CN1076768A - Gas mantle - Google Patents

Abstract

A kind of improved gas mantle, it does not contain radioactive substance and more solid more in the past than the lampshade of producing.Lampshade provided by the present invention is made up of zirconia, yittrium oxide, erbium oxide and cerium oxide, and effective light output and color that it produces can compare favourably with traditional thorium lampshade on reality is used.Although the present invention is specially adapted to the lampshade of the form of swinging to, it also is applicable to other form.

Description

Gas mantle

The present invention puts it briefly and relates to gas mantle in the light fixture that is used in burning gases or liquid fuel, especially for the lampshade of this class portable lamp.

Only after nineteen eighty-three Ka Eraoerfengweiersi Bach (Carl Auer Von Welsbach) adopts a kind of lampshade of the cerium oxide composition that contains have an appointment 99% thorium oxide and about 1%, gas mantle just become a kind of commercial can the actual product that uses.This composition is by to determining after the experiment of numerous metal oxide of comprising rare earth element.

Thorium is the radioactive metal that a kind of nature exists.Its disintegration product comprises α and β radiation, radium isotope and thorium emanation, i.e. a kind of isotope of radon gas.It is carcinogenic that thorium is classified as by mechanism of U.S. government, and its processing is under strict governmental approval and the monitoring.

The thorium lampshade is very crisp, usual uses the impact that causes can cause rapid pulverizing and needs are changed continually.Each old lampshade of lampshade of changing is just thrown away, and the low and thorium oxide that be powdery of about 0.3 gram hardness is not discharged in the environment under the situation that have supervision, and this makes user and other people be exposed in the potential healthy public hazards.

Attempt to provide the making great efforts to concentrate on the imagination of walking around this Wei Ersi Bach patent in early days rather than remove thorium oxide of substitute of this thorium/cerium composition, but these patents one are to after date, this thorium/cerium composition has just been adopted widely, be considered to even necessity owing to effectively substitute, thereby except the less change that different manufacturers enjoy alone, in fact this composition does not change.Yet but exist a kind of will the minimizing now, preferably eliminate radioactive substance and unnecessarily be discharged into needs in the global environment.

Also having, a kind ofly can increase the maintenance cost that reliability reduces incandescent hand lamp and gas lamp than existing traditional thorium/more solid gas mantle of cerium lampshade, allow the novel type of this kind equipment of exploitation, then is impossible for the thorium lampshade of fragility.

Although it has been recognized that zirconia replacement thorium oxide can be firmer and "dead" as the gas mantle material, people are seeking the method by zirconia actual production lampshade always.

Narrated the early history of gas mantle in Great Britain's encyclopedia the 1st volume in more detail.Mentioning zirconia and yittrium oxide on 656 pages is the possible substituent of thorium oxide, but owing to their fragility is considered to improper.Zirconia also because of shrinkage and slowly volatilization be excluded.

Lampshade the earliest is vertical, and lampshade is propped up the top that is held in non-luminous flame by the wire framework.Although old-fashioned, this class lampshade still is used for decoration in manufacturing, referring to lampshade sample item D.

The problem of fragility proposes in the United States Patent (USP) 546,792 of Sandra V (Voelker), and this patent proposes a kind of ceramic material filament that is impregnated with rare earths salt, or adds the gas mantle that rare earth oxide forms in the porcelain sill.There is not the document record to show that this gas mantle has obtained the commerciality success.

Early, the United States Patent (USP) of delivering Reed people such as (Reid) 3, mentioned the problem of thorium oxide lampshade fragility in 738,793, this patent system is deposited upon a thorium and cerium oxide on the outer surface by the porous ceramic element of the gas burner of surface combustion principle work.

The manufacturing process complexity of being narrated, it needs deposit multilayer metal oxide in a special substrate (walking to the 3rd row 49 row from the 2nd row 29) to heat-treat processing again, and everything process all needs to carry out under the condition of strictness control.There is no indication patent 3,738,793 incandescent lighting equipment has dropped into production on the industrialness basis.

