U.S. patent number 3,886,396 [Application Number 05/397,913] was granted by the patent office on 1975-05-27 for fluorescent lamp with protective coating.
This patent grant is currently assigned to General Electric Company. Invention is credited to Edward E. Hammer, Edward E. Kaduk.
United States Patent |
3,886,396 |
Hammer , et al. |
May 27, 1975 |
FLUORESCENT LAMP WITH PROTECTIVE COATING
Abstract
In a fluorescent lamp which is coated internally with a
phosphor, a protective coating of fine alumina particles of
sub-micron size is applied over the phosphor layer as a porous
discontinuous coat. The protective postcoating improves maintenance
and reduces end discoloration of the oxide ring type. It is most
beneficial in lamps having relatively poor maintenance such as
green zinc silicate aperture lamps and very highly loaded calcium
halophosphate lamps.
Inventors: |
Hammer; Edward E. (Mayfield
Village, OH), Kaduk; Edward E. (Lyndhurst, OH) |
Assignee: |
General Electric Company
(Schenectady, NY)
|
Family
ID: |
26883723 |
Appl.
No.: |
05/397,913 |
Filed: |
September 17, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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188096 |
Oct 10, 1971 |
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Current U.S.
Class: |
313/486; 313/488;
313/113; 313/489 |
Current CPC
Class: |
H01J
61/46 (20130101) |
Current International
Class: |
H01J
61/38 (20060101); H01J 61/46 (20060101); H01j
061/42 () |
Field of
Search: |
;313/109,113,220,221,489,488,486 ;117/33.5L |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Demeo; Palmer C.
Attorney, Agent or Firm: Legree; Ernest W. Kempton; Lawrence
R. Neuhauser; Frank L.
Parent Case Text
This application is a continuation-in-part of our earlier copending
application Ser. No. 188,096 filed Oct. 10, 1971, similarly titled
and assigned and now abandoned.
Claims
What we claim as new and desire to secure by Letters Patent of the
United States is:
1. A fluorescent lamp comprising an elongated vitreous tube
containing an ionizable medium including mercury vapor and having
electrodes sealed into its ends, a coating of phosphor on a major
portion of the inside surface of said tube, and a postcoat of
finely divided aluminum oxide of submicron size forming a porous
discontinuous coating on the particles of said phosphor layer to
improve maintenance and reduce end discloration, the quantity of
aluminum oxide in said postcoat being but a small fraction of the
quantity required to achieve complete coverage of the phosphor
particles, the weight of said aluminum oxide postcoat being in the
range of 10 to 160 micrograms per square centimeter.
2. A lamp as in claim 1 wherein a particulate reflector layer
underlies the phosphor layer.
3. A lamp as in claim 1 wherein a particulate reflector lamp
underlies the phosphor layer and an aperture is provided therein
extending over a minor portion of the tube periphery.
4. A lamp as in claim 1 wherein a particulate reflector layer of
TiO.sub.2 underlies the phosphor layer and an aperture is provided
therein extending over a minor portion of the tube periphery.
5. A lamp as in claim 1 of the aperture type comprising a reflector
layer of TiO.sub.2 underlying a Zn.sub.2 SiO.sub.4 phosphor layer,
an aperture therein extending over a minor portion of the tube
periphery, and a postcoat of Al.sub.2 O.sub.3 of about 40
micrograms/cm.sup.2 over the phosphor layer.
Description
BACKGROUND OF THE INVENTION
The invention relates to fluorescent lamps wherein a low pressure
discharge through mercury vapor produces ultraviolet radiation
which excites a phosphor coated internally on the envelope walls to
produce light.
It is well-known that the light output of the usual fluorescent
lamp decreases during the course of its life. Various factors
contribute to the drop-off in light output during operation. Some
contributing causes are deposits of impurities from the cathode and
formation of oxides of mercury, changes in the phosphor itself, and
changes in the glass particularly where it is subject to
ultraviolet radiation causing a decrease in transmission. The
ability of a fluorescent lamp to resist drop-off in light output
during life is generally termed maintenance, and it is measured as
the ratio of light output at a given life span compared to initial
light output and expressed as a percentage.
The more common fluorescent lamps have excellent maintenance. For
instance, white 40-watt fluorescent lamps for ordinary lighting
have maintenance as high as 85 percent at 20,000 hours of life.
