US3845805A - Liquid quenching of free jet spun metal filaments - Google Patents

Liquid quenching of free jet spun metal filaments Download PDF

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US3845805A
US3845805A US00306472A US30647272A US3845805A US 3845805 A US3845805 A US 3845805A US 00306472 A US00306472 A US 00306472A US 30647272 A US30647272 A US 30647272A US 3845805 A US3845805 A US 3845805A
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jet
molten
quench
metal
fluid
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S Kavesh
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Honeywell International Inc
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Allied Chemical Corp
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Priority to CA184,026A priority patent/CA1012328A/en
Priority to DE19732355524 priority patent/DE2355524A1/de
Priority to GB5222173A priority patent/GB1458017A/en
Priority to IT70324/73A priority patent/IT996955B/it
Priority to JP48127405A priority patent/JPS5926685B2/ja
Priority to FR7340421A priority patent/FR2225239B1/fr
Priority to US05/499,386 priority patent/US3960200A/en
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Priority to CA252,692A priority patent/CA1012325A/en
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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
    • B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire

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  • Patent 1 Kavesh 1 Nov. 5, 1974 [5 1 LIQUID QUENCHING or FREE JEIMSPUNB METAL FILAMENTS [75] Inventor: Sheldon Kavesh,'Whippany, NJ.
  • ABSTRACT A process is provided whereby filaments of metals may be formed by rapid solidification of a molten jet in a fluid medium. Filaments of metastable alloys such as amorphous metals and filaments of fine grained structure having novel orientation may be obtained.
  • the jet is extruded into a gaseous atmosphere capable of chemical reaction with one or more of the components of the jet. Stabilization occurs by formation of a solid sheath or skin on the liquid jet. Alternatively, electrostatic charges have been used to stabilize the jet.
  • the reactive gaseous atmosphere may be noxious, inflammable, explosive, corrosive or expensive.
  • An object of this invention is to provide a method and apparatus for the production of filaments from their melts which are applicable to materials exhibiting sharp melting behavior and broad melting ranges, i.e., to pure metals and to alloys.
  • Another object of the invention is to provide a method and apparatus for the production of filaments of this kind from their melts wherein there is no dependency upon special techniques of jet stabilization.
  • a further object of the invention is to provide a method and apparatus for the production of filaments of metastable alloys, such as amorphous metals and of non-ductile alloys not readily formed into filaments by conventional means.
  • Still a further object of the invention resides in the preparation of filaments having a fine grained structure of novel orientation.
  • the melt spinning process of the invention involves the formation of a free jet of the molten material in a gaseous or evacuated environment, traversal of the free jet through an interface into a fluid medium, the fluid medium flowing cocurrent with the jet and at essentially the same velocity as the jet and the rapid solidification of the jet in filamentary form.
  • a free jet is defined as a stream of fluid unconfined by solid boundaries.
  • the fluid medium may be a pure liquid, a solution, an emulsion, or a solid-liquid dispersion.
  • the fluid medium may react with the molten jet to form a stabilizing surface skin or it may be chemically unreactive with the molten jet.
  • the fluid medium and its temperature are selected to suppress formation of a film boiling regime along the jet surface and to enhance the formation of a high heat flux regime, i.e., a nucleate surface boiling regime or a forced convection heat transfer re-, gime in which the coefficient of heat transmission is at least 0.4 cal/sq. cm.-C sec.
  • a high heat flux regime i.e., a nucleate surface boiling regime or a forced convection heat transfer re-, gime in which the coefficient of heat transmission is at least 0.4 cal/sq. cm.-C sec.
  • film boiling and nucleate boiling are well known in the art.
  • the term regime connotes the condition or pattern, usually dynamic, which obtains at a specified point or stage in the process.
  • the quenching of metals in liquids under conventional conditions is disclosed, for example, by Hollomon and .laffe in Ferrous Metallurgical Design, pg. 6265, John Wiley and Sons, New York, 1947. Normally, when the metal is first immersed in the medium, the adjacent liquid is rapidly heated to the boiling point and transformed into vapor. A vapor film is set up around the metal which 3 retards the further transport of heat. A film boiling regime is said to exist.
  • jets of molten materials entering liquid media demonstrate nucleate surface boiling heat transfer or forced convection heat transfer with total suppression of film boiling along the critical entry region.
  • cooling and solidifieation of the jets have been greatly enhanced.
  • This result coupled with unexpected stability of molten jets within fluid media has enabled the transformation of the jets into solid filaments in the brief interval before jet disruption.
  • the very rapid heat transfer permits the preparation of substantially improved continuous round filaments of amorphous metals as well as the preparation of novel crystalline filaments of fine grained equiaxed or oriented structure.
  • FIG. 1 illustrates diagrammatically an apparatus which may be utilized in making metal filaments according to the invention.
  • FIG. 2 is a detail of one embodiment of a quenching means wherein a baffle is used to suppress formation of a vortex.
  • FIG. 3 and FIG. 3a illustrate details of an alternate arrangement for preventing vortex formation during quenching.
  • FIG. 4 illustrates still another means to avoid vortex formation during the quenching step.
