Method of making improved strontium magnesium pyrophosphate phosphor activated by divalent europium
United States Patent [1 1 Shaffer 1 Apr. 29, 1975 METHOD OF MAKING IMPROVED STRONTIUM MAGNESIUM PYROPHOSPHATE PHOSPHOR ACTIVATED BY DIVALENT EUROPIUM [75] Inventor: Francis N. Shaffer, Towanda, Pa.  
 [73] Assignee: GTE Sylvania Incorporated,  
 Stamford, Conn.  
 [22] Filed: Feb. 5, 1973 [21] Appl. No.: 329,627  
 [52] US. Cl. 252/30l.4 P [51] Int. Cl C09k H36 [58] Field of Search 252/3014 P [56] References Cited UNITED STATES PATENTS 3,484.383 12/1969 Hoffman 252/3014 P 3.599.028 8/1971 Wanmaker 252/30L4 P Primary E.\&#39;aminer.lack Cooper Attorney, Agent, or Firm-Norman J. OMalley; William H. McNeil]; Donald R. Castle [57] ABSTRACT Divalent europium activated strontium magnesium pyrophosphate phosphors (SrMgP O :Eu having improved brightness when used in low pressure mercury vapor lamps are prepared by using EuPO,X H O as the europium source and firing in covered containers. Also disclosed is a novel method for preparing EuPO 2 Claims, No Drawings 1 METHOD OF MAKING IMPROVED STRONTIUM MAGNESIUM PYROPIIOSPIIATE PI-IOSPHOR ACTIVATED BY DIVALENT EUROPIUM &#39;BACRGROI&#39;JND OF THE INVENTION &#39;Phosphors of the type with which&#39; this invention is concerned; i.e.,divalent europium activated strontium magnesium pyrophosphate. are known in the art. See for example, Philips Research Reports, Volume 22, No. 4, page 355, W. L. Wanmaker et 21]., published August 1967 and Journal of-the Electrochemical Society, Volume N5, N0. 5, page 560, M. V. Hoffman, published May 1968. These&#39;phosphors peak at 3&#39;93 nm at 26 nm bandwidth with good efficiency&#39;when suitably fired at close to the sintering point. t  
  Such phosphors have. previously been prepared from starting materials comprising, SrHPO MgNH PO H and, as activator source, Eu- O plus (NH HPO When these materials are fired at temperatures&#39;in excess of l,l00C a partial melt results forming a glasslike phase which cannot be reduced to a fine powder. When such materials are fired in covered. containers at as high a temperature as possible without forming the glass-like sintered phase they,.are reducible to a fine powder and have efficient narrow band emission peakingat 393, nrn .when measured as phosphor plaques; however,,when processed-to a lampcoating, which .involves mixing the phosphorwith a lacquer slurry. coating the inside of the lamp tube and baking to remove the lacquer, these compositions retain considerable residual carbon that produces a darkened body color with a consequent decrease in brightness.  
 OBJECTS AND SUMMARY OF THE INVENTION It is. therefore, an object of this invention to obviate the disadvantages of the prior art.  
  It is another object of this invention to enhance the emission characteristics of lamps using the subject phosphors.  
  Yet another object of this invention is the provision of a method of making improved phosphors.  
  Still another object of the invention is the provision of a method for making one of the raw materials employed in these improved phosphors.  
  These objects are accomplished in one aspect of the invention by the substitution of EuPO X H O for Eu O plus (NH,,) HPO previously used as the source of the europium activator. This substitution allows the use of higher firing temperatures without the formation of a glass-like phase and provides a phosphor giving increased brightness when utilized in a lamp.  
 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.  
  Referring now to the invention with greater particularity, it has been found that the substitution of EuPO, H O for Eu O plus (NH HPO when used in combination with SrHPO and MgNI-LPO, H O as homogeneous starting material mixtures allows increased firing temperatures during phosphor synthesis before melting occurs. Such new compositions when fired in the temperature range of l,lC to l,l50C are hard, but free of the glass-like phase and friable to the extent that they-can be mortared to a finepowder. Placque brightness of the new higher temperature fired composition&#39; using the EuPO, substitute is equal to the best previous preparations containing Eu O plus (NHJ HPQ, used as a control. However, these new materials do not darken during the lacquer bake-out step of lamp fabrication when used as the phosphor coating of low pressure mercury lamps and remain at appreciably their original phosphor placque intensity. Under microscopicexamin&#39;ation, the new higher temperature fired phosphors have improved particle clarity when compared with the prior art material. Further, the new phosphor exhibits less pits and fractures for the retention of residual carbon from the lacquer bake-out step.  
