Cross-Reference to Related Application

This application is a continuation-in-part of my copend ing U . S . application Serial No . 904 , 945 , filed May 11 ,

1978 . BACKGROUND OF THE INVENTION AND THE PRIOR ART

It is known to make flat, continuous metal strip, of crystalline as well as amorphous (glassy) structure, directly from the melt by impinging molten metal onto the flat surface of a rapidly moving chill body whereon it is quenched to the solid state. The chill body may be a rotating wheel or cylinder, and the molten metal may be impinged onto the flat peripheral surface of the wl-eel or onto the inner surface of the cylinder. The chill body may also be a traveling belt, usually an endless belt. The metal may be impinged onto the surface of the chill body by methods such as jetting the molten metal onto the surface. It is also known to form metal filament directly from the melt by contacting a pendant, unconfined drop of molten metal with the V-shaped circumferential edge or lip of a rotating heat extraction member, as disclosed, for example, in U.S. Patents 3,896,203 to Maringer et al. and 4,124,664 to Maringer. The methods disclosed in these patents may employ a heat extracting edge or lip composed of metals such as copper, aluminum, nickel, molybdenum and iron. These methods, however, do not produce flat strip, but instead produce what appears to be rounded fibers, having opposed ccnvex/concave surfaces.

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The surface of the chill body must meet several requirements. First, it must be wetted by the molten met or else formation of continuous strip will not take place Second, it must be non-reactive with the molten metal, th is to say the molten metal must not attack, and must not weld to the chill surface, or"else the strip cannot be cleanly separated therefrom. Third, it must have good th mal conductivity to permit rapid removal of large amounts heat as is necessary to effect rapid solidification of th molten metal. Lastly, it must have sufficient wear resis ance in continuous production of metal strip by the above described quench casting process. Wear resistance is an extremely important aspect of chill body performance. We resistance does not usually pose a problem in the above- described melt extraction processes, wherein metal fibers are drawn out of a pendant drop of molten metal. However in the melt-spin process wherein molten metal is impinged on the chill surface, severe erosion of the chill surface usually results from a combination of factors, including momentum of the impinging stream in combination with the high temperature of the molten metal.

High heat conductivity metals previously propos to serve as chill body surface, such as copper, aluminum, beryllium copper or silver, do not have the desired wear characteristics. Others, such as stainless steel, which would be expected to have good, wear characteristics, fall short in other respects, such as failure to provide suffi cient wetting.

It is an object of the present invention to pro vide improved chill bodies for the quench casting process for making flat metal strip directly from the melt by impinging the molten metal onto the flat surface of a rapidly moving chill body.

SUMMARY OF THE INVENTION In accordance with the present invention there provided an improvement in the method for making flat met strip directly from the melt by impinging the molten meta onto the flat surface of a rapidly moving chill body, whi

improvement comprises impinging the molten metal onto the flat surface of a chill body made of molybdenum.

The present invention further provides an improve¬ ment in the apparatus for making metal strip directly from the melt by impinging molten metal onto the flat surface of a rapidly moving chill body, -which apparatus includes a chill body having a flat surface adapted to receive molten metal to be impinged thereon for rapid quenching together with means functionally connected with said chill body for impinging molten metal onto its surface, wherein the improve¬ ment comprises providing a chill body having a surface of molybdenum.

I have surprisingly found that the molybdenum chill surface is readily wetted by the molten metal - espe- cially by iron, nickel or cobalt-based alloys which upon rapid quenching from the melt form amorphous structures . The molybdenum surface further provides for good adhesion of the solidified metal strip, which is essential to effect thorough quenching of the metal if a ductile, amorphous metal strip is desired, yet it also affords clean release of the solidified strip from the surface. Most importantly, the molybdenum surface has excellent wear-resistant proper¬ ties as compared to chill surfaces previously, used in the melt-spin process wherein molten metal is impinged onto the chill surface. In addition, the molybdenum has adequate heat conductivity to permit sufficiently rapid quenching, at rates in excess of 10 4 or 105 degrees centigrade per second, of thin layers of molten metal (in the order of a few thousands inch thickness), as is required for formation of amorphous metal strip.