  • FIG. 5 is a perspective illustration of an alternate quenching and filament support arrangement for the extruded jet.
  • FIG. 6 is a photomicrograph (magnification 6X) of a melt-spun filament made according to the invention and characterized by a smooth surface.
  • FIG. 7 is a photomicrograph (magnification 12X) of a melt-spun filament according to the invention characterized by a corrugate-like surface texture.
  • FIG. 8 is a photomicrograph (magnification 6X) of a melt-spun filament made by the invention and having a pearl necklace"-like surface texture, i.e., a surface texture having alternating linear and spheriodal segments.
  • FIG. 9 is a photomicrograph (magnification 12X) of a melt-spun filament prepared according to the invention characterized by a serrated or saw-tooth structure.
  • FIG. 10 is a photomicrograph (magnification 12X) of a melt-spun filament prepared according to the invention having a kinked texture.
  • FIG. 11 is a photomicrograph (magnification 12X) of a melt-spun filament prepared according to the invention having a corkscrew-like configuration.
  • FIG. 12 is a photomicrograph (magnification l76X) of a cross section of a cast commercial gray iron bar.
  • FIG. 13 is a photomicrograph (magnification I76X) of a cross section of a filament melt spun according to the invention from the composition illustrated in FIG. 12.
  • FIG. 14 is a photomicrograph (magnification 145X) of a cross section of melt spun zinc wire prepared according to the invention.
  • FIG. 15 is a comparative photomicrograph (magnification 38OX) ofa zinc wire made by conventional prior art wire drawing techniques.
  • FIGS. 1-4 The process and a laboratory spinning apparatus are illustrated in the accompanying FIGS. 1-4.
  • the crucible has one or more bottom openings or spinning orifices, one of which is shown at 23 and whose diameters are the order of size of the desired diameter of the filaments, e.g. 0002-0060 cm.
  • the crucible 21 lies within a chamber defined by a quartz cylinder 24, an insulated copper plate at the top 25, and a ceramic plate 26 such as boron nitride at the bottom.
  • the chamber assembly is suitably held together such as by external tie rods 27.
  • a quartz window 28 may be conveniently inserted in the top cover plate to permit measurement of charge temperatures such as by an optical pyrometer 29 which is provided with a suitable readout 29a.
  • An inert gas pressure source e.g., helium
  • a pressure tight seal is effected between the crucible 21 and the bottom plate 26 by a suitable commercial ceramic casting compound.
  • a suitable commercial ceramic casting compound For example, when using a quartz crucible and a boron nitride plate, a commercial compound Ceramacast-505, available from Aremco Products Inc., Briarcliffe Manor, New York, yields a tight seal.
  • Energy to melt the metal charge is provided by a power source such as a 450 KHZ induction power supply connected to a coil 31 concentrically wound about the melting chamber 24.
  • a quartz crucible having a wall thickness of at least 1 mm may be used with metals whose melting points are less than about 1300 C.
  • the spinning orifices 23 may comprise holes drilled through the bottom wall of the crucible using diamond tools or laser methods although other orifice arrangements or dies may be employed. Since tapered nozzles enhance jet stability, it is preferred that the holes be tapered.
  • a zirconia crucible ofabout one-fourth wall thickness is preferred for spinning metals whose melting points are 1300-1700 C.
  • the crucible 31 when formed of zirconia, is drilled and reamed to accept a separately fabricated zirconia spinnerette (not shown) containing the spinning orifices. Mating of the spinnerette to the spinning crucible is accomplished by means of a zirconia based ceramic cement such as Ultratemp 516, available from Aremco Products, Inc., Briarcliffe Manor, New York.
  • the melting chamber is suspended immediately above a reservoir 47 containing the fluid quench medium 40.
  • the level of the fluid medium 40 is controlled as close as possible but without contacting the bottom plate 26 of the melting chamber 24. Generally, this distance is of the order of about 0.2 cm.
  • the space 41 between the spinning nozzle and the surface of the fluid quench medium confined by walls 38 may be evacuated or it may be filled with an inert gas or a gas which enhances the formation ofa stabilizing skin or the molten filament jet.
  • This inert or gas filled zone 41 isolates the melting and jet formation zones from the quenching zone and permits the establishment of wide temperature differentials which would not be practical if the chamber 24 and the fluid 40 were in contact.
  • a quartz cylinder 38 cemented on one end to the bottom 26 of the melting chamber and on the other end immersed in the fluid quench medium 40 provides the chamber 41 into which the inert gaseous atmospheres from a source 45a through line 45 may be admitted.
  • the space 41 may be evacuated.
  • a vertical standpipe 33 Within the fluid reservoir 47, disposed vertically below the spinning orifices 23 is a vertical standpipe 33.
  • the fluid quench medium 40 enters the reservoir 47 at one end 48, passes horizontally through a calming screen 34, flows vertically down through the standpipe 33 into a catch basin 35 and finally by means of a pump 39 is passed through a heat exchange, in this case a refrigeration unit 37, and is returned via line 46 to the reservoir '47.
  • Fine jets of the quench fluid 44 are sprayed from the sparger ring 30 into the mouth of the standpipe 33.
