Process for Preparing Yttrium Oxide and Rare Earth Metal Oxide Phosphors

A europium-activated gadolinium oxide phosphor having the formula Gd.sub.1.96 Eu.sub..04 O.sub.3 was prepared by use of the co-precipitation procedures described in U.S. Pat. No. 3,668,143 as follows:

A solution A was prepared by mixing 375 milliliters of 2 molar gadolinium trichloride solution, 37.5 milliliters of 0.4 molar europium trichloride solution and sufficient distilled water to make 5 liters. A solution B was prepared by mixing 1600 milliliters of 1 molar oxalic acid solution with sufficient distilled water to make 5 liters. A solution C was prepared by mixing 200 milliliters of 2 molar gadolinium trichloride solution and 20 milliliters of 0.4 molar europium trichloride solution with sufficient distilled water to make 4 liters. Solutions A and B were heated to 80.degree. C. Solution C was placed in the fluted 22 liter flask described in U.S. Pat. No. 3,668,143 and heated to 95.degree. C. Solutions A and B were then simultaneously added to solution C at a rate of 100 milliliters of each per minute and solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle and was washed four times by decantation with distilled water. It was then collected and dried in air at room temperature overnight. The dry precipitate was placed in a quartz tray and heated in air for 1.5 hours at a temperature of 1115.degree. C. in a muffle furnace and then rapidly cooled in air. The phosphor obtained by this procedure was placed in a metal planchet in the form of a layer with a thickness of 0.078 inch and an area of 0.76 square inches. A similar planchet was filled with a layer of a commercially available calcium tungstate phosphor. The planchets were placed close to a sheet of black and white, high-speed, pan-sensitized negative film (code 2403 Tri-X recording film manufactured by Eastman Kodak Company) and exposed to 70 kvp X-rays filtered by 0.5 millimeters of copper and 1 millimeter of aluminum. After exposure, the film was developed, stopped, fixed, washed and dried in the conventional manner. The film was also exposed through an aluminum step wedge to determine the relationship between exposure and developed density. The exposure produced by the europium-activated gadolinium oxide phosphor with excitation by the filtered 70 kvp X-rays was found to be 3.8 times that obtained with the calcium tungstate phosphor used as a control.

A ten-gram portion of the europium-activated gadolinium oxide phosphor prepared in the manner described above was placed in a glassy carbon boat and was heated for 4 hours at 825.degree. C. in a tube furnace with 1.6 cubic feet per hour of nitrogen and 2 cubic feet per hour of argon passing through the tube. Before entering the furnace, the gas stream passed through a 500-milliliter capacity gas bubbler filled with distilled water. At the end of the heating period, the sample was rapidly cooled to room temperature in the atmosphere within the furnace. The exposure with excitation by the filtered 70 kvp X-rays was measured and was found to be 4.6 times that obtained with the calcium tungstate control and, thus, approximately 20 percent greater than that obtained with the phosphor prior to heating it in the atmosphere of argon and nitrogen. A second ten-gram portion of the phosphor was heated for 2 hours at 925.degree. C. under the same argon-nitrogen atmosphere and the exposure produced was 4.94 times that obtained by the control, giving a speed increase of about 30 percent compared to the untreated phosphor. A third ten-gram portion of the phosphor was heated in the same manner in a Corning Vycor boat for 3 hours at 825.degree. C. and the exposure produced was 4.37 times that of the control, giving an increase in X-ray speed of about 15 percent. Similar results were obtained by heating the phosphor in the carbon boat in a dry atmosphere of argon and nitrogen, that is, with use of a bubbler being omitted. However, when the phosphor was heated in the Vycor boat with air passing through the bubbler in place of the mixture of argon and nitrogen, no improvement in the speed of the phosphor was obtained. A fourth ten-gram sample of the phosphor was placed in a quartz boat inside the carbon boat and heated for 3 hours at 825.degree. C. with the mixture of argon and nitrogen passing through the water and a 30 percent increase in speed was obtained.

