US3658979A - Method for forming fibers and filaments directly from melts of low viscosities - Google Patents

Method for forming fibers and filaments directly from melts of low viscosities Download PDF

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US3658979A
US3658979A US829216A US3658979DA US3658979A US 3658979 A US3658979 A US 3658979A US 829216 A US829216 A US 829216A US 3658979D A US3658979D A US 3658979DA US 3658979 A US3658979 A US 3658979A
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stream
atmosphere
film
melt
molten
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Stanley A Dunn
Lawrence F Rakestraw
Robert Ernest Cunningham
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Monsanto Co
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Monsanto Co
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES, PROFILES OR LIKE SEMI-MANUFACTURED PRODUCTS OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C23/00—Extruding metal; Impact extrusion
    • B21C23/002—Extruding materials of special alloys so far as the composition of the alloy requires or permits special extruding methods of sequences
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/06—Melting-down metal, e.g. metal particles, in the mould
    • B22D23/10—Electroslag casting
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor

Definitions

  • This invention relates generally to shaped articles produced from melts and their method of manufacture and, more particularly, to the formation of fibers and filaments directly from free-streaming materials of low melt viscosity.
  • the production of shaped articles directly from a melt has required that the molten material have a rather substantial viscosity, usually greater than 500 poises.
  • the present invention is primarily directed towards, and most beneficially applicable to, the many important materials of considerably less, even negligible, viscosity; many, such as the metals in general, possess a viscosity in the molten state approaching the range of only a few hundredths of a poise to several poises.
  • the minimum viscosity essential to successful meltspinning by conventional modes is a function of, inter alia, stream size and the physical properties of the melt (particularly surface tension) and is, therefore, difficult of any precise definition; viewed pragmatically, the term low viscosity has reference to any material whose interrelationship of viscosity, surface tension and density is such as to thwart filament-like formation by convention melt-spinning techniques, especially when attempting small diameter production.
  • the materials employed in the instant invention to form fibers and filaments are generally those normally solid metals and non-metals having melt viscosities below about ten poises.
  • metals is intended to include not only essentially pure metals, but also their alloys and intermetallic compounds.
  • non-metals includes ceramics, metalloids, salts and organic materials.
  • low viscosity is here employed as referring to those materials in which the time necessary to effect stream solidification exceeds stream breakup time.
  • metals which can be spun according to this invention are beryllium, cobalt, aluminum, thorium, nickel, iron, copper, gold, uranium, Zinc, manganese, magnesium, tin and alloys made from such metals.
  • low melt viscosity ceramics useful for fiber and filaments by the process of this inven- 3,658,979 Patented Apr. 25, 1972 tion are alumina, calcia, magnesia, zirconia and mixtures of these and other oxides wherein such mixtures exhibit low melt viscosities; i.e., less than about 10 poises.
  • Metalloids such as boron silicon, salts such as potassium chloride and a variety of other normally solid materials having melt viscosities below 10 poises under the spinning conditions can be employed to make fibers and filaments according to the process of this invention are hereinafter described.
  • Still another method employed in the production of continuous, small diameter filaments or wire involves the drawing of the molten metal while encased in a vitreous sheath, otherwise known as the vitreous sheath technique.
  • a vitreous sheath otherwise known as the vitreous sheath technique.
  • the presence of the vitreous sheath is undesired and must be removed, a problem often difiicult and expensive of solution.
  • the unbroken jet length is a function of jet diameter
  • certain of these materials could be melt-extruded in relatively large diameter, rodlike forms wherein the sheer size of the extruded body affords a sufiicient resistance to disruptive forces, and therefore, a sufiicient length of time for the material, during its traverse through the length of the jet, to undergo at least partial solidification prior to stream breakup.
  • the jet disintegrates so rapidly that the traverse time of the material through the length of the jet is insufiicient to allow freezing into forms of useful length.
  • the period of time elasping between initial issuance of the stream and its breakup will, of course, depend upon, inter alia, the physical properties of the liquid, particularly its viscosity, density and surface tension.
  • the physical properties of many desirable materials are such that they are incapable of being solidified prior to traversal of the jet length, especially when the diameter does not exceed at least several millimeters, or even centimeters. It is unsurprising, therefore, that the process of free-stream melt spinning by the formation of a liquid jet in which the material is solidified or frozen to form an article of the desired shape and dimension has been successfully applied only with regard to relatively viscous liquids such as polymers and glasses. With liquids of low viscosity, however, the material issues from the end of the jet stream in the form of drops or shot before it can be frozen in its extruded form.
  • Liquid jets are subject to breakup by the action of forces which result initially from normally unavoidable stream disturbances in the form of turbulence, vibration, etc. It becomes, therefore, a fundamental limitation that any liquid jet is unstable with respect to its surface energy. Breakup of the jet is enhanced by such surface energy or surface tension and is resisted by the inertia of the material and its viscosity. In spinning fibres from low-viscosity melts, stream instability due to varicose breakup, as below defined, must be overcome. At higher spinning velocities, stream instability in the form of sinuous breakup will occur.
  • Varicose breakup is believed to result from the surfacetension-driven tendency of slightly attenuated portions of a liquid cylinder to further attenuate.
  • the surface tension gives rise to localized pressures within the cylinder, which pressures are, quite significantly, approximately proportional to the local curvature of the surface of the cylinder.
  • a liquid cylinder of perfectly cylindrical configuration would, theoretically, be stable; unavoidable variations in diameter along the cylinder, however, give rise to pressure differentials that result in transfer of material from regions of smaller diameter to adjacent regions of larger diameter. Once established, this transfer of material progresses with increasing rapidity until the cylinder is severed between the nodes thus generated.
  • This degeneration of the cylinder is not limited to the point of initial diameter variation, but radiates in both directions, each enlarging region receiving material from both directions and each attenuating region expelling it in both directions.
  • a jet stream it will be apparent that the time which has been available for disruption of the stream will increase with increasing distance from the point of jet origin.
  • the jet will initially appear smooth, some variation in the jet diameter becoming apparent further along the stream, and, at the end of the jet, the liquid appears as a series of drops or shot.
  • the causes of the initial disturbance which generate the incipient and, ultimately, disruptive variations in stream diameter can be traced to numerous minor turbulences within the stream, action of turbulent gases around the stream, external vibrations, interaction between the jet liquid and the face of the extrusion orifice, and the like.
  • the time from emergence of material at the stream origin until its varicose breakup at the end of the stream is thus limited.
  • the effect of viscosity is to hinder the local growth of a disturbance as well as its wave propaga tion. With relatively low melt viscosity materials, such as molten metals, however, the degenerative effects occur substantially unretarded and with extreme rapidity.
