IE46863B1 - Fixation of radioactive materials in a glass matrix - Google Patents

Abstract

The new nonporous glass composition contains a radioactive material in the form of oxides or elements which is embedded and immobilised in the glass matrix. The said composition contains at least 75 moles per cent of SiO2, in addition to a radiation activity higher than 1 millicurie per cm<3> of the composition and a high chemical durability in aqueous solution. The composition may be in the form of a glass article showing an outer enclosure or glass skin comprising at least 90 moles per cent of SiO2 and substantially free from radioactive material, and an inner core formed by the said composition. The composition is used for binding radioactive materials. The attached figure is a graphic representation of the fraction of waste released into the environment after 20,000 years' storage.

Description

The disposal of large quantities of high level radioactive wastes generated in the reprocessing of spent power reactor fuel is a problem of considerable importance to the utilization of nuclear power. It is generally accepted that the most promising approach is to convert these radioactive wastes to a dry solid form which would render such wastes chemically, thermally and radiolytically stable. This problem of dry solid stability is closely related to the safety of human life on earth for a period of over 20,000 years. For example, radioactive waste contains the isotopes Sr^°, Ρυ^θ, and whose half lives are 29 years, 66,000 years, and 30 years respectively. These isotopes alone pose a significant threat to life and must be put into a dry, solid form which is stable for thousands of years. The solid radioactive waste form must be able to keep the radioactive isotopes inmobilized for this length of time, preferably even in the presence of a water environment.

A process for fixating radioactive materials in a dry solids form having high resistance to leaching and other forms of chemical attack would not only be suitable for the disposal of radioactive nuclear wastes, but also for the fabrication of radioactive sources useful in industry, medicine, and in the laboratory.

There does not presently exist any practical, foolproof means for the safe disposal, storage and immobilization of pernicious radioactive waste material. Present day storage containers do not provide sufficient isolation and immobilization of such radioactive material, sufficient long-term resistance to chemical attack by the surroundings, and sufficient stability at high temperature.

One present route is the so-called dry solids approach which involves the method of fixation of waste materials in glasses via melting glass procedures. This approach offers some improvement regarding isolation and decrease in the rate of release of radioactive elements when the outer envelopes or containers are destroyed. Further, glasses remain relatively more stable at high temperatures than plastics and are generally more chemically durable in saline solutions than are metals. Glasses with high chemical durability and low alkali ion conductivities are melted at very high temperatures, e.g. 1800°C and higher. Such high melting processes are economically unsound and moreover, cause a dangerous problem due to the volatilization of pernicious radioactive materials. In view of the overall difficulty of handling radioactive material, and especially in view of the danger of volatilization of radioactive material into the atmosphere, attention was directed to using glasses having relatively low melting temperatures, that is to say, using glasses with Si02 content as low as 27 weight percent. While the problem of volatilization of radioactive materials was reduced, it was not completely controlled. Moreover, the resultant glass composition exhibited greatly reduced chemically durability and increased ion diffusion rates for the radioactive materials present therein. The greater this diffusion rate, the lower is the ability of the glass to keep the radioactive materials immobilized in its matrix. For long-term containment of radioactive waste, demanded under present day standards, these glass compositions were inadequate. Additionally, none or very small amounts of gaseous radioactive materials are trapped by the foregoing procedures.

As will be apparent hereinafter from the various aspects of the applicants' contributions to the art, there are provided novel methods to obtain novel compositions and articles for the containment of pernicious and dangerous radioactive material over extraordinarily long periods of time. Unlike melting glass containment procedures, the methods of the invention need not involve any steps which would expose radioactive material to temperatures above 900°C thereby eliminating the environmental hazard due to volatilization of radioactive material into the atmosphere. In addition, there are provided novel methods for the fixation and immobilization of radioactive gas wastes such as Kr. I, Xe, Ra, etc., in a glass matrix.

The invention contemplates novel non-porous glass compositions or articles with high chemical durability to aqueous corrosion and with sufficiently low radioisotope diffusion coefficient values to provide protection of the environment from the release of radioactive material such as radioactive isotope, nuclear waste material, etc., encapsulated or entrapped therein. Such glass compositions are characterized by at least 75 mole percent of SiOg and by a radiation activity above one millicurie, preferably greater than one curie, per cubic centimeter of said glass compositions. In one aspect, the amount of radioactive material contained in the novel glass compositions is at least 0.1 mol percent, generally in the form of the oxide of at least five and preferably at least ten of the radioactive elements listed hereinafter. Preferably the novel glass compositions should contain at least 82 mol percent SiOg, most preferably greater than 89 mol percent SiOg.

According to one aspect of the present invention there is provided a non-porous glass composition containing radioactive material encapsulated and immobilized in the glass matrix, said composition being characterised by at least 75 mol percent SiOg.

According to another aspect of the present invention there is provided a glass article comprising an outer glass cladding or skin composition of at least 90 mol percent SiOg and substantially free of radioactive material and an inner core composition of at least 75 mol perecent SiOg and radioactive material encapsulated and immobilized therein.

According to a further aspect of the present invention there is provided a method of preventing the dissemination of radioactive material into the environment which comprises impregnating the pores of a porous glass preform with radioactive material, the preform including at least 75 mol percent SiOg, and obtaining a non-porous glass product containing an amount of radioactive material encapsulated and immobilized therein.

From a practical standpoint, the upper limit of radioactive material contained in the novel non-porous glass composition will be governed, to a degree, by such factors as: the SiOg concentration in the glass, by the concentration and type of other ingredients which may be present in the glass such as BgOj, AlgOj, TiOg, zirconia, alkali metal oxides, and COg, by the concentration and type of radioactive material encapsulated in the glass, by the volume fraction of the porous structure in the porous glass preform, by the various techniques employed to encapsulate the radioactive material in the glass, and other factors.