Planchets containing samples of the phosphors prepared in the manner described above were placed a distance of 54 inches from two fluorescent lamps and exposed for 30 minutes to a radiant flux of 70 microwatts per square centimeter. As a result of this exposure, the X-ray speed of the europium-activated gadolinium oxide phosphors which had not been heated in a non-oxidizing atmosphere decreased by 25-29 percent. The speed of the phosphor heated in contact with carbon in a dry inert gas atmosphere decreased by 15 percent, while the speed of the phosphor heated in the absence of carbon in an atmosphere of inert gas and water vapor decreased by 10 percent and the speed of the phosphors heated with carbon in an atmosphere of inert gas and water vapor did not decrease at all. Thus, the stability of the phosphor to light is best when it is heated in the mildly reducing atmosphere generated by reaction of carbon with water vapor.

All gas flow rates specified in these examples were measured at standard temperature and pressure and all speeds were determined as indicated in Example 1.

A terbium-activated gadolinium oxide phosphor having the formula Gd.sub.1.998 Tb.sub..002 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 375 milliliters of 2 molar gadolinium trichloride solution, 2 milliliters of 0.4 molar terbium trichloride solution, and 125 milliliters of 37.5 percent hydrochloric acid with sufficient distilled water to make 5 liters of solution. A solution B was prepared by mixing 1125 milliliters of 1 molar oxalic acid with sufficient distilled water to make 5 liters. A solution C was prepared by mixing 100 milliliters of 1 molar oxalic acid and sufficient distilled water to make 4 liters. Solutions A and B were heated to 70.degree. C. Solution C was placed in the fluted 22-liter flask and heated to 95.degree. C. After adding 81.5 milliliters of 37.5 percent hydrochloric acid to solution C, solutions A and B were simultaneously added to solution C at a rate of 250 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle and was washed four times by decantation with distilled water. It was then collected and dried in air at room temperature overnight. The dry precipitate was placed in a quartz tray and heated in air for 1.5 hours at a temperature of 1115.degree. C. The resulting Gd.sub.2 O.sub.3 :Tb phosphor was rapidly cooled in air and the X-ray speed was determined in the same manner as in Example 1. The exposure was found to be one third of that produced by the calcium tungstate control. When ten grams of this phosphor was placed in a carbon boat and heated for 4 hours at 825.degree. C. in a tube furnace through which wet nitrogen and argon were passed under the conditions specified in Example 1, the exposure produced was found to be 6 times greater than that of the untreated phosphor. This constitutes an increase in X-ray speed of about 500%. A second ten-gram portion of the phosphor was placed in a Corning Vycor boat and heated for 2 hours at 500.degree. C. with 1.6 cubic feet per hour of hydrogen and 2 cubic feet per hour of argon passing through the bubbler and the treatment was found to increase the speed by a factor of five times. This constitutes an increase in X-ray speed of about 400%.

A dysprosium-activated gadolinium oxide phosphor having the formula Gd.sub.1.92 Dy.sub..08 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 1 liter of 0.3 molar gadolinium trichloride solution, 3 milliliters of 0.4 molar dysprosium trichloride solution and 49 milliliters of 37.5 percent hydrochloric acid with sufficient distilled water to make 2 liters. A solution B was prepared by mixing 450 milliliters of 1 molar oxalic acid solution with sufficient distilled water to make 2 liters. A solution C was prepared by mixing 75 milliliters of 1 molar oxalic acid with sufficient distilled water to make 4 liters. Solution C was placed in the fluted 22 liter flask and heated to 95.degree. C. Then 81.5 milliliters of 37.5 percent hydrochloric acid was added and solutions A and B were simultaneously added to solution C at a rate of 100 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle, washed four times by decantation with distilled water, collected and dried in air at room temperature. The dry precipitate was placed in a quartz tray and heated in air for 1.5 hours at a temperature of 1115.degree. C. The resulting Gd.sub.2 O.sub.3 :Dy phosphor was rapidly cooled in air and the X-ray speed was determined in the same manner as in Example 1. The exposure was found to be 0.8 times that obtained with the calcium tungstate control. When ten grams of this phosphor was placed in a Vycor boat and heated for 2 hours at 500.degree. C. in the tube furnace used in Example 1 with 1.6 cubic feet per hour of hydrogen and 2 cubic feet of argon passing through the bubbler, the speed was found to be twice that of the untreated phosphor. This constitutes an increase in X-ray speed of about 100%. The same improvement in X-ray speed was obtained when the phosphor was heated at 825.degree. C. for 4 hours in a glassy carbon boat with 1.6 cubic feet per hour of nitrogen and 2 cubic feet per hour of argon passing through the bubbler. Similar results were also obtained with a dry atmosphere of argon and nitrogen.

