WO1981000030A1

WO1981000030A1 - Strontium calcium fluorapatite phosphors and lamps incorporating same

Info

Publication number: WO1981000030A1
Application number: PCT/US1980/000687
Authority: WO
Inventors: C Chenot
Original assignee: GTE Products Corp
Current assignee: Osram Sylvania Inc
Priority date: 1979-06-22
Filing date: 1980-06-02
Publication date: 1981-01-08
Anticipated expiration: 1981-12-22
Also published as: JPH0124197B2; CA1145133A; EP0030547A4; EP0030547A1; US4266160A; JPS56500746A

Abstract

A fluorescent lamp can incorporate a new strontium-calcium fluorapatite of the formula CA<u5.0-a-w-x-y>u Sra Cdw Mnx Sby (PO4)3 F1-y Oy wherein a is from about 0.25 to about 4.75-w-x-y; w is from 0 to about 0.2; x is from about 0.05 to about 0.5; y is from about 0.02 to about 0.2. The compositions have unexpected chromaticity properties.

Description

STRONTIUM CALCIUM FLUORAPATITE PHOSPHORS AND LAMPS

INCORPORATING SAME

BACKGROUND OF THE INVENTION

This invention relates to alkaline earth fluorophos- phate luminescent materials. More particularly it relates to strontium-calcium fluorapatite phosphors activated with manganese and antimony and to fluorescent lamp incorpora¬ ting these phosphor materials.

United States Patent 2,488,733 discloses various alkaline earth halophosphate phosphors. The halophosphate host is described by the formula

3M₃ ( 0₄)₆ M¹ L₂ where L is a halogen or a mixture of halogens and M and M are either different or identical alkaline earth metals. Specific alkaline earth halophosphate materials disclosed are calcium fluorapatite, calcium fluoro-chlorapatite, calcium chloroapatite, calcium-strontium fluoro-chloro- apatite strontium fluorapatite calcium bromo-chloro- apatite, barium fluorapatite, barium fluorochloroapatite and barium chlorapatite. The materials are activated with antimony and manganese. In lieu of antimony, bismuth, tin or lead can be used.

U.S. Patent 2,965,786 discloses that cadmium can be added to halophosphate of the above formula where M and M are calcium.

U.S. Patent 3,549,552 discloses calcium fluorochlo¬ roapatite materials which are useful in the production of lamps exhibiting a "daylight" color. "Daylight" is a color defined by an oval that has x values ranging from

OMPI ^1W) about .307 to about 0.319 and y values ranging from about 0.330 to about 0.345. As defined in the American

National Standard Specifications for the Chromaticity of

Fluorescent Lamps the objective for daylight is x=0.313, y=0.337.

U.S. Patent 4,075,532 discloses the composition defined by the formula

Ca1__n0-w-x-y Cdw Mnx Sby (PO4-)'6, F2-y 0y wherein w is from 0 to 0.2 x is from 0.25 to 0.5 y is from 0.02 to 0.2 The chromaticity of the foregoing composition is stated to vary along a line x in Fig. 3 of the above patent. The variation is due to the manganese content. A material having x in the above formula of about 0.03 is stated to have chromaticity coordinates of x=0.409 and y=0.432. The values given take into account the effect of the mercury emission. Manganese at low levels causes the halophosphates to emit a light blue and at higher levels, e.g. wherein x in the formula given in U.S. Patent 4,075,532 is about 5% of the total phosphor weight, the emission of the phosphors shifts toward the red portion of the spectrum.

When strontium is substituted for all of the cal- cium in the fluorapatite system and the levels of man¬ ganese and antimony are kept constant the emission is shifted toward the green portion of the spectrum.

It is believed, therefore, that new halophosphate compositions that yield chromaticity values that were unexpected from the prior art constitutes an advance¬ ment in the art. SUMMARY OF THE INVENTION

New strontium calcium fluorapatite phosphors having the formula Ca 5-.0 _n-a-w-x-y Sra Cdw Mnx Sby (PO4.)^;3-, F1,-y Oy

O ^< wherein a is from about 0.25 to about 4.75-w-x-y w is from 0 to about 0.2 x is from about 0.05 to about 0.5 y is from about 0.02 to about 0.2 have chromaticity values that vary significantly from the chromaticity values that would be predicted from the calcium fluorapatite or the strontium fluorapatite. BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a fluorescent lamp employing the phosphor of the present invention.

