EP0034494B1 - Lampe de fluorescence de type curviligne - Google Patents
Lampe de fluorescence de type curviligne Download PDFInfo
- Publication number
- EP0034494B1 EP0034494B1 EP19810300626 EP81300626A EP0034494B1 EP 0034494 B1 EP0034494 B1 EP 0034494B1 EP 19810300626 EP19810300626 EP 19810300626 EP 81300626 A EP81300626 A EP 81300626A EP 0034494 B1 EP0034494 B1 EP 0034494B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide
- glass
- fluorescent lamp
- type fluorescent
- tube
- 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
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/30—Vessels; Containers
- H01J61/35—Vessels; Containers provided with coatings on the walls thereof; Selection of materials for the coatings
Definitions
- This invention relates to a curvilinear type fluorescent lamp comprising a curvilinear, light-transmitting sealed tube made of soda-lime glass or low lead glass.
- a circular fluorescent lamp for example, is manufactured in the following manner. First, the inner surface of a straight, light-transmitting glass tube is coated with a phosphor. Then, a stem holding an electrode coated with an electron-emitting substance is sealed to either end of the straight glass tube. The tube is then heated and softened in a furnace. It is bent about a drum, thus being shaped like a circle. Thereafter, the tube is cooled and subsequently evacuated. Finally, an inert gas and mercury are introduced into the tube.
- the light-transmitting, sealed tube of the known curvilinear fluorescent lamp is made of lead glass which contains 24 to 29 percent by weight of lead oxide and which has a low softening point.
- the lead glass is used because a tube made of it can easily be bent to form a circle at low temperatures.
- the glass is expensive because it contains a great quantity of expensive lead oxide.
- a curvilinear type fluorescent lamp will be costly if provided with a curvilinear tube made of lead glass.
- lead is one of the proimnent sources of environmental pollution. Used and broken fluorescent lamps made of lead glass can hardly be disposed of in such a way that the lead does not promote environmental pollution.
- soda-lime glass containing no oxide of lead is used on trial basis as the material of a straight, light-transmitting sealed tube.
- a straight tube of soda-lime glass cannot be bent easily, however, unless it is heated to a higher temperature than a tube of lead glass. This is because soda-lime glass has a higher softening point than lead glass.
- the phosphor laid on the inner surface of the tube is moved into the glass layer. As the tube is cooled, it may be broken by tension generated due to the difference in thermal expansion coefficient between phosphor and soda-lime glass. If not broken at the end of the cooling process, the tube has its strength reduced to an alarming degree. In addition, the radiant efficiency of the phosphor will be reduced, therefore the initial luminous flux of the lamp will be lowered.
- Low lead glass which may be used instead of high lead glass or soda-lime glass is disclosed in Japanese Patent Publication No. 50-15804 and Japanese Patent Disclosure (Kokai) No. 54-60778.
- the low lead glass disclosed therein has a softening point lower than that of soda-lime glass.
- the low lead glass disclosed in Japanese Patent Publication No. 50-15804 contains 1.91 to 10 percent by weight of lead oxide, whereas the low lead glass disclosed in Japanese Patent Disclosure (Kokai) No. 54-60778 contains 4 to 19 percent by weight of lead oxide.
- the low lead glass similar to that disclosed in Japanese Patent Publication No. 50-15804 has such an oxide composition (wt. %) as shown in Table 1.
- the oxide compositions of two examples A, B are shown in Table 2 together with those of the lead glass and soda-lime glass which are used as the materials of the known curvilinear and straight fluorescent tubes respectively.
- the coefficients of linear thermal expansion and softening points of the low lead glasses A and B, the lead glass and the soda-lime glass are shown also in Table 2.