A terbium-activated yttrium oxide phosphor having the formula Y.sub.1.92 Tb.sub..08 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 1 liter of 0.3 molar yttrium trichloride solution, 30 milliliters of 0.4 molar terbium trichloride solution, and 49 milliliters of 37.5 percent hydrochloric acid in sufficient distilled water to make 2 liters. A solution B was prepared by mixing 450 milliliters of 1 molar oxalic acid with sufficient distilled water to make 2 liters. A solution C was prepared by mixing 75 milliliters of 1 molar oxalic acid with sufficient distilled water to make 4 liters. Solution C was placed in the fluted 22 liter flask and heated to 95.degree. C. Then 81.5 milliliters of 37.5 percent hydrochloric acid was added and solutions A and B were simultaneously added to solution C at a rate of 100 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle, washed four times by decantation with distilled water, collected and dried in air at room temperature. The dry precipitate was placed in a quartz tray and heated in air for 1 hour and 20 minutes at a temperature of 1000.degree. C. The resulting Y.sub.2 O.sub.3 :Tb phosphor was cooled in air and the X-ray speed was determined in the same manner as in Example 1. The speed was found to be 1/25 that of the calcium tungstate control. When ten grams of this phosphor was placed in a Vycor boat and heated for 2 hours at 500.degree. C. in the tube furnace used in Example 1 with 1.6 cubic feet per hour of hydrogen and 2 cubic feet per hour of nitrogen passing through the tube (the gases used were dry as the bubbler was not employed), the X-ray speed of the phosphor was found to be increased by about 480%.

A gadolinium-activated yttrium oxide phosphor having the formula Y.sub.1.99 Gd.sub..01 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 1 liter of 0.3 molar yttrium trichloride solution, 4 milliliters of 0.4 molar gadolinium trichloride solution, and 49 milliliters of 37.5 percent hydrochloric acid in sufficient distilled water to make 2 liters. A solution B was prepared by mixing 450 milliliters of 1 molar oxalic acid with sufficient distilled water to make 2 liters. A solution C was prepared by mixing 75 milliliters of 1 molar oxalic acid with sufficient distilled water to make 4 liters. Solution C was placed in the fluted 22-liter flask and heated to 95.degree. C. Then 81.5 milliliters of 37.5 percent hydrochloric acid was added and solutions A and B were simultaneously added to solution C at a rate of 100 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle, washed four times by decantation with distilled water, collected and dried in air at room temperature. The dry precipitate was placed in a quartz tray and heated in air for 1 hour and 20 minutes at a temperature of 1000.degree. C. The resulting Y.sub.2 O.sub.3 :Gd phosphor was cooled in air and the X-ray speed was determined in the same manner as in Example 1. The speed was found to be 0.23 times that of the calcium tungstate control. When ten grams of this phosphor was placed in a carbon boat and heated for 4 hours at 825.degree. C. in the tube furnace used in Example 1 with 2.0 cubic feet per hour of argon and 1.6 cubic feet per hour of nitrogen passing through the bubbler, the X-ray speed of the phosphor was found to be increased by about 60%.

A europium-activated lanthanum oxide phosphor having the formula La.sub.1.96 Eu.sub..04 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 375 milliliters of 2 molar lanthanum trichloride solution and 37.5 milliliters of 0.4 molar europium trichloride solution with sufficient distilled water to make 5 liters. A solution B was prepared by mixing 1600 milliliters of 1 molar oxalic acid and sufficient distilled water to make 5 liters. A solution C was prepared by mixing 200 milliliters of 2 molar lanthanum trichloride solution and 20 milliliters of 0.4 molar europium trichloride solution with sufficient distilled water to make 4 liters. Solutions A and B were heated to 80.degree. C. Solution C was placed in the fluted 22-liter flask and heated to 95.degree. C. Solutions A and B were then simultaneously added to solution C at a rate of 100 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle, washed four times by decantation with distilled water, collected and dried in air at room temperature overnight. The dry precipitate was placed in a quartz tray and heated in air for 11/2 hours at a temperature of 1115.degree. C. The resulting La.sub.2 O.sub.3 :Eu phosphor was cooled in air and the X-ray speed was determined in a similar manner to that described in Example 1. The exposure produced was found to be 1.15 times that of the calcium tungstate control. When ten grams of this phosphor was placed in a carbon boat and heated for 3 hours at 925.degree. C. in the tube furnace used in Example 1 with 2.0 cubic feet per hour of argon and 1.6 cubic feet per hour of nitrogen passing through the water in the bubbler, the exposure produced by the phosphor was found to be 1.35 times that of the calcium tungstate control. This constitutes an increase in X-ray speed of about 17%. The reflectance spectrum of the La.sub.2 O.sub.3 :Eu phosphor, both before and after the heat treatment in the inert atmosphere, was compared with the reflectance spectrum of Eastman White Reflectance Standard barium sulfate. This comparison indicated that heating the phosphor in the inert atmosphere increased the reflectance substantially in the region of wavelengths between 325 and 700 nanometers.