  • the quench medium 40 and its temperature be controlled so as to suppress formation of a film boiling regime along the jet interface.
  • the quench medium and its temperature are selected to create a nucleate surface boiling regime along the region of entry of the jet into the quench fluid.
  • the selection of the quench medium and its temperature must be made in relation to the thermal capacity of molten jet.
  • the thermal capacity of the jet increases in direct proportion to its temperature, specific heat, latent heat of fusion and its cross-sectional area. Suppression of film boiling in the thin boundary layer of quench fluid surrounding the molten jet can be accomplished by causing the thermal capacity of the jet to become depleted in raising the quench fluid boundary layer to the boiling point.
  • the greater the thermal capacity of the .molten jet the colder must be the quench fluid and/or the higher its specific heat, density, heat of vaporization and thermal conductivity.
  • water at Ol0C. is a satisfactory medium for spinning materials whose melting points are less than about 700 C., e.g. aluminum, zinc, lead, tin, bismuth, cadmium, etc.
  • a refrigerated (-C.) 23 weight percent aqueous sodium chloride solution is satisfactory.
  • quench fluids merely represent typical fluids which may be employed in the practice of the present invention and that a variety of alternative quench fluids compatible with the particular jet composition and its temperature may be employed.
  • the quench fluid into which the molten jet is injected is arranged so as to flow cocurrent with the jet and is everywhere during the main quench period, i.c.. during the time interval that the molten jet is in its transition to a solid phase, at the same velocity as the jet.
  • the molten jet and the quench fluid flow together at substantially the same velocity in the standpipe.
  • the motion of the quench fluid is in the same direction as the jet but the fluid velocity accelerates from zero at the air-fluid interface to a maximum in the standpipe.
  • the top of the standpipe is placed as close as practicable to the surface of the quench fluid; typically, it may be within 2 cm of the fluid surface.
  • Vortex forma tion above and within the standpipe is substantially minimized by positioning a vortex baffle near the standpipe.
  • Illustrated in FIG. 2 is a simple asymmetric vortex baffle consisting of a bar of rectangular cross section 50 placed to one side ofthe standpipe and extending to the surface of the fluid 40.
  • a vortex baffle comprising an annular sparger ring 30 placed above the standpipe 33 and extending to the surface of the fluid 40 is shown to minimize the vortex formation and control the fluid velocity flow indicated by arrows 52 in standpipe 33.
  • Fine jets of the quench fluid are sprayed from the sparger ring 30 into the mouth of the standpipe 33.
  • the velocity of the fluid medium in the standpipe is determined by the diameter of the standpipe 33, the height of fluid surface above the standpipe, and the velocity and volume of flow sprayed into the standpipe from the sparger ring 30 which is fed from line 51 (also shown in FIG. I); for example, a typical fluid velocity using a 1.4 cm I.D. standpipe of 40 cm length, an aqueous quench medium of 1.0 cps viscosity, 1.0 g/cc density, a fluid level 2 cm above the standpipe, and zero spray velocity is 200 cm/sec.
  • FIG. 4 another alternative comprising one or two rotating cylinders (two being shown in FIG. 4) may be placed at the mouth of the standpipe.
  • the presence and rotation of the cylinder 53 and 54 substantially curtails vortex formation and increases the uniformity of the fluid velocity field above the standpipe.
  • the motion of the quench fluid cocurrent with the molten jet 58 may be motivated by overflowing a weir 56'onto an inclined plane 57.
  • the melting chamber shown in phantom is mounted directly above the inclined plane 57.
  • the solidified jet 59 is collected in a suitable catch basin 60 containing a cooling fluid which is circulated at 61 and returned via pump 62 and line 63 to the reservoir 64. It will be apparent that a suitable arrangement for continuous winding of the filaments passing into the catch basin 60 may be made.
  • the level of the quench fluid 40 in the reservoir 47 and the fluid velocity in the standpipe 33 are adjusted to desired levels.
  • the metal material is charged to the melting receptacle 21 which is substantially sealed off or isolated so that the charge may be preferably melted in an inert atmosphere and at substantially atmospheric pressure.
  • the metal temperature is approximately 50-l00 C. above the melting point, the pressure of the inert gas in the melting chamber is raised to l-20 psig or until a molten jet issues from the spinning orifice at the desired velocity.
  • the molten jet is ejected down into the space 41 and thereafter contacts quench medium 40 upon entering the standpipe 33 where it is solidified as it moves cocurrently with the fluid moving in the standpipe. Adjustment of spinning conditions to suit the form of the solidified material desired may be effected as noted in conjunction with FIGS. 6-11 of the drawing. Where sinuous filaments are formed, it is an indication that the jet velocity exceeds the fluid velocity in the standpipe. If discontinuous filaments with tapered ends are formed, it is an indication that jet velocity is substantially less than the fluid velocity in the standpipe. If the filaments show axisymmetrical nodes, melt temperature may be reduced to produce smooth continuous filaments. Alternatively, the temperature and pressure may be adjusted to produce filaments of another desired surface texture or length.
