Classifications

• • 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
  • C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
  • C03B37/047—Selection of materials for the spinner cups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
  • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
• • 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
  • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
  • C03B37/0805—Manufacturing, repairing, or other treatment of bushings, nozzles or bushing nozzle plates
• • 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
  • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
  • C03B37/083—Nozzles; Bushing nozzle plates
• • 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
  • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
  • C03B37/095—Use of materials therefor

Definitions

• the invention disclosed herein relates to a metallic laminate comprising a refractory metal substrate having an oxygen impervious, precious metal layer intimately bonded thereto by means of hot isostatically pressing the precious metal layer to the refractory metal substrate.
• the present invention provides an article generally free from structural defects having a relatively thick, oxygen impervious, precious metal outer layer intimately bonded to a refractory metal substrate to provide a laminate having good high temperature serviceability.
• the laminate is expediently and economically produced by a technique which surprisingly obviates the need for the use of cost-increasing barrier layers. Additionally, it will be found that such laminates are superior to those produced by ion plating, sputtering, electrodeposition and simple mechanical compression.
• Feeders in the textile art, or fixed bushing art have historically been made from alloys of platinum and rhodium.
• Feeders in the wool art, or rotatable feeders have been produced employing Cobalt based alloys.
• the present invention provides inorganic fiber forming feeders wherein the high temperature strength characti sites of refractory metals are combined with the oxidation resistance of precious metals to produce feeders capable of operating at temperatures higher and for longer periods of time than heretofore commercially practicable.
• This invention pertains to an article comprised of a refractory metal substrate having an oxygen impervious, precious metal layer intimately bonded thereto by means of hot isostatically pressing the substrate and precious metal layer together.
• Such articles are outstandingly adapted as members in numerous apparatus which operate in contact with molten or heat softened glass.
• This invention pertains to a laminated wall for a feeder for supplying molten streams of inorganic material to be atttenuated into filaments
• a refractory metal core having an oxygen impervious, precious metal sheath intimately bonded thereto by hot isostatic pressing, said wall having at least one orifice extending therethrough adapted to pass said molten material therethrough.
• FIGURE 1 is a plan view of a laminate during fabricati on.
• FIGURE 2 is a side view of the laminate at another point during fabrication.
• FIGURE 3 is a side view of the laminate after hot isostatic pressing.
• FIGURE 4 is a semi-schematic front elevational view of a glass textile type fiber forming system.
• FIGURE 5 is a semi-schematic front elevational view of a glass wool or rotary fiber forming system.
• FIGURE 6 is an enlarged cross sectional view of orificed walls like the stream feeders shown in FIGURES 4 and 5.
• FIGURE 7 is an enlarged cross sectional view of orificed walls of stream feeders like those shown in FIGURES 4 and 5.
• FIGURE 8 is an enlarged cross sectional view of a portion of the feeder wall similar to FIGURE 7 having a hollow tubular member inserted therethrough.
• FIGURE 9 is an enlarged cross sectional view of a feeder wall similar to that shown in FIGURE 7 having a hollow tubular member externally attached thereto.
• FIGURE 10 is a cross sectional view of a feeder wall of a fiber forming system as shown in FIGURE 5.
• FIGURE 11 is an enlarged cross sectional view of the mid-flanged eyelet employed in the system shown in FIGURES 12 and 13.
• FIGURE 12 is an enlarged cross sectional view of a portion of the feeder wall during fabrication having a mid-flanged, hollow, tubular member inserted therethrough.
• FIGURE 13 is an enlarged cross sectional view of a feeder wall according to the principles of this invention.
• FIGURE 14 is an enlarged cross sectional view of an orificed wall of a stream feeder like those shown in FIGURES 1 and 2.
• FIGURE 15 is an enlarged cross sectional view of a portion of the feeder wall similar to FIGURE 14 having a hollow tubular member inserted therein.
• an article is produced having good high temperature strength characteristics and is serviceable at elevated temperatures in an oxidizing atmosphere.
• the substrate or core is a refractory metal or alloy.
• refractory metals are selected from the group of materials consisting of molybdenum (Mo), columbium (Cb), tungsten (W), rhenium (Re) , tantalum (Ta), hafnium (Hf), titanium (Ti), chromium (Cr), zirconium (Zr), vanadium (V), manganese (Mn) and alloys thereof.
• the cladding or outer layer is a precious metal or alloy.
• the precious metals are selected from a group consisting of platinum (Pt), palladium (Pd), irridium (Ir), osmium (Os), rhodium (Rh), gold (Au), silver (Ag), and ruthenium (Ru) and alloys thereof.
• compositions for the laminates of the present invention in terms of the economics of fabrication, including material costs, and optimum operating characteristics will vary with the composition of the molten glass with which it is in contact.
• the laminates are used as the orificed bottom wall of a glass feeder, or bushing, for forming fibrous glass products of various glass forming oxide compositions. Normally, the fibrous products are formed at temperatures generally corresponding to the temperatures at which the molten glass has a viscosity of between about log 2.5 and log 3 poise.
• E type glasses are generally known as low alkali, or substantially alkali free, alkaline earth aluminoborosilicates and have temperatures corresponding to a viscosity of log 2.5 between about 2300°F (1260°C) to about 2400°F (1316°C); such glasses usually contain less than about 1 % by weight of alkali metal oxides and may include small amounts, usually less than 1% by weight, of fluorine.
• C type fibers are alkali, alkaline earth aluminoborosilicates having a temperature corresponding to the viscosity (poise) of log 2.5 of about 2300°F (1260°C).
