Photo catalyzer and discharge lamp having a photo catalytic layer

Information

  • Patent Grant
  • 6515422
  • Patent Number
    6,515,422
  • Date Filed
    Friday, May 17, 1996
    28 years ago
  • Date Issued
    Tuesday, February 4, 2003
    21 years ago
Abstract
A photo catalyzer includes a light-transmitting substrate and a catalytic layer provided on the substrate. The catalytic layer substantially includes anatase form of titanium oxide and has a thickness of 0.01 to 0.3 microns. The photocatalyzer can be part of a lamp or lighting fixture arrangement.
Description




BACKGROUND OF THE INVENTION




1. Field of the Invention




The present invention relates to a photo catalyzer and discharge lamp having a photo catalytic layer.




2. Description of the Related Art




Recently, photo catalytic materials, which are activated by receiving ultraviolet rays, have been researched for various purposes.




One known photo catalytic material is titanium oxide. In particular, titanium oxide having anatase form is known to be a good catalytic material. Titanium oxide is a semiconductor having a forbidden band width of about 3.0 eV. Electron and hole mobilization occur in the titanium oxide when it absorbs ultraviolet rays having sufficient energy to cause an excited state. The energy is equivalent to a wavelength of about 410 nm. Radiation generated by conventional lamps, such as fluorescent lamps, incandescent lamps and high intensity discharge lamps include such ultraviolet rays which excite the titanium oxide. When energized, “holes” move on a surface of the titanium oxide. The holes attract electrons of a material in contact with the surface to oxidize it. The holes extract electrons from the material which correspond to the energy of the forbidden band width. The titanium oxide can be used as deodorizer and also used as a catalyzer to decompose a source of bad smell, such as acetaldehyde, methy-methylation-butane, hydrogen-sulfide ammonia and so on. It can also be utilized as a sterilizer in sewage disposal plants, hospitals and other places.




Japanese Laid Open Patent Application No. 1-169866 discloses a catalyzer having a layer of titanium oxide coated on the outer surface of an ultraviolet lamp. The bulb of the lamp is made of quartz glass so as to directly transmit a resonance line of mercury at 254 nm plus small additions of other ultraviolet lines such as 185 nm. The titanium oxide layer coated on the lamp operates as a photo catalyzer due to a catalytic reaction that occurs when the titanium oxide layer receives ultraviolet radiation emitted by the lamp.




Similarly, Japanese Laid Open Patent Application No. 6-304480 discloses a lamp for decomposing ethylene. The lamp is coated with a titanium oxide layer of 2 microns thickness or more.




Japanese Laid Open Patent Application No. 6-278241 discloses plate glass using for a pane. The glass plate is coated metal oxide material of several microns thickness so that the glass plate occurs a catalytic reaction when it transmits solar lays.




Japanese Laid Open Patent Application No. 7-111104 discloses a lighting fixture having a light-transparent cover coated metal oxide thereon.




However, in those prior arts, ultraviolet rays are almost all absorbed during the ultraviolet rays transmission through the titanium oxide layer. Therefore, the amount of ultraviolet rays reaching the outer surface of titanium oxide layer becomes low. As a result, it is not able to oxidize materials attached on the outer surface thereof, because there are little holes around the outer surface. Furthermore, as the transmission factor within visible light range is reduced based on the titanium oxide layer, the amount of light which transmits through the layer is reduced. Therefore, the luminous flux transmitted or radiated through the plate glass, the lighting fixture or the lamp becomes lower.




SUMMARY OF THE INVENTION




Accordingly, a primary object of the present invention is to provide a catalyzer that provides sufficient oxidation of materials in contact with a surface of the catalyzer while still providing a sufficient transmission factor.




A photo catalyzer according to the present invention has a light-transmitting substrate. A catalytic layer is provided on the substrate. The catalytic layer substantially includes anatase form of titanium oxide and has thickness of 0.01 to 0.3 microns.




Second, the present invention provides a photo catalytic apparatus including the photo catalyzer described above and a light source radiating ultraviolet radiation having a wavelength below 410 nm. The light source is provided on the other side of the substrate from the catalyzing material.




Third, the invention provides a light source having a light-transmitting envelope, means for radiating light including ultraviolet rays and a photo catalytic layer coated on an outer surface of the envelope.




Fourth, the present invention provides a lighting fixture including the light source described above and a luminaire housing the light source.