  • FIGS. 6-11 Some of the filament textures and/or shapes which can be produced by adjustment of the melt temperature and the relative velocity of the molten jet and quench medium are illustrated in FIGS. 6-11 where FIG. 6 illustrates a smooth filament; FIG. 7 a corrugated configuration; FIG. 8 an intermitten globular shape; FIG. 9 a serrated shape; FIG. 10 has a kinked form and FIG. 11 a spiral or corkscrew configuration.
  • the smooth filament of FIG. 6, for example, is prepared by matching the fluid velocity in the standpipe to the velocity of the molten jet as described above.
  • the corrugated filament of FIG. 7 may result when the fluid velocity in the standpipe is slower, i.e., about 10 percent less than the velocity of the jet.
  • the pearl necklace" appearance of the filament of FIG. 8 may be obtained when the molten jet is superheated, e.g. about 250 C. above its melting point, while the serrated filaments of FIG. 9 may be obtained at conditions otherwise yielding smooth filament but by permitting a vortex to form in the standpipe.
  • the kinked filaments of FIG. 10 are produced when a fluid velocity in the standpipe is substantially, i.e., about 40 percent, less than the jet velocity.
  • the corkscrew-like resulting filament of FIG. 11 results from the same conditions as the kinked filaments of FIG. 10 except that a vortex was permitted to form in the standpiepe 33.
  • the invention is further illustrated by consideration of the examples which follow.
  • the first two examples demonstrate that the filament forming process of the present invention is based upon achieving high heat flux cooling and that it is independent of special techniques ofjet stabilization such as oxide film formation.
  • EXAMPLE I An 8 mm quartz tube whose end was drawn out into a fine tip of 0.025 cm ID. was charged with silver metal of 99.999 percent purity. The quartz tube was placed within an induction heating coil and connected to a helium source. The silver was melted under a helium atmosphere and discharged at l000 C, 10 psig from the quartz tube into the laboratory atmosphere. The velocity of the silver jet determined from the diameter of the jet and the weight of metal collected in a timed period was approximately 250 cm/sec.
  • a photograph of the molten jet was taken using a 8 microsecond General Radio flash source. The photograph showed the jet became disrupted into discrete droplets at a distance of 0.5 cm from the nozzle or in a time of flight of 2 milliseconds.
  • EXAMPLE 2 The quartz tube of Example 1 was again charged with silver of 99.999 percent purity. The quartz tube was mounted over the quench fluid reservoir in the same position but in place of the melting chamber illustrated in FIG. 1. The tip of the quartz tube was 0.2 cm above the surface of a 23 percent sodium chloride quench fluid maintained at 20 C. The top of the standpipe was 2 cm below the surface of the quench fluid. Fluid velocity in the standpipe was 2l0 cm/sec.
  • the silver was melted in a helium atmosphere and the melt extruded from the quartz tube at I00O C.. 10 psig. .let velocity was approximately 250 cm/sec.
  • the molten silver jet traversed the air gap, entered the quench fluid and was solidified in the form of filaments of 0.025 cm average diameter.
  • High speed macrophotographs of the silver jet entering the quench bath showed nucleate surface boiling and forced convection cooling but not film boiling along the jet.
  • a lower bound to the coefficient of heat transmission between the jet and the quench fluid may be calculated from the condition that the surface of the jet is solidified before 2 milliseconds have elapsed.
  • the heat transfer coefficient so calculated is at least 0.4l cal/sq.- cmCsec.
  • the corresponding quench rate based on the average temperature of the jet is at least 2 X l0 C/sec. Both the heat transfer coefficient and the quench rate are at least an order of magnitude greater than could be obtained with gaseous cooling.
  • Examples 3-5 illustrate the novel continuous filament structures obtainable as a result of the rapid solidification intrinsic to the present invention.
  • EXAMPLE 3 The apparatus depicted in FIG. 1 was charged with a bar of grey iron containing 3.4 weight percent carbon, 2.2 weight percent silicon, 0.6 weight percent maganese, 0.2 weight percent phosphorus and 0.01 percent sulphur. The alloy was melted in a helium atmosphere at I200 C. and extruded through an orifice of 0.025 cm diameter at 2l5 cm/sec. The molten jet was quenched in refrigerated 23 weight percent sodium chloride brine at 20 C. Brine velocity in the standpipe was 2l5 cm/sec. Filaments of 0.030 cm diameter were thereby prepared.
  • FIG. 12 is a polished and etched section of the original grey iron bar magnified I76 fold.
  • FIG. 13 is an axial cross section of the melt spun filament prepared as described and shown at the same magnification.
  • the as-received bar shows large flakes and granules of graphite typical of grey cast iron.
  • the filaments melt spun from the above were of a fine grained equiaxed dendritic structure novel for grey iron. Dendrite spacing was 2-microns.
  • dendrite spacings are commonly IQO-JQQOmiatms. While Dun e ln U v, o- 3,658,979 disclose dendrite spacings of 5-25 microns in continuous metal filaments, dendrite spacings obtained with the present invention are of the order of 1-2 microns and represent a significant improvement.