Fig. 2 is a portion of the CIE diagram containing information useful in understanding the present invention. Fig. 3 through 8 are the spectral energy distribution curves for a number of manganese-antimony activated cal- cium-strontium fluorapatite materials.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims in connection with the above-described drawings.

EXAMPLE I Samples of various manganese and antimony activated calcium fluorapatite, calcium-strontium fluorapatite and strontium fluorapatite are prepared following the general procedure given in U.S. Patent 2,965,786. For the manga¬ nese-antimony activated calcium fluorapatite the following raw materials are used:

CaHP0₄ 3.00 moles CaF₂ .485 moles

Sb₂0₃ 0.15 moles Cac0₃ 1.325 moles MnC0₃ 0.15 moles CdO .025 moles

OMPI For those samples where strontium is substituted for a portion or all of the calcium the substitution can be made by substituting SrHPO., SrF-, or SrCO-, for the appro¬ priate amount of CaHPO., CaF₂ or CaCO.-. Thus phosphor compositions of the following formula are prepared:

^Ca 4.795 - ^Sra ^Cd0.025 ^Mn0.15 ^Sb0.03 ^(P04^}3 ^F0.97 °0.03

The following Table I gives the chromaticity co¬ ordinates, the peak emission and the 50% bandwidth for a number of materials in which a in the foregoing formula is varied.

TABLE I

Chromaticity

Value Peak (Na¬ 50% Bandwidth Coordinates of a nometers) Nanometers X y

0 573.4 74.1 0. ,436 0. ,465

11..00 557777..99 77.8 0. .457 0. ,464

2.0 577.5 80.4 0, ,460 0. ,467

3.0 573.8 82.3 0. ,450 0. ,474

4.0 569.9 84.0 0. ,440 0. ,485

4.795 564.7 84.2 0. ,423 0. ,490 The chromaticity coordinates of these compositions are plotted in Figure 2 and the spectral energy distri¬ bution of these compositions under 254 nanometer excita¬ tion are plotted in Figures 3 through 8. As can be seen from Figure 2 the chromaticity shifts to higher "x" values until "a" is equal to about 2.0 which corresponds to about a 40% replacement of the cation content with strontium. The "y" values remain relatively constant. As the value of "a" is increased from about 2.0 to about 4.795, the "x" value decreases and the "y" increases from the 40% sub- stitution material.

With particular reference to Fig. 3 through 8, the spectral energy distribution is shown for the samples reported in Table I. Fig. 3 is the material having a value of "a" equal to zero. Figs. 4-7 are for the a-

O P terials having "a" values of 1 to 4 respectively while Fig. 8 is for the material having no calcium in which "a" is equal to 4.795. Figure 3 through 8 show that samples that have "a" values of 1.0 and 2.0 have peak wavelength 5 at higher wavelengths calcium fluorapatite while at about an "a" value of about 3.0 the peak is about the same wavelength as calcium fluorapatite. At "a" values of 4.00 and 4.795, the peak emission was lower wavelength values than calcium fluorapatite. From the peak wave-

10 length data for calcium fluorapatite and strontium fluo¬ rapatite, which are phosphors that have been previously disclosed, it would have been expected that all of the peak emissions would have been in the range of about 565 to about 573 nanometers. 5 With particular reference to Fig. 2, a composition of the formula

^Ca4.795 ^Cd0.025 ^Mn0.15 ^Sb0.03 <^P04^}3 ^F0.97 °0.03 has been found to have chromaticity coordinates of x=0.436 and y=0.465 and is depicted in Fig. 2 by point

20 18. A similar phosphor with essentially the same compo¬ sition except that strontium is substituted for calcium has chromaticity coordinates of x=0.423 and y=0.490 and is plotted as point 20 in Fig. 2. It was expected that composition containing both calcium and strontium would

25 have chromaticity coordinates falling along line A in Fig. 2.