The benefits of chill bodies having a molybdenum surface in the process of making flat metal strip directly from the melt by impinging the molten metal onto the rapidly moving flat surface of a chill body are obtained regardless o-f the configuration of the chill body. That is to say, the chill body may be a rapidly rotating drum having a flat exterior surface which serves as the chill surface; it may be a rapidly rotating cylinder whereof the flat inner

surface furnishes the chill surface, a moving belt or an other suitable structure which provides a flat sur ace. For purposes of the present invention, a flat strip is a slender body whose transverse dimensions are less than its length, and whose thickness is much less t its width, typically having a width at least about ten t its thickness, and having smooth and even top and bottom surfaces which are generally parallel to each other.

A flat chill body surface is an endless surfac provided by an endless belt, or the exterior or interior surface of a drum or cylinder, and which is smooth and e and which is straight ^' in transverse direction, upon whic a flat strip, as above-defined, may be cast.

BRIEF DESCRIPTION OF THE DRAWINGS The annexed drawings further illustrate the present invention.

Fig. 1 is a cross-sectional view of an annular chill roll, the exterior surface of which is provided wi layer of molybdenum metal, to provide a casting surface- molybdenum.

Fig. 2 is a cross-sectional view of an annular chill roll having, a ring of molybdenum inserted in its surface.

Fig. 3 is a cross.-sectional view of a cylindri chill body having an inner molybdenum-clad chill surface inclined with respect to the axis of rotation.

Fig. 4 is a side view in partial cross section showing means for jetting molten metal onto a rotating c roll and a rotating chill roll provided with a chill sur of molybdenum metal. Fig. 5 is a somewhat simplified perspective vi of apparatus including means for depositing molten metal onto a chill surface in the form of a moving endless bel having a surface of molybdenum.

DETAILED DESCRIPTION OF THE INVENTION OF THE PREFERRE EMBODIMENTS AND OF THE BEST MODE PRESENTLY CONTEMPLATE FOR ITS PRACTICE

Chill casting processes for making flat metal strip polycrystalline as well as amorphous (glassy) metal stri

by impinging molten metal onto the flat surface of a rapidly moving chill surface of a heat extracting member (chill body) are well known. It has now been found that for use in such chill casting processes molybdenum has a desirable com- bination of properties required of a good chill surface, namely high melting point (2650 ^β C); relatively low coeffi¬ cient of thermal expansion (lower than that of copper); moderately high thermal conductivity (about 35% of that of copper); and moderately high hardness. It has further been found that molybdenum has the required wetting properties for the molten metal and release properties for the solidi¬ fied strip which, in combination with the aforementioned properties, make it eminently suitable for use as chill surface in quench casting of amorphous metal strips, espe- cially ductile amorphous metal strips. Most significant is the ability of molybdenum chill surfaces to resist ero¬ sion and wear by the impinging stream of molten metal, whether the casting takes place under vacuum or in a gaseous atmosphere, which may be air or a protective atmosphere such as nitrogen, helium and the like. This is in contrast to the presently employed copper chill surfaces.

When flat amorphous metal strips are made by jetting molten glass ^' forming ^' alloy against the surface of a rapidly rotating chill body as, e.g., described in O.S.P, 4,077,462 to Bedell et al. , or in U.S.P. 3,856,074 to

Kavesh, the surface of the chill body becomes gradually eroded. A rough, uneven track is developed around the periphery of the chill body surface whereon casting of the strip takes place. Further casting into the same track pro- duces strip of unacceptable quality, having a rough surface and ragged edges. The problem of chill surface wear in these processes is even more acute when casting takes place under vacuum. The absence of an intervening gas layer in vacuum casting allows a larger area of the, chill surface to be impacted and wetted by the molten jet. Another factor which leads to severe wear on conventional chill surfaces is inclusion in the alloy being cast of appreciable amounts of refractory metals, e.g., molybdenum, tungsten, chromium,

hafnium, iridium, niobium, osmium, platinum, rhenium, rh dium, ruthenium, tantalum, thorium, vanadium, and zircon Hence, use of a chill surface of mo-L^bden rn is particula advantageous when casting under vacuum (say under absolu -pressure of less than about 1 in. Hg.), or when casting glass-forming alloys containing one or more refractory metals, and especially when casting such alloys under vacuum.