• S and R type fibers, or alkaline earth aluminosilicates have temperatures corresponding to a viscosity of log 2.5 ranging from around 2500°F (1371°C) to about 2800°F (1538°C) depending on the specific formulation.
• refractory metal or metals as used herein, comprehends any of the metals of Groups IVB and VB and VIB (of the Periodic Chart) rhenium (Re) and manganese (Mn) , alloys consisting essentially of such metals and base alloys of any one or more of such metals. It will be apparent that alloy comprehends within its scope, the inclusion of normal impurities as well as the inclusion of conventional nonmetallic materials, e.g., carbon. Especially desirable refractory metals are W, Mo, Cb, Ta and Re. Mo and W, including alloys thereof and base alloys of either or both, are outstandingly adapted for use as the bottom wall of glass feeder when forming fibers of many of the common high volume fibers.
• a preferred alloy is an alloy of Ti , Zr and Mo.
• a TZM alloy is an Mo base alloy and contains effective recrystallization-temperature improving amounts of Ti and Zr; while such alloys consist essentially of Mo, Ti, and Zr it may also include carbon, nitrogen and minor impurities.
• Such TZM alloys perform well as bushing bottom walls when fiberizing glasses, for example, magnesia aluminosilicates, having log viscosity of 2.5 at temperatures of around. 2700°F (1482°C) to about 2800°F (1538°C).
• An especially suitable TZM alloy will consist essentially of up to about 0.6% Ti , up to about 0.15% Zr and the balance being substantially Mo; such alloy may also show less than about 0.02% C and trace amounts of oxygen, hydrogen, nitrogen, iron, nickel and silicon.
• Such TZM alloys relative to Mo show increased hot strength and resistance to recrystallization and are obtainable from AMAX Inc.
• Another alloy suitable for many applications are the so-called Fan-Steel materials like the alloys consisting essentially of Cb, Ta, W and Zr; they are essentially Cb base alloys and more specifically exemplified by FS-85 material.
• the precious metals comprehend Au and Ag as well as the so-called platinum metals, namely, Pt, Pd, Ir, Rh, Ru, Os, and alloys thereof.
• Pt and Pt-Rh alloys have been and presently are, the materials substantially commercially used as bushing bottom walls. It will be found that in accordance with the present invention, such precious metals, e.g., Pt a nd Pt-Rh a l l oys , m ay n o w b e more economically employed to fabricate bushings wh i ch wi l l h av e hi gher high temperature strength, greater creep resistanceand, consequently, increased sag resistance. The impact of this will be readily apparent.
• thematerials for the substrateand sheath can be selected to optimize the system for a number of parameters, such asstrength, durability, creep resustance, temperature serviceability and cost.
• care should betanken inthe preparation of the surfacesof the substrate and the precious metal layer. Any impurities on the surfaces of the substrateand first layer that are to be intimatelybonded together can seriously affect the integrity of the laminate. Such surfaces canbe cleaned byconventional techniques.
• the substrate and first layer are positioned one against the other and are ready to be hot isostatically pressed or "HIP'ed" in a conventional isostatic pressing system.
• the abutting surfaces should generally conform to one another to provide a good bond between the layers.
• hot isostatic pressing is a technique whereby an article is temperature while under a uniform pressure from all directions.
• a chamber is pressurized with an inert gas or fluid, such as argon, so as to provide the uniform (isostatic) pressure and heated by means of electrical resistance elements located therein.
• the HIP'ing temperatureemployed should be lessthan the recrystallization temperature of the coren and theHIP' ing pressure should be greater than the yield strengthof the sheath material at the selected HIP'inf temperature.
• the refractory metal core should be fabricated to the desired shape, and the precious metal sheath should be formed to closely conform to the exterior surface of the core.
• the core and sheath should be thoroughly cleaned and then the core inserted into the sheath. With at least one edge or seam of the sheath remaining unsealed, the sheath containing the core should be "hot vacuum out gased". Hot vacuum out gasing is comprised of heating the core and sheath to an elevated temperature in a vacuum for a period of time to remove any residue or other impurities from the cleaning operations.
• the remaining unsealed edge or edges of the sheath should be welded together to hermetically seal the sheath around the core.
• such edges are electron beam welded since such welding is done in a vacuum.
• laser beam welding could also produce an acceptable article if done in a vacuum.
• the sheath should be checked for leaks or porosity.
• One such test consists of subjecting the article to gaseous pressure in a chamber, e.g., approximately 250 psi (1.72 x 10 6 N/m 2 ) for 1 to 2 hours. Upon removal from the chamber the article is immersed in an alcohol bath. If there are any pores present in the sheath, bubbles will appear in the alcohol.
• the article Assuming the article has satisfactorily passed the leak check test, the article is ready to be hot isostatically pressed to intimately bond the sheath to the core. Proper HIP'ing will produce a diffusion or metallurgical bond.
• the HIP'ing process should preferably have the following parameters. During the HIP'ing process, the temperature should fall within a range from about 2200 to about 2400°F (1204°C - 1316°C).
• the temperature should not exceed the recrystallization temperature of the TZM material which is generally within the range from 2200°F to 3000°F (1204°C to 1649°C) depending upon the amount of cold working of the TZM alloy.
• the pressure exerted should fall within a range from about 10,000 to about 15,000 psi. (6.89 x 10 7 N/m 2 to about 1.03 x 10 8 N/m 2 ), and the article should be maintained at those temperatures and pressures for a period from about 1 to about 3 hours.
• the platinum or platinum alloy plates or sheathing should be oxygen impervious and have a thickness from about 0.005 inches (0.0127 cm) to 0.030 inches (0.0762 cm). However, thinner or thicker sheets may also be employed.
