Patent Application
20060290284
The present invention is directed to fluorescent lamps, and more particularly to fluorescent lamps that have a coating of phosphor particles on an exterior surface of the lamp envelope.
The interior of a tubular glass envelope of a prior art fluorescent lamp is typically coated with a mixture of luminescent materials (phosphors) that are selected to produce light with the desired brightness and color characteristics when the lamp is operated. The phosphors emit visible light when stimulated by ultraviolet radiation that is produced when the gas in the envelope is electrically activated. Until recently, this gas has included mercury.
Recent efforts have been made to reduce or eliminate mercury from lighting applications, e.g., fluorescent lamps are being made with a mercury-free gas (meaning no or insubstantial amounts of mercury). Mercury-free fluorescent lamps have a gas discharge with emissions in the near-ultraviolet/blue portion of the electromagnetic spectrum. However, the molecular species present with these gas discharges can react with the phosphors on the interior of the lamp envelope and cause the phosphors to suffer unacceptably high degradation rates.
U.S. Pat. No. 5,866,039 discloses a way of protecting phosphors on an interior surface of a lamp envelope from the plasma contained within the envelope. A luminescent composition applied to the interior surface is a uniform admixture of phosphors and a sufficient amount of a sol-gel compound to substantially encapsulate the phosphors. The phosphors and the sol-gel are first blended together and then uniformly coated on the substrate and dried. The sol-gel dielectric formed from the mixture protects the encapsulated phosphors from the plasma in the device.
Another way to solve the problem is to isolate the phosphors from the gas discharge by placing the phosphors on the exterior of the lamp envelope, instead of the interior. The lamp envelope can be made of SiO2-based glass that transmits light with wavelengths of 300 nm or more to ensure that the phosphors on the exterior are activated by the ultraviolet radiation from the gas discharge. However, this solution causes a further problem because the phosphors on the exterior of the lamp can be removed, destroyed, or physically modified during normal handling of the lamp or by accidental contact.
The inventors have solved this problem by providing a novel lamp having phosphor particles attached to its exterior surface with sufficient strength so that the lamp can be handled as if the phosphor particles were on the interior of the envelope.
Another aspect of the present invention is a novel method of applying and resisting removal of the phosphor particles in which the phosphor particles are held on the exterior surface of the lamp envelope with a residue material from a sol-gel process.
A further aspect of the present invention is a novel mercury-free fluorescent lamp and method of making the lamp in which a layer of phosphor particles are applied to an exterior surface of the lamp envelope as a network of phosphor particles, in which a sol-gel precursor solution is prepared so that, when dried, the solution leaves a sol-gel residue material, such as thin film SiO2, that coats the phosphor particles and resists removal of the phosphor particles from the exterior surface, and in which the envelope with the phosphor particles applied is dipped into the sol-gel precursor solution and the sol-gel precursor solution is dried to form a network of the sol-gel residue material on the exterior surface that meshes with the network of phosphor particles. The sol-gel residue material attaches the phosphor particles to the exterior surface with sufficient strength so that the lamp can be handled as if the layer of phosphor particles were on the interior of the envelope.
These and other features, objects, and advantages of the invention will be apparent to those of skill in the art of the present invention after consideration of the following drawings and description of preferred embodiments.
a is a scanning electron micrograph of a phosphor layer without the sol-gel residue material and
a is a scanning electron micrograph of a cross section of a phosphor layer without the sol-gel residue material and
a is a scanning electron micrograph of a phosphor layer surface without the sol-gel residue material and
With reference now to
The gas in lamp 10 is preferably mercury-free.
The first network of phosphor particles 16 is porous and deposited conventionally on the exterior surface of envelope 12. The exposed surfaces of the phosphor particles and the exposed parts of the underlying exterior surface are conformally coated with a thin film of the material that is formed with a sol-gel process. The resulting sol-gel residue material 18 forms a network that firmly bonds the phosphor particles to each other and strongly bonds the entire network of phosphor particles to the exterior surface of envelope 12. The resulting structure is two interpenetrating networks of phosphor particles 16 and sol-gel residue material 18, with the latter effectively immobilizing the former and attaching the former to the envelope. The sol-gel residue material 18 protects the phosphor particles 16 from being removed, destroyed, or physically modified during normal handling of the lamp or by accidental contact. The residue material 18 also provides the strength, resistance to peeling, adherence and scratch resistance required of the phosphors particles on the exterior of the lamp so that the that the lamp can be handled as if the phosphor particles were on the interior of the envelope.
The lamp is made by a method that includes the steps of applying the first network of phosphor particles 16 to the exterior surface of envelope 12, preparing the sol-gel precursor solution that, when dried, leaves sol-gel residue material 18 described above, dipping envelope 12 with the first network applied to the exterior surface into the sol-gel precursor solution, and drying the sol-gel precursor solution to form the second network of the sol-gel residue material 18 on the exterior surface that meshes within the first network.