- the inventors thereof made a number of curvilinear type fluorescent lamps of the same dimensions, whose curvilinear tubes were made of different glasses, i.e. low lead glasses A and B, the conventional lead glass and the soda-lime glass. These lamps were tested to determine their characteristics. The test showed that the lamps made of glass A and the lamps made of glass B had an initial lumen comparable with that of the lamps made of the conventional lead glass and better than that of the lamps made of soda-lime glass. However, these lamps were disadvantageous in the following respects:
- Table 3 shows the initial luminous flux, luminous flux at 3000 Hr and luminous flux at 5000 Hr of the curvilinear type fluorescent lamps made by the inventors and subsequently tested. "Initial luminous flux" was detected at the 100th hour of use, in accordance with the regulation JISC7601. All the lamps were circular fluorescent lamps of 100V, 30W. The numerical data given in Table 3 were the average of 50 lamps of every type tested.
- Fig. 1 shows the typical outer appearance of a circular flourescent lamp made of the conventional low lead glass, upon lapse of 3000 hours of continuous use.
- PbO lead oxide
- Binders generally contained in the phosphor for fluorescent lamps contains boron oxide (B 2 0 3 ) '
- the boron oxide therefore is partly in contact with soda-lime glass or low lead glass.
- a portion of the boron oxide therefore melts when the tubes of either soda-lime glass or low lead glass are heated and bent in the furnace.
- the molten borate is fused with the glass, thus forming a Bz03 SiOz-Na20 glass.
- the viscosity of the glass sharply decreases when the glass is heated to about 800°C.
- the inner surfaces as well as their outer surfaces are softened, whereby the phospher moves into them.
- the inner surface portion of each tube has fine cracks due to the difference in thermal expansion coefficient between the phosphor and the glass. The fine cracks seem to weaken the tubes.
- a binder will more strongly bind phosphor particles if it contains barium oxide (BaO). But barium oxide will lower the melting pont of the binder. And the binder may be possibly melt before the glass softens. If this happens, more phosphor particles will move into the glass layer of a tube while the tube is being heated, softened and bent.
- Figs. 2(a), 2(b) and 2(c) it will be described how phosphor particles containing the binder consisting barium calcium borate move into the glass layer of the tube.
- Fig. 2(a) shows the particles 28 of phosphor coated on the inner surface of the glass tube 22 and subsequently baked.
- Fig. 2(b) illustrates the phosphor particles 28, some of which lie in the glass layer of the tube 22 which has been already heated, softened and bent.
- Fig. 2(c) illustrates a part 26 of the portion 24 of the tube 22 which has been used.for 3000 hours (see Fig. 1). Since mercury vapor has flowed into the recesses 30 through the spaces among the phosphor particles 28, the portion 24 of the tube is turned into yellow brown by reaction between dangling bond of glass and this mercury.
- Japanese Utility Model Disclosure (Kokai) No. 53-92976 discloses the technique of providing a metal oxide layer between the inner surface of a curvilinear glass tube and a phosphor layer thereby to reinforce the glass tube. This technique may indeed be effective if the tube is made of glass having a softening point of about 600°C. But the technique does not seem to work if the tube is made of soda-lime glass or low lead glass which has a relatively high softening point ranging from 640°C to 720°C. Japanese Utility Model Disclosure (Kokai). No.
- 53-92976 further teaches that on the metal oxide layer there is formed layer of phosphor containing 0.1 to 4 percent by weight of a B 2 0 3- containing binder and that the binder may be a barium calcium borate binder.
- a barium calcium borate binder melts before soda-lime glass or low lead glass softens which has a high softening point. If the tube according to Disclosure (Kokai) No 53-92976 is made of soda-lime glass or low lead glass, the binder will help many phosphor particles move into the glass layer of the tube and hence will create many dangling bond when the tube is heated, softened and bent. The dangling bond thus formed in great numbers will eventually reduce the performance of luminous flux of the resultant curvilinear fluorescent lamp.
- Japanese Patent Publication No. 35-12085 discloses a binder consisting of CaO and B 1 0 3 in weight ratio of 3:1 to 1:2.
- the binder is mixed with phosphor, and the mixture is coated on the inner surface of a glass tube and subsequently baked, thereby forming calcium borate.
- This technique aims to enhance the strength of the phosphor layer without reducing the luminous efficacy of a fluorescent lamp comprising the glass tube.
