EP0962691A2 - Yttriumoxid enthaltender Gasglühkörper - Google Patents
Yttriumoxid enthaltender Gasglühkörper Download PDFInfo
- Publication number
- EP0962691A2 EP0962691A2 EP99304169A EP99304169A EP0962691A2 EP 0962691 A2 EP0962691 A2 EP 0962691A2 EP 99304169 A EP99304169 A EP 99304169A EP 99304169 A EP99304169 A EP 99304169A EP 0962691 A2 EP0962691 A2 EP 0962691A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide
- mol
- mantle
- yttrium
- magnesium
- 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.)
- Granted
Links
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 24
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000292 calcium oxide Substances 0.000 claims abstract description 17
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 241001465382 Physalis alkekengi Species 0.000 abstract description 3
- 230000002285 radioactive effect Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 229910009246 Y(NO3)3.6H2O Inorganic materials 0.000 description 6
- ICSSIKVYVJQJND-UHFFFAOYSA-N calcium nitrate tetrahydrate Chemical compound O.O.O.O.[Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ICSSIKVYVJQJND-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010987 cubic zirconia Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 229910003452 thorium oxide Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- SYUHGPGVQRZVTB-YPZZEJLDSA-N radon-220 atom Chemical compound [220Rn] SYUHGPGVQRZVTB-YPZZEJLDSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- -1 triethanolamine Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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 incandescent low-pressure gas mantles useful for fixed fuel-burning lanterns, such as stationary lamp posts, patio lights or wall-bracket mounted lights. Typically, such mantles are used with gas pressures of about 2.7 KPa (280mm H 2 O gauge). More particularly, the present invention relates to pre-formed (hard) gas mantles.
- incandescent gas mantle depends on a number of factors. Of primary importance is the illumination provided by the mantle (illuminating power and colour), both in absolute terms and in respect of the amount of fuel consumed. Also important is the durability of the mantle both in terms of its physical strength and period of useful light output.
- incandescent gas mantles have been made from thorium oxide with small quantities of cerium oxide and magnesium oxide and are known as Welsbach mantles (see, for example, US 563524). Thorium is radioactive and decays to give, inter alia, thoron-220 (radon-220) and lead. Although the quantity of thorium used in each mantle is small and may be considered to present an insignificant health risk in the finished article, the industrial production of gas mantles uses large quantities of thorium which require careful and expensive handling procedures. Thus, there is a potential health and environmental hazard at manufacturing sites. In addition these compositions are brittle and so may require an additional hardening procedure during manufacture.
- EP 0082062 discloses non-radioactive mantles based on zirconia which contain calcium oxide (10 to 25 mol%), aluminium oxide and magnesium oxide (0 to 5 mol% total), and oxides selected from iron, manganese, praseodymium and cerium (0 to 1 mol% total). Calcium oxide is used to promote a cubic zirconia crystal structure which is desirable for resistance to mechanical and thermal shocks.
- EP(UK) 0159212 discloses mantles based on those described in EP 0082062 in which the calcium oxide is replaced partially or completely by yttrium oxide as the cubic zirconia stabiliser.
- Yttrium oxide is present in the range of 5 to 20 mol%, with magnesium oxide/aluminium oxide (2 to 15 mol%) and one or more of the oxides of iron, chromium, manganese, praseodymium and cerium (0.01 to 1.0 mol% total).
- EP 0101086 discloses gas mantles comprising a host metal oxide (eg. yttrium, thorium, zirconium or rare earth metal oxide), a rare earth metal oxide (different to the host metal oxide) as a radiation modifying dopant, and a strengthening dopant (eg. an oxide of aluminium, magnesium, beryllium or calcium).
- a host metal oxide eg. yttrium, thorium, zirconium or rare earth metal oxide
- a rare earth metal oxide different to the host metal oxide
- a strengthening dopant eg. an oxide of aluminium, magnesium, beryllium or calcium
- GB 2145811 discloses an yttrium oxide based gas mantle mainly for use in portable lanterns which are supplied with high pressure gas from a bottle or cylinder.
- the mantle contains cerium oxide to improve the illuminating power and a small amount of a crystal growth inhibitor such as magnesium oxide and/or aluminium oxide.
- a critical amount of cerium oxide of 1.8 to 3.8 parts per 100 parts of yttrium oxide by weight is essential. This corresponds to a maximum range of 2.3 to 4.8 mol% of the total composition.
- the disclosed quantity of magnesium oxide and aluminium oxide corresponds to 0.54 to 9.9 mol% magnesium oxide and 0.21 to 4.2 mol% aluminium oxide of the total composition.
- the only composition specifically disclosed is unsatisfactory for low pressure gas mantles because it has inadequate light output characteristics and tensile strength (see Table 1).
- pre-formed is used herein to describe a mantle which has been burnt off by the manufacturer of the mantle before sale, the mantle usually being tied onto a ring prior to the burning off.
- the object of the present invention is to provide a low pressure pre-formed gas mantle having good light output, tensile strength and durability.
- a pre-formed low pressure gas mantle having a body comprising: (A) 77.1 to 85.3 mol% yttrium oxide as the predominant metal oxide, (B) 1.4 to 3.1 mol% of at least one lanthanide oxide, (C) 2.2 to 5.0 mol% of at least one of magnesium oxide and aluminium oxide, and (D) 11.1 to 14.8 mol% of calcium oxide, based on the total molar content of (A), (B), (C) and (D).
- the above ratio of components (A), (B), (C) and (D) is critical in obtaining a low-pressure gas mantle which is of high illuminating power and produces a light of satisfactory colour. More particularly, the durability (i.e. length of time over which the mantle can be burnt without significant deterioration of the light output) of mantles according to the present invention is good.
