International Wrought Copper Council

IWCC Technical Seminar Melting and Casting Barcelona

8. 12. March 2009

Vacuum Metallurgy Production of Special Copper Alloys under Vacuum

Andreas Eich, Henrik Franz and Hans-Johann Kemmer of ALD Vacuum Technologies GmbH presented by Hans-Johann Kemmer

Seite 1 von 16

Vacuum Metallurgy Production of Special Copper Alloys under Vacuum

Andreas Eich, Hans-Johann Kemmer ALD Vacuum Technologies GmbH, Hanau Abstract Based on the metallurgical experience with vacuum processing of special alloys with highly reactive alloy additions, the state of the art application of vacuum refining of copper alloys by means of Vacuum Induction Melting (VIM) and casting is presented. This paper will give a short review of the metallurgical advantages and limitations of the VIM process and the achievable copper alloy grades and their properties. Finally todays and future equipment technology and systems concepts are presented. 1. Introduction Copper is mans oldest metal dating back more than 10,000 years. A copper pendant discovered in what is now northern Iraq goes back to about 8,700 B.C. Archaeologists have recently recovered a apportion of a water plumbing system from the Pyramid of Cheops in Egypt. The copper tubing was found in serviceable condition after more than 5,000 years. The annual worldwide production of copper amounts to more than 18 Mio tons in 2008, but this does not mean at all that copper is to be considered a mass product. Especially in highly clean conditions and due to its special physical properties, to name above all its electrical and thermal conductivity, copper is suited for use in the special machine building industry, in high temperature and refrigeration applications, in the electronics, consumer and aircraft industries. Besides the classical bronze and brass alloys, copper alloys with additions of reactive elements have only been developed in more recent years. Some of the elements added to high copper alloys readily react with oxygen (e.g., beryllium, chromium, zirconium, aluminium and silicon) and are, therefore, easily lost as oxides, if melting and casting steps are not well controlled. If foundry practice is poor, these elements can either disappear in the dross that floats to the surface of the melt or they remain suspended in the liquid metal, transforming it to a semi-viscous sludge that can only be cast with difficulty. Chemical analysis may confirm that a casting is within compositional specification, but the alloying elements may be present as compounds that will not dissolve when subjected to solution treatment. Control of beryllium additions is critical also for health reasons. The use of controlled atmosphere, respectively vacuum is recommended for these alloys. The Vacuum Induction Melting (VIM) process is utilized to avoid reactions of reactive alloying elements with the atmosphere, and to produce melts of exceptional compositional accuracy and high cleanliness. It is known that vacuum melting can provide close control of melt composition and temperature while
Seite 2 von 16

simultaneously preventing undesired contamination by reactive gases such as oxygen and hydrogen. (1) The major benefits of Vacuum Induction Melting have been reviewed in the literature frequently. Benefits of the Vacuum Melting and Casting Process
Process Characteristics Isolation of the Melt Results * Vacuum or alternatively inert-gas operation : Prevents contact and reactions with air (oxygen, nitrogen, humidity). Melting under oxygen-free atmosphere limits formation of nonmetallic inclusions and prevents oxidation of reactive elements, such as Cr, Zr, Ti, Co, Be and Mn * Use of graphite crucibles for ultra low oxygen content * Achievement of very close compositional tolerances and gas contents * Casting of reasonably clean and sound ingots Accelerated Refining Reactions * Favours dissociation of compounds (oxides, nitrides, etc) * Removes dissolved gases and volatile constituents. * Provides high degree of purity. Induction Stirring * Homogenizes melt composition and temperature. * Brings reactants to melt surface and accelerates reactions. * Provides excellent reproducibility of composition and properties.

2. Applications for high-purity Copper Alloys It is characteristic, that alloying concentrations amount only to lower percentage ranges and that by suitable combination of various alloying additions, the desired properties in regard to conductivity, strength and toughness can be engineered in combination with a proper thermo-mechanical treatment.

Seite 3 von 16

Data for some selected high-purity copper grades and micro alloyed copper-alloys (according to 2, 3 and own data).
Analysis Cr Zr 0,00002 0,5-1,2 0,04-0,3 0,1-0,3 -

Material Cu-OF B224 Cu-OFLH-HC CuCrZr CuZr CuCo2Be CuBe2

Fe Si 0,0006 0,0001 0,0001 n.d. 0,0001 n.d.

Cu bal. bal.