It has been found that as up to about 40% of the cation ions are replaced by strontium that the chroma¬ ticity of the resulting compositions fall along line B

-^{■ Q} in Fig. 1. When from about 40 to 100% of the cations are replaced by strontium, the chromaticity of the resul¬ ting compositions fall along line C in Fig. 1. While the above data is for a constant manganese content of 0.15 in the above formula, the same effect is noted with com-

³⁵ positions having higher or lower levels of manganese except the compositions containing lower levels of man¬ ganese are more blue and those containing higher levels are more yellow.

With particular reference to Fig. 1, the sealed glass envelope 1 has the lead-in wires 2, 3, sealed through one of its ends and corresponding lead-in wires sealed through the other end. The usual coiled-coil 4 of tungsten wire is supported between, and electrically connected to, the pair of lead-in wires 2, 3, and a similar coil is supported by and connected to the lead-in wires at the other end of the envelope 1. An insulating base piece 5 having contact pins 6 and 7, each pin being connected to one of the lead-in wires, held in the metal cap 8, which is fixed by the ce¬ ment 9 to one end of the envelope 1, and a similar base piece 16, having contact pins 10 and 11, is cemented to the other end by cup 12.

The tungsten coils carry the usual electron-emitting coating of alkaline earth oxides, generally including also a small percentage of zirconium dioxide. A filling of inert gas such as argon, neon, krypton, and mixtures thereof, at about 2 millimeters of mercury pressure, and the usual small quantity of mercury is inside the glass envelope 1. The lamp has the usual stem press 14 and sealed exhaust tube 15. The phosphor compositions of the present invention can be used alone or in conjunction with other phosphor materials. If a fluorescent lamp is desired which is the color that would be achieved with the phosphor composition of this invention alone, one skilled in the art can deter- mine the color of emission from Fig. 2 taking into account the emission of mercury. Similarly if used in conjunction with other materials the resulting chromaticity of the lamp can be determined from Fig. 2, the mercury lines, and the chromaticity of the materials with which it is desired to combine with the phosphors of this invention. EXAMPLE 2 Energy saving 35 watt fluorescent lamps are prepared from the materials reported in Table I and the brightness is measured initially and after 100 hours of operations. These data are given in Table II below.

TABLE II

Value a Brightness (lumens)

Initi .al 100 Hours

0 3220 3128

1. .0 2939 2827

2. ,0 2748 2574

3. .0 2844 2682

4, ,0 2618 2459

4. ,795 2744 2480 Analytical results indicate that the lower brightness for the materials containing strontium may be due to a decrease in the retained antimony in the composition. To obtain a comparable level of antimony it is necessary to increase the initial amount of antimony oxide approximately by a factor of two when pure strontium fluorapatite is pro¬ duced. When antimony is at comparable level with the strontium containing material the brightness is at a com¬ parable level to that achieved with the calcium fluora¬ patite. INDUSTRIAL APPLICABILITY

The alkaline earth fluorophosphate luminescent materials are useful in fluorescent lamps.

OMPI A

Claims

1. A luminscent composition consisting essentially of manganese and antimony activated strontium-calcium flu¬ orapatite compositions having the formula Ca 5_. _n0-a-w-x-y Sra Cdw Mnx Sby (PO4.)'3- F1,-y Oy wherein a is from about 0.25 to about 4.75-w-x-y w is from 0 to about 0.2 x is from about 0.05 to about 0.5 y is from about 0.02 to about 0.

2 2. A composition according to Claim 1 wherein the value of a is from about 1 to about 4.

3. A composition according to claim 1 wherein the value of a is from about 1 to about 2.

4. A composition according to claim 1 wherein the value of a is from about 2 to about 4.

5. A fluorescent lamp comprising a light-transmit¬ ting envelope having electrodes, an inert ionizable gas and a charge of mercury therein and a coating of phosphor on the inside surface of said envelopes, said phosphor com- prising manganese and antimony activated strontium-calcium fluorapatite compositions having the formula,

Ca 5_c._A0-a-w-x-y Sra Cdw Mnx Sbx (PO4.)^;3_ F1,-y 0y wherein a is from about 0.25 to about 4.75-w-x-y w is from about 0 to about 0.2 x is from about 0.05 to about 0.5 y is from about 0.02 to about 0.2

6. A lamp according to claim 5 wherein in said for¬ mula the value of a is from about 1 to about 4.

^■ _BU

O.