The present invention also provides a lighting apparatus including the lighting fixture described above and an operating circuit supplying electric power to the light source.




Various embodiments of the invention will be described in detail with reference to the following drawings.











BRIEF DESCRIPTION OF THE DRAWINGS




The invention will be described in more detail below in conjunction with the following drawings of which:





FIG. 1

is a detailed portion cross sectional and broken view of the catalyzer according to first embodiment of the present invention;





FIG. 2

is a graph showing experimental results relating a change of decomposition power of the catalyzer to the thickness of catalytic layer;





FIG. 3

is a graph showing experimental results relating a change of decomposition power of the catalyzer to the intensity of ultraviolet radiant energy;





FIG. 4

is an elevation partly in section of the incandescent lamp according to second embodiment of the present invention;





FIG. 5

is an elevation view of an incandescent lamp according to third embodiment of the present invention;





FIG. 6

is a sectional schematic illustration of a lighting fixture according to fourth embodiment of the present invention;





FIG. 7

is a perspective and broken away view of a discharge lamp according to fifth embodiment of the present invention;





FIG. 8

is a detailed portion cross sectional and broken view of the discharge lamp shown in

FIG. 7

;





FIG. 9

is a side elevation view of a lighting apparatus using the discharge lamp shown in

FIG. 7

; and





FIG. 10

is a cross sectional view of a lighting apparatus according to sixth embodiment of the present invention.











DETAILED DESCRIPTION OF THE PRESENTLY PREFERRED EXEMPLARY EMBODIMENT




A first embodiment of this invention will be explained with reference to

FIGS. 1

to


3


.





FIG. 1

shows a photo catalyzer


1


. Catalyzer


1


has a substrate


2


and a photo catalytic layer


3


. Substrate


2


is made from quartz glass so as to transmit ultraviolet rays in a wavelength range below 410 nm. However, other light-transmitting materials, such as soda-lime glass, borosilicate glass, optical ceramics or some equivalent thereof, may be used. Catalytic layer


3


is coated on a surface of substrate


2


, which substantially includes anatase form of titanium oxide (TiO


2


). It may be used for the catalytic materials that anatase form titanium oxide containing other materials less than 50 percent by weight of the entire weight of photo catalytic layer


3


. Those materials are metal oxide or metal having catalytic reaction, such as ZnO, WO


3


, Fe


2


O


3


, FeTiO


3


, SrTiO


3


, CeO


2


, Tb


2


O


3


, MgO, Er


2


O


3


, Pt, Ag, Pd and Au. Catalytic layer


3


is preferably formed by the hydrolysis method of titan-alcholate, for instant, spray coating with a previously prepared solution of the TiO


2


and by firing at a temperature of about 700 degrees. The temperature is slightly lower than the brookite transformation point of TiO


2


. The previously prepared solution is a mixture of tetraisopropylene titanatemonomer chelated by glycerol and acetylacetone, and ethyl acetate ethanol for regulating the titanium oxide alkoxide. The firing temperature is preferably selected around 700 degrees described above, because if the temperatures are around 500 and 900 degrees, the titanium oxide has a different structure of crystal from the anatase, for example, the structure tends to be amorphous and rutile, respectively. Alternatively, catalytic layer


3


can be formed by dip coating method with titania alkoxide (manufactured by NIPPON-Soda; NTi-92) and by firing for 15 minutes after drying. In the case of this dip coating, the firing temperature is selected to be between 500 and 900 degrees. The thickness (d) of catalytic layer


3


should be provided between 0.01 and 0.3 microns, preferably selected between 0.01 and 0.1 microns. Photo catalytic layer


3


can also be used as a deodorizer to decompose a source of bad smell when photo catalytic layer


3


receives ultraviolet rays having a wavelength below 410 nm emitted by a lamp


4


, because the titanium oxide has a band gap energy of 3 eV which is equivalent to the above wave length.





FIG. 2

shows experimental results relating a change of relative decomposition power of catalyzer


1


to the thickness (d) of catalytic layer


3


in a closed space where seven test catalyzers are operated. Each test catalyzer


1


is made identical to others except for the thickness (d) of photo catalytic layer


3


. Each photo catalyzer


1


, had cigarette smoke thereon so that particles of the smoke stuck thereto. The catalyzer was then illuminated by ultraviolet rays by a light source disposed on the other side of photo catalytic layer


3


as shown in FIG.