• refractory metal substrate for example TZM
• an acid bath comprised of (by volume) 2.34% of 95-98% sulfuric acid, 15.63% of 69-71% nitric acid, 35.16% of 99-100% acetic acid, 35.16% of 85% phosphoric acid and 11.71% water for 6 minutes at room temperature is sufficient to cleanse the surface of the core.
• the core should be rinsed in water and then in alcohol and then air dried. From FIGS. 1, 2 and 3 it can be seen that a frame or edging 2 is positioned in abutting relationship at the lateral edges of core 1, which is in plate form.
• Strips of precious metal preferably the same material as plates 3 and 4, can be welded together to form frame 2.
• the thickness of the frame 2 should be substantially equal to the thickness of core plate 1, as shown in FIG. 2.
• the core 1, frame 2 and plates 3 and 4 should be cleaned as previously set forth herein.
• first precious metal plate 3 and second precious metal plate 4 which should be of the same material, preferably.
• prelaminate unit is then "hot vacuum out-gassed" as described herein and the remaining edge is electron beam welded to hermetically seal the prelaminate unit around the core 1, thus forming a sheath 6 around core 1. That is, the final edge should be welded in a vacuum to remove gases from the interior of the prelaminate unit.
• the prelaminate unit is ready to be hot isostatically pressed into the laminate 5 or 69 according to the principles of this invention, after passing the leak check as set forth herein.
• a laminated article was produced according to the principles of this invention utilizing one 30 mil thick core of TZM, a molybdenum base alloy, and two 15 mil thick platinum base alloy sheets.
• the sheathing plates were J alloy which is about a 75%/25% alloy of platinum and rhodium, respectively, as is known in the art.
• TZM is a commercially available alloy containing about 0.5% titanium, 0.08% zirconium, 0.015% carbon, and the remainder molybdenum.
• the plates and frame were formed into a sheath to receive the core material by welding along the edges of the plates and frame leaving one edge open for the insertion of the core material into the pocket formed therein.
• the sheath was formed such that it closely conformed to the exterior of the core material.
• the J alloy sheath materials were immersed in aqua regia for 20 minutes at 350°F (177°C) to clean the surface thereof.
• the TZM core was immersed in the aforementioned acid bath for 6 minutes at room temperature.
• both the J alloy sheath and the TZM core were rinsed in water and then alcohol and a-ir dried.
• the sheath was established around the core to form a prelaminate unit.
• the prelaminate unit was then subjected to the hot vacuum out gasing treatment. That is, with one edge of the sheath remaining open, the prelaminate unit was positioned in an autoclave and heated to 2000°F (1093°C) at a vacuum of 1.8 x 10 - 5 torr for approximately one hour for further cleaning.
• the prelaminate unit was placed in a vacuum chamber and the remaining edge was welded to totally enclose or hermetically seal the core within the sheath.
• the welding must take place in a vacuum to remove gas from within the pocket of the sheath for proper bonding.
• electron beam welding the final edge is preferred since electron beam welding is normally done within a vacuum chamber.
• an evacuated chamber employing laser welding may be acceptable.
• the prelaminate unit should be checked for porosity. This was accomplished by subjecting the sealed prelaminate unit to a gaseous helium at a pressure of 250 psi (1.72 x 10 6 N/m 2 ) for 1 to 2 hours. Upon removal from the compressed environment, the sealed prelaminate unit was immersed in alcohol to look for any bubbles that would indicate the presence of a pin hole or porous section. After having passed the leak check test, the prelaminate unit was hot isostatically pressed at a temperature of about 2400°F (1316°C) at about 15,000 psi
• a laminate (1.03 x 10 8 N/m 2 ) for about 1 hour to produce a laminate according to the principles of this invention.
• Such a laminate exhibits the capability to operate at temperatures and stresses much higher than a similar article made solely of either the TZM or platinum alloy or laminates thereof made by other processes.
• H alloy is an alloy comprised of about 90% platinum and about 10% rhodium, as is known in the art. Since the materials have different properties, the parameters for hot isostatically pressing the core and sheath together were different from that in Example I.
• H alloy and TZM laminate it is preferred that the article be HIP'ed at about 2300°F (1260°C) at about 15,000 psi 1.03 x 10 8 N/m 2 ) for about 2 hours. Employing such materials processes, the laminated article also exhibits properties superior to the individual materials and/or other laminates of the same materials formed by other processes.
• EXAMPLE III Using similar steps to the foregoing Examples, a laminated article was produced having a TZM core and a substantially pure or unalloyed platinum sheath.
• the sheathing material in this instance was 99.9+% pure platinum.
• the parameters for HIP'ing were altered to accommodate the differences in sheating material.
• the article was HIP'ed at a temperature of 2200°F (1204°C) at 1250 psi (8.6 x 10 6 N/m 2 ) for 3 hours.
• the laminated article exhibited superior properties over the individual elements and/or laminates produced according to other processes.
• Fansteel 85 is a columbium base alloy having about 60.65% columbium, 27.5% tantalum 11.0% tungsten, and 0.85% zirconium.
• the columbium alloy was immersed in an acid bath containing, by volume, 1.5 parts of 48% hydrofluoric acid, 2 parts of 70% nitric acid, 1 part of 95% sulphuric acid, and 5.5 parts distilled water.
• the platinum was immersed in aqua regia to clean the surface thereof. Both the core and the sheath were subsequently rinsed in water and then in alcohol and then air dried.
• the unalloyed platinum was hot isostatically pressed to the columbium based alloy at 2400°F (1316°C) at 15,000 psi (1.03 x 10 8 N/m 2 ) for about three hours. Accordingly, a good metallurgical bond was produced between the core and the sheath.