- the binder used in the present invention consists chiefly of calcium borate. It is used in order to prevent phosphor particles from entering a layer of soda-lime glass or low lead glass having a high softening point, while a tube made of such glass is being heated, softened and bent, thereby to improve the strength of the glass tube. It is used also in order to suppress diffusion of sodium ions into the glass layer, thereby to enhance the luminous efficacy of the lamp.
- a fluorescent lamp comprising a curvilinear, light-transmitting sealed tube having an electrode attached to either end and coated with electron-emitting substance, said tube being made of soda-lime glass or low lead glass containing 12 percent by weight or less of lead oxide, whose softening point is 640 to 720°C and whose coefficient of linear thermal expansion is 92 to 105 x 10- 7 °C- 1 ; and a phosphor layer formed directly or indirectly, on the inner surface of the tube and containing binder consisting chiefly of calcium borate.
- the lamp of the above-mentioned structure has initial luminous flux comparable with that of a curvilinear type fluorescent lamp made of the conventionally used high lead glass.
- the binder melts at the same time that a straight tube made of said glass is bent, thus suppressing movement of phosphor particles into the glass layer of the tube. Further it is possible with the lamp to prevent sodium ions from difussing from the glass layer while the lamp is being used.
- a metal oxide layer is coated on the inner surface of the tube in an amount of 0.6 to 6.2 mg per square centimeter and is of at least one of the group consisting of aluminum oxide, magnesium oxide, silicon oxide and titanium oxide, the phosphor layer being formed on the metal oxide layer.
- the curvilinear sealed tube of the latter-mentioned lamp is stronger to the use of the metal oxide layer.
- the metal oxide layer effectively works to suppress movement of phosphor particles into the glass layer and thus suppress creating of radical of the glass. Moreover, it prevents the radical (dangling bond), if any, from trapping Hg + , thereby improving the life performance of luminous flux of the lamp. Still further, the metal oxide layer suppresses reaction between Hg and sodium ions diffused from the glass layer.
- the phosphor layer becomes strong and the initial luminous flux of the lamp is improved. Further, if the phosphor containing the binder is coated on the inner surface of the glass tube or on the metal oxide layer coated on the inner surface of the tube in an amount of 2.9 to 3.9 mg per square centimeter, the characteristics of the lamp will be improved.
- the above-mentioned glass contains 12 to 17 percent by weight of sodium oxide (Na 2 0).
- the characteristics of the lamp will be further improved if the above-mentioned glass contains 3 to 8 percent by weight of calcium oxide, which effectively suppresses diffusion of sodium ions.
- both the initial luminous flux and life performance of luminous flux of the lamp will be further enhanced if the calcium borate contained in the binder is obtained from a mixture of CaO and B Z O 3 , the mol ratio of CaO to B 1 0 3 being 1/2 to 3/2 and is deposited on the inner surface of the glass tube or on the metal oxide layer.
- the lamp of either structure mentioned above can be manufactured at a reduced cost. Further, since the glass used contains a small amount of lead, the lamp of this invention is preferred in view of environmental pollution.
- Fifty circular flourescent lamps of the structure shown in Figs. 3 and 4 were made which were provided with phosphor layers of the same thickness. These were 100 V-30 W fluorescent lamps. They were continuously used for 3000 hours. Upon lapse of these hours all the fifty lamps were found to have performance of luminous flux ranging from 92 to 94%. Further, their sealed glass tubes 34 had almost never turned yellow brown, unlike the conventionally used glass tubes inner surfaces of which are coated with phosphor containing barium-calcium borate binder.
- caclium borate should be used in mixing of 0.2 to 2.0 percent by weight with respect to the phosphor. If calcium borate is used in a mixing ratio outside this specific range, the phosphor layer will not be sufficiently strong and the initial luminous flux of the lamp will not be sufficiently high.
- Fig. 5 illustrates the relationship between the strength of phosphor layer and the mixing ratio of a binder.
- Curve a indicates this relationship observed in the above-mentioned another fifty fluorescent lamps according to this invention.