  • the length, L, of the liquid stream decreases with increasing surface tension. Because the length of the stream is approximately proportional to the velocity, no appreciable increase in the time required for material to traverse the jet length is gained by higher velocity. That is, the breakup time (that time elapsing between the entry of the material into the jet source or origin and its passage through the length of the jet to the point of breakup and consequent shot formation) is substantially constant over the optimum range of extrusion velocity and decreases on either side of this range; an increase in extrusion velocity, at least up to a point, therefore results in an increase in the jet length, but has little effect on breakup time and, therefore, little effect upon the brief interval of time which is available to effect solidification of the jet.
  • a further object is the production of novel articles of extrusion from materials having a low melt viscosity.
  • a further object is the manufacture of articles having a high aspect ratio from materials of low melt viscosity by the eflicient retardation and suppression of those forces normally disruptive of the free-streaming melt prior to solidification.
  • Yet another object is the provision of shaped metallic articles exhibiting a reduced dendrite spacing as compared to conventionally shaped articles.
  • Still another object is the production of metallic articles which may be rapidly homogenized by conventional heattreating techniques.
  • the foregoing and still other objects are attained in the provision of a method for the manufacture of shaped articles by the free-streammelt-extrusion of materials having such low melt viscosities as to normally experience disruption prior to stream solidification.
  • this has been accomplished by the discovery that, by causing such materials to be jetextruded as free streams into controlled atmospheres chosen according to the present invention, there may be effected a rapid, almost instantaneous formation of a rigid or viscous jet-stabilizing film about the liquid jet material which serves to prevent breakup pending solidification.
  • a rigid or viscous jet-stabilizing film about the liquid jet material which serves to prevent breakup pending solidification.
  • the stabilizing film may be generated by one or a combination of modes, which may be generally characterized as (1) reactive fihn formation, wherein the surface of the jet material enters into a chemical reaction with the atmosphere of the spinning chamber (2) decomposition, wherein either or both the surface of the stream and the spin chamber atmosphere undergo controlled decomposition resulting in the formation of a thin film along the surface of the jet (as by pyrolysis) and (3) deposition, as by evaporation or sputtering.
  • modes may be generally characterized as (1) reactive fihn formation, wherein the surface of the jet material enters into a chemical reaction with the atmosphere of the spinning chamber (2) decomposition, wherein either or both the surface of the stream and the spin chamber atmosphere undergo controlled decomposition resulting in the formation of a thin film along the surface of the jet (as by pyrolysis) and (3) deposition, as by evaporation or sputtering.
  • a layer is deposited on the surface from the vapor.
  • the spinning of metal fiber involving the formation of a stabilizing layer in this manner may require several evaporation sources in order that all sides of the stream be coated evenly. This technique is obviously most suitable to spinning of high melting materials where sufficient heat loss by radiation could be accomplished in a spinning chamber of reasonable size.
  • Sputtering the second commonly known means of depositional coating, consists of placing the object to be coated and the coating material in a partial vacuum, usually on the order of one to a few torr. An electrode is placed in the system and a connection is made to the source materials so that it also acts as an electrode. A high potential is then applied between the two electrodes. Gaseous ions created by the high potential strike the source surface giving sufficient energy to atoms or molecules so they escape into the vapor phase, thus supersaturating the vapor with the molecules of the coating material. The supersaturated source material in the gas phase then coats fairly uniformly on all objects inside the enclosure. Thus a single source is suitable for sputting.
  • the sputtering technique also provides alternative possibilities. For example, sputtering in an oxygen atmosphere could result in oxidation of the sputtered material. Nickel sputtered onto a stream in an oxygen atmosphere, for example, forms a layer of nickel oxide to stabilize the stream. Other examples are obvious.
  • the film material should possess certain attribtues relative to the jet material if optimum results are to be achieved.
  • the solubility of the stabilizing film or layer in the molten stream material should not exceed 10% by weight of the stream material at temperatures between the melting point of the stream material and the desired extrusion temperature.
  • the present invention comprehends as well, however, those film-stream combinations Wherein the interrelationship between film solubility, film formation rate and difiusion rate is such that film solubilities well in excess of 10% can be accommodated to excellent advantage; this follows from the recognition that the filmformation event is necessarily of such rapid occurrence that a relatively high rate of film solution in the stream being stabilized may easily be offset by a rapid rate of film formation.
  • melts may best be film-stabilized by the addition of a small amount of a constituent whose decomposition or reaction product possesses a lower diffusion rate and/ or solubility in the melt material, as typified in Examples 27 and 29.
  • the film material In the case of rigid, as opposed to viscous, film formations, the film material must possess a melting point higher than that of the stream material if stabilization is to occur. Again, as out of considerations of film solubility, there may be added to the melt a small amount of a constituent whose decomposition or reaction product possesses a higher melting point that the film material that may otherwise beformed. The same purpose may as well be served by melt modifications resulting in streams of lower melting points, as for example, the formation of various alloys and eutectics. Where the supporting film composition is non-rigid, but viscous, the viscosity of the film material should be greater than 1,000 poises at the melting point of the stream material.
  • the examples recited in the ensuing description illustrate the versatility of the invention for the manufacture of fibers and filaments of a broad variety of materials having low melt viscosities and for the use of a broad Variety of film forming atmospheres.
  • the invention can be used to form fibers and filaments from the general classes of metals and non-metallic materials having low melt viscosities.
  • the invention contemplates the use not only of oxygen containing film-forming atmospheres, but those atmospheres which are essentially oxygen-free as well.
  • essentially oxygen-free film-forming atmosphere as employed herein means that the atmosphere contains a gas other than elemental oxygen as the effective film-forming ingredient of the film-forming atmosphere.
  • a gaseous hydrocarbon such as propane
  • ammonia, boron trichloride and water, carbon disulfide, carbon dioxide, carbon monoxide or other gas may not be harmful and, therefore, such essentially oxygen-free, film-forming atmospheres may contain elemental oxygen where it is not the principal stabilizing ingredient of the atmosphere and where there is no advantage to its removal from the system.
  • the velocity of the free-streaming melt should be controlled (so that the Rayleigh parameter, a dimensionless quantity, V ⁇ /pD/'y which quantity is the square root of the well known Weber Number and in which V is stream veloci-ty, D is stream diameter and p and 'y are density and surface tension, respectively, of the melt) lies within the range of 1 to 50 and preferably within the range of 2 to 25. It has been discovered that, where the velocity of extrusion fails to satisfy this condition, the breakup time of the jet becomes so shortened that effective film stabilization is not established. For a.
  • the optimum velocity lying within the Rayleigh parameter range of 1 to 50 will normally be determined experimentally, primary consideration being given to the relative density of the melt to that of the atmosphere into which extrusion takes place and the temperature of extrusion relative to the temperature of the spin chamber atmosphere.
