Compositions – Inorganic luminescent compositions – Compositions containing halogen; e.g. – halides and oxyhalides
Reexamination Certificate
2002-10-09
2003-12-23
Koslow, C. Melissa (Department: 1755)
Compositions
Inorganic luminescent compositions
Compositions containing halogen; e.g., halides and oxyhalides
C252S30140H
Reexamination Certificate
active
06666993
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to an improvement in electric lamps having a lamp envelope with a phosphor coating, and more particularly to a fluorescent lamp comprising a single-component phosphor.
BACKGROUND OF THE INVENTION
Halophosphate phosphors have been produced for some time. These have a wide range of colors ranging from the blue luminescence of a blue halo phosphor to the almost red-orange color of the warm white phosphor. The range in color in halophosphate phosphors is achieved by changing the formulation of the raw mix of the phosphor. While some colors, such as cool-white, warm-white and blue halo have been produced and sold for many years in the U.S., newer “cool” colors are desirable for particular markets such as South America. A conventional lamp available from Philips Lighting Company under the designation “Artic Brite” (also referred to as Arctic Bright) contains a two phosphor mix of about 84% Cool White phosphor (calcium halophosphate activated with manganese and antimony, color
35
) and about 16% Blue Halo (calcium halophosphate activated with antimony only). However, due to the differences in color points for the phosphor produced, tests have indicated that a three-component blend is necessary to achieve the correct color when color
75
is desired.
Additionally, the biggest disadvantage with such multi-component phosphors is the difficulty in precise color reproduction. This difficulty is inherent to all multi-component mixtures and is the result of various factors including variations in the color points for the phosphors, variations in the intensities of the phosphors, differences in the UV absorption of the phosphors, heterogeneities in each phosphor lot, and variations in the particle size and morphology. Another disadvantage is the fact that the two phosphors must be blended. While this represents an added process step which adds to the cost of manufacturing, even more importantly, the act of blending results in some degree of mechanical damage to the phosphor. Mechanical damage results in the formation of crystal lattice defects, e.g., vacancies, or may result in overmilling of the particles and often in the formation of fines. Such damage adversely affects phosphor performance.
There is a continued need in the art for a cost-effective, single-component phosphor and ARTIC BRITE™ lamps derived therefrom.
SUMMARY OF THE INVENTION
An object of the invention is to provide a cost-effective, single-component ARTIC BRITE phosphor and lamps derived therefrom.
Another object of the invention is to provide a single-component ARTIC BRITE phosphor and lamps derived therefrom of a color suitable for special markets, and in especially preferred embodiments, having color coordinates on the CIE chromaticity diagram within a MacAdam four step oval centered on X=346 and Y=359, and an acceptable color rendering index (“CRI”) value, preferably, a CRI value equal to at least 69, and preferably 75.
Yet another object is to provide a single component ARTIC BRITE phosphor and lamps derived therefrom in which low cost, mined calcium carbonate is used as a raw material and the amount of calcium pyrophosphate generated during processing is minimized.
Another object of the invention is to provide a method for the production of a single-component calcium halophosphate phosphor activated with antimony and manganese, and lamps derived therefrom, of a color suitable for special markets, and in especially preferred embodiments, having color coordinates on the CIE chromaticity diagram within a MacAdam four step oval centered on X=346 and Y=359, and an acceptable color rendering index (“CRI) value, preferably, a CRI value equal to at least 69, and preferably 75.
These and other objects of the invention are realized in the provision and utilization of at least one layer of a single-component Artic Brite calcium halophosphate phosphor, preferably having CIE color coordinates of X=346 and Y=359 and a CRI of at least 65, preferably 75. The phosphor is derived from a starting raw mix with a unique relative quantity of the components that allows for the desired luminescent color in the finished phosphor. In the phosphor of the invention, the host lattice has the formula Ca
10
X
2
(PO
4
)
6
and the dopants fit in said lattice in the following ratios, in which the moles of the dopant reactants are based on six phosphate ions,: about 0.142 of manganese, preferably derived from manganese carbonate; about 0.904 of fluoride, preferably derived from calcium fluoride; about 0.146 of chloride, preferably derived from ammonium chloride; and about 0.602 of antimony, preferably derived from antimony oxide, respectively. Most preferably, the phosphor is a single-component phosphor of the formula:
Ca
5−x−y
Sb
x
Mn
y
(PO
4
)
3
Cl
z
F
1−x−z
wherein x, y and z are integers as follows: x is from about 0.032 to 0.037; y is from about 0.06 to 0.14; and z is about 0.025 to 0.05. In particular, the invention is most preferably directed to a calcium chlorofluorophosphate phosphor activated by antimony and manganese having a CRI of 75 and selected from compounds having the formula:
Ca
4.52
Sb
0.037
Mn
0.06
(PO
4
)
3
Cl
0.05
F
0.426
(a)
or
Ca
4.52
Sb
0.032
Mn
0.14
(PO
4
)
3
Cl
0.025
F
0.452
(b)
To produce ARTIC BRITE phosphor suitable for certain markets, for example, South American markets, it is also necessary to have a small particle phosphate for the synthesis of a fine-particle phosphor, and to use low-cost calcium carbonate, for example mined calcium carbonate, to be price-competitive. One of the disadvantages of using mined calcium carbonate is the relatively high concentration of sodium and other impurity elements that are normally present. Many of these IA or IIA alkali and alkaline earth metals tend to act as sintering aids and produce a “hard” phosphor cake that requires additional milling. It has been found that a high metals-to-phosphate (Ca+Mn) formulation helps to counteract this effect. A high metals-to-phosphate (Ca+Mn) ratio results in minimal calcium pyrophosphate, which is a non-luminescent secondary phase. It has also been found that minimizing the amount of calcium pyrophosphate formed can produce a “softer” cake. For these reasons, the phosphor and lamps of this invention also are derived from a formulation that employs a high metals-to-phosphate (Ca+Mn) ratio of about 9.890 (based on six phosphate ions) to achieve a friable (readily crumbled) phosphor cake resulting in less fines formation with a tighter size distribution as shown by the number average particle size of 6.3 &mgr;m (compared to 1.9 for the conventional two-component phosphor used as the comparative phosphor standard herein and identified as M47M36). The final medium particle size is 10.44 &mgr;m. The invention also utilizes mined calcium carbonate as an inexpensive raw material.
According to the invention, a single-component ARTIC BRITE phosphor having an acceptable CRI is provided via a process that comprises the steps of:
(a) combining a source of phosphate, preferably dicalcium phosphate; a source of calcium, preferably calcium carbonate and especially mined calcium carbonate; a source of fluoride, preferably calcium fluoride; a source of chloride, preferably ammonium chloride; a source of manganese, preferably manganese carbonate; and a source of antimony, preferably antimony oxide; said components being present in a metals-to-phosphate (Ca+Mn) ratio of about 9.890 (based on six phosphate atoms) and in which, preferably the moles of the reactants, based on six phosphate ions, are about 0.142 manganese, preferably derived from manganese carbonate, about 0.904 fluoride, preferably derived from calcium fluoride, about 0.146 chloride, preferably derived from ammonium chloride, and about 0.062 antimony, preferably derived from antimony oxide, respectively;
(b) firing the mixture at a temperature to form a friable calcium halophosphate phosphor activated with antimony and manganese, preferably havin
Bartlett Ernestine C.
Koslow C. Melissa
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