" communication is adjusted in gas apparatus and space " summarized the present situation of gas mantle in March, 1987, and provides a data to show, and be relatively poor at the light output facet compared with other lampshade compositions of thorium/cerium.Also commented the above-mentioned patent of having mentioned 3,738, disclosed equipment in 793, this patent attempts to apply thorium oxide/cerium oxide mixture in carborundum or zirconic substrate, because it has excellent elevated temperature strength and hot shock resistance thereby is considered to most promising material, but these effort show not succeed and will test sintering process and replace coating.No sign shows it is itself to be used as the incandescent lighting illuminator with this base material in the document.

(Nernst) United States Patent (USP) 685,730 that can this spy has been described filament for electric lamp and has been made up of 85% zirconia and 15% yittrium oxide or other rare earth oxides.Can this special United States Patent (USP) 685,732 have described filament for electric lamp by 80% zirconia, 10% yittrium oxide and 10% erbium oxide form.This special United States Patent (USP) 685,733 of energy has been described filament for electric lamp and has been made up of with the rare earth oxide that naturally occurring ratio was obtained from containing the yttrium ore the zirconia combination.No matter yet be can this spy or any other not mentioned per capita zirconia, yittrium oxide and erbium oxide of in lamp mantle, using up to now.

In this special patent of above-mentioned arbitrary energy, these materials can by binding agent mix be pressed into strip and tubulose and in heating furnace, fire for ceramic component be the so-called illuminator (referring to Great Britain's encyclopedia, 669 pages) that is used for Nernst glower.The illuminator of making generally has the thickness of about 1-2mm, much larger than the thickness of the fiber that is applied in lamp mantle.The characteristic that these lamps have utilized certain ceramic material to have becomes good electrical insulator and become good conductor when being heated when promptly cooling off.After the pipeline start up by preheating conducting, make illuminator rise and maintain needed temperature by the feeding electric current and like this this element is become the incandescent lighting illuminator.

As the light source between Edison's carbon lamp of a kind of carbon arc lamp that belongs to high light and the low light level, Nernst glower is owing to the introducing of tengsten lamp is eliminated, but Nernst glower is still produced as spectroscopic light source on small lot ground.Yet light emission characteristics that can this special illuminator does not depend on the electric current that is flow through, and any theoretically suitable thermal source can both be used for making the material of this illuminator to become white heat, is not reported and use together in conjunction with gas lamp.

A kind of ceramic material new varieties that form based on this quasi-metal oxides of aluminium oxide, zirconia and magnesia discussed in " make pottery more solid " literary composition (84-89 page or leaf) in " Machine Design " on June 27th, 1987.Some are called the pottery that sex change is toughness reinforcing or sex change is stable, molten other metal oxide that the base material oxide is arranged or support by the arm little percentage in this class pottery, make structure be strengthened and stable by reducing the metal oxide particle size, thereby improved ceramic break resistance.

The pottery that a kind of sex change is toughness reinforcing be the tetragonal crystal system zirconia polycrystalline (Y-ZTP) of stabilized with yttrium oxide, it is the yittrium oxide (routine 8-10%) that adds little percentage in the zirconia.This pottery has the intensity property that meets the requirements, it can split the structure phenomenon performance is further improved to eliminate some temperature with adding second kind of stable rare earth oxide, the composition that can notice this Y-ZTP material has and the close analogous components of this special luminiferous material of above-mentioned energy, and these materials did not propose can be used for lamp mantle.The toughening ceramic of another form adopts zirconia and/or the chromium oxide malleableize of aluminium oxide with little percentage.

Ceramic fibre has special value as heat insulation and refractory material, but because the fragility of this suitable material and high-melting-point thereby make its preparation difficulty.The United States Patent (USP) 3 of Kurt Hamrin, 385,915 have disclosed a kind of technology, by a kind of underlying structure that is constituted by for example this fibrid cellulosic material of textile fabric of this technology, formerly textile fabric being expanded with clear water is used as absorbing the parent of the metallic compound that has dissolved then with it, the compound that has dissolved enters into the space of the microstructure of the cellulose fibre that has expanded.Then heat-treat in the atmosphere that can control oxygen in a special heating furnace, the organic fiber pyrolysis obtains amorphous fire-resistant metal oxide structures, is shaped as the shapes of substrates that fibrous material has.The finished product ceramic fibre has tensile strength and pliability.Yet heat treatment need strictly be controlled the temperature and the oxygen content of fiber surrounding atmosphere.At the 7th row 23 row having emphasized in the 8th row 5 row open must to avoid directly the igniting material that flooded otherwise product intensity can be low and crisp.The technology of the disclosure typically refers to the parent technology of producing ceramic fibre.

