US 5,382,452 AGrant
Luminescent Materials Prepared by Coating Luminescent Compositions Onto Substrate Particles
Issue Date:1995-01-17
•10 Claims
•8 Drawing Sheets
Abstract
The present invention relates to a novel cost efficient luminescent composition comprising particles of a core material which have been coated with a luminescent material that is distributed in the form of a chemically homogeneous layer. The average diameter of the core particle is in the range of from about 0.5 to 20 microns, and the coating corresponds to between about 2 and 30 wt % of the total composition. One aspect the invention relates to a process for preparing the composition which comprises decomposing chelated metal luminescent compositions in solution at a relatively high pH while in the presence of dispersed core particles, thereby coating the core particles with hydrous metal oxides, recovering the coated particles, optionally washing the coated particles substantially free from soluble species, drying and calcining. In another aspect, a hydrous oxide coating is converted to a sulfide coating by treating the hydrous coating with a source of active sulfur. In yet another aspect, the invention relates to adding an acidic solution of metal oxides along with a solution of oxalic acid to a slurry of dispersed core particles which become coated with the metal oxalates, recovering the product, washing the coated particles substantially free from soluble species, drying the oxalate composition. In a further aspect of the invention, the core material and metal oxalate powders can be dry mixed and calcined at a temperature high enough to induce at least a portion of the oxalate to form a phosphor coating over the surface of the core particles.
Metadata
Assignee
- E. I. Du Pont de Nemours and Company
Inventors
- Salvatore A. Bruno
- Donald K. Swanson
Application Information
Application Number:US 2028670
Filing Date:1994-02-25
Priority Date:1992-12-18
Art Unit:112
Classifications
IPC:
B05D 700
Field of Search:
427215;64;66;67;226;372.2;384
Patent Drawings (8 sheets)
Description
Field of the Invention
The present invention relates to a novel, cost efficient, luminescent composition, and processes for making the composition.
Background of the Invention
Luminescent materials or phosphors comprise a host material which together with one or more activators converts absorbed energy into radiant energy. Some of the most widely used host materials are calcium halophosphate, barium magnesium aluminate, magnesium aluminate, strontium chloroapatite, zinc silicate and the oxides, oxysulfides, phosphates, vanadates and silicates of yttrium, gadolinium or lanthanum. Commonly compounds containing used activators are rare-earth ions such as europium II and III, terbium III, cerium III, and tin II. Conventionally compounds containing the host and activator materials are mixed together by a mechanical procedure, such as milling or micronizing, and then calcined to produce fine powder phosphors of relatively uniform composition. These powders may be bonded as coatings to the surface of a substrate, typically glass, for use in a variety of applications.
Rare-earth oxide (REO) activated phosphors are used in trichromatic lamps, cathode ray tubes (CRT), color television (CTV), high definition television (HDTV) screens, among others. Many of the rare-earth oxides are very expensive and this has limited their use in a number of applications. For example, conventional three-wavelength fluorescent lamps emit white natural light by correctly blending three narrow spectral bands of blue-violet, red-orange and green. Europium II-activated barium magnesium aluminate or europium II-activated strontium chloroapatite can be used as the blue phosphor, europium III-activated yttrium oxide can be used as the red phosphor and cerium/terbium-activated magnesium aluminate can be used as the green phosphor. Such fluorescent lamps have greater color rendition, a longer useful life, and are more energy efficient in comparison to incandescent lamps. The marketability of these fluorescent lamps has been hindered, however, because of their high cost which is attributable to the necessity of using expensive rare-earth oxides.
Czechoslovakian Patent No. 266,856 B1, to Hajek et al., claims a luminescent composition comprising a silica core, on the surface of which is created a luminescent layer of mixed rare-earth element oxides. Hajek et al, purport that this achieves a reduction in the amount of expensive rare-earth phosphors used while the required light parameters are retained. These compositions are prepared by using a rare-earth salt solution/oxalic acid diethyl ester system to precipitate rare-earth element oxalates onto the surface of activated silica particles, and subsequently calcining the oxalates to obtain an oxide luminophor. The examples in this patent describe coated silica particles in which the rare-earth phosphor layer is between about 60 and 95 wt % of the composition. At the coating thicknesses described in the examples of this patent, only a modest, if any, reduction in the consumption of expensive rare earth elements is achieved.
The disclosure of the above-identified Patent is hereby incorporated by reference.
Summary of the Invention
The present invention relates to a cost efficient luminescent composition comprising fine particles of an inert core material wherein at least a portion of the surface of the particles is coated with a luminescent material which is distributed about the surface of the particles in the form of a chemically homogeneous coating. The average diameter of the core particle ranges from about 0.5 to 20 microns, normally about 1.0 to 10 microns, and the coating normally corresponds to about 2 through about 30 wt % of the total composition.
In one aspect, the invention relates to processes for preparing the composition of this invention. In one process, a chelate solution of the luminescent composition is decomposed at a relatively high pH while in the presence of dispersed core particles, whereby at least a portion of the core particles become coated with hydrous metal oxides of the luminescent composition. The coated core particles can be recovered, optionally washed substantially free of soluble species, dried and calcined in a manner which is sufficient to convert the hydrous metal oxides into a luminescent material.
In another process, oxalates of the luminescent composition are formed by simultaneously adding aqueous solutions of an oxalic acid and at least one metal salt of the luminescent composition into a stirred aqueous slurry of the core particles. The coated core particles are recovered, optionally washed substantially free of soluble species, dried and calcined in a manner that is sufficient to form and activate the luminescent material.
In yet another process, the above described chelate solution is decomposed at a relatively high pH while in the presence of dispersed core particles, then treated with a source of active sulfur for converting the hydrous oxide coating to a sulfide coating, recovering the product, optionally washing substantially free of soluble species, drying and calcining in a substantially inert atmosphere, to activate the luminescent material.
The composition of the invention can be adhered, or applied onto the surface of a substrate, e.g., a glass substrate. Such coated substrates are useful in trichromatic lamps, cathode ray tubes (CRT), color television (CTV), high definition television (HDTV) screens, flat panel displays, among many other uses.
The present invention solves the problems which are associated with known luminescent materials by improving the cost effectiveness of rare-earth components in luminescent materials, e.g., the present invention achieves luminescence by using a luminescent coating instead of bulk particles.
Conventionally it was believed that luminescent materials which are relatively small particles, e.g., less than 5 microns, were inefficient. Notwithstanding conventional beliefs, the average particle size of the present luminescent compositions can be less than 5 microns, e.g., less than about 0.5 micron, and obtain an acceptable R(I), e.g., a R(I) similar to conventional materials. Indeed, the present luminescent coating is typically present upon the core particles as crystallites, e.g., luminescent crystallites which range from about 50 to at least about 250 nanometers. Accordingly, the results which are achieved by the present invention are surprising and unexpected in comparison to conventional luminescent materials.
Brief Description of the Drawings
FIG. 1--FIG. 1 is an optical photomicrograph at 600X magnification of a portion of a commercially available bulk phosphor powder.