Radioactive material which can be encapsulated and immobilized in the glass matrix include radioactive elements (naturally occurring isotopes and man-made isotopes and existing as liquids, solids or gases), generally in the form of the oxide, such as carbon, rubidium, strontium, lanthanides, cobalt, cadmium, silver, zirconium, molybdenum, technetium, niobium, ruthenium, rhodium, palladium, tellurium, cesium, barium, francium, yttrium, radium, actinides and the gases of krypton, iodine, bromine, xenon and radon. Especially suitable in the practice of the invention are radioactive wastes from nuclear reactors or other waste producing processes.

One embodiment of the invention is directed to novel glass articles with enhanced containment properties and characterised by an outer cladding whose composition is at least 90 mol percent silica, preferably greater than 95 mol percent» and whose inner core contains the radioactive materials The high silica content of the cladding imparts to the articles a considerably greater chemical durability. The inner core has a lower silica concentration as set forth hereinbelow, i.e. at least 75 mol percenti silica, preferably 82 mol percent and most preferably 89 mol percent..

Various aspects of the invention are directed to novel methods for producing the aforesaid novel compositions or articles. The broad method is directed to encapsulating or entrapping radioactive material in a glass matrix which comprises impregnating the pores of a porous glass preform with radioactive material, drying when necessary, heating said porous glass preform until collapse of the porous structure occurs, thereby trapping said material in the resultant chemically inert, non-porous glass product.

The radioactive isotopes, as indicated previously, exist as gases, liquids or solids. The liquid isotopes are generally compounded into salts or other compounds, which, as with the solid isotopes, are dissolved into solution. Below, we treat such solutions separately from the gaseous isotopes. In the case of the solutions, two embodiments of the invention are described.

The literature adequately describes the preparation of porous glass preforms. Suitable preforms which may be utilized in the novel methods contain SiOg as a major component. In the practice of various embodiments of the invention the concentration of SiOg is at least 75 mol percent SiOg, preferably at least 82 mol percent SiOg, and most preferably at least 89 mol percent SiOg (and preferably less than 1 mol percent alkali metal oxide). Such glasses are described in the literature, see U.S. Patents Numbers 2,106,744, 2,272,342 and 2,326,059, for example. According to the first embodiment, the dopant consisting of the radioactive isotopes in the form of salts, oxides or other compounds are diffused into the pores of the preform; the preform is then removed from the dopant solution and is dried. Sintering of the molecular stuffed porous glasses allows for decomposition of the salts into oxides and incorporation into the glass matrix. Sintering is conducted at temperatures generally far lower than glass melting temperatures and thus minimizes the chances of radioactive material evaporation into the atmosphere. The resultant non-porous glass thus produced has a finite concentration of dopant throughout. According to the second embodiment, the dopant solution containing the radioactive compounds is diffused into the pores of the preform; the preform is removed from the dopant solution and immersed in one or several solutions of solvent for the dopant such as water, methanol, ethanol, acetone and nitric acid; the preform is then removed from the solvent solution(s) after a substantially dopant-free shell of sufficient thickness has developed at the surface of the preform and is dried. Sintering as in the method of the first embodiment ensues to form a non-porous glass with an inner core region containing the radioactive dopant, and an outer cladding region with a silica content of at least 90 mol percent preferably greater than 95 mol percent, and essentially containing no radioactive material.

Two embodiments of the invention are likewise set forth hereinafter for entrapping radioactive gases into the glass matrix. According to the first embodiment the porous glass preform is dried and then exposed to the radioactive (waste) gas at a pressure determined by the desired trapped gas concentration in the glass, allowing the gas to dissolve into the glass matrix, and the pores are sintered at high temperatures in the presence of the radioactive gas. According to the second embodiment, the porous glass preform is first immersed in a solution containing one or more other dopant compounds desirably in the form of their salts, prior to drying. These dopant compounds may be chosen to increase the surface area of the porous glass which in turn increases the amount of radioactive gas which can be absorbed in the glass or they may lower the glass transition temperature. The concentration of dopant compounds in the glass may be varied if desired. After precipitating said dopant compounds, the preform is dried and, if necessary, further heated to decompose the dopant compounds generally to their oxide form. The preform is then exposed to the radioactive waste gas at a pressure determined by the desired trapped gas concentration in the glass, allowing the gas to be absorbed into the glass matrix, and the pores are sintered at high temperatures in the presence of the radioactive waste gas.

The variation of dopant concentration in the glass preform prior to drying and Incorporation of the radioactive waste gas may be desirable for several reasons. If the dopant is another radioactive waste product, it will be desirable for its concentration to be as low as possible near the surface of the glass preform to further reduce the chance of leakage to the environment. Secondly, if the dopant used increases the amounts of gas held in the porous structure of the preform, it will also be desirable to decrease its concentration to as low a value as possible near the surface of the preform since this will result in a lowered concentration of radioactive gas near the surface of the glass and thus decrease the chance of leakage into the environment. Thirdly, if the dopant lowers the glass transition temperature of the glass matrix, and its concentration is varied to have a maximum at the interior of the preform and a minimum in a layer adjacent to the surface, then corresponding differences in the concentration of the dissolved radioactive gases will be obtained.

In an earlier fiber optics patent, U.S. Patent No. 3,938,974, we have limited the range of dopants used because high optical transmission was necessary and those dopants which caused the glass to attenuate light could not be used. However, in the radioactive fixation contemplated herein no such criteria need be applied.

A dopant is a compound which is deposited in the porous glass.

Said compound, or in the case of gases, element or molecule, may be incorporated in the glass during collapsing, either as deposited, or after conversion to the appropriate oxide. In the case of metals it is' often introduced as a nitrate in solution, or precipitated as a nitrate crystal. Upon heating, it decomposes to an oxide crystal, which upon collapsing of the structure, is incorporated in the silica structure.