The above-mentioned example 7 that discloses in the 14th row 67 row the 15th row 19 row is described the application of the production technology that themes as thorium/cerium gas mantle that suitability for industrialized production is used for mantle lantern.The finished product of producing is a kind of thorium oxide fibre structure with desirable intensity and flexility, and these performances make it be suitable for the application of gas mantle.Yet the discussion to this example shows with patentee's Kurt Hamrin, when testing as gas mantle, light output is lower than from one that conventional lampshade obtained, pack the above as lampshade, make it be installed on the burner of hand lamp and lighting before the fuel feed burner, the amorphous value structure of thorium oxide fiber just is returned to the identical crystal form that is produced in the conventional lampshade having used a period of time of after.

Qi Keer (Zirvar) product manual has been introduced the end product of the preceding body technology made from trade name Qi Keer industrialization.Wherein a kind of scheme utilize zirconium and yttrium compound by hafnium as second kind of stabilizing agent to reduce ceramic fibre.In the product that Qi Keer manufacturer provides, there is not gas mantle.

The row dimension, S.I, (the 75th page to 91 pages of the incandescent lightings of pitman's a public goods and an industrial book, Xi Eryisake pitman father and son Co., Ltd, London, nineteen twenty-two), described actual gas mantle manufacturing process in greater detail, itself is a kind of form of preceding body technology.The cellulosic yarn is generally the silk screen that staple fibre is woven into tubular, it is cut into the silk screen section forms the precursor lampshade.The one end knotting sealing of these silk screen sections, the other end is then being opened.The salt that their are immersed thorium and cerium is normally in the nitrate solution.With the excessive solution removal and with silk screen section drying.

Manufacturing at this stage lampshade can be finished in several different modes.For as portable mantle lantern and similar hand lamp (seeing lampshade sample item A) soft or swing to the lampshade of fastening, an end of opening is passed by the heat-resisting yarn of certain-length, lampshade can be may be tied on the burner tip of hand lamp with it.Under the situation that does not have fuel gas to flow through lampshade is lighted during use, pyrolytic is burnt based on the cellulosic yarn of staple fibre and with the nitrate of thorium and cerium and is converted into oxide, so just forms the oxide skeleton of initial braiding structure.This oxide skeleton is very very thin and fragile.After pyrolytic finishes, with fuel gas feeding burner and ignite, thereby make lampshade reach incandescent attitude, this also can make the oxide skeleton solid and its shape and gas flame are adapted.

On the burner that is used in the other types lamp, above-mentioned softer lampshade is attached on the ceramic ring that portion inner flange provided that is engaged by the protuberance with the gas lamp burner.On gas lamp, carry out initial pyrolysis process in fact identical (referring to lampshade sample item B) with aforesaid gas and oil hand lamp.

Another kind of the lampshade product of swinging to is to be made of above-mentioned soft lampshade and ceramic ring assembly, but pyrolytic is what just to have been carried out in the mill.Formed lampshade is called hard or preformed lampshade is to prepare to be used on the fixing gas lamp, but because the oxide skeleton is very crisp, just it is immersed in earlier in collodion (nitrocellulose) solution to be dried again.So the nitrocellulose of deposition has strengthened oxide structure and has been convenient to transportation.The collodion deposit is burnt (referring to lampshade sample item C) in the lamp the consumer before the material gas that ignites.The fiber that wove is particularly suitable for making gas mantle, because they can directly make single tubular, they all have elasticity at vertical and horizontal, the contraction when this characteristic helps pyrolytic and the processing that is shaped, and textile fabric is actually and does not have this character.

The composite braided stitching that is used in the lampshade manufacturing has the intensity that various ways is come oxidation reinforced thing structure.The making that is used for some soft lampshade also has, and the plain loop braiding also claims plain stitch (Jersey knit), or degree of tightness knitting (stockinette knit).The wire loop of this type of weave utilization interconnection makes each ring all have the ring identical with other at vertical and horizontal.Yet the actual strength that improvement brought that the great fragility of thorium oxide has been offset by structure improves.1 the 499th page of " formation of wire loop and the structure of circulary fibres " science and technology volume, George Niu Ensi Co., Ltd (London 1904) has described the structure and the performance of jersey in greater detail.