1


. The decomposition power is indicated by the divided differences (T2-T1) between the visible light transmission factor in 550 nm of test catalyzer before and after each test catalyzer operates for 10 hours. Therefore, the divided difference becomes higher as catalyzer


1


has strong decomposition power, since the factor T2 (after the catalyzer operates) becomes lower compared with the initial factor T1 (before the catalyzer operates) due to the decomposition of the smoke.




The decomposition power rapidly drops when the thickness (d) of catalytic layer


3


is less than 0.01 microns, because the ultraviolet rays absorption of catalytic layer


3


is reduced. Reversely, the power also rapidly drops when the thickness (d) exceeds 0.3 microns as the amount of ultraviolet rays approached to the surface of catalytic layer


3


is reduced. Accordingly, the thickness (d) of photo catalytic layer


3


should be selected to be within 0.01 to 0.3 microns mentioned above in order to provide efficiently decomposition power. Catalyzer


1


also has a good transmission factor in the range of visible wavelengths when the catalytic layer


3


has the thickness (d) mentioned above. Furthermore, the thickness (d) is preferably selected to be less than 0.1 microns.





FIG. 3

shows experimental results indicating change of the decomposition power as a function of intensity of incident ultraviolet radiant energy on photo catalytic layer


3


. The decomposition power increases according to the incident ultraviolet rays becomes stronger. In order to strengthen the decomposition power, it is an advantage to use a light source having strong ultraviolet radiant energy. For that purpose, it is efficient to use a light source which enables to provide catalyzer


1


the incident ultraviolet rays having at least 0.01 mW/cm


2


intensity.




Other embodiments in accordance with the present invention will now be explained. Like reference characters designate identical or corresponding elements to those above-disclosed with respect to the first embodiment. The construction and operation of the following embodiment are substantially the same as those of the first embodiment and, therefore, detailed explanations of operations are not provided.





FIG. 4

shows a single ended incandescent lamp


10


according to second embodiment of the present invention. Lamp


10


is preferably utilized for conventional spotlights and downlights. An envelope


11


of incandescent lamp


10


is continuously formed with a cylindrical portion


12


and sealed portion


13


. Envelope


11


is made from silica glass so that ultraviolet rays transmit through envelope


11


. Envelope


11


also includes an exhaust tube


14


which is used for pumping air from envelope


11


and refilling envelope


11


with a mixture of an inert gas and a halogen gas. Sealed portion


13


is formed at opposite end to exhaust tube


14


, where is attached a base


15


. A filament


16


is provided along the central axis of envelope


11


in a space surrounded by cylindrical portion


12


, so as to span lead wires


17


passed through sealed portion


13


.




A photo catalytic layer


3


shown as a dot line is coated on an outer surface of envelope


11


so as to have a thickness of 0.1 microns, which is anatase form of titanium oxide (TiO


2


). Catalytic layer


3


is formed by a dip coating method. Envelope


11


is immersed in a previously prepared solution and fired at a temperature of 700 degree for 5 minutes after drying. The previously prepared solution is a medium of tetraisopropylene-titanate monomer in organic solvent, which contains tetraisopropylene-titanate within 2 to 10 weight percent and has a viscosity of about 2.0 cps. An optical interference layer (not shown), which includes a plurality of high refractive index layers made of a metal oxide substance, is preferably arranged between catalytic layer


3


and an outer surface of envelope


11


to reflect infrared rays toward to filament


16


in accordance with light interference.




Ultraviolet rays radiated by filament


16


almost transmits envelope


11


. Photo catalytic layer


3


coated on an outer surface of envelope


11


absorbs the ultraviolet rays. Therefore, materials attached on the surface of photo catalytic layer


3


, such as sulfur compounds, nitrogen compounds and aldehydes and so on, are sufficiently decomposed due to a catalysis reaction of photo catalytic layer


3


. Therefore, lamp


10


is able to deodorize such a source of bad smell. Lamp


10


also has a disinfecting action against various germs and a purification effect. Furthermore, it can be prevented the brightness of the lamp


10


from decreasing as the thickness of catalytic layer


3


is thinner than that of prior arts. As photo catalytic layer


3


also prevents dust, nicotine or oil stains from accumulating on envelope


11


, it can prevent the reduction of its brightness.





