal conductivity can be produced in an economical way. Such alloys k. Can also improve the aging properties can be loaned out, and only relatively small amounts are needed the alloying constituents au use. The alloys They also have good casting * S «*» properties.

Erfindungsgeinm is provided a copper-based alloy with high conductivity and excellent strength at temperatures ä biue to 60O ⁰ C. consisting 0,0,03-1 wt .- ^ zirconium, and .-, 005 to 0.1 wt. - ic vanadium, with the best consisting practically of copper together with impurities and residual deoxidizing agents.

The present invention further provides a method for Reduction of the zirconium losses during melting and casting of Kupfor-Zirj.onium-Vanadium alloys, which is characterized is to melt the copper and then the vanadium before adding zirconium to the copper melt. j

The present invention relates very generally to the treatment of copper-zirconium alloys with: Juteii F-ati ^ koites and hardnesses at Teiuj eratures over 50U ⁰ C, ,, ...:. i> j ° C. The eri'iridiengeiiiussen copper alloys contain

/ vOy-, 0.1 Gu n.-; '. Vanadium and 0.003-1- wt .- #, zE U, 01-0.3 f;.-.-. , Ziri: oniuiii. Gew'öhülich a relatively flume hafnium> is contained in zirconium in its commercially available forms.

Zirconium, for example, as a Iie ^ isjrunsöSCiivvaLjiu, the nominally consists of Ms to 4 wt. -Fo hafnium, zB0,5 f ° hafnium, erhilltlich, wherein the Best substantially zirconium. Thus, the alloys according to the invention also contain the hafnium introduced with the zirconium, and such hafnium in an amount of up to 20 % of the zirconium is regarded as zirconium for the purposes according to the invention. Quake vanadium and zirconium in the amounts specified above contain the alloys according to the invention copper, which makes up the remaining material of the alloy, in addition to the usual impurities and remaining deoxidizing agents.

It is essential that the copper used in the present invention is of high denomination and practically oxygen-free. Although any chemically deoxidized copper, such as phosphorus or Lithium deoxidized copper, used to make the alloy is generally satisfactory, a practically oxygen-free copper without any necessary treatment is expedient used with one of the common deoxidizers. Cathode copper is therefore particularly suitable, as is copper made in a reducing atmosphere, e.g. "OFHO" copper (valued at $ 99.99), copper that goes into an inert atmosphere, under a charcoal cover or in a vacuum.

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The alloys according to the invention containing the above components, namely. Copper, zirconium and vanadium, contained in the specified amounts, are characterized by a high recrystallization temperature and resistance to grain growth at elevated temperatures. Apparently, the initial grain growth between about 550-60O ⁰ G. carried These alloys are further distinguished by a good castability and workability under the usual processing methods.

As indicated above, include alloys of the invention copper, zirconium and vanadium in particular and controlled quantities etc., and each of these elements in conjunction with playing, each of the other two components of an important Bolle in controlling the properties of the alloys. For example, the zirconium content is between 0.003-1% by weight, for example 0.01-0.3% by weight, based on the alloy. The use of zirconium in the specified amounts in the copper alloys according to the invention contributes significantly to the tensile strength if corresponding amounts of vanadium are present at the same time. If, therefore, too little zirconium is present (less than 0.003 °) , the strength of the alloy is disadvantageously reduced. It is advisable to have at least $ 0.01> zirconium, as its contribution to the strength of the alloy is significantly improved. Zirconium seems to have at least one other important function, ie zirconium evidently favors an increase in the solubility of vanadium in the copper alloys according to the invention. Despite

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With these advantages, the maximum zirconium quantities must also be regulated in order to achieve a better combination of properties, such as workability, strength, conductivity, etc. Thus, the amount of zirconium present should be no more than about I $> , and where maximum conductivity is an important factor it should be present in an amount less than about 0.5 ^c / °, suitably less than about 0.15 $ be.