  • the rate of propagation of varicose breakup determines the lower limit of the stated Rayleigh parameter range, while either or both sinuous breakup and/or aerodynamic deceleration (wherein the partially or fully solidified stream is caused to jam upon itself to create a jointed appearance) determines its upper limit.
  • the upper limit of the range is approached as the relative density of the melt to the spin atmosphere increases; i.e. the greater the density of the melt and/or the lesser the density of the spin atmosphere, the higher the Rayleigh parameter at which successful spinning may be accomplished, though optimum performance may dictate a somewhat lower level.
  • the cooling rate of a molten stream falling through a gaseous atmosphere may readily be calculated by conventional techniques.
  • rapidly cooling in reference to a molten filamentary stream is defined as cooling which inherently takes place due to heat transfer from the fiber due to radiation, conduction, and gaseous convection.
  • the minimum self-stabilization diameter is several orders of magnitude larger than the filament dimensions which can be obtained using a stabilizing atmosphere.
  • this invention is particularly concerned with the manufacture of fine diameter fibers and filaments.
  • the process herein described is applied to the manufacture of fibers and filaments having diameters of less than about mils and provides a particularly attractive means for making wire and other filaments of low viscosity melts having diameters below about 35 mils.
  • Metal properties including fracture strength, susceptibility to corrosion, deformability and surface character depend significantly on the degree of homogeneity of the alloy. It is therefore desirable in metal fabrication to minimize the inhomogeneity brought on by the microsegregation of materials during the freezing process. This is usually done by post-heating, or annealing.
  • the annealing process brings about increased thermal diffusion and causes the regions of discontinuity, i.e., the regions of impurity concentration, to diifuse and disperse, yielding a material of improved strength and reduced brittleness.
  • the eflicacy of annealing treatments is dependent on the initial solidification structure of the metal or alloy, i.e., on the size of the internal structures, or dendrites, and on the solute distribution in the structures. That is, homogenization or dispersal of impurities will depend on the extent of microsegregation in the original material, and on the relative distances over which they must be redistributed to achieve a uniform structure. Since redistribution of impurities by thermal diffusion depends on the square of the distances through which redistribution or homogenization must occur, it is an obvious advantage to have a minimum distance between these dendrites or regions of inhomogeneity.
  • dendrite arm spacings In normal macroscale castings, it is common to find dendrite arm spacings of about 100-1000 microns. It has been found, however, that when metal alloys or metals containing minor impurities are shaped by the techniques of this invention, a highly unusual internal structure is obtained wherein the dendrite spacings, which is the visible evidence of the microsegregation of materials, are much reduced over spacingc normally encountered in other methods of fabrication, such as casting, and are usually in the range of a few microns. Although the spacings are dependent somewhat on composition and on extrusion conditions, they are usually noted to be about 5-25 microns apart. That is, about 5-25 microns separates the minor component or relatively higher impurity regions from one another. In typical castings, these spacings are normally found to be up to 200 times as large as the equivalent structures of this invention.
  • Heat-treating of the conventionally drawn, unworked wire would still require, therefore, relatively longer times to achieve comparable homogenization of the microsegregated impurities or minor components than would the heat treating of the filaments of this invention.
  • Metal filaments obtained from Example 2.7, composed of 406 stainless steel, and having filament diameters of approximately 75 microns were mounted in Transoptic (a cold-curing epoxy resin mounting material) and successively dry ground and polished, wet ground and polished with 600 mesh silicon carbide, 0.3 micron alpha alumina and 0.05 micron gamma alumina, the latter three steps using conventional polishing cloths. Care was exercised throughout to avoid any substantial heating or excessive working of the samples. The samples were then etched with a standard metallographic etching solution composed of 4.0 g. CuSO 20 ml. cone. HCl and 20 ml. H O for 30 seconds to reveal the internal structure. Typical dendrite spacings ranged from to 20 microns as measured on micrographs of the etched samples, with the majority being separated by 5-10 microns.
  • Transoptic a cold-curing epoxy resin mounting material
  • Example 31 Examination of the filaments of Example 31 by mounting, grinding, polishing and etching for seconds with a Kellers solution of 1.0 ml. conc. HP, 1.5 ml. cone. HCl, 2.5 ml. conc. HNO and 95.0 ml. water revealed average dendrite spacings of approximately 10 microns.
  • Chromel R filaments of Example 22 were mounted, prepared and etched with solution of ferric chloride in hydrochloric acid/nitric acid solution. Dendrite spacings in the filaments were observed to be approximately 4-5 microns.
  • Gold filaments of Example 42 were ductile and dilficult to grind and polish. Mounted samples etched with an aqueous solution containing 10% potassium cyanide and 10% ammonium persulfate showed no evidence of dendrites. This was as expected since the gold was extremely pure; i.e. the high purity level resulted in no discernible microsegregation. Similarly, the high purity zinc fibers from Example 33, when prepared and etched with Palmertons reagent (200 g. CF0 g. Na SO and 1000 ml. H O), showed no dendritic structure, but only a few grain boundaries in what appeared to be predominately a single crystal structure.
  • Palmertons reagent 200 g. CF0 g. Na SO and 1000 ml. H O
  • the present invention relates to methods for and products resulting from free-stream melt extrusion of materials having low melt viscosities into selected atmospheres productive of a rapid, jetstabilizing film formation, whether by reaction, decomposition or deposition, which film is of a composition so chosen or modified as to have a melting point above that of the stream material or, in the case of non-rigid films, a viscosity above 1,000 poises at the melting point of the stream material.
  • such an apparatus may comprise an induction-heated spinning assembly, generally indicated by arrowed numeral 10, mounted upon an elongated cylindrical catch chamber 12.
  • the spinning assembly comprises a melt crucible 14 which, for the examples which follow, was fabricated from boron' nitride or alumina (A1 0 but may be formed from any suitable refractory material which is found compatible, i.e., nonreactive, with the melt it is desired to process.
  • the bottom surface of the crucible is carefully drilled to provide either a small diameter orifice 16, or a carefully machined hole in which a watch-sized jewel, such as a sapphire, having a small diameter orifice formed therein is seated.
  • the crucible illustrated is provided with only a single spinning orifice, production versions would, of course, be provided with a plurality of similar such orifices.
  • the crucible rests upon a supporting and insulating cylinder 18 of quartz construction, which, in turn, rests upon support plate 20.
  • the crucible thusly mounted may be enclosed by a conventional susceptor 22 which encircles the crucible when it is desired to process non-conductive/non-coupling materials; i.e. materials which cannot be directly heated inductively.
  • the susceptor may be held in place by suitable refractory cording, not shown.
  • the crucible and susceptor are enclosed, within a heavy-walled housing 24 of Pyrex or quartz construction.
  • a fitting 26 suitable for connection to source of pressure which fitting is clamped in gas-tight relationship between upper plate 28 and support plate 20 by means of suitable stud bolts 30.