  • EXAMPLE 4 The apparatus depicted in FIG. 1 was charged with an ingot of an alloy composed of 38 at. percent iron, 39 at. percent nickel, 14at. percent phosphorus, 6 at. percent boron and 3 at. percent aluminum. The alloy was melted in a helium atmosphere at 1050C. and extruded through an orifice of 0.008 inch'diameter at approximately 200 cm/sec. The molten jet was quenched in refrigerated 21.6 percent magnesium chloride brine at 30 C. Brine velocity in the standpipe was 195 cm/sec. Continuous filaments of 0.006 inch diameter were thereby prepared. The filaments were examined for crystallinity by x-ray diffraction using MoKa radiation. Only a broad diffraction peak, characteristic of the amorphous state, was observed. Differential scanning calorimetry showed a crystallization temperature of 424 C. The as-spun filaments were non-crystalline.
  • a flanged carbon crucible was charged with electrolytic zinc of 99.99 percent purity and mounted over the quench fluid reservoir in the same position but in place of the melting chamber of FIG. 1.
  • the zinc was melted in a helium atmosphere and extruded through a 0.025 cm orifice at 430 C. and 4 psig. Water at 11 C. was employed as the quench medium. Water velocity in the standpipe W.% .l. ..lSI!? SF
  • FIGS. 14 and 15 Tensile properties of these materials were as follows:
  • Zinc is an illustrative exampleofmetal whose crystal structure is hexagonal close packed (H.C.P.).
  • H.C.P. metals include beryllium, cadmium, calcium, cerium, chromium, cobalt, erbium, hafnium, holmium, lanthanum, magnesium, neodymium, nickel, osmium, praseodymium, rhenium, ruthenium, scandium, thallium, titanium and yttrium.
  • the (001 planes of H.C.P. metals are the primary slip planes of this crystal system. Grain orientation in the melt spun zinc was therefore such that tensile stress along the wire produced nearly minimal shear stress along the (001 slip planes.
  • Filaments of H.C.P. metals and their alloys wherein the 001 axis are preferentially oriented at an angle greater than to the filament axis are novel.
  • the crystalline orientation achieved is a result of the high cooling rates (greater than 10 C/sec) achieved in the present invention coupled with preferential growth of H.C.P. metals in the 1 10 direction.
  • the preferred H.C.P. metals in accordance with the present invention are beryllium, cadmium, cobalt, magnesium, titanium, zirconium and zinc.
  • EXAMPLE 6 The apparatus of FIG. I was charged with a series of pure metals and alloys and filaments were melt spun of these.
  • the alloys and spinning conditions are listed in Table 1. Alloys previously described in Examples 1-5 are notincluded.
  • Lead (99.9%) 350 water l- 0.006 Lead-Tin Solder 220-280 water l-20 0005-0030 (5071 Pb. 5071 Sn) Tin (99.9%) 235-600 water l-20 0.006-0.0l2
  • wt. 7 Aqueous Zinc Chloride MgCI 21.6 wt. /r Aqueous Magnesium Chloride NaCl 23.3 wt. 7: Aqueous Sodium Chloride
  • the following examples illustrate chemical stabilization of a molten jet in a liquid medium.
  • EXAMPLE 7 An 8 mm quartz tube whose end was drawn out into a fine tip of 0.015 cm [.D. was charged with the same copper metal of 99.95 percent purity cited in Table l.
  • the quartz tube was mounted over the quench fluid reservoir in the same position but in place of the melting chamber illustrated in FIG. 1.
  • the tip of the quartz tube was 0.2 cm above the surface ofa 23.3 weight percent sodium chloride quench fluid maintained at 20 C.
  • the top of the standpipe was 2 cm below the surface of the quench fluid. Fluid velocity in the standpipe was 220 cm/sec.
  • the copper was melted in a helium atmosphere and the melt extruded from the quartz tube at 1 100 C., 220 cm/sec.
  • the molten copper traversed the air gap and entered the quench fluid.
  • the molten jet was disrupted in the quench fluid and solidified as discrete spheroidal particles.
  • copper filaments were not obtained with the less rapid quenching afforded by sodium chloride brine at 20 C.
  • EXAMPLE 8 The quartz tube of Example 7 was again charged with copper of 99.95 percent purity. The copper was melted in a helium atmosphere and the melt extruded at 1 100 C., 220 cm/sec. The tip of the quartz tube was 0.2 cm above the surface of a quench fluid consisting of 23.3 weight percent sodium chloride and 10 weight percent Na S'9H O maintained at 20 C. The standpipe position and fluid were as in Example 7.
  • the molten copper-jet traversed the air gap, entered the quench fluid and was solidified as a 0.0l 5 cm diameter filament.
  • the surface of the filament was covered with adark deposit identified as copper sulfide.
  • a method of making filaments from normally solid metal which comprises the steps of:
  • a method for forming filament from a melt of normally solid metal which comprises:
  • said quench medium comprises a liquid which provides a high heat flux regime to exist along the interface with the molten jet and the heat flux is at least 0.4 cal/sq. cmC-'sec.
