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WO1993019021A1 - Manchons incandescents - Google Patents

Manchons incandescents Download PDF

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Publication number
WO1993019021A1
WO1993019021A1 PCT/US1992/002248 US9202248W WO9319021A1 WO 1993019021 A1 WO1993019021 A1 WO 1993019021A1 US 9202248 W US9202248 W US 9202248W WO 9319021 A1 WO9319021 A1 WO 9319021A1
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WO
WIPO (PCT)
Prior art keywords
mantle
solution
precursor
erbium
yttrium
Prior art date
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Ceased
Application number
PCT/US1992/002248
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English (en)
Inventor
John P. Edgar
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Individual
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to AU23344/92A priority Critical patent/AU2334492A/en
Publication of WO1993019021A1 publication Critical patent/WO1993019021A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21H—INCANDESCENT MANTLES; OTHER INCANDESCENT BODIES HEATED BY COMBUSTION
    • F21H1/00—Incandescent mantles; Selection of imbibition liquids therefor
    • F21H1/02—Incandescent mantles; Selection of imbibition liquids therefor characterised by the material thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21H—INCANDESCENT MANTLES; OTHER INCANDESCENT BODIES HEATED BY COMBUSTION
    • F21H3/00—Manufacturing incandescent mantles; Treatment prior to use, e.g. burning-off; Machines for manufacturing