Illustrative dopants include, of course, the radioactive material contemplated and described, the alkali metals, the alkaline earths, boron, germanium, aluminium, titanium, lead, bismuth, phosphorous and the rare earths, as nitrates, carbonates, acetates, phosphates, oxides, borates, arsenates and silicates in either hydrated or unhydrated form or mixtures thereof.

Fabrication of the porous glass matrix may follow any of the available methods used by one practiced in the art to form porous glass in any desired shape, preferably cylindrical or rectangular, with a composition greater than 75% silica. We prefer to form our porous glass matrices in the shape of cylinders according to the following method which is described more fully in our Patent Specification No. 44145. Briefly, a glass is melted containing silica, boron trioxide and two alkali metal oxides (such as Na20 and KgjO) and drawn into long rods. By suitable heat-treatment, these rods are phase separated into two phases; one phase, a silica-rich phase containing also, BgOg and alkali metal oxide and a silica-poor phase which contains greater amount of BgOg and alkali metal oxide.

The heat-treated rods are then immersed in a suitable leaching solution in order to dissolve and remove the phase containing the lower silica concentration. Removal of this phase and subsequent washing yields a porous glass preform characterised by a SiOg content greater than 90 mol percent which is ready for use as a matrix for the encapsulation of the radioactive material. Herein several procedures are followed depending upon whether the radioactive materials to be encapsulated are in the form of solids and liquids, or gases.

In the case of solid or liquid radioactive material including nuclear waste materials, the materials are generally available as an aqueous salt or other compound mixture of the various materials to be encapsulated. High level waste generally consists mainly of the aqueous raffinate for the first cycle of the well known Purex Solvent Extraction Process as well as other miscellaneous waste streams. Significant variation in the waste composition can occur. A typical composition is given in Table I below. Solvent is added to the waste material until all components have substantially gone into solution. Some processing plants also extract individual components from the waste mixtures such as Cs and Sr for specific use.

TABLE II Fission Products Concentration (atomic %) Replacements in stuffing solution Rb 1.0 Rb(NOg) Sr 5.2 Sr(N03)2 rare earths 17.8 rare earth nitrate mixture 2r 20.3 Zr(N03)4.5H20 Mo 18.1 - Tc 2.1 -Fe(N03)2-6H20 Ru 11.4 - Rh 1.0 Co(N03)3-6H20 Pd 6.2 Ni(N03)2-5H20 Te 2.3 Cs 5.2 Cs(N03) Ba 5.2 Ba(N03)2 actinides 4.2 rare earth nitrate mixture In this specification the expressions rare earth and lanthanides both mean the series of elements consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

In the non-waste applications the radioactive elements may occur singly, or as groups or compounded into salts or other compounds. In any case, they must be dissolved into solution or melted.

Porous glass substrates (in convenient rod shape) are submerged in the dopant solutions containing the radioactive materials for a period long enough to allow diffusion of the dopant material solution (stuffing solution) into the pores. This time depends upon the temperature of the stuffing solution, the pore structure, and the size of the porous glass host.

Various methods may be followed once the stuffing solution has filled the pores with waste material or other dopant. According to one method, the porous glass preform is removed from the stuffing solution; then the dopant is caused to precipitate within the preform by any of several routes for example evaporating the solvent from the solution, decreasing the temperature of the solution, or by chemical means. If desired, the preform may be given a brief wash to clean its surface area. Optionally, the preform may then be immersed in washing solution such as a solvent with low solubility for the dopant for several hours of soaking. Thereafter, the preform is dried, e.g., in a desiccator, vacuum chamber, etc., preferably at relatively low temperatures. This method when completed by the drying and sintering procedure described hereinafter, yields non-porous glass compositions with an essentially homogeneous concentration of waste materials.

According to a second method, the porous glass preform is removed from the stuffing solution; the dopant is allowed to begin precipitation; and thereafter the preform is immersed in a solvent with intermediate solubility for the dopant materials for several hours. This latter soaking procedure allows the formation of a thick skin or cladding at the outer surface of the preform by virtue of dopant being redissolved into the solvent. Soaking in several solvents with decreasing solubility for the dopants allows the removal of dopant from this skin region. Once accomplished, the preform is dried as illustrated above. This method, when completed by the drying and sintering procedures described hereinafter, yields non-porous· glass compositions with a skin of substantially lower concentration of dopant at the outside surface of the preform. Since it contains a lower dopant concentration, this skin acts to protect the interior of the glass from chemical attack and acts to further delay diffusion of radioactive materials from the glass interior to the surface where they may react with the environment.

Illustrative drying and sintering procedures including keeping the preform prepared by either of the aforesaid illustrated two methods under vacuum at low temperatures for approximately a day and then heating them, essentially at a rate of 15°C/hr still under vacuum, to a temperature above the decomposition temperature of the dopant and approximately 100°C below the glass transition temperature of the dopant-free porous glass matrix. At this point, any desired redox conditions for the dopant may be accomplished by various routes such as by further heating to the sintering temperature of the preform under vacuum for a reduced valence state of the dopant, or heating to the sintering temperature of the preform under a hydrogen-containing atmosphere for a highly reduced valence state of the dopant, or by heating to the sintering temperature of the preform under an oxygen-containing atmosphere of suitable pressure for a partially or totally oxidized dopant.

This ability to alter oxidation-reduction states of the radio-: active materials allows a fine control of the resistance of the glass to chemical attack since many of the radioactive materials, especially the actinides, are less soluble in water when in a reduced state. The ability to alter the oxidation-reduction state of such dangerous materials provides an additional safeguard against premature dispersion of such materials into the environment.

After sintering at high temperatures the products are cooled to ambient temperature whereby they form a non-porous glass completely encapsulating and immobilizing the radioactive material in its glass structure.

