EP0082062B1 - Matériau candoluminescent, son procédé de préparation et son utilisation comme manchon de lampe à gaz - Google Patents

Matériau candoluminescent, son procédé de préparation et son utilisation comme manchon de lampe à gaz Download PDF

Info

Publication number
EP0082062B1
EP0082062B1 EP82402227A EP82402227A EP0082062B1 EP 0082062 B1 EP0082062 B1 EP 0082062B1 EP 82402227 A EP82402227 A EP 82402227A EP 82402227 A EP82402227 A EP 82402227A EP 0082062 B1 EP0082062 B1 EP 0082062B1
Authority
EP
European Patent Office
Prior art keywords
oxide
salts
oxides
calcium
zirconium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82402227A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0082062A1 (fr
Inventor
Aimé Cornu
Anne-Marie Perroud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique CEA filed Critical Commissariat a lEnergie Atomique CEA
Priority to AT82402227T priority Critical patent/ATE12303T1/de
Publication of EP0082062A1 publication Critical patent/EP0082062A1/fr
Application granted granted Critical
Publication of EP0082062B1 publication Critical patent/EP0082062B1/fr
Expired legal-status Critical Current

Links

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

Definitions

  • the present invention relates to a candoluminescent material, usable in particular as a sleeve for gas lamps, and its manufacturing process.
  • the gas lamp sleeves consist of a fine combustible fabric impregnated with a mineral forming, after the first combustion in the gas flame, a network in the solid state giving in the flame an intense phenomenon of candoluminescence.
  • the solid network forms quickly from the first ignition, and it acquires its final shape and a solid texture resistant to mechanical and thermal shocks. To obtain this resistance, it is preferable that the solid network has the cubic crystalline structure of fluorine type.
  • the candoluminescent material to have a high gloss in the visible, it is necessary that it emits little in the infrared, which allows it to reach a high temperature in the practically colorless flame of the gas.
  • the sleeves consist of a mesh of fabric impregnated with a mixture of salts which form, after the first combustion, a fine and divided tissue of thorium oxide containing a little cerium oxide or other oxides, for example an oxide comprising 99.2 mol% of Th0 2 and 0.8 mol% of CeO z .
  • thorium is a naturally radioactive element alpha emitter which has a period of 1 A.1 0 1 years and gives by descent various radioactive isotopes which are alpha emitters, beta or gamma, short-lived, including a radioactive gas, thoron 220, leading to lead 208.
  • a tonne of natural thorium represents approximately 1 Ci of 232 Th and 1 Ci of 228 Th.
  • the quantities of thorium used for the production of sleeves are not negligible since, according to global statistics, the production of candoluminescent sleeves is around 300 million / year. Also, at a rate of 0.3 g of thorium per sleeve, the amount of thorium involved is 100 t / year, which leads to a dissemination of thorium.
  • the impalpable thorium oxide powder is disseminated in the environment.
  • the suppliers of sleeves there are stocks of several tens of kilograms of thorium which emit radioactive thoron, which should impose certain precautions for the handling, storage and transport of these sleeves.
  • thorium can be used as nuclear fuel in fast neutron reactors, it would be preferable to reserve it for this use and to use other materials to make the sleeves of gas lamps.
  • the object of the present invention is precisely a candoluminescent material which can be used as a gas lamp sleeve, which has the advantage of not containing thorium and of exhibiting satisfactory properties.
  • this mixture of oxides has the essential properties to be suitable for lighting, that is to say a strong candoluminescence and a good mechanical solidity in the flame and after its extinction.
  • the aforementioned mixtures of oxides in the molar proportions indicated are poorly adsorbent in the infrared when they are heated in the divided state in a flame, and they produce in the flame an intense white candoluminescence which can be slightly modified the shade by varying the content of iron oxide, praseodymium oxide, manganese oxide and / or cerium oxide.
  • these oxide mixtures exhibit good stability to mechanical and thermal shocks, since they have the cubic crystalline structure of the fluorite type, which alone allows good stability thanks to its isotropic expansion.
  • the chemical stability of the mixture of oxides crystallized in an oxidizing flame is very good, since it is insensitive to carbonation in the cubic crystalline form.
  • the candoluminescent material of the invention has properties equivalent to those of materials based on thorium oxide.
  • the candoluminescent material only comprises a mixture of zirconium oxide and calcium oxide, ie 80 to 90% by moles of zirconium oxide and 10 to 20% by moles d calcium oxide.
  • the candoluminescent material comprises a mixture of zirconium oxide, calcium oxide and aluminum and / or magnesium oxide, ie 80 to 90% by moles of zirconium oxide, 5 to 20% in moles of calcium oxide and either 1 to 5% of aluminum oxide, or 1 to 5% in moles of magnesium and aluminum oxides.
  • compositions of this type mention may be made of the composition containing, by mole, 80% of ZrO 2 , 16% of CaO and 4% of Al 2 O 3 .
  • the mixture comprises zirconium oxide Zr0 2 , calcium oxide CaO, aluminum and / or magnesium oxide and a small addition of a or several oxides chosen from the group comprising iron oxide, manganese oxide, praseodymium oxide and cerium oxide.