FIG. 2--FIG. 2 is an optical photomicrograph at 600X magnification of a portion of the product formed in accordance with Example 1.
FIG. 3--FIG. 3 is an optical photomicrograph at 1000X magnification of a portion of the product formed in accordance with Example 1.
FIG. 4--FIG. 4 is an optical photomicrograph at 600X magnification of a portion of the product formed in accordance with Example 2.
FIG. 5--FIG. 5 is an optical photomicrograph at 1000X magnification of a portion of the product formed in accordance with Example 3.
FIG. 6--FIG. 6 is a graphical representation of the relative intensities R(I) of the products formed in accordance with Examples 1-3, and the commercially available product shown in FIG. 1.
FIG. 7--FIG. 7 is an optical photomicrograph at 1,000X magnification of a portion of the product formed in accordance with Example 4.
FIG. 8--FIG. 8 is a graphical representation of the relative intensities R(I) of the product formed in accordance with Example 4, and a commercially available bulk phosphor product.
FIG. 9--FIG. 9 is an optical photomicrograph at 600X magnification of a portion of the product formed in accordance with Example 6.
FIG. 10--FIG. 10 is an optical photomicrograph at 600X magnification of a portion of the product formed in accordance with Example 6.
FIG. 11--FIG. 11 is a graphical representation of the relative intensities R(I) of the product formed in accordance with Example 6, and the commercially available product shown in FIG. 1.
Detailed Description
The present invention relates to a cost efficient luminescent composition comprising particles of an inert core material the surface of which has been at least partially coated with a luminescent material in the form of a substantially chemically homogeneous coating. The average diameter of the core particle ranges from about 0.5 to at least about 20 microns, normally about 1.0 to at least about 10 microns, and the coating corresponds to between about 2 to at least about 30 wt % of the total composition.
In one aspect, the invention relates to a process for preparing the luminescent composition which comprises decomposing a solution of chelated metal luminescent materials at high pH while in the presence of dispersed inert core particles wherein the particles become coated with hydrous metal oxides, recovering the coated particles, optionally washing the particles substantially free from soluble species, drying; and calcining.
In another aspect, a hydrous oxide coating upon the core particles is converted to a sulfide coating by being treated with a source of active sulfur. For example, the source of active sulfur can comprise at least one water soluble member from the group of sodium sulfide, potassium sulfide, ammonium sulfide, mixtures thereof, among others.
In yet another aspect, the invention is a process comprising preparing an acidic solution of at least one metal oxide along with a solution of an oxalic acid, adding the solutions to a slurry of dispersed particles wherein the particles become coated with metal oxalates, recovering the oxalate coated particles, washing the particles substantially free from soluble species, drying the oxalate composition, and calcining to form and activate the luminescent material. By "activate" it is meant that at least a portion of the coated particles, e.g., a calcined coating upon the particle, becomes luminescent when excited by a suitable energy source.
In a further aspect of the invention, a luminescent composition can be obtained by dry mixing core particles and metal oxalate powders together, and calcining the mixed powders. The calcination temperature should be sufficient to cause 1) formation of a luminescent material coating over at least a portion of the core particle's surface, and; 2) activate the luminescent coating on the particle.
Still further, the core particle may be coated by using an appropriate vapor deposition method. The core particles may be exposed to a vapor, which contains a precursor of a luminescent material, that is deposited upon at least a portion of the core particle's surface. For example, a vapor precursor of the luminescent material may be passed through a chamber which contains the core particles. In some cases, a volatile source, e.g., a material that decomposes when heated, of the vapor precursor may be used for in situ generation of the vapor precursor. While any suitable vapor precursor of the luminescent material may be employed, for best results the vapor precursor should neither interact with the core particle nor adversely affect further processing of the coated core particle.
The novel composition of the invention is a cost efficient luminescent composition comprising a core material or particle having an average diameter in the range of from about 0.5 to at least about 20 microns; normally about 1.0 to at least about 10.0 microns. The surface of the core particle has been suitably coated with a luminescent material which is distributed about the particle in a substantially chemically homogeneous layer wherein the layer corresponds to about 2 through at least about 30 wt %, usually between 5 and 20 wt % of the total composition. While the luminescent material need not completely cover the entire surface of the core particles, the quantity of luminescent material should be sufficient to provide a R(I) spectrum which is similar or equivalent to conventional phosphor materials, e.g., the composition of the invention achieves about 50 to at least about 90% of the R(I) exhibited by conventional bulk phosphor materials. For example, at least a portion of the luminescent material may comprise a layer of generally interconnected or dispersed luminescent crystallites.
The luminescent composition of the invention is characterized by a relative luminescent intensity R(I). The R(I) of an emission peak is defined as the number of counts observed at the peak's maximum height divided by the number of counts measured at a reference detector from a split portion of the excitation intensity for a given spectrometer configuration. However, merely reporting the R(I) for a given phosphor, without more information, may be misleading because the R(I)s which are generated by a spectrometer typically are unique for that spectrometer. For example, two different spectrometers, which have identical settings, may produce two distinct R(I) spectrums for the same powder. A more useful R(I) is obtained by generating the R(I) spectrum, for a powder being tested, opposite at least one standard reference phosphor of similar composition (refer to FIGS. 6, 8, and 11 which are discussed below in greater detail).
The quantity of luminescent material and the activator concentration within the coating upon the core particles can be tailored in order to obtain a predetermined intensity. However, the quality of the luminescent coating may not be desirable at loadings above 30 wt % of the total composition, e.g., such loadings may induce agglomeration of the luminescent material and/or the formation of fine particulate debris. For best results, the loading of coated material ranges from about 5 through at least about 20 wt % of the total composition which typically achieves the optimal combination of raw material cost and luminescent intensity. It will be appreciated, however, that this optimal loading will vary with 1) the size of the core particles, 2) the relative densities of the core and luminescent coating, 3) factors relating to the end use application, among other factors. It is important to distinguish between the quantity of luminescent material that is used to obtain the present coating, and the total amount of such material which is present in conventional phosphors. For example, the concentration of luminescent activator in the present coating may be greater than the concentration of such activator throughout conventional bulk phosphors; however, the total weight of luminescent activator is less in the present composition than conventional phosphors.
The luminescent coating of the invention may include at least one activator such as a member selected from the group of rare earth elements, tin II, antimony III, Cu, Ag, Mn, among others, and at least one suitable host material. A suitable host material may comprise at least one member from the group Y.sub.2 O.sub.3, YVO.sub.4, Sr.sub.2 P.sub.2 O.sub.7, (Ca,Sr).sub.5 (F,Cl)(PO.sub.4).sub.3, ZnS, among others.
The characteristics of the core material or particle are a key aspect of the invention. For best results, the core particle is substantially inert. By "inert", it is meant that the core particle substantially avoids reacting with the coating composition in a way that adversely impacts luminescence. Because many luminescent compositions are heated to temperatures greater than about 1000.degree. C. in order to activate the luminescent material, it is particularly important that the core material be substantially stable and non-reactive at such temperatures. Relatively low levels of certain undesirable impurities can significantly diminish luminescence and, accordingly, for best results, the core composition should be substantially completely devoid of such impurities or such impurities are substantially prevented, if present, from being extracted into the luminescent layer.