Ni 0,0005 -

Be -

Co Al 0,00005 0,00001 -

O (ppm) 3 3

bal. bal. bal. 0,2 bal. All other elements max. total

n.d. All other elements max. total 0,2% 0,4-0,7 2,4-2,7 0,1 max. n.d. 1,8-2,1 Ni+Co n.d. 0,2-0,5

450

Tempered Steel
400

350

IN718 K500

CuBe2 CuBe1.7 CuCoNiBe

Hardness HB/HV

300

250

CuAl 10Ni
200

CuNiBe.Sp CuNi2Si CuCrZr

625
150

1810 CrNi Ms58 Ni CuZr E-Cu

100

50

0 0 50 100 150 200 250 300 350 400 450

Thermal Conductivity (W/mK)

Comparison of hardness and thermal conductivity of various materials

(Schmelzmetall AG)

Corresponding with that is a very wide range of actual and future applications of oxygen-free coppers on one hand and of micro-alloyed copper qualities on the other hand.

Seite 4 von 16

Applications for high purity copper, respectively micro-alloyed copper alloys Electrical and Electronics Applications - Cable: superconducting coaxial cable (deep sea) - Terminals and connectors for electrical, electronic and automotive applications - Glass/ metal feed troughs - Vacuum switches and vacuum capacitors - Superconductor wires - Electron beam tubes, x-ray tubes - Wires with small capacitive resistance - Connections to be electron beam welded - Spot welding electrodes, seam welding wheels. - Commutators, stators, rotors for large electro motors and generators - Hollow shaped conductors for accelerators (physics and medical) - Plasma technology - Microwaves / satellite communication / Magnetrons - Integrated circuit lead frames - Heavy electrical switchgear - Printed circuit board conductors

Foil Resistors (Isabellenhtte)

Circuit Leadframe (IBM)

Engineering Applications - Components exposed to high thermal/ electrical stresses - Cooling tubes, cooling ribs (also CuSn) - Heads of blow lances (O2) and busbars - Molds for continuous and static casting. - Plasma torche components and induction coils - Offshore drilling and tools - Aircraft components - Cooling circuits in nuclear power plants - Photovoltaic panels made from coated Cu(InGa)Se2 alloy - Combustion chambers for rocket engines

Seite 5 von 16

The alloys are also readily available in all of the common product forms as rolled flat strip, extruded and drawn bars, mechanical wire, forgings, castings and sprayformed billets. Copper has sufficient strength, ductility and hardness for many standard applications. For many special applications, however, the demands of new technology require copper to have higher mechanical properties and to be capable of use at elevated operating temperatures while still retaining the good conductivity for which it is selected in the first place.

ARIANE Rocket Launch

(Schmelzmetall AG)

ARIANE Thrust Chamber

(Schmelzmetall AG)

The copper industry has invested much research effort over the years to create materials capable of meeting these demanding needs. These high-copper alloys includes, in wrought shapes, cadmium coppers, beryllium coppers, chromium coppers, zirconium coppers, chromium-zirconium coppers and combinations of copper with these and other volatile elements. Though melting of copper and copper alloys in vacuum induction furnaces has been known for a long time for its metallurgical advantages, vacuum melting is covering today only a small niche market, because of the rather low demand for alloys with extreme properties and because of cost considerations. However, future increasing needs for more sophisticated alloys will draw more attention to vacuum processing of advanced copper alloys. 3. Basic Correlations in the Refining Metallurgy for Copper The solubility curve for hydrogen in copper as a function of temperature with a significant solubility jump at the melting point. The negative effect of hydrogen on the product quality is widely known. Oxygen is predominantly dissolved in form of Cu2O. Carbon has a solubility of only 1ppm in liquid copper at a temperature of 1100 (4). The solubility of carbon in solid copper instead is higher by an order C of magnitude of 1 to 2. Up to 1440 the solubility of nitrogen in solid as well as C liquid copper is practically zero (5).
Seite 6 von 16

Solubility Curve of Hydrogen in Copper, according to (4) The solubility of oxygen and hydrogen in copper are dependent from each other due to vapour formation and are a function of temperature and pressure.

Relationship between oxygen and hydrogen content in copper for various temperatures and pressures, according to (10)
Seite 7 von 16

Graph shows the correlation under fine vacuum conditions (calculation according to Fromm (5). At partial pressures of water vapour in the range of 10-2 mbar, hydrogen contents of 0,1ppm and oxygen contents of less than 1ppm are in equilibrium at a temperature of 1200 C. So far, smaller contents of oxygen (< 10 ppm) have been realized predominantly by the use of reducing gas atmospheres during melting (6). By vacuum melting, oxygen contents in the order of 1 ppm are more easily obtained.