A europium-activated yttrium oxide phosphor having the formula Y.sub.1.96 Eu.sub..04 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 375 milliliters of 2 molar yttrium trichloride solution and 37.5 milliliters of 0.4 molar europium trichloride solution with sufficient distilled water to make 5 liters. A solution B was prepared by mixing 1600 milliliters of 1 molar oxalic acid with sufficient distilled water to make 5 liters. A solution C was prepared by mixing 200 milliliters of 2 molar yttrium trichloride solution and 20 milliliters of 0.4 molar europium trichloride solution with sufficient distilled water to make 4 liters. Solutions A and B were heated to 80.degree. C. Solution C was placed in the fluted 22-liter flask and heated to 95.degree. C. Solutions A and B were then simultaneously added to solution C at a rate of 100 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle, washed four times by decantation with distilled water, collected and dried in air at room temperature overnight. The dry precipitate was placed in a quartz tray and heated in air for 11/2 hours at a temperature of 1115.degree. C. The resulting Y.sub.2 O.sub.3 :Eu phosphor was cooled in air and the X-ray speed was determined in a similar manner to that described in Example 1. The exposure produced was found to be 1.6 times that of the calcium tungstate control. When ten grams of this phosphor was placed in a carbon boat and heated for 3 hours at 925.degree. C. in the tube furnace used in Example 1 with 2.0 cubic feet per hour of argon and 1.6 cubic feet per hour of nitrogen passing through the water in the bubbler, the exposure produced by the phosphor was found to be 1.9 times that of the calcium tungstate control. This constitutes an increase in X-ray speed of about 19%. Measurement of the reflectance spectrum of this phosphor in the same manner as in Example 6 showed that the heat treatment in an inert atmosphere brought about substantial improvement in the reflectance between 325 and 750 nanometers.

A dysprosium-activated gadolinium oxide phosphor having the formula Gd.sub.1.996 Dy.sub..004 O.sub.3 was prepared in a manner similar to that described in Example 1. In preparing this phosphor, a solution A was prepared by mixing 750 milliliters of 1 molar gadolinium trichloride and 4 milliliters of 0.4 molar dysprosium trichloride with 125 milliliters of 37.5 percent hydrochloric acid solution and sufficient distilled water to make 5 liters. A solution B was prepared by mixing 1125 milliliters of 1 molar oxalic acid solution with sufficient distilled water to make 5 liters. A solution C was prepared by mixing 100 milliliters of 1 molar oxalic acid with sufficient distilled water to make 4 liters. Solutions A and B were heated to 70.degree. C. Solution C was placed in the fluted 22-liter flask and heated to 95.degree. C. Then 81.5 milliliters of 37.5 percent hydrochloric acid was added to solution C followed by simultaneous addition of solutions A and B at a rate of 100 milliliters of each per minute. Solution C was vigorously stirred during the addition. When the addition was complete, the precipitate was allowed to settle, washed four times by decantation with distilled water, collected and dried in air at room temperature overnight. The dry precipitate was placed in a quartz tray and heated in air for 11/2 hours at a temperature of 1115.degree. C. The resulting Gd.sub.2 O.sub.3 :Dy phosphor was cooled in air and the X-ray speed was determined in a similar manner to that described in Example 1. The exposure produced was found to be equal to that of the calcium tungstate control. When 20 grams of this phosphor was placed in a carbon boat and heated for 3 hours at 925.degree. C. in the tube furnace used in Example 1 with 2.0 cubic feet per hour of argon and 1.6 cubic feet per hour of nitrogen passing through the water in the bubbler, the exposure produced by the phosphor was found to be 2.3 times that of the calcium tungstate control. This constitutes an increase in X-ray speed of about 130%. Measurement of the reflectance spectrum of this phosphor in the same manner as in Example 6 showed that the heat treatment in an inert atmosphere brought about substantial improvement in the reflectance between 320 and 750 nanometers.