Moreover, these undesirable impurities may cause poisoning, e.g., non-radiative energy transfer in the form of vibrational energy. Ions that have non-radiative transitions to their ground state, and which should be avoided in the preparation of the present composition include Fe.sub.2 +, Co.sub.2 +, Ni.sub.2 +, Al, Si, among others. In some cases, the sensitivity of a luminescent material to a poison, varies inversely with the activator concentration. An s-center phosphor can typically tolerate about 100 times more of a given poison than an i-center phosphor. An s-center refers to a substitutional activator such as Eu substituting for Y in Eu:Y.sub.2 O.sub.3, whereas an i-center refers to an interstitial activator atom as is postulated to be the case for Cu activated ZnS.
Any poisons that are present in the composition may reduce luminescence efficiency by:
1. Decreasing the solubility of the activator compound in the host crystal during formation of the phosphor,
2. Absorbing primary excitation energy directly and converting the energy into heat,
3. Dissipating (as heat) excitation energy which has been absorbed by the host crystal and is intercepted by the poison center while the excitation energy is en route to or from activator centers,
4. Interfering with activator centers, so as to increase their probability of making nonradiative transitions, for example, by lowering the crossover point between the excited and ground-state potential energy curves of the luminescent composition,
5. Taking excitation energy from nearby activator centers, by q-overlap energy transfer, and converting the potential luminescence energy into heat, and;
6. Optically absorbing luminescence radiation which is seeking to escape from within the phosphor crystal,
The suitability of the particles of core material can also be determined, in part, by the composition of the luminescent coating and the potential for an undesirable reaction between the two. In some cases, the core material should not absorb light at the frequencies of interest, e.g., the activating radiation and emitted radiation. However, such absorption may be desirable when providing a plurality of coatings, and/or coatings containing more than one luminescent material, upon the core particles. In general, the core should avoid interfering with any electrical processes which are associated with operating a light-emitting device.
Typically, water-soluble core materials will be unsatisfactory for use in this invention; although such materials may be satisfactory for use in non-aqueous coating processes provided they are otherwise acceptable. In any event, normally unacceptable core particles can be rendered suitable for use in the invention by being coated with a substance which substantially counteracts or eliminates the unsatisfactory property. For example, normally unacceptable particulate core materials can be rendered suitable for use in the invention by applying a coating of a suitable core material that would serve as an "inert" barrier between the core particle material and the luminescent coating. Moreover, whether or not a core material or a barrier coated core material is suitable for use in the present invention is dependent upon the particular luminescent material being coated upon the core material and, accordingly, for best results, the core material which is employed in the invention is one that is inert with respect to a specific luminescent coating. Suitable particulate core particles comprise at least one member selected from the group of alkaline earth sulfate, alkaline earth phosphate, metal silicate, mixed metal oxides, alkaline earth fluoride, metal titanates, mixtures thereof, among others. Normally, best results are obtained by employing core particles comprising BaSO.sub.4 and/or CaSO.sub.4.
The core particles are usually essentially iso-dimensional, and typically have an average diameter between about 0.5 to 20 microns, and normally from about 1.0 to 10.0 microns. It is desirable for the core particles to be characterized by a relatively narrow particle size distribution. For example, a desirable distribution is one wherein about 90% of the core particles have a diameter which ranges from about 0.1 D to 10.0 D ("D" is defined as the weight average particle diameter). A narrow particle size distribution is particularly advantageous when employing the inventive composition as a luminescent material in fluorescent lamps, television screens, flat panel displays, among others. Without wishing to be bound by any theory or explanation it is believed that a narrow particle size distribution improves particle packing efficiency.
Average particle size and particle size distribution can be determined by methods described in "Measurement of Suspended Particles by Quasi-Electric Light Scattering", E. B. Dahneke, Wiley Interscience, N.Y. 1983; which is hereby incorporated by reference. Particularly useful for performing these methods is the Microtrac II Small Particle Analyzer manufactured by Leeds Northrop and Company.
The exterior surface of the core particle is coated with a substantially chemically homogeneous layer comprising a luminescent material which typically corresponds to between about 2 and 30 wt %, and normally about 5 to 20 wt % of the total composition. The coating materials may comprise at least one member selected from the group of (Y.sub.2 O.sub.3 :Eu), (Y.sub.2 O.sub.2 S:Eu), (YVO.sub.4 :Eu), (Zn.sub.2 SiO.sub.4 :Mn), (BaMg2Al16O27:Eu), (SrB.sub.4 O.sub.7 :Eu), Ce.sub.0.65 Tb.sub.0.35 MgAl.sub.11 O.sub.19, (ZnS:Cu), (ZnS:Ag), barium titanium phosphate, MgWO.sub.4, Sn and Eu activated alkaline earth ortho and pyrophosphates, Sb and/or Mn activated calcium halophosphates, mixtures thereof, among others. Particularly useful coating materials are (Y.sub.2 O.sub.3 :Eu), (YVO.sub.4 :Eu), (BaMg.sub.2 Al.sub.16 O.sub.27 :Eu), (Ce.sub.0.65 Tb.sub.0.35 MgAl.sub.11 O.sub.19) and (ZnS:Cu), (ZnS:Ag), e.g., these coating materials can be used in a number of commercial applications such as lamps, TV screens, flat panel displays, among others. The luminescent material is normally present as interconnected or dispersed crystallites about the surface of the core particles, whereas in some cases the core particles may be crystalline and/or amorphous.
A composition of the invention may be prepared in a variety of ways. One process utilizes a chelate of the luminescent components as a carrier to deposit the luminescent composition as a hydrous metal oxide and/or metal oxide onto slurried core particles. In another process, the luminescent component is precipitated as an oxalate and/or carbonate onto a slurry of core particles. During subsequent calcination, the deposited hydrous metal oxide, oxalate, carbonate, among others, can be activated to form a luminescent coating upon the surface of the core particles.
In one aspect of the invention, a luminescent composition can be obtained by dry mixing core particles and metal oxalate powders together, and calcining the mixed powders. The calcination temperature should be sufficient to cause 1) formation of a luminescent material coating over at least a portion of the core particle's surface, and; 2) activate the coated particle.
In another aspect of the invention, the core particle may be coated by using an appropriate vapor deposition method. The core particles may be exposed to a vapor, which contains a precursor of a luminescent material, that is deposited upon at least a portion of the core particle's surface. For example, a vapor precursor of the luminescent material may be passed through a chamber which contains the core particles. In some cases, a volatile source, e.g., a material that decomposes when heated, of the vapor precursor may be used for in situ generation of the vapor precursor. While any suitable vapor precursor of the luminescent material may be employed, for best results the vapor precursor should neither interact with the core particle nor adversely affect further processing of the coated core particle.