Vanadium should be used in amounts of $ 0.005-0.1, e.g. 0.01-0.1 wt .- ^, the alloy must be present- as there is a synergistic effect

P has with the zirconium and copper in the production of alloys with high conductivity and excellent strengths and hardening at elevated temperatures. If less than 0.005 ° F is present, there is little or no noticeable improvement in the properties of the copper-zirconium alloys at elevated temperatures. If more than 0.1 ^a / c Vaisdium is present, inclusions (which may be vanadium carbide or a copper-zirconium-vanadium complex) are formed, which significantly impair the machinability of the alloy.

^ The upper vanadium quantity is expediently in the range of $ 0.05, since only minor improvements can be expected from further additions of vanadium. Furthermore, it is expedient that the added vanadium has a unit of at least $ 99.5, the best consisting mainly of iron. However, it will be understood by those skilled in the art that an iron-vanadium alloy containing 90% vanadium and 10% iron can be used in the manufacture of the alloys of the present invention which are adapted to uses with less severe conditions.

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In carrying out the present invention, particularly unexpected results are achieved when the alloys are 0.01-0.15 wt. $ Zirconium, 0.01-0.05 wt. - ^ Contains impurities and residual deoxidizing agents, originally oxygen-free copper. Such alloys have a superior combination of physical, mechanical and / or metallurgical properties. For example, at room temperature the alloys have an "ultimate tensile strength" UTS of at least 4200 kg / cm and a 0.1 $ "offset yield strength" (YS) of at least 3850 kg / cm in 90 ° cold . After the 90 tso cold worked alloys have been further subjected to a processing and heat treatment "procedures, including an aging treatment at 600 ⁰ C, which will be described in more detail below, have processed state aie a UTS at room temperature of at least 3560 kg / cm and a conductivity in relation to the "International Annealed Copper Standard" (IAOS) of at least 92 * / o.

Alloys within the broad and beneficial ranges are age hardenable whenever they are first subjected to cold working. The alloys are expediently processed cold to at least 40? », For example at least 50 $, in order to achieve a stronger response to age hardening.

The alloys produced have a Bel..ta üun ^ a-

("jtr.iii.-l-.tidciu")

Lattice structure / ^ dio obviously contributes to the valuable properties of the alloys at elevated temperatures _P

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The aging temperatures are between 350-65O ⁰ C, the aging time is about 30 minutes to 3 hours, preferably one hour. Better results are achieved if the heat treatment for aging aid is carried out at temperatures between 450-600 °, in particular between -500-600 ° »and this temperature is maintained for one hour. After such hot processing have the inventiveness alloys according conductivities up to 94 $ IACS at room temperature and strength (UTS) of up to 1890 kg / cm, when tested at the high temperature of 600 ⁰ C., after about one Were held at this temperature for hour.

For the effective production of the invention. Alloys and to reduce the zirconium and vanadium damage due to their reactivity, a special sequence of stages with specially regulated process conditions is used. This new process consists in melting extremely pure copper and then adding varalium to the melt (before adding the zirconium) at a temperature between 1450-1600 C. If, on the other hand, the zirconium is added before or at the same time as the vanadium, considerable losses occur . If the zirconium is therefore added before the vanadium, the zirconium losses can be up to 40-56 ". If, on the other hand, the vanadium is added before the zirconium under appropriate conditions, practically no losses occur. In order to ensure complete alloying of the vanadium , the melt is at least 5 minutes, but preferably not more than 30 minutes, e.g. 10 minutes,

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kept at this temperature in order to keep vanadium losses to a minimum. Before adding the zirconium (which is preferably in the form of zirconium sponge, although other forms can be used, such as a copper-zirconium alloy containing nominally 30 ^a / o zirconium), the temperature of the melt is raised to 1200-1325 ° C The melt is set up in such a way that all losses of alloying constituents are kept in storage, and the melt contains 0.003-1% by weight of zirconium, 0.005-0.1% by weight of vanadium and as Best Copper. Appropriately, the "

Melt 0.01-0.15 wt .- # zirconium and 0.01-0.05 wt .- ^ vanadium, the best consisting essentially of copper. The temperature is then increased to about 135O-HOO ⁰ and maintained for about 5-30 minutes before casting is carried out at a temperature between 1250-135O ⁰ G. in order to ensure a practically complete alloy without unnecessary losses. The castings produced by the above process are free of defects and have a good surface.