• the foregoing laminate was placed in contact with molten glass at about 2400°F (1316°C) with a portion of the laminate extending into the atmosphere. Again, the laminate exhibited superior strength and oxidation resistance.
• Another laminate or article was similarly prepared employing substantially pure or unalloyed tungsten intimately bonded to a platinum base alloy.
• the platinum base alloy otherwise known as J alloy, is comprised of about 75% platinum and about 25% rhodium.
• the precious metal alloy was immersed in aqua regia, rinsed in water and then rinsed in alcohol to prepare the surface thereof.
• the tungsten core was immersed in an acid solution comprised of, by volume, 3 parts of 70% nitric acid, 1 part 48% hydrofluoric acid, and 4 parts distilled water for a period sufficient to cleanse the surface of the core. Subsequently, the core was rinsed in water and then in alcohol.
• the prelaminate unit was hot isostatically pressed as set forth herein.
• the article was then placed in contact with molten glass at 2400°F (1316 °C) for a period of time to establish that such a laminate can provide superior strength and corrosion resi stance.
• the stress factor ( ⁇ E) of the coefficient of the expansion ( ⁇ ) in microinches per inch oF and the modulus of elasticity (E) in million PSI should be as close to the to the stress factor ( ⁇ E) of the coefficient of the expansion ( ⁇ ) and the modulus of elasticity (E) of the precious metal layer or sheath as is possible.
• the thermal stress ratio (R) of the stress factor of the refractory metal ( ⁇ rm Erm) divided by the stress factor of the precious metal layer ( ⁇ pm Epm) should be within the range from about 0.4 to about 1.6. And if the ratio is within the range from about 0.6 to about 1.4, the metals are more compatible. Preferably, however, the ratio should be within the range from about 0.7 to about 1.3 for outstanding results. That is:
• Laminates having thermal stress ratios outside of the broadest range set forth herein are not recommended for extreme high temperature applications. But it is to be understood that such laminates may be appropriate for applications where extremely high temperatures are not encountered. Since the thermal stress generated is also a function of the temperature encountered by the laminate, such stress may be within acceptable limits even if the stress ratio is outside of such range because the temperature encountered is low enough.
• the laminate should also be designed such that the melting point of the refractory metal core and the melting point of the precious metal sheath should be greater than the operating temperature encountered during service.
• the molten glass may be at a temperature of about 2100°F (1149°C); the fiber forming feeder may have an operating temperature generally equal to the temperature of the molten glass. In general, such fiber forming feeders are within ⁇ 100°F ( ⁇ 50°C) of such molten glass.
• a zone of intermetallic compounds will generally exist due to the diffusion of the core and sheath into one another.
• the intermetallic compounds of such zone will exist as a full spectrum through the zone.
• the melting points of such compounds may v ary greatly from either one or both of the core or sheath materials.
• the melting point of the lowest melting compound formed in the interdiffusion zone should also be greater than the operational temperature encountered.
• the melting points for such compounds may be found, in some instances, in the binary phase or constitutional diagrams that have been developed for some of the refractory metals and precious metal alloys.
• the recrystallization temperature of the core be greater than said operational temperature. In most instances, when the material encounters a temperature greater than the recrystallization temperature, the material crystallizes and loses strength.
• Such laminates may be operable at temperatures greater than the recrystallization temprature thereof. If so, the core generally will lose some of its strength, but this can be compensated by modifying the geometric limits of the core to change the section modulus. For example, increasing the thickness of the core plate by about 20% should compensate for core material losing about 35% of its strength.
• laminated articles produced according to the principles of this invention such articles a r e capable of withstanding temperatures of up to 2400°F or 2800°F (1316°C or 1538°C) or above quite readily.
• laminates can be designed to withstand temperatures greater than 3500°F (1927°C), 4000°F (2204°C) or above.
• the melting point of rhenium (Re), a refractory metal has been established at 5755°F ⁇ 35° (3179 C ⁇ 18°C).
• the melting point of osmium (0s), a precious metal has been established at 4900°F ⁇ 350° (2704 C ⁇ 175°C) . Since rhenium and osmium form a solid solution, the melting point of the lowest melting compound formed between osmium and rhenium will be that of osmium which is 4900°F +_350° (2704°C +175°C).
• the thermal stress ratio of the Re/Os laminate is equal to about 1.18. Therefore, an exceptionally high temperature service laminate can be formed therefrom.
• tungsten (V) core clad with osmium (Os) should produce an intermetal 1 ic compound having a melting point of about 4946°F (2730°C), the lowest formed by the series of tungsten and osmium compounds.
• the thermal stress ratio thereof is about 0.61.
• Iridium (Ir) has a melting temperature of 4449°F +5° (2454°C ⁇ 3°C).
• the melting point of the lowest melting compounds of the spectrum of compounds formed between a laminate of rhenium (Re) and iridium is about 5081 F (2805°C). Since the lowest melting point of the three melting points involved is that of unalloyed iridium at 4449°F ⁇ 5° (2454°C ⁇ 3°C), the operational temperature should be less than the melting point of the unalloyed iridium. Further, the stress ratio of rhenium to irridium is about 0.86. Thus, the laminate should provide good high temperature serviceability
• a fiber forming feeder having blind tips employing a laminate produced according to the parameters set forth in Example I was heated to 2200°F (1204°C)in an oxidizing atmosphere in contact with molten glass. E"en after a period in excess of 380 days at such a temperature, there is no external evidence of oxidation of the core or delamination between the core and sheathing material.