Thirty-four grams of 99.99 percent gadolinium oxide was thoroughly mixed with 9.4 milliliters of 0.4 M europium trichloride (99.9 percent) in a glass mortar, then dried at 100.degree. C. After drying, the mixture was ground and ignited for 11/2 hours at 1115.degree. C. After ignition, the phosphor was tested in the manner described in Example 2 and the speed was measured in the manner described in Example 2, with the exception that the film was developed for 12 minutes in Kodak Developer D-19 at 75.degree. F. The exposure produced by this europium-activated gadolinium oxide phosphor, having the formula Gd.sub.1.96 Eu.sub..04 O.sub.3, with the excitation by filtered 70 kvp X-rays, was about 1.02 X that produced by the commercial calcium tungstate phosphor.

Fifteen grams of the gadolinium oxide phosphor was placed in the glassy carbon boat and ignited in wet argon and nitrogen at 925.degree. C. for 2 hours (gas flow rates were 2.0 and 1.6 cfh, respectively, measured with flow meters calibrated with air). After cooling in the inert atmosphere, the sample was removed and the speed was measured as decribed before. This measurement showed that the speed had increased to 1.51 X that produced by the commercial calcium tungstate phosphor, producing an increase in X-ray speed of about 49%.

Fifteen grams of the gadolinium oxide phosphor was placed in a Corning Vycor boat and heated in hydrogen and argon for 2 hours at 500.degree. C. (gas flow rates were 1.6 and 2.0 cfh, respectively). The phosphor was then cooled in an inert atmosphere and the speed was measured as described before. This measurement showed that the speed had increased to 1.65 X that produced by the commercial calcium tungstate phosphor, giving an increase in X-ray speed of about 63%.

Finally, fiften grams of the phosphor was ignited in a quartz boat in air for 2 hours at 1100.degree. C. Again, the speed was about 1.0 X that produced by the commercial calcium tungstate.

Exposure of these phosphor samples to the light from two fluorescent lamps in the manner described before decreased the speed of the sample that had been ignited in air to a value that was 0.64 X that of the commercial calcium tungstate, but had little or no effect on the speed of samples that had been heated in the inert or reducing atmosphere.

This example again illustrates the increases in X-ray speed that result from the use of a heating step with a non-oxidizing atmosphere, and the particularly beneficial increases that result when the non-oxidizing atmosphere is a mildly reducing atmosphere. The example further illustrates that minor amounts of other oxides may be present without adversely affecting the increases in X-ray speed that result from the invention, and that use of higher firing temperature in the first heating step (oxygen containing atmosphere) enhances the increases in X-ray speed obtained in the firing in the non-oxidizing atmosphere.

A solution (A) was prepared by mixing 1 liter of 0.6 M yttrium trichloride, 60 ml of 0.4 M terbium trichloride, and 98 ml of 37.5 percent hydrochloric acid with sufficient distilled water to make 4 liters. A second solution (B) was prepared by mixing 900 ml of 1 M oxalic acid with sufficient distilled water to make 4 liters. A third solution (C) was prepared by mixing 150 ml of 1 M oxalic acid and 163 ml of 37.5 percent hydrochloric acid with sufficient distilled water to make 8 liters. The purity of the yttrium and terbium oxides with respect to other rare earth oxides was 99.99 and 99.9 percent, respectively, and the other constituents of the solutions were Reagent Grade. Solution (C) was heated to 95.degree. C. and Solutions (A) and (B) were heated to 70.degree. C. Solution (C) was then vigorously agitated while Solutions (A) and (B) were added simultaneously at a rate of 67 ml/min. The yttrium terbium oxalate precipitate was washed with distilled water, then collected, dried in air, and fired at 1000.degree. C. in air for one hour. The procedure was repeated and the Y.sub.2 O.sub.3 :Tb was blended to provide sufficient material for the following experiments.