In another process of the invention, the luminescent component is deposited as a hydrous oxide onto at least a portion of the surface of slurried core particles. If desired, the hydrous oxide can be converted to a sulfide by exposure to a source of active sulfur, e.g., treatment with a solution comprising sulfur salts such as potassium, ammonium, and sodium sulfides. The treated hydrous oxide coating may be converted to a sulfide coating by being heated to a temperature of about 90.degree. C. The sulfide coated particles can be isolated, washed to remove soluble species, dried, e.g., at a temperature of about 120.degree. C., and admixed with a second sodium salt such as sodium chloride, e.g., about 2 to 20 wt % dry NaCl is added to the dried sulfide coated particles. A subsequent calcination step at a temperature of about 800.degree. to 1000.degree. C. in a non-oxidizing atmosphere, e.g., nitrogen, generates formation of a sulfide-containing luminescent coating about the core particle. Optionally, the sulfide coated particles may be washed for removing the second sodium salt.
Each luminescent material has an optimum calcination temperature, and in some cases may require operation within an oxidizing, a reducing or an inert environment. The specific calcination conditions are selected in order to optimize luminescent intensity and particle size distribution.
When employing particulate BaSO.sub.4 as a core material, it is advantageous to calcine the core particles, and subsequently mill the calcined particles, e.g., the calcined particles may be hammer milled or ball milled. The calcined particles are then ready to be coated with a luminescent material. Calcination and milling achieves formation of a final product which possesses a relatively narrow particle size distribution (PSD). Without wishing to be bound by any theory or explanation, it is believed that calcining the core particles, prior to applying the luminescent coating, reduces formation of intractable agglomerates when the luminescent coated core particles are again calcined for activating the coated particles. For example, a calcined/milled BaSO.sub.4 core particle, which is acid washed by slurrying in a mineral acid, e.g. HCl, to substantially remove undesirable acid soluble species, may achieve a conductance of less than about 50 umhos, resulting in an enhanced R(I) for the subsequent coated luminescent phosphor composition.
A method that is particularly useful for depositing a chemically homogeneous coating on a particulate substrate is described in U.S. Pat. No. 5,082,811 entitled "Ceramic Dielectric Compositions And Method For Enhancing Dielectric Properties"; the disclosure of which is incorporated herein by reference. A process of the present invention comprises the following steps:
(a) preparing an agitated aqueous or aqueous organic slurry of core particles;
(b) adding a solution comprising metal chelates of luminescent precursors to the agitated slurry;
(c) raising the pH of the slurry above about 9 by adding a basic substance;
(d) heating the slurry to a temperature of from about 50.degree. C. to reflux, and maintaining the temperature for a period of about 1 to 8 hours, normally 4 to 8 hours, to decompose at least a portion of the metal chelates, thereby depositing a coating of luminescent precursors onto at least a portion of the surface of the particles;
(e) recovering, optionally washing and drying the coated particles; and
(f) calcining the dried powder under appropriate conditions to activate the coating upon the particles.
The above-identified aqueous organic slurry may be prepared with a fluid selected from mixtures of deionized water with at least one water miscible organic liquid which does not adversely interact with the core particles or the luminescent coating. For example, the water miscible organic fluid may be selected from C.sub.1 -C.sub.4 branched or straight chain alcohols, glycols, mixtures thereof, among others.
A solution comprising metal chelates of the luminescent components, at least one suitable chelate solvent, and at least one chelating agent, is prepared. By "chelating agent", it is intended to refer to one or more polydentate ligands whose structure permits the simultaneous attachment of two or more donor sites onto the same metal ion, thereby forming a closed ring structure. A "ligand" is defined as any atom, ion, or molecule which is capable of functioning as a donor partner in one or more coordinate bonds. Chelating agents useful in practicing the invention comprise at least one member from the group of alpha-hydroxycarboxylic acids, such as lactic, glycolic, malic and citric acid or alpha-aminocarboxylic acids, such as ethylene diamine tetracetic acid (EDTA), glycine, mixtures thereof, among others. A solution of the chelating agent is prepared using a solvent, for example, deionized water or mixtures of deionized water with water miscible solvents such as methanol, ethanol, isopropanol, mixtures thereof, among others. The solvent may optionally contain small amounts of wetting agents or surfactants for enhancing dissolution of the metal compounds.
The quantity of chelating agent should be sufficient to create a solution of metal chelates. The appropriate metal chelate compound(s) can be stirred into the above described chelating agent and solvent solution. The metal compounds comprise the general formula, MXn, wherein "M" is a metal cation comprising at least one member selected from the group of magnesium, aluminum, zinc, copper, silver, calcium, strontium, barium, antimony, manganese, vanadium, tantalum, tungsten, yttrium, lanthanum, terbium, europium, lutetium, mixtures thereof, among others; wherein "X" is an anion or a radical selected from HCO.sub.2 --, CH.sub.3 CO.sub.2 --, --OH, --OR, --NO.sub.3 and --Cl, mixtures thereof, among others; and "n" is a whole number which ranges from 1 through 6 and is a function of the valence state of the metal cation M.sup.+n. Certain metal oxides, which are soluble in mineral acids, may also be used as a source of the metal cation, e.g., Y.sub.2 O.sub.3, Eu.sub.2 O.sub.3, ZnO, Sb.sub.2 O.sub.3, V.sub.2 O.sub.5, mixtures thereof, among others.
The pH of the previously described solution is adjusted to a value which ranges from about 5 through at least about 10; typically by adding a strong base selected from ammonium hydroxide, tetramethyl-ammonium hydroxide, sodium hydroxide, potassium hydroxide, mixtures thereof, among others. Normally, a pH between 5 to 8 is suitable for obtaining a stable solution of metal chelates. While the solution pH is a key factor which determines whether or not a stable solution of metal chelates is obtained, other important factors include the metal compound, valence state of the metal compound, chelating agent, among others. By appropriately adjusting the pH of the solution, the chelating agent is capable of forming soluble chelates with metal cations which were provided by the metal compound.
It is desirable that the metal compounds be substantially completely dissolved in the solution, and that the quantity of chelating agent be sufficient to accomplish substantially complete dissolution. In some cases, a relatively clear solution is obtained by adding the chelating agent after introducing the metal compounds to the solution.
After adding the solution of metal chelates to the slurry of core particles, the pH of the slurry can be increased to greater than about 9, typically above about 10, by adding a strong base, e.,g., potassium hydroxide and/or sodium hydroxide. The slurry may be heated to a temperature in the range between about 50.degree. C. to reflux, and maintained for a period of up to about 8 hours, typically for at least 4 hours, in order to decompose the metal chelates, thereby depositing a generally chemically homogeneous coating of the luminescent precursor material upon the surface of the core particles. Ammonium hydroxide may also be employed as a base. If ammonium hydroxide is employed, then relatively high temperature may be required to decompose the metal chelates. Typically, decomposition can be accomplished by heating the slurry of core particles in an autoclave at a temperature of from about 100.degree. C. to at least about 200.degree. C. When sodium hydroxide is employed for converting the metal chelate to form a corresponding hydrous metal oxides and/or metal oxides, the conversion can be illustrated by the following equation: ##STR1## wherein, for example, lactic acid R is CH.sub.3 --, or for example, malic acid R is --CH.sub.2 COO--Na+.