In a further embodiment, the invention provides for the storage and immobilization of radioactive contaminated boric acid aqueous solutions resulting during its use as a heat transfer media for pressured water nuclear reactors. Such contaminated solutions contain various radioactive impurities including Co, Cs, Mn, Cr, Sr and Zn as well as inert impurities such as Fe. At present such contaminated solutions are disposed of by fixation in cement forms and then buried a few feet beneath the ground. This disposal technique is very unsatisfactory since the cement has a low loading factor because the boric acid at room temperature has about a 5% solubility.

Furthermore, cement is not especially insoluble and leaches into the water table. Thus, even though one is dealing with the disposal of low level nuclear fuel cycle wastes, the detrimental impact on the environment and the population is obvious.

The novel methods disclosed herein orovide for the stuffing of such low level radioactive contaminated boric acid solutions into the porous glass preform. Such stuffing procedures can be effected at temperatures which will afford loadings several times greater than that achieved in the cement fixation technique. For example, the solubility of boric acid in water at 100°C is approximately 30 weight percent which permits about six fold greater loadings than are achieved at room temperature using the cement fixation technique.

The non-porous glass compositions of this latter embodiment are characterized by the encapsulation and immobilization of low level radioactive contaminated boric acid wastes (from pressurized water nuclear reactors), such waste being fixed in the glass matrix in the form of oxides of boron and the radioactive contaminants including cobalt and chromium. Other contaminants such as strontium, cesium, magnanese and/or zinc may also be present in oxide form. Such compositions generally contain less than one weight percent of radioactive contaminants (in the form of their oxide). However, in serious leakage problems in the pressurized water nuclear reactor, the boric acid wastes can contain much higher levels of contaminants.

In Examples I and II, the dopant solution contains only cesium nitrate in order to demonstrate simply the behaviour of dopant and porous glass system. Cesium is chosen because of its high concentration in the waste material and because by virtue of being an alkali metal its diffusion coefficient through glass is higher than other constituents except for rubidium (another alkali metal) which, however, is present at low concentrations. All compositions are on a mole basis. Cesium poses a further problem because of its high vapour pressure at the high temperatures normally required to melt glasses, which we circumvent by the practice of the novel methods contemplated herein. Thus, of all the radioactive isotopes in reactor waste, Cs probably poses the most problems in containment in glass and the greatest dangers in the near term. Accordingly, a procedure which will immobilize cesium in a glass matrix will also solve containment problems associated with other radioactive isotopes. Accordingly, a method which will result in the immobilization of Cesium will also immobilize other radioactive isotopes.

In Examples III to VI below, the molecular stuffing process of Example I is followed. In Example III, the stuffing solution contains SrNOg which like CsNOg is present in pernicious waste streams. The solution in Example IV simulates possible low level waste products in boric acid. The solutions in Examples V and VI resemble the actual unseparated waste material with Example VI simulating the major components of typical radioactive wastes generated in reprocessing fuel elements from utility-company reactors.

Examples I and II A porous glass preform is obtained by melting a glass having the composition: 60.2 mol percent Si02, 32.8 mol percent BgOg, 3.6 mol percent ha^O and 3.4 mol percent KgO, in a platinum crucible near 1400°C, homogenizing the melt with a platinum stirrer, thereafter pulling the melt into rods using a glass bait, cutting into cylinders or rods 7 mm. diameter x 30.5 cm. long, heat-treating these rods at 550°C for 1.5 to 2 hours, annealing the glass, washing in 2.5» aqueous solution of HF for 60 seconds, leaching in 3N HCl and 15 to 20% aqueous NH^Cl solution, and than washing in water. The resulting porous glass preform is characterized fay the interconnective porous structure and has the following composition: 95 mol percent SiOgj 5 mol percent BgOg, and less than 0.1 mol percent alkali metal oxide.

A porous glass preform rod so prepared is then placed into a so-called stuffing solution containing the waste material which in this case is an aqueous solution of CsN03 (concentration is 55 weight percent CsN03) for at least three hours while maintaining the solution at 105°C. In Example I, the stuffing solution of CsN03 is then replaced by a mixture of cold water and methanol for a few minutes until precipitation of CsN03 occurs in the porous structure, then the rod is soaked in methanol for three hours. In Example II, the stuffing solution is replaced by cold water and methanol for less than 2 minutes whereupon precipitation of CsNOg occurs. Then the glass rod is soaked in water for 3 hours at 2°C, followed by soaking in methanol for at least another 3 hours at 0°C. These two soakings produce a thin skin or cladding of the order of 1 mm. around the cylindrical surface of the rod. The skin was devoid of CsNO^.

In both Examples I and II, after maintaining the glass rods for 24 hours at 0°C under vacuum (about 0.1 mm, of Hg), the rods are dried under vacuum at increasing temperatures ranging from 0°C to 625°C to remove solvent, water and methanol, and to decompose the cerium nitrate dopant to its oxide. A heating rate of 15°C/hour is used. Further heating to 840°C, which is the sintering temperature of the porous glass rod, is conducted under an oxygen atmosphere. Once the porous glass structure collapses, consolidation is considered to be complete and the sintered non-porous rod is removed from the furnace and brought to ambient temperature.

Thereafter, both non-porous rods obtained from Examples I and II were tested for cesium concentration and associated refractive index profile. The composition of the centre of the rods from both Examples I and II was 92.1 mol percent Si02, 4.9 mol percent B203, and approximately 3 mol percent Cs20 (which corresponds to an index of refraction of 1.487) with trace amount of alkali metal oxide.

In Example I, this concentration remained essentially the same up to a very thin layer (or skin) appreciably less than 1 mm, at the surface. Analysis of the non-porous rod from Example II have a refractive index value of 1.458 in a 1 mm. thick surface layer about the rod. This value index indicates no measurable Cs20 dopant content in this layer.