- Curve [3 shows this relationship observed in fifty circular fluorescent lamps of the same size and structure but using a known binder consisting of barium calcium borate.
- Curve y indicates said relationship observed in fifty circular fluorescent lamps of the same size and structure but using a known binder consisting of calcium phosphate and thus having an extremely high melting point.
- the binders used in the lamps of the three categories have such melting point as given in Table 4. This melting point was obtained by detecting the maximum heat-absorption temperature of the respective binders, using differential thermal analysis.
- the phosphor layers of all the fluorescent lamps of the three categories were formed by coating the phosphors on the inner surfaces of the respective glass tubes and subsequently baking the phosphor thus coated.
- the strength of each of the phosphor layer was detected by blowing air at the rate of 0.4 Bar I/sec agains the layer through a nozzle spaced from the layer by 10 mm.
- the strength of the layer is the reciprocal of the ratio of the diameter of the largest flake of phosphor exfoliated from the inner surface of the glass tube to the diameter of the largest flake of known phosphor exfoliated from the inner surface of a tube made of the conventionally used lead glass, said known phosphor containing a binder consisting of barium calcium borate and calcium phosphate in weight mixing ratio of 2:1.
- said reciprocal is given in percentage.
- Fig. 6 illustrates the relationship between the total luminous flux of each fluorescent lamp tested and the mixing ratio of a binder used.
- Curve ⁇ ' indicates this relationship observed in the fifty fluorescent lamps according to this invention.
- Curve /3' shows the relationship observed in fifty fluorescent lamps using the known binder consisting of barium calcium borate.
- Curve y' shows the relationship observed in the fifty fluorescent lamps using the known binder consisting of calcium phosphate.
- the circular fluorescent lamps using calcium borate in a mixing ratio of 0.2 to 2.0% exhibited performance of luminous flux better than than of the fluorescent lamps made of the conventionally used lead glass and exhibited a total luminious flux greater than the fluorescent lamps using the known binder consisting of barium calcium borate or calcium phosphate.
- the fluorescent lamps using calcium borate in a mixing ratio of more than 2.0% exhibited a poor performance of luminous flux, and the phosphor containing calcium borate in a mixing ratio of less than 0.2% was found likely to exfoliate from the inner surface of the glass tubes.
- barium calcium borate has a melting point 44°C to 77°C lower than the softening points of the soda-lime glass, glass A and glass B - all given in Table 2.
- Barium calcium borate if used as a binder, will melt before any of these glasses softens. While the sealed glass tube is being heated, softened and bent, Na + diffused from the glass used will enter the molten barium calcium borate. This may be why the lamps using barium calcium borate as a binder exhibited a total luminous flux smaller than the lamps using calcium borate as a binder.
- calcium phosphate has an extremely high melting point, 1670°C. For this reason, the layer of the phosphor containing calcium phosphate did not adhere to the glass layer so strongly as did the layer of the phosphor containing calcium borate and the layer of the posphor containing barium calcium borate.
- the calcium halophosphate phosphor containing calcium borate in a mixing ratio of 0.2 to 2.0% is coated on the inner surface of the glass tube in an amount of, perferably, 2.9 to 3.9 mg per square centimeter.
- Curve 8 in Fig. 7 shows the relationship between the initial luminous flux of the lamps using calcium borate in a mixing ratio in said range and the amount of the phosphor used (mg/cm 2 ).
- curve ⁇ in Fig. 7 illustrates the relationship between the amount of phosphor used (mg/cm 2 ) and the ratio of generated blackening of the glass tubes.
- the binder be prepared by calcium oxide (CaO) and boric anhydride (B 2 0 3 ) in mol ratio of 1:2 to 3:2.
- a number of 100 V-30 W white circular fluorescent lamps were made which comprises a circular sealed tube made of glass A and phosphor layer coated on the inner surface of the tube and made of the above-mentioned calcium halophosphate phosphor containing a binder prepared by calcium oxide and boric anhydride in mol ratio (CaO/B 2 0 3 ) ranging from 0.28 to 1.82. These fluorescent lamps were put to an impact strength test.