FIG. 5

shows a tubular incandescent lamp


20


according to third embodiment of the present invention.




A silica glass envelope


21


of incandescent lamp


20


is continuously formed with a cylindrical portion


22


and sealed portions


23


at each ends. Each sealed portion


23


is attached a base


24


. A filament


25


is provided along the central axis of envelope


21


, which is supported by support ring


26


contacting to the inner surface of envelope


21


. A photo catalytic layer


3


shown as a dot line is coated on an outer surface of envelope


21


so as to have a thickness of 0.01 to 0.3 microns, which is anatase form of titanium oxide (TiO


2


).




Lamp


20


is preferably assembled within reflector unit


30


shown in FIG.


6


. Reflector unit


30


is composed with lamp


20


and reflector


31


housing lamp


20


. Then, reflector unit


30


is utilized for a scanner unit of plain paper copier and a facsimile machine. According this embodiment, lamp


20


assembled within such machines tends to be covered with dust because the inside of such machine is dusty, however, photo catalytic layer


3


prevents such dust from accumulating envelope


21


. As a result, lamp


20


avoids reducing visible luminous flux.





FIG. 7

shows a fluorescent lamp


40


according to an embodiment of the present invention. Fluorescent lamp


40


has a rated power of 37 watt, which is defined by Japanese Industrial Standard as FL40SS. An envelope


41


of lamp


40


is constituted by a straight tube having an outer diameter of about 28 mm and stems


42


sealed into each end of the tube in the customary manner. The tube is made of a soda lime glass which will not pass ultraviolet rays under 300 nm in wavelength. As an alternative, other light-transmitting material can be used for tube, such as fused silica, ceramic or borosilicate glass. Each stem


42


supports a pair of electrodes


43


which, during operation, generate a discharge therebetween. Each electrode


43


is formed from a tungsten coiled wire which itself is coiled (double coiled) and employed as a preheating type arrangement. However, other electrode arrangement, such as a cold cathode, an exciting coil for supplying magnetic power to the lamp


40


or an external electrode, may be used. Electrodes


43


are coated with an emitter (not shown), such as BaO, SrO, or CaO, for emitting thermal electrons.




Each stem


42


is provided with an exhaust tube (not shown) that communicates with an opening in the stem wall and has its outer end hermetically sealed after envelope


41


has been evacuated, charged with a discharge sustaining fill, such as mercury vapor, and suitable fill gas in accordance with a standard lamp-manufacturing process. Suitable fill gases are argon, neon, krypton and mixture thereof.




Each electrode


43


is connected to lead wires


44


which are sealed through the inner end of stem


42


and extend into base. Bases


45


are cemented to and enclose ends of envelope


41


. Each base


45


is provided with a pair of metal pins that are electrically connected to lead wires


44


.




A phosphor layer


46


is coated on the inner surface of envelope


41


. Phosphor layer


46


converts ultraviolet rays of 185 nm and 254 nm emitted from a discharge into visible light and ultraviolet radiation in the wavelength range of 320 nm to 410 nm. Phosphor layer


46


is preferably made of a mixture of four luminescent compounds having peak emissions near 610 nm (red light), 540 nm (green light), 450 nm (blue light) and 370 nm (ultraviolet light), respectively. The luminescent compound emitting red, blue and green are yttrium oxide activated by divalent europium indicated as Y


2


O


3


:Eu


3+


, barium magnesium aluminate activated by divalent europium indicated as BaMg


2


Al


16


O


27


:Eu


2+


and lanthanum ceriumphosphate activated by trivalent terbium indicated as (La,Ce,Tb)PO


4


:Tb


3+


, respectively. The luminescent compound emitting ultraviolet radiation is strontia boron oxide activated by divalent europium indicated as SrB


4


O


7


:Eu


2+


which has a peak emission at 368 nm. The mixing ratio of the ultraviolet luminescent compound to all of the compounds is selected to be between 1 and 10 percent by weight. Although in the present embodiment, the ultraviolet luminescent compound is selected to be SrB


4


O


7


:Eu


2+


, other luminescent compounds may be used. It is preferable to select from the group consisting of alkaline earth metal borate activated by europium, alkaline earth metal silicate activated by lead, alkaline earth metal phosphate activated by europium and rare earth metal phosphate activated by cerium. For instant, those compounds are indicated as SrB


4


O


7


:Eu


2+


, (Ba,Sr,Mg)