• Articles produced according to the principles of this invention are well suited for utilization in high temperature oxidizing environments. As such they are especially suitable for use in contact with molten glass. Specifically, such laminated articles are suitable for fabricating elements employed in glass fiber forming feeders and spinners or rotors; flow channels, electrodes and stirrers for glass furnaces and forehearths; and for fabrication of pumps for pressurizing molten glass.
• the rotor and stator of a progressive cavity type pump can be fabricated from a laminate produced according to the principles of this invention.
• the power supply and control system may have to be adapted to compensate for differences in thermal and electrical resistance between the conventional wall and a laminated wall, if any.
• feeder 10 which is comprised of containment or sidewalls 12 and a bottom, Working or stream defining wall 14, is adapted to provide plurality of Streams of molten inorganic material, such as glass.
• the streams of molten glass can be attenuated into filaments 16 through the action of winder 26.
• size applicator means 18 is adapted to provide a coating or sizing material to the surface of the glass filaments which advance to gathering shoe or means 20 to be gathered into a strand or bundle 22. Strand 22 is then wound into package 24 upon a collet of winder 26.
• FIGURE 4 schematically represents a "textile" fiber forming system.
• rotary system 40 is comprised of a flow means or channel 42 having a body of molten inorganic material 44, such as glass, therein.
• a stream of molten glass 46 is supplied to rotary feeder or rotor 50 from channel 42, as is known in the art.
• Rotor 50 which is adapted to be rotated at high speeds is comprised of a quill 52 and a circumferential stream defining or working wall 54 having a plurality of apertures 71, orifices 77 or passageways 88 therethrough adapted to supply a plurality of streams of molten inorganic material to be fiberized.
• a shroud 56 and circumferential blower or fluidic attenuation means 57 are adapted to fluidically assist in the attenuation of the streams of molten material into fibers or filaments 60.
• a binder material or coating may be applied to fiber 60 by means of binder applicators 58 as is known in the art.
• the fiberization or working walls 14 and 54 of the feeders 10 and 50 should be based upon laminate comprised of a refractory metal core having an oxygen impervious, precious metal sheath intimately bonded thereto by hot isostatic pressing (i.e. HIP) as is disclosed herein.
• HIP hot isostatic pressing
• such refractory metals are selected from the group of materials consisting of molybdenum (Mo), columbium (Cb), tungsten (W), rhenium (Re), tantalum (Ta) , hafnium (Hf), titanium (Ti), chromium (Cr), zirconium (Zr), vanadium (V) and base alloys of such refractory metals.
• Mo molybdenum
• columbium Cb
• W tungsten
• Re rhenium
• tantalum Ta
• titanium (Ti) titanium
• Cr chromium
• Zr zirconium
• vanadium (V) vanadium
• base alloys of such refractory metals for example, an alloy of molybdenum, titanium and zirconium, known as TZM, has been shown to provide a superior laminated wall for a fiber forming feeder when clad with a precious metal alloy of platinum and rhodium
• the precious metals are selected from a group consisting of platinum (Pt), paladium (Pd), irridium (Ir), osmium (Os), rhodium (Rh), ruthenium (Ru), and alloys based on such metals. Included in the platinum alloys are H alloy and J alloy which are alloys of platinum and rhodium of 905/10% and 75%/25% composition, respectively.
• the sheath is formed to closely conform to the exterior of the core, with the surfaces thereof being appropriately cleaned to promote a good metallurgical bond therebetween.
• the core is inserted or enclosed within the sheath to form a prelaminate unit having at least one edge or portion thereof open to the atmosphere to facilitate "out gasing".
• the prelaminate unit is heated in a vacuum to "out gas" the unit.
• the open edge or seams of the unit are welded or sealed in a vacuum, whereupon the unit is ready to be hot isostatically pressed to form laminate 69.
• laminate 69 is formed by hot isostatically pressing core or substrate 7&- to sheath 72 to form laminate 69. At this point, sheath 72 should completely surround the exterior of core 70.
• a pluraltity of apertures 71 extending through laminate 69 or 5 are formed by any suitable means, such a by drilling.
• apertures 71 are formed in the core 70 and sheath 72 subsequent to the HIP'ing operation or procedure to form laminate 69.
• Aperture 71 exposes a portion of refractory metal core 70 which may become exposed to an oxidizing atmosphere during operation.
• the laminate with aperture 71 therethrough still may function if molten glass is continuously maintained in the orifice over the refractory metal core to preclude the oxygen containing atmosphere from contacting the core.
• orifice 71 of laminate 69 should be provided with a precious metal coating or liner 74 sealed or bonded to the sheathing 72 and/or core 70 to prevent the oxidation of the core material.
• Insert or element 74 is, preferably, of the same type of precious metal material as the sheath 72. However, different but compatible materials can be employed.
• element 74 is inserted in laminate 69 whereupon first flange or head 78 and second flange or head 79 are formed therein to abut the exterior surfaces of sheath 72. That is, a portion of sheath 72 is positioned intermediate the core 70 and each flange 78 and 79.
• Insert 74 may be a solid plug or preferably, may be a hollow eyelet or element having an orifice 77 extending therethrough. Orifice 77 is defined by sleeve 76 which is intermediate and contiguous with flanges 78 and 79.
• element 74 is provided as a hollow, precious metal eyelet having one flange such as flange 78 preformed therein. Eyelet 74 is then inserted into aperture 71, and the other flange is formed therein such that flanges 78 and 79 are in firm abutting engagement with the sheath 72.
• element 74 may be welded or sealed to laminate 69.
• flanges 78 and 79 may be electron beam or laser welded to the portion of sheath 72 associated therewith to seal core 70 from the environment or atmosphere surrounding bottom wall 14.