  • the quench medium comprises an aqueous solution containing a sulphide ion and the molten metal is an alloy containing at least 50 weight percent copper.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Continuous Casting (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Extrusion Of Metal (AREA)
  • Inorganic Fibers (AREA)
US00306472A 1972-11-14 1972-11-14 Liquid quenching of free jet spun metal filaments Expired - Lifetime US3845805A (en)

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Application Number Priority Date Filing Date Title
US00306472A US3845805A (en) 1972-11-14 1972-11-14 Liquid quenching of free jet spun metal filaments
CA184,026A CA1012328A (en) 1972-11-14 1973-10-23 Metal spinning process and apparatus
DE19732355524 DE2355524A1 (de) 1972-11-14 1973-11-07 Verfahren und vorrichtung zur herstellung von faeden aus normalerweise festen materialien
GB5222173A GB1458017A (en) 1972-11-14 1973-11-09 Method of and apparatus for spinning metallic filaments
IT70324/73A IT996955B (it) 1972-11-14 1973-11-13 Procedimento e apparecchiatura per filatura di metalli e prodotti cera mici
JP48127405A JPS5926685B2 (ja) 1972-11-14 1973-11-14 金属またはセラミツクのフイラメントおよびその製造法
FR7340421A FR2225239B1 (enrdf_load_stackoverflow) 1972-11-14 1973-11-14
US05/499,386 US3960200A (en) 1972-11-14 1974-08-21 Apparatus for liquid quenching of free jet spun metal
CA252,692A CA1012325A (en) 1972-11-14 1976-05-17 Metal spinning process and apparatus

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DE (1) DE2355524A1 (enrdf_load_stackoverflow)
FR (1) FR2225239B1 (enrdf_load_stackoverflow)
GB (1) GB1458017A (enrdf_load_stackoverflow)
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Cited By (28)

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Publication number Priority date Publication date Assignee Title
US4030892A (en) * 1976-03-02 1977-06-21 Allied Chemical Corporation Flexible electromagnetic shield comprising interlaced glassy alloy filaments
US4056411A (en) * 1976-05-14 1977-11-01 Ho Sou Chen Method of making magnetic devices including amorphous alloys
US4174419A (en) * 1978-11-08 1979-11-13 Allied Chemical Corporation Stabilized magnetic shields
US4268325A (en) * 1979-01-22 1981-05-19 Allied Chemical Corporation Magnetic glassy metal alloy sheets with improved soft magnetic properties
US4337886A (en) * 1979-04-09 1982-07-06 United Technologies Corporation Welding with a wire having rapidly quenched structure
US4339508A (en) * 1977-11-28 1982-07-13 Shiro Maeda Method for manufacturing a thin and flexible ribbon of superconductor material
US4405535A (en) * 1980-06-27 1983-09-20 Battelle Memorial Institute Preparation of rapidly solidified particulates
US4415512A (en) * 1979-07-20 1983-11-15 Torobin Leonard B Method and apparatus for producing hollow metal microspheres and microspheroids
DE3424958A1 (de) * 1983-07-06 1985-01-17 Mitsubishi Denki K.K., Tokio/Tokyo Drahtelektrode fuer eine elektrische entladungsbearbeitung mittels schneidedraht
DE3425394A1 (de) * 1983-07-11 1985-01-24 Mitsubishi Denki K.K., Tokio/Tokyo Drahtelektrode fuer eine elektrische entladungsbearbeitung mittels schneidedraht
US4496395A (en) 1981-06-16 1985-01-29 General Motors Corporation High coercivity rare earth-iron magnets
US4568389A (en) * 1981-03-18 1986-02-04 Torobin Leonard B Shaped form or formed mass of hollow metal microspheres
US4582534A (en) * 1981-03-18 1986-04-15 Torobin Leonard B Metal microspheres, filamented hollow metal microspheres and articles produced therefrom
US4607683A (en) * 1982-03-03 1986-08-26 Unitika Ltd. Method of manufacturing thin metal wire
US4614221A (en) * 1981-09-29 1986-09-30 Unitika Ltd. Method of manufacturing thin metal wire
US4615846A (en) * 1983-09-30 1986-10-07 Kabushiki Kaisha Toshiba Method of manufacturing a low-melting point alloy for sealing in a fluorescent lamp
DE3706490A1 (de) * 1987-02-27 1988-09-08 Agie Ag Ind Elektronik Vorrichtung und verfahren zur elektroerosiven bearbeitung
US4808464A (en) * 1987-07-23 1989-02-28 Westinghouse Electric Corp. Insulating ferromagnetic amorphous metal strips
USRE32925E (en) * 1972-12-26 1989-05-18 Allied-Signal Inc. Novel amorphous metals and amorphous metal articles
DE3739847A1 (de) * 1987-11-25 1989-06-08 Hoesch Stahl Ag Verfahren und vorrichtung zur herstellung duenner metallischer fasern