The following examples illustrate the present inventions "dung, without limiting it. In these examples, a Beihe of copper castings having different zirconium and vanadium content was prepared. ¹¹ OiHC" -copper of 99,99- ^ purity was melted in a crucible and the temperature of the melt aui "1500 ⁰ C, placed. Then, to the melt vanadium rods a purity of 99" 5 i ° were (the Best consisted mainly of iron) was added. the temperature of the melt was held for 7 minutes 1500 ⁰ C. before going on

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1300 C. was lowered. Then a zirconium o-id containing nominally 0.5 l = hafnium was added, the temperature of the melt was increased by 50 G. to 135O ⁰ C. and maintained for 7 minutes. After lowering the melt temperature to 1300 ⁰ G. The alloys were about 2.5 cm in diameter rods τοη poured. The composition of these alloys in weight percent is given in Table 1.

Tabdle 1 Vanadium copper
^a / ° alloy
No. Zirconium g 0.03 Best 1 0.04 0.05 Best 2 0.08 0.05 Best 3 0.13 0.028 Best 4th 0.16 0.037 Best 5 U, 16 0.05 Best 6th 0.42 0.04 Best 7th 0.69

The castings became hot rods 6 mm in diameter at 95O ° C. verwalzt and solution-annealed then 1 hour with animal charcoal at 100O ⁰ G.. As is known, the solution starting temperatures can be varied between 900-1Ό00 G. and the times at

these

Temperature can be varied between 20 minutes and 2 hours

will. Then the solution-tempered rods 6 mm in diameter were quenched in water. After quenching, the bars were worked 90 % cold, into bars 2 mm x diameter, and mechanically tested for breakage at room temperature. The results of these tests are given in Table 2.

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BTS Table 2 Stretch in 5 cm, alloy kg / cm 0.1 96 "Offset" YS % Ir. 4270 kg / am. 4th 1 4410 5920 3 2 4620 4060 3 3 4620 4270 3 4th 4830 not tested 3 VJl 5110 not tested 3 6th 5180 4760 2 7th 4830

From Table 2 it can be seen that the alloys according to the invention in the non-aged, but cold-processed state have valuable mechanical properties.

To illustrate the effects of aging, the alloys 1, 2, 3, 6 and 7 were used at different temperatures Aged for 1 hour under animal charcoal, quenched with water and then tested. The results of these tests are in Table 3

specified • Aging Table 3 $ 0.1 off strain Lei tf ^; . iiigke it temp .; oC. BTS ₂ set YS * in 5 cm (fc IACS) alloy kg / cm kg / cm rf ° Mr. 350 3780 7th 73 < η 4270 4130 9 69 1 Il 4760 4340 8th 65 2 η 4970 4830 8th 64 3 η 5390 4970 VJl 64 6th 450 5530 3950 6th 85 7th η .4340 4060 8th 83 1 η 4690 4340 7th 80 2 η 4970 4760 9 78 3 Il 5320 4830 9 77 6th 1> 50 5390 3570 6th 93 7th η 4130 3780 7th 93 1 η 4340 3920 8th 93 H 4410 413Ο 7th 91 3 Λ 4690 413Ο 6th 90 600 4690 3220 8th 94 7th Il 3780 3360 8th 94 1 η 3990 3430 9 92 ; _ '■ II 4060 2870 14th 92 π 3780 2240 20th 92 3430 7th

It can be seen from Table 3 that the alloys of the invention have excellent properties including conductivity after aging, particularly at the higher aging temperatures. For comparison, an alloy was produced without the zirconium content according to the invention and tested like alloys 1-7. This alloy containing 0.027 i ° vanadium, less than 0.001 ° / o zirconium and the balance being substantially .Kupfer. After 1 stüiidigein aging at 55O ⁰ C * was tested and had a. UTS of only 3850 kg / cm and a YS of only 3290 kg / cm. Another copper alloy with 0.2 ψ ™ titanium (the remainder was made of copper) was tested in a similar way. This alloy was cold worked to 84- f <> and as the alloys aged at 600 ⁰ C. 1-7. Although she's a pretty good one

Had strength at room temperature (UTS = 2660 kg / cm), its conductivity was only 38 $ IACS. It appears from this that attempts to improve known copper-based alloys by adding certain additions have not been entirely successful. If such a known alloy is improved, for example in terms of its strength, this was done only at the expense of other desirable properties, such as conductivity, which is in direct contrast to the alloys obtained according to the invention.