Definitions

  • This invention relates in general to incandescen mantles used in lamps burning fuels in gas or liquid form, and in particular to mantles used in portable lamps of thi 15 type.
  • Incandescent mantles became a commercially practicabl product following the introduction by Carl Auer Von Welsbac in 1893 of a mantle having a composition of about 9% thoriu 20 oxide and about 1% cerium oxide. This composition wa determined by experimentation covering a wide range of meta oxides including rare earth elements.
  • Thorium is a naturally occurring radioactive metal. It decay products include alpha and beta radiation, radiu 25 isotopes, and thoron gas, which is an isotope of radon gas Thorium is listed by US government agencies as carcinogenic and its processing is kept under strict governmenta licensing and control.
  • % mantle discarded about 0.3 grams of thorium oxide, which i soft and powdery, is released into the environment in a uncontrolled manner, exposing the user and others to
  • incandescent mantle than the conventional thorium/cerium mantle heretofore provided would enhance the reliability and reduce the maintenance expenses of incandescent lanterns and gaslights, and permit the development of new forms of such devices, not possible with the fragile thorium mantle.
  • zirconium oxide would be a stronger and non-radioactive alternative to thorium oxide as a material for incandescent mantles, a method for the practical production of mantles based on zirconium oxide has been wanting.
  • Nernst US Pat. No. 685,730 describes electric la glowers composed of 85% zirconia and 15% of yttria or oth rare earth oxides.
  • Nernst US Pat. No. 685,732 describ electric lamp glowers composed of 80% zirconia, 10% yttri and 10% erbia.
  • Nernst US Pat. No. 685,733 describes electric lamp glowers composed of zirconia combined with rare earth oxides derived from yttrium containing minerals in their natural-state proportions.
  • the materials were to be mixed with binding agents, compressed into bars or tubes, and fired in a furnace to produce ceramic elements termed glowers for use in Nernst lamps (see Encyclopedia Britannica, p. 669) .
  • the resulting glowers typically have thicknesses of about 1-2 mm, much greater than those of the fibers employed in gas mantles.
  • These lamps made use of the property possessed by certain ceramic materials to be good electrical insulators when cold but good conductors when hot. After pre-heating to initiate conduction, the glower element was raised to, and maintained at, the required temperature by passage of an electric current thus rendering the element an incandescent light emitter.
  • Nernst light was rendered obsolete by the introduction of the tungsten filament lamp, although Nernst glowers are still produced in small quantities as spectroscopic light sources. While the light emitting property of the Nernst glower does not depend on the passage of electric current, and in theory any suitable heat source can be employed to cause the materials of the glower to incandesce, use in conjunction with a gas flame is not known. "Making Ceramics Tougher" (July 27, 1987) MACHINE
  • transformation-toughened ceramic is yttria-stabilized tetragonal zirconia polycrystal (Y-ZTP) , * 5 which is zirconium oxide with the addition of a small percentage of yttrium oxide (8-10% for example) .
  • This ceramic has desirable strength properties, which may be improved further by the addition of a second stabilizing rare earth oxide to eliminate certain temperature degradation
  • composition of the Y- ZTP materials bears a close resemblance to the Nernst glower materials described above, but also, that these materials have not been suggested for use in gas mantles.
  • Another form of toughened ceramic utilizes aluminum oxide toughened with
  • Ceramic fibers are of special value as heat insulating and refractory materials, but their preparation has been difficult due to the brittleness and high melting point of the appropriate materials.
  • a host structure composed of a cellulosic material, such as a woven fabric, is used as a precursor to absorb dissolved metallic compounds after prior dilation of the woven fibers with plain water.
  • the dissolved compounds enter into spaces within the microscopic
  • SUBSTITUTE SHEET referred to as the precursor process for producing ceramic fibers.
  • Example 7 of the above disclosure Column 14, line 67 through Column 15, line 19, describes application of the subject process to a thorium/cerium incandescent mantle commercially manufactured for use in gasoline lanterns.
  • the resulting product was a thoria fiber structure having the desirable properties of strength and flexibility, which should render it suitable for incandescent mantle applications.
  • the Zircar Product Brochure describes an end product of the precursor process which is commercially manufactured under the trade name of Zircar.
  • One version of this utilizes zirconium and yttrium compounds, with hafnium as a second stabilizing agent, to reduce ceramic fibers.
  • Incandescent mantles are not among the products offered by the manufacturers of Zircar. Levy, S. I., Pitman's Common Commodities and Industries;
  • incandescent Lighting Sir Isaac Pitman and Sons Ltd.: London (1922) , pages 75 through 91, describes in some detail the actual processes of incandescent mantle manufacture, which is itself a form of precursor process.
  • a cellulosic yarn usually rayon, is knitted into the form of a tubular webbing which is cut in sections to form precursor mantles. These sections are closed by stitching at one end, leaving the other end open. They are then impregnated by immersion in a solution of salts of thorium and cerium, usually the nitrates. Excess solution is removed and the sections are dried. At this stage the mantle manufacture may be complete in several different ways.
  • the open end is threaded with a length of heat resisting yarn by which means the mantle may be tied to the burner nozzle of the lantern.
  • the mantle is ignited without the fuel gas flowing. This pyrolysis burns away the rayon base yarn and converts the thorium and cerium nitrates into oxides, so forming an oxide skeleton of the original knitted structure. This oxide skeleton is very delicate and easily damaged.
  • the fuel gas is admitted to the burner and ignited, so rendering the mantle incandescent, this also consolidates the oxide skeleton and shapes it to fit the gas flame.
  • the soft mantle described above is attached to a ceramic ring provided with internal lugs which engage with projections on the nozzle of the gaslight burner.
  • the initial pyrolysis procedure is performed on the gaslight exactly as described above for a gasoline lantern (see Mantle Examples Item B) .
  • inverted mantle manufacture is based on the soft mantle and ceramic ring assembly described above, but the pyrolysis is performed during manufacture.
  • the resulting mantle termed a hard or pre-for ed mantle, is intended for use on fixed gaslights, but since the oxide skeleton is very fragile it is dipped in a collodion (nitro ⁇ cellulose) solution and dried. The nitro-cellulose so deposited strengthens the oxide structure for transportation. The collodion deposit is burned off at the consumer's lamp prior to ignition of the fuel gas (see Mantle Examples Item C) .
  • Knitted fabrics are particularly suitable for the fabrication of incandescent mantles since they can be produced directly in one-piece tubular form, and they possess elasticity in both the vertical and horizontal directions, which property aids the shrinking and forming process during pyrolysis, and which property is virtually absent from woven fabrics.
  • That invention provides a mantle comprised of zirconia, yttria and erbia which produces a resulting light output and color comparable for practical purposes to that of traditional thorium mantles. Although that invention is particularly adapted to mantles of inverted form, it is also applicable to other forms.