Theming as of application 07/458,313 a kind of radioactive substance and improved gas mantle more firmer than the lampshade of producing in the past of not containing jointly awaits the reply.This invention provides a kind of lampshade of being made up of zirconia, yittrium oxide and erbium oxide, and effective light output and color that it produces can compare favourably with traditional thorium lampshade on reality is used.Though this invention is suitable for the lampshade of the form of swinging to especially, it also is applicable to other forms.

It is further improved to the invention provides a kind of warp, and than the more solid gas mantle of lampshade that traditional approach is produced, effective light output that it produces and color can compare favourably with the thorium lampshade on reality is used and not contain radioactive substance.Lampshade of the present invention is by zirconia, the lampshade structure to produce needed light output and color and to have industrial reliable intensity that yittrium oxide, erbium oxide and ceria are formed with the certain proportion combination.Light output be almost in the aforementioned co-applications lampshade obtained two times.

More fully narrated in the detailed below in conjunction with the accompanying drawings explanation of the present invention, wherein

Fig. 1 is the preferred range that is illustrated in the ratio of the preferable weight percentage ranges of zirconium content before the pyrolytic lampshade and erbium and yttrium.

Fig. 2 expresses before the pyrolytic lampshade, with respect to the preferred range of the relative yttrium mol ratio with erbium of preferred range of the molar percentage of the zirconium metal of tenor total mole number and ce metal; With

Fig. 3 is the functional arrangement with the variation light output of cerium content in the lampshade of the present invention.

Fiber precursor lampshade structure is thread by modrella, is preferably the socket shape form that is made of pile knit. Owing in following process considerable contraction can take place, made socket shape diameter is about 2 times of after changing into the ceramic wire form required finished product lampshade diameter. Owing to shrink and to help fine and close in the thermal sintering process of ceramic wire thereby be desirable. The precursor lampshade obtains from one section of woven tubular silk screen intercepting. Still because shrinkage, the pipe range that intercepts should be about 2 times of lampshade length of needed finished product. If this original tubular sections needs can be tied or sew in order to produce the lampshade with the form that is suitable for special requirement light fixture kind.

In the technology of preparing the required slaine of suction, the precursor lampshade is immersed in the pure distilled water. This play make cellulose fibre swelling or expansion work in order to promote metal salt solution to enter into the absorption of the microstructure of fiber.

Initial water is immersed in room temperature and continues nearly 2 hours, shifts out from water-bath when it finishes and passes through centrifugal action, blots or additive method is removed unnecessary moisture content.

As another way, the precursor lampshade can place the water-soluble bath of liquid that contains required slaine at the very start and need not to soak in advance as mentioned above lampshade.The time of dipping is about 10-15 minute, and aqueous temperature is 120 °F.A kind of solution preferably comprises zirconyl chloride, erbium chloride and yttrium chloride.Acceptable weight percentage ranges is shown among Fig. 1 before pyrolytic.The acceptable scope of the percentage of zirconyl chloride changes from about 60% to 66%, and remaining percentage is then combined with certain ratio by erbium chloride and yttrium chloride, and this erbium chloride changes in from 2.20 to 1 to 2.40 to 1 scope than the ratio of yttrium chloride.An optimum range comprises about zirconyl chloride of 62% to 64%, and constitutes remaining percentage by erbium chloride and yittrium oxide with about 2.25 to 1 to 2.35 to 1 ratio combination.

In the finished product lampshade, contain erbium and be considered to desirable, can in the yttrium toughened zirconia ceramics silk that generates, play second function of stabilizer because be sure of it, and be sure of that it can be used as and compare the suitableization agent that more can strengthen light output with the prescription that only contains zirconia and yittrium oxide.

Take out the precursor lampshade from dipping bath after, excessive solution is removed with for example centrifugation method, and by hot-air or other easily method make this structure dry rapidly.Remove, and by hot-air or other easily method make this structure dry rapidly.