• element 74 is hot isostatically pressed or gas pressure welded to laminate 69 such that sleeve 76 is intimately bonded to sheath 72 and core 70, and such that flanges 78 and 79 are intimately bonded to sheath 72.
• good electrical and thermal conductivity are established through the junction of element 74 and laminate 69.
• the hollow elements 74 may be HIP welded to laminate 69.
• the laminate 69 With the elements 74 inserted in the laminate 69 as shown in FIGURE 6, the laminate 69 is placed inside a sheet metal container having a pressure transmitting media tightly packed between the container and the laminate 69 and in the orifice 77 of each element 74. That is, the pressure transmitting media is tightly packed in all the space within the container not occupied by the laminate 69 and elements 74.
• the pressure transducing or transmitting media can be of the type known in the art such as powdered metal, beaded or granulated glass such as "Vycor,” or amorphous silica.
• orifices 77 are press fit with a solid or fully densified rod of the pressure transducing media, metal or silica, which fluidizes or softens upon the application of heat and pressure during the HIP'ing process as should the rest of the transmitting medium to insure a full application of pressure to the walls of sleeve 76 to intimately bond the exterior of sleeve 76 to core 70 and/or sheath 72 at orifice 77.
• the pressure transducing media should not become so fluid so as to "wick" between the surfaces to be bonded together. Subsequently, the pressure transducing media is removed by any suitable means, such as leaching. It is to be noted, however, that the elements 74 and/or members 84 may be HIP welded to laminate 69 and/or each other in the argon fluid of a conventional HIP'ing system if the flanges 78, 79 and 87 a r e previously hermetically sealed or welded (e.g., EB welded) to laminate 69. That is, the sheet metal box and special pressure transducing media may be dispensed with.
• flanges 78 or 79 are metallurgically bonded to sheath 72 and sleeve 76 is metallurgically bonded to laminate 69 to provide a laminated fiberization wall 14.
• Orifices 77 can be sized to provide the proper passageway adapted to permit molten glass or inorganic material to flow therethrough as either a stationary or rotatable fiber forming system, that is, for textile or wool operation.
• member 84 is of the same material as element 79 and sheath 72.
• tubular member 84 is comprised of a hollow, precious metal shaft 86 having a flange 87 at one end thereof.
• Passageway 88 extends through shaft 86 and flange 87 and is adapted to permit molten glass and/or inorganic material to flow therethrough.
• any portion of member 84 may be attached to element 74 that has been joined to laminate 69.
• flange 87 of member 84 can be electron beam or laser welded to flange 79 to permanently attach tubular member 84 to laminate 69.
• tubular member 84 is HIP welded to element 74 and/or laminate 69 consistent with the method set forth above to provide good electrical and thermal contact from member 84 to laminate 69. That is, passageway 88 should be, preferably filled with a solid rod of a suitable pressure transmitting media; of course, orifice 7 is only occupied by member 84.
• a hollow element 74 may be inserted and flanged or swagged into abutting engagement and then tubular member 84 inserted therein whereupon hollow element 74 and tubular member 84 are bonded together and to laminate 69 substantially simultaneously by means of a single HIP'ing operation.
• Working wall 14 can be combined with sidewalls 12 to form a textile type feeder 10 having a tipless bottom wall.
• a hollow tubular member or tip 84 can be attached to the laminate 69 to form a "tipped" working wall 14 as shown in FIGURE 6.
• the hollow tubular member 84 is also formed of one of the aforementioned precious metals or base alloys thereof, such as platinum.
• fiber forming feeders produced according to the principles of this invention have good "sag” resistance. That is, the fiberization walls should not deform or bow as much as an all precious metal feeder. In some instances "sag” can be substantially eliminated over the life of the feeder. Thus, finshield alignments and the like with respect to the fiberization wall and/or tips can remain essentially fixed over the life of the feeder.
• Laminate 69 can be fabricated as a substantially flat wall to provide a fiberization wall 14, generally, for a textile type feeder, or laminate 59 can be fabricated into a cylindrical fiberization wall 54 having orifices 77 and/or passageway £8 extending radially outward from the axis of rotation thereof, generally, for wool operations. In either case, orifices 77 or passageways 88 should be properly sized to permit the molten glass or inorganic material to flow therethrough in either a stationary or rotatable fiber forming system.
• the circumferential fiberization wall 54 may be formed substantially identical to the system shown in FIGURE 6 except that a circumferential wall 54 would be formed as a hoop instead of a substantially flat bottom wall 14.
• working wall 54 may be adapted to flow the molten glass directly through orifices 71, that is, without tubular member 84 inserted in orifices 71.
• tubular members 84 may be incorporated as set forth above.
• bottom wall 14 is comprised of a laminate 69 or 5 adapted to flow molten glass therethrough.
• core or substrate 170 is provided with a plurality of apertures 172 therethrough by any suitable means, such as drilling.
• An insert or element 174 is positioned in or press fit into each of the apertures 172 in core 170. To ensure a snug fit between the element 174 and core 170 a press fit is preferred.
• the planar end surfaces 173 and 175 of element 174 should be substantially flush or coplanar with the planar surfaces of the core 170. That is, perferably, the plugs are formed having an axial height substantially equal to the thickness of core 170.
• Each element can be a cylindrically shaped solid plug of precious metal adapted to snugly fit within each aperture 172. If the plug is longer than the thickness of core 170, any excess insert extending out of aperture 1-72 is preferably removed.
• sheath 176 is fabricated or formed around core 170.
• Sheath 170 should be formed of a precious metal as disclosed herein.
• the substantially parallel or end surfaces 173 and 175 of each element or plug 174 are intimately bonded to the interior surfaces 177 and 179 of sheath 176 after HIP'ing.