The Solution

Vacuum Metallurgy for Copper Alloys

pCO atm

C + O2 = CO
2C +O2 = 2CO

10-2 10-3

Temperature and pressure for CO dependency on the oxygen potential of metal oxides

Richardson-Jeffes Diagram (11)

Seite 8 von 16

Especially advantageous under vacuum is the reduction of metal-oxides with carbon as reducing agent. As shown in the (Richardson-Jeffes diagram), carbon stands out with its unique properties. The declining equation lines display the equilibrium values of the reaction C + O2 = CO as a function of varying pressures (11). Its potential to reduce oxides increases at higher temperatures and lower pressures, so that at a certain temperature and below a certain pressure, practically every metal oxide can be reduced to metal by carbon. The stability of an oxide increases with the increase of its oxygen potential, that means the more its curve is located in the lower part of this diagram, such as Al, Mg and Ca. In principle these basic correlations for vacuum refinement also apply for bronze and brass alloys. The result of vacuum refining is especially effective in applications where constituents have to be removed from the copper melt that, in relation to copper, have a higher vapour pressure, such as Barium, Calcium, Magnesium, Tellurium, Zinc, Cadmium, Selenium (Arsenic, Antimony), Lead, Bismuth etc. These effects have already been discussed previously and in connection with considerations of using revert scrap for remelting (7,8,9).

Mass transfer coefficient in vacuum degassing (4)

One has to consider three limiting steps for the transfer of undesirable constituents from the bulk liquid metal. The overall mass transfer coefficient K will be a function of the liquid phase mass transport coefficient KL, the evaporation mass transfer coefficient KE and the gas phase mass transport coefficient KG (4) Todays material requirements do not only focus on the melting of required alloy compositions but also rather on the possibility to influence their solidification, of course, always within the limits of justifiable operating cost. This applies for instance to conventional ingot casting and continuous casting as well as to spray forming of billets for the production of superconductor wire and drilling equipment (11).
Seite 9 von 16

4. Requirements for Refining and Casting Processes in Vacuum and Inert Gas Metallurgy Complementary to Conventional Production Processes

Metallurgical Goals/ Required Properties Low gas contents: H N O

Achieved by

Vacuum and gas purging/ melt agitation Carbon de-oxidation under vacuum and with purge gas Precipitation de-oxidation Addition of reactive elements into the well agitated melt only shortly before tapping (graphite crucible) Melting in ceramic crucibles Good melt agitation at high vacuum

Low C-content during melting with carbide-forming alloying elements in a graphite crucible Low contents of elements evaporating under vacuum (Pb, As, Sb, Bi) Low melting losses, high yields of oxygen affinitive elements (Cr, Zr, Li, Ti, V) High yields of alloying elements evaporating under vacuum

Charge of clean raw materials, good vacuum/clean protective gas atmosphere, late add. prior to tapping After degassing increase of (inert gas) pressure above melt surface to levels above vapour press. of the critical elem. Graphite crucible/purge gas treatment slag barrier or filters during pouring Clean raw materials, slag barriers, deslagging, filters, reproducible operation conditions Exact and reproducible analytical methods Gas-tight melting chamber, appropriate venting and filter systems, vacuum cleaner, etc. Super heating under consideration of late alloys additions, Addition of elements under increased melt agitation

Lowest contents of oxidic inclusions Lowest levels of slag inclusions

Narrow analytical tolerances Melting of alloys with hazardous elements (Be, Cd, Ni, Co) Defined homogeneous pouring temperature

Seite 10 von 16

5. Equipment Technology and Systems Concepts Vacuum induction furnaces (VIM) with capacities of 0,5 15t are especially suitable for the vacuum metallurgy applied to copper. Besides the classical vacuum chamber concept (VIM), the compact furnace type VIM-VIDP is of interest.

One 1500 kg VIM-furnace production system at SCHMELZMETALL AG, Switzerland.

Schematic of a conventional chamber-type VIM-furnace (ALD)

Compared to the conventional vacuum chamber concept, important advantages prevail with regard to productivity and cost structure.

Seite 11 von 16

Certain restrictions of pouring the metal under air must be considered though. In order to be able to melt and pour under vacuum and inert gas respectively, the VIM-VIDP furnace concept was developed for special applications in the nonferrous metallurgy.

The schematic shows the schematic cut through the VIM-VIDP concept (9).

The furnace is loaded through a charging system and is usually not vented during a process campaign. The metal is poured into a launder which is inserted through a lock valve system. The launder receives the liquid metal from the furnace pour lip and transfers it into a separate casting chamber. Depending on the type of system, this casting chamber can provide a possibility for casting of ingots arranged on a turn table, vertical or horizontal continuous casting or pouring with direct subsequent gas atomizing to produce metal powders respectively spray formed billets.