Dried precursor lampshade reacts with ammoniacal liquor then.This reaction is transformed to their corresponding hydroxide with metal chloride, promptly becomes zirconium hydroxide, erbium hydroxide and yttrium hydroxide.This step plays several effects.Its acidity of different salt that neutralized at first, the second, it can make being kept perfectly property of lampshade fiber because the acidity of slaine can be damaged the lampshade fiber.The 3rd, it can help pyrolytic during the post forming of oxide filament.At last, obviously impel the filament that scatters separately single to form modrella, can increase the exposure of flame by this and strengthen light output.

At this moment the precursor lampshade is provided with the annex of the spout that is hung on burner, and for example a long heat-resisting fiber yarn is sewn to openend.For the thorium lampshade, need strengthen extraly lampshade usually in the place of lampshade attached to the light fixture spout.But lampshade of the present invention does not need to strengthen except special circumstances usually.This reinforcement can obtain to form extra burning sediment with salt solution impregnation by this zone at lampshade.This enhancing solution does not need to have the common the sort of identical photographic property that has in the light launch site as lampshade.

The precursor lampshade is converted into ceramic filament form attached to burner nozzle and by igniting such as the oil/gas mixture that is generally used for producing incandescent attitude.This precursor lampshade can also be ignited under the situation of fuel oil not having.Combustion high temperature is decomposed rayon fiber and is formed carbon, and it is as carbon dioxide-depleted and dissipation then, and meanwhile, slaine becomes the duplicate that the oxide ceramics filaments bundles forms cellulose precursor skeleton the earliest, reduces by half but its size is intimate.

In process, fuse mutually between various oxide compositions like this and obtain Ideal Characteristics by forming the stable zirconia of yttrium/erbium.

The embodiment I

The precursor lampshade of swinging to that goes out constructed in accordance, long approximately for the 2-1/2 inch diameter is 2 inches, adopted the mesh-like fabric that weaves with the plain loop skill of handling needles from 600 modrellas.This precursor lampshade then at 120 °F by containing the aqueous solution dipping 15 minutes that zirconyl chloride in the 62-64% scope of having an appointment and rest solution percentage mixes than erbium/yttrium chloride of 1 ratio by about 2.25-2.35.Excess liquid is by centrifugal removal and with dry this sample of hot-air.

The heat-resisting yarn of one long section is passed the openend that fiber forms lampshade, then this lampshade is tied on the burner nozzle of Coleman (Coleman) propane hand lamp 5107C type.This lampshade is ignited carbonization and blackening.It just becomes red heat then, and is converted into a white pottery filament form.This lampshade becomes incandescent, and the light that sends is similar to the faint yellow/white light of commercial thorium lampshade very much.

Lampshade shrinks to reduce to and is 52% of its original size in this processing.

Light output during the burning of this hand lamp on reality is used can with the comparing favourably of thorium lampshade.Lampshade of the present invention is dismantled from hand lamp there, and is used for extension test by bonding segment thin slice as supporting the sample bar for preparing ceramic filament fiber in strap ends.Fiber can break facing to own folding is flat easily and not along trunnion axis, and plain loop is listed in and mobilely mutually on the vertical direction can break.

The vibration-testing that carries out on the lampshade that pyrolytic is crossed shows that lampshade of the present invention is firmer compared with the thorium lampshade.

In present preferred embodiment, a kind of with respect to above-mentioned work further improved gas mantle can make as described below.Contain zirconium chloride in the aqueous solution, erbium chloride, yttrium chloride and cerous nitrate.The tolerance interval of zirconium and cerium represents to be shown in Fig. 2 by accounting for the hundreds of proportions by subtraction of this metal molar that GOLD FROM PLATING SOLUTION belongs to the total mole number of content, and effective ratio of erbium content and yttrium content also is shown in Fig. 2.The tolerance interval of the molar percentage of zirconium is generally from about 69% to 72% and preferably from about 66.55% to 70.55%.The acceptable molar ratio of erbium and yttrium is generally in about 3.23 to 1 to 3.63 to 1 scope and be preferably in about 3.38 to 1 to 3.48 to 1.The molal quantity percentage optimum range that ce metal accounts for the total mole number of tenor is about 1.00% to 5.00%.As shown in Figure 3, be that the lampshade of 3.29 molar percentages has maximum light output for having cerium content.