• Each of the end surfaces of each plug being substantially coplanar with the side of sheath 176 associated therewith.
• At least one orifice 178 is formed through element 174, preferably, without exposing any of the refractory metal core 170 to form working wall 14.
• Working wall 14 can be combined with sidewalls 12 to form a textile type feeder 10 having a tipless bottom wall.
• a hollow tubular member or tip 180 can be attached to the laminate 69 to form a "tip-type" working wall 14 as shown in FIGURES 8 and 9.
• the hollow tubular member 180 and element 174 are also formed of one of the aforementioned precious metals or base alloys thereof, such as platinum.
• the shaft 182 of hollow tubular member 180 is positioned within orifice 178 of laminate 69. Further, the flange 184 of member 180 is positioned in abutting engagement with one side of sheath 176 and is subsequently sealed to said sheath 176 by any suitable means such as by electron beam cr laser welding.
• the portion of shaft 182 extending beyond the opposite surface of sheath 76 forms the "tip" and passageway 183 through member 180 is adapted to permit the passage of molten glass or inorganic material therethrough to issue a stream therefrom.
• hollow tubular member 180 can be gas pressure welded or HIP welded to laminate 69 as set forth herein.
• flange 184 is metallurgically bonded to sheath 176, and shaft 182 is metallurgically bonded to element 174 to provide a laminated feeder fiberization wall 14 wherein the tubular member 180 is in good electrical and thermal contact with laminate 69.
• modified laminate 69 having core 170, element 174, sheath 176 fabricated as set forth herein, is provided with a hollow tubular member 180 depending from one side of sheath 176.
• member 180 is attached to the non-glass contacting side of the fiber forming feeder.
• flange 184 can be welded to sheath 176 by a ny suitable means such as resistance, electron beam, laser, or HIP welding.
• a rotary feeder 50 can be fabricated from a laminate 69 comprised of a refractory metal core or substrate 190 intimately bonded to precious metal sheath 196 by means of hot isostatic pressing.
• the fabrication steps for the rotary feeder wall as shown in FIGURE 10 are substantially the same as the foregoing disclosed for feeder 10 wherein aperture 192 is first formed in substrate 190 with element or insert 194 being press fit or snugly positioned therein.
• orifice 198 can be formed in element 194 to permit the passage of molten glass therethrough.
• insert elements 174 and 194 need not be solid plugs of precious metal material, but elements 174 and 194, prior to the insertion thereof in core 170 and core 190, may have passageways 183 and 198 previously established therein. Further, the fiberization wall 54 may be adapted with elements 184 and/cr 194 if desired.
• tubular member 284 is comprised of a sleeve 285 having a projection 286 extending beyond first flange 288. That is, first flange 288 is located intermediate the two ends 293 and 294 of sleeve 285.
• Sleeve 285 defines passageway 291 which is or will be adapted to permit molten glass to flow therethrough.
• Tubular member 284 may have passageway 291 extending from one end to the other or second end 294 may be closed as shown in FIGURE 11. As such, after tubular member 284 is inserted into the laminate 269, according to the principles of this invention second end 294 will then be machined or opened to expose passageway 291 at the second end 294.
• hollow tubular element 284 is a precious metal and preferably is substantially identical with the precious metal sheath material, although different but compatible materials may be employed.
• laminate 69 is comprised core or substrate 270 and precious metal sheath 272 that has been hot isostatically pressed to intimately bond the sheath 272 to core 270.
• Sheath 272 is comprised, at least in part, of first plate 280 and second plate 281 intimately bonded to core 270.
• FIGURES 12 and 13 Only one such aperture 271 and a fragment of laminate 69 are shown in FIGURES 12 and 13.
• aperture 271 is formed in laminate subsequent to the HIP'ing process to form laminate 69.
• aperture 271 which extends through core 270 and sheath 272, may be establish by providing a core and sheath having mating holes which can be registered with respect to one another to establish apertures 271.
• tubular member 284 is inserted in aperture 271 such that first flange 288 is brought into contact or abutting engagement with first plate 280 of sheath 272.
• a portion of sleeve 285 or first end 293 thereof, projects beyond the exterior surface of second plate 281 a distance sufficient to permit second flange 28 to be formed therefrom.
• Flange 289 is formed so as to firmly contact the exterior surface of second plate 281.
• tubular member 284 should be sealed to laminate 69.
• first and second flanges 288 and 289 a re welded to first and second plates 280 and 281 respectively by any suitable welding technique, such as electron beam or laser welding.
• welding should take place in a vacuum to remove any gas from between the wall of orifice 271 and tubular member 284.
• tubular member 284 should be HIP welded or gas pressure bonded to seal tubular member 284 to laminate 69.
• sleeve 285 is intimately bonded to core 270 and sheath 272, and first and second flanges 288 and 289 are intimately bonded to first and second plates 280 and 281 respectively.
• Hollow tubular member 280 can be gas pressure welded or HIP welded to laminate 69 as set forth herein.
• flanges 288 end 289 are metallurgically bonded to sheath 272, and sleeve 285 is metallurgically bonded to core 270 and sheath 272 to provide a laminated feeder fiberization wall 14 wherein the tubular member 284 is in good electrical and thermal contact with laminate 69.
• projection 286 extends outwardly from first plate 280, and generally into the fiber forming zone. While second plate 281 of sheath 272 would normally be placed in contact with a molten glass or inorganic material. Thus, a "tip-type" fiberization wall is produced from a laminate 69 and a unitary member 284.
• laminate 59 is formed by hot isostatically pressing core or substrate 370 to sheath 372 and element 374.