  • an inert, pressurized gas may be imposed upon the material being melted within the crucible to effect its extrusion through the orifice.
  • an induction coil 32 of suitable electrical characteristics encircles the crucible to supply heat to the contents thereof according to the principles of magnetic induction.
  • a support cylinder 34 of quartz of Pyrex construction which stands upon base plate 36 and bears against the crucible support plate 20.
  • Suitable flexible gaskets 38 are provided between the base plate and support plate connections to assure a gas-tight assembly.
  • Formed in the base plate 36 is a relatively large catch chamber entry port 40 which is located to be in substantial alignment with the central aperture 42 formed in support plate 20.
  • the catch chamber 12 is provided with connection 44 through which suitable spinning atmospheres may be introduced or withdrawn. Provision is also made for an observation port 46 arranged to give a diametrical view across the catch chamber and an access plate 48 of relatively generous dimensions to facilitate installation and removal of suitable take-up equipment in the bottom of the catch chamber. At the very bottom of the catch chamber, a capped collection port 50 is provided for product removal.
  • spinning apparatus merely represents a typical assembly which may be employed in the practice of the present invention, which is in no way limited to the details of construction of the apparatus.
  • a resistanceheated spinning assembly could as well be employed in conducting many of the experiments.
  • extrusion pressures i.e., pressure over the melt, are gauge and percentages are by weight.
  • Examples 1-35 demonstrate the suppression of stream breakup by the formation of a stabilizing film via a chemical combination of the extruded molten stream and reactive atmosphere.
  • EXAMPLE 1 The entire system was evacuated to 0.5 mm. Hg pressure and an aluminum alloy having a melt viscosity of 0.03 poise and containing 4.0 percent Cu, 0.5 percent Mn, 0.5 percent Mg and 95 percent Al was melted by inductive heating to 700 C. After melting was complete, argon at 10 p.s.i.g. pressure was applied to eject the molten alloy through a 180 micron orifice into the vacuum within the chamber below the orifice maintained at a temperature of 25 C. The stream of aluminum, in the absence of a film-forming atmosphere, rapidly disintegrated and failed to solidify within a fall of 8 feet to the bottom of the spin chamber.
  • Example 2 The experiment described in Example 1 was repeated with the exception that a 100 micron orifice was employed, the vacuum was replaced with nitrogen at 1 atmosphere pressure and the pressure on the melt was increased to 16.5 p.s.i.g., resulting in an extrusion velocity 465 cm./sec. As in Example 1, the nitrogen did not per form as a film-forming atmosphere and only aluminum shot was formed. Molten aluminum will react with nitrogen to form aluminum nitride which might then function as a stabilizing film. This reaction, however, does not take place rapidly enough to provide a film of aluminum nitride of sufficient thickness to stabilize the molten stream; consequently, no fiber formation.
  • EXAMPLE 3 The experiment described in Example 1 was repeated with the exception that the vacuum was replaced with an atmosphere which consisted of argon at 1 atmosphere pressure. Again, as was the case in the previous experiments Where film-forming atmospheres were absent, no fibers were detected and only shot was formed.
  • Example 1 was repeated with the exception that the vacuum was replaced with an atmosphere which contained 0.004 atmosphere oxygen and 0.996 atmosphere nitrogen. In this case, the major portion of the spun charge was in the form of shot. Approximately 1% of the total charge exhibited incipient fiber formation, indicating that the oxygen concentration was insufficient to establish an eflective stabilizing film.
  • EXAMPLE 5 The experiment described in Example 1 was repeated with the exception that the extrustion pressure was increased to 20 p.s.i.g. and the vacuum in the spin chamber was replaced with pure oxygen at 1 atmosphere pressure; extrusion velocity was approximately 525 cm./sec. The oxygen was introduced after the molten alloy stream had commenced streaming smoothly. It was observed that if oxygen was present below the orifice during melting, the aluminum exposed in the orifice formed an oxide film which plugged the orifice and prevented spinning.
  • EXAMPLE 6 The experimental described in Example 5 was repeated with the exception that the oxygen pressure was reduced to 0.033 atmosphere in the area beneath the orifice. At this reduced spin chamber pressure, only a very small amount of extremely short fiber was obtained, indicating that the oxygen concentratoin was too low.
  • EXAMPLE 7 The experiment described in Example 6 was repeated with the exception that the oxygen pressure were increased to 0.067 atmosphere.
  • the extruded molten alloy stream formed fibers similar to those described in Example 5. It is apparent, in comparing Example 6, that the concentration of the reactive spinning atmosphere must be maintained at levels adequate to assure a sufi'iciently high rate of film formation.
  • EXAMPLE 8 The experiment described in Example 1, was repeated with the exception that the extrusion pressure was increased to 15 p.s.i.g. and the vacuum was replaced with an atmosphere consisting of 4.5% ammonia and 95.5% argon at 1 atmosphere pressure, resulting in the formation of an aluminum nitride film which effectively stabilized the stream.
  • the fibers obtained had a diameter of approximately 100 microns and an analysis of the fibers indicated the composition of the alloy was essntially unchanged, indicating that only a thin surface film is involved in the stabilizing process. It is also demonstrated that any inert diluent, in this case argon, can be used in the presence of a suflicient concentration of the reacting atmosphere, in this case ammonia.
  • Example 9 Example 8, was repeated with the exception that the spin chamber atmosphere consisted of 0.9 atmosphere nitrogen and 0.1 atmosphere hydrogen sulfide and the extrusion pressure was increased to 30 p.s.i.g. Reaction with the spin chamber gas resulted in the formation of an aluminum sulfide film which effectively stabilized the stream until fiber formation was established.
  • the fibers averaged microns in diameter.
  • Example 10 Example 1, was repeated with the exception that pure electrical conductivity grade aluminum (99.45% aluminum) was used instead of aluminum alloy, a spin chamber gas consisting of 0.97 atmosphere nitrogen, 0.015 atmosphere hydrogen and 0.015 atmosphere hydrogen sulfide was employed and extrusion was carried out under a pressure of 30 p.s.i.g. Spherical and elongated shot and strings of beads resulted, demonstrating that the hydrogen sulfide concentration was not sufiicient to permit successful fiber formation. These results, however, do indicate that fiber formation was in the incipient stages, i.e. stream disruption was occuring at a very late stage.
  • pure electrical conductivity grade aluminum 99.45% aluminum
  • a spin chamber gas consisting of 0.97 atmosphere nitrogen, 0.015 atmosphere hydrogen and 0.015 atmosphere hydrogen sulfide was employed and extrusion was carried out under a pressure of 30 p.s.i.g. Spherical and elongated shot and strings of beads resulted, demonstrating that the hydrogen sulfide concentration was
  • Example 10 was repeated with the exception that the spin gas was replaced by one consisting of 0.90 atmosphere nitrogen, 0.033 atmosphere hydrogen, and 0.067 atmosphere hydrogen sulfide, resulting in good fiber formation, thus demonstrating that a concentration of 0.067 atmosphere hydrogen sulfide is sufficiently rich to obtain good fiber formation, whereas, in Example 10, 0.015 atmosphere hydrogen sulfide was inadequate.