  • the mixture of oxides comprising in moles 75 to 90% of zirconium oxide, 5 to 20% of calcium oxide, or 1 to 5% of alumina, or 1 to 5% of oxide d aluminum and magnesium oxide and 0.01 to 1% in total of one or more oxides chosen from the group comprising iron oxide, manganese oxide, praseodymium oxide and oxide cerium.
  • composition of this type mention may be made of the composition 79% ZrO 2 , 16% CaO, 4% Al 2 O 3 and 1% Fe 2 O 3 .
  • iron oxide or other oxides makes it possible to enhance and adapt the color of the lighting.
  • the invention also relates to a process for the preparation of a candoluminescent material meeting the above characteristics.
  • the contents ni of zirconium atoms and n 2 of calcium atoms of the solution are such that the ratio either from 8/10 to 9/10 and that the ratio or from 1/10 to 2/10.
  • the contents ni of zirconium atoms, n z of calcium atoms and n 3 of aluminum atoms of the solution are such that the ratio either from 8/10 to 9/10, the ratio is from 5/100 to 2/10 and the ratio or from 1/100 to 5/100.
  • the addition of an aluminum salt has the secondary effect of softening the impregnated textile, no doubt because its salts are very hygroscopic.
  • the combustion of the textile is carried out in the flame of the gas lamp during the first use of the sleeve.
  • the combustible textile used can be a cotton-based, rayon, acetate or other textile natural or synthetic fibers such as those which are generally used for the production of candoluminescent sleeves.
  • the textile can be in the form of a canvas, gauze, tulle, veil, etc.
  • the best results are obtained with very ventilated fabrics, because textiles generally burn with a large shrinkage.
  • a very ventilated fabric is better than a canvas, because the establishment of the mineral structure is easier and the sleeve is more resistant.
  • the weaving threads of the fabric it is preferable for the weaving threads of the fabric to be made up of extremely fine bundles of threads rather than fairly large strands. In fact, after conversion into oxide filaments, the extremely fine wires are generally less good thermal conductors and lose less energy by conduction.
  • the solutions used for the impregnation can be aqueous solutions or organic solutions, for example alcoholic solutions.
  • the salts used can be salts originating from a mineral or organic acid or alternatively alcoholates.
  • aqueous solutions are used, since it has been found that the mechanical strength of the sleeves obtained was better in this case. This undoubtedly comes from the fact that a better impregnation of the cellulosic tissue is obtained with these solutions, since the cellulose tissues do not have a great affinity for organic products.
  • zirconium calcium, aluminum, magnesium, iron, praseodymium, manganese and cerium salts, salts of mineral acids to obtain an impregnation homogeneity and easy conversion to oxides.
  • salts of mineral acids can be used, nitrates are preferably used, since they have the advantage of breaking down without problems into oxides and being suitable for the preparation of solutions having sufficient concentrations of salt.
  • the impregnated sleeves are subjected to drying, then stored in the dry state, as in the case of sleeves based on thorium oxide.
  • mosquito netting was used as the combustible textile in the form of 5 cm high sleeves.
  • mosquito net small sleeves provided with an asbestos wire at each end allowing their fixing on the lamp.
  • These textile sleeves were then subjected to an impregnation by means of different solutions and this impregnation was carried out by immersing the textile in the solution, then wringing it out using a small painter's roller on a glass plate and allowing it to dry on the same plate at room temperature for 1 h.
  • the other addition elements are also in the form of nitrates.
  • a solution of magnesium nitrate was also used to make sleeves based on zirconium oxide doped with magnesia, and a solution of thorium nitrate was made to make sleeves based on oxide. of thorium.
  • a zirconium butylate solution was used which was mixed with an alcoholic solution of calcium nitrate, in the presence or not of a plasticizer.
  • composition of the various solutions used in the examples is given in the table.
  • the impregnated and dried textile After having placed the impregnated and dried textile on the support of the lamp, it is subjected to a first combustion in the flame of the lamp to transform the impregnated fabric into a network of mixed oxide of cubic crystalline texture, of fluorite type.
  • the properties of the sleeve obtained are then checked with regard to the gloss of the candoluminescent material and the mechanical strength of the sleeve.
  • an optical pyrometer with disappearance of filaments is used and the point is made on the surface of the sleeve to determine its gloss temperature by observing it through a frosted glass such as those which are usually installed on camper lamps.
  • the shine temperature of the sleeve is determined with an offset of approximately 100 ° C.
  • the lime is lower than magnesia from the point of view of shine, because it lowers the shine temperature of the zirconia as can be seen by comparing the results obtained in Examples 2, 3 and 6.
  • the most satisfactory sleeve is that comprising 80% of moles of Zr0 2 , 16% of moles of CaO and 4% of moles of Al 2 O 3 .