  • the present invention provides a further improved incandescent mantle which is stronger than conventionally produced mantles,and which produces a resulting light output and color comparable for practical purposes to that of traditional thorium mantles and which is free of radioactive materials.
  • the mantle of the present invention is comprised of zirconia, yttria, erbia and ceria combined in proportions to produce the intended light output and color and a mantle structure of commercially reliable strength.
  • the light output is approximately double that obtained by the mantle of the above-noted copending application.
  • Fig. 1 is a graph indicating the preferred percent by weight range of zirconium content and the preferred range of erbium to yttrium ratios before pyrolization of the mantle
  • Fig. 2 is a graph indicating the preferred range of % moles of zirconium and cerium metals out of the total moles 10 of metal content and the preferred range of erbium to yttrium mole ratios before pyrolization of the mantle; and
  • Fig. 3 is a graph of light output as a function of cerium content in a mantle according to the invention.
  • a fabric precursor mantle structure is prepared from rayon yarn.
  • a preferred form is a tubular webbing comprised of knitted loops. Because considerable shrinkage occurs during subsequent processing, the webbing is fabricated so as to have approximately twice the diameter of the desired
  • a precursor mantle is prepared from a section cut from the knitted tubing. Again because of shrinkage, the selected
  • 25 length of tubing is about twice the length of the desired finished mantle.
  • This precursor tubing section may be tied or sewn if required so as to produce mantles of a form suitable for a particularly intended variety of lamp.
  • the precursor mantle is soaked in plain distilled water. This has the effect of swelling or dilating t the cellulosic fibers so as to promote the imbibition of the metal salts solution into the crystallite structure of the fibers.
  • the initial water soaking is extended over approximately
  • the precursor mantle may be initially placed in a bath of an aqueous solution of the desired metal salts without first presoaking the mantle as described above.
  • the length time of impregnation is approximately 10-15 minutes at a solution temperature of 120°F.
  • One preferred solution is comprised of zirconyl chloride, erbium chloride and yttrium chloride. The acceptable ranges of the percentages by weight before pyrolysis are shown in the drawing Fig. 1.
  • Acceptable ranges of percentages of zirconyl chloride vary from about 60% to 66% zirconyl chloride with the remaining percentage to be made up of a combination of erbium chloride and yttrium chloride at a ratio which varies from about 2.20 to 1 to 2.40 to 1 erbium chloride to yttrium chloride.
  • a most preferred range is comprised of about 62% to 64% zirconyl chloride with the remaining percentage to be made up of a combination of erbium chloride and yttrium chloride at a ratio of about 2.25 to 1 to 2.35 to l erbium chloride to yttrium chloride.
  • erbium in the product mantle is considered desirable since it is believed to act as a second stabilizing agent in the resulting yttrium toughened zirconium oxide ceramic filaments, and it is also believed to behave as an activating agent which enhances the light output beyond that obtained from a formulation of zirconia and yttria alone.
  • SUBSTITUTESHEET corresponding hydroxides, that is, to zirconium hydroxide, erbium hydroxide and yttrium hydroxide.
  • This step serves ' several functions. First, it neutralizes the acidity of the various salts. Second, it preserves the integrity of the 5 mantle fabric as the acidity of the metal salts may cause the mantle fabric to deteriorate. Third, it may assist pyrolysis during the subsequent formation of oxide filaments. Finally, it appears to promote the spreading apart of individual filaments making up rayon yarn thereby increasing exposure
  • the precursor mantle is provided with a means of attachment to a burner nozzle, such as a length of heat resistant yarn stitched around the open end. Additional reinforcement of the mantle where it is attached to the
  • the mantle of the present invention usually does not require added reinforcement except in special situations. This reinforcement may be achieved by impregnation of this zone of the mantle with a metal salt
  • the reinforcing solution does not need to have the same illuminating properties as those used in the light emitting area of the mantle.
  • the precursor mantle is attached to a burner nozzle and
  • An inverted precursor mantle measuring about 2-1/2 inches long and 2 inches in diameter, was prepared in accordance with this invention, using webbing knitted in plain loop stitches from 600 denier rayon yarn.
  • the precursor mantle was then impregnated for 15 minutes at 120°F with an aqueous solution composed of zirconyl chloride in the range of about 62%-64% with the remaining percentage of the solution composed of an erbium/yttrium chloride ratio of about 2.25-2.35 to l. Excess fluid was removed by centrifugation and the sample was dried with warm air.
  • a length of heat resistant yarn was threaded through the fabric forming the open end of the mantle and the mantle was then tied to the burner nozzle of a Coleman propane lantern type 5107C.
  • the mantle was ignited, carbonized and turned black. It then became red hot, and converted to a white ceramic filament form.
  • the mantle became incandescent, emitting a light very similar to the pale yellow/white color of a commercial thorium mantle. Shrinkage during this operation reduced the mantle to about 52% of its former size.
  • the light output when the lantern was burning was comparable for practical purposes to that of a thorium mantle.
  • the mantle of this invention was removed from the lantern and sample strips of ceramic filament fabric were prepared for tensile tests by cementing small sections of thin card as supports at the ends of the strip.
  • the fabric folded flat upon itself on the horizontal axis easily and without breakage, and the rows of knitted filament loops moved vertically over each other without breakage.
  • Vibration tests on the pyrolized mantle showed the mantle of the present invention to be stronger than that of a thorium mantle.
  • An incandescent mantle which is further improved over that described above is fabricated in the presently preferred embodiment as follows.
  • An aqueous solution is comprised of zirconium chloride, erbium chloride, yttrium chloride and cerium nitrate.
  • the acceptable ranges of zirconium and cerium as measured in percent moles of metal out of the total moles of metal content of the solution is shown in the drawing Fig. 2 as well as the effective ratios of erbium content to yttrium content.
  • An acceptable range of percent moles of zirconium is generally from about 69% to 72% and preferably from about 66.55% to 70.55%.
  • An acceptable mole ratio of erbium to yttrium is generally in the range of about 3.23 to 1 to 3.63 to 1 and preferably about 3.38 to 1 to 3.48 to 1.
  • the preferred range of percent moles of cerium metal out of the total moles of metal content is about 1.00% to 5.00%. As shown in Fig. 3, the maximum light output was for a mantle having a cerium content of 3.29 percent moles.
  • An inverted precursor mantle having the same dimensions was prepared in the manner discussed above in relation to Example I.
  • the precursor mantle was impregnated with an aqueous solution of metal salts having proportions of metal indicated in the drawing Fig. 2.
  • a specific mantle made in accordance with this Example II was found to have concentration of the metals in the aqueous solution of 29.9 grams per liter of zirconium, 2.7 grams per liter of yttrium, 17.5 grams per liter of erbium and 2.2 grams per liter of cerium.
  • the pyrolized mantle showed a light output of about two times the light output of the mantle produced according to Example I.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Knitting Of Fabric (AREA)
  • Glass Compositions (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Microscoopes, Condenser (AREA)