The drying step may include the steps of removing a solvent from the sol-gel precursor solution by drying the envelope in an air-filled oven at a first temperature, repeating the dipping and the solvent removing steps, and removing residual solvent by drying the envelope at a temperature higher than the first temperature in the oven.
The lamp and method described herein are relatively inexpensive and compatible with large-scale production methods. Further, the process does not modify the carefully engineered physical and optical properties of the phosphors or significantly diminish the visible light from the lamp.
An example of the method follows and is but one of many possible applications of the method. The sol-gel process is a developed technology and the interactions among the processing variables are fairly will understood, especially in the case of SiO2 sol-gel processes. The process variables include: choice of precursor (typically tetraethoxysilane (TEOS) or tetramethoxysilane (TMOS) for SiO2 sol-gel materials); choice of solvent (typically ethanol (EtOH) or methanol (MeOH) with TEOS or TMOS precursor); catalyst type, identity and concentration; precursor concentration and H2O/precursor molar ratio; deposition conditions (time, temperature, withdrawal and drainage rates, solvent vapor pressure, etc.); solvent evaporation rate; aging conditions (time and temperature after gellation); rate of heating (to eliminate residual solvent, complete the condensation reactions, and eliminate organics) and maximum temperature; use of a subsequent sintering process (to remove last traces of solvent and products of condensation reactions, and to densify the material), and temperature and time profiles. The properties of the sol-gel residue material and thus the network it forms are largely controlled by these processing variables, and one of skill in the art will appreciate how to select values for the variables to achieve the desired result.
In an exemplary embodiment, a layer of phosphor particles (Sylvania type 251 YAG, namely Y3Al5O12:Ce3+) was deposited on a glass substrate by dipping the substrate in an organic dispersion of the phosphors. The substrate was then heated to remove the volatile components of the dispersion. The resulting phosphor layer was between 20 and 25 micrometers thick and was only weakly bonded to the glass substrate (it could be removed by even slight contact). A second substrate was also prepared and was not subjected to the further treatment below in order to compare the treated and untreated phosphor layers.
A sol-gel precursor solution appropriate for an SiO2 type of sol-gel residue material was prepared using TEOS as the metalorganic precursor with ethanol as the solvent, and an acid catalyst (HNO3), with an H2O/precursor molar ratio of 4.0. More particularly, 183 ml of EtOH was added to a solution of 3 ml of HNO3 in 16 ml of H2O. To this was added, with rapid stirring, 50 ml of TEOS.
The phosphor-coated substrate was placed into the precursor solution and withdrawn (this includes processes wherein the phosphor coated substrate is at least partially surrounded by the solution all at once or in steps, such as complete or partial submersion, pouring the solution onto the substrate and misting the solution onto the substrate). Submersion (e.g., dipping the substrate into the solution) is the simplest and preferred technique. The excess solution was drained and the solvent was removed by heating the substrate in an air-filled oven at 125° C. This process was repeated three more times, after which the substrate was placed in the air-filled oven and heated to about 450° C. for two hours to eliminate residual solvent and to complete the condensation reactions leading to the formation of the dense SiO2. The substrate was then cooled in air.
The sol-gel treatment may be carried out either before or after the lamp envelope is filled with the appropriate gas mixture and sealed.
A comparison was made between an untreated phosphor layer and a treated phosphor layer.
The cross sections of the treated and untreated layers were also compared.
In addition, the treated and untreated layers were compared with higher resolution images of the surfaces of the treated and untreated phosphor layers.
The fluorescent yield of the silica-bonded and untreated phosphor layers were tested for fluorescence yield under ultraviolet excitation at 254 nm. The 254 nm radiation was supplied by a Sylvania G8T5 germicidal fluorescent lamp. An Ocean Optics SD2000 portable UV/VIS spectrometer was used to measure the spectrum reflected from the phosphor-coated substrates via a silica optical fiber. To quantify the fluorescence, a region of the spectrum was chosen where the phosphor emission is large and where no major atomic emission interferes. One such region is 565 nm, and the results of tests at this wavelength revealed that the silica-bonded phosphor layer emitted at about 98% of the unprotected phosphor layer.
A conventional cellophane tape test was employed to test both the strength of the phosphor layer and its adherence to the substrate. The tape was placed on the phosphor layer and pressed or “burnished” to ensure complete contact with the phosphors. The tape was then peeled away at right angles to the surface, and the degree of material removal was estimated. This test was applied to both the unprotected phosphor layer and to the sol-gel treated layer. The result was virtually complete removal of the unprotected phosphor from the glass substrate. In contrast, almost none of the protected phosphor layer was removed during the test.
While embodiments of the present invention have been described in the foregoing specification and drawings, it is to be understood that the present invention is defined by the following claims when read in light of the specification and drawings.