- Fig. 8 shows a cross sectional view of another circular type fluorescent lamp according to this invention.
- this lamp comprises a ring-shaped sealed glass tube 34, metal oxide layer 38 formed on the inner surface of the tube 34 and a phosphor layer 36 formed on the metal oxide layer 38.
- the tube 34 is made of the same low lead glass as the tube of the lamp shown in Figs. 3 and 4.
- the phosphor layer 36 is made of the same phosphor as the phosphor layer of the lamp shown in Figs. 3 and 4.
- the metal oxide layer 38 is made of y-alumina and 0.1 to 1.0 micron thick. The thickness of the layer 38 may be detected by a scanning electron microscope.
- Fifty circular fluorescent lamps of the structure shown in Fig. 8 were made which were provided with phosphor layer of the same thickness within said range and of different mixing ratios of calcium borate contained in the phosphor. These were 100 V-30 W fluorescent lamps. They were continuously used for 3000 hours. Upon lapse of these hours it was found that their sealed glass tubes 34 has turned far lighter yellow brown than those of the lamps shown in Figs. 3 and 4. Further it was found that less phosphor particles were partly embedded in the glass layer while the glass tube was being heated, softened and bent.
- Fig. 9(a) schematically shows metal oxide layer 38 formed on the inner surface of a straight glass tube and phosphor layer 36 formed on the metal oxide layer 38.
- Fig. 9(b) schematically shows the metal oxide layer 38 and the phosphor layer 36 of the glass tube now bent in the form of circle.
- Fig. 9(c) schematically illustrates the metal oxide layer 38 and the phosphor film 36 of the lamp which has been continuously used for 3000 hours.
- far less phosphor particles were partly embedded in the glass layer while the glass tube was being heated, softened and bent.
- no mercury did not enter the recess 30 between the phosphor particles and the metal oxide layer 38. This is perhaps because the creation of dangling bond was effectively suppressed as is proved by the fact that the glass tube did not turn yellow brown.
- the metal oxide layer 38 i.e. y-alumina layer successfully prevented the diffusion of Na + from the glass tube 22.
- the metal oxide layer 38 is 0.1 to 1.0 micron thick according to this invention. This is because it was found that the layer 38 failed to effectively suppress the creating of dangling bond and failed to prevent Na + diffusion when it was less than 0.1 micron thick and that the phosphor layer 36 exfoliated from it when it was more than 1.0 micron thick.
- the metal oxide layer 38 may be formed 0.1 to 1.0 micron thick if p-alumina is used in an amount of 0.6 to 6.2 mg per square centimeter.
- calcium borate be used in an amount of 0.2 to 2.0 percent of the phosphor used.
- the metal oxide layer 38 is 0.5 micron thick
- the phosphor layer 36 will exfoliate from the layer 38 if it is made of phosphor containing less than 0.2 percent by weight of calcium borate. If the phosphor layer 36 is made of phosphor containing more than 2.0 percent by weight of calcium borate, boron oxide will increase and thus promote Na + diffusion despite the metal oxide layer 38 and will wrap up the phosphor particles, whereby the radiant efficiency of the phosphor is inevitably degraded.
- the lamps of category IV which were made of soda-lime or low lead glass and provided with an alumina layer, proved stronger than the lamps of category III which were made of soda-lime glass or low lead glass but not provided with an alumina layer.
- the lamps of categories IV and V the lamps made of soda-lime glass or low lead glass and provided with an alumina layer, proved far stronger than those made of the conventionally used lead glass.
- lamps made of soda-lime glass or low lead glass will become stronger if their phosphate layer contains a binder consisting of calcium borate.
- the metal oxide layer used in the second embodiment of this invention is not limited to an alumina layer. Use may be made of other metal oxide such as magnesium oxide, silicon oxide, titanium oxide and the mixture of them to bring forth the same effect as does alumina.