The sole Figure is a plot of the fraction of waste material estimated as being released into the environment after 20,000 years of storage for a sintered glass product from Example II compared with a waste product obtained by the melting glass technique from Battelle Pacific Northwest Laboratory, Richland, Washington, U.S.A.

In order to obtain estimates of the diffusivity of cesium ions to allow estimates of the loss of radioactive waste as a function of time, electrical conductivity measurements were made on the two non-porous glass products obtained via the teachings of Examples I and II above and on a glass product (melting process) obtained from Battelle Pacific Northwest Laboratory. The values obtained are listed in Table II below.

TABLE II Conductivity at two temperatures Glass Product Temp. Conductivity (ohm-m) 1 Diffusivity (cm1 2 3 * * * */sec) Example 1 Example iB2^ Battelle^ 100 100 100 8 x IO18 9 x IO15 3.5 x 10-13 1 x 10'24 1.4 x IO’22 5.3 x 10“20 Example I 400 1 x 10'9 * * * 3 x 1016 Example 11^ 400 3 x 108 1 x IO14 Battelle 400 7 x 10-7 2 x 10-13 (1) These are calculated using the Stokes-Einstein relationship and are therefore only estimated values. (2) The data reported for Example II are for the surface layer only.

The central region has the same values as reported for Example I. (3) Battelle Pacific Northwest Laboratory, Richland, Washington.

This glass product contained less than one-half the cesium concentration of dopant encapsulated in glass products from Examples I and II.

In Table II above, diffusivity is estimated from conductivity values using the Stokes-Einstein relationship. These data establish that the non-porous glass product of Examples I and II when compared with the glass product (a melting procedure product from Battelle Pacific Northwest Laboratory) at room temperature, exhibit diffusivity values which are lower by several orders of magnitude notwithstanding the fact that the former products contained more than twice as much dopant as the latter product.

From the data, the theoretical weight loss after 20,000 years of exposure to a perfect sink (material which does not allow buildup of diffused molecules or atoms at the boundary - which is the most pessimistic estimate) is shown in the sole Figure plotted as a function, of storage temperature for a non-porous rod product made according to the method outlined in Example II.

Example III A porous glass preform (in the shape of a rod) prepared as described in Example I was immersed in a solution containing 95 grams of Sr^OgJg per 100 ml. of water at 60°C. The rod was allowed to soak in this solution for 4 hours, then the rod was removed from this solution and placed in cold isopropyl alcohol. Precipitation of SrNOg occurred slowly within the porous structures, taking 2 to 3 hours to reach completion. The rod was then soaked in a solution consisting of 66% ethanol and 34% water at 0°C for 5 hours to remove the SrNOg dopant from a cladding region at the surface of the rod. Finally, the rod was soaked in a cold 90% ethanol-10% water mixture and then in a cold isopropanol bath. Thereafter, the rod was dried and collapsed (sintered) as in Examples I and II, beginning with a stage in vacuum for 24 hours at 0°C. The rod when withdrawn from the furnace after sintering contained strontium incorporated into the glass structure in a core region of the rod; the cladding region was essentially free of strontium. 46833 Example IV A porous glass prpform rod prepared in Example I is soaked in a solution at 100°C containing 25 grams H3B03, 0.27 gram Fe(N03)3*9 HgO 0.27 gram Cs(N03), 0.27 gram Sr(N03)2, 0.27 gram Co(N03)2-6 HgO, 0.27 gram Cr(N03)3'9 HgO, 80 ml of water, and 1 ml of HN03 (13.4 molar concentration) for 3 hours. The rod is removed from the solution and it is then immersed in 0°C water for 30 minutes, and dried in vacuum at 0°C for 24 hours. The rod is subsequently heated at a rate of 15°C/hr to 625°C under vacuum to remove remaining solvent and to decompose the metal nitrate dopants, and then heated at a rate of 50°C/hr to 850°C under vacuum to collapse the pores and consolidate the glass. The final product is non-porous glass solid containing Si02, β2°3» an<* the oxides of Cs, Sr, Fe, Co, and Cr as an integral part of the matrix. The water immersion step after the soaking (stuffing) step decreases the dopant concentration near the surface of the rod. The rod may also be soaked in methyl acetate or acetone after removal of same from the stuffing solution in order to form a cladding region at the surface of the rod with lower dopant concentrations. However, rods prepared in this latter manner exhibit a tendency to split along its length during the drying and collapsing steps. However, such splitting of the rods is not detrimental to the fixation and immobilization of the radioactive material therein.

Example V A solution is prepared comprising: 12 grs Sr(N03)2 18 grs Rb(N03) 15.9 grs Ba(N03)2 104.1 grs Zr(N03)4'5H20 153.6 grs Fe(N03)3-9H20 4.2 grs Co(N03)2-6H20 21.3 grs Νι(Ν03)2·6Η20 lo 12.3 grs Cs(N03) 89.4 grs rare earth nitrate mixture and sufficient water to cause the above metal dopants to dissolve therein at approximately 100°C. A porous glass preform (in the shape of a rod) made as described in Example I was soaked in the above (stuffing) solution for 3 hours. The rod was then removed from the solution and inserted into a solution of 3N HN03 at 0°C for 10 minutes. The rod was then soaked in acetone for 2 hours at 0°C and was then placed in a drying chamber maintained at 0°C with suction pumping means operating a period of 24 hours (for withdrawing solvent from the rod). Thereafter, the rod was heated under vacuum up to 625°C at a rate of 15°C/hour. The rod was held at 525°C for 24 hours under vacuum, then heated slowly to 840°C, also under vacuum to obtain a highly reduced state from the waste material dopants contained in the porous structure of the preform. The rod was sintered near 840°C and formed a solid non-porous glass product with the waste material as an integral part of its structure.