  • Example 2 is a good illustration; here, the reaction between molten aluminum and nitrogen to form aluminum nitride is well known, but the reaction rate is obviously too slow to provide a film of sufiicient thickness to permit a degree of stabilization requite to good fiber formation.
  • the reaction between aluminum and ammonia see Example 8 is sufficiently fast to provide good fiber formation.
  • these experiments show that a minimum concentration of the filmforming atmosphere is necessary and that the quality of the fiber is dependent on such concentration.
  • Examples 12-16 demonstrate the utility of the sheathstabilized spinning process in preparing filaments from metalloids. Such materials are extremely difficult to shape by any known means.
  • Example 12 further demonstrates that a boron nitride film is a very effective stabilizing agent.
  • EXAMPLE 12 The equipment of Example 1 was charged with zonerefined boron having a purity of 99.9995%. The apparatus was evacuated to a pressure of 50 microns and the boron charge was melted (M.P. approx. 2300 C.). A 50 p.s.i.g. argon pressure was then applied to the melt and the boron extruded through a 150 micron orifice into a gaseous mixture composed of 10% nitrogen and 90% ammonia maintained at 1 atmosphere pressure. Very long lengths of boron filament were obtained. The filaments were rather lustrous, smooth and uniform, averaging about 115 microns in diameter and having a tensile strength of greater than 100,000 p.s.i.
  • Examples 13-16 further demonstrate the necessity for observing the various limitations discussed with respect to reactivity of the atmosphere, solubility limitations of the stabilizing sheath, and the like.
  • EXAMPLE 13 Utilizing the apparatus of the previous examples equipped with a 125 micron extrusion orifice, there was placed in the crucible a charge of pure silicon in the form of small pellets. The system was evacuated to less than 0.1 torr pressure and heated to melting at approximately 1450 C., at which point the vacuum below the orifice was replaced with a gaseous mixture comprised of 10% by volume of nitrogen and 90% ammonia at 1 atmosphere pressure. Concurrently, the vacuum above the orifice was replaced with argon at 35 p.s.i.g. Although the molten silicon began streaming, the chamber atmosphere was ineffective to form a suitable sheath and only silicon shot was obtained.
  • EXAMPLE 14 As before, silicon was charged to the apparatus and the same procedure followed except the atmosphere into which extrusion took place was pure ammonia and an argon pressure of 80 p.s.i.g. was used for extrusion. Somewhat nodular fibers were obtained which had diameters of approximately 120 to 150 microns.
  • EXAMPLE 17 Following the general procedure of Example 1, oerryllium was charged to the crucible, melted and extruded through a 220 micron orifice under an argon pressure of 50 p.s.i.g. into a spin chamber gas containing argon at a pressure of 0.87 atmosphere. The temperature of the molten beryllium was maintained between l,3001,350 C. during spinning. No fiber was formed and only beryllium shot was collected.
  • EXAMPLE 18 The experiment described in Example 17 was repeated with the exception that the argon atmosphere was replaced with an atmosphere containing 17.3% by volume of oxygen and 82.7% argon. A beryllium oxide film was formed about and effectively stabilized the stream to give good fiber formation. The fiber surface was delustered and gray in color.
  • EXAMPLE 19 An alloy was prepared which consists of 9% aluminum alloy and 91% 1030 steel. The final composition of the alloy was: 89.6% Fe, 8.6% A1, 0.36% Cu, 0.77% Mn, 0.31% C, 0.23% Si, 0.05% Mg, 0.026% S, and 0.013% P. The alloy was melted in a vacuum at a temperature of 1,500 O, held in the molten state for five minutes, cooled and the surface machined smooth. The alloy was then placed in the illustrated apparatus and melted. The vacuum was replaced in the spin chamber below the orifice with argon at one atmosphere and the argon pressure over the melt was raised to 15 p.s. i.g. to extrude the melt through a micron orifice. No fibers were formed in the argon atmosphere.
  • Example 19 was repeated with the exception that the argon below the orifice was replaced with the oxygenargon atmosphere of Example 18 at one atmosphere pressure. This atmosphere, was introduced after streaming of the melt was initiated and resulted in a stabilizing film of aluminum oxide on the molten stream. Fiber formation 17 occurred as the vacuum was replaced by the film-forming atmosphere. The fibers formed had diameters ranging from 90 to 100 microns.
  • EXAMPLE 23 This example demonstrates that a stabilizing film must be applied to the streaming melt rapidly in order to stabilize against varicose breakup and that the reaction of either aluminum or iron with nitrogen takes place too slowly to stabilize the stream.
  • An alloy was prepared which consisted of National Bureau of Standards 90% steel (containing 0.8% carbon) and 10% electrical conductivity grade aluminum. The alloy was melted in vacuo, held for 10 minutes, cooled, and the surface of the slug machined smooth. The alloy was charged to the spinning apparatus, heated to 1,345" C. in vacuo and the pressure of the melt raised to one atmosphere argon while melting took place. The alloy was completely molten at 1,425 C. The argon pressure above the melt was increased to 100 p.s.i.g. and the vacuum below the orifice replaced with one atmosphere of nitrogen. The molten alloy was extruded through a 100 micron diameter sapphire orifice. Due to the low rate of reactivity of aluminum with nitrogen, the aluminum nitride sheath did not form rapidly enough to completely stabilize the stream and a mixture of spherical shot and bead-like chains were obtained.
  • EXAMPLE 24 This example demonstrates that the reaction between aluminum and ammonia proceeds rapidly enough to provide a stabilizing film of aluminum nitride which then protects the stream against breakup.
  • An alloy was prepared consisting of 90% steel (containing 0.1% carbon) and 10% electrical conductivity grade aluminum. The alloy was melted in vacuo, held in the molten state and mixed with a gentle stream of argon for about minutes, cooled and the surface machined smooth. The alloy was placed in the spinning apparatus, melted and extruded under 100 p.s.i.g. argon pressure into a chamber atmosphere containing 0.9 atmosphere pressure of NH;, and 0.1 atmosphere of nitrogen. The fibers obtained were 75100 microns in diameter, up to 80 cm. in length and showed ultimate tensile strength of 5 6,000- 58,000 p.s.i. and an elongation of 4.0-4.6%.
  • EXAMPLE 25 This example demonstrates that thorium and oxygen react sufliciently rapid to provide a thorium oxide stabilizing sheath to allow filament formation.