The form of the chill body and the mode of the casting operation are not critical for purposes of the p sent invention, so long as a flat casting surface is pro vided. For example, casting may take place against the peripheral surface of a rapidly rotating drum by jetting molten metal against that surface, as disclosed in the above-mentioned patents to Bedell et al. and Kavesh. Th molten metal may be deposited under pressure from a slot nozzle onto the flat chill surface, as described in U.S. 4,142,571 to Narasimhan. Furthermore, the chill surface be furnished by the interior surface of a rotating cylin as described in U.S.P. 3,881,540 to Kavesh and U.S.?.

3,881,542 to Polk et al., or as shown by Pond and Maddin Trans. Met. Soc. AIME, 245 (1969) 2,475-6. .

The chill surface of molybdenum may, in accord with the present invention, be provided by fabricating t chill body of molybdenum, or by merely providing a surfa layer of molybdenum on a chill body constructed of other material, suitably material having high thermal conducti such as copper or silver. Chill bodies made of molybden may be fabricated employing methods usually employed for fabrication of molybdenum, including machining from soli stock, such as cast pieces, or fabrication by known powd metallurgical methods. A particularly desirable embodime of the present invention is a composite chill body, espe cially a chill roll, made of copper provided with a hoop of molybdenum, as illustrated in Figs. 1 and 2. With reference to Fig. 1, chill roll 1 made of copper is moun for rotation on shaft 2. The flat exterior surface of c roll 1 is provided with a hoop of molybdenum 3. In Fig.

the hoop of molybdenum covers the total peripheral surface of the chill roll. With reference to Fig. 2, a narrower hoop of molybdenum 3 is provided covering only part of the peri¬ pheral surface of the chill roll. The molybdenum hoop may be affixed to the copper chill roll-, e.g. by shrink fitting. Alternatively, a molybdenum surface may be provided by any other conventional surface coating method, as for example oxyacetylene spraying, a method which involves feeding a molybdenum wire into the cone of an oxygen/acetylene flame to melt the metal, and then propelling the molten metal in droplet form against the surface to be coated. Other ^' suit¬ able methods include plasma arc spraying and conventional cladding procedures.

Detailed design and construction of apparatus of the present invention is within the capability of any com¬ petent worker skilled in the art.

The following example further illustrates the pre¬ sent invention and sets forth the best mode presently con¬ templated for its practice. Example 1

Apparatus, employed was similar to that depicted in

Fig". 4 employing a chill _, roll of construction as shown in ^'

Fig. 2. The chill roll had an outer diameter of 8 inches, and its quench surface was 0.5 inches wide. It was rotated at a speed of about 2000 rpm. The apparatus was enclosed in a vacuum chamber. All tests were conducted under vacuum of about 100 mm. Concurrent experiments employing a chill roll made of copper having an outer diameter of 8 inches and a width of 1 inch rotated at 2000 rpm, were conducted, also under vacuum of about 100 mm. A number of different glass forming alloys (alloys which upon rapid quenching from the

_ 5 melt, at a rate in excess of about 10 ^" to 10 °C/sec. form an amorphous solid structure (see, e.g. U.S.P. 3,856,513 to Chen and Polk) having melting points in excess of 1,500°C were cast by jetting the molten metal against the rotating chill surface through an orifice of 0.025 inch diameter under pressure of 5 psig. It was difficult to cast contin¬ uous ductile strips on the copper chill surface. In all

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cases the molten alloys attacked the copper chill surface causing erosion,, cracking and pitting. The chill surface roughened caused subsequent mechanical locking of pieces strip onto the chill surface along the track where the st was cast. The pieces of strip welded to or mechanically interlocked with the chill surface, causing disintegratio of the molten puddle on the chill surface, and prevented subsequent formation of continuous strip on the same trac The yield of usable strip was very low. In contrast ther the same alloys, when cast on a molybdenum chill surface, yielded good quality ribbon. The comparative results are summarized in Table 1, below.