However, other fluorescent lamps are not nearly as good. A green
zinc silicate aperture lamp used for xerographic reprography may
have lumen maintenance no better than 65 percent at 100 hours. In
these lamps the fluorescent coating is applied over a reflector
coating and the coatings extend only part way around the
circumference of the envelope leaving a longitudinally extending
clear strip or aperture through which the light is emitted. Other
fluorescent lamps having poorer maintenance are extremely highly
loaded lamps of both circular and non-circular cross section in
which the power input ranges up to 50 watts per foot length.
SUMMARY OF THE INVENTION
The objects of the invention are to improve the lumen maintenance
in fluorescent lamps where the maintenance tends to be low, and to
reduce end discoloration.
In accordance with our invention, we have found that lumen
maintenance in such lamps may be improved by postcoating with
aluminum oxide wherein a thin layer of fine alumina is applied over
the phosphor layer, suitably as a suspension in a binder. Both the
phosphor layer and the Al.sub.2 O.sub.3 postcoat may be lehred in a
single operation in the same way as the phosphor layer alone would
be lehred.
The aluminum oxide postcoat in accordance with our invention is
beneficial in two ways. In lamps wherein lumen maintenance tends to
be very low, as in green zinc silicate aperture lamps for
reprographic applications, the postcoat achieves a remarkable
improvement in maintenance, as much as sixfold. In other lamps
wherein lumen maintenance is not so low but which are subject to
end discoloration, the postcoat achieves an improvement in end
discoloration and a substantial reduction in oxide ring
darkening.
DESCRIPTION OF DRAWING
FIG. 1 shows an aperture fluorescent lamp having an Al.sub.2
O.sub.3 postcoat according to the invention.
FIG. 2 is a cross section through the lamp to an enlarged scale
showing the various layers internally deposited on the glass.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown a fluorescent lamp 1 comprising
an elongated soda lime silica glass tube 2 of circular cross
section. It has the usual electrode 3 at each end supported on
inlead wires 4,5 which extend through a glass press 6 in a mount
stem 7 to the contacts of a base 8 affixed to the end of the lamp.
The sealed tube is filled with an inert gas such as argon or a
mixture of argon and neon at a lower pressure, for example 2 torr,
and a small quantity of mercury, at least enough to provide a low
vapor pressure of about six microns during operation.
As best seen in FIG. 2 showing a section through the tube wall, the
inner surface of the glass tube is protectively coated with a thin
clear film 9 consisting of titanium dioxide. To form this clear
layer, a metallo-organic compound of titanium such as tetrabutyl
titanate or tetraisopropyl titanate dissolved in an appropriate
solvent such as butyl alcohol or butyl acetate, is applied to the
glass. The solvent evaporates almost upon application and the
titanate is left deposited upon the inner surface of the glass
tube. Moisture from the air hydrolizes the titanate almost as fast
as the solvent evaporates forming titanium dioxide which remains as
a very thin clear continuous film in a thickness from 0.002 to 0.02
microns.
The illustrated lamp is provided with a reflector coating 10 and
thereover a coextensive phosphor coating 11, both coatings
extending around the major portion of the glass tube's
circumferential surface. This leaves a narrow uncoated strip or
aperture 12 extending lengthwise of the lamp. The coatings 10 and
11 may be applied at first over the entire glass tube internal
surface and then scraped or brushed off to form the aperture 12 in
the desired width, for instance over a 45.degree. portion of the
circumference of the tube. A preferred material for the reflective
layer is a particulate coating of titanium dioxide having a
particle size less than 1 micron, for instance centering on about
0.3 micron which is about half the median wavelength of the visible
spectrum. The TiO.sub.2 may be applied as a suspension in a
solution of ethyl cellulose in an organic solvent to serve as a
binder, the suspension being drawn up into the tube supported
vertically and then allowed to drain out. Thereafter the tube is
lehred in order to decompose and drive out the organic binder.
Alternatively the reflector coat may consist of magnesium oxide
MgO.
The phosphor consisting of zinc orthosilicate Zn.sub.2 SiO.sub.4 is
next applied as a suspension in a solution of nitrocellulose in
butyl acetate which is drawn up into the tube and allowed to drain
out. At this stage the clear area or aperture 12 is scraped out in
the desired width. The scraping removes the relatively thick
powdery reflective layer of TiO.sub.2 and phosphor layer of
Zn.sub.2 SiO.sub.4, but the clear protective layer of TiO.sub.2
which resulted from the hydrolysis of tetrabutyl titanate is very
adherent and is not affected. Instead of applying the coating over
the entire periphery and then scraping, an alternative method is to
introduce a pool of suspension of the desired coating in a
horizontally supported tube which is then rocked back and forth to
achieve the desired angular width of reflective coating, followed
by drying and lehring, as taught in U.S. Pat. No. 2,892,440 -
Fulton et al.