FR2636552A1 (fr) * 1988-09-21 1990-03-23 Michelin & Cie Procedes et dispositifs pour obtenir des fils en alliages metalliques amorphes
US5130209A (en) * 1989-11-09 1992-07-14 Allied-Signal Inc. Arc sprayed continuously reinforced aluminum base composites and method
US5392838A (en) * 1991-02-08 1995-02-28 Compagnie Generale Des Establissements Michelin - Michelin & Cie Method and device for the continuous production of a thread by extrusion into a liquid
EP1057897A3 (en) * 1999-06-03 2002-01-23 Kabushiki Kaisha Toshiba Apparatus and process for heat treating metallic material
US20080251163A1 (en) * 2004-11-19 2008-10-16 Iwate University Bio-Co-Cr-Mo Alloy With Ion Elution Suppressed by Structure Control, And Process For Producing Same
US20090007728A1 (en) * 2005-03-02 2009-01-08 Japan Metals And Chemicals Co., Ltd Method For Melting an Alloy Containing a Metal of a High Vapor Pressure
US20120086154A1 (en) * 2010-10-07 2012-04-12 Physical Sciences, Inc. Near Field Electrospinning of Continuous, Aligned Fiber Tows
US20180071826A1 (en) * 2015-03-30 2018-03-15 Jfe Steel Corporation Method for producing water-atomized metal powder

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JPS5825536B2 (ja) * 1974-12-12 1983-05-27 ユニチカ株式会社 キンゾクフイラメントノ セイゾウホウホウ
CA1068470A (en) * 1975-02-24 1979-12-25 Allied Chemical Corporation Production of improved metal alloy filaments
DE2856795C2 (de) * 1977-12-30 1984-12-06 Noboru Prof. Sendai Tsuya Verwendung einer Stahlschmelze für ein Verfahren zum Stranggießen eines dünnen Bandes
JPS56165016A (en) * 1980-04-17 1981-12-18 Takeshi Masumoto Preparation of metal filament
JPS5729505A (en) * 1980-06-27 1982-02-17 Battelle Dev Corp Preparation of solid particulate material
JPS5860017A (ja) * 1981-09-29 1983-04-09 Takeshi Masumoto 金属フイラメントの製造方法
JPS60204844A (ja) * 1984-03-27 1985-10-16 Sumitomo Electric Ind Ltd 銀合金線の製造方法
DE3367867D1 (en) * 1983-03-04 1987-01-15 Toray Industries Lead fibers, a method of producing same and radiation shielding materials comprising same
JPS6087952A (ja) * 1983-10-17 1985-05-17 Sumitomo Electric Ind Ltd 細物Ｃｕ−Ｃｒ系合金線の製造方法
JPH0221628A (ja) * 1987-12-28 1990-01-24 Tanaka Electron Ind Co Ltd 超電導素子用ボンディングｐｂ合金線及び超電導装置
DE3844114C3 (de) * 1987-12-28 1999-03-18 Tanaka Electronics Ind Verwendung eines Kontaktierdrahtes aus einer Bleilegierung in einer Supraleitervorrichtung
DE3844879C3 (de) * 1987-12-28 1999-06-24 Tanaka Electronics Ind Supraleitervorrichtung mit einem Kontaktierdraht
US5850776A (en) * 1996-04-18 1998-12-22 Ckd Corporation Fluid pressure cylinders provided with impact absorbing mechanisms
DE102004060730B4 (de) 2004-12-15 2023-08-03 A Priori Gmbh & Co. Kg Dosierbares Zahngoldmaterial
JP6087113B2 (ja) * 2012-11-19 2017-03-01 公益財団法人神奈川科学技術アカデミー 金属もしくは半導体細線の製造方法

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US2879566A (en) * 1956-02-16 1959-03-31 Marvalaud Inc Method of forming round metal filaments
US3347959A (en) * 1964-10-08 1967-10-17 Little Inc A Method and apparatus for forming wire from molten material
US3430680A (en) * 1966-06-16 1969-03-04 George R Leghorn Method of forming structural shapes from molten material by stream casting
US3602291A (en) * 1968-09-04 1971-08-31 Battelle Development Corp Apparatus for casting metal filaments through an aerosol atmosphere

Cited By (38)

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USRE32925E (en) * 1972-12-26 1989-05-18 Allied-Signal Inc. Novel amorphous metals and amorphous metal articles
US4126287A (en) * 1976-03-02 1978-11-21 Allied Chemical Corporation Flexible electromagnetic shield comprising interlaced glassy alloy filaments
US4030892A (en) * 1976-03-02 1977-06-21 Allied Chemical Corporation Flexible electromagnetic shield comprising interlaced glassy alloy filaments
US4056411A (en) * 1976-05-14 1977-11-01 Ho Sou Chen Method of making magnetic devices including amorphous alloys
US4339508A (en) * 1977-11-28 1982-07-13 Shiro Maeda Method for manufacturing a thin and flexible ribbon of superconductor material
US4174419A (en) * 1978-11-08 1979-11-13 Allied Chemical Corporation Stabilized magnetic shields
US4268325A (en) * 1979-01-22 1981-05-19 Allied Chemical Corporation Magnetic glassy metal alloy sheets with improved soft magnetic properties
US4337886A (en) * 1979-04-09 1982-07-06 United Technologies Corporation Welding with a wire having rapidly quenched structure
US4415512A (en) * 1979-07-20 1983-11-15 Torobin Leonard B Method and apparatus for producing hollow metal microspheres and microspheroids