3


Si


2


O


7


:Pb


2+


, BaSi


2


O


5


:Pb


2+


, (SrMg)


2


P


2


O


7


:Eu


2+


and YPO


4


:Ce


3+


. Furthermore, it is preferably to add halogen to the compound made of alkaline earth metal borate activated by europium in order to intensify its luminous flux. Further, the spectrum of Ce


3+


, including a green luminescent compound indicated as (La,Ce,Tb)PO


4


:Tb


3+


, has ultraviolet radiation in the wavelength range of 320 nm to 410 nm, it is also possible to intensify the ultraviolet radiation by increasing the amount of cerium. As shown in

FIG. 8

, a photo catalytic layer


3


having 0.1 microns thickness is coated on an outer surface of envelope


41


. It is preferable that a thin silica layer (not shown) is coated between the outer surface of envelope


41


and photo catalytic layer


3


to maintain an effective catalytic reaction, because sodium ingredient of soda lime glass tends to move into catalytic layer


3


.





FIG. 9

shows a lighting apparatus


50


. Lamp


40


is attached to a luminaire


51


through sockets


52


. Luminaire


51


houses an operating circuit


53


for supplying electric power to lamp


40


. Operating circuit


53


can be a conventional high frequency inverter circuit or a conventional ballast arrangement, or some equivalent thereof.




As operating circuit


53


generates a lamp current which flows through lamp


40


, the discharge generated between a pair of electrodes


43


is extinguished according to the lamp current. The discharge excites mercury vapor which emits ultraviolet rays at wavelengths of 185 nm and 254 nm. The ultraviolet rays are converted into visible light and ultraviolet radiation having a peak at 368 nm by phosphor layer


46


coated on inner surface of envelope


41


, then visible light and ultraviolet radiation are radiated through envelope


41


. As photo catalytic layer


3


is coated on outer surface of envelope


41


, it is excited by the ultraviolet radiation. Electron and hole mobilization occurs in photo catalytic layer


3


and, holes move on its surface. Materials attached on the surface of photo catalytic layer


3


, such as sulfur compounds, nitrogen compounds, aldehydes and so on, are decomposed by a catalysis reaction of photo catalytic layer


3


.





FIG. 10

shows a lighting apparatus


60


as a road lighting lantern according to an embodiment of the present invention. Lamp


61


is a high intensity discharge lamp such as a high pressure mercury vapor discharge lamp. A luminaire


62


housing lamp


61


has a glass globe


63


so as to transmit the light radiated by lamp


61


and a pole


64


supported by the ground at its end. Photo catalytic layer


3


is coated on an outer surface of globe


63


. An operating circuit (not shown) for supplying electric power to lamp


61


is enclosed in pole


64


.




As it is known that conventional high pressure mercury vapor discharge lamps have strong ultraviolet radiation around 365 nm and 410 nm in wavelength, catalytic layer


3


coated on outer surface of globe


63


is sufficiently excited by the ultraviolet radiation. Materials attached on the surface of photo catalytic layer


3


are decomposed by a catalysis reaction of photo catalytic layer


3


. Accordingly, photo catalytic layer


3


prevents dust, based on exhaust gas and so on, from accumulating globe


63


. As a result, lighting apparatus


60


avoids reducing desirable luminous flux.




While the invention has been described in connection with what are presently considered to be the most practical and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the sprit and scope of the appended claims.



Claims
  • 1. A lighting apparatus comprising:a luminaire having a light-transmitting portion; a light source housed in the luminaire, the light source radiating ultraviolet rays having a wavelength below 410 nm; a photo catalytic layer provided on an outer surface of the light-transmitting portion, the photo catalytic layer substantially including anatase form of titanium oxide and having a thickness of 0.01 to 0.3 microns; and wherein the light source is housed in the luminaire so that the light source irradiates an inner surface of the light-transmitting portion and the catalytic layer receives the ultraviolet rays having at least 0.01 mW/cm2 intensity through the light-transmitting portion.
  • 2. A lighting apparatus according to claim 1, wherein the catalytic layer has a thickness of 0.01 to 0.1 microns.
US Referenced Citations (4)
Number Name Date Kind
4634919 Yuge et al. Jan 1987 A
4692662 Wada et al. Sep 1987 A
5113109 Kawakatsu et al. May 1992 A
5650126 Taoda et al. Jul 1997 A