In the case of a very highly loaded fluorescent lamp for general
illumination, the reflective layer is omitted and the phosphor
layer is applied directly over the clear protective film of
titanium dioxide. A phosphor commonly used for white fluorescent
lamps is calcium halophosphate activated with manganese and
antimony and it is commonly applied as a suspension in a water
soluble binder.
In accordance with our invention, a postcoat 13 consisting of
Al.sub.2 O.sub.3 particles in a size less than 1 micron is applied
over the phosphor coat. The Al.sub.2 O.sub.3 particles may be
applied as a suspension in a solution of ethyl cellulose in an
organic solvent serving as a binder. The suspension is brought up
into the tube while vertically supported and then allowed to drain
out and dry. The tube is then lehred at a temperature from about
550.degree.C to 600.degree.C for 3 to 5 minutes to decompose and
drive out the binder of both the phosphor layer and the alumina
postcoat layer thereover. The lehring procedure is the same as is
conventionally used in regular fluorescent lamp production without
postcoat, so that no additional burden is imposed thereby on the
manufacture of the lamp.
By way of example of postcoating technique, a relatively thick
suspension may be prepared by dispersing 200 grams of Al.sub.2
O.sub.3 powder of 0.02 micron average particle diameter pre-fired
at 1100.degree.C, in 5.6 liters of binder comprising 100 grams of
ethyl cellulose dissolved in thinner consisting of equal parts by
volume butyl acetate and naphtha. A ball mill or a suitable high
speed dispersion mill (Kady mill) may be used. Before application,
the foregoing thick suspension is thinned down by diluting 100 cc
thereof with binder comprising 2.5 grams of ethyl cellulose in 740
cc of the same thinner. This thinned suspension contains about 4.24
mg Al.sub.2 O.sub.3 per cc and about 3.25 cc are retained in the 18
inch T8 aperture fluorescent lamp previously described,
corresponding to 14 Mg Al.sub.2 O.sub.3 per bulb or 40 micrograms
per cm.sup.2 of bulb surface. We prefer to have the postcoat extend
over the clear aperture, as shown in FIG. 2 of the drawing.
Table 1 below compares the light output of 18 inch T8 green zinc
silicate aperture lamps, some postcoated with Al.sub.2 O.sub.3 as
previously described, and others similar in all respects except not
postcoated, serving as control.
TABLE 1 ______________________________________ Main- Test Light
Output tenance 0 hr. 1/2 hr. 100 hr. 300 hr. 300/1/2
______________________________________ Post- coat 130.5 127.1 98.4
90 71% Con- trol 133.6 127.7 84.5 65 51%
______________________________________
The marked improvement in maintenance of the postcoated lamps is
apparent. Lumen maintenance calculated as the ratio of light output
at 300 hours relative to light output at 1/2 hour, is 71 percent
for the postcoated lamp, as against 51 percent for a control lamp
similar in all respects except for the absence of the postcoat. The
comparison has been made on the basis of the 1/2 hour rather than
the zero hour figure to avoid the very rapid drop-off during the
first minutes of operation which distorts the maintenance figures
and has no practical significance.
Tests on very highly loaded fluorescent lamps wherein the power
input ranges up to 50 watts per foot length show similar
improvements in maintenance as a result of postcoating. In one
series of lamps wherein maintenance was 70 percent at 3000 hours
life, postcoating raised the maintenance to 75 percent.
The improvement in end discoloration due to oxide rings made
possible by the use of a postcoat according to the invention is
apparent in the following Table 2 comparing end discoloration in
cool white fluorescent lamps operated with frequent starts at a
loading of 10 watts per foot. The comparison is made in demerit
points wherein 1 represents barely noticeable graying, and 10
represents heavy blackening all around.
TABLE 2 ______________________________________ Test End
Discoloration 0 hr. 100 hr. 1000 hr. 3000 hr.
______________________________________ Postcoat 0 0 0 1 Control 0 0
3 10 ______________________________________
It is apparent from the table that barely noticeable graying, whose
onset occurs before 1000 hours in the control lamps, is delayed to
3000 hours by postcoating.