  • An alloy was prepared by melting in vacuo 2.25 grams of thorium metal and 20.19 grams of nickel, each of which had purities greater than 99.5%. When the melt had reached 1300 C., a gentle stream of argon was bubbled through to insure complete mixing. After minutes at 1400-1500 C., the melt was cooled and polished. The alloy was then introduced into the spinning apparatus and melted in vacuum. When the temperature of the melt reached approximately 1400 C., the chamber was pressurized with 100 p.s.i. argon and the alloy extruded into a mixture of 80 volume percent nitrogen and 20% oxygen at 1 atmosphere pressure. Short fibers were obtained which were smooth, irridescent, and coated with i a thin film of the greyish oxide of thorium.
  • EXAMPLE 26 This example, as distinguished from the results obtained in Example 2, demonstrates that with more highly reactive metals, the reaction with nitrogen is sufliciently rapid to yield a stabilizing nitride film.
  • Uraninum metal having an analysis of 0.10% chromium, 0.10% iron, 0.005% manganese, 0.010% nickel, 0.002% vanadium and greater than 99.75% uranium was introduced into the melt crucible and melted in vacuo at about 1200 C.-The melt was then pressurized with p.s.i.g. argon and the melt extruded into nitrogen at 1 atmosphere pressure through multiple orifices 100 microns in diameter. Fibers ranging in length up to about 1 foot were obtained. The fiber was slightly rough surfaced, shiny and grey in color. The stabilizing sheath was DTP-'- sumed to be uranium nitride.
  • EXAMPLE 27 This example demonstrates that, with utilization of the proper stabilizing atmosphere, such desirable materials as stainless steel can be successfully spun into filaments.
  • Type 406 stainless steel in the form of 25 gauge strip was pre-melted in vacuo, cooled and machined.
  • the alloy had an analysis of 12.6% chromium, 3.50% aluminum, 2.10% nickel, 0.25% manganese, 0.15% carbon, 0.10% copper and 81.30% iron.
  • the alloy was charged to the spinning apparatus, melted in vacuo and pressure extruded under 65 p.s.i.g. argon into 0.8 atmosphere of nitrogen pressure and 0.2 atmosphere oxygen at a melt temperature of about 1480 C. Fibers with average diameters of microns were obtained in lengths up to several feet.
  • EXAMPLE 28 Metal: Percent by weight Copper 93.45 Aluminum 5.83 Magnesium 0.36 Manganese 0.36
  • the alloy was exposed to aqua regia, rinsed and placed in the apparatus for spinning.
  • the alloy was melted and a pressure of 15 p.s.i.g. nitrogen applied to extrude the melt into an argon atmosphere at 1 atmosphere pressure. No fiber was obtained.
  • EXAMPLE 29 The experiment described in Example 28 was repeated with the exception that the atmosphere below the orifice was replaced with the oxygen-argon atmosphere of Ex ample 18 at 1 atmosphere pressure, resulting in the forma- 19 tion of an aluminum oxide film on the molten stream to give successful fiber formation.
  • the fibers exhibited an average diameter of 70 microns.
  • EXAMPLE 30 An alloy containing 34 electrolytic grade zinc (99.99% Zn) and 66% high purity aluminum (99.99% Al) was extruded.
  • the procedure adopted consisted of charging the material to be extruded into the crucible and placing the crucible in the apparatus shown in the drawing. The system was closed and evacuated to a vacuum of approximately 0.1 torr. The vacuum in the section containing the crucible was broken with arogn to p.s.i.g. pressure. The sample was heated to 760 C. to provide a uniform melt and the pressure over the melt was increased to 25 p.s.i.g. The molten stream of the Zinc-aluminum alloy failed to form fiber when extruded into the vacuum.
  • Example 31 The experiment described in Example 30 was repeated with the exception that the vacum below the orifice was replaced with the oxygen-argon atmosphere of Example 18 at atmospheric pressure, resulting in the formation of either an aluminum oxide or a zinc oxide stabilizing film. Fibers with diameters ranging from 160-300 microns were tained. The tensile strength of the fibers averaged 40,000 p.s.i. with an elongation of 3.5%. The surface of the fibers was observed to be smooth.
  • Example 30 was repeated with the exceptions that the vacuum below the orifice was replaced with argon at 1 atmosphere pressure and that electrolytic grade zinc (99.99% Zn) was used instead of the zinc-aluminum al- 103;. No fiber was formed when the metal was heated to 470 C. and extruded through a 450 micron orifice into the inert atmosphere.
  • Example 32 was repeated with the exception that the argon atmospere below the orifice was replaced with an atmosphere consisting of 17.5 volume percent anhydrous ammonia and 82.5% argon at 1 atmosphere pressure. Fibers with diameters ranging from 160-300 microns were obtained. The fibers were observed to be very ductile and had a lustrous appearance, indicating that the stabilizing film (presumably zinc nitride) was quite thin.
  • Example 30 was repeated with the exception that high purity grade tin (99.99% Sn, M.P. 232 C.) was employed in place of the zinc-aluminum alloy. An orifice with a diameter of 180 microns was employed. No fiber was formed in the inert argon atmosphere and only tin shot was collected.
  • high purity grade tin 99.99% Sn, M.P. 232 C.
  • Example 34 was repeated with the exception that the atmosphere below the orifice was replaced with one containing 20% by volume of oxygen and 80% argon. Tin fibers with an average diameter of 120 microns were obtained. The as-spun fibers were ductile and highly lustrous, indicating that the tin oxide (SnO or SnO stabilizing film was of a minute thickness.
  • EXAMPLE 36 The illustrated apparatus was employed to melt high purity manganese (99.96% Mn). The space above the melt was charged with argon gas at 100 p.s.i.g. The melt was extruded into 1 atmosphere of argon. The molten manganese, when spun through a 100-micron diameter orifice, failed to form fiber.
  • Example 36 was repeated with the exception that carbon disulfide was introduced into the area below the orifice to maintain a pressure of 0.39 atmosphere. Black-coated manganese fibers with an average diameter of 100 microns were obtained. The coating was easily removed to give a lustrous surface.
  • the stabilizing film in this case was either manganous sulfide or carbon.
  • EXAMPLE 38 High purity copper (99.99% Cu) was melted in a vacuum. The space above the melt was charged with argon gas at 100 p.s.i.g. while argon was introduced into the space below the orifice to bring the pressure to 1 atmosphere. No fiber was formed in the inert argon atmosphere.
  • Example 38 was repeated with the exception that carbon disulfide was vaporized into the area beneath the orifice to maintain a pressure of 0.27 atmosphere in place of the argon atmosphere employed in Example 38. Copper fibers with an average diameter of microns were formed. The fibers exhibited a black-coated surface which was easily removed by rubbing with a cotton cloth to reveal a shiny copper surface. It is postulated that the black coating (presumably the stabilizing layer) was carbon. The tensile strength of the copper fibers was 13,500 p.s.i. and their elongation was 22.0%.