To illustrate the unexpected properties with increased Te) .ij, erature of the alloys according to the invention, samples of some of the specified alloy compositions with a diameter of 2.5 cm were reduced in their area by an additional degree of cold working, 1 hour under animal charcoal at 40O ^{Aged 0} C. and quenched with water. These samples were brought to different temperatures and mechanically broken.

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tested after keeping "I hour at the elevated temperature had been. The results are given in Table 4.

Cold processing Table 4 3500 0.1 I »
Offaetgl
kg / cm Stretch in 2.5 cm Leg.
No. 85 Test- ÜTS p
temp.j kg / om
⁰ G. 2940 2940 7th 2: 85 400 2940 2660 6th 2 85 450 1890 2660 6th 2 85 500 1750 1680 5 '2 ·. 90 600 2170 ' 1400 8th 4th 90 600 2660 1610 6th 5 54 600 1820 259O 6th 5 54 500 1890 1820 VJ! 4th 54 600 1890 VJI 5 600

The data in Table 4 show the extraordinarily good properties of the alloys according to the invention at elevated temperatures, aelbat at temperatures up to 60O ⁰ C, at which most of the known, common alloys are very soft. Of particular interest iat alloy 2, no reduction in their properties aeigte, although the temperature of 45O ⁰ G. 500 ⁰ O, has been increased.

The alloys of the invention are useful because of their excellent · Eigenaohaften at temperatures bia to 600 ⁰ O. in conjunction with conductivities up to 94 $ IAOS for many important Verwendungazwöökö For example, forged alloys as electrical and electronic StruktureJaaente, for example, in the production of Klyatron-Hohren are used, their strength at temperatures above ⁰ 5Ou G, BEV / have Ahren. In many such 3 poles _r> the structure-;

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component soldered or ±: i other ϊογμ .be connected with other structural ,, components using bonding processes or an alloy,:., which causes a weakness of the overall system. The alloys according to the invention now make it possible to use solder alloys with higher melting temperatures (and thus higher strengths) without impairing the high conductivity of the structural alloy made of copper, zirconium and vanadium. Can continue to erfindungageioißen alloys will be used in structural elements., V / o high WiirEieleitf ^ hi ^ ness combined with good strength at Tenperaturin up to 600 ⁰ C. A / important factor. One such use of the alloy is in rocket tubes. The Legie, who enjoys invention. " Structures are also attractive from a economic point of view, as they contain relatively small amounts of alloying constituents, e.g. only 0.01% by weight or less, based on the total material.

ORIGINAL )

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Claims (1)