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TABLE I

Results of Chill Casting of 30 gms of Molybdenum and Tungsten Base Glassy Alloys on Copper and Molybdenum

Chill Surfaces

Copper Chill Surface

Chill

Alloy Surface Composition Ribbon Ribbon Condition Yield (atom Fabric- Character¬ after of percent) ability istics Casting Ribbon

^MO 40 ^CO 40 ^B 20 extremely discontinous gorged;metal 2% poor -rough edge pieces weldec 1 to surface

^MO 40 ^Fe 40 ^B 20 2% ^MO 50 ^CO 30 ^B 20

^MO 60 ^Fe 20 ^B 20 ^M °65 ^FS 15 ^B 20

^W 40 ^Ni 50 ^B 10

^MO 45 ^Ni 45 ^B 10 40 ^C °50 ^B 10

^Mθ 60 ^C °20 ^B 20

^Mθ 30 20 ^Fe 30 ^B 20

M ^θ 45Feιo iιoCoi5B2θ"

^MO 50 ^Fe 20 ^C °10 ^B 20 "

^MO 40 ^Fe 20 ^C °20 ^B 20 "

Ni Mo B "

50 30 20

-10-

TABLE I (Continued)

Results of Chill Casting of 30 gms of Molybdenum and Tungsten Base Glassy Alloys on Copper and Molybden

Chill Surfaces '

Molybdenum Chill Surface

Chill

Alloy Surface Composition Ribbon Ribbon Condition Yi (atom Fabric- Character¬ after percent) ability istics Casting Ri

^M0 40 ^C0 40 ^B 20 Excellent Continuous- Insignifi¬ 9 good edge & cant wear surface

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^Mo 40 ^Fe 40 ^B 20

II M π

^Mθ 50 ^C °30 ^B 20

^MO 60 ^Fe 20 ^B 20

^Mθ 65 ^Fe 15 ^B 20

^W 40 ^Fe 20 ^C °20 ^B 20

^W 40 ^Ni 50 ^B 10 9

I

^M °45 ^Ni 45 ^B 10 I

^W 40 ^Co 50 ^B 10

^MO 60 ^CO 20 ^B 20 9 n

^MO 30 ^W 20 ^Fe 30 ^B 20 n

M ^θ 45 eιoNiιoCoi5B2θ ^"

^MO 50 ^Fe 20 ^C °10 ^B 20

^Mθ 40 ^Fe 20 ^C °20 ^B 20

^Fe 47 ^W 35 ^B 18

^Fe 40 ^W 40 ^B 20

^Ni 50 ^Mθ 30 ^B 20

Example 2

Following the general procedure of Example 1, 50 gram portions of molten, glass-forming alloy of the com¬ position Fe Ni B Mo.Cr Co. (atom percent) were impinged

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(squirted) onto the flat peripheral surface of chill rolls of 8-12 in. diameter fabricated of different materials of construction and the quality of the strip (whether or not ductile, glassy metal strip was obtained), and chill sur¬ face wear and casting qualities were visually observed. Results are summarized in Table 2, below.

Table 2

Makes

Chill Surface Ductile Material Strip Remarks:

Nickel No Melt welds to substrate at spots, jet breaks up on impingement.

Monel

^(Ni 60 ^Cu 40 ⁾ Yes Only limited lengths; melt welds to substrate as beads.

Cupronickel No Melt does not wet, puddle breaks u .

Stainless 304 No Same as above. Cold Rolled Mild Steel

Tool Steel (hardened) No Melt welds to the substrate at spots .

Chro plate (.001") Yes Makes continuous ribbons, on Hardened Tool Steel no spalling of chromium

Invar ^™ (Fe-Ni) No Melt welds to the substrate,

Chromeplate (.001") Yes Makes good ribbon, no on Invar ^™ spalling of chromium.

Chromeplate (.001") Yes Only limited lengths, chro¬ on Copper mium spalls off afterwards.

Molybdenum (hot Yes Makes continuous ribbons. pressed, 95% dense)

BeO (hot pressed No Puddle breaks up. 90% dense)

Pyrex No Puddle breaks up.

Tungsten (chemical Yes Makes ribbon. vapor deposited 100% dense)

Platinum No Puddle breaks up,- melt does not wet the substrate.

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Since various changes and modifications may be made in the invention without departing from the scope an essential characteristics thereof, it is intended that al matter contained in the above description shall be inter- preted as illustrative only, the invention being limited only by the scope of the appended claims.

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