Example VI A solution containing 10 major components from a typical radwaste composition often denoted as PW8a is used in this Example. The relative concentration of these components is representative of the waste stream composition with a reconcentration factor of three times.

The solution contains the following: 148.8 grs Fe(N03)3‘9H20 21.3 grs U02(N03)2*6 HgO 33.6 grs NaN03 18.6 grs Zr(N03)4-5H20 19.8 grs Nd(N03)5-5H20 9.0 grs Ce(N03)3-6H20 4.2 grs La(!W3)3*6H20 4.2 grs CsNOg 2.4 grs Se(fiO^)g 3.0 grs Ba(N03)2 254.9 grs HNOg 150 ml HgO Sufficient v/ater and nitric acid in amounts indicated above were added to maintain the above metal nitrates in solution. The preparation of the solution was accomplished stage-wise at varying temperature levels; the final temperature being 99°C.

Six porous rods prepared as in Examples I and II were immersed in the above solution maintained at 99°C for 3 hours, rinsed in 20°C water for 5 seconds, and then placed in a desiccator maintained at 20°C for 16 hours (hereinafter non-clad rods). Three non-clad rods were removed from the desiccator and were subjected to the following immersion treatments to produce a cladding region at the surface of the rod having a lower concentration of dopants (waste materials) than the inner core of the rod (hereinafter clad rods): 30 minutes in isopropanol containing 8 weight percent U0g(N03)g'6Hg0, 4 weight percent Ce(N03)2-6Hg0 and weight percent La(N03)3‘5HgO, and an additional 30 minutes in another solution of 80% chloroform and 20% isopropanol. These three clad rods were then dried for 24 hours at 0°C, at (a) 95% N2 and 5% Hg at one atm. (high reducing condition); (b) Under vacuum, i.e., <1 mm. of Hg (a moderate reducing condition); and (c) One atm. of air (an oxidizing condition).

At about 860°C sintering and collapse of the porous structure of the rods occurred.

Analysis of the resulting 3 pairs of non-porous glass rod products showed the metal oxide dopants to be in appropriately varying oxidation states. It is quite apparent that by the practice of this invention there can be obtained novel non-porous, chemically inert, glass products containing radioactive materials (in their lower state of oxidation), e.g., the actinides, encapsulated and immobilized therein for extraordinary long periods of time, e.g., centuries.

(B). Gases Various embodiments of the invention, as noted hereinabove, are directed to novel methods for the encapsulation and immobilization of radioactive gases in glass.

One such novel method is illustrated by Examples VII and VIII wherein the porous glass rod, as the host, is partially dried at 0°C under vacuum for about 24 hours, then further dried under vacuum by heating progressively to an upper drying temperature which is 50°C to 15O°C below the glass transition temperature of the undoped consolidated glass used as the host. This drying temperature is about 625°C for the porous glass rod employed. At 625°C, one or several radioactive gases are introduced into the enclosed chamber containing the rod. The temperature is held at 625°C for approximately 24 hours, then the rod is heated at approximately 50°C/hour up to 835-900°C where sintering occurs under an atmosphere of the radioactive gases, thereby trapping the absorbed gases within the glass matrix. The heating rates and holding temperatures may be readily altered, if desired. heating may in some cases break the rod. has no effect on the fixation and immobilization of the radioactive gas within the glass host.

In a second novel method, the porous glass rod is immersed in a solution containing one or several dopants. If desired, these dopants may be chosen to increase the radioactive waste gas solubility in the rod. After the dopants have diffused into the pores of the glass rod, the rod is removed from the dopant solution and immersed in a dopant-free solvent.

Rapid This breakage, however, If desired, the concentration of dopant within the pore structure may be varied by various routes. First, for no dopant concentration variation in the glass rod, the solvent bath will be chosen to cause precipitation of the dopants evenly within the pores of the rod. Then the solvent is removed and the rod dried. Secondly, (see Example IX) if a dopant-free layer forming the surface of the rod is desired, the dopant is precipitated as in the first case, but then the rod is transferred to another solvent or solvents whereby the dopant in the surface layer is redissolved and allowed to diffuse.out of the rod, before drying. Thirdly, if a graded variation of dopant is desired with the structure of the rod, the rod is first soaked in a solvent which does not precipitate the dopant and allows its diffusion out of the pore structure. Then it is transferred to another solvent or solvents which induce precipitation and thereafter the rod is dried.

If desired, the drying step can begin at 0°C in vacuum. The rods are then slowly heated, i.e., rate of 15°C/hr, to 625°C under vacuum to remove remaining solvent and allow for dopant decomposition. At 625°C, one or several radioactive gases are introduced into the heating chamber containing the porous rods, and the temperature is held at 625°C for about 24 hours. Then the rods are heated at a rate of 50°C/hr up to 835-900°C where sintering occurs thereby incorporating the dissolved gas into the glass matrix.

In a third novel method, one can develop a radial variation in the concentration of the radioactive gases dissolved within the glass structure. Here the porous glass rod is doped with a material which will reduce its glass transistion temperature, such as potassium in the form of potassium nitrate. After the dopant has completely diffused into the pores of the rod, the dopant is precipitated within the pores either thermally by cooling the rod or by introducing a solvent with very low solubility for the dopant. The rod is then immersed into a solvent with from 5 to 10% solubility for the dopants in order to remove dopant from a layer adjacent to the surface of the rod. After drying of the solvent, the rod will have a high concentration of dopant in the interior and a low concentration in the surface layer thereof.

As a result, the rod will have a higher sintering temperature for its surface layer and a lower sintering temperature for its interior. The sample is dried under vacuum at 0°C for about 24 hours. It is then heated to 600°C under vacuum at 15°C/hr. At 600°C one or several radioactive gases are introduced into the chamber containing the rod.