US4405535A (en) * 1980-06-27 1983-09-20 Battelle Memorial Institute Preparation of rapidly solidified particulates
US4582534A (en) * 1981-03-18 1986-04-15 Torobin Leonard B Metal microspheres, filamented hollow metal microspheres and articles produced therefrom
US4568389A (en) * 1981-03-18 1986-02-04 Torobin Leonard B Shaped form or formed mass of hollow metal microspheres
US4496395A (en) 1981-06-16 1985-01-29 General Motors Corporation High coercivity rare earth-iron magnets
US4614221A (en) * 1981-09-29 1986-09-30 Unitika Ltd. Method of manufacturing thin metal wire
US4607683A (en) * 1982-03-03 1986-08-26 Unitika Ltd. Method of manufacturing thin metal wire
US4839487A (en) * 1983-07-06 1989-06-13 Mitsubishi Denki Kabushiki Kaisha Wire electrode for wire-cut electrical discharge machining
DE3424958A1 (de) * 1983-07-06 1985-01-17 Mitsubishi Denki K.K., Tokio/Tokyo Drahtelektrode fuer eine elektrische entladungsbearbeitung mittels schneidedraht
DE3425394A1 (de) * 1983-07-11 1985-01-24 Mitsubishi Denki K.K., Tokio/Tokyo Drahtelektrode fuer eine elektrische entladungsbearbeitung mittels schneidedraht
US4615846A (en) * 1983-09-30 1986-10-07 Kabushiki Kaisha Toshiba Method of manufacturing a low-melting point alloy for sealing in a fluorescent lamp
DE3706490A1 (de) * 1987-02-27 1988-09-08 Agie Ag Ind Elektronik Vorrichtung und verfahren zur elektroerosiven bearbeitung
US4808464A (en) * 1987-07-23 1989-02-28 Westinghouse Electric Corp. Insulating ferromagnetic amorphous metal strips
DE3739847A1 (de) * 1987-11-25 1989-06-08 Hoesch Stahl Ag Verfahren und vorrichtung zur herstellung duenner metallischer fasern
EP0317738A3 (de) * 1987-11-25 1990-05-16 Hoesch Stahl Aktiengesellschaft Verfahren und Vorrichtung zur Herstellung dünner metallischer Fasern
FR2636552A1 (fr) * 1988-09-21 1990-03-23 Michelin & Cie Procedes et dispositifs pour obtenir des fils en alliages metalliques amorphes
EP0360104A1 (fr) * 1988-09-21 1990-03-28 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Procédés et dispositifs pour obtenir des fils en alliages métalliques amorphes
US5000251A (en) * 1988-09-21 1991-03-19 Compagnie Generale Des Etablissements Michelin-Michelin & Cie Methods and apparatus for obtaining wires of amorphous metallic alloys
US5130209A (en) * 1989-11-09 1992-07-14 Allied-Signal Inc. Arc sprayed continuously reinforced aluminum base composites and method
US5392838A (en) * 1991-02-08 1995-02-28 Compagnie Generale Des Establissements Michelin - Michelin & Cie Method and device for the continuous production of a thread by extrusion into a liquid
WO1993001322A1 (en) * 1991-07-12 1993-01-21 Allied-Signal Inc. Arc sprayed continuously reinforced aluminum base composites
EP1057897A3 (en) * 1999-06-03 2002-01-23 Kabushiki Kaisha Toshiba Apparatus and process for heat treating metallic material
US6630038B1 (en) 1999-06-03 2003-10-07 Kabushiki Kaisha Toshiba Processing apparatus for forming metallic material
US20080251163A1 (en) * 2004-11-19 2008-10-16 Iwate University Bio-Co-Cr-Mo Alloy With Ion Elution Suppressed by Structure Control, And Process For Producing Same
US20110023661A1 (en) * 2004-11-19 2011-02-03 Akihiko Chiba Bio-co-cr-mo alloy with ion elution suppressed by structure control, and process for producing same
US20090007728A1 (en) * 2005-03-02 2009-01-08 Japan Metals And Chemicals Co., Ltd Method For Melting an Alloy Containing a Metal of a High Vapor Pressure
US20120086154A1 (en) * 2010-10-07 2012-04-12 Physical Sciences, Inc. Near Field Electrospinning of Continuous, Aligned Fiber Tows
US8980158B2 (en) * 2010-10-07 2015-03-17 Physical Sciences, Inc. Near field electrospinning system for continuous, aligned fiber tows
US20180071826A1 (en) * 2015-03-30 2018-03-15 Jfe Steel Corporation Method for producing water-atomized metal powder
US10589356B2 (en) * 2015-03-30 2020-03-17 Jfe Steel Corporation Method for producing water-atomized metal powder

Also Published As

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FR2225239A1 (enrdf_load_stackoverflow) 1974-11-08
GB1458017A (en) 1976-12-08
IT996955B (it) 1975-12-10
JPS49135820A (enrdf_load_stackoverflow) 1974-12-27
CA1012328A (en) 1977-06-21
FR2225239B1 (enrdf_load_stackoverflow) 1977-09-09
JPS5926685B2 (ja) 1984-06-29
DE2355524A1 (de) 1974-07-18

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