  • Example 38 was repeated with the exception that gold (99.97% Au) was employed instead of copper and the temperature of the melt was maintained at approximately 1100" C. No fiber formed after ejection of the molten gold into the inert argon atmosphere.
  • Example 40 was repeated with the exception that the argon was replaced with 0.33 atmosphere of carbon disulfide. No fiber was formed on extruding the molten gold into the carbon disulfide atmosphere. It is speculated that the potentially stabilizing film of carbon formed by decomposition of the carbon disulfide was disrupted by volatilization of sulfur (which has a boiling point of only 445 0.), since the temperature of the molten streams was approximately 1100 C.
  • Example 40 was repeated with the exception that the argon atmosphere was replaced with propane gas at 1 atmosphere pressure. Gold fibers with the diameter of 50 microns were obtained.
  • Examples 43 and 44 demonstrate that the process of spinning materials with low viscosities by suppressing Rayleigh Wave formation is not restricted to metals and may be applied to organic substances.
  • the material selected for the substrate in these examples was unsubstituted adipamide.
  • Adipamide when melted has a viscosity, when measured at 236 C. with a conventional Ostwald viscometer, of approximately 1 poise. This viscosity is obviously unsuitable for melt spinning by conventional techniques where polymeric organic substances with viscosities in excess of 500 poises are normally required.
  • the objective in these examples was to deposit a boron oxide stabilizing film on the surface of the streaming liquid adipamide stream by the reaction of a gaseous boron trichloride with the moisture in the system to stabilize the stream.
  • Example 43 was repeated with the exception that after the molten adipamide began to flow from the orifice, boron trichloride gas was introduced beneath the orifice at a pressure of 1 atmosphere. A slightly tacky, amber fiber was obtained which melted at 192-210 C. The fiber gave a positive flame test for boron.
  • Examples 45 and 46 demonstrate that the process of spinning materials with low viscosities by suppressing varicose instability with a stabilizing film can be extended to include, for example, the refractory inorganic oxides.
  • the material selected for the inorganic oxide was a mixture of calcium oxide and aluminum oxide.
  • EXAMPLE 45 The illustrated apparatus was employed to melt the refractory inorganic oxide sample, which was prepared by fusing a thoroughly mixed powder consisting of calcium oxide and aluminum oxide. The cooled melt was machined and subsequently fused at 1600 C. by inductively heating in a graphite crucible. The area above the melt was charged with argon gas at 50 p.s.i.g. and the molten mixture extruded through a 225 micron orifice into an atmosphere of argon. No fiber was produced, only shot being formed.
  • Example 45 was repeated with the exception that pro pane was introduced into the area below the orifice to maintain a pressure of 1 atmosphere. Fibers from the aluminum oxide-calcium oxide mixture with an average diameter of 200 microns were obtained. The stabilizing film of carbon was readily removed to give almost transparent fibers which had a tensile strength of 105,000 p.s.i.
  • EXAMPLE 47 The following example demonstrates that the presence of the stabilizing film is capable of effecting successful spinning even when the emerging stream remains well above its melting point for a considerable distance beyond the spinning orifice, thus emphasizing its stabilizing infiuence.
  • Example 1 The system of Example 1 was evacuated to 0.5 mm. Hg pressure and a charge composed of high purity tin, as employed in Example 34, was used.
  • the molten tin was extruded through a 100 micron orifice at a temperature of 260235 C. into a film-forming atmosphere of 67 volume percent helium and 33% oxygen at 1 atmosphere pressure. Although this entire temperature range is above the melting point of tin, whereby solidification was delayed, good fibers were obtained over the entire range utilized via formation of a tin oxide layer resulting from the reaction of the molten tin stream with the oxygencontaining atmosphere.
  • EXAMPLE 48 The following example further demonstrates the elficacy of stabilizing the molten stream with a surface film at temperatures wherein the stream remains molten for a considerable distance beyond the orifice. In addition, the adverse effect of using a higher density atmosphere is also demonstrated.
  • Example 47 Utilizing the apparatus of Example 47 and again employing highly pure tin (99.99% Sn), the system was evacuated to less than 5 mm. Hg pressure and the tin melted. The vacuum above the orifice was replaced with 40 p.s.i.g. argon and the vacuum below the orifice with one atmosphere pressure of nitrogen-20% oxygen mixture. Again, although the melt temperature was varied from 245460 C., fiber was formed throughout the temperature range. Because the N /O mixture was more dense than the O /He mixture of Example 47, the extruded filaments exhibited a number of joints or enlarged segments along its length.
  • Examples 49 and 50 illustrate the capability of forming small diameter filaments.
  • Example 49 shows the effect of excessively high spinning velocity.
  • Tin metal at 340 C. was extruded through a 35 micron orifice into an atmosphere of 67 volume percent helium and 33% oxygen and the spin velocity was maintained within a Rayleigh parameter range from 6 to 7.
  • Tin fiber 25 microns in diameter was obtained in lengths exceeding 5 feet.
  • the stabilizing film must have a rather low solubility in the molten metal, in addition to a relatively higher melting point.
  • Table IV shows the relatively low solubility of stabilizing films in several representative metals.
  • the sulfide of manganese besides having the requisite highmelting point (360 above that of the metal), is also relatively insoluble in the molten metal (see above Table IV.) An attempt to spin manganese into a third of an atmosphere of carbon disulfide, Where the reaction.
  • the stream may be generated by centrifugal disc spinning within a reactive atmosphere, wherein a cone rotated at high speed and supplied centrally by the melt would form a uniform film over the face of the cone, which film would depart the periphery of the cone in the form of ligaments that may be gas-stream attenuated pending solidification.
  • conjugated filamentary structures can be extruded according to the present film-stabilization concept, wherein two or more discrete sources of melt are brought into confluence in the vicinity of the extrusion orifice.
  • the method of forming a filament from a normally solid inorganic material having a melt viscosity of less than about ten poises comprising spinning the material as a free molten filamentary stream into an atmosphere containing a film-forming gas such that the value lies between 1 and 50 and where V is the velocity of the stream, D is the cross-section diameter of the stream, p is the density of the molten material, and 'y is the surface tension of the molten material, said film-forming gas in the presence of the molten stream having a concentration and reactivity sufiicient to form an essentially insoluble, oxide-free stabilizing film on the stream prior to the stream being disrupted by surface tension, the stream thereafter solidifying into a filament.