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Glass Compositions (AREA)
  • Disintegrating Or Milling (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
EP82402227A 1981-12-11 1982-12-06 Matériau candoluminescent, son procédé de préparation et son utilisation comme manchon de lampe à gaz Expired EP0082062B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82402227T ATE12303T1 (de) 1981-12-11 1982-12-06 Candolumineszierendes material, verfahren zu seiner herstellung und seine anwendung als gasgluehlichtstrumpf.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8123202A FR2518218A1 (fr) 1981-12-11 1981-12-11 Materiau candoluminescent, son procede de preparation et son utilisation comme manchon de lampe a gaz
FR8123202 1981-12-11

Publications (2)

Publication Number Publication Date
EP0082062A1 EP0082062A1 (fr) 1983-06-22
EP0082062B1 true EP0082062B1 (fr) 1985-03-20

Family

ID=9264927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82402227A Expired EP0082062B1 (fr) 1981-12-11 1982-12-06 Matériau candoluminescent, son procédé de préparation et son utilisation comme manchon de lampe à gaz

Country Status (5)

Country Link
EP (1) EP0082062B1 (enrdf_load_stackoverflow)
AT (1) ATE12303T1 (enrdf_load_stackoverflow)
DE (1) DE3262717D1 (enrdf_load_stackoverflow)
FR (1) FR2518218A1 (enrdf_load_stackoverflow)
MT (1) MTP920B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19715413C1 (de) * 1997-04-10 1998-10-15 Auergesellschaft Gmbh Verfahren zur Herstellung eines thoriumfreien Gasglühkörpers sowie mit dem Verfahren hergestellter Gasglühkörper

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532073A (en) * 1983-02-25 1985-07-30 Commissariat A L'energie Atomique Candoluminescent material and its preparation
FR2560604B1 (fr) * 1984-03-02 1986-09-05 Commissariat Energie Atomique Nouveau materiau candoluminescent et son procede de preparation
FR2762003B1 (fr) * 1997-04-15 1999-05-21 Commissariat Energie Atomique Materiau candoluminescent, son procede de preparation et son utilisation dans des manchons durs pour l'eclairage public au gaz
GB9812110D0 (en) 1998-06-06 1998-08-05 Levelrecall Limited Yttrium oxide based gas mantle
EP1331435A1 (de) 2002-01-23 2003-07-30 MSA Auer GmbH Gasglühkörper und Verfahren zu dessen Herstellung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE105172C (enrdf_load_stackoverflow) *
FR403195A (fr) * 1909-01-22 1909-10-27 Vivian Byam Lewes Perfectionnements apportés aux manchons à gaz à incandescence

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19715413C1 (de) * 1997-04-10 1998-10-15 Auergesellschaft Gmbh Verfahren zur Herstellung eines thoriumfreien Gasglühkörpers sowie mit dem Verfahren hergestellter Gasglühkörper

Also Published As

Publication number Publication date
DE3262717D1 (en) 1985-04-25
FR2518218A1 (fr) 1983-06-17
EP0082062A1 (fr) 1983-06-22
MTP920B (en) 1984-02-13
ATE12303T1 (de) 1985-04-15
FR2518218B1 (enrdf_load_stackoverflow) 1984-02-03

Similar Documents

Publication Publication Date Title
EP0082062B1 (fr) Matériau candoluminescent, son procédé de préparation et son utilisation comme manchon de lampe à gaz
US5837011A (en) Method for making metal oxide textiles for spectral emitters
RU2008141689A (ru) Электролюминесцентное устройство
CN1531585A (zh) 具有彩色火焰的蜡烛
EP0159212B1 (fr) Nouveau matériau candoluminescent et son procédé de préparation
US4533317A (en) Yttrium oxide mantles for fuel-burning lanterns
US4532073A (en) Candoluminescent material and its preparation
US575261A (en) Gas-in can descent
JPH03504781A (ja) ガスマントル技術
CN101434877A (zh) 工艺彩焰灯及其燃料
US5124286A (en) Incandescent mantles
CA1206014A (en) Candoluminescent material, its preparation process and its use as a gas lamp mantle
CN1043340A (zh) 彩焰蜡烛及其制造方法
US575262A (en) Gas-incandescent
US5071799A (en) Incandescent mantles
US575263A (en) Gas-incandescent
US5904881A (en) Procedure for preparing a incandescent material and its use in hard mantles for gas lighting of public places
US599018A (en) Angelo simonini
US659515A (en) Incandescent structure suitable for lighting.
AU633876B2 (en) Incandescent mantles
JPS6256200B2 (enrdf_load_stackoverflow)
US588077A (en) Gas-incandescent
JP2983143B2 (ja) ガス灯用マントル
JPS6336033Y2 (enrdf_load_stackoverflow)
SU1237722A1 (ru) Состав дл карбонизации шерст ных текстильных материалов

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT DE GB IT

17P Request for examination filed

Effective date: 19831105

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT DE GB IT

REF Corresponds to:

Ref document number: 12303

Country of ref document: AT

Date of ref document: 19850415

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3262717

Country of ref document: DE

Date of ref document: 19850425

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20011205

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20011212

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20020306

Year of fee payment: 20

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20021205

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20021206

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Effective date: 20021205