Seite 12 von 16

ISABELLENHTTE - Germany
VIM - VIDP 300 for Special Copper and Ni-base Alloys Furnace Capacity: 1 to 3 ton Melt Chamber Vacuum: O,01 mbar Power Supply: 850 KW Production of Resistance Alloys, Thermocouple Material, Material for high precision current sensing and measuring systems
IWCC Technical 3 ton VIDP at Isabellenhtte - Dillenburg, FRG Seminar 18

In 2006 a VIM-VIDP-furnace with a capacity of 3 ton was installed at Isabellenhtte - Dillenburg, FRG for the production of Cu-Ni alloys controlled resistance alloys, thermoelectric alloys - for the electronic and automotive industries. Beside conventionally cast-ingots vacuum melted Cu-alloys are also filled into transfer ladles for charging a spray forming unit for producing billets(12).

The Solution

Spray-formed Copper Billets

1 - Holding furnace 2 - Tundish 3 - Atomizer 4 - Billet 5 - Withdrawal/rotation unit 6 - Exhaust gas 7 - Overspray container 8 - Spray chamber 9 - Particle injector

Spray-formed Billets (Wieland)

Above schematic shows a spray forming unit at Wieland-Werke AG (12) The billets have a diameter between 160 and 500 mm and a length of 2,2 m. Spray forming is known to generate material with homogeneous element
Seite 13 von 16

distribution, a fine and homogeneous grain structure, a fine and homogeneous internal structure as well as isotropic properties.

The Solution

Spray-formed Copper Alloy Billets

550mm dia. billet at Wieland

As-cast structure : coarse & variable

As-sprayed structure : fine, uniform grains ; no macro-segregation

Different grain structure of CuCrZr billet produced by continuous casting and by spray forming. Wieland-Werke AG(12). The conceptual design of a VIM productions unit for cleanest copper and high grade copper alloys should include the following features: possibility of operation under vacuum and protective gas exclusion of air in the process from charging to pouring reduction of desorption gas sources highest degree of automation exact temperature and partial pressure control in the furnace avoidance of venting of the furnace during the melting cycle crucible made of high-grade alumina or graphite in order to achieve extremely clean products with lowest oxygen use of electromagnetic stirring of the melt for optimal homogenisation of the melt use of gas lances and porous plugs for stirring and introducing reactive gases exact control of pouring speed casting chamber separated from the furnace chamber in order to service both components independently provision for the application of various casting procedures: o ingot casting o horizontal and vertical continuous casting o spray forming
Seite 14 von 16

VIDI 2000 for Special Copper Alloys Furnace Capacity: 18 ton Melt Chamber Vacuum: O,1 mbar Power Supply: 2400 KW Casting under protective Atmosphere into a Vertical Continuous Caster

18 t VIDI installation at KME, Osnabrck - FRG for the production of Cu- alloys 6. Summary High quality copper alloys of several tons capacity are produced today under vacuum or protective atmosphere achieving reproducible specification parameters. ALD VACUUM TECHNOLOGIES GmbH has developed with all its resources in engineering and metallurgy and together with forward looking producers in the copper industry, innovative vacuum processes for making high quality copper products on an industrial scale. We are convinced that increasing market needs for high quality copper alloys will in the future draw more attention to the application of vacuum processing in the production of these alloys.

Seite 15 von 16

References
1. FN. Damara, J.S. Huntington, and E.S. Machlin: Journal of Iron & Steel Inst., 1959, No. 191, pp 266-75. 2. Dies, K.: Kupfer und Kupferlegierungen in der Technik, Springer Verlag, 1967, pp- 123/124. 3. VDI-Taschenbuch Nr. 26, DIN-Normen, 1984, S. 29/31 4. Hansen, et al.: Binary Alloys, pp. 353, 587, 600. 5. Fromm, E.: Gase und Kohlenstoff in Metallen, pp. 663. 6. Heberlein, Max F. W.: Zeitschrift fr Metallkunde, 1954, pp. 317-321. 7. Harris, R.: metallurgical Transactions B, 1984, pp. 251-257 8. Lombeck, K. G. et al.: METALL, 11, 1982, pp. 1192-1196. 9. German patent application: 19122936, (LH). 10. Barron et al.: BSC Swindon Publication, pp. 379.387. 11. Knppel, H.: Desoxidation und Vakuumbehandlung von Stahlschmelzen, Verlag Stahleisen, Dsseldorf, 1970, pp. 23. 12. H.R. Mller, R. Zauter, Sprayformed Copper Alloys- Process and Industrial Erzmetall 56 (2003), No. 11, pp 643-650 applications,

Seite 16 von 16