The embodiment II

A kind of have a same size swing to the precursor lampshade with the preparation of the method for embodiment I discussed above.This original lampshade is by having the aqueous metal salt dipping of metal ratio as shown in Figure 2.

It is every liter 29.9 gram that the special lampshade of being made according to the embodiment II is found the metal zirconium of concentrating the aqueous solution, and yttrium is every liter 2.7 gram, and every liter 17.5 gram of erbium and cerium restrain for every liter 2.2.

The lampshade that pyrolytic is crossed shows that its light output is about 2 times that export according to the light of the lampshade of making in the embodiment I.

Although people will recognize that of the present inventionly openly provide preferred embodiment of the present invention and have to a certain degree particularity, composition and structural change can be classified as do not break away from below desired main idea of the present invention and scope.

Claims (17)

1, a kind of precursor lampshade that is used for incandescent Gas lamps and lanterns is characterized in that comprising:

A kind of substrate of being crossed by the salt solution impregnation of zirconium, yttrium, erbium and cerium forms corresponding oxide behind the pyrolytic.

2, precursor lampshade as claimed in claim 1 is characterized in that, ce metal account for described solution tenor total mole number 1.0% to 5.0%.

3, precursor lampshade as claimed in claim 1 is characterized in that, the ratio separately of the metal concentration in described salting liquid is every liter 29.9,2.7,17.5 and 2.2 grams.

4, precursor lampshade as claimed in claim 1 is characterized in that, the zirconium metal accounts for described GOLD FROM PLATING SOLUTION and belongs to the molal quantity percentage of content total mole number in 69% to 72 scope.

5, precursor lampshade as claimed in claim 1 is characterized in that, the erbium in the described solution and the mol ratio of yttrium about 3.23-3.63 than 1 scope in.

6, precursor lampshade as claimed in claim 1 is characterized in that, described substrate is the cellulosic fabric substrate.

7, precursor lampshade as claimed in claim 6 is characterized in that, described cellulosic fabric is an artificial silk.

8, precursor lampshade as claimed in claim 1 is characterized in that, described substrate is the socket shape screen fabric that is made of the pile knit thing.

9, a kind of precursor lampshade that is used for incandescent Gas lamps and lanterns is characterized in that comprising:

The substrate that contains the salt of zirconium, yttrium, erbium and cerium forms corresponding oxide behind pyrolytic.

10, a kind of lampshade that is used for incandescent Gas lamps and lanterns is characterized in that comprising zirconia, erbium oxide, yittrium oxide and cerium oxide.

11, lampshade as claimed in claim 10 is characterized in that, described oxide is to come from a kind of solution in proportion, and it comprises:

Zirconates wherein zirconium accounts for the molar percentage of tenor total mole number in 64% to 72% scope;

Cerium salt wherein cerium accounts for the molal quantity percentage of tenor total mole number in 1.0% to 5.0% scope; With

The mol ratio of its erbium/yttrium of salt of erbium and yttrium is about 3.23-3.61 than 1.

12, lampshade as claimed in claim 10 is characterized in that described oxide is to be produced by the respective metal of metal salt solution, and wherein the ratio separately of metal is every liter 29.9,2.7,17.5 and 2.2 grams.

13, a kind of preparation method of being used in the lampshade of incandescent Gas lamps and lanterns is characterized in that comprising step:

With the flammable substrate of the salt solution impregnation of zirconium, erbium, yttrium and cerium;

From described solution, fetch described flammable substrate;

Dry described flammable substrate.

14, it is characterized in that as the method for claim 13 as described in solution comprise:

Zirconates wherein zirconium accounts for the molar percentage of tenor total mole number in 64% to 72% scope;

Cerium salt wherein cerium accounts for the molar percentage of tenor total mole number about 1.0% to 5.0%; With

The mol ratio of its erbium/yttrium of salt of erbium and yttrium is about 3.23-3.63 than 1.

15, as the method for claim 13 it is characterized in that also comprising pyrolytic with as described in solution impregnation cross as described in flammable substrate.

16, a kind of lampshade in the incandescent Gas lamps and lanterns of being used in by the method in the claim 13 preparation.

17, a kind of lampshade in the incandescent Gas lamps and lanterns of being used in by the method in the claim 14 preparation.

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