Abstract

Manchon incandescent pour lampe à gaz dépourvu de matières radioactives et présentant une plus grande résistance que les manchons produits auparavant. Le manchon ci-décrit comprend de la zircone, de l'yttria, de l'erbine et de l'oxyde cérique, et présente un rendement lumineux et une couleur comparables dans la pratique à ceux des manchons en thorium classiques. Bien que la présente invention concerne plus particulièrement des manchons de forme inversée, elle est également applicable à d'autres types de manchons.
PCT/US1992/002248 1989-01-03 1992-03-18 Manchons incandescents Ceased WO1993019021A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23344/92A AU2334492A (en) 1992-03-18 1992-03-18 Incandescent mantles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US29276789A 1989-01-03 1989-01-03

Publications (1)

Publication Number Publication Date
WO1993019021A1 true WO1993019021A1 (fr) 1993-09-30

Family

ID=23126108

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US1990/000056 Ceased WO1990007478A1 (fr) 1989-01-03 1990-01-03 Manchons incandescents
PCT/US1992/002248 Ceased WO1993019021A1 (fr) 1989-01-03 1992-03-18 Manchons incandescents

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PCT/US1990/000056 Ceased WO1990007478A1 (fr) 1989-01-03 1990-01-03 Manchons incandescents

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EP (1) EP0452419A4 (fr)
JP (1) JPH05501848A (fr)
AU (1) AU633876B2 (fr)
BR (1) BR9007003A (fr)
CA (1) CA2047227A1 (fr)
WO (2) WO1990007478A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1993778A (en) * 1932-12-03 1935-03-12 Celanese Corp Method of making incandescent mantles
US4532073A (en) * 1983-02-25 1985-07-30 Commissariat A L'energie Atomique Candoluminescent material and its preparation
US5071799A (en) * 1989-01-03 1991-12-10 Edgar John P Incandescent mantles
US5124286A (en) * 1989-01-03 1992-06-23 Edgar John P Incandescent mantles

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US685730A (en) * 1899-08-24 1901-10-29 George Westinghouse Material for electric-lamp glowers.
US685732A (en) * 1899-08-24 1901-10-29 George Westinghouse Glower for electric lamps.
US943488A (en) * 1907-03-18 1909-12-14 Thomas Terrell Incandescent mantle.
US1030787A (en) * 1911-09-29 1912-06-25 David J Monosmith Incandescing element.
US3385915A (en) * 1966-09-02 1968-05-28 Union Carbide Corp Process for producing metal oxide fibers, textiles and shapes
US4975044A (en) * 1982-08-16 1990-12-04 Tpv Energy Systems, Inc. Gas mantle technology
FR2560604B1 (fr) * 1984-03-02 1986-09-05 Commissariat Energie Atomique Nouveau materiau candoluminescent et son procede de preparation
US4877553A (en) * 1988-06-06 1989-10-31 Tpv Energy Systems, Inc. Gas mantle technology

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1993778A (en) * 1932-12-03 1935-03-12 Celanese Corp Method of making incandescent mantles
US4532073A (en) * 1983-02-25 1985-07-30 Commissariat A L'energie Atomique Candoluminescent material and its preparation
US5071799A (en) * 1989-01-03 1991-12-10 Edgar John P Incandescent mantles
US5124286A (en) * 1989-01-03 1992-06-23 Edgar John P Incandescent mantles

Also Published As

Publication number Publication date
EP0452419A1 (fr) 1991-10-23
CA2047227A1 (fr) 1990-07-04
AU5041290A (en) 1990-08-01
WO1990007478A1 (fr) 1990-07-12
AU633876B2 (en) 1993-02-11
JPH05501848A (ja) 1993-04-08
BR9007003A (pt) 1991-10-22
EP0452419A4 (en) 1993-08-04

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