The temperature is then slowly raised until the inner region of the porous glass rod is sintered, while remaining below the temperature at which the outer region of the rod sinters. Now the radioactive gases are removed from the environment of the rod and the temperature raised to sinter the surface layer. By this method the inner region of the rod will contain dissolved radioactive gases while the surface layer will be essentially free of dissolved radioactive gas content.

Example VII A porous glass preform prepared as described in Example 1 was immersed in methanol for 3 hours at ambient temperature. It was then transferred to a drying chamber maintained at 0°C for 24 hours with suction pumping means operating to dry the rod. The rod was heated to 650°C at a rate of 50°C/hr to complete drying. At 650°C, Kr gas was introduced into the chamber containing the rod at 1 atmosphere.

The rod was then kept at 650°C for 18 hours in a Kr environment and heated to 880°C to achieve sintering in the Kr environment, thus trapping the dissolved Kr gas in the glass matrix.

Example VIII The procedure of Example VII is repeated except that instead of krypton, iodine gas was introduced into the chamber at 650OC by boiling iodine pellets to achieve an atmosphere of iodine at 1/10 bar of pressure. The rod was kept for 18 hours at 650°C in this iodine environment and was heated to 880°C to achieve sintering of the pores of the rod thus trapping the dissolved iodine gas into the glass matrix as evidenced by a pink colour of the resulting non-porous glass rod product.

EXAMPLE IX This example illustrates incorporating both a dissolved solid and a gaseous dopant into the glass matrix.

A porous glass preform prepared as described in Example I was immersed in a 67 weight percent CsNO^ solution at 105°C for 4 hours. The rod was then transferred to, and immersed into, pure water at 0°C to induce precipitation of the cesium nitrate within the pores of the rod.

Total precipitation took 30 seconds. The rod was left in water at 0°C for 3 hours to induce a variation in cesium nitrate concentration within the pores, resulting in a cylindrical layer free of cesium nitrate adjacent to the surface. The rod was then transferred to and immersed in methanol at 0°C where it was kept for 3 hours to further reduce the cesium nitrate concentration at the surface. Dryihg began immediately thereafter by inserting the rod into a vacuum chamber at 0°C for 24 hours. Thereafter, the rod was heated to 625°C at a rate of 15°C/hr to complete drying and to induce decomposition of the cesium 6 8 6 3 nitrate to cesium oxide. The rod was maintained under vacuum at 625°C for 24 hours. Krypton gas was then introduced into the chamber until a pressure of one atmosphere was reached. The rod was maintained at 625°C for an additional 24 hours in this Kr environment, followed by heating at 50°C/hr to the sintering temperature of the rod to thus encapsulate and immobilize dissolved Kr as well as Cs in the glass matrix.

As a result of the improved encapsulation of radioactive material especially radioactive nuclear waste by this invention, these radioactive materials can be put to beneficial use for mankind instead of posing an irrepressible threat to life on earth. Some examples of useful applications are discussed below.

After sintering the porous glass, the radioactive elements are completely encapsulated within the glass matrix. These radioactive elements are chemically bonded and immobilized within the novel glass article and in such form represent a safe, extraordinarily long-term containment of pernicious and hazardous radioactive nuclear waste streams. The novel glass articles may be transported with little risk of leakage of the radioactive isotopes into the environment. They can be deposited into subterranean vaults for long-term storage. These vaults would be preferably more than LOGO feet below the surface of the ground.

Soma radioactive isotopes, including some which do not come from radioactive wastes can be used for beneficial applications rather than storage. Some applications include sterilization of foodstuffs and drugs by destroying bacteria, viruses and other microorganisms; uses in medical and industrial instrumentation, in educational devices, and in research. For sterilization, glass articles containing selected isotopes including radioactive cesium, strontium and cobalt can be used to preserve foods and to recover the nutrients in sewage sludge for inclusion into the food cycle. These applications are not widely used commercially today because suitable containers must be developed to prevent contamination of the foodstuffs by radioactive isotopes and to prevent the associated high probability of radiation poisoning which would occur from their ingestion. Our invention will allow the use of radioactive materials which are produced in large quantities in nuclear reactors by safely encapsulating them as described herein to sterilize food products.

The safe encapsulation of radioactive waste materials in glass articles by our invention also allows their use in medical, industrial, educational and research instrumentation where radiation sources are required for ionization, sterilization, irradiation of patients, quality control and miscellaneous equipment for the detection of flaws in materials by gamma ray irradiation.

Claims (42)

1. A non-porous glass composition containing radioactive material encapsulated and immobilized in the glass matrix, said composition being characterised by at least 75 mol percent SiOg.

2. A non-porous glass composition as claimed in claim 1 wherein the composition has a radiation activity above one millicurie per cubic centimetre of said composition.

3. A non-porous glass composition as claimed in claim 2 wherein said activity is at least one curie per cubic centimetre of said composition.

4. A composition as claimed in any preceding claims wherein the SiOg content is at least 82 mol percent.

5. A composition as claimed in claim 4 wherein the SiOg content is at least 89 mol percent.

6. A composition as claimed in any preceding claim wherein at least 0.1 mol percent radioactive material is encapsulated and immobilized in the glass matrix.

7. A composition as claimed in any preceding claim wherein at least 5 radioactive materials are encapsulated and immobilized in the glass matrix.

8. A composition as claimed in any preceding claim wherein said radioactive material is an oxide of the group of carbon, rubidium, strontium, lanthanides, cobalt, cadmium, silver, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, tellerium, cesium, barium, francium, yttrium, radium and actinides.

9. A composition as claimed in any one of claims 1 to 6 wherein said radioactive material comprises dissolved radioactive gases in the glass matrix.