"■ ¹⁵ ""H8318G i? a te ii- t a η a y r ü c ii e 1 .- Copper-based alloy with high conductivity and excellent strengths "for te.rjoratures up to 60O ⁰ O. consisting of 0.003-1 Gexi .- '/ o zirconium, 0.005-0.1 wt .-? & Vanadium, the It consists practically of copper, along with impurities and residual deoxidizing agents. 2. Alloy according to aluminum, characterized in that it contains 0.01-0.3% by weight of zirconium and at least 0.01% by weight of vanadium; a meage below 0.001 wt .- ^ are present. Ä ■ j, - alloy NaCN Ansprucn 1 and 2, characterized dadurcxi that the Best säuerst from anfiaiiglich off-free copper. 4. Alloy ng xiaca claims i and Z, characterized in that the reads are made of copper of high heat. 5 · - Alloy according to claim 1, characterized in that it from 0.01-0.15 Gev /.-^ »zirconium and 0.01-0.05 weight% vanadium consists, v / obei der Hest of extremely pure. Copper with random consists. υ.- alloy according to Ansir.rucii 5, characterized in that the. m üir.e lioiiuiüit vou iaindestena $ 99.5. 'J, - Jileivtr'Oiiiache iJtrulctur component, da υ ^ ei'reii'ijeraturen up to o00 ° 0. äiii-ä J? -ü3ti-; koit bev / axirt, thereby germinating that they iUj yjxror £ vitfCi_ti. _t ied-j1; ui- ("wrou- rü") Ιιΰ.; ίοι. · υ.α., Uoatsnt, die Ü, w1-Ü, l5 ijüMU-r i'jirJronium, u, ü'l-0, 05 wt .-> vanadium and as Eest j.,. I </ Güe jtlioliiiji -j.ua. ociigradie, pure copper, with the 'jiogieruiig at ZiMiüertejiij>er-a1; ur final tensile strengths up to 4CÖ0 h / i / oiu ² and a LeitfWiigJceit up to 94> IACS according to 9Ö -' / oiger 909838/0338 '- Ί6 cold working and aging at 60O ⁰ G. has. · - · .-. Process for reducing zirconium losses during melting and casting Ivupfer / Zirconium / Vanadium alloys, thereby ..-, e ^ ennzeichiiet that one achkilzt the copper and "the copper melt add vanadium before adding zirconium. 9.- Verfaiiren according to claim 8 for alloying copper with Zirkoniuiü and vanadium, characterized in that the vanadium is added to the copper melt, wdirend it has a temperature between 1450-160O ⁰ O., and the temperature is maintained for 5-30 minutes, dio temperature of the melt at 1200-1325 ⁰ O. reduced, adding zirconium to the melt, the temperature of the melt to 1'350- "i40O ° Q. increased, this temperature aufre 5-30 minutes CHT-sustaining and the melt at a temperature between ⁰ 10.- Verfaiiren according to claim 9, characterized dadurcii, ä ä & ZirLonium- the VanadiummBngen and in such a relationship ote ..- (3_, daia the alloy produced υ, 0ϋ3-Ί wt .- '/ c zirconium "and U, 005 .-0.1% by weight, contains vanadium, where the order k 'i ... 11.- Veri'a.rj .'- uii xiacn Anrj-rucxi 10, dadurcii gekemizeiclinat that the LSüier ^: ng Ο, υΐ-0.15 Gev /.- χϊ Zirironiuiü and at least (J, 01 Gew.-5 * Vaxiaäium 2.- Available exactly ..- Claims 9 to ii, characterized by the fact that the vanadium of the so- ^ ielze ^ u ^ e ^ just v / ies,> .v -__ rend this one part. λ sratiir of 1500 ° 0, and ctie Scl: r.elze 7 minutes at this temperature. ^ e .-. 3.1th ./ird, -, / oron the temperature of the öc '; ^, elze before the Ziri -Oiiiumzuj .-. Ibe reduced to 1300 ⁰ C. and then the temperature of the melt to Ij50 C. 3r .._ öht and 7 ..! - imutsii iaif- 909838/0338 _BADORiG1NAL H83180 re hurriedly is obtained, the Saoaelze is poured at a temperature of 1300 ⁰ C. 13 · - Process according to claims 8 to 12, for the production of alloys based on copper with high conductivity and good mechanical properties at Te .- / ^ eraturexi up to 600 ⁰ G, characterized in that the cast alloy is processed hot, the hot worked Alloy 20 minutes to 2 hours at a temperature of 900-1000 ° 0. anläßt solution, the solution annealed alloy cold-worked and cold worked alloy 30 minutes to 3 hours at a temperature zv / aging regard 350-650 ⁰ C.. 14 · - Method according to claim 13 »characterized in that the hot processing is carried out at 95O ⁰ O., the loafing Ί hour at 1000 ⁰ O. and the cold processing is carried out ^{one hour at 500-60 0 C before aging.} 15.- The method according to claim 8 to 14, characterized in that that the copper is of high purity and practically free of oxygen before melting, and that the vanadium is one before melting Has purity of at least $ 99> 5. The "patent attorney / 909838/0338