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US3856513A (en) * 1972-12-26 1974-12-24 Allied Chem Novel amorphous metals and amorphous metal articles
US3861452A (en) * 1971-05-10 1975-01-21 Establissements Michelin Raiso Manufacture of thin, continuous steel wires
US3884289A (en) * 1972-06-22 1975-05-20 Monsanto Co Inviscid spinning of silicon steel
US3889739A (en) * 1973-11-12 1975-06-17 Monsanto Co Pressurized nitrogen to extrude molten steel-silicon alloy
US3904381A (en) * 1972-12-29 1975-09-09 Monsanto Co Cast metal wire of reduced porosity
US3926248A (en) * 1973-10-11 1975-12-16 Monsanto Co Orifice structure for extruding molten metal to form fine diameter wire
US3945240A (en) * 1972-10-16 1976-03-23 United Technologies Corporation Diffusion bonding separator
FR2365530A1 (fr) * 1976-09-23 1978-04-21 Owens Corning Fiberglass Corp Procede et appareil de traitement du verre a l'etat fluide afin qu'il ne colle pas
US4303119A (en) * 1979-07-02 1981-12-01 Compagnie Generale Des Etablissements Michelin Process for cooling a metal wire obtained from a liquid jet
EP0181696A1 (en) * 1984-10-08 1986-05-21 Johnson Matthey Public Limited Company Production of metallic material
US4614221A (en) * 1981-09-29 1986-09-30 Unitika Ltd. Method of manufacturing thin metal wire
USRE32925E (en) * 1972-12-26 1989-05-18 Allied-Signal Inc. Novel amorphous metals and amorphous metal articles
US5041512A (en) * 1986-09-04 1991-08-20 E. I. Du Pont De Nemours And Company Melt-formable organoaluminum polymer
US5061663A (en) * 1986-09-04 1991-10-29 E. I. Du Pont De Nemours And Company AlN and AlN-containing composites
US6585151B1 (en) 2000-05-23 2003-07-01 The Regents Of The University Of Michigan Method for producing microporous objects with fiber, wire or foil core and microporous cellular objects
US6609119B1 (en) 1997-03-14 2003-08-19 Dubai Aluminium Company Limited Intelligent process control using predictive and pattern recognition techniques
US20080047736A1 (en) * 2006-08-25 2008-02-28 David Levine Lightweight composite electrical wire
WO2008099058A1 (en) 2007-02-13 2008-08-21 Vivoxid Oy A system and method for manufacturing fibres
CN107324816A (zh) * 2017-07-25 2017-11-07 云南省科学技术院 一种耐高温高纯氧化铝棉的制备方法及制备设备
US11802351B2 (en) * 2016-06-16 2023-10-31 Eurekite Holding B.V. Method of making flexible ceramic fibers and polymer composite

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Publication number Priority date Publication date Assignee Title
US3593775A (en) * 1969-04-11 1971-07-20 Monsanto Co Heat transfer means in inviscid melt spinning apparatus
US3645657A (en) * 1969-07-02 1972-02-29 Monsanto Co Method and apparatus for improved extrusion of essentially inviscid jets
DE3372254D1 (en) * 1982-09-27 1987-08-06 Hermann Budmiger Fire-proof cover
FR2716129A1 (fr) * 1994-02-14 1995-08-18 Unimetall Sa Réservoir de métal liquide pour une installation de coulée continue de fils métalliques très minces.

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3861452A (en) * 1971-05-10 1975-01-21 Establissements Michelin Raiso Manufacture of thin, continuous steel wires
US3884289A (en) * 1972-06-22 1975-05-20 Monsanto Co Inviscid spinning of silicon steel
US3946794A (en) * 1972-06-22 1976-03-30 Monsanto Company Method for producing fine diameter wire from steel-titanium melts
US3945240A (en) * 1972-10-16 1976-03-23 United Technologies Corporation Diffusion bonding separator
USRE32925E (en) * 1972-12-26 1989-05-18 Allied-Signal Inc. Novel amorphous metals and amorphous metal articles
US3856513A (en) * 1972-12-26 1974-12-24 Allied Chem Novel amorphous metals and amorphous metal articles
US3904381A (en) * 1972-12-29 1975-09-09 Monsanto Co Cast metal wire of reduced porosity
US3926248A (en) * 1973-10-11 1975-12-16 Monsanto Co Orifice structure for extruding molten metal to form fine diameter wire
US3889739A (en) * 1973-11-12 1975-06-17 Monsanto Co Pressurized nitrogen to extrude molten steel-silicon alloy
FR2365530A1 (fr) * 1976-09-23 1978-04-21 Owens Corning Fiberglass Corp Procede et appareil de traitement du verre a l'etat fluide afin qu'il ne colle pas
US4303119A (en) * 1979-07-02 1981-12-01 Compagnie Generale Des Etablissements Michelin Process for cooling a metal wire obtained from a liquid jet
US4614221A (en) * 1981-09-29 1986-09-30 Unitika Ltd. Method of manufacturing thin metal wire
EP0181696A1 (en) * 1984-10-08 1986-05-21 Johnson Matthey Public Limited Company Production of metallic material
US5041512A (en) * 1986-09-04 1991-08-20 E. I. Du Pont De Nemours And Company Melt-formable organoaluminum polymer
US5061663A (en) * 1986-09-04 1991-10-29 E. I. Du Pont De Nemours And Company AlN and AlN-containing composites
US6609119B1 (en) 1997-03-14 2003-08-19 Dubai Aluminium Company Limited Intelligent process control using predictive and pattern recognition techniques
US6585151B1 (en) 2000-05-23 2003-07-01 The Regents Of The University Of Michigan Method for producing microporous objects with fiber, wire or foil core and microporous cellular objects
US20080047736A1 (en) * 2006-08-25 2008-02-28 David Levine Lightweight composite electrical wire
US7626122B2 (en) 2006-08-25 2009-12-01 David Levine Lightweight composite electrical wire
US20100071931A1 (en) * 2006-08-25 2010-03-25 David Levine Lightweight composite electrical wire with bulkheads
US8697998B2 (en) 2006-08-25 2014-04-15 David Levine Lightweight composite electrical wire with bulkheads
WO2008099058A1 (en) 2007-02-13 2008-08-21 Vivoxid Oy A system and method for manufacturing fibres
US20100132410A1 (en) * 2007-02-13 2010-06-03 Nypeloe Tiina system and method for manufacturing fibres
US8371142B2 (en) 2007-02-13 2013-02-12 Purac Biochem Bv System and method for manufacturing fibres
EP2118028A4 (en) * 2007-02-13 2014-04-09 Purac Biochem Bv SYSTEM AND METHOD FOR FIBER MANUFACTURE
US11802351B2 (en) * 2016-06-16 2023-10-31 Eurekite Holding B.V. Method of making flexible ceramic fibers and polymer composite
CN107324816A (zh) * 2017-07-25 2017-11-07 云南省科学技术院 一种耐高温高纯氧化铝棉的制备方法及制备设备

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CH472250A (de) 1969-05-15
GB1153577A (en) 1969-05-29
DK121919B (da) 1971-12-20
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