- soda-lime glass or low lead glass containing 12 percent by weight or less of lead oxide Both embodiments thus far described use soda-lime glass or low lead glass containing 12 percent by weight or less of lead oxide. If the tube is made of soda-lime glass which contains 12 to 17 percent by weight of Na 2 0 or low lead glass which contains the same amount of Na 2 0, the effect of the present invention will become apparent. The more the content of Na 2 0 in the glass is, the more the diffusion of Na + is. Soda-lime glass containing 12 to 17 percent by weight of Na 2 0 and low lead glass containing the same amount of Na 2 0 in addition to 12 percent by weight or less of lead will more effectively prevent diffusion of Na + if they contain further 3 to 8 percent by weight of calcium oxide (CaO).
- CaO calcium oxide
- the phosphor used in this invention contains binder consisting of calcium borate alone. In view of this it is desired that the phosphor be antimony-manganese activated calcium halophosphate.
- the basic idea of this invention may be applied to a U-shaped fluorescent lamp and a W-shaped fluorescent lamp, besides a circular fluorescent lamp.
Landscapes
- Vessels And Coating Films For Discharge Lamps (AREA)
Claims (14)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16578/80 | 1980-02-15 | ||
JP1657880A JPS56114275A (en) | 1980-02-15 | 1980-02-15 | Curved fluorescent lamp |
JP26519/80 | 1980-03-05 | ||
JP2651980A JPS56123661A (en) | 1980-03-05 | 1980-03-05 | Curved fluorescent lamp |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0034494A1 EP0034494A1 (fr) | 1981-08-26 |
EP0034494B1 true EP0034494B1 (fr) | 1984-01-11 |
Family
ID=26352944
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19810300626 Expired EP0034494B1 (fr) | 1980-02-15 | 1981-02-16 | Lampe de fluorescence de type curviligne |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0034494B1 (fr) |
AU (1) | AU530404B2 (fr) |
CA (1) | CA1158704A (fr) |
DE (1) | DE3161854D1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HU214130B (en) * | 1994-03-29 | 1997-12-29 | Ge Lighting Tungsram Rt | Low-pressure mercury vapour discharge lampe pinched on one side |
CN1363113A (zh) | 2000-02-01 | 2002-08-07 | 皇家菲利浦电子有限公司 | 低压水银蒸汽放电灯和小型荧光灯 |
EP1734563A3 (fr) * | 2005-06-17 | 2009-08-12 | Toshiba Lighting & Technology Corporation | Lampe fluorescente ayant une couche protectrice, et dispositif d'éclairage l'utilisant |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2905572A (en) * | 1958-10-02 | 1959-09-22 | Gen Electric | Phosphor coating of improved adherence and preparation thereof |
US3012168A (en) * | 1960-03-23 | 1961-12-05 | Sylvania Electric Prod | Fluorescent lamp |
US3094641A (en) * | 1960-04-27 | 1963-06-18 | Sylvania Electric Prod | Fluorescent lamp |
US3377494A (en) * | 1965-05-24 | 1968-04-09 | Westinghouse Electric Corp | Fluorescent lamp envelope with transparent protective coatings |
GB1176211A (en) * | 1966-05-27 | 1970-01-01 | Matsushita Electronics Corp | A Method of Manufacturing Fluorescent Lamps |
US3599029A (en) * | 1969-10-31 | 1971-08-10 | Gen Electric | Fluorescent lamp envelope with transparent protective coating |
US3890530A (en) * | 1973-01-22 | 1975-06-17 | Gen Electric | Precoat for fluorescent lamp |
-
1981
- 1981-02-11 AU AU67202/81A patent/AU530404B2/en not_active Ceased
- 1981-02-13 CA CA000370811A patent/CA1158704A/fr not_active Expired
- 1981-02-16 EP EP19810300626 patent/EP0034494B1/fr not_active Expired
- 1981-02-16 DE DE8181300626T patent/DE3161854D1/de not_active Expired
Also Published As
Publication number | Publication date |
---|---|
CA1158704A (fr) | 1983-12-13 |
AU6720281A (en) | 1983-03-10 |
AU530404B2 (en) | 1983-07-14 |
EP0034494A1 (fr) | 1981-08-26 |
DE3161854D1 (en) | 1984-02-16 |
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