• Sheath 372 and element 374 should completely cover all the exterior surfaces of core 370 to prevent the oxidation of the core during fiberization.
• a plurality of apertures 371, or at least one aperture 371, extending through core 370 are formed by any suitable process, such as by drilling.
• hollow tubular element 374 is inserted or positioned in each of the apertures 371.
• Element 374 may be initially supplied as a solid rod, a hollow tubular sleeve, or a hollow eyelet having a preformed first flange or head 378 along the length thereof.
• flange 378 is at one end of sleeve 376 of element 374.
• element 374 is provided with a preformed firs flange 378, element 374 is swaged or flared to provide a second flange 379 at the opposite end thereof to provide a precious metal liner or grommet for aperture 371 in core 370.
• flanges 378 and 379 are preferably in firm abutting engagement with the exterior surfaces of core 370.
• a precious metal sheath 372 is established around core 370.
• a window or picture frame of precious metal strips are provided in abutting engagement with the lateral edges of the plate-shaped core 370.
• Core 370 having inserts 374 therein and the picture frame of precious metal material are sandwiched between first plate 373 and second plate 375.
• Plates 373 and 375 are preferably of the same precious metal as the window frame and inserts 374.
• core 370, sheath 372 and element 374 should be appropriately prepared for hot isostatic pressing as set forth herein.
• plates 373 and 375 are without any holes extending therethrough prior to laminate formation.
• HIP'ing core 370 and sheath 372 form a laminate 69 having a precious metal element intimately bonded together.
• the element 374 having a first flange 378 at one end and a second flange 379 at the opposite end thereof, flanges 378 and 379 being located intermediate core 370 and sheath 372.
• Tubular member 384 may have passageway 388 incorporated therein prior to the insertion of tubular member 384 within orifice 377 of element 374.
• element 374 is provided as a hollow element having a sleeve 376 positioned intermediate first and second flanges 378 and 379 with an orifice 377 extending therethrough, and plates 373 and 375 are substantially hole free, orifices 377 may be easily located, since recessed dimples generally will form in the plates 373 and 375 at each orifice 377 associated therewith as a result of the HIP'ing.
• passageway 381 as an extension of orifice 377, can be formed through plates 373 and 375 in communication with orifice 377 to permit the molten material to flow therethrough.
• a "tipless" fiber forming feeder can be fabricated.
• a "tip-type" fiber forming feeder may be fabricated, as shown in FIGURE 15, by inserting tubular member 384 within orifice 377 such that shaft 386 extends at least partially therethrough and such that flange 387, which is established at one end of shaft 386 of tubular member 384, is in abutting engagement with sheath 372. Then, tubular member 384 having passageway 388 therethrough should be sealed to sheath 372 and/or element 374.
• Flange 387 of tubular member 384 should be sealed to sheath 372 by welding, such as by electron beam or laser welding.
• tubular member 384 is hot isostatically pressed to laminate 69 such that flange 387 and shaft 386 of tubular member 384 are intimately bonded to element 374 and sheath 372 to provide electrical and thermal conductivity in addition to providing additional protection for core 370 from oxidation.
• Hollow tubular member and/or the inserts can be gas pressure welded or HIP welded to laminate 69, as set forth herein.
• the laminate 69 and all such inserts and/or members are placed inside a sheet metal container having a pressure transmitting media tightly packed between the container and the laminate 69 and in the orifices and/or passageways of each insert and/or tubular member. That is, the pressure transmitting media is tightly packed in all the space within the container not occupied by the laminate 69 and the inserts and the tubular members.
• the element and/or members may be HIP welded to laminate 69 and/or each other if the flanges are hermetically sealed or welded (e.g., EB welded) to laminate 69, in the argon fluid of a conventional HIP'ing system. That is, the sheet metal box and special pressure transducing media may be dispensed with.
• flange 387 is metallurgically bonded to sheath 372
• shaft 386 is metallurgically bonded to element 374 to provide a laminated feeder fiberization wall 14 wherein the tubular member 384 is in good electrical and thermal contact with laminate 69.
• the element and/or member are of the same type of precious metal material as the sheath, although different but compatible materials may be employed.
• Laminate 69 can be fabricated as a substantially flat wall to provide a fiberization wall 14, generally, for a textile type feeder, or laminate 69 can be fabricated into a cylindrical fiberization wall 54 having orifices and/or passageways extending radially outward from the axis of rotation thereof generally for wool operations respectively.
• the invention described herein is readily applicable to the glass industry and, in particular, the glass fiber industry.

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• 1981
  • 1981-10-15 AU AU77259/81A patent/AU546580B2/en not_active Ceased
  • 1981-10-15 JP JP56503393A patent/JPS57501625A/ja active Pending
  • 1981-10-15 DE DE19813152485 patent/DE3152485C2/de not_active Expired
  • 1981-10-15 NL NL8120396A patent/NL8120396A/nl unknown
  • 1981-10-15 FI FI822258A patent/FI822258A0/fi not_active Application Discontinuation
  • 1981-10-15 GB GB08216866A patent/GB2103135B/en not_active Expired
  • 1981-10-15 WO PCT/US1981/001395 patent/WO1982001510A1/en active Application Filing
  • 1981-10-16 CA CA000388124A patent/CA1174812A/en not_active Expired
  • 1981-10-26 BE BE0/206349A patent/BE890870A/fr not_active IP Right Cessation
  • 1981-10-26 FR FR8120065A patent/FR2492806B1/fr not_active Expired
• 1982
  • 1982-06-25 NO NO822160A patent/NO822160L/no unknown
  • 1982-06-28 SE SE8203972A patent/SE450883B/sv not_active IP Right Cessation

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