- mantle bodies having this composition are of a sufficient strength that a hardening procedure to avoid rupture of the mantle is not required.
- said body consists only of components (A), (B), (C) and (D).
- component (B) consists of at least one of cerium oxide, praseodymium oxide and erbium oxide and more preferably is cerium oxide.
- Component (C) is preferably magnesium oxide.
- a preferred molar composition range is:
- a highly preferred molar composition is:
- a process for the preparation of a pre-formed low pressure gas mantle including the steps of:-
- Step (ii) may be achieved using ammonia vapour, aqueous ammonia solution, an amine and/or a caustic alkali solution.
- an amine such as triethanolamine
- step (iii) is effected using an aqueous KOH solution (25% by weight) at room temperature, when such loss does not occur.
- the combustible reticulated material may be any woven combustible filamentary material.
- Such filamentary material preferably has a fineness of about 220 to 350 Dtex, with a Dtex of about 330 being particularly preferred.
- Preferably said material is rayon.
- the concentration of the metal salts in step (i) is 25 to 50 % by weight.
- the metal salts are preferably nitrates. It has been found that, at lower concentrations, there is a risk that insufficient metal salt may be absorbed into the reticulated material, resulting in weak mantles. At higher concentrations, the conversion step (ii) tends to be less efficient, which can lead to uneven conversion. In addition, the impregnated material tends to be stiff and it becomes progressively more difficult to achieve the required mantle shape without breakage.
- Knitted tubes of rayon mesh (330 Dtex) are soaked in an impregnating solution of metal nitrates having the following composition:
- the mesh tubes When dry, the mesh tubes are cut and the mantles shaped in a manner known per se. Since no hardening procedure is necessary, the mantles are now tied to ceramic rings by means of a non-combustible yarn, eg. an aramid or asbestos, for health reasons an aramid is preferred.
- a non-combustible yarn eg. an aramid or asbestos
- the rayon is then burnt off, to leave a hard lattice of metal oxides. This is done in a manner known per se, with a powerful flame having a high flow of an air and gas mixture.
- the mantles thus prepared have a molar composition of:-
- the mantles thus prepared have a molar composition of:-
- the mantles thus prepared have a molar composition of:-
- the mantles thus prepared have a molar composition of:-
- the mantles thus prepared have a molar composition of:-
- Example 1 The same method is employed as for Example 1 above, using the following impregnating solution, which has the same molar composition as that disclosed in GB-B-2145811:
- Mantles 1 to 3 and C1 to C3 are indicated in Table 1 below.
- Examples 1 to 3 are superior to Comparative Examples 2 and 3 in terms of average light output, light quality, tensile strength and durability.
- Examples 1 to 3 are comparable to Comparative Example 1 in terms of average light output and light quality, but superior in terms of tensile strength and durability.
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Artificial Filaments (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9812110.6A GB9812110D0 (en) | 1998-06-06 | 1998-06-06 | Yttrium oxide based gas mantle |
| GB9812110 | 1998-06-06 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0962691A2 true EP0962691A2 (de) | 1999-12-08 |
| EP0962691A3 EP0962691A3 (de) | 2000-10-25 |
| EP0962691B1 EP0962691B1 (de) | 2003-05-14 |
Family
ID=10833264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19990304169 Expired - Lifetime EP0962691B1 (de) | 1998-06-06 | 1999-05-28 | Yttriumoxid enthaltender Gasglühkörper |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0962691B1 (de) |
| DE (1) | DE69907806T2 (de) |
| GB (1) | GB9812110D0 (de) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US563524A (en) | 1896-07-07 | Incandescent lighting substance | ||
| EP0082062A1 (de) | 1981-12-11 | 1983-06-22 | Commissariat à l'Energie Atomique | Candolumineszierendes Material, Verfahren zu seiner Herstellung und seine Anwendung als Gasglühlichtstrumpf |
| EP0101086A1 (de) | 1982-08-16 | 1984-02-22 | The Gillette Company | Metalloxidgegenstände, Verfahren zu deren Herstellung und Lichtquellen |
| GB2145811A (en) | 1983-08-29 | 1985-04-03 | Coleman Co | Mantles for lanterns |
| EP1599212A2 (de) | 2003-02-14 | 2005-11-30 | Combinatorx, Incorporated | Kombinationstherapien zur behandlung von immunologisch bedingten entzündlichen erkrankungen |
-
1998
- 1998-06-06 GB GBGB9812110.6A patent/GB9812110D0/en not_active Ceased
-
1999
- 1999-05-28 DE DE69907806T patent/DE69907806T2/de not_active Expired - Fee Related
- 1999-05-28 EP EP19990304169 patent/EP0962691B1/de not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US563524A (en) | 1896-07-07 | Incandescent lighting substance | ||
| EP0082062A1 (de) | 1981-12-11 | 1983-06-22 | Commissariat à l'Energie Atomique | Candolumineszierendes Material, Verfahren zu seiner Herstellung und seine Anwendung als Gasglühlichtstrumpf |
| EP0101086A1 (de) | 1982-08-16 | 1984-02-22 | The Gillette Company | Metalloxidgegenstände, Verfahren zu deren Herstellung und Lichtquellen |
| GB2145811A (en) | 1983-08-29 | 1985-04-03 | Coleman Co | Mantles for lanterns |
| EP1599212A2 (de) | 2003-02-14 | 2005-11-30 | Combinatorx, Incorporated | Kombinationstherapien zur behandlung von immunologisch bedingten entzündlichen erkrankungen |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0962691A3 (de) | 2000-10-25 |
| GB9812110D0 (en) | 1998-08-05 |
| DE69907806T2 (de) | 2004-01-22 |
| DE69907806D1 (de) | 2003-06-18 |
| EP0962691B1 (de) | 2003-05-14 |
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