10. A composition as claimed in claim 9 wherein the gas is one or more of krypton, iodine, bromine, xenon and radon.

11. A composition as claimed in any preceding claim wherein the radioactive material is radioactive nuclear waste.

12. A non-porous glass composition as claimed in claim 1 including the oxides of boron, cobalt and chromium fixed and immobilized in the glass matrix, said oxides being derived from lowlevel radioactive contaminated boric acid wastes.

13. A composition as claimed in claim 12 which further comprises the oxides of cesium, manganese and strontium.

14. A glass article comprising an outer glass cladding or skin composition of at least 90 mol percent Si0 2 and substantially free of radioactive material and an inner core composition of at least 75 mol percent SiOg and radioactive material encapsulated and immobilised therein.

15. A glass article as claimed in claim 14 wherein said cladding or skin composition is at least 95 mol percent SiOg and wherein said inner core composition is at least 82 mol percent SiOg.

16. A glass article as claimed in claim 14 or claim 15 wherein the concentration of radioactive material is sufficient to provide at least one millicurie per cubic centimetre of the glass article.

17. A glass article as claimed in claim 14 wherein the radioactive material comprises an oxide of cesium.

18. A method of preventing the dissemination of radioactive material into the environment which comprises impregnating the pores of a porous glass preform with radioactive material, the preform including at least 75 mol percent SiOg, and obtaining a non-porous 4@S63 glass product containing an amount of radioactive material encapsulated and immobilized therein.

19. A method as claimed in claim 18 including the steps of heating the preform to sintering temperature to collapse the porous structure thereof.

20. A method as claimed in claim 18 or claim 19 wherein said preform contains at least 89 mol percent SiOg.

21. A method as claimed in claim 20 wherein said radioactive material comprises at least five radioactive isotopes.

22. A method as claimed in any one of claims 18 to 21 wherein said radioactive material comprises radioactive nuclear wastes.

23. A method as claimed in any one of claims 18 to 22 wherein the preform, after the impregnation step, is treated to remove radioactive material from the surface thereof thereby producing an outer surface layer which is substantially free of radioactive material.

24. A method as claimed in claim 18 wherein a dried porous glass preform is impregnated with a radioactive gaseous isotope.

25. A method as claimed in claim 19 wherein the heating step is carried out in a reducing atmosphere thereby converting the radioactive material to a lower valence state.

26. A method as claimed in claim 18 wherein said radioactive material is selected from the group of normally radioactive gases and volatilizable materials which yield radioactive gases and the method comprises impregnating the pores of said porous glass preform with a dopant to increase the surface area thereof, removing said dopant from the surface of the preform to thus produce a skin or outer cladding which is substantially free of said dopant and an inner core region containing substantial quantities of dopant therein, drying said preform, impregnating the pores of the dried preform with the abovesaid radioactive material, and heating said preform to sintering temperature to collapse the porous structure of the preform thereby encapsulating and immobilizing the radioactive material in the glass matrix.

27. A method as claimed in claim 26 wherein said dopant is introduced into the pores of the glass in the form of non-radioactive solution.

28. A method as claimed in claim 26 wherein the temperature of the heating step is controlled to first collapse the porous structure of the inner core region while remaining below the temperature at which the skin or outer cladding of the preform sinters, removing radioactive gases from the environment of the preform, thereafter raising the temperature to sinter and collapse the porous structure of the skin or outer cladding.

29. A method as claimed in claim 18 and comprising causing said radioactive material to precipitate within the pores of said preform, drying said preform, causing said radioactive material to be converted to the oxide form at a temperature below the sintering temperature of said preform, heating said preform to sintering temperature to collapse the pores of said preform whereby the radioactive material in the form of its oxide is incorporated into the silica structure, and obtaining a radioactive, non-porous glass product characterised by immobilized radioactive material in the form of its oxide incorporated into the silica structure thereof whereby leakage of said immobilized radioactive material to the environment at environmental temperatures is prevented for extraordinarily long periods of time.

30. A method as claimed in claim 29 wherein said radioactive material is a liquid waste comprising radioactive nuclear waste products comprising radioactive material capable of decomposing into its oxide form at a temperature below the sintering temperature of said preform.

31. A method as claimed in claim 29 or claim 30 wherein said product is stored beneath the surface of the earth.

32. A method as claimed in claim 29 or claim 30 further comprising incorporating the glass product into an instrument as a source of radioactivity.

33. A method as claimed in claim 32 further comprising destroying Sicroorganism employing said instrument.

34. A method as claimed in claim 32 further comprising sterilizing sewage sludge employing said instrument.

35. A method as claimed in claim 29 or claim 30 wherein said radioactive material comprises nitrate compounds.

36. A method as claimed in any one of claims 29 to 35 comprising the further steps of immersing the glass preform containing precipitated radioactive material in the pores thereof in a liquid which has a lower solubility for the radioactive material than the liquid which forms said solution, the immersion step being for a period of time sufficient to produce an outer clad which is substantially free of said radioactive material and an inner core containing said radioactive material, and obtaining a radioactive, non-porous glass product which is characterised by an outer clad which is substantially free of radioactive material and an inner core of immobilized radioactive material 468 63 in the form of its oxide incorporated in the silica structure thereof.

37. A method as claimed in claim 18 wherein the preform, after impregnation, is dried under vacuum or in a desiccator.

38. A method as claimed in claim 37 wherein said drying is carried 5 out at a relatively low temperature.

39. A method as claimed in claim 19 wherein said heating comprises two stages, the preform being heated to a higher temperature during the second stage than during the first stage.

40. A non-porous glass composition substantially as hereinbefore 10 described with reference to the examples.

41. A glass article as claimed in claim 14 and substantially as hereinbefore described.

42. A method of preventing the dissemination of radioactive material into the environment substantially as hereinbefore described with reference to the examples.