  The following non-limiting example is shown emplary of the&#39;composition and method:  
 EXAMPLE 1 As actual quantities of combining materials Strontium ().78.\&#39; gram atoms Magnesium x gram atoms Europium (102x gram atoms Phosphate (P04) 2.00.\&#39; gram moles where A equals any positive whole or fractional number.  
  As a specific example using theabove concentrations 727 grams strontium diorthophosphate (98.58% SrHPO 949 grams magnesium ammonium phosphate (98.2% MgNH PO H 0) and 27 grams europium phosphate (93.9% EuPO were rendered to a homogeneous mixture by blending, passing through a micropulverizer and then reblending. This material was then first-step fired for about 2 hours at a cycling temperature ranging from l,l25C to l,l50C in covered 6 inch x 3 inch X 2 inch deep silica boats in a hydrogennitrogen atmosphere comprising about 5% hydrogen. The flow rate was about 20 liters per minute through a 4 inch diameter furnace tube. After the firing the material was cooled to near room temperature in the same atmosphere. At this stage, the first-step fired material was a very dense cake which was then broken down to a soft white powder in a porcelain mortar and sifted through a 200 mesh sieve. The material was then second-step fired for about 6 hours at a cycling temperature ranging from l,l25C to l,l50C (just under its melting temperature) in similar silica boats in a hydrogen-nitrogen atmosphere containing 25% hydrogen. The flow rate and furnace were the same as for the first-step firing. After the 6 hour firing step was completed the atmosphere was adjusted to 5% hydrogen and the boats cooled to near room temperature, after which they were removed from the furnace and exposed to air. The second-step fired material was also a very dense cake which was broken down to a soft white powder in a porcelain mortar with pestle and sifted through a 200 mesh sieve. When compared as placques with controls using phosphor prepared by the prior art compounds and method, the brightness of the new material, measured by comparing the relative emission intensity at the 393 nm band area under a constant 254 nm exciting source, was completely equal with the best this example remained a white body color, and thefinished lamp luminesced at an efficient level and showed excellent maintenance;both in excess of phosphor prepared by previous techniques.  
  The EuPO used in the above-described example was prepared by adding about 15% in excess P over a molar equivalent as (NH HPO in hot solution to a hot Eu(NO solution. The pH of the resultant slurry was then adjusted to about 4.5 by the addition of NH OH, while maintaining agitation. The precipitated product, after-decantation of the supernatant liquid, was washed with water on a Buchner funnel and then oven dried at 110C to hexagonalEuPO containing about 6% zeolitic water. The excess (NH HPO provides ample phosphate to insure close to theoretical yield and at the pH range of 4.4 to 4.6 the ratio of Eu to P0 is 1:1. The drying temperature of 1 10C should be considered near maximum as too high a drying temperature can drive off all the zeolitic water and convert the EuPO structure from the unstable hexagonal form to the stable monoclinic form.  
  While there have been shown and described what are at present considered to be the preferred embodiments of the invention, it will be apparent to those skilled in the art that various changes and modifications can be made herein without departing from the scope of the invention as defined by the appended claims.  
 What is claimed is:  
  l. A method of making strontium magnesium pyrophosphate phosphor activated by divalent europium comprisingthe steps of; preparing a substantially homogeneous mixture of starting host materials consisting essentially of strontium diorthophosphate and magnesium ammonium phosphate and a starting activator material consisting essentially of europium phosphate as EuPO X H 0 and heat treating said materials to form said phosphor. said heat treating comprising:  
 placing said homogeneous mixture in covered silica boats and first heat treating at a temperature between about 1,125C to 1,150C for about 2 hours in a first nitrogen-hydrogen atmosphere comprising about 5% hydrogen; cooling said mixture to about room temperature in said atmosphere; pulverizing the cake formed by said first heat treating in a porcelain mortar and sifting through a 200 mesh sieve; second heat treating said sieved mixture in covered silica boats at about 1,125C to 1,150C for about 6 hours in a nitrogen-hydrogen atmosphere comprising about 25% hydrogen; cooling said mixture to about room temperature in a nitrogen-hydrogen atmosphere comprising about 5% hydrogen; and  
  pulverizing said cake in a porcelain mortar and sieving through a 200 mesh sieve.  
  2. The method of claim 1 wherein said homogeneous mixture includes at least 0.78.\&#39; gram atoms of strontium; 1.20.\- gram atoms of magnesium; O.O2.\&#39; gram atoms of europium; and 2.00.\&#39; gram moles of phosphate and wherein is a positive number.