By controlling the reaction conditions, hydrous metal oxides and/or metal oxides of a luminescent material can be deposited upon the surface of the core particles. The coated core particles can be recovered by filtration or centrifugation, and optionally washed several times with deionized water to substantially remove any soluble organic or inorganic materials, if any, and dried in an air or vacuum oven.
The dried coated powder can then be calcined at a temperature, for example, in the range of about 800.degree. to 1300.degree. C. which activates the coating of luminescent material. Normally, the luminescent material is crystalline, e.g., the luminescent coating comprises interconnected or dispersed crystallites upon the surface of the core material. For any particular composition, the R(I) of the luminescent material is normally a function of the calcining temperature.
The composition of the coated powders can be determined by using x-ray fluorescence analysis, or inductively coupled plasma (ICP) analysis. The crystalline phases core material or the luminescent coating may be determined by x-ray diffraction analysis. The characteristics of the surface coating may be ascertained by optical microscopy, transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). Surface areas can be determined by single point B.E.T. on a Micromeritics Flowsorb II 2300, and particle size can be determined on a Microtrac II Small Particle Analyzer.
The relative intensity, R(I) of the coated core material or phosphor composition can be measured using an SLM-8000 fluorescent spectrometer. The relative intensity can be measured by loading the coated particles into a quartz cuvette, and centering in the sample holder of the instrument. The excitation wavelength, which is typically used to excite most photoluminescent compositions in a fluorescent lamp, is about 254 nm, which is the primary wavelength emitted by a mercury vapor discharge lamp. In a fluorescent spectrometer, the excitation wavelength is typically generated by a xenon lamp and a double-grating excitation monochromator. The R(I) of each sample is measured four times, one measurement for each face of the quartz cuvette, and the average value is calculated, i.e., an average value minimizes any systematic error caused by the sample holders. For certain coated particles, a bulk composition such as Y.sub.2 O.sub.3 :5 mole % Eu, which was prepared by the oxalate process described above, can be used as a standard. Prior to measuring the R(I) of the coated particles, the spectrometer is configured to give an R(I) value of about 2.1 for this standard.
While particular emphasis in the above description has been placed on coating a single luminescent material about a core particle, it is to be understood that the invention covers a plurality of luminescent coatings, e.g., the luminescent material may comprise a plurality of, for example, successive coatings that absorb and/or emit the same and/or different colors. Further, the invention may be employed to provide a mixed composition luminescent coating, e.g., a coating comprising at least one layer which includes a plurality of luminescent materials. Moreover, subsequent to formation, the composition may be treated or tailored by a post-treatment which, for example, protects the luminescent coating from degradation, attack from moisture containing moities, among others. For example, a composition of the invention can be modified by being coated with silica, thereby minimizing any reaction of the composition after the composition has been placed into service, e.g., used as a phosphor in a fluorescent lamp. In some cases, it can be desirable to employ a mechanical mixture of luminescent coated particles which have distinct sizes, compositions, among other characteristics. Accordingly, by appropriately selecting a core material(s), luminescent coating(s), coating process, mixtures of coated materials, and optional post-treatments, the luminescent composition of the invention can be tailored to satisfy a virtually unlimited array of end product applications
The following examples are provided to illustrate certain aspects of the invention, and not to limit the scope of the appended claims.
Example 1
This Example describes a method for making a phosphor containing barium sulfate coated with approximately 2.04% Eu.sub.2 O.sub.3 and 24.86% Y.sub.2 O.sub.3 by using a chelate process.
Deionized water (about 540 ml) and approximately 31.4 g (0.2318 mole) of D,L-malic acid were charged to a 2-liter flask under a nitrogen atmosphere at a temperature of about 23.degree. C. A solution comprising yttrium oxide in aqueous hydrochloric acid (about 125.4 g, 19.84% Y.sub.2 O.sub.3 ; 22.69% HCl), and a solution of europium oxide in aqueous hydrochloric acid (about 10.46 g, 19.49% Eu.sub.2 O.sub.3 ; 20.83% HCl) were added to the 2-liter flask while being agitated; the resulting generally clear solution was allowed to agitate for about 30 min.
A sodium hydroxide solution (approximately 119.4 g, 30% NaOH, 0.8955 mole) was added to the previously described solution in a dropwise fashion over a period of about 35 minutes while maintaining a temperature of about 25.degree. C. The resultant solution, which was generally colorless and had a pH of about 9.2, was diluted to about 1200 g by adding deionized water.
The diluted colorless solution was combined with a slurry of about 73.1 g of barium sulfate (known as Blanc Fixe Micro Grade, a precipitated barium sulfate supplied by Sachtleben Corp.), in about 300 g of deionized water. The barium sulfate for this example had a surface area of about 2.6 m2/g. The resultant mixture was agitated overnight. By means of a syringe pump, aqueous sodium hydroxide solution (about 21.1 g, 30% NaOH, 0.1583 mole), was added to the slurry over approximately 1 hr., while maintaining a temperature of about 25.degree. C. The white slurry, which had a pH of about 11.4, was then heated under reflux, to about 100.degree. C. for 6 hrs.
After cooling the white slurry to approximately 25.degree. C. (pH about 10.6), a portion of the slurry was filtered, and given a 1000 ml displacement wash with deionized water. The filter cake was dried at a temperature of about 120 C., thereby producing about 59.2 g of a white solid having a surface area of about 6.3 m2/g. A portion of the white solid was ground in a mortar and pestle, and calcined in air at a temperature of about 1100.degree. C. to produce a powder whose typical properties are summarized below.
Referring now to the Drawings, FIG. 1 is an optical photomicrograph at 600X magnification of the commercially available phosphor which was used as the reference standard for the R(I) data summarized above. The commercially available material corresponds to a bulk phosphor powder comprising Y.sub.2 O.sub.3 doped with approximately 5 wt. % Eu.sub.2 O.sub.3, supplied by GTE, which is sold under the trademark "Sylvania Type 2340". FIG. 2 is an optical photomicrograph at 600X magnification of a portion of the powder formed in accordance with Example 1, and FIG. 3 is an optical photomicrograph at 1,000X magnification of the powder shown in FIG. 2. FIGS. 1 and 2 were taken with a NIKON optical microscope, which was equipped with a 60X ELWD (extra-long working distance) lens, by placing a small sample of the powder upon a glass slide, and immersing the powder in a drop of oil which had a refractive index of about n=1.54. A cover glass was placed over each sample and lightly pressed down so as to displace the powder. FIG. 3 was taken with the above-identified microscope by using a 100X oil immersion lens that was immersed into a drop of oil that had been placed on top of the cover glass.