The thickness of coating applied over the phosphor is very
difficult to measure because both phosphor particles penetrate into
the voids throughout the phosphor. The coating thickness for a
particular suspension of Al.sub.2 O.sub.3 depends on phosphor
particle size and coating texture or laydown characteristics, and
the weight of Al.sub.2 O.sub.3 per unit area is more easily
measured. The effect of weight of postcoat on window brightness and
lumen maintenance in 18 inch T8 green zinc silicate aperture lamps
is given in Table 3 below.
TABLE 3
__________________________________________________________________________
Coating Weight Light Output Maintenance Mg/Bulb G/cm.sup.2 0.5 hr.
100 hr. 300 hr. 500 hr. 500/1/2
__________________________________________________________________________
None-control 0 691 517 422 380 55.0% 10 30 667 569 503 481 72.1% 20
60 652 505 460 471 72.2% 30 90 601 318 225
__________________________________________________________________________
As may be expected, an excessive weight of Al.sub.2 O.sub.3 is not
good, due in part to the greater difficulty of properly lehring the
underlying layers. The optimum weight of Al.sub.2 O.sub.3
postcoating will vary with the phosphor and lamp combination. We
have found the desirable range to extend from 10 to 160 micrograms
per cm.sup.2 of bulb surface, and prefer approximately 40
micrograms/cm.sup.2 for the 18 inch T8 green zinc silicate aperture
lamp previously described.
The colloidal aluminum oxide postcoat in accordance with the
invention is discontinuous, that is porous and pervious, rather
than continuous, nonporous and impervious. This result follows
necessarily from the weight or quantity of Al.sub.2 O.sub.3 applied
as previously described herein, and its method of application by
deposition out of a liquid suspension. It is well-known that a
phosphor coating is not a smooth uniform dense coating but consists
of protuberances and cavities, or hills and valleys. According to
published data, phosphor particles as used in lamps vary in size
from a few to several microns, and 4 microns may be taken as
typical for a zinc silicate phosphor. In order to have a phosphor
film without bare spots, the phosphor layer must be several
particles thick and the top layer of particles will project at
least 4 microns above the mass. If a projection of 5 microns is
assumed, this determines the thickness or depth of Al.sub.2 O.sub.3
coating that must be applied in order to have a continuous coat or
impervious barrier.
Suppliers of colloidal Al.sub.2 O.sub.3 powder having 0.02 micron
average particle diameter (v.g. Cabot Corp.) give the density of
the material as 3.6 grams per cc. Thus for instance where 40
micrograms of colloidal alumina are applied per square centimeter,
the volume of this quantity will be 40 .times. 10.sup.-.sup.6
gm/3.6 gm/cm.sup.3 = 1.1 .times. 10.sup.-.sup.5 cm.sup.3. Assuming
that the upper 5 micron layer of phosphor is half filled with
phosphor particles, then the volume of Alon needed for complete
filling of the empty spaces to assure complete coverage of the
phosphor particles will be 5 .times. 10.sup.-.sup.4 /2 cm.sup.3 =
2.5 .times. 10.sup.-.sup.4 cm.sup.3. Comparing the volume of Alon
supplied to the volume required for complete coverage, the ratio is
seen to be 1.1 .times. 10.sup.-.sup.5 /2.5 .times. 10.sup.-.sup.4 =
4.4 .times. 10.sup.-.sup.2. In other words when 40 micrograms of
colloidal alumina are provided per square centimeter of phosphor
coated surface, there is 4.4 percent of the quantity needed to
provide complete coverage of the phosphor particles.
In fact, there is not even that much coverage because the hill and
valley effect of the phosphor particles is appreciably greater than
the 5 micron thickness that has been assumed. For instance, W.
Elenbaas in Light Sources says that the phosphor film has to be 3
mean particle diameters thick in order to have no bare spots on the
glass not covered by phosphor. Thus, a hill and valley depth of 12
microns is needed to avoid bare spots and on that basis the
percentage of phosphor surface coated by Alon is less than 2
percent. In the case of a cool white phosphor wherein the average
phosphor particle size is 10 microns, the thickness required would
be 30 microns and the percentage coating effected by Al.sub.2
O.sub.3 would be even less. Clumping of the colloidal alumina
further reduces the proportion of the phosphor particles coated or
covered. It is apparent from the foregoing data that the quantity
of aluminum oxide in the postcoat according to our invention is
only a minor fraction of the quantity required to provide complete
coverage of the phosphor particles.
The discontinuous, that is porous and pervious nature of the
colloidal alumina postcoat applied over the phosphor layer in
accordance with the invention has been confirmed by
photo-micrographs taken by scanning electron microscope.
* * * * *