Three mixtures with the following composition were prepared: Y.sub.2 O.sub.3 :Tb, 53.7 g and MgO (Reagent Grade), 0.5 g; Y.sub.2 O.sub.3 :Tb, 53.7 g, and Al.sub.2 O.sub.3 (99.99 percent), 1.27 g; and Y.sub.2 O.sub.3 :Tb, 53.7 g, and B.sub.2 O.sub.3 (Ventron Ultra Pure Crystal), 0.87 g. Each mixture was placed in an aluminum oxide crucible, covered, and heated in air to 1000.degree. C. for three hours. A portion of the of the Y.sub.2 O.sub.3 :Tb without any addition was also processed in the same way. A similar set of examples was heated in air to 1400.degree. C. for 31/2 hours. At the conclusion of this procedure, there were eight samples; four prepared at 1000.degree. C. and four at 1400.degree. C.

Each of the eight samples was separated into four portions. The first portion was not treated further. The second was placed in a quartz boat in a quartz tube furnace and heated to 500.degree. C. with 2.6 cubic feet per hour of hydrogen and 3.0 cubic feet per hour (cfh) of nitrogen flowing through the tube for two hours. At the end of this treatment, the sample was cooled in an atmosphere of nitrogen to room temperature before removing it from the quartz tube. The third portion was heated in the same boat and tube furnace to 500.degree. C. for two hours with only 4.0 cfh of nitrogen flowing through the tube. It was then cooled in nitrogen to room temperature as before. The fourth portion was heated in the same boat and tube furnace to 800.degree. C. for two hours with 4.0 cfh of nitrogen flowing through the tube. It was then cooled in nitrogen to room temperature as before.

The resulting 32 samples and a sample of commercial calcium tungstate (DuPont No. 501) were placed in metal planchets. Then the planchets were placed close to a sheet of black-and-white, high-speed, pan-sensitized negative film (KODAK TRI-X Recording Film, Code 2403, manufactured by Eastman Kodak Company) and exposed to 70 kVp X-rays filtered by 0.5 mm of copper and 1 mm of aluminum. After exposure, the film was developed, stopped, fixed, washed, and dried in the conventional manner. The film was also exposed through an aluminum step wedge to determine the relationship between exposure and developed density. The exposure produced by the terbium-activated phosphors with excitation by the filtered 70 kVp X-rays was compared with that produced by the calcium tungstate phosphor (speed= 100) and the results are summarized in Table I below.

Oxide phosphors prepared in accordance with the method of this invention find utility in a number of fields, for example, in cathode ray tubes for television applications and in fluorescent lamps. However, they are especially useful in the preparation of intensifying screens for use in radiography. Because of their high X-ray speed, they make it possible to decrease the speed and granularity of the radiographic film that is used to record the image. The intensifying screens can be used in film-screen combinations in which the film is double-coated or coated on only one side. The high speed of the phosphor also permits the use of absorbing layers to provide cross-over control in double-coated films without excessive loss in system speed. These phosphors are also advantageous in intensifying screens because of their high density, typically in excess of 6 grams per cubic centimeter, which aids in providing improved radiographic sharpness without excessive mottle. The intensifying screens can be prepared in accordance with the usual practice in the art by dispersing the phosphor in a suitable binder, such as a copolymer of acrylic acid and an alkyl acrylate, a vinyl chloride polymer, polyvinyl butyral, a polycarbonate resin, and the like, and coating it on a suitable support such as a polyester film, or layers without binder can be used. Good results are obtained with a phosphor to binder ratio on a weight basis of from about 4:1 to about 30:1 and more preferably from about 10:1 to about 20:1 and with a phosphor coverage in the range of from about 15 to about 120 grams per square foot of screen and more preferably from about 30 to about 60 grams per square foot of screen.

An especially useful radiographic system employing the oxide phosphors prepared by the process of this invention consists of two intensifying screens, each having a coating of the phosphor dispersed in a binder, used in combination with a double-coated spectrally sensitized film that contains enough dye or other absorbing material to make the exposure of the back emulsion layer of the film less than 30 percent of the total exposure of both emulsion layers when the film is exposed to X-rays with only a single screen in contact with the front emulsion layer. In this combination, the high density of the phosphor improves the definition of the image that is produced and this improvement in definition is not obtained at the expense of system speed or mottle because the phosphor has high efficiency of fluorescence when excited by X-rays and for this reason relatively slow films with good physical characteristics and low granularity can be used.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.