FIG. 1 shows a conventional bulk phosphor powder that has a particle size which ranges from approximately 2 to 15 microns. FIGS. 2 and 3 show BaSO4 particles, which range in size from about 3 to 20 microns, that are coated with Eu:Y.sub.2 O.sub.3 phosphor crystallites. The generally clear outline of the particles shown in FIGS. 2 and 3 corresponds to BaSO.sub.4, whereas the relatively dark spots are crystallites of Eu:Y.sub.2 O.sub.3 which were coated on the surface of the BaSO.sub.4 particles.
Example 2
This example describes a method for making phosphor containing barium sulfate coated with approximately 0.76% Eu.sub.2 O.sub.3 and 9.24% Y.sub.2 O.sub.3 using a chelate process.
Deionized water (about 270 ml) and approximately 20.4 g (0.1507 mole) of D,L-malic acid were charged to a 1-liter flask under a nitrogen atmosphere while maintaining a temperature of about 25.degree. C. A solution of yttrium oxide in aqueous hydrochloric acid (approximately 62.2 g, 20% Y.sub.2 O.sub.3 ; 22.57% HCl), and a solution of europium oxide in aqueous hydrochloric acid (approximately 5.1 g, 20% Eu.sub.2 O.sub.3 ; 20.72% HCl), were added to the contents of the 1-liter flask while being agitated and maintaining a temperature of about 25.degree. C. The resulting solution was allowed to agitate for about 10 min. An aqueous ammonium hydroxide solution (approximately 33.2 g, 29.2% NH.sub.3, 0.5692 mole), was added dropwise over a period of about 40 min while maintaining a temperature of about 25.degree. C. A generally colorless solution was produced, which had a pH of about 8.0, and was diluted to about 600 g by the addition of deionized water.
Barium sulfate (approximately 90 g) was slurried in 500 g of deionized water (the barium sulfate was known as Blanc Fixe Micro Grade a precipitated barium sulfate that was supplied by Sachtleben Corp., which had been calcined previously at about 900.degree. C. for 1 hr and hammer-milled by using a Brinkman Mill). Aqueous ammonium hydroxide (about 40 g, 29.2% NH.sub.3) was added to the sulfate slurry while maintaining a temperature of about 25.degree. C., and agitating the slurry. Agitation of the slurry was continued overnight. The slurry was heated to about 91.degree. C., and about 446.1 g of the above-described colorless yttria-europia chelate solution was added to the slurry over a period of about 2.5 hrs. The slurry was heated further under reflux to about 106.degree. C. for 6 hrs.
After cooling to about 25.degree. C., a white slurry was obtained which had a pH of about 8.6. The white slurry was filtered, and the filter cake washed with 16 liters of deionized water. The filter cake was dried to produce about 107.8 g of a white solid having a surface area of about 1.3 m2/g, and a particle size distribution of: D.sub.90, 8.49 um; D.sub.50, 3.00 um; and D.sub.10, 0.94 um. A portion of the solid was pulverized by hammer milling, and calcined in air at a temperature of about 1200.degree. C. for 1 hr. The resulting white powder had a surface area of about 0.6 m2/g, and a particle size distribution of: D.sub.90, 18.1 um; D.sub.50, 7.13 um; and D.sub.10, 1.62 um.
Referring now to FIG. 4, FIG. 4 is an optical photomicrograph at 600X of a portion of the powder formed in accordance with Example 2. FIG. 4 illustrates a coating of relatively small phosphor crystallites upon the BaSO.sub.4 particles.
Example 3
This example describes a method for making a phosphor containing barium sulfate coated with approximately 0.76% Eu.sub.2 O.sub.3 and 9.24% Y.sub.2 O.sub.3 using an oxalate process.
Barium sulfate (approximately 90 g) was slurried into 1500 ml of deionized water, and the slurry was agitated at a temperature of about 25.degree. C. for 2 days. (The barium sulfate was known as Blanc Fixe Micro Grade which is a precipitated barium sulfate supplied by Sachtleben Corp.) The slurry was heated to about 91.degree. C.
A solution was prepared by combining solutions of yttrium oxide in aqueous hydrochloric acid (approximately 46.2 g, 20% Y.sub.2 O.sub.3 ; 22.57% HCl), and europium oxide in aqueous hydrochloric acid (approximately 3.79 g, 20% Eu.sub.2 O.sub.3 ; 20.72% HCl), with about 50 ml deionized water which had a temperature of about 25.degree. C. A second solution was prepared by dissolving about 17.9 g (0.1422 mole) of oxalic acid dehydrate into about 46 ml of deionized water which had a temperature of about 60.degree. C. The barium sulfate slurry was heated to about 91.degree. C., and the two previously described solutions were added simultaneously to the sulfate slurry over a period of about 2 hrs. The resulting slurry was heated further under reflux to a temperature of about 102.degree. C. which was maintained for about 6 hrs.
After cooling to about 25.degree. C., a white slurry was obtained which was filtered, and the filter cake washed with 10 liters of deionized water. The filter cake was dried at about 120.degree. C. to obtain about 106.6 g of a white solid having a surface area of about 3.1 m2/g. A portion of the powder was calcined in air at a temperature of about 1,100.degree. C. for 1 hr. to produce a white powder.
Referring now to FIG. 5, FIG. 5 is an optical photomicrograph at 1,000X magnification of a portion of the powder formed in accordance with Example 3. FIG. 5 shows one BaSO.sub.4 particle which essentially has no coated phosphor crystallites, and another adjacent particle that is substantially completely coated with phosphor crystallites.
FIG. 6 is a graphical representation of the R(I) spectrums in terms of emission wavelength (x-axis) and R(I) (y-axis), for the conventional powder shown in FIG. 1, and powders which were formed in accordance with Examples 1-3. Curves "A" through "B" of FIG. 6 correspond, respectively, to R(I) spectrums which were emitted by powders which were formed by Examples 1-3, and Curve "D" corresponds to a R(I) for the commercial phosphor shown in FIG. 1. The R(I) spectrums or curves were generated by using a SLM-8000 spectrometer that was operated at the following settings: Exictation Resolution=4 nm, Emission Resolution=4 nm, Increment=0.2 nanometers, Integration Time=0.1 sec, Measured Function=C/B, Gain Channel C=10, High Voltage C=420, Gain Channel B=100, and High Voltage B=505. A review of Curves A-D illustrates that the powders of the present invention are capable of achieving R(I) values approximately 65 to 70% of conventional bulk phosphor powders, while using a significantly less total amount of luminescent material.
Example 4
This example describes a method of making a phosphor containing barium sulfate coated with approximately 0.38% Eu and 9.62% YVO.sub.4.
D,L-Malic acid (approximately 7.67 g ,0.0566 mole) was dissolved in a solution of about 15.7 g of 37% hydrochloric acid and 2.4 g of deionized water. The solution was heated to about 45.degree. C., and about 5.16 g(0.0283 mole) of vanadium pentoxide (99.9% V.sub.2 O.sub.5) was added to the solution over a period of about 1 hr., while maintaining a temperature of about 45.degree.-70.degree. C., thereby producing a dark blue solution.
In a separate beaker D,L- malic acid (approximately 10.5 g, 0.0775 mole) was dissolved in 200 g of deionized water. A solution of yttrium oxide in aqueous hydrochloric acid (approximately 31.9 g, 20% Y.sub.2 O.sub.3 ; 22.57% HCl), and a solution of europium oxide in aqueous hydrochloric acid (approximately 2.62 g, 20% Eu.sub.2 O.sub.3 ; 20.72% HCl), were added to the malic acid solution while being agitated and maintaining a temperature of about 25.degree. C. The previously described blue vanadium solution was poured into the agitated solution along with about 40 g of deionized water. A sodium hydroxide solution (approximately 65.1 g, 30% NaOH; 0.4883 mole), was also added to the agitated solution in a dropwise manner while maintaining a temperature of about 25.degree. C. A greenish black chelate solution, which had a pH of about 8.0, was obtained, that was in turn diluted to about 600 g by adding deionized water.
A portion of the greenish black chelate solution (approximately 500 g) was added to a slurry comprising about 90 g of barium sulfate particles (known as "F" Grade, a precipitated barium sulfate supplied by Sachtleben Corp., which had been calcined previously at 700.degree. C. and treated with 10% hydrochloric acid), into 500 g of deionized water. A sodium hydroxide solution (approximately 23.3 g, 30% NaOH; 0.1748 mole), was added to the slurry while maintaining a temperature of about 25 C. over a period of about 30 min. The slurry, which had a pH of about 11.8, was heated further under reflux to a temperature of about 101.degree. C. for 8 hrs. After cooling to about 25.degree. C., a tan colored slurry was obtained, which had a pH of about 12.2, that was filtered and the filter cake washed with 10 liter of deionized water. The filter cake was dried at a temperature of about 120.degree. C. to produce about 100 g of a cream colored solid having a surface area of about 17.7 m2/g. A portion of the solid was calcined at about 1,100.degree. C. for 30 minutes to produce a light yellow powder.
Referring now to FIG. 7, FIG. 7 is an optical photomicrograph at 1,000X magnification of a portion of the powder formed according to Example 4. FIG. 7 shows a variety of different sized particles of BaSO.sub.4, which have unequal amounts of Eu:YVO.sub.4 phosphor crystallites deposited thereon.
FIG. 8 is a graphical representation of the R(I) spectrums, in terms of emission wavelength (x-axis) and R(I) (y-axis), for a portion of the powder formed in accordance with Example 4, and a commercially available powder comprising YVO.sub.4 containing approximately 4 wt. % Eu.sub.2 O.sub.3, which was supplied by GTE, under the trademark "Sylvania Type 2390". In FIG. 8, Curve "E" corresponds to the R(I) emitted by the powder of Example 4, whereas Curve "F" corresponds to the R(I) emitted by the Sylvania Type 2390 powder. The R(I) was generated by using a SLM-8000 spectrometer, which used settings corresponding substantially to those set forth in Example 3. FIG. 8 shows that the powder formed according to Example 4 is capable of emitting a R(I) which is about 45 to 60% of commercially available phosphor materials.
Example 5
This example describes a procedure for making a Y.sub.2 O.sub.3 :Eu phosphor composition coated onto a BaSO.sub.4 substrate by a dry powder process.
The two substantially dry powders which are employed in this example comprise BaSO.sub.4 (supplied by Sachtleben Corp. Blanc Fixe Micro Grade), which had been calcined previously at about 900.degree. C. for one hour and then hammer milled, and a europium doped yttrium oxalate powder that was formed substantially in accordance with the oxalate process described in Example 3; except that the oxalate powder was not deposited upon a core material.
About five grams of the oxalate was dry mixed in an alumina crucible with about 15 grams of the BaSO.sub.4, and then calcined in air at a temperature of about 1200.degree. C. for one hour. The final composition of this phosphor is essentially about Y.sub.2 O.sub.3 :Eu(5)/BaSO.sub.4 (84) which corresponds to an approximately 16 wt % coating of a 5 mole % europium doped yttria upon barium sulfate particles. The R(I) of a sample of the powder formed by the method of Example 5 was determined substantially in accordance with the procedure discussed in Example 1, and indicated a peak at about 1.64.
Example 6
This Example describes preparing a phosphor of barium sulfate particles that were coated with about 1.48% Eu.sub.2 O.sub.3 and 8.52% Y.sub.2 O.sub.3 which was obtained by using an oxalate process.
The barium sulfate particles which were used in this example are Blanc Fixe N Grade (a precipitated barium sulfate supplied by Sachtleben Corp.). The barium sulfate was treated prior to coating by being calcined at a temperature of about 700.degree. C. for 1 hr., and hammer milled. The calcined barium sulfate was slurried into about 4% aqueous hydrochloric acid at a temperature of about 60.degree. C. for about 1 hr, followed by washing with deionized water, and drying at a temperature of about 100.degree. C.
A sample of the dried barium sulfate (about 90 g) was slurried into about 1500 ml of deionized water, and the slurry was agitated overnight while maintaining a temperature of about 25.degree. C. The slurry was then heated to about 90.degree. C.
A first solution was prepared by combining a solution of yttrium oxide in aqueous hydrochloric acid (approximately 42.6 g, 20% Y2O3; 22.57% HCl), a solution of europium oxide in aqueous hydrochloric acid (approximately 7.38 g, 20% Eu2O3; 20.72% HCl) with about 50 g of deionized water at a temperature of about 25.degree. C. A second solution was prepared by dissolving about 17.3 g (0.1384 mole) oxalic acid dehydrate into 46 g of deionized water at about 60.degree. C. The first and second solutions were added simultaneously to the previously described barium sulfate slurry over a period of about 2 hrs while maintaining the temperature of the reaction mixture at about 90.degree. C. The resulting white slurry was heated under reflux (102.degree. C.) for about 6 hrs.
After cooling the slurry to a temperature of about 25.degree. C., the white slurry was filtered, and the filter cake was washed with about 4 liters of deionized water. The filter cake was dried at a temperature of about 120.degree. C., thereby forming about 108.9 g of a white solid having a surface area of about 1.2 m2/g, and a particle size distribution of: D.sub.90, 9.24 um; D.sub.50, 4.99 um; and D.sub.10, 1.96 um.
A portion of the dried white powder was calcined in air at a temperature of about 1200.degree. C. for 10 min., which produced another white powder with a surface area of about 0.32 m2/g, and a particle size distribution of: D.sub.90, 28.9 um; D.sub.50, 9.91 um; and D.sub.10, 2.21 um.
Referring now to FIG. 9, FIG. 9 is an optical photomicrograph at 600X magnification taken under crossed-nicols, and with an immersion oil, which has a refractive index of 1.64, of a powder formed according to Example 6. FIG. 9 shows two major BaSO.sub.4 particles, which are birefringant, and appear bright white on a black background. The relatively large particle possesses a less dense coating of Eu:Y.sub.2 O.sub.3 phosphor crystals, whereas the density of Eu:Y.sub.2 O.sub.3 phosphor crystallites is greater on the smaller particle.
FIG. 10 is an optical photomicrograph of the same powder shown in FIG. 9, with the exception that FIG. 10 was taken without the crossed-nicols. Because the refractive index of the immersion oil is substantially equivalent to the refractive index of BaSO.sub.4, the BaSO.sub.4 particles were essentially invisible in FIG. 10, and only the relatively small and dark phosphor crystallites are clearly visible. The phosphor crystallites are more easily seen in FIG. 10 because the refractive index of Eu:Y.sub.2 O.sub.3 is much greater than 1.64.
The R(I) of the powder shown in FIGS. 9 and 10 was measured substantially in accordance with the method described in Example 1. FIG. 11 is a graphical representation, in terms of emission wavelength (x-axis) and R(I) (y-axis), of the powder shown in FIGS. 9 and 10, as well as the commercially available powder shown in FIG. 1. Curve "H" on FIG. 11 corresponds to the emitted R(I) for the powder shown in FIG. 1, whereas Curve "G" corresponds to the emitted R(I) for the powder made in accordance with Example 6. The R(I) was generated by using a SLM-8000 spectrometer which was operated substantially at the settings set forth in Example 3.
A review of FIG. 11 demonstrates that the composition of the invention is capable of achieving a peak R(I) value, i.e., about 2.0, which is commensurate with commercially available phosphors.
Comparative Example 7
This Example illustrates that the phosphor coated powders of the invention achieve an improved measured R(I) over an uncalcined mechanical mixture of BaSO.sub.4 and Eu:Y.sub.2 O.sub.3.
About 4 grams of commercially available BaSO.sub.4, and about 1 gram of Eu:Y.sub.2 O.sub.3 (supplied by GTE as Sylvania Type 2340), were mechanically dry mixed together by shaking in a glass vial. The resultant powder contained a total of about 20% by weight phosphor. The peak measured R(I) of Eu:Y.sub.2 O.sub.3 portion of the mixed powder, prior to being mixed with BaSO.sub.4, was about 1.96, and the peak R(I) of the mixed powder was about 0.54.
For purposes of comparison, a coated phosphor product of the invention was prepared substantially in accordance with Example 1 which comprised a coating of about 5 mole % Eu:Y.sub.2 O.sub.3 upon the BaSO.sub.4 powder described in Example 1. The coating corresponded to about 20% by weight of the total phosphor coated product. After being calcined at a temperature of about 1,100.degree. C. for a period of about 4 hours, the phosphor coated product of the invention had a peak R(I) of about 1.57. Based upon the measured R(I) intensities, the coated powder of the invention can employ an equivalent weight of phosphor as the dry mechanical mixture for achieving superior intensities.
While certain aspects of the invention have been described in detail one of ordinary skill would recognize that other aspects or embodiments and variations are encompassed by the appended claims.
Claims
The following is claimed:
1. A process for preparing a luminescent composition comprising the steps of: (a) preparing an aqueous or aqueous organic slurry of particles comprising one or more inert particles, (b) adding a stable solution comprising at least one metal chelate to the slurry, (c) raising the pH of the slurry to above about 9, (d) heating the slurry to a temperature of at least about 50.degree. C. for a time sufficient to deposit at least one hydrous metal oxide onto at least a portion of the surface of said particles, (e) recovering the particles, and; (f) calcining the particles at a temperature sufficient to activate said hydrous metal oxide upon the particles thereby obtaining the luminescent composition.
2. A process for preparing a luminescent composition comprising the steps of: (a) preparing an aqueous or aqueous organic slurry comprising one or more inert particles selected from the group consisting of an alkaline earth sulfate, alkaline earth phosphate, a metal silicate, mixed metal oxides, an alkaline earth fluoride, and a metal titanate, (b) adding oxalic acid to the slurry of particles, (c) adding an acidic aqueous or aqueous organic solution of at least one metal to the slurry, (d) heating the slurry to a temperature sufficient to deposit at least one oxalate metal salt onto the surface of the inert particles, (e) recovering the particles, and; (f) calcining the particles at a temperature sufficient to activate said salt upon the particles thereby obtaining the luminescent composition.
3. A process for preparing a luminescent sulfide composition comprising the steps of: (a) preparing an aqueous or aqueous organic slurry of particles comprising one or more inert particles, (b) adding a stable solution comprising at least one metal chelate to the slurry, (c) raising the pH of the slurry to above about 9 and depositing at least one hydrous metal oxide onto at least a portion of the surface of said particles, (d) adding a solution comprising at least one sulfide salt, and heating the slurry containing said salt to a temperature sufficient to convert said hydrous metal oxide to a sulfide on the surface of the inert particles, (g) recovering the particles, (h) calcining the recovered particles to produce a luminescent sulfide upon the surface of the particles thereby obtaining the luminescent sulfide composition.
4. A process for preparing a luminescent composition comprising the steps of: (a) blending oxalate metal salts with particles comprising at least one inert material selected from the group consisting of an alkaline earth sulfate, alkaline earth phosphate, a metal silicate, mixed metal oxides, an alkaline earth fluoride, and a metal titanate, and; (b) calcining the blend at a temperature sufficient to cause formation of an activated luminescent material upon the surface of said particles thereby obtaining the luminescent composition.
5. The process of claim 1, or 3 wherein the particles comprises at least one member selected from the group consisting of an alkaline earth sulfate, alkaline earth phosphate, a metal silicate, mixed metal oxides, an alkaline earth fluoride, and a metal titanates.
6. The process of claim 1, 2 or 4 wherein the activated luminescent material comprises at least one member selected from the group consisting of (Y.sub.2 O.sub.3 :Eu), (Y.sub.2 O.sub.2 S:Eu), (YVO.sub.4 :Eu), (Zn.sub.2 SiO.sub.4 :Mn), (BaMg.sub.2 Al.sub.16 O.sub.27 :Eu), (SrB.sub.4 O.sub.7 :Eu), Ce.sub.0.65 Tb.sub.0.35 MgAl.sub.11 O.sub.19, (ZnS:Cu), (ZnS:Ag), (MgWO.sub.4), barium titanium phosphate, Sn and Eu activated alkaline earth ortho and pyrophosphates, and Sb and/or Mn activated calcium halophosphates.
7. The process of claim 1, 2, 3 or 4 wherein the activated luminescent material comprises 5 to 20 weight percent of the total composition and the average diameter of the particles ranges from 1.0 to 10 microns.
8. The process of claim 1, 2, or 3, wherein said slurry comprises water, and a water miscible organic fluid selected from the group consisting of C.sub.1 -C.sub.4 branched or straight chain alcohols, and glycols.
9. The process of claim 1 or 3, wherein said chelating agent comprises at least one member from the group of alpha-hydroxycarboxylic acids, malic and citric acid, alpha-aminocarboxylic acids, and glycine.
10. The process of claim 1, 2 or 3, wherein said